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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. In situ high pressure and temperature carbon-13 nmr for the study of carbonation reactions of carbon dioxide

    NASA Astrophysics Data System (ADS)

    Surface, James Andrew

    The aqueous reactions of carbon dioxide with various Mg-containing minerals [MgO, Mg(OH)2, and Mg2SiO4] at several different pressures (1-200 bar) and temperatures (25-150C) have been studied using a novel, elevated pressure and temperature 13C NMR probe. Critical observations about reaction rates, chemical exchange, and pH measurements throughout these reactions and the implications of the in situ measurements made during these reactions are discussed. A new method is used to elucidate pH under high pressure and temperature conditions which utilizes a calculation scheme wherein experimental data and a computational model are combined. Additionally, a 1D pH imaging method is employed to observe pH gradient effects across mineral samples during their reaction with CO2. Finally, other experimental details are discussed including ex situ analysis on carbonate products using pXRD, Raman, and MAS NMR. Detailed discussion outlines how to use 13C NMR to study CO2 mineralization reactions.

  3. Carbon-13 and deuterium isotope effects on the reaction catalyzed by glyceraldehyde-3-phosphate dehydrogenase

    SciTech Connect

    Canellas, P.F.; Cleland, W.W. )

    1991-09-10

    Carbon-13 and deuterium isotope effects have been measured on the reaction catalyzed by rabbit muscle glyceraldehyde-3-phosphate dehydrogenase in an effort to locate the rate-limiting steps. With D-glyceraldehyde 3-phosphate as substrate, hydride transfer is a major, but not the only, slow step prior to release of the first product, and the intrinsic primary deuterium and {sup 13}C isotope effects on this step are 5-5.5 and 1.034-1.040, and the sum of the commitments to catalysis is {approximately} 3. The {sup 13}C isotope effects on thiohemiacetal formation and thioester phosphorolysis are 1.005 or less. With D-glyceraldehyde as substrate, the isotope effects are similar, but the sum of commitments is {approximately} 1.5, so that hydride transfer is more, but still not solely, rate limiting for this slow substrate. The observed {sup 13}C and deuterium equilibrium isotope effects on the overall reaction from the hydrated aldehyde are 0.995 and 1.145, while the {sup 13}C equilibrium isotope effect for conversion of a thiohemiacetal to a thioester is 0.994, and that for conversion of a thioester to an acyl phosphate is 0.997. Somewhat uncertain values for the {sup 13}C equilibrium isotope effects on aldehyde dehydration and formation of a thiohemiacetal are 1.003 and 1.004.

  4. Au-containing all-carbon 1,3-dipoles: generation and [3+2] cycloaddition reactions.

    PubMed

    Zhang, Guozhu; Zhang, Liming

    2008-09-24

    A novel approach to generate Au-containing all-carbon 1,3-dipoles is developed via an unprecedented migration-fragmentation of ketals/acetals. These in situ generated dipoles undergo rapid [3+2] cycloaddition under mild conditions with various enones/enals, electron-rich aromatic aldehydes, and N-benzylindole, leading to flexible formation of highly functionalized dihydrofurans and cyclopentenes. PMID:18754587

  5. 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.

  6. Probing Metal Carbonation Reactions of CO2 in a Model System Containing Forsterite and H2O Using Si-29, C-13 Magic Angle Sample Spinning NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Hu, J.; Kwak, J.; Hoyt, D. W.; Sears, J. A.; Rosso, K. M.; Felmy, A. R.

    2009-12-01

    Ex situ solid state NMR have been used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration using a model silicate mineral forsterite (Mg2SiO4)+scCO2 with and without H2O. Run conditions were 80C and 96 bar. Si-29 NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce Mg2+, and mono- and oligomeric hydroxylated silica species. The 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. Si-29 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. C-13 MAS NMR identified a possible reaction intermediates as (MgCO3)4*Mg(OH)2*5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed. This research is part of a broader effort at PNNL to develop experimental tools and fundamental insights into chemical transformations affecting subsurface CO2 reactive transport. Si-29 (left) and C-13 (right) MAS NMR spectra of Mg2SiO4 under various reaction conditions. Si-29 NMR reveals that in scCO2 without H2O, no reaction is

  7. 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.

  8. 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. PMID:25708541

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. Chemical Reactions in Supercritical Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Wai, Chien M.; Hunt, Fred; Ji, Min; Chen, Xiaoyuan

    1998-12-01

    Utilizing supercritical fluids as environmentally benign solvents for chemical synthesis is one of the new approaches in the "greening" of chemistry. Carbon dioxide is the most widely used gas for supercritical fluid studies because of its moderate critical constants, nontoxic nature, and availability in pure form. One unique property of supercritical carbon dioxide (sc-CO2) is its high solubility for fluorinated compounds. Thus sc-CO2 can be used to replace Freons that are conventionally used as solvents for synthesis of perfluoro-polymers. Another property of sc-CO2 is its miscibility with gases such as H2. Heterogeneous reactions involving these gases may become homogeneous reactions in sc-CO2. Reactions in sc-CO2 may offer several advantages including controlling phase behavior and products, increasing speed of reactions, and obtaining specific reaction channels. This paper describes the following nine types of chemical reactions reported in the literature utilizing sc-CO2 as a solvent to illustrate the unique properties of the supercritical fluid reaction systems: (i) hydrogenation and hydroformylation, (ii) synthesis of organometallic compounds, (iii) metal chelation and extraction, (iv) preparation of inorganic nanoparticles, (v) stereo-selectivity of lipase-catalyzed reactions, (vi) asymmetric catalytic hydrogenation, (vii) polymerization, (viii) Diels-Alder reaction, and (ix) free radical reactions.

  14. 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. PMID:27301444

  15. Synthesis of carbon-13-labeled tetradecanoic acids.

    PubMed

    Sparrow, J T; Patel, K M; Morrisett, J D

    1983-07-01

    The synthesis of tetradecanoic acid enriched with 13C at carbons 1, 3, or 6 is described. The label at the carbonyl carbon was introduced by treating 1-bromotridecane with K13CN (90% enriched) to form the 13C-labeled nitrile, which upon hydrolysis yielded the desired acid. The [3-13C]tetradecanoic acid was synthesized by alkylation of diethyl sodio-malonate with [1-13C]1-bromododecane; the acid was obtained upon saponification and decarboxylation. The label at the 6 position was introduced by coupling the appropriately labeled alkylcadmium chloride with the half acid chloride methyl ester of the appropriate dioic acid, giving the corresponding oxo fatty acid ester. Formation of the tosylhydrazone of the oxo-ester followed by reduction with sodium cyanoborohydride gave the labeled methyl tetradecanoate which, upon hydrolysis, yielded the desired tetradecanoic acid. All tetradecanoic acids were identical to unlabeled analogs as evaluated by gas-liquid chromatography and infrared or NMR spectroscopy. These labeled fatty acids were used subsequently to prepare the correspondingly labeled diacyl phosphatidylcholines. PMID:6631228

  16. Laser-initiated chemical reactions in carbon suspensions.

    SciTech Connect

    McGrath, T. E.; Diebold, G. J.; Bartels, D. M.; Crowell, R. A.; Chemistry; Brown Univ.

    2002-10-31

    We report on laser-initiated chemical reactions in colloidal carbon suspensions. Irradiation of carbon particles ranging in size from 13 to 75 nm in diameter suspended in water, toluene, and benzene with high power nanosecond, picosecond, and femtosecond laser pulses leads to the formation of a number of gaseous hydrocarbons as well as a series of liquid-phase products. In the product gas above irradiated carbon suspensions in water, H{sub 2} and CO, the main reaction products of the carbon-steam reaction, and numerous hydrocarbons ranging from C{sub 1}-C{sub 4} were detected. Irradiation of particulate carbon in toluene and benzene gave H{sub 2} as the main gas product with small amounts of C{sub 1}-C{sub 3} hydrocarbons. Bibenzyl and biphenyl were found as the main liquid products produced in toluene and benzene suspensions, respectively, but with numerous polycyclic aromatic hydrocarbons in smaller concentrations. The amount of products generated by pulsed laser irradiation is shown to depend on particle size and concentration, as well as the laser fluence and pulse width. The chemical reactions reported take place under conditions characterized by extremely high temperatures and pressures of short duration.

  17. 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.

  18. Systematic analysis of reaction cross sections of carbon isotopes

    SciTech Connect

    Horiuchi, W.; Suzuki, Y.; Abu-Ibrahim, B.; Kohama, A.

    2007-04-15

    We systematically analyze total reaction cross sections of carbon isotopes with N= 6-16 on a {sup 12}C target for wide range of incident energy. The intrinsic structure of the carbon isotope is described by a Slater determinant generated from a phenomenological mean-field potential, which reasonably well reproduces the ground-state properties for most of the even N isotopes. We need separate studies not only for odd nuclei but also for {sup 16}C and {sup 22}C to improve their wave functions. The density of the carbon isotope is constructed by eliminating the effect of the center-of-mass motion. For the calculations of the cross sections, we take two schemes, the Glauber approximation and the eikonal model using a global optical potential. Both the reaction models successfully reproduce low and high incident energy data on the cross sections of {sup 12}C, {sup 13}C, and {sup 16}C on {sup 12}C. The calculated reaction cross sections of {sup 15}C are found to be considerably smaller than the empirical values observed at low energy. We find a consistent parametrization of the nucleon-nucleon scattering amplitude, differently from previous ones. Finally, we predict the total reaction cross section of {sup 22}C on {sup 12}C.

  19. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates.

    PubMed

    McDougal, Nolan T; Virgil, Scott C; Stoltz, Brian M

    2010-01-01

    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate. PMID:21072327

  20. 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.

  1. 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.

  2. 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.

  3. Towards understanding global variability in ocean carbon-13

    NASA Astrophysics Data System (ADS)

    Tagliabue, Alessandro; Bopp, Laurent

    2008-03-01

    We include a prognostic parameterization of carbon-13 into a global ocean-biogeochemistry model to investigate the spatiotemporal variability in ocean carbon-13 between 1860 and 2000. Carbon-13 was included in all 10 existing carbon pools, with dynamic fractionations occurring during photosynthesis, gas exchange and carbonate chemistry. We find that ocean distributions of δ13CDIC at any point in time are controlled by the interplay between biological fractionation, gas exchange, and ocean mixing. In particular, the deep ocean δ13CDIC is sensitive (by > 0.5‰) to the degree of ocean ventilation. On interannual timescales, although the variability in δ13CDIC is a first order function of the atmospheric δ13CO2 and overall carbon flux, the spatial distributions are controlled by the degree to which surface waters are exposed to the atmosphere. The δ13CPOC is highly sensitive to the species of inorganic carbon assimilated during photosynthesis (by 10 to 17‰), as well as the intrinsic growth rate and in situ [CO2(aq)], suggesting that phytoplankton utilize both HCO3- and CO2(aq). The relationship between Δδ13CDIC and anthropogenic carbon (Cant) varies by ±70% regionally and circulation and biotic effects can influence estimates of Cant that are based on Δδ13CDIC.

  4. 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.

  5. Structural effects in solvolytic reactions; carbon-13 NMR studies of carbocations†: Effect of increasing electron demand on the carbon-13 NMR shifts in substituted tert-cumyl and 1-aryl-1-cyclopentyl carbocations—correlation of the data by a new set of substituent constants, σC+*†

    PubMed Central

    Brown, Herbert C.; Kelly, David P.; Periasamy, Mariappan

    1980-01-01

    The cationic carbon substituent chemical shifts (ΔδC+) for nine representative meta-substituted tert-cumyl carbocations are correlated satisfactorily by the σm+ substituent constants (slope ρ+ = -18.18, correlation coefficient r = 0.990). However, the substituent chemical shifts (ΔδC+) for the corresponding para derivatives are not correlated by the σp+ substituent constants. The possibility of developing a set of substituent constants capable of correlating such 13C NMR shifts was examined. The slope of the line defined by the meta substituents (ρ+ = -18.18) was utilized to calculate σC+ constants for both meta and para substituents. The utility of these constants was then tested by their ability to correlate the 13C NMR shifts in the cations for a different system, the 1-aryl-1-cyclopentyl cations. Indeed, these σC+ values correlate very well with the ΔδC+ values, yielding ρC+ = -16.84, r = 0.999. PMID:16592926

  6. Reaction of dichlorocarbene with 2-phenyl-1,3-oxathiolane

    SciTech Connect

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

    1987-10-20

    It was established that the reaction of 2-phenyl-1,3-oxathiolane (I) with dichlorocarbene, generated from chloroform in 50% aqueous solution of sodium hydroxide with the use of triethylbenzylammonium chloride as phase-transfer catalyst, leads to the formation of dichloromethyl thiobenzoate (II) and ethylene with yields of 24 and 38% respectively and 60% conversion in the substrate (I). The reaction was conducted at 35-40/sup 0/C for 24 h with the following amounts of the reagents; 0.5 mole of the substrate (I); 5 moles of chloroform; 600 mol of 50% aqueous sodium hydroxide solution; 1 g of triethylbenzylammonium chloride. Compound (II) was isolated by column liquid chromatography on aluminum oxide (40-250 ..mu..) with a 1:5 mixture of diethyl ether and hexane as eluant. The product was identified by means of the IR, PMR, and /sup 13/C NMR spectra.

  7. Reaction studies of hot silicon, germanium and carbon atoms

    SciTech Connect

    Gaspar, P.P.

    1986-11-15

    Research has been continued on hot silicon, germanium and carbon atoms. Progress in the period November 16, 1985 to November 15, 1986 is reviewed in the following areas: (1) Recoil atom reaction studies. (2) Reactions of thermally generated free atoms.

  8. 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.

  9. 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)

  10. Population of 13Be with a Nucleon-Exchange Reaction

    NASA Astrophysics Data System (ADS)

    Marks, Bradon; Deyoung, Paul; Smith, Jenna; Thoennessen, Michael; MoNA Collaboration

    2015-10-01

    Neutron-unbound nuclei are traditionally formed by the removal of one or more nucleons from a fast beam of ions. This method often results in a background, which is difficult to separate from the particle of interest. Nucleon-removal entrance-channels also require the ion beam to be more massive than the particle of interest, which presents the additional challenges of the beam being difficult to make. The present work was done with a nucleon-exchange entrance channel. At the National Superconducting Cyclotron Laboratory, a 71 MeV/u 13B beam impinged on a 47 mg/cm2 thick target of 9Be. As a result numerous reactions occurred, including the population of 13Be through the nucleon-exchange entrance-channel. The 13Be nuclei decayed to 12Be and one neutron in approximately 10-21 seconds. The resulting neutrons were detected by either the Modular Neutron Array (MoNA) or the Large multi-Institution Scintillator Array (LISA), while the 12Be nuclei were directed through an array of charged particle detectors by a 4T superconducting sweeper magnet. The four-momentum vectors of the fragment nucleus and the neutron were calculated to determine the decay energy of 13Be. Monte-Carlo simulations consistent with results from previous analyses of 13Be were satisfactorily fit to the decay-energy spectrum. Additionally, the cross-section for the nucleon-exchange entrance-channel is consistent with a theoretical prediction. This material is based upon work supported by the National Science Foundation under Grant No. PHY-1306074.

  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. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Carbon-13-rich diagenetic carbonates in miocene formations of California and Oregon

    USGS Publications Warehouse

    Murata, K.J.; Friedman, I.I.; Madsen, B.M.

    1967-01-01

    Carbon unusually rich in C13 (??C13 = +5.4 to +19.0 per mil relative to the Peedee belemnite carbonate standard of the University of Chicago) is characteristic of certain diagenetic limestones and dolomites in the Miocene Monterey Shale of California and the Nye Mudstone of Oregon. This heavy carbon may have originated through low-temperature equilibration between CO3- and CO2 in migrating carbonated waters or between CH4 and CO2 in natural gas. Light carbon (??C13 = -5.6 to -18.2 per mil) derived through nonequilibrium oxidation of organic matter also occurs in the carbonate of Monterey Shale in some localities, but at most places it is much less common than heavy carbon.

  18. The production of lipids alternately labelled with carbon-13.

    PubMed

    Boyle-Roden, Elizabeth; German, J B; Wood, B J B

    2003-07-01

    Chlorella cells were shown to have similar fatty acid profiles when grown photoautotrophically or if grown photoheterotrophically with ethanoate (acetate) as carbon source. When supplied with ethanoate labelled with carbon-13 in the methyl group, the alga incorporated it into fatty acids with retention of the sequence of labelling on alternate carbon atoms, thus providing a convenient method for synthesising lipids in a form useful for nuclear magnetic resonance (NMR) studies of lipids in situ in membranes. Marine algae used in fish farming may have higher levels of very highly unsaturated fatty acids; proposals for producing these compounds labelled with carbon-13 are, therefore, presented, based on using centrally labelled glycerol. The scope for producing other substances labelled in a form suitable for NMR studies, such as carotenoids, is discussed. PMID:12919810

  19. Sensitive, quantitative carbon-13 NMR spectra by mechanical sample translation

    NASA Astrophysics Data System (ADS)

    Donovan, Kevin J.; Allen, Mary; Martin, Rachel W.; Shaka, A. J.

    2009-04-01

    Collecting a truly quantitative carbon-13 spectrum is a time-consuming chore. Very long relaxation delays, required between transients to allow the z-magnetization, M z, of the spin with the longestT1 to return to the equilibrium value, M0, must precede each transient. These long delays also reduce sensitivity, as fewer transients per unit time can be acquired. In addition, sometimes T1 is not known to within even a factor of two: a conservative guess for the relaxation delay then leads to very low sensitivity. We demonstrate a fresh method to bypass these problems and collect quantitative carbon-13 spectra by swapping the sample volume after each acquisition with a different portion where the magnetization is already equilibrated to M0. Loading larger sample volumes of 10-20 mL into an unusually long (1520 mm) 5 mm OD. NMR tube and vertically sliding the tube between acquisitions accomplishes the swap. The relaxation delay can then be skipped altogether. The spectra are thus both quantitative, and far more sensitive. We demonstrate the moving tube technique on two small molecules (thymol and butylhydroxytoluene) and show good carbon-13 quantification. The gain in sensitivity can be as much as 10-fold for slowly-relaxing 13C resonances. These experiments show that quantitative, sensitive carbon-13 spectra are possible whenever sufficient sample volumes are available. The method is applicable to any slow-relaxing nuclear spin species, such as 29Si, 15N and other low-γ nuclei.

  20. 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.

  1. Reaction studies of hot silicon, germanium and carbon atoms

    SciTech Connect

    Gaspar, P.P.

    1989-02-01

    Research has been continued on hot silicon, germanium and carbon atoms. The results of experiments directed toward attaining the goals of this research program are briefly presented for the period September 1, 1987 to January 31, 1989 in sections entitled: (1) The mechanism of hydrogen acquisition by high energy silicon atoms. (2) The mechanism of disilene formation in the reactions of recoiling silicon atoms with silane. (3) The contribution of ionic processes to the primary reactions of recoiling silicon atoms. (4) The role of phosphine in hydrogen acquisition by recoiling silicon atoms. (5) Mechanism of reaction of recoiling carbon atoms with aromatic molecules.

  2. 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.

  3. Reaction studies of hot silicon, germanium and carbon atoms

    SciTech Connect

    Gaspar, P.P.

    1990-11-01

    The goal of this project was to increase the authors understanding of the interplay between the kinetic and electronic energy of free atoms and their chemical reactivity by answering the following questions: (1) what is the chemistry of high-energy carbon silicon and germanium atoms recoiling from nuclear transformations; (2) how do the reactions of recoiling carbon, silicon and germanium atoms take place - what are the operative reaction mechanisms; (3) how does the reactivity of free carbon, silicon and germanium atoms vary with energy and electronic state, and what are the differences in the chemistry of these three isoelectronic atoms This research program consisted of a coordinated set of experiments capable of achieving these goals by defining the structures, the kinetic and internal energy, and the charge states of the intermediates formed in the gas-phase reactions of recoiling silicon and germanium atoms with silane, germane, and unsaturated organic molecules, and of recoiling carbon atoms with aromatic molecules. The reactions of high energy silicon, germanium, and carbon atoms created by nuclear recoil were studied with substrates chosen so that their products illuminated the mechanism of the recoil reactions. Information about the energy and electronic state of the recoiling atoms at reaction was obtained from the variation in end product yields and the extent of decomposition and rearrangement of primary products (usually reactive intermediates) as a function of total pressure and the concentration of inert moderator molecules that remove kinetic energy from the recoiling atoms and can induce transitions between electronic spin states. 29 refs.

  4. 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

  5. Reactions over catalysts confined in carbon nanotubes.

    PubMed

    Pan, Xiulian; Bao, Xinhe

    2008-12-21

    We review a new concept for modifying the redox properties of transition metals via confinement within the channels of carbon nanotubes (CNTs), and thus tuning their catalytic performance. Attention is also devoted to novel techniques for homogeneous dispersion of metal nanoparticles inside CNTs since these are essential for optimization of the catalytic activity. PMID:19048128

  6. Kinetics of the reaction between carbon dioxide and tertiary amines

    SciTech Connect

    Crooks, J.E.; Donnellan, J.P. )

    1990-02-16

    The reaction between carbon dioxide and amines is of great technical importance and has been the subject of many investigations. The authors have shown that the reaction for secondary amines in anhydrous ethanol and in aqueous solution is exclusively second-order in amine and that the zwitterion intermediate postulated by Danckwerts is probably of negligible significance in the mechanism. The reaction with tertiary amines has also been studied, but the data are less controversial. In order to complete their studies of the reactions of carbon dioxide with amines, using their conductimetric stopped-flow apparatus, they have studied this reaction for MDEA (methyldiethanolamine, IUPAC name N-methyl-2,2{prime}-iminodiethanol) and TEA (triethanolamine, IUPAC name 2,2{prime},2{double prime}-nitrilotris(ethanol)).

  7. Reaction kinetics of hydrothermal carbonization of loblolly pine.

    PubMed

    Reza, M Toufiq; Yan, Wei; Uddin, M Helal; Lynam, Joan G; Hoekman, S Kent; Coronella, Charles J; Vásquez, Victor R

    2013-07-01

    Hydrothermal carbonization (HTC) is a pretreatment process to convert diverse feedstocks to homogeneous energy-dense solid fuels. Understanding of reaction kinetics is necessary for reactor design and optimization. In this study, the reaction kinetics and effects of particle size on HTC were investigated. Experiments were conducted in a novel two-chamber reactor maintaining isothermal conditions for 15s to 30 min reaction times. Loblolly pine was treated at 200, 230, and 260°C. During the first few minutes of reaction, the solid-product mass yield decreases rapidly while the calorific value increases rapidly. A simple reaction mechanism is proposed and validated, in which both hemicellulose and cellulose degrade in parallel first-order reactions. Activation energy of hemicellulose and cellulose degradation were determined to be 30 and 73 kJ/mol, respectively. For short HTC times, both reaction and diffusion effects were observed. PMID:23651600

  8. Recent developments in enzyme promiscuity for carbon-carbon bond-forming reactions.

    PubMed

    Miao, Yufeng; Rahimi, Mehran; Geertsema, Edzard M; Poelarends, Gerrit J

    2015-04-01

    Numerous enzymes have been found to catalyze additional and completely different types of reactions relative to the natural activity they evolved for. This phenomenon, called catalytic promiscuity, has proven to be a fruitful guide for the development of novel biocatalysts for organic synthesis purposes. As such, enzymes have been identified with promiscuous catalytic activity for, one or more, eminent types of carbon-carbon bond-forming reactions like aldol couplings, Michael(-type) additions, Mannich reactions, Henry reactions, and Knoevenagel condensations. This review focuses on enzymes that promiscuously catalyze these reaction types and exhibit high enantioselectivities (in case chiral products are obtained). PMID:25598537

  9. 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.

  10. 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.

  11. 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.

  12. Kinetics of heterogeneous reactions of carbon and oxygen during combustion of porous carbon particles in oxygen

    SciTech Connect

    Gremyachkin, V.M.

    2006-05-15

    A model of combustion of a high-porosity carbon particle in oxygen is considered, which takes into account heterogeneous and homogeneous chemical reactions inside the particles and radiative heat transfer. The boundaries of the domain where the burning rate depends on the particle temperature are determined. The possibility of two combustion regimes is demonstrated: regime with a high burning rate, where the carbon-oxygen reaction proceeds in a layer adjacent to the particle surface, and regime with a low burning rate, where the reaction proceeds in the entire particle volume. In the regime with a high burning rate, the main product of the reaction between carbon and oxygen is carbon monoxide, whereas both carbon monoxide and carbon dioxide can be formed in the regime with a low burning rate. The kinetic equations of heterogeneous reactions C + O{sub 2} = CO{sub 2} and 2C + O{sub 2} = 2CO are determined, which reveal the retarding effect of carbon monoxide and dioxide on the rates of these reactions.

  13. 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

  14. 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

  15. 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.

  16. 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. PMID:26276544

  17. 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. PMID:25420634

  18. Adverse reactions in treatment with lithium carbonate and haloperidol.

    PubMed

    Baastrup, P C; Hollnagel, P; Sorensen, R; Schou, M

    1976-12-01

    Hospital records of 425 patients who had been treated simultaneously with lithium carbonate and haloperidol were examined. Adverse reactions in these patients were the same as in patients given lithium alone or haloperidol alone. None of the patients developed a syndrome resembling that described by others in patients treated with a lithium and haloperidol combination. PMID:1036539

  19. 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.

  20. 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

  1. Reactions of atomic carbon with oxygenated compounds and the investigation of fullerene chemistry

    SciTech Connect

    Chang, Tsongming.

    1993-01-01

    The reaction of atomic carbon with oxygenated organics produces CO and an energetic fragment. Reactions involving deoxygenation of carbonyl compounds to carbenes, epoxides to alkenes, and ethers to a pair of radicals have been investigated. Carbon atom deoxygenation of cyclopentanone and cylcopentene oxide give the cleavage products, ethylene and allene, along with cyclopentene. The use of 2,2,5,5-d[sub 4]-cyclopentanone as the substrate reveals the direct cleavage of cyclopentanylidene carbene is occurring. A calculation of the energetics of this reaction at the MP4/6-31G[sup *]//6-31G[sup *] level suggests a nonconcerted cleavage via a biradical intermediate. Carbon atoms deoxygenate cyclohexene. Inert gas deactivated energetic cyclohexene. The deoxygenation of other oxygenated compounds by atomic carbon, such as 7-oxabicyclo[2.2.1]heptane to cyclohexane-1,4-diyl biradical, 1,2-epoxy-5-hexane to energetic 1,S-hexadiene, allyl ether to allyl radicals, and [gamma]-butyrolactone to trimethylene-1,3-diyl biradical have also been carried out. Methylketene was deoxygenated to vinylidene carbene which rearranges to propyne via a 1,2-H shift. Dimethylketene was deoxygenated to dimethylethylidene carbene which gives 2-butyne via a 1,2-methyl shift and 1,3-butadiene via a vicinal C-H bond insertion. The addition of hydrogen donors to systems in which C[sub 60] is generated results in the formation of polycyclic aromatic hydrocarbons whose carbon skeleton might represent intermediates in fullerene formation. Based on this result, the author proposed a mechanism of fullerene formation. The use of various amounts of propene as a trap showed that the yield of fullerenes decreases as the amount of the trapped product increases. Attempts to trap intermediates in fullerene formation using halides and metals have been studied. The author has attempted metal encapsulation reactions and investigated some possible chemical reactions of fullerenes.

  2. 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

  3. Conversion of carbon dioxide to resorcylic acid under ultrasonication by Kolbe-Schmitt reaction.

    PubMed

    Shanthi, B; Palanivelu, K

    2015-11-01

    The present work focuses on a new approach for the synthesis of β-resorcylic acid based on Kolbe-Schmitt reaction using carbon dioxide under ultrasonic and mild condition. The Kolbe-Schmitt reaction is a process for the synthesis of β-resorcylic acid (2,4-dihydroxybenzoic acid) from resorcinol in aqueous potassium hydroxide solution with gaseous CO2. The influences of carbonation time, flow rate of CO2 and the molar ratio of resorcinol/potassium hydroxide on the yield percentage of resorcylic acid were investigated. The study was assessed with the conventional thermal method (non ultrasonic method) for Kolbe-Schmitt reaction and it was observed that applying ultrasound to save more than 95% and 38.6% energy as shown by energy consumption calculations in bath type and horn type sonicator respectively. β-Resorcylic acid formed was characterized by (1)H NMR, (13)C NMR, DEPT NMR and FTIR spectroscopy. The amount of CO2 utilized in the reaction was evaluated from the yield percentage of β-resorcylic acid yield. The maximum yield of resorcylic acid of 30% and 65% was obtained at the resorcinol/potassium hydroxide ratio of 1:3, carbonation time of 150 min and the CO2 flow rate of 2L/min in bath type and horn type ultrasonicator, respectively. The applicability of the research work was examined in two different positional isomers of resorcinol under optimum conditions. PMID:26186845

  4. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 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 1,3... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Formaldehyde, reaction products with...

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

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 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 1,3... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Formaldehyde, reaction products with...

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

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 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 1,3... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 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

    ... 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 1,3... 40 Protection of Environment 31 2011-07-01 2011-07-01 false 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

    ... 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 1,3... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Formaldehyde, reaction products with...

  9. REACTIONS OF CHLORITE WITH ACTIVATED CARBON AND WITH VANILLIC ACID AND INDAN ADSORBED ON ACTIVATED CARBON

    EPA Science Inventory

    The reaction between chlorite (CO2(-1)) and vanillic acid, at pH 6.0 in the presence of granular activated carbon (GAC), yielded several reaction products identifiable by GC/MS; no products were found in the absence of GAC. Indan and ClO2 or ClO2(-1) reacted in aqueous solution a...

  10. 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.

  11. Modeling of the peritectic reaction and macro-segregation in casting of low carbon steel

    NASA Astrophysics Data System (ADS)

    El-Bealy, M.; Fredriksson, H.

    1996-12-01

    Macro-microscopic models have been developed to describe the macrosegregation behavior associated with the peritectic reaction of low carbon steel. The macrosegregation model has been established on the basis of previously published work and experimental data. A microscopic model of a three-phase reaction L+ δ→ γ has been modeled by using Fredriksson’s approach. Four horizontal and unidirectional solidified experimental groups simulating continuous casting have been performed with a low carbon steel containing 0.13 wt pct carbon. The extent of macrosegregation of carbon was determined by wet chemical analysis of millings. It is confirmed, by comparing calculated results with experimental results, that this model successfully predicts the occurrence of macrosegregation. The results indicate that a peritectic reaction which is associated with a high cooling rate generates high thermal contraction and a high tensile strain rate at the peritectic temperature. Therefore, the macrosegregation, particularly at the ingot surface, is very sensitive to the cooling rate, where extremely high positive segregation was observed in the case of a high cooling rate. However, in the case of slow cooling rate, negative segregation was noted. The mechanism of macrosegregation with peritectic reaction is discussed in detail.

  12. Characteristics of catalyst for carbon monoxide coupling reaction

    SciTech Connect

    Xu, G.H.; Ma, X.; He, F.; Chen, H.F.

    1995-07-01

    The use of carbon monoxide to produce organic compounds is an important research area for the future. In particular the carbon monoxide coupling reaction takes place at moderate reaction conditions,with low consumption of energy, to produce oxalic acid and oxalate. The chemicals are feedstocks for ethylene glycol synthesis by hydrogenation of oxalate, as well as for products such as pesticides, pharmaceuticals, foodstuffs, polymers, and fine chemicals. The carbon monoxide coupling reaction on supported metal catalysts Pd/Al{sub 2}O{sub 3} and Pd-Fe/Al{sub 2}O{sub 3} was used to study the characteristics of the catalyst under different conditions. The results indicated that the catalytic activation temperature influenced the catalytic activity and that there was an optimum activation temperature. The characteristics of effective coupling catalysts were found to be smaller surface areas and bigger pores, for example the {alpha}-phase of aluminum oxide. X-ray photoelectron spectroscopic analysis results show that the catalytic reaction of CO coupling occurs via a redox mechanism.

  13. Towards a vibrational analysis of spheroidene. Resonance Raman spectroscopy of 13C-labelled spheroidenes in petroleum ether and in the Rhodobacter sphaeroides reaction centre.

    PubMed

    Kok, P; Köhler, J; Groenen, E J; Gebhard, R; van der Hoef, I; Lugtenburg, J; Hoff, A F; Farhoosh, R; Frank, H A

    1994-04-28

    We report resonance Raman spectra of the carotenoid spheroidene and its 14'-13C and 15'-13C substituted analogues in petroleum ether and bound to the reaction centre of Rhodobacter sphaeroides R26. The spectra in petroleum ether correspond to planar all-trans spheroidene while those of the reaction centres are consistent with a nonplanar 15,15'-cis spheroidene. The effect of 13C labelling is largest in the carbon-carbon double-bond stretching region. The 15'-13C substitution of the reaction centre bound spheroidene, however, hardly changes the C=C band as compared to that for the natural abundance spheroidene apart from a new weak band at 1508 cm(-1). This observation has been interpreted as a decoupling of the C15=C15' stretch from the other double-bond stretches in combination with a small intrinsic Raman intensity of this local mode for 15,15'-cis spheroidene. PMID:8167135

  14. Conversion of alkenes to enol silyl ethers of acylsilanes by iridium-catalyzed reaction with a hydrosilane and carbon monoxide

    SciTech Connect

    Chatani, Naoto; Ikeda, Shin-ichi; Ohe, Kouichi

    1992-11-18

    We wish to report that iridium complexes [IrCl(CO){sub 3}]{sub n} and Ir{sub 4}(CO){sub 13} catalyze the reaction of alkenes with a hydrosilane HSiR{sub 3} and carbon monoxide (eq 1) to yield enol silyl ethers of acylsilanes. This unprecedented reaction results in regioselective introduction of carbon monoxide into the terminal carbon atom of alkenes, forming a siloxy(silyl)methylene unit(=C(SiR{sub 3})-OSiR{sub 3}). The present Ir-catalyzed reaction represents the first example of formation of acylsilane derivatives form the HSiR{sub 3}/CO combination. The new catalytic reaction can be applied to a wide variety of terminal alkenes. The acetal, cyano, and epoxide functional groups remain intact through this catalysis. The mechanism of the reaction may involve the possible intervention of a siloxycarbyne comple intermediate. 12 refs., 1 fig., 1 tab.

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. 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

  20. 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

  1. 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

  2. Reaction cross sections of carbon isotopes incident on a proton

    SciTech Connect

    Abu-Ibrahim, B.; Horiuchi, W.; Kohama, A.; Suzuki, Y.

    2008-03-15

    We systematically study total reaction cross sections of carbon isotopes with N=6-16 on a proton target for wide range of incident energies. An emphasis is put on the difference from the case of a carbon target. The calculations include the reaction cross sections of {sup 19,20,22}C at 40A MeV, the data of which have recently been measured at RIKEN. The Glauber theory is used to calculate the reaction cross sections. To describe the intrinsic structure of the carbon isotopes, we use a Slater determinant generated from a phenomenological mean-field potential, and construct the density distributions. To go beyond the simple mean-field model, we adopt two types of dynamical models: One is a core+n model for odd-neutron nuclei, and the other is a core+n+n model for {sup 16}C and {sup 22}C. We propose empirical formulas which are useful in predicting unknown cross sections.

  3. 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.

  4. Electrode reaction mechanisms in molten carbonate fuel cells

    SciTech Connect

    Selman, J.R.; Nishina, T.; Lin, Y.P.; Yeager, E.B.; Tryk, D.A.

    1989-07-01

    This report describes the results of a joint research effort at Illinois Institute of Technology (IIT) and Case Western Reserve University (CWRU) to elucidate the reaction mechanism of oxygen reduction at the cathode of the molten carbonate fuel cell (MCFC). This research project was aimed at developing novel experimental approaches to the chemistry and electrode kinetics of oxygen reduction under MCFC conditions, and improving our fundamental understanding of the reaction mechanism as it applies to the MCFC. IIT's contribution was focused on developing and using rotating electrodes with well-defined mass-transfer properties, to characterize the electrode kinetics of oxygen reduction in molten carbonate. CWRU's contribution was focused on developing and using micro-electrodes for the same purpose, and also on developing spectroscopic cells and carrying out various types of spectroscopic measurements to characterize the oxygen species in molten carbonate under MCFC conditions. This report is divided into two main parts. Part 1 provides the technical background of the questions concerning oxygen reduction in molten carbonate as they apply to the MCFC system. The methodological approach and the objectives of the research are also presented. The second part describes the development of the rotating electrodes, micro-electrodes and spectroscopic cells and the results of measurements, as well as the interpretation of the data. Conclusions of this project, including some recommendations for further research, are also given in this part. 111 refs., 69 figs., 7 tabs.

  5. 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

  6. Controlling Asymmetric Remote and Cascade 1,3-Dipolar Cycloaddition Reactions by Organocatalysis.

    PubMed

    Poulsen, Pernille H; Vergura, Stefania; Monleón, Alicia; Jørgensen, Danny Kaare Bech; Jørgensen, Karl Anker

    2016-05-25

    The regio- and stereoselective control of cycloaddition reactions to polyconjugated systems has been demonstrated by applying asymmetric organocatalysis. Reaction of 2,4-dienals with nitrones allows for a highly regio- and stereoselective 1,3-dipolar cycloaddition in the presence of an aminocatalyst. The first cycloaddition on the remote olefin can be followed either by a cascade reaction or by other selective reactions of the remaining olefin. The chiral products are obtained in good to high yields and excellent diastereo- and enantioselectivities. The remote selective concept has been extended to 2,4,6-trienals by means of a novel enantioselective triple cascade 1,3-dipolar cycloaddition reaction. The formation of chiral poly 1,3-amino alcohols is also demonstrated. PMID:27160510

  7. Carbon kinetic isotope effect in the reaction of CH4 with Cl atoms

    NASA Astrophysics Data System (ADS)

    Saueressig, G.; Bergamaschi, P.; Crowley, J. N.; Fischer, H.; Harris, G. W.

    1995-05-01

    The carbon kinetic isotope effect in the reaction between Cl and CH4 (KIE(sub Cl)) has been measured using tunable diode laser absorption spectroscopy to determine (13)CH4/(12)CH4 ratios. Cl atoms were generated by the irradition of Cl2 in static mixtures of Cl2/CH4/N2 or Cl2/CH4/N2/O2. Both methods resulted in a (KIE(sub Cl)) of 1.066 +/- 0.002 at 297 K. The KIE(sub Cl) displayed a slight temperature dependence, increasing to 1.075 +/- 0.005 at 223 K. This result suggests a significant influence of the title reaction on the stratospheric CH4 isotopic composition and may help to resolve discrepancies between measurements of stratospheric (13)CH4/(12)CH4 profiles and laboratory measurements of KIE(sub OH).

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. R-Matrix Analysis of the 13C(α,n)16O Reaction

    NASA Astrophysics Data System (ADS)

    Kock, Arthur; Rogachev, Grigory

    2015-10-01

    The 13C(α,n)16O reaction plays a crucial role in the main s-process occurring in low-mass thermally-pulsing asymptotic giant branch (TP-AGB) stars, which produces about half of all nuclei heavier than iron. However, direct measurements of this reaction cross section near the Gamow-peak energy are currently not possible due to very small reaction cross sections. Additionally, available cross-section data at higher energy have some inconsistencies, leading to significant uncertainties in low energy extrapolations. A global R-matrix fit was conducted, using all available data for the 13C(α,n)16O, 13C(α, α)13C, and 16O(n,n)16O reactions. Of particular importance was the inclusion of the fixed ANC for the 1 / 2 + state at 6 . 356 MeV in 17O, which was measured recently using the sub-Coulomb α-transfer reaction, as well as the new 13C+ α elastic-scattering data measured in the low-energy region 1 . 6 - 3 . 8 MeV. Important constraining information on various resonances was found, and the uncertainty for the astrophysical 13C(α,n)16O reaction rate was dramatically reduced. Much work on the analysis was done by A. K. Nurmukhanbetova from National Laboratory Astana in Astana, Kazakhstan.

  13. 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...

  14. All-Carbon [3+3] Oxidative Annulations of 1,3-Enynes by Rhodium(III)-Catalyzed C-H Functionalization and 1,4-Migration.

    PubMed

    Burns, David J; Best, Daniel; Wieczysty, Martin D; Lam, Hon Wai

    2015-08-17

    1,3-Enynes containing allylic hydrogens cis to the alkyne function as three-carbon components in rhodium(III)-catalyzed, all-carbon [3+3] oxidative annulations to produce spirodialins. The proposed mechanism of these reactions involves the alkenyl-to-allyl 1,4-rhodium(III) migration. PMID:26224377

  15. All-Carbon [3+3] Oxidative Annulations of 1,3-Enynes by Rhodium(III)-Catalyzed C–H Functionalization and 1,4-Migration**

    PubMed Central

    Burns, David J; Best, Daniel; Wieczysty, Martin D; Lam, Hon Wai

    2015-01-01

    1,3-Enynes containing allylic hydrogens cis to the alkyne function as three-carbon components in rhodium(III)-catalyzed, all-carbon [3+3] oxidative annulations to produce spirodialins. The proposed mechanism of these reactions involves the alkenyl-to-allyl 1,4-rhodium(III) migration. PMID:26224377

  16. Interstitial Reactions in Electron Irradiated Carbon-Doped Silicon.

    NASA Astrophysics Data System (ADS)

    Chappell, Simon Peter

    Available from UMI in association with The British Library. Reactions of interstitial atoms in silicon have been investigated using a combination of infra-red (IR) absorption and deep level transient spectroscopies. The defects were introduced into samples by 2 MeV electron irradiation whilst they were maintained below 200 K; the evolution of the damage was studied during subsequent anneals. Two deep levels at Ev + 0.18 eV and Ev + 0.20 eV, observed in p-type (boron-doped) silicon, were attributed to divacancies (VV) perturbed by a nearest or next-nearest neighbour self-interstitial (I) atom. At 130 K these centres either dissociated to produce VV and I defects or they recombined to form isolated vacancies. I atoms are mobile during the irradiation and exchange sites with the substitutional carbon (C _{rm s}) atoms. The resulting interstitial carbon (C_{rm i }) atoms were selectively trapped by other C_{rm s} or oxygen (O_{rm i}) impurities during anneals near 300 K. In oxygen-free silicon, the lifetime ( tau) for the loss of C_{ rm i} atoms from solution was given by tau = 4.7 times 10^{-10}e^ {(0.88rm eV/kT)} s for both C _{rm i}^+ and C _{rm i}^0. A delay was observed between the loss of C_{ rm i} atoms and the formation of dicarbon centres, indicating the formation of an intermediate precursor defect (CC*). IR absorption lines at 860 and 966 cm ^{-1} were observed and assigned to this defect. It was established, later, that the formation of CC* centres did not lead to a modification of the previously determined value of the diffusion coefficient of C _{rm i}^0. In oxygen-rich silicon, the time constant for the loss of C_{rm i}^+ defects from solution (tau = 1 times 10^{ -13}e^{(0.99rm eV/kT) } s) was more than three times larger than that measured for C_{rm i} ^0 (tau = 1 times 10^{-12}e ^{(0.89rm eV/kT)} s). It was proposed that the high electronegativity of the O_{rm i} impurity results in positive charges on neighbouring silicon atoms which repel the

  17. 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

  18. The cluster and single-particle states in 13C (α,α)13C reactions

    NASA Astrophysics Data System (ADS)

    Mynbayev, N. A.; Nurmukhanbetova, A. K.; Goldberg, V. Z.; Rogachev, G. V.; Golovkov, M. S.; Koloberdin, M.; Ivanov, I.; Nauruzbayev, D. K.; Berdibek, Sh S.; Rakhymzhanov, A. M.; Tribble, R. E.

    2016-06-01

    The excitation functions of elastic scattering of 13C on alpha particle have been measured using the thick-target inverse kinematic method at the heavy ion DC-60 cyclotron. The helium gas was used as a target and also as a degrader to stop the beam. New data (including 180°degree) of the resonances close to the threshold in 17O have been obtained.

  19. 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

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. Heterogeneous processing of {sup 13}NO{sub 2} at zero concentration by monodisperse carbon aerosols

    SciTech Connect

    Tabor, K.; Kalberer, M.; Parrat, Y.

    1995-12-31

    The heterogeneous chemical processing of atmospheric cases by both natural and anthropogenic aerosols plays a key role in the regional as well as global environment. The oxides of nitrogen in the presence of soot present a particularly interesting and relevant topic covering a wide range of such diverse phenomena as acid rain and stratospheric ozone depletion. Detailed investigations of such systems is difficult due to low aerosol and gas species concentrations and, to date, most studies have investigated the chemistry using bulk samples. Nitrogen dioxide is known to be the most important reactive species in this system proceeding as, NO{sub 2} + (C) {r_arrow} (NO{sub 2}{lg_bullet} C){r_arrow} NO + (O {lg_bullet} C). In our current study, we have used {sup 13}N(T{sub 1/2} = 9.96 min) radioisotope labeling techniques to investigate the uptake and chemical conversion of NO{sub 2} in the presence of monodisperse carbon aerosols under real atmospheric conditions, which represents a significant improvement over earlier studies in our lab. {sup 13}N was produced using 14 MeV protons from the PSI Philips cyclotron and a gas target of 2% O{sub 2} in He for the reaction {sup 16}O(p,{alpha}) {sup 13}N. The resulting {sup 13}NO{sub y} were reduced to {sup 13}NO over molybdenum and subsequently oxidized to {sup 13}NO{sub 2} over CrO{sub 3}. Carbon aerosol was generated by spark discharge between graphite rods in argon. Mono-disperse size cuts were selected with a differential mobility analyzer operated with synthetic air. The NO{sub 2} and aerosol streams were admixed and passed through a reaction volume for a reaction time of 10s. A series of selective traps and one filter were used to separate products and reactants: (1) triethanolamine (TEA) denuder to remove unreacted gas phase NO{sub 2}, (2) TEA impregnated class fiber filter to remove aerosol fraction and NO{sub 2} released after uptake, and (3) Co{sub x}O{sub y} trap to remove all residual NO{sub x}.

  5. Reassessing the dissolution of marine carbonates: II. Reaction kinetics

    NASA Astrophysics Data System (ADS)

    Gehlen, M.; Bassinot, F. C.; Chou, L.; McCorkle, D.

    2005-08-01

    We studied dissolution kinetics of the carbonate fraction >150 μm of sediments sampled along two bathymetric transects in the eastern tropical Atlantic: the Sierra Leone Rise (SLR) and the Cape Verde Plateau (CVP). The reaction was followed by monitoring solution pH during freedrift experiments lasting between 46 and 50 h (20 °C, pCO 2≈3100 ppm and 1 atm pressure). The alkalinity reached at the end of the dissolution experiments ranged between 2.444 and 2.798 meq/kg sw. The dissolution time series was extrapolated to equilibrium by fitting an empirical relation to the data. The estimated asymptotic concentration products ([Ca 2+] ∞×[CO 32-] ∞, for t→∞ and dA/dt=0) range from 4.27×10 -7 to 6.77×10 -7 mol 2/kg sw2. These asymptotic concentration products are comparable with the stoichiometric concentration product of aragonite (6.56×10 -7 mol 2/kg sw2) and calcite (4.37 (±0.22)×10 -7 mol 2/kg sw2) derived for the same sediment material during long-term equilibration experiments. They are indicative of the presence of trace amounts of a higher solubility carbonate phase in sediments of the shallow stations (SLR station A, 2637 m; CVP station M, 3104 m). While it is likely that this phase is aragonite, the presence of authigenic carbonate precipitated in contact with supersaturated bottom waters cannot be excluded. Calcite is the main dissolving carbonate mineral in sediments from deeper stations. The order of reaction is always greater than unity. It varies between 1.4 (SLR station C) and 2.8 (CVP station M2), with an average n=2.3±0.4. The higher order reaction is explained in terms of a multiphase system. Specific rate constants range from 0.09 to 0.53 meq/m 2/d.

  6. 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).

  7. 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. PMID:27303826

  8. Asymmetric 1,3-Dipolar Cycloaddition Reactions Catalyzed by Heterocycle-Based Metal Complexes

    NASA Astrophysics Data System (ADS)

    Suga, Hiroyuki

    Highly enantioselective 1,3-dipolar cycloaddition reactions of several 1,3-dipoles, such as nitrones, nitrile oxides, nitrile imines, diazoalkanes, azomethine imines and carbonyl ylides, catalyzed by heterocyclic supramolecular type of metal complexes consisting of chiral heterocyclic compounds and metal salts were described in terms of their ability of asymmetric induction and enantioface differentiation. The scope and limitations of each cycloaddition reactions were also briefly described. Of the chiral hererocycle-based ligands, chiral bisoxazoline, 2,6-bis(oxazolinyl)pyridine, and related oxazoline ligands are shown to be quite effective in obtaining high levels of asymmtric induction. The combination of the bisoxazoline ligand derived from (1S,2R)-cis-1-amino-2-indanol and metal salts was especially efficient for asymmetric cycloaddition reactions of a number of 1,3-dipoles, such as nitrones, nitrile oxide, nitrile imines, diazoacetates and azomethine imines. The metals utilized for the heterocycle-based complexes show a crucial role for degree of asymmetric induction depending upon the 1,3-dipole used. High levels of enantioselectivity were achieved in 1,3-dipolar cycloaddition reactions of unstable carbonyl ylides with benzyloxyacetaldehyde derivatives, α-keto esters, 3-(2-alkenoyl)-2-oxazolidinones, and even vinyl ethers, which were catalyzed by Pybox-lanthanoid metal complexes.

  9. The Nature of Carbonate and Organic δ13C Covariance Through Geological Time

    NASA Astrophysics Data System (ADS)

    Oehlert, A. M.; Swart, P. K.

    2014-12-01

    Significant evolutionary, climatic, and oceanographic events in Earth history are often accompanied by excursions in the carbon isotope composition (δ13C) of marine carbonates and co-occurring sedimentary organic material. The observation of synchronous excursions in the δ13C values of marine carbonates and coeval organic matter is commonly thought to prove that the deposit has not been altered by diagenesis, and that the variations in the δ13C records are the result of a significant change in global carbon cycling. Furthermore, this model suggests that the covariance of carbonate and organic δ13C records is driven only by changes in the δ13C value of the dissolved inorganic carbon in the surface waters of the ocean. However, recent work suggests that there may be at least two alternate models for generating covariance between carbonate and organic δ13C values in the geologic record. One of the models invokes sea-level driven syndepositional mixing between isotopically distinct sources of carbonate and organic material to produce positive covariance between carbonate and organic δ13C values. The second model suggests that post-depositional alteration to the carbonate δ13C values during meteoric diagenesis, in concert with concurrent contributions of terrestrial organic material during subaerial exposure, can also produce co-occurring negative excursions with tightly covariant δ13C records. In contrast to earlier interpretations of covariant δ13C values, these models suggest that both syndepositional and post-depositional factors can significantly influence the relationship between carbonate and organic δ13C values in a variety of depositional environments. The implications for reconstructions of ancient global carbon cycle events will be explored within the context of these three models, and their relative importance throughout geologic time will be discussed.

  10. 12C/13C kinetic isotope effects in the reactions of CH4 with OH and Cl

    NASA Astrophysics Data System (ADS)

    Gupta, Mohan L.; McGrath, M. P.; Cicerone, R. J.; Rowland, F. S.; Wolfsberg, M.

    1997-11-01

    In qualitative agreement with previous MP2 level calculations of the 12C/13C kinetic isotope effects (KIEs) for H-abstraction of CH4 by OH and Cl, higher level calculations yield KIEs at 300 K that differ from the corresponding experimental values, but in different directions. At QCISD(T)/6-311+G(2df,p), the theoretical KIE for CH4+Cl is 32‰ less than the measured value, while for CH4+OH, the theoretical KIE is greater than the measured value, but only by 5‰. Noticeable differences in atmospheric model simulation studies can occur if the measured KIEs are replaced by the analogous theoretical values. For example, the effect of carbon isotopic fractionation from the CH4 + Cl reaction on stratospheric δ13CH4 will be significantly lower than that obtained by Bergamaschi et al. [1996]. It is suggested, for the CH4+OH reaction and especially for the CH4+Cl reaction, that additional KIE measurements are needed.

  11. 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.

  12. 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

  13. 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...

  14. 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

  15. Expression stability of 13 housekeeping genes during carbon starvation of Pseudomonas aeruginosa.

    PubMed

    Alqarni, Budoor; Colley, Brendan; Klebensberger, Janosch; McDougald, Diane; Rice, Scott A

    2016-08-01

    Quantitative real-time polymerase chain reaction (qRT-PCR) is a reliable technique for quantifying mRNA levels when normalised by a stable reference gene/s. Many putative reference genes are known to be affected by physiological stresses, such as nutrient limitation and hence may not be suitable for normalisation. In this study of Pseudomonas aeruginosa, the expression of 13 commonly used reference genes, rpoS, proC, recA, rpsL, rho, oprL, anr, tipA, nadB, fabD, ampC, algD and gyrA, were analysed for changes in expression under carbon starvation and nutrient replete conditions. The results showed that rpoS was the only stably expressed housekeeping gene during carbon starvation. In contrast, other commonly used housekeeping genes were shown to vary by as much as 10-100 fold under starvation conditions. This study has identified a suitable reference gene for qRT-PCR in P. aeruginosa during carbon starvation. The results presented here highlight the need to validate housekeeping genes under the chosen experimental conditions. PMID:27297333

  16. 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.

  17. "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

  18. Reaction Mechanisms of a Photo-Induced [1,3] Sigmatropic Rearrangement via a Nonadiabatic Pathway

    NASA Astrophysics Data System (ADS)

    Wu, Weiqiang; Liu, Kunhui; Yang, Chunfan; Zhao, Hongmei; Wang, Huan; Yu, Youqing; Su, Hongmei

    2009-11-01

    Time-resolved Fourier transform infrared absorption spectroscopy measurements and B3LYP/cc-pVDZ calculations have been conducted to characterize the reaction dynamics of a remarkable photoinduced 1,3-Cl sigmatropic rearrangement reaction upon 193 or 266 nm excitation of the model systems acryloyl chloride (CH2CHCOCl) and crotonyl chloride (CH3CHCHCOCl) in solution. The reaction is elucidated to follow nonadiabatic pathways via two rapid ISC processes, S1 → T1 and T1 → S0, and the S1/T1 and T1/S0 surface intersections are found to play significant roles leading to the nonadiabatic pathways. The S1 → T1 → S0 reaction pathway involving the key participation of the T1 state is the most favorable, corresponding to the lowest energy path. It is also suggested that the photoinduced 1,3-Cl migration reaction of RCHCHCOCl (R = H, CH3) proceeds through a stepwise mechanism involving radical dissociation-recombination, which is quite different from the generally assumed one-step concerted process for pericyclic reactions.

  19. 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.

  20. 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.

  1. Harnessing mineral carbonation reactions to seal fractured shales and sequester carbon

    NASA Astrophysics Data System (ADS)

    Clarens, A. F.; Tao, Z.

    2014-12-01

    Shale oil and gas are being developed widely in the United States despite the potential for long-term climate impacts driven by burning these new hydrocarbon resources and by fugitive emissions from fractured formations. Here the carbonation of calcium-based silicates is studied as a method to re-seal fractured shale formations and to store significant amounts of CO2 after hydrocarbon extraction. Ex situ mineral carbonation has been studied extensively for trapping CO2 from power plants but the application of these reactions directly within shale matrix under in situ conditions to seal shales and sequester carbon has not been studied. The reaction requires the solid calcium-based silicates being present within the shale fracture matrix and flooded with high-pressure CO2. The pressure and temperature within most shale formations would enable this carbonation reaction to precipitate solid calcium carbonate, which would clog fractures. Silicates could be injected in the same way that proppants are injected into shale gas wells. Wollastonite was tested here but other silicate minerals such as olivine could also be used in much the same way. To prove this concept, batch experiments were carried out under reservoir conditions representative of the Marcellus Shale in the presence of ground shale particles (39-177μm) and CaSiO3 powder. X-ray diffraction (XRD) patterns revealed the conversion of CaSiO3 into CaCO3 after 24 hours. Quantitative XRD analysis was used to determine that the conversion ratio of CaSiO3 was ~55% at 3100 Psi and 75oC. The reaction was sensitive to both temperature and pressure with ~58% conversion at an increased temperature of 95oC and only ~50% at lower pressure (2200psi). The morphology observed by Scanning Electron Microscopy (SEM) reveals that the shale particle surfaces are covered with precipitated calcite crystals ranging in size from 1 to 5 μm. Using energy-dispersive X-ray spectroscopy (EDS), the locations of residual CaSiO3and

  2. Preferential formation of 13C- 18O bonds in carbonate minerals, estimated using first-principles lattice dynamics

    NASA Astrophysics Data System (ADS)

    Schauble, Edwin A.; Ghosh, Prosenjit; Eiler, John M.

    2006-05-01

    Equilibrium constants for internal isotopic exchange reactions of the type: Ca12C18O16O2+Ca13C16O3↔Ca13C18O16O2+Ca12C16O3 for individual CO 32- groups in the carbonate minerals calcite (CaCO 3), aragonite (CaCO 3), dolomite (CaMg(CO 3) 2), magnesite (MgCO 3), witherite (BaCO 3), and nahcolite (NaHCO 3) are calculated using first-principles lattice dynamics. Calculations rely on density functional perturbation theory (DFPT) with norm-conserving planewave pseudopotentials to determine the vibrational frequencies of isotopically substituted crystals. Our results predict an ˜0.4‰ excess of 13C18O16O22- groups in all studied carbonate minerals at room-temperature equilibrium, relative to what would be expected in a stochastic mixture of carbonate isotopologues with the same bulk 13C/ 12C, 18O/ 16O, and 17O/ 16O ratios. The amount of excess 13C18O16O22- decreases with increasing temperature of equilibration, from 0.5‰ at 0 °C to <0.1‰ at 300 °C, suggesting that measurements of multiply substituted isotopologues of carbonate could be used to infer temperatures of ancient carbonate mineral precipitation and alteration events, even where the δ 18O of coexisting fluids is uncertain. The predicted temperature sensitivity of the equilibrium constant is ˜0.003‰/°C at 25 °C. Estimated equilibrium constants for the formation of 13C18O16O22- are remarkably uniform for the variety of minerals studied, suggesting that temperature calibrations will also be applicable to carbonate minerals not studied here without greatly compromising accuracy. A related equilibrium constant for the reaction: Ca12C18O16O2+Ca12C17O16O2↔Ca12C18O17O16O+Ca12C16O3 in calcite indicates formation of 0.1‰ excess 12C 18O 17O 16O 2- at 25 °C. In a conventional phosphoric acid reaction of carbonate to form CO 2 for mass-spectrometric analysis, molecules derived from 13C18O16O22- dominate (˜96%) the mass 47 signal, and 12C 18O 17O 16O 2- contributes most of the remainder (3%). This suggests

  3. 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. PMID:26666314

  4. CARBON-13 NUCLEAR MAGNETIC RESONANCE. 13C CHEMICAL SHIFTS AND 13C-199HG COUPLING CONSTANTS FOR SOME ORGANOMERCURY COMPOUNDS

    EPA Science Inventory

    The (13)C shieldings and (13)C-(199)Hg coupling constants of fourteen phenyl- and seven alkyl- and alkenyl-mercury compounds have been obtained. Substituent effects on the (13)C shieldings are similar to those in nonmercurated phenyl compounds, with a similar relationship between...

  5. 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.

  6. 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

  7. Carbonates in leaching reactions in context of 14C dating

    NASA Astrophysics Data System (ADS)

    Michalska, Danuta; Czernik, Justyna

    2015-10-01

    Lime mortars as a mixture of binder and aggregate may contain carbon of various origins. If the mortars are made of totally burnt lime, radiocarbon dating of binder yields the real age of building construction. The presence of carbonaceous aggregate has a significant influence on the 14C measurements results and depending on the type of aggregate and fraction they may cause overaging. Another problem, especially in case of hydraulic mortars that continue to be chemically active for a very long time, is the recrystallization usually connected with rejuvenation of the results but also, depending on local geological structures, with so called reservoir effect yielding apparent ages. An attempt in separating the binder from other carbonaceous components successfully was made for samples from Israel by Nawrocka-Michalska et al. (2007). The same preparation procedure, after taking into account the petrographic composition, was used for samples coming from Poland, Nawrocka et al. (2009). To verify the procedure used previously for non-hydraulic samples determination an experimental tests on carbonaceous mortars with crushed bricks from Novae in Bulgaria were made. Additionally, to identify different carbonaceous structures and their morphology, a cathodoluminescence and scanning electron microscope with electron dispersive spectrometer were applied. The crushed bricks and brick dust used in mortars production process have been interpreted as an alternative use to other pozzolanic materials. The reaction between lime and pozzolanic additives take place easily and affects the rate and course of carbonates decomposition in orthophosphric acid, during the samples pretreatment for dating. The composition of the Bulgarian samples together with influence of climate conditions on mortar carbonates do not allow for making straightforward conclusions in chronology context, but gives some new guidelines in terms of hydraulic mortars application for dating. This work has mainly

  8. Metal doped carbon nanoneedles and effect of carbon organization with activity for hydrogen evolution reaction (HER).

    PubMed

    Araujo, Rafael A; Rubira, Adley F; Asefa, Tewodros; Silva, Rafael

    2016-02-10

    Cellulose nanowhiskers (CNW) from cotton, was prepared by acid hydrolysis and purified using a size selection process to obtain homogeneous samples with average particle size of 270 nm and 85.5% crystallinity. Purified CNW was used as precursor to carbon nanoneedles (CNN) synthesis. The synthesis of CNN loaded with different metals dopants were carried out by a nanoreactor method and the obtained CNNs applied as electrocatalysts for hydrogen evolution reaction (HER). In the carbon nanoneedles synthesis, Ni, Cu, or Fe worked as graphitization catalyst and the metal were found present as dopants in the final material. The used metal appeared to have direct influence on the degree of organization of the particles and also in the surface density of polar groups. It was evaluated the influence of the graphitic organization on the general properties and nickel was found as the more appropriate metal since it leads to a more organized material and also to a high activity toward HER. PMID:26686184

  9. 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

  10. 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.

  11. Relayed 13C magnetization transfer: Detection of malate dehydrogenase reaction in vivo

    NASA Astrophysics Data System (ADS)

    Yang, Jehoon; Shen, Jun

    2007-02-01

    Malate dehydrogenase catalyzes rapid interconversion between dilute metabolites oxaloacetate and malate. Both oxaloacetate and malate are below the detection threshold of in vivo MRS. Oxaloacetate is also in rapid exchange with aspartate catalyzed by aspartate aminotransferase, the latter metabolite is observable in vivo using 13C MRS. We hypothesized that the rapid turnover of oxaloacetate can effectively relay perturbation of magnetization between malate and aspartate. Here, we report indirect observation of the malate dehydrogenase reaction by saturating malate C2 resonance at 71.2 ppm and detecting a reduced aspartate C2 signal at 53.2 ppm due to relayed magnetization transfer via oxaloacetate C2 at 201.3 ppm. Using this strategy the rate of the cerebral malate dehydrogenase reaction was determined to be 9 ± 2 μmol/g wet weight/min (means ± SD, n = 5) at 11.7 Tesla in anesthetized adult rats infused with [1,6- 13C 2]glucose.

  12. Global-through-urban nested three-dimensional simulation of air pollution with a 13,600-reaction photochemical mechanism

    NASA Astrophysics Data System (ADS)

    Jacobson, Mark Z.; Ginnebaugh, Diana L.

    2010-07-01

    To date, gas photochemistry has not been simulated beyond a few hundred reactions in a three-dimensional (3-D) atmospheric model. Here, we treat 4675 gases and 13,626 tropospheric and stratospheric reactions in the 3-D GATOR-GCMOM climate-pollution model and compare results with data and with results from a condensed 152-gas/297-reaction mechanism when the model was nested at increasing resolution from the globe to California to Los Angeles. Gases included C1-C12 organic degradation products and H-, O-, N-, Cl-, Br-, Fl-, and S-containing inorganics. Organic reactions were from the Master Chemical Mechanism. Photolysis coefficients for 2644 photoprocesses and heating rates for 1909 photolyzing gases were solved with an online radiative code in each grid cell using quantum yield/cross section data over 86 UV/visible wavelengths. Spatial/temporal emissions of > 110 gases were derived from the 2005 U.S. National Emission Inventory. The condensed mechanism was a modified Carbon-Bond IV (MCBIV). Three-day simulation results indicate that the more-explicit mechanism reduced the O3 gross error against data versus the MCBIV error against data by only ˜2 percentage points (from 28.3% to 26.5%) and NO2 and HCHO by ˜6 percentage points in Los Angeles. While more-explicit photochemistry improved results, the condensed mechanism was not the main source of ozone error. The more explicit mechanism, which treated absorptive heating by more photolyzing gases, also resulted in a different magnitude of feedbacks to meteorological variables and back to gases themselves than did the less-explicit mechanism. The computer time for all processes in GATOR-GCMOM with the more explicit mechanism (solved with SMVGEAR II in all domains) was only ˜3.7 times that with the MCBIV despite the factors of 31 and 46 increases in numbers of species and reactions, respectively.

  13. Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

    2015-04-01

    Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

  14. 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.

  15. 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.

  16. Autotrophic carbon budget in coral tissue: a new 13C-based model of photosynthate translocation.

    PubMed

    Tremblay, Pascale; Grover, Renaud; Maguer, Jean François; Legendre, Louis; Ferrier-Pagès, Christine

    2012-04-15

    Corals live in symbiosis with dinoflagellates of the genus Symbiodinum. These dinoflagellates translocate a large part of the photosynthetically fixed carbon to the host, which in turn uses it for its own needs. Assessing the carbon budget in coral tissue is a central question in reef studies that still vexes ecophysiologists. The amount of carbon fixed by the symbiotic association can be determined by measuring the rate of photosynthesis, but the amount of carbon translocated by the symbionts to the host and the fate of this carbon are more difficult to assess. In the present study, we propose a novel approach to calculate the budget of autotrophic carbon in the tissue of scleractinian corals, based on a new model and measurements made with the stable isotope (13)C. Colonies of the scleractinian coral Stylophora pistillata were incubated in H(13)CO (-)(3)-enriched seawater, after which the fate of (13)C was followed in the symbionts, the coral tissue and the released particulate organic carbon (i.e. mucus). Results obtained showed that after 15 min, ca. 60% of the carbon fixed was already translocated to the host, and after 48 h, this value reached 78%. However, ca. 48% of the photosynthetically fixed carbon was respired by the symbiotic association, and 28% was released as dissolved organic carbon. This is different from other coral species, where <1% of the total organic carbon released is from newly fixed carbon. Only 23% of the initially fixed carbon was retained in the symbionts and coral tissue after 48 h. Results show that our (13)C-based model could successfully trace the carbon flow from the symbionts to the host, and the photosynthetically acquired carbon lost from the symbiotic association. PMID:22442377

  17. 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

  18. Formal Asymmetric (4+1) Annulation Reaction between Sulfur Ylides and 1,3-Dienes.

    PubMed

    Rousseau, Olivier; Delaunay, Thierry; Dequirez, Geoffroy; Trieu-Van, Tran; Robeyns, Koen; Robiette, Raphaël

    2015-09-01

    A highly enantioselective synthesis of functionalized cyclopentanoids by a formal asymmetric (4+1) annulation strategy was developed. The methodology consists of a stereoselective cyclopropanation reaction between chiral sulfur ylides and 1,3-dienes followed by a, in situ, stereospecific MgI2 -catalyzed rearrangement of vinylcyclopropanes. This method is distinguished by a remarkable compatibility with functional groups and a high stereocontrol. PMID:26235566

  19. 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

  20. 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

  1. A theoretical study on the reaction pathways and the mechanism of 1,3- dipolar cycloaddition of vinyl acetylene and methyl azide.

    PubMed

    Siadati, Seyyed Amir; Mahboobifar, Ali; Nasiri, Ramin

    2014-01-01

    1,3-dipolar cycloaddition procedure is one of the most widely practiced methods in order to synthesize heterocyclic compounds. Although, it seems very simple, but, there are numerous precursors of heterocyclic molecules who have more than one positions to react with a 1,3-dipole species. As a result, while using a precursor with more than one position for reaction, it is probable to synthesize several products with different structures. This paper studies all possible interactions of vinyl acetylene, which has two positions for reaction, with methyl azide. This reaction could lead to the emergence of any 1,3-dipolar cycloaddition products. Our ultimate goal is to help researchers to find out how precursors containing both carbon-carbon double, and the triple bonds interact with 1,3- dipolar species. The present study used the DFT calculations at B3LYP/6-311++G(3df,pd) level to check all probable interactions between vinyl acetylene and methyl azide, and determined Potential Energy Surface, and optimized all species. PMID:24852164

  2. Drought indicated in carbon-13/carbon-12 ratios of southwestern tree rings

    SciTech Connect

    Leavitt, S.W. ); Long, A. )

    1989-04-01

    Stomatal closure during periods of moisture deficiency should theoretically lead to elevated {sup 13}C/{sup 12}C ratios as reduction of available CO{sub 2} leads to diminished photosynthetic discrimination against {sup 13}C in favor of {sup 12}C. Stable-carbon isotope ratio chronologies developed from 5-yr tree-ring groups at 17 sites in six southwestern states were tested for a drought relationship by first fitting a spline curve to each chronology to remove the long-term trend and calculating indices as the ratio of actual to spline curve value. The time series of Del Indices so developed are significantly correlated with 5-yr mean Palmer Hydrological Drought Indices and reconstructed July Palmer Drought Severity Indices from respective areas. Overall, in the period since 1790, and driest pentads were 1900-04 and 1960-64, whereas the wettest were 1980-84 and 1915-19. Maps of drought represented for two pentads seem to be reasonable representations, although spatial correlations of Del Indices with PHDI were generally not significant. These Del Index drought reconstructions may provide a useful measure of past physiological response to drought, although the present cost of analysis would prevent this from being a routine method.

  3. 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

  4. Electrical and morphological characterization of multiwalled carbon nanotubes functionalized via the Bingel reaction

    NASA Astrophysics Data System (ADS)

    Brković, Danijela V.; Ivić, Milka L. Avramov; Rakić, Vesna M.; Valentini, Luca; Uskoković, Petar S.; Marinković, Aleksandar D.

    2015-08-01

    Covalent sidewall functionalization of multiwalled carbon nanotubes (MWCNTs) has been performed using two approaches, direct and indirect cycloaddition through diethyl malonate, based on the Bingel reaction. The results revealed that functionalized MWCNTs demonstrated enhanced electrical properties and significantly lower sheet resistance, especially after electric field thermal assisted annealing at 80 °C was performed. The presence of 1,3-dicarbonyl compounds caused the surface of MWCNTs to be more hydrophilic, approachable for the electrolyte and improved the capacitance performance of Au/MWCNTs electrodes. The modified MWCNTs have been incorporated into nanocomposites by using solution mixing method with polyaniline and drop-casting resulting mixture on the paper substrate. The reduction in the sheet resistance with increasing the content of MWCNTs in the prepared nanocomposite films has been achieved.

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

    PubMed

    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. PMID:27102684

  6. 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.

  7. REACTION OF ACTIVATED CARBON WITH AQUEOUS CHLORINE AND CHLORINE DIOXIDE

    EPA Science Inventory

    The objective of this research was to determine whether aqueous chlorine and chlorine dioxide react with activated carbon, or with compounds adsorbed on activated carbon, to produce compounds that would not form in the absence of activated carbon. The experimental conditions were...

  8. 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

  9. Global carbon sinks and their variability inferred from atmospheric O2 and delta13C.

    PubMed

    Battle, M; Bender, M L; Tans, P P; White, J W; Ellis, J T; Conway, T; Francey, R J

    2000-03-31

    Recent time-series measurements of atmospheric O2 show that the land biosphere and world oceans annually sequestered 1.4 +/- 0.8 and 2.0 +/- 0.6 gigatons of carbon, respectively, between mid-1991 and mid-1997. The rapid storage of carbon by the land biosphere from 1991 to 1997 contrasts with the 1980s, when the land biosphere was approximately neutral. Comparison with measurements of delta13CO2 implies an isotopic flux of 89 +/- 21 gigatons of carbon per mil per year, in agreement with model- and inventory-based estimates of this flux. Both the delta13C and the O2 data show significant interannual variability in carbon storage over the period of record. The general agreement of the independent estimates from O2 and delta13C is a robust signal of variable carbon uptake by both the land biosphere and the oceans. PMID:10741962

  10. Natural abundance measurements of 13C indicate increased deep soil carbon mineralization after forest disturbance

    NASA Astrophysics Data System (ADS)

    Diochon, Amanda; Kellman, Lisa

    2008-07-01

    Northern forest soils represent globally important stores of carbon (C), yet there is no consensus about how they are altered by the widespread practice of harvesting that dominates many forested landscapes. Here we present the first study to systematically investigate the utility of δ 13C and C content depth profiles to infer temporal changes in belowground carbon cycling processes following disturbance in a pure C3 ecosystem. We document carbon concentration and δ 13C depth profile enrichment trends consistent with a kinetic fractionation arising from soil organic carbon (SOC) humification across a northern forest chronosequence (1, 15, 45, 80 and 125+ yrs). Reduced soil C storage that coincided with observed soil profile δ 13C-enrichment patterns which intensified following clearcut harvesting, pointed to losses of SOC in the deeper (>20 cm) mineral soil. This study suggests the δ 13C approach may assist in identifying mechanisms responsible for soil C storage changes in disturbed C3 forest ecosystems.

  11. 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)

  12. 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.

  13. The first observation of Carbon-13 spin noise spectra

    PubMed Central

    Schlagnitweit, Judith; Müller, Norbert

    2012-01-01

    We demonstrate the first 13C NMR spin noise spectra obtained without any pulse excitation by direct detection of the randomly fluctuating noise from samples in a cryogenically cooled probe. Noise power spectra were obtained from 13C enriched methanol and glycerol samples at 176 MHz without and with 1H decoupling, which increases the sensitivity without introducing radio frequency interference with the weak spin noise. The multiplet amplitude ratios in 1H coupled spectra indicate that, although pure spin noise prevails in these spectra, the influence of absorbed circuit noise is still significant at the high concentrations used. In accordance with the theory heteronuclear Overhauser enhancements are absent from the 1H-decoupled 13C spin noise spectra. PMID:23041799

  14. Computational design of organometallic oligomers featuring 1,3-metal-carbon bonding and planar tetracoordinate carbon atoms.

    PubMed

    Zhao, Xue-Feng; Yuan, Cai-Xia; Wang, Xiang; Li, Jia-Jia; Wu, Yan-Bo; Wang, Xiaotai

    2016-01-15

    Density functional theory computations (B3LYP) have been used to explore the chemistry of titanium-aromatic carbon "edge complexes" with 1,3-metal-carbon (1,3-MC) bonding between Ti and planar tetracoordinate Cβ . The titanium-coordinated, end-capping chlorides are replaced with OH or SH groups to afford two series of difunctional monomers that can undergo condensation to form oxide- and sulfide-bridged oligomers. The sulfide-linked oligomers have less molecular strain and are more exergonic than the corresponding oxide-linked oligomers. The HOMO-LUMO gap of the oligomers varies with their composition and decreases with growing oligomer chain. This theoretical study is intended to enrich 1,3-MC bonding and planar tetracoordinate carbon chemistry and provide interesting ideas to experimentalists. Organometallic complexes with the TiE2 (E = OH and SH) decoration on the edge of aromatic hydrocarbons have been computationally designed, which feature 1,3-metal-carbon (1,3-MC) bonding between titanium and planar tetracoordinate β-carbon. Condensation of these difunctional monomers by eliminating small molecules (H2O and H2S) produce chain-like oligomers. The HOMO-LUMO gaps of the oligomers decreases with growing oligomer chain, a trend that suggests possible semiconductor properties for oligomers with longer chains. PMID:26399226

  15. A large metabolic carbon contribution to the δ 13C record in marine aragonitic bivalve shells

    NASA Astrophysics Data System (ADS)

    Gillikin, David P.; Lorrain, Anne; Meng, Li; Dehairs, Frank

    2007-06-01

    It is well known that the incorporation of isotopically light metabolic carbon (C M) significantly affects the stable carbon isotope (δ 13C) signal recorded in biogenic carbonates. This can obscure the record of δ 13C of seawater dissolved inorganic carbon13C DIC) potentially archived in the shell carbonate. To assess the C M contribution to Mercenaria mercenaria shells collected in North Carolina, USA, we sampled seawater δ 13C DIC, tissue, hemolymph and shell δ 13C. All shells showed an ontogenic decrease in shell δ 13C, with as much as a 4‰ decrease over the lifespan of the clam. There was no apparent ontogenic change in food source indicated by soft tissue δ 13C values, therefore a change in the respired δ 13C value cannot be the cause of this decrease. Hemolymph δ 13C, on the other hand, did exhibit a negative relationship with shell height indicating that respired CO 2 does influence the δ 13C value of internal fluids and that the amount of respired CO 2 is related to the size or age of the bivalve. The percent metabolic C incorporated into the shell (%C M) was significantly higher (up to 37%, with a range from 5% to 37%) than has been found in other bivalve shells, which usually contain less than 10%C M. Interestingly, the hemolymph did contain less than 10%C M, suggesting that complex fractionation might occur between hemolymph and calcifying fluids. Simple shell biometrics explained nearly 60% of the observed variability in %C M, however, this is not robust enough to predict %C M for fossil shells. Thus, the metabolic effect on shell δ 13C cannot easily be accounted for to allow reliable δ 13C DIC reconstructions. However, there does seem to be a common effect of size, as all sites had indistinguishable slopes between the %C M and shell height (+0.19% per mm of shell height).

  16. Base-promoted reactions of bridged ketones and 1,3- and 1,4-haloalkyl azides: competitive alkylation vs azidation reactions of ketone enolates.

    PubMed

    Yao, Lei; Smith, Brenton T; Aubé, Jeffrey

    2004-03-01

    The reactions of 1,3- and 1,4-haloalkyl azides with enolates of 2-norbornanone (and a ring-expanded analog) afford polycyclic 1,2,3-triazolines in good yields. The reaction occurs by the initial azidation of the ketone enolate, followed in order by triazoline formation and O-alkylation. An interesting element of this process is the preferential reaction of the alkyl azide with an enolate anion as opposed to the more familiar reaction of the alkyl halide (including Cl and I derivatives). Reactions of acyclic or monocyclic enolates generally lead to 1,2,3-triazoles but none of the alternative C-alkylation product. PMID:14987033

  17. 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

  18. 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

  19. Theoretical study of dehydration-carbonation reaction on brucite surface based on ab initio quantum mechanic calculations

    NASA Astrophysics Data System (ADS)

    Churakov, S. V.; Parrinello, M.

    2003-04-01

    The carbonation of brucite (Mg(OH)2) has been considered as a potential technology for cleaning industrial carbon dioxide waste. The kinetics of the reaction Mg(OH)2 + CO2 -> MgCO3 + H2O have been studied experimentally at 573°C by Bearat at al. [1]. Their experiments suggest that the carbonation of magnesium hydroxide proceeds by the reaction Mg(OH)2 -> MgO + H2O followed by the adsorption of CO2 molecules on the dehydrated brucite surface. Due to the large difference in volumes between Mg(OH)2 and MgO, dehydration causes the formation of dislocations and cracks, allowing water molecules to leave the brucite surface and facilitating the advance of the carbonation front in the bulk solid. The detailed mechanism of this process is however unknown. We used the Car-Parrinello ab initio molecular dynamics method to study the structure and dynamics of the (0001), (1-100) and (11-20) surfaces of brucit and calculated the enthalpy and activation barrier of H2O nucleation and dehydration on different surfaces. The results obtained are in agreement with previous studies of brucite dehydration by Masini and Bernasconi [2]. The reactive Car-Parrinello molecular dynamics method [3] has been applied to investigate the detailed mechanism of the dehydration-carbonation reaction at the (1-100) interface of brucite with the gas phase. Based on the results of our MD simulations and the calculated enthalpy of CO2 adsorption on the dehydrated brucite surfaces we propose a mechanism for the dehydration/carbonation reaction. [1] Bearat H, McKelvy MJ, Chizmeshya AVG, Sharma R, Carpenter RW (2002) J. Amer. Ceram. Soc. 85(4):742 [2] Masini P and Bernasconi M (2001) J. Phys. Cond. Mat. 13: 1-12 [3] Iannuzzi M, Laio A and Parrinello M (2003) Phys. Rev. Lett. (submitted)

  20. Carbon partitioning into cell wall structural carbohydrates by following 13C label in Switchgrass

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Carbon isotope ratio analyses of stover tissue from both the lowland (Kanlow) and the upland (Summer) cultivars of switchgrass indicated that the value of Kanlow was less negative (-12.7 per mil.) than the upland variety Summer (-13.1). Preliminary observations on the carbon isotope ratio of cellulo...

  1. In vivo 13 carbon metabolic imaging at 3T with hyperpolarized 13C-1-pyruvate.

    PubMed

    Kohler, S J; Yen, Y; Wolber, J; Chen, A P; Albers, M J; Bok, R; Zhang, V; Tropp, J; Nelson, S; Vigneron, D B; Kurhanewicz, J; Hurd, R E

    2007-07-01

    We present for the first time dynamic spectra and spectroscopic images acquired in normal rats at 3T following the injection of (13)C-1-pyruvate that was hyperpolarized by the dynamic nuclear polarization (DNP) method. Spectroscopic sampling was optimized for signal-to-noise ratio (SNR) and for spectral resolution of (13)C-1-pyruvate and its metabolic products (13)C-1-alanine, (13)C-1-lactate, and (13)C-bicarbonate. Dynamic spectra in rats were collected with a temporal resolution of 3 s from a 90-mm axial slab using a dual (1)H-(13)C quadrature birdcage coil to observe the combined effects of metabolism, flow, and T(1) relaxation. In separate experiments, spectroscopic imaging data were obtained during a 17-s acquisition of a 20-mm axial slice centered on the rat kidney region to provide information on the spatial distribution of the metabolites. Conversion of pyruvate to lactate, alanine, and bicarbonate occurred within a minute of injection. Alanine was observed primarily in skeletal muscle and liver, while pyruvate, lactate, and bicarbonate concentrations were relatively high in the vasculature and kidneys. In contrast to earlier work at 1.5 T, bicarbonate was routinely observed in skeletal muscle as well as the kidney and vasculature. PMID:17659629

  2. Medium effects on reactions of the carbonate radical with thiocyanate, iodide, and ferrocyanide ions

    NASA Astrophysics Data System (ADS)

    Lymar, Sergei V.; Schwarz, Harold A.; Czapski, Gidon

    2000-10-01

    Results are presented which show that there is no pH dependence of the carbonate radical reactivity toward SCN -, I -, and Fe(CN) 64- above pH 8.5. It is demonstrated that observations in the literature on these reactions which have been interpreted to show a p Ka of 9.5 for the carbonate radical, in disagreement with other reports that the radical is not protonated in this pH region, can be explained by the medium effects. It is also shown that previous studies of the reaction between carbonate radical and thiocyanate are in error, and the mechanism of this reaction is elucidated.

  3. Coupling and higher-order effects in the {sup 12}C(d,p){sup 13}C and {sup 13}C(p,d){sup 12}C reactions

    SciTech Connect

    Delaunay, F.; Nunes, F.M.; Lynch, W.G.; Tsang, M.B.

    2005-07-01

    Coupled-channel calculations are performed for the {sup 12}C(d,p){sup 13}C and {sup 13}C(p,d){sup 12}C reactions between 7 and 60 MeV to study the effect of inelastic couplings in transfer reactions. The effect of treating transfer beyond Born approximation is also addressed. The coupling to the {sup 12}C 2{sup +} state is found to change the peak cross section by up to 15%. Effects beyond Born approximation lead to a significant renormalization of the cross sections, between 5% and 10% for deuteron energies above 10 MeV and larger than 10% for lower energies. We also performed calculations including the remnant term in the transfer operator, which has a small impact on the {sup 12}C(d,p){sup 13}C(g.s.) and {sup 13}C(p,d){sup 12}C(g.s.) reactions (where g.s. indicates ground state). Above 30-MeV deuteron energy, the effect of the remnant term is larger than 10% for the {sup 12}C(d,p){sup 13}C(1/2{sup +}, 3.09 MeV) reaction and is found to increase with decreasing neutron separation energy for the 3.09-MeV state of {sup 13}C. This is of importance for transfer reactions with weakly bound nuclei.

  4. 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.

  5. Elastic scattering and neutron transfer of the 26Mg + 13C reaction

    NASA Astrophysics Data System (ADS)

    McCleskey, Matthew; Alharby, A.; Banu, A.; Goldberg, V. Z.; McCleskey, E.; Roeder, B. T.; Spiridon, A.; Trache, L.; Tribble, R. E.

    2013-10-01

    Direct proton capture on 26Si is of interest for its role in the destruction of 26Si that would otherwise be available to β+ decay into 26mAl. This is part of the network of reactions that influence the production and destruction of the important astrophysical observable 26Al. The 13C(26Mg,27Mg)12C reaction at 12 MeV/nucleon has been measured at Texas A &M University Cyclotron Institute with the aim to determine ANC for 27P <--> p + 26Si via mirror symmetry. Details of the experiment as well as preliminary results will be presented. Present address: Faculty of Sciences, Physics Department, Princess Nora University Riyadh, Saudi Arabia.

  6. Studies of reductive elimination reactions to form carbon-oxygen bonds from Pt(IV) complexes.

    PubMed

    Williams, B S; Goldberg, K I

    2001-03-21

    The platinum(IV) complexes fac-L(2)PtMe(3)(OR) (L(2) = bis(diphenylphosphino)ethane, o-bis(diphenylphosphino)benzene, R = carboxyl, aryl; L = PMe(3), R = aryl) undergo reductive elimination reactions to form carbon-oxygen bonds and/or carbon-carbon bonds. The carbon-oxygen reductive elimination reaction produces either methyl esters or methyl aryl ethers (anisoles) and L(2)PtMe(2), while the carbon-carbon reductive elimination reaction affords ethane and L(2)PtMe(OR). Choice of reaction conditions allows the selection of either type of coupling over the other. A detailed mechanistic study of the reductive elimination reactions supports dissociation of the OR(-) ligand as the initial step for the C-O bond formation reaction. This is followed by a nucleophilic attack of OR(-) upon a methyl group bound to the Pt(IV) cation to produce the products MeOR and L(2)PtMe(2). C-C reductive elimination proceeds from L(2)PtMe(3)(OR) by initial L (L = PMe(3)) or OR(-) (L(2) = dppe, dppbz) dissociation, followed by C-C coupling from the resulting five-coordinate intermediate. Our studies demonstrate that both C-C and C-O reductive elimination reactions from Pt(IV) are more facile in polar solvents, in the presence of Lewis acids, and for OR(-) groups that contain electron withdrawing substituents. PMID:11456927

  7. 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

  8. Reactivity of Single-Walled Carbon Nanotubes in the Diels-Alder Cycloaddition Reaction: Distortion-Interaction Analysis along the Reaction Pathway.

    PubMed

    Li, Yingzi; Osuna, Sílvia; Garcia-Borràs, Marc; Qi, Xiaotian; Liu, Song; Houk, Kendall N; Lan, Yu

    2016-08-26

    Diels-Alder cycloaddition is one of the most powerful tools for the functionalization of single-walled carbon nanotubes (SWCNTs). Density functional theory at the B3-LYP level of theory has been used to investigate the reactivity of different-diameter SWCNTs (4-9,5) in Diels-Alder reactions with 1,3-butadiene; the reactivity was found to decrease with increasing SWCNT diameter. Distortion/interaction analysis along the whole reaction pathway was found to be a better way to explore the reactivity of this type of reaction. The difference in interaction energy along the reaction pathway is larger than that of the corresponding distortion energy. However, the distortion energy plots for these reactions show the same trend. Therefore, the formation of the transition state can be determined from the interaction energy. A lower interaction energy leads to an earlier transition state, which indicates a lower activation energy. The computational results also indicate that the original distortion of the SWCNTs leads to an increase in the reactivity of the SWCNTs. PMID:27465519

  9. 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.

  10. An Unusual Carbon-Carbon Bond Cleavage Reaction During Phosphinothricin Biosynthesis

    PubMed Central

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

    2010-01-01

    Natural products containing phosphorus-carbon bonds have found widespread use in medicine and agriculture1. One such compound, phosphinothricin tripeptide (PTT), contains the unusual amino acid phosphinothricin (PT) attached to two alanine residues (Fig. 1). Synthetic PT (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 PTT biosynthesis 2-hydroxyethylphosphonate (HEP) is converted to hydroxymethylphosphonate (HMP) (Fig. 1)2. Reported here are the in vitro reconstitution of this unprecedented C(sp3)-C(sp3) bond cleavage reaction and X-ray crystal structures of the enzyme. The protein is a mononuclear non-heme 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 catalyzed by the 2-His-1-carboxylate mononuclear non-heme iron family of enzymes. PMID:19516340

  11. 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.

  12. 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.

  13. Cryogenic abnormal thermal expansion properties of carbon-doped La(Fe,Si)13 compounds.

    PubMed

    Li, Shaopeng; Huang, Rongjin; Zhao, Yuqiang; Wang, Wei; Li, Laifeng

    2015-12-14

    Recently, La(Fe,Si)13-based compounds have attracted much attention due to their isotropic and tunable abnormal thermal expansion (ATE) properties as well as bright prospects for practical applications. In this research, we have prepared cubic NaZn13-type carbon-doped La(Fe,Si)13 compounds by the arc-melting method, and their ATE and magnetic properties were investigated by means of variable-temperature X-ray diffraction, strain gauge and the physical property measurement system (PPMS). The experimental results indicate that both micro and macro negative thermal expansion (NTE) behaviors gradually weaken with the increase of interstitial carbon atoms. Moreover, the temperature region with the most remarkable NTE properties has been broadened and near zero thermal expansion (NZTE) behavior occurs in the bulk carbon-doped La(Fe,Si)13 compounds. PMID:26549525

  14. 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.

  15. Overcoming Barriers to the Remediation of Carbon Tetrachloride Through Manipulation of Competing Reaction Mechanisms

    SciTech Connect

    Tratnyek, Paul G.; Amonette, James E.; Bylaska, Eric J.

    2004-03-29

    Most approaches that have been proposed for the remediation of groundwater contaminated with carbon tetrachloride produce chloroform as the major product and methylene chloride as a minor product. Both of these products are nearly as persistent and problematic as the parent compound, but competing reaction pathways produce the more desirable products carbon monoxide and/or formate. Branching between these reaction pathways is highly variable, but the controlling factors have not been identified. To improve the applicability of reductive remediation technologies to the large plumes of carbon tetrachloride at several DOE sites, we are pursuing the complete characterization of the mechanisms and kinetics of competing degradation reactions of carbon tetrachloride through laboratory experiments closely coordinated with theoretical modeling studies. The results are beginning to suggest strategies for maximizing the yield of desirable products from carbon tetrachloride degradation, which will be tested in column model systems using real site waters and matrix materials.

  16. The carbon kinetic isotope effects of ozone-alkene reactions in the gas-phase and the impact of ozone reactions on the stable carbon isotope ratios of alkenes in the atmosphere

    NASA Astrophysics Data System (ADS)

    Iannone, R.; Anderson, R. S.; Rudolph, J.; Huang, L.; Ernst, D.

    2003-07-01

    The kinetic isotope effects (KIEs) for several ozone-alkene reactions in the gas phase were studied in a 30 L PTFE reaction chamber. The time dependence of the stable carbon isotope ratios and the concentrations were determined using a gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) system. The following average KIE values were obtained: 18.9 +/- 2.8 (ethene), 9.5 +/- 2.5 (propene), 8.7 +/- 1 (1-butene), 8.1 +/- 0.4 (E-2-butene), 7.9 +/- 0.4 (1,3-butadiene), 6.7 +/- 0.9 (1-pentene), 7.3 +/- 0.2 (Z-2-pentene), 6.7 +/- 0.7 (cyclopentene), 6.1 +/- 1 (isoprene), 5.0 +/- 0.7 (1-hexene), 5.6 +/- 0.5 (cyclohexene), and 4.3 +/- 0.7 (1-heptene). These data are the first of their kind to be reported in the literature. The ozone-alkene KIE values show a systematic inverse dependence from alkene carbon number. Based on the observed KIEs, the contribution of ozone-alkene reactions to the isotopic fractionation of alkenes in the atmosphere can be estimated. On average this contribution is generally small compared to the impact of reaction with OH radicals. However, when OH-concentrations are very low, e.g. during nighttime and at high latitudes in winter, the contribution of the ozone reaction dominates and under these conditions the ozone-alkene reaction will have a clearly visible impact on the stable carbon isotope ratio of atmospheric alkenes.

  17. 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.

  18. Natural abundance carbon-13 nuclear magnetic resonance studies of histone and DNA dynamics in nucleosome cores.

    PubMed

    Hilliard, P R; Smith, R M; Rill, R L

    1986-05-01

    Natural abundance carbon-13 nuclear magnetic resonance spectra (67.9 MHz) were obtained for native nucleosome cores: cores dissociated in 2 M NaCl and 2 M NaCl, 6 M urea; and cores degraded with DNase I plus proteinase K. Phosphorus-31 NMR spectra of native and dissociated cores and core length DNA were also obtained at 60.7 MHz. The 31P resonance and spin-lattice relaxation time (T1) of DNA were only slightly affected by packaging in nucleosome cores, in agreement with other reports, but 13C resonances of DNA were essentially unobservable. The loss of DNA spectral intensity suggests that rapid internal motions of DNA sugar carbons in protein-free DNA previously demonstrated by 13C NMR methods are partly restricted in nucleosomes. The 13C spectrum of native cores contains many narrow intense resonances assigned to lysine side chain and alpha-carbons, glycine alpha-carbons, alanine alpha- and beta- carbons, and arginine side chain carbons. Several weaker resonances were also assigned. The narrow line widths, short T1 values, and non-minimal nuclear Overhauser enhancements of these resonances, including alpha- and beta-carbons, show that some terminal chain segments of histones in nucleosomes are as mobile as small random coil polypeptides. The mobile segments include about 9% of all histone residues and 25% of all lysines, but only 10% of all arginines. The compositions of these segments indicate that mobile regions are located in amino- or carboxyl-terminal sequences of two or more histones. In addition, high mobility was observed for side chain carbons of 45-50% of all lysines (delta and epsilon carbons) and about 25% of all arginines (zeta carbon) in histones (including those in mobile segments), suggesting that basic residues in terminal histone sequences are not strongly involved in nucleosome structure and may instead help stabilize higher order chromatin structure. PMID:3700380

  19. Synthesis and carbon-13 NMR studies of liquid crystals

    NASA Astrophysics Data System (ADS)

    Sun, Hong

    2000-08-01

    The orientation of different segments of 4'-cyanophenyl 4-heptylbenzoate (7CPB) has been investigated using 13C NMR. The method of proton encoded local field (PELF) spectroscopy was used in combination with off-magic-angle spinning (OMAS) of the sample. High-resolution 2D spectra were obtained and the order parameters were calculated from the spectra. Linear relationships between the obtained order parameters and anisotropic chemical shifts determined by 1D 13C NMR were established and semi-empirical parameters were obtained. A 1:2 mixture of 7CPB and its chain-perfluorinated analog (7PFCPB) shows interesting phase behavior with changing of temperature. The mixture was studied by the use of 13C NMR and polarizing optical microscopy. The order parameters of 7CPB in the smectic A phase of the mixture were calculated using the semi-empirical parameters obtained by the 2D NMR method. Eight series of liquid crystals containing an electron- donating group at one end of a conjugated system and an electron-withdrawing group at the other end have been synthesized. The electron-donating group is 4- n-alkylpiperazinyl group, the electron- withdrawing group is nitro group and the conjugated system is diphenyldiazene with zero, one or two substituents on the phenyl rings. The substituents are -F, -Cl, and -CH3. Two series of compounds with cyano group as electron-withdrawing group were also synthesized. Most of the compounds synthesized are nematogenic and exhibit rather broad liquid crystalline ranges. The effects of the lateral substituents on the optical absorption and phase transition temperatures are correlated with their nature and position of substitution. Birefringence, dielectric anisotropy, elastic constant ratio and rise time of the liquid crystals were carried out using 10 wt% LC mixtures in E7. It has been found that lateral substituents have subtle effects on the properties. The presence of lateral substituents depresses melting points and clearing points of the

  20. Stereoselective entry to beta-linked C-disaccharides using a carbon-Ferrier reaction.

    PubMed

    Gemmell, Natasha; Meo, Paul; Osborn, Helen M I

    2003-05-15

    [structure: see text] The synthesis of unsaturated beta-linked C-disaccharides by the Lewis acid-mediated reaction of 3-O-acetylated glycals with monosaccharide-derived alkenes is described. Deprotection and selective hydrogenation of an exocyclic carbon-carbon double, in the presence of an endocyclic double bond, for representative targets is also illustrated. PMID:12735743

  1. 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.

  2. 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

  3. Analysis of the carbon-13 and proton NMR spectra of bovine chromaffin granules.

    PubMed

    Sharp, R R; Richards, E P

    1977-03-29

    Natural abundance carbon-13 and proton NMR spectra of bovine chromaffin granules have been obtained and analyzed using computer simulation techniques. High resolution spectra show the presence of a fluid aqueous phase containing epinephrine, ATP and a random coil protein. The protein spectrum contains unusually intense resonances due to glutamic acid and proline and has been simulated satisfactorily using the known amino acid composition of chromogranin A. The lipid phase of chromaffin granules gives rise to intense, but very broad, resonances in the carbon-13 spectrum. Protons in the lipid phase are also observable as a very rapid component of the proton-free induction decay (T2 approximately equal to 15 microns). Linewidths of the carbon-13 spectra have been used to set upper limits on rotational correlation times and on the motional anisotropy in the aqueous phase. These limits show that the aqueous phase is a simple solution (not a gel) that is isotropic over regions much larger than solute dimensions. No gel transition is observed between -3 and 25 degrees C. The carbon-13 spectra are definitely inconsistent with a lipoprotein matrix model and chromaffin granules previously proposed by Helle and Serck-Hanssen ((1975) Mol. Cell, Biochem. 6, 127-146). Relative carbon-13 intensities of ATP and epinephrine are not consistent with the known 1 : 4 mol ratio of these components. This fact suggests that epinephrine and ATP are not directly complexed in intact chromaffin granules. PMID:849474

  4. Reactions of heteroatom and carbon nucleophiles with the cationic bridging methylidyne complex

    SciTech Connect

    Casey, C.P.; Crocker, M.; Vosejpka, P.C.; Fagan, P.J.; Marder, S.R.; Gohdes, M.A.

    1988-03-01

    The reaction of the ..mu..-methylidyne complex /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CH)//sup +/PF/sub 6//sup -/ (1) with NMe/sub 3/ and (C/sub 6/H/sub 5/)/sub 2/C=NH gave the cationic 1:1 adducts /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CHNMe/sub 3/)//sup +/PF/sub 6//sup -/ (3) and /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CHNH=C(C/sub 6/H/sub 5/)/sub 2/)//sup +/PF/sub 6//sup -/ (9), respectively, arising from attack of nitrogen on the methylidyne carbon. The reaction of 1 with KOC(CH/sub 3/)/sub 3/ gave the neutral ..mu..-carbene complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CHOC(CH/sub 3/)P/sub 3/) (4). Reaction of 1 with water afforded a 1:1 mixture of ..mu..methylene complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CH/sub 2/) (2) and ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)/sub 2/; these products are proposed to arise from disproportionation of an initially formed hydroxy carbene species. Reaction of 1 with Et/sub 4/N/sup +/Br/sup -/ gave the unstable /sup +/-carbene complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CHBr) (6). Reaction of 1 with the carbon nucleophiles CH/sub 3/Li and Li(C/sub 6/H/sub 5/CuCN) gave the ..mu..-carbene complexes ((C/sub 5/H/sub 5/)(CO)Fe/sub 2/(..mu..-CO)(..mu..-CHCH/sub 3/) (11) and ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CHC/sub 6/H/sub 5/ (12), while reaction of 1 with HFe(CO)/sub 4//sup -/ afforded 2. 1 reacted with acetone via nucleophilic addition of the enol affording the neutral ..mu..-carbene complex (C/sub 5/H/sub 5/)-(CO)Fe)/sub 2/(..mu..-CO)(..mu..-CHCH/sub 2/COCH/sub 3/)) (13). 1 also reacted with cyclohexanone, 2-butanone, 4-methyl-2-pentanone, 2,4-pentanedione, 5,5-dimethyl-1,3-cyclohexanedione, ethyl acetoacetate, and the sodium salt of diethyl malonate to give similar ..mu..-carbene products.

  5. 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

  6. 40 CFR 721.10472 - 1,3-Benzenedimethanamine, polymers with epichlorohydrin-polyethylene glycol reaction products.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10472 1,3-Benzenedimethanamine, polymers with epichlorohydrin-polyethylene glycol reaction products. (a) Chemical substance and... with epichlorohydrin-polyethylene glycol reaction products. 721.10472 Section 721.10472 Protection...

  7. 40 CFR 721.10472 - 1,3-Benzenedimethanamine, polymers with epichlorohydrin-polyethylene glycol reaction products.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10472 1,3-Benzenedimethanamine, polymers with epichlorohydrin-polyethylene glycol reaction products. (a) Chemical substance and... with epichlorohydrin-polyethylene glycol reaction products. 721.10472 Section 721.10472 Protection...

  8. 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.

  9. Effects of water-gas shift reaction on simulated performance of a molten carbonate fuel cell

    NASA Astrophysics Data System (ADS)

    Kim, Mi-Hyun; Park, Hong-Kyu; Chung, Gui-Yung; Lim, Hee-Chun; Nam, Suk-Woo; Lim, Tae-Hoon; Hong, Seong-Ahn

    A molten carbonate fuel cell (MCFC) is simulated. In order to determine the effects of the water-gas shift reaction, the calculated results such as temperature distribution, voltage distribution, conversion and performance, are compared with those calculated excluding the shift reaction. Uniformity in the temperature profile is deteriorated due to the shift reaction. At the entrance, hydrogen is consumed rapidly in order to reach the equilibrium state of the shift reaction. The conversion of hydrogen decreases along the direction of gas flow because of hydrogen generated by the shift reaction. Therefore, when the shift reaction is excluded, the conversion of hydrogen is higher than that in a practical cell. Additionally, at the same current density, the voltage calculated without the shift reaction would be higher than the real value. The effect of the shift reaction on the voltage distribution and cell performances is quite small.

  10. 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

  11. Determination of site-specific carbon isotope ratios at natural abundance by carbon-13 nuclear magnetic resonance spectroscopy.

    PubMed

    Caer, V; Trierweiler, M; Martin, G J; Martin, M L

    1991-10-15

    Site-specific natural isotope fractionation of hydrogen studied by deuterium NMR (SNIF-NMR) spectroscopy is a powerful source of information on hydrogen pathways occurring in biosyntheses in natural conditions. The potential of the carbon counterpart of this method has been investigated and compared. Three typical molecular species, ethanol, acetic acid, and vanillin, have been considered. Taking into account the requirements of quantitative 13C NMR, appropriate experimental procedures have been defined and the repeatability and reproducibility of the isotope ratio determinations have been checked in different conditions. It is shown that the carbon version of the SNIF-NMR method is capable of detecting small differences in the carbon-13 content of the ethyl fragment of ethanols from different botanical or synthetic origins. These results are in agreement with mass spectrometry determinations of the overall carbon isotope ratios. Deviations with respect to a statistical distribution of 13C have been detected in the case of acetic acid and vanillin. However, since the method is very sensitive to several kinds of systematic error, only a relative significance can be attached at present to the internal parameters directly accessible. Isotope dilution experiments have also been carried out in order to check the consistency of the results. In the present state of experimental accuracy, the 13C NMR method is of more limited potential than 2H SNIF-NMR spectroscopy. However it may provide complementary information. Moreover it is particularly efficient for detecting and quantifying adulterations that aim to mimic the overall carbon-13 content of a natural compound by adding a selectivity enriched species to a less expensive substrate from a different origin. PMID:1759714

  12. 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.

  13. Bovine Serum Albumin-Catalyzed Deprotonation of [1-13C]-Glycolaldehyde: Protein Reactivity Toward Deprotonation of α–Hydroxy α–Carbonyl Carbon

    PubMed Central

    Go, Maybelle K.; Malabanan, M. Merced; Amyes, Tina L.; Richard, John P.

    2010-01-01

    Bovine serum albumin (BSA) in D2O at 25 °C and pD 7.0 was found to catalyze the deuterium exchange reactions of [1-13C]-glycolaldehyde ([1-13C]-GA) to form [1-13C, 2-2H]-GA and [1-13C, 2,2-di-2H]-GA. The formation of [1-13C, 2-2H]-GA and [1-13C, 2,2-di-2H]-GA in a total yield of 51 ± 3% was observed at early reaction times, and at latter times [1-13C, 2-2H]-GA was observed to undergo BSA-catalyzed conversion to [1-13C, 2,2-di-2H]-GA. The overall second-order rate constant for these deuterium exchange reactions is (kE)P = 0.25 M−1 s−1. By comparison, values of (kE)P = 0.04 M−1 s−1 (Go, M. K., Amyes, T. L., and Richard, J. P. (2009), Biochemistry 48, 5769–5778) and 0.06 M−1 s−1 (Go, M. K., Koudelka, A., Amyes, T. L., and Richard, J. P. (2010), Biochemistry 49, 5377–5389) have been determined, respectively, for the wildtype- and K12G mutant TIM-catalyzed deuterium exchange reactions of [1-13C]-GA to form [1-13C, 2,2-di-2H]-GA. These data show that TIM and BSA exhibit a modest catalytic activity towards deprotonation of α-hydroxy α-carbonyl carbon. It is suggested that this activity is intrinsic to many globular proteins, and that it must be enhanced to demonstrate successful de novo design of protein catalysts of reactions through enamine intermediates. PMID:20687575

  14. 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.

  15. Magnetic susceptibility effects on 13C MAS NMR spectra of carbon materials and graphite.

    PubMed

    Freita, J C; Emmerich, F G; Cernicchiaro, G R; Sampaio, L C; Bonagamba, T J

    2001-01-01

    13C high-resolution solid-state nuclear magnetic resonance (NMR) was employed to study carbon materials prepared through the thermal decomposition of four different organic precursors (rice hulls, endocarp of babassu coconut, peat, and PVC). For heat treatment temperatures (HTTs) above about 600 C, all materials presented 13C NMR spectra composed of a unique resonance line associated with carbon atoms in aromatic planes. With increasing HTT a continuous broadening of this resonance and a diamagnetic shift in its central frequency were verified for all samples. The evolution of the magnitude and anisotropy of the magnetic susceptibility of the heat-treated carbon samples with HTT explains well these findings. It is shown that these results are better understood when a comparison is made with the features of the 13C NMR spectrum of polycrystalline graphite, for which the magnetic susceptibility effect is also present and is much more pronounced. PMID:11529420

  16. 13C-MFA delineates the photomixotrophic metabolism of Synechocystis sp. PCC 6803 under light- and carbon-sufficient conditions.

    PubMed

    You, Le; Berla, Bert; He, Lian; Pakrasi, Himadri B; Tang, Yinjie J

    2014-05-01

    The central carbon metabolism of cyanobacteria is under debate. For over 50 years, the lack of α-ketoglutarate dehydrogenase has led to the belief that cyanobacteria have an incomplete TCA cycle. Recent in vitro enzymatic experiments suggest that this cycle may in fact be closed. The current study employed (13) C isotopomers to delineate pathways in the cyanobacterium Synechocystis sp. PCC 6803. By tracing the incorporation of supplemented glutamate into the downstream metabolites in the TCA cycle, we observed a direct in vivo transformation of α-ketoglutarate to succinate. Additionally, isotopic tracing of glyoxylate did not show a functional glyoxylate shunt and glyoxylate was used for glycine synthesis. The photomixotrophic carbon metabolism was then profiled with (13) C-MFA under light and carbon-sufficient conditions. We observed that: (i) the in vivo flux through the TCA cycle reactions (α-ketoglutarate → succinate) was minimal (<2%); (ii) the flux ratio of CO2 fixation was six times higher than that of glucose utilization; (iii) the relative flux through the oxidative pentose phosphate pathway was low (<2%); (iv) high flux through malic enzyme served as a main route for pyruvate synthesis. Our results improve the understanding of the versatile metabolism in cyanobacteria and shed light on their application for photo-biorefineries. PMID:24659531

  17. Hard and elastic amorphous carbon nitride thin films studied by 13C nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Gammon, W. J.; Malyarenko, D. I.; Kraft, O.; Hoatson, G. L.; Reilly, A. C.; Holloway, B. C.

    2002-10-01

    The chemical bonding of hard and elastic amorphous carbon nitride (a-CNx) thin films was examined using solid-state 13C NMR spectroscopy. The films were deposited by DC magnetron sputtering in a pure nitrogen discharge on Si(001) substrates at 300 °C. Nanoindentation tests reveal a recovery of 80%, a hardness of 5 GPa, and an elastic modulus of 47 GPa. This combination of low modulus and high strength means the material can be regarded as hard and elastic; the material gives when pressed on and recovers its shape when the load is released. The 13C NMR results conclusively demonstrate that hard and elastic a-CNx has an sp2 carbon bonded structure and that sp3 hybridized carbons are absent. Our results stand in contrast with earlier work that proposed that the interesting mechanical properties of hard and elastic a-CNx were due, in part, to sp3 bonded carbon.

  18. 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

  19. 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).

  20. 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

  1. 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.

  2. Ultra-low-temperature Reactions of Carbon Atoms with Hydrogen Molecules

    NASA Astrophysics Data System (ADS)

    Krasnokutski, S. A.; Kuhn, M.; Renzler, M.; Jäger, C.; Henning, Th.; Scheier, P.

    2016-02-01

    The reactions of carbon atoms with dihydrogen have been investigated in liquid helium droplets at T = 0.37 K. A calorimetric technique was applied to monitor the energy released in the reaction. The barrierless reaction between a single carbon atom and a single dihydrogen molecule was detected. Reactions between dihydrogen clusters and carbon atoms have been studied by high-resolution mass spectrometry. The formation of hydrocarbon cations of the type {{{C}}}m{{{{H}}}n}+ with m = 1-4 and n = 1-15 was observed. With enhanced concentration of dihydrogen, the mass spectra demonstrated the main “magic” peak assigned to the {{{CH}}5}+ cation. A simple formation pathway and the high stability of this cation suggest its high abundance in the interstellar medium.

  3. Catalytic Enantioselective Desymmetrization Reactions to All-Carbon Quaternary Stereocenters.

    PubMed

    Zeng, Xing-Ping; Cao, Zhong-Yan; Wang, Yu-Hui; Zhou, Feng; Zhou, Jian

    2016-06-22

    This Review summarizes the advances in the construction of all-carbon quaternary stereocenters via catalytic enantioselective desymmetrization of prochiral and meso-compounds, highlights the power and potential of this strategy in the total synthesis of natural products and biologically active compounds, and outlines the synthetic opportunities still available. PMID:27251100

  4. 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.

  5. Synthesis of spiro[dihydropyridine-oxindoles] via three-component reaction of arylamine, isatin and cyclopentane-1,3-dione

    PubMed Central

    Sun, Yan; Sun, Jing

    2013-01-01

    Summary A fast and convenient protocol for the synthesis of novel spiro[dihydropyridine-oxindole] derivatives in satisfactory yields was developed by the three-component reactions of arylamine, isatin and cyclopentane-1,3-dione in acetic acid at room temperature. On the other hand the condensation of isatin with two equivalents of cyclopentane-1,3-dione gave 3,3-bis(2-hydroxy-5-oxo-cyclopent-1-enyl)oxindole in high yields. The reaction mechanism and substrate scope of this novel reaction is briefly discussed. PMID:23399791

  6. Uranyl triazolate formation via an in situ Huisgen 1,3-dipolar cycloaddition reaction

    SciTech Connect

    Knope, Karah E.; Cahill, Christopher L.

    2010-08-27

    A two dimensional UO22+ coordination polymer, (UO2)3(C10H5N3O4)2(OH)2(H2O)2, has been synthesized under solvothermal conditions. The triazolate ligand, 1-(4-carboxyphenyl)-1H-1,2,3-triazole-4-carboxylic acid (CPTAZ) has been generated via a 1,3-dipolar cycloaddition of 4-azidobenzoic acid and propiolic acid. Reactions of the UO22+ cation with both the in situ generated triazolate ligand and the presynthesized ligand have been explored. The structure, fluorescent and thermal behaviour of this material are presented, as is a discussion of the utility of in situ ligand formation versus direct assembly.

  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

    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.

  8. 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

  9. 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

  10. Ab initio Study of Ultrafast Photochemical Ring-Opening Reaction of 1,3-Cyclohexadiene

    SciTech Connect

    Kobayashi, Takao; Murakami, Akinori; Nakamura, Shinichiro; Shiga, Motoyuki

    2007-12-26

    The mechanism of ultrafast photochemical ring-opening reaction of 1,3-cyclohexadiene (CHD), which has been inferred based on CASPT2//CASSCF(6,6) calculations of potential energy surfaces (PESs) by Garavelli et al. (J. Phys. Chem. A, 105, 4458-4469 (2001)), has not been fully understood. The unsolved problem is that within the framework of the CASPT2//CASSCF(6,6) method the S{sub 1}/S{sub 0} conical intersection (CI) is located too far from a pericyclic minimum of the S{sub 1} state (S{sub 1} pmin) for the photochemical ring-opening reaction of CHD to proceed to produce cZc-1,3,5-hexatriene (cZc-HT) on a ultrafast time scale of around 200 fs. In this study, it has been shown that the PESs obtained by the CASPT2//CASPT2 calculations give a reasonable explanation to why the photochemical ring-opening reation of CHD proceeds on the ultrafast time scale. The most important and remarkable feature of the CASPT2//CASPT2 PESs is that both energetic and structural distances between the S{sub 1} pmin and the S{sub 1}/S{sub 0} CI, both of which have structures largely breaking from C{sub 2} symmetry, are small enough for a nonadiabatic transition to occur in the vicinity of the S{sub 1} pmin.

  11. Solubility of carbon dioxide in aqueous solutions of 2-amino-2-methyl-1,3-propanediol

    SciTech Connect

    Baek, J.I.; Yoon, J.H.

    1998-07-01

    The equilibrium solubility of carbon dioxide in aqueous solutions of 2-amino-2-methyl-1,3-propanediol (AMPD) has been measured at (30, 40, and 60) C and the partial pressure of carbon dioxide ranging from (0.5 to 3065) kPa. The concentrations of the aqueous solutions were (10 and 30) mass % AMPD. The tendency of the solubility of carbon dioxide in 30 mass % AMPD aqueous solution at 40 C was found to be similar to that in 30 mass % N-methyldiethanolamine aqueous solution.

  12. 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.

  13. 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.

  14. Multiphase fluid-rock reactions among supercritical carbon dioxide, brine, aquifer, and caprock: relevance to geologic sequestration of carbon

    SciTech Connect

    Kaszuba, J. P.; Janecky, D. R.; Snow, M. G.

    2004-01-01

    The reactive behavior of a multiphase fluid (supercritical CO{sub 2} and brine) under physical-chemical conditions relevant to geologic storage and sequestration in a carbon repository is largely unknown. Experiments were conducted in a flexible cell hydrothermal apparatus to evaluate multiphase fluid-rock (aquifer plus caprock) reactions that may impact repository integrity.

  15. Model of cathode reaction resistance in molten carbonate fuel cells

    SciTech Connect

    Morita, H.; Mugikura, Y.; Izaki, Y.; Watanabe, T.; Abe, T.

    1998-05-01

    A model of the performance of a molten carbonate fuel cell (MCFC) is required to estimate the efficiency of an MCFC power plant or to simulate the internal state of a stack. The model should provide an accurate representation of the performance under various operating conditions. However, the performance estimated by previous models has been found to deviate from the measured performance under low oxygen and carbon dioxide cathode partial pressures. To solve this problem, the authors carried out a systematic analysis of the performance of several bench-scale cells operated under various cathode gas conditions and investigated a model of cathode polarization according to the oxygen reduction mechanism in molten carbonate. As a result, it has been clarified that the behavior of cathode polarization under various conditions is described well by the dependence of mixed diffusion of superoxide ion O{sub 2}{sup {minus}} and CO{sub 2} in the melt on the assumed partial pressures at each total operating pressure.

  16. Reduction of nitroaromatics sorbed to black carbon by direct reaction with sorbed sulfides.

    PubMed

    Xu, Wenqing; Pignatello, Joseph J; Mitch, William A

    2015-03-17

    Sorption to black carbons is an important sink for organic contaminants in sediments. Previous research has suggested that black carbons (graphite, activated carbon, and biochar) mediate the degradation of nitrated compounds by sulfides by at least two different pathways: reduction involving electron transfer from sulfides through conductive carbon regions to the target contaminant (nitroglycerin) and degradation by sulfur-based intermediates formed by sulfide oxidation (RDX). In this study, we evaluated the applicability of black carbon-mediated reactions to a wider variety of contaminant structures, including nitrated and halogenated aromatic compounds, halogenated heterocyclic aromatic compounds, and halogenated alkanes. Among these compounds, black carbon-mediated transformation by sulfides over a 3-day time scale was limited to nitroaromatic compounds. The reaction for a series of substituted nitroaromatics proceeded by reduction, as indicated by formation of 3-bromoaniline from 3-bromonitrobenzene, and inverse correlation of log kobs with energy of the lowest unoccupied molecular orbital (ELUMO). The log kobs was correlated with sorbed sulfide concentration, but no reduction of 3-bromonitrobenzene was observed in the presence of graphite and sulfite, thiosulfate, or polysulfides. Whereas nitroglycerin reduction occurred in an electrochemical cell containing sheet graphite electrodes in which the reagents were placed in separate compartments, nitroaromatic reduction only occurred when sulfides were present in the same compartment. The results suggest that black carbon-mediated reduction of sorbed nitroaromatics by sulfides involves electron transfer directly from sorbed sulfides rather than transfer of electrons through conductive carbon regions. The existence of three different reaction pathways suggests a complexity to the sulfide-carbon system compared to the iron-carbon system, where contaminants are reduced by electron transfer through conductive carbon

  17. 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

  18. 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.

  19. On the 1,3-dipolar cycloaddition reactions of indenone with N-N-C dipoles: density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Jalbout, Abraham F.; Jiang, Z.; Abou-Rachid, H.; Najat Benkaddour, N.

    2004-02-01

    Density functional theory (DFT) calculations at the B3LYP/6-311G ∗ theoretical level have been performed to study the 1,3-dipolar cycloaddition (1,3-DC) reactions between indenone ( 1) and different 1,3-dipoles (diazomethane and N-methyl C-methoxy carbonyl nitrilimine, compounds 2 and 3, respectively). The geometrical and energetic properties were analysed for the different reactives, transition states and cycloadducts formed (compounds 4- 11). The reactions proceed in the gas-phase by an asynchronous concerted mechanism, yielding different regiochemistry dependent on the 1,3-dipole chosen, although with dipole 3 some degree of synchrony was found in the formation of cycloadduct 5. The 1,3-DC between 1 and 3 was regioselective, being the cycloadduct 11 favoured against 9. The NMR chemical shift parameters (GIAO method) were also calculated for the reactives and cycloadducts.

  20. Dynamic carbon 13 breath tests for the study of liver function and gastric emptying.

    PubMed

    Bonfrate, Leonilde; Grattagliano, Ignazio; Palasciano, Giuseppe; Portincasa, Piero

    2015-02-01

    In gastroenterological practice, breath tests (BTs) are diagnostic tools used for indirect, non-invasive assessment of several pathophysiological metabolic processes, by monitoring the appearance in breath of a metabolite of a specific substrate. Labelled substrates originally employed radioactive carbon 14 ((14)C) and, more recently, the stable carbon 13 isotope ((13)C) has been introduced to label specific substrates. The ingested (13)C-substrate is metabolized, and exhaled (13)CO2 is measured by mass spectrometry or infrared spectroscopy. Some (13)C-BTs evaluate specific (microsomal, cytosolic, and mitochondrial) hepatic metabolic pathways and can be employed in liver diseases (i.e. simple liver steatosis, non-alcoholic steato-hepatitis, liver fibrosis, cirrhosis, hepatocellular carcinoma, drug and alcohol effects). Another field of clinical application for (13)C-BTs is the assessment of gastric emptying kinetics in response to liquids ((13)C-acetate) or solids ((13)C-octanoic acid in egg yolk or in a pre-packed muffin or the (13)C-Spirulina platensis given with a meal or a biscuit). Studies have shown that (13)C-BTs, used for gastric emptying studies, yield results that are comparable to scintigraphy and can be useful in detecting either delayed- (gastroparesis) or accelerated gastric emptying or changes of gastric kinetics due to pharmacological effects. Thus, (13)C-BTs represent an indirect, cost-effective and easy method of evaluating dynamic liver function and gastric kinetics in health and disease, and several other potential applications are being studied. PMID:25339354

  1. Dynamic carbon 13 breath tests for the study of liver function and gastric emptying

    PubMed Central

    Bonfrate, Leonilde; Grattagliano, Ignazio; Palasciano, Giuseppe; Portincasa, Piero

    2015-01-01

    In gastroenterological practice, breath tests (BTs) are diagnostic tools used for indirect, non-invasive assessment of several pathophysiological metabolic processes, by monitoring the appearance in breath of a metabolite of a specific substrate. Labelled substrates originally employed radioactive carbon 14 (14C) and, more recently, the stable carbon 13 isotope (13C) has been introduced to label specific substrates. The ingested 13C-substrate is metabolized, and exhaled 13CO2 is measured by mass spectrometry or infrared spectroscopy. Some 13C-BTs evaluate specific (microsomal, cytosolic, and mitochondrial) hepatic metabolic pathways and can be employed in liver diseases (i.e. simple liver steatosis, non-alcoholic steato-hepatitis, liver fibrosis, cirrhosis, hepatocellular carcinoma, drug and alcohol effects). Another field of clinical application for 13C-BTs is the assessment of gastric emptying kinetics in response to liquids (13C-acetate) or solids (13C-octanoic acid in egg yolk or in a pre-packed muffin or the 13C-Spirulina platensis given with a meal or a biscuit). Studies have shown that 13C-BTs, used for gastric emptying studies, yield results that are comparable to scintigraphy and can be useful in detecting either delayed- (gastroparesis) or accelerated gastric emptying or changes of gastric kinetics due to pharmacological effects. Thus, 13C-BTs represent an indirect, cost-effective and easy method of evaluating dynamic liver function and gastric kinetics in health and disease, and several other potential applications are being studied. PMID:25339354

  2. 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

  3. 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.

  4. The Carbon-13 Pockets in AGB Stars and Their Fingerprints in Mainstream SiC Grains

    NASA Astrophysics Data System (ADS)

    Liu, N.; Davis, A. M.; Gallino, R.; Savina, M. R.; Bisterzo, S.; Gyngard, F.; Dauphas, N.; Pellin, M. J.

    2014-09-01

    Strontium, Zr, and Ba isotopic compositions of mainstream presolar SiC grains are used to constrain the concentration and distribution of carbon-13, the main neutron source for the s-process, in the intershell region of asymptotic giant branch stars.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. C/sup 13/-depleted authigenic carbonate buildups from hydrocarbon seeps, Louisiana Continental Slope

    SciTech Connect

    Roberts, H.H.; Sassen, R.; Aharon, P.; Carney, R.

    1989-03-01

    Geohazard and geochemical survey data consisting of high-resolution profiles, side-scale sonographs, drop cores, dredge samples, and borings have substantiated the consistent association between carbonate buildups and hydrocarbon seeps on the Louisiana continental slope. Analyses indicate a range of carbonate mineralogies including aragonite, Mg-calcite, and dolomite that are extremely depleted in the C/sup 13/ isotope (/approximately/dC/sup 13/ values to /minus/48/per thousand/ PDB). Microbial oxidation of methane (biogenic and thermogenic) and crude oil creates a source of pore water CO/sub 2/ containing isotopically light carbon, which triggers carbonate precipitation. Geophysical and geochemical evidence suggests that both surface and subsurface lithification is taking place. Recent observations and samples collected using a Pisces class research submersible confirm the abundance of C/sup 13/-depleted sedimentary carbonates and massive authigenic buildups associated with the tops and flanks of shallow salt diapirs and gas hydrate hills. Although chemosynthetic communities (including tube worms and bivalves) with isotopically light carbon in tissues have been described from gas seeps, bacterial mats sampled from several seep areas using a submersible have /delta/C/sup 13/ values of /minus/28 to /minus/ /per thousand/ PDB, suggesting a crude oil contribution to microbial biomass. Lithoherms 15 m in vertical dimension are not unusual on dome crests. These features dominate mesoscale sea-floor topography on the slope and have important short-term impacts on platform locations as well as pipeline routing. They are of long-term importance as sites for low sea level reefs. Moreover, these observations provide new insight into the earliest stages of salt-dome cap-rock evolution.

  10. Quantifying the chemical composition of soil organic carbon with solid-state 13C NMR

    NASA Astrophysics Data System (ADS)

    Baldock, J. A.; Sanderman, J.

    2011-12-01

    The vulnerability of soil organic carbon (SOC) to biological decomposition and mineralisation to CO2 is defined at least partially by its chemical composition. Highly aromatic charcoal-like SOC components are more stable to biological decomposition than other forms of carbon including cellulose. Solid-state 13C NMR has gained wide acceptance as a method capable of defining SOC chemical composition and mathematical fitting processes have been developed to estimate biochemical composition. Obtaining accurate estimates depends on an ability to quantitatively detect all carbon present in a sample. Often little attention has been paid to defining the proportion of organic carbon present in a soil that is observable in solid-state 13C NMR analyses of soil samples. However, if such data is to be used to inform carbon cycling studies, it is critical that quantitative assessments of SOC observability be undertaken. For example, it is now well established that a significant discrimination exists against the detection of the low proton content polyaromatic structures typical of charcoal using cross polarisation 13C NMR analyses. Such discrimination does not exist where direct polarisation analyses are completed. In this study, the chemical composition of SOC as defined by cross polarisation and direct polarisation13C NMR analyses will be compared for Australian soils collected from under a diverse range of agricultural managements and climatic conditions. Results indicate that where significant charcoal C contents exist, it is highly under-represented in the acquired CP spectra. For some soils, a discrimination against alkyl carbon was also evident. The ability to derive correction factors to compensate for such discriminations will be assessed and presented.

  11. Selective hydrogenation of 1,3-cyclooctadiene and diphenylacetylene on copper using the water-gas shift reaction as a hydrogen source

    SciTech Connect

    Fragale, C.; Gargano, M.; Rossi, M.

    1983-04-01

    Selective catalytic hydrogenation of polyenes and acetylenes to monoolefins of a particular configuration is a matter of great interest in synthetic chemistry. Studies in this field have been principally devoted to the efficiency of catalytic systems and to the mechanism of the dihydrogen activation; many examples of stereo and regioselectivities have been discussed using either homogeneous or heterogeneous catalysts for the reduction of various compounds (substrates) with molecular hydrogen. In the course of studies on selective hydrogenation reactions catalyzed by transition metal derivatives, it has been found that water and carbon monoxide can be employed as reagents in place of the more expensive pure dihydrogen for the partial hydrogenation of 1,3-cyclooctadiene (C/sub 8/H/sub 12/) and of diphenylethyne (C/sub 14/H/sub 10/); these reactions are promoted by copper catalysts under relatively mild conditions. Experimental conditions and results are reported.

  12. 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.

  13. 12C/ 13C kinetic isotope effects of the gas-phase reactions of isoprene, methacrolein, and methyl vinyl ketone with OH radicals

    NASA Astrophysics Data System (ADS)

    Iannone, Richard; Koppmann, Ralf; Rudolph, Jochen

    The stable-carbon kinetic isotope effects (KIEs) for the gas-phase reactions of isoprene, methacrolein (MACR), and methyl vinyl ketone (MVK) with OH radicals were studied in a 25 L reaction chamber at (298 ± 2) K and ambient pressure. The time dependence of both the stable-carbon isotope ratios and the concentrations was determined using a gas-chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) system. The volatile organic compounds (VOCs) used in the KIE experiments had natural-abundance isotopic composition thus KIE data obtained from these experiments can be directly applied to atmospheric studies of isoprene chemistry. All 12C/ 13/C KIE values are reported as ɛ values, where ɛ = (KIE - 1) × 1000‰, and KIE = k12/ k13. The following average stable-carbon KIEs were obtained: (6.56 ± 0.12)‰ (isoprene), (6.47 ± 0.27)‰ (MACR), and (7.58 ± 0.47)‰ (MVK). The measured KIEs all agree within uncertainty to an inverse molecular mass (MM) dependence of OHɛ(‰) = (487 ± 18)MM -1, which was derived from two previous studies [ J. Geophys. Res.2000, 105, 29329-29346; J. Phys. Chem. A2004, 108, 11537-11544]. Upon adding the isoprene, MACR, and MVK OHɛ values from this study, the inverse MM dependence changes only marginally to OHɛ(‰) = (485 ± 14)MM -1. The addition of these isoprene OHɛ values to a recently measured set of ɛO3 values in an analogous study [ Atmos. Environ.2008, 42, 8728-8737] allows for estimates of the average change in the 12C/ 13C ratio due to processing in the troposphere.

  14. Evidence for Localization of Reaction Upon Reduction of Carbon Tetrachloride by Granular Iron

    SciTech Connect

    Gaspar, Daniel J.; Lea, Alan S.; Engelhard, Mark H.; Baer, Donald R.; Miehr, R.; Tratnyek, Paul G.

    2002-10-01

    The distribution of reaction sites on iron particles exposed to water containing carbon tetrachloride has been examined by measuring the locations of reaction products. The uniformity or localization of reaction sites has implications for understanding and modeling the reduction of environmental contaminants by iron in ground water systems. Granular iron surfaces similar to those being used for environmental remediation applications were studied using surfaces analysis techniques to develop an understanding of the physical and chemical structure of the surface and oxide films. Scanning Auger microscopy and imaging time-of-flight secondary ion mass spectrometry revealed that granular iron exposed to carbon tetrachloride-saturated water exhibits chloride-enriched regions occurred at pits rather than on the passive oxide film on the metal. Understanding the nature of the local solute reduction sites will play an important role in modeling the kinetics of reaction at passive iron oxide films in environmental systems.

  15. DFT Study of Oxygen Reduction Reaction on N-substituted Carbon Electrodes. Adsorption

    NASA Astrophysics Data System (ADS)

    Kobayashi, Hisayoshi; Tomoya, Nakzono; Miyazaki, Soichi; Miura, Toshiko; Takeuchi, Nobuyuki; Yamabe, Tokio

    2011-05-01

    Carbon alloys attract attention as metal-free cathode catalysts. Mechanisms of oxygen reduction reactions are investigated using the DFT calculations and molecular models such as N-substituted coronene, circum pyrene, and corannulene. The overall oxygen reduction reaction (ORR) is decomposed into five elementary reactions. Adsorption of O2 is important as the first step of reduction, and it depends strongly on the spin density on C atoms, introduced by the N atom. Secondly the peripheral C atoms have an advantage due to the rehybridization freedom to the sp3 configuration. Based on the reversible electrode potential (REP) for each elementary reaction, the overpotential is expected for the first reduction of O2 to OOH and the final reduction of OH to H2O. These features indicate that N-substituted carbon electrode resembles Pt electrode compared to other less active metals, such as Au.

  16. 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

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

    SciTech Connect

    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.

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

    SciTech Connect

    Werpy, Todd A; Zacher, Alan H

    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.

  19. Activated carbon becomes active for oxygen reduction and hydrogen evolution reactions.

    PubMed

    Yan, Xuecheng; Jia, Yi; Odedairo, Taiwo; Zhao, Xiaojun; Jin, Zhao; Zhu, Zhonghua; Yao, Xiangdong

    2016-06-21

    We utilized a facile method for creating unique defects in the activated carbon (AC), which makes it highly active for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). The ORR activity of the defective AC (D-AC) is comparable to the commercial Pt/C in alkaline medium, and the D-AC also exhibits excellent HER activity in acidic solution. PMID:27277286

  20. 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.

  1. 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.

  2. Melting of carbonated pelites at 8-13 GPa: generating K-rich carbonatites for mantle metasomatism

    NASA Astrophysics Data System (ADS)

    Grassi, Daniele; Schmidt, Max W.

    2011-07-01

    The melting behaviour of three carbonated pelites containing 0-1 wt% water was studied at 8 and 13 GPa, 900-1,850°C to define conditions of melting, melt compositions and melting reactions. At 8 GPa, the fluid-absent and dry carbonated pelite solidi locate at 950 and 1,075°C, respectively; >100°C lower than in carbonated basalts and 150-300°C lower than the mantle adiabat. From 8 to 13 GPa, the fluid-present and dry solidi temperatures then increase to 1,150 and 1,325°C for the 1.1 wt% H2O and the dry composition, respectively. The melting behaviour in the 1.1 wt% H2O composition changes from fluid-absent at 8 GPa to fluid-present at 13 GPa with the pressure breakdown of phengite and the absence of other hydrous minerals. Melting reactions are controlled by carbonates, and the potassium and hydrous phases present in the subsolidus. The first melts, which composition has been determined by reverse sandwich experiments, are potassium-rich Ca-Fe-Mg-carbonatites, with extreme K2O/Na2O wt ratios of up to 42 at 8 GPa. Na is compatible in clinopyroxene with D_{{Na}}^{{{{cpx}}/{{carbonatite}}}} = 10{-}18 at the solidus at 8 GPa. The melt K2O/Na2O slightly decreases with increasing temperature and degree of melting but strongly decreases from 8 to 13 GPa when K-hollandite extends its stability field to 200°C above the solidus. The compositional array of the sediment-derived carbonatites is congruent with alkali- and CO2-rich melt or fluid inclusions found in diamonds. The fluid-absent melting of carbonated pelites at 8 GPa contrasts that at ≤5 GPa where silicate melts form at lower temperatures than carbonatites. Comparison of our melting temperatures with typical subduction and mantle geotherms shows that melting of carbonated pelites to 400-km depth is only feasible for extremely hot subduction. Nevertheless, melting may occur when subduction slows down or stops and thermal relaxation sets in. Our experiments show that CO2-metasomatism originating from subducted

  3. 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

  4. 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

  5. High-Temperature Measurements and a Theoretical Study of the Reaction of OH with 1,3-Butadiene

    SciTech Connect

    Vasu, Subith; Zador, J.; Davidson, David F.; Hanson, Ronald K.; Golden, David; Miller, James A.

    2010-07-27

    The reaction of hydroxyl (OH) radicals with 1,3-butadiene (C4H6) was studied behind reflected shock waves over the temperature range 1011-1406 K and at pressures near 2.2 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH3)3-CO-OH, and were monitored by narrow line width ring dye laser absorption of the well-characterized R1(5) line of the OH A-X (0,0) band near 306.7 nm. OH time histories were modeled using a comprehensive 1,3-butadiene oxidation mechanism, and rate constants for the reaction of OH with 1,3-butadiene were extracted by matching modeled and measured OH concentration time histories. Detailed error analyses yielded an uncertainty estimate of ±13% at 1200 K for the rate coefficient of the target reaction. The current data extends the temperature range of the only previous high-temperature study for this reaction. The rate coefficient and the branching fractions for the H-abstraction channels of the target reaction were also calculated over the temperature range 250-2500 K using variational transition-state theory based on QCISD(T)/cc-pV∞Z//B3LYP/6-311++G(d,p) quantum chemistry. The calculations are in good agreement with the experimental results above 1200 K.

  6. 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.

  7. 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).

  8. 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.

  9. 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.

  10. 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

  11. 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

  12. Large 13C enrichment in primary carbonates from Andean Altiplano lakes, northwest Argentina

    NASA Astrophysics Data System (ADS)

    Valero-Garcés, Blas L.; Delgado-Huertas, Antonio; Ratto, Norma; Navas, Ana

    1999-08-01

    We report here extreme 13C enrichments up to +13‰ PDB in primary calcite and aragonite precipitates in saline, well oxygenated waters from high-altitude lakes in the southern Andean Altiplano, northwestern Argentina. Biological effects, as well as variations in carbon source inputs, and in the exchange rate with atmospheric CO 2, are commonly considered the main controls on the carbon isotope values of authigenic lacustrine carbonate. We present sedimentological and geochemical evidence that favors physical processes — evaporation effects and CO 2-degassing — as major controls on 13C enrichment. We propose that large enrichments may result from the non-equilibrium gas-transfer isotope fractionation during CO 2-degassing from thermal springs and evaporation effects in arid environments. The dilution effect by large quantities of 14C-free CO 2 hinders accurate 14C chronology of these lake records based on lacustrine organic matter and aquatic plants. Our results indicate that geothermal and volcanic CO 2 sources in lake basins located in volcanic settings, and physical fractionation may have a greater significance than commonly accepted to explain lacustrine carbon isotope records.

  13. Stable Carbon Isotope Ratios for Giant Stars in the Globular Cluster M13

    NASA Astrophysics Data System (ADS)

    Rhee, Jaehyon; Pilachowski, C. A.

    2013-01-01

    Recently, our paradigm for the formation and evolution of globular clusters has shifted. We now understand that the majority of present-day stars in globular clusters formed as second-generation stars, primarily from the ejecta of first-generation AGB stars, while the majority of first generation, less centrally concentrated stars, have been dynamically lost to the cluster (D'Ercole et al. 2011). This paradigm explains the observed star-to-star variations in the abundances of light element observed in globular clusters, and suggests that the carbon isotope ratio should be similarly differentiated between first and second generation stars. In an effort to verify this scenario, we have recently utilized the Gemini/NIFS to determine carbon isotope abundances (12C and 13C) for 18 giant stars in the globular clusters M13 through medium-resolution (R ˜ 5300) infrared spectroscopy of the first-overtone CO bands near 2.3 μm. Our program stars are distributed from the tip of the RGB to the BLF (the bump in the luminosity function) of M13, and their Na, Mg, and Al abundances are already known from homogeneous data set analysis. Therefore, adding reliable abundances of the stable carbon isotopes to this homogeneous spectroscopic sample permits systematic tests of cluster chemical evolution models. We report preliminary results of the carbon abundance analysis for our NIFS K-band spectra and present an overview of our ongoing effort with other globular clusters.

  14. Synthesis of carbon nanotubes using SBA-15 as a template by the reaction of methane and carbon dioxide.

    PubMed

    Guo, Xiao-Feng; Kim, Geon-Joong

    2011-02-01

    Multiwalled carbon nanotubes (CNTs) were synthesized using Ni loaded mesoporous SBA-15 as a template by reaction of methane and carbon dioxide. The influences of nickel content on the selectivity and crystallinity of CNTs were investigated. It can be seen that the crooked CNTs with a diameter varied from 9.9, 12.5 to 36.5 nm with creasing content of Ni from 5, 15, and 30 wt%/SBA-15. A uniform diameter and good quality CNTs were obtained in our system. PMID:21456259

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. High-pressure 13C-diamond-forming reaction of decomposition of Na213CO3 melt at 20 - 60 GPa

    NASA Astrophysics Data System (ADS)

    Solopova, N.; Spivak, A.; Kupenko, I.; Litvin, Yu.; Dubrovinsky, L.

    2012-04-01

    higher temperature 2400 K. In the sample heated at 33 GPa and 2600 K, we found a broad G-band at 1545 cm-1 (12C -graphite originated, probably, from diamond anvils) and a sharp band at 1315 cm-1 (newly formed 13C-diamond). The bands correspond to mixture of graphite and diamond with isotopic 13C:12C ratio about 1:1. The 13C -diamond was synthesized, evidently, due to the reaction of decomposition of sodium carbonate melt with formation of dense fluid phase CO2 decomposed with liberation of elemental carbon. Further studies of CaCO3 are in progress in order to determine a melting curve and decomposition boundary of sodium carbonate melt, as well as PT-parameters of its phase stability region. This work was funded by grants of President of RF MK-913.2011.5, FPP 2011-1.3.1-151-0066 and RFBR 10-05-00654, 11-05-00401.

  20. Kinetics of Several Oxygen-Containing Carbon-Centered Free Radical Reactions with Nitric Oxide.

    PubMed

    Rissanen, Matti P; Ihlenborg, Marvin; Pekkanen, Timo T; Timonen, Raimo S

    2015-07-16

    Kinetics of four carbon-centered, oxygen-containing free radical reactions with nitric oxide (NO) were investigated as a function of temperature at a few Torr pressure of helium, employing flow tube reactors coupled to a laser-photolysis/resonance-gas-discharge-lamp photoionization mass spectrometer (LP-RPIMS). Rate coefficients were directly determined from radical (R) decay signals under pseudo-first-order conditions ([R]0 ≪ [NO]). The obtained rate coefficients showed negative temperature dependences, typical for a radical-radical association process, and can be represented by the following parametrizations (all in units of cm(3) molecule(-1) s(-1)): k(CH2OH + NO) = (4.76 × 10(-21)) × (T/300 K)(15.92) × exp[50700/(RT)] (T = 266-363 K, p = 0.79-3.44 Torr); k(CH3CHOH + NO) = (1.27 × 10(-16)) × (T/300 K)(6.81) × exp[28700/(RT)] (T = 241-363 K, p = 0.52-3.43 Torr); k(CH3OCH2 + NO) = (3.58 ± 0.12) × 10(-12) × (T/300 K)(-3.17±0.14) (T = 221-363 K, p = 0.50-0.80 Torr); k(T)3 = 9.62 × 10(-11) × (T/300 K)(-5.99) × exp[-7100/(RT)] (T = 221-473 K, p = 1.41-2.95 Torr), with the uncertainties given as standard errors of the fits and the overall uncertainties estimated as ±20%. The rate of CH3OCH2 + NO reaction was measured in two density ranges due to its observed considerable pressure dependence, which was not found in the studied hydroxyalkyl reactions. In addition, the CH3CO + NO rate coefficient was determined at two temperatures resulting in k298K(CH3CO + NO) = (5.6 ± 2.8) × 10(-13) cm(3) molecule(-1) s(-1). No products were found during these experiments, reasons for which are briefly discussed. PMID:26000890

  1. 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

  2. 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.

  3. Carbon-carbon bond-forming reactions of α-thioaryl carbonyl compounds for the synthesis of complex heterocyclic molecules.

    PubMed

    Biggs-Houck, James E; Davis, Rebecca L; Wei, Jingqiang; Mercado, Brandon Q; Olmstead, Marilyn M; Tantillo, Dean J; Shaw, Jared T

    2012-01-01

    Strategies for the formation of carbon-carbon bonds from the α-thioaryl carbonyl products of substituted lactams are described. Although direct functionalization is possible, a two step process of oxidation and magnesium-sulfoxide exchange has proven optimal. The oxidation step results in the formation of two diastereomers that exhibit markedly different levels of stability toward elimination, which is rationalized on the basis of quantum mechanical calculations and X-ray crystallography. Treatment of the sulfoxide with i-PrMgCl results in the formation of a magnesium enolate that will undergo an intramolecular Michael addition reaction to form two new stereogenic centers. The relationship between the substitution patterns of the sulfoxide substrate and the efficiency of the magnesium exchange reaction are also described. PMID:22023077

  4. 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.

  5. Separation of root respiration from total soil respiration using carbon-13 labelling during free-air carbon dioxide enrichment (FACE)

    SciTech Connect

    Andrews, J.A.; Harrison, K.G.; Matamala, R.; Schlesinger, W.H.

    1999-10-01

    Soil respiration constitutes a major component of the global carbon cycle and is likely to be altered by climate change. However, there is an incomplete understanding of the extent to which various processes contribute to total soil respiration, especially the contributions of root and rhizosphere respiration. Here, using a stable carbon isotope tracer, the authors separate the relative contributions of root and soil heterotrophic respiration to total soil respiration in situ. The Free-Air Carbon dioxide Enrichment (FACE) facility in the Duke University Forest (NC) fumigates plots of an undisturbed loblolly pine (Pinus taeda L.) forest with CO{sub 2} that is strongly depleted in {sup 13}C. This labeled CO{sub 2} is found in the soil pore space through live root and mycorrhizal respiration and soil heterotroph respiration of labile root exudates. By measuring the depletion of {sup 13}CO{sub 2} in the soil system, the authors found that the rhizosphere contribution to soil CO{sub 2} reflected the distribution of fine roots in the soil and that late in the growing season roots contributed 55% of total soil respiration at the surface. This estimate may represent an upper limit on the contribution of roots to soil respiration because high atmospheric CO{sub 2} often increases in root density and/or root activity in the soil.

  6. 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. PMID:27455763

  7. Exploring variations in microbial carbon sources and cycling in the deep terrestrial subsurface using PLFA and δ13C analysis

    NASA Astrophysics Data System (ADS)

    Simkus, D.; Slater, G. F.; Wilkie, K. M.; Li, L.; Sherwood Lollar, B.; Onstott, T. C.; Wommack, E.; Sakowski, E.

    2012-12-01

    In deep crystalline rock of the terrestrial subsurface, water-filled fracture networks represent potential microbial habitats. The geochemical environments within such fraction systems, and concurrently potential microbial carbon sources and metabolic activities, can vary widely. In systems where organic carbon is limited or highly recalcitrant, microbial ecosystems must rely on autotrophy of dissolved inorganic carbon (DIC) or metabolism of organic compounds produced abiotically via water-rock interaction. In either case, CH4 is a key potential species as it is produced autotrophically by CO2-reducing organisms, as well as abiotically by reactions analogous to the Fischer-Tropsch synthesis. Utilization of this methane by microbial communities requires the ability to oxidize it, either aerobically or anaerobically. In this study, the concentrations, distribution and δ13C compositions of phospholipid fatty acids (PLFA), as well as DIC and CH4 pools, were characterized in boreholes in mines in the Johannesburg area of South Africa. Water flow rates from these boreholes were in the liters per minute range and concurrent gas flow rates ranged from 3 to 800 mL/min. Water temperature, pH, Eh and salinity ranged from 27 to 55 °C, from 7.3 to 8.9, from -130 to 375 mV and from 0.2 to 110 ppt, respectively. CH4 concentrations ranged from 2 to 70 % of gas by volume and δ13C of methane ranged from -55 to -36 ‰. δ18O and δ2H analysis indicated that waters in the majority of boreholes were paleometeoric. One borehole was indicated to be off the global meteoric water line, consistent with large extents of water-rock interaction. PLFA concentrations and distributions varied between boreholes, indicating variations in the microbial communities, concurrent with variations in the environments being sampled. δ13C of PLFA also varied between boreholes; for instance, δ13C values of PLFA in the Beatrix mine 326 Bh2 ranged from -55 to -65 ‰ , whereas in Bh1, located circa 100 m

  8. Basalt catalyzed carbonate precipitation reactions using carbon dioxide at low temperatures and low pressures

    NASA Astrophysics Data System (ADS)

    Petrik-Huff, C.; Finkelstein, D. B.; Mabee, S. B.

    2011-12-01

    Increased attention is being paid to basalts as host formations for the geologic sequestration of anthropogenically produced CO2. Here, we present preliminary results of batch experiments conducted on basalts from the Hartford Basin, the Deerfield and the Holyoke Basalt, to better constrain the optimum conditions to maximize carbon sequestration through the precipitation of carbonate. The purpose of this work is to explore options for CO2 sequestration in a locality where there is a lack of large geologic reservoirs appropriate for storage. In these experiments, 10 grams of 400 micron Deerfield and Holyoke basalt was reacted with deionized water for three hours both at and below supercritical conditions. These experiments showed carbonate precipitation of 15% was consistent at low pressures of CO2 (800 psi) both at high (100 Celsius) and low (20 Celsius) temperatures. These ranges of carbonate precipitation were greatest (15%) when CO2 was at low pressures. Experiments conducted at supercritical conditions precipitated a maximum of 4.7% carbonate. This information is valuable when considering alternative sequestration mechanisms that could be operated adjacent to power generation facilities or more industrial pure sources of CO2. The possibility of low pressure/temperature sequestration reactors to be operated in areas where transport to regional or national sequestration facilities may be cost prohibitive is a parallel course of action that should also be considered. Additionally, it is important to consider how a small ex-situ carbon sequestration project can help increase public acceptance of carbon capture and sequestration.

  9. 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.

  10. Foaming and the Rate of the Carbon-Iron Oxide Reaction in Slag

    NASA Astrophysics Data System (ADS)

    Corbari, Rodrigo; Matsuura, Hiroyuki; Halder, Sabuj; Walker, Matthew; Fruehan, Richard J.

    2009-12-01

    Foaming in the electric arc furnace is achieved by injecting carbon into slag, where the resulting reaction of the carbon with FeO dissolved in the slag generates gas (CO) that causes the slag to foam. In this research, the rate of the reaction of FeO in slag with carbon and the resulting foam height were measured. In these experiments, the FeO content of the slag ranged from 15 to 45 mass pct, and several different types of carbon were used including graphite, coals, and chars. The rate of the slag-carbon reaction and the consequent CO generation increased with FeO content of the slag from 15 to 45 mass pct. However, the slag foam height reached a maximum at about 25 mass pct FeO and decreased at higher FeO contents. The decrease in foaming is apparently due to a decrease in the foam index or foamability caused by a decrease in viscosity and an increase in density of the slag with FeO content. The results of this work indicate that the foam height is influenced more significantly by the decrease in the foam index compared to the increase in the CO gas generation rate at higher FeO contents. The decrease in the foam index with FeO agrees with that predicted from the slag properties.

  11. 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.

  12. 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 )% .

  13. 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

  14. 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

  15. 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.

  16. Mineral sequestration of carbon dioxide in San Carlos olivine: An atomic level reaction study

    NASA Astrophysics Data System (ADS)

    Nunez, Ryan

    Since the late 19th century, atmospheric carbon dioxide (CO2) levels have been steadily on the rise. Approximately one third of all human emissions come from fossil fuel power plants. As countries become more dependent on electrical energy and bring on line new power plants, these atmospheric CO2 levels will continue to rise, generating strong environmental concern. Potential avenues to address this problem convert the CO2 from the gaseous phase to a liquid, supercritical fluid, or solid state and store it. Oceans, subsurface reservoirs such as depleted oil fields, and terrestrial carbon pools have all been suggested. The essential problem with all of these possible solutions is the issue of permanency. Mineral sequestration of CO2 is a candidate technology for reducing the amount of anthropogenic CO2 that is being released into the atmosphere. Olivine (e.g. forsterite, Mg2SiO4) is a widely available mineral that reacts with CO2 to form magnesite (MgCO3) and silica (SiO2). Magnesite is capable of immobilizing CO2 over geological time periods. Thus the issue of permanency has been addressed. The most promising mineral sequestration process developed to date is aqueous solution mineral carbonation. The solid/aqueous solution reaction interface provides insight to the mechanisms that govern the carbonation reactivity of olivine. Study of these mechanisms at the atomic level is critically important to facilitate engineering new processes that will enhance the reactivity of olivine with CO2 bearing media and to lower process costs. The study of the olivine carbonation reaction herein can be divided into three separate areas of research. The first area is a comprehensive study of olivine under conditions of electron irradiation. Analyzing radiation damage is critical to the verification and reliability of data collected from the samples using electron beam techniques. The next area of research is the analysis of the reaction layer composition and structure using High

  17. 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.

  18. 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

  19. Olivine Hydration and Carbonation Reactions in Porous Open Systems: Insights from Reactive Percolation Laboratory Experiments

    NASA Astrophysics Data System (ADS)

    Godard, M.; Peuble, S.; Gouze, P.; Andreani, M.; Luquot, L.

    2013-12-01

    Hydrothermal exchanges between fluids (seawater, hydrothermal and mantle-derived CO2-rich fluids) and mantle-dominated lithosphere at ridges represent a major means of mass exchange between the mantle and the Earth's envelopes. It results from/in a suite of strongly interconnected thermal, mineralogical, and (bio-) chemical processes within the seafloor, that contributes to the Earth's carbon budget through carbonation reactions (dissolution of silicates and precipitation of carbonates) and the production of complex carbon compounds. Recent experimental studies were realized to constrain the chemical parameters controlling these reactions (pH, T, kinetics, catalysis), one of the main applications being the development of techniques for geological storage of excess atmospheric CO2 into ultramafic ophiolitic massifs and in basaltic reservoirs. However, although these reactions will occur only if fluids can flow through the reacting rocks, the mechanisms controlling the hydrodynamic properties of the system during hydration and carbonation reactions remain poorly constrained. We present the results of three sets of percolation-reaction experiments during which CO2-depleted to CO2-saturated fluids were injected into olivine cores, dunitic samples and magmatic olivine with trace basalts. These experiments allowed us to explore the role of the initial mineralogy and structure of rocks, the composition of fluids (pCO2...) and flow rate and their effects on hydrodynamic properties and carbonation/hydration efficiency. The experiments produced broadly similar results, i.e. dissolution of olivine (× mafic minerals and glass when present), precipitation of carbonates and of serpentine type minerals and a steady decrease in permeability with time. In details, differences in the compositions of the fluids and of the reaction products were observed from one set of experiments to the other as well as in the rate at which chemical and permeability changes occurred during the

  20. 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

  1. 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.

  2. 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...

  3. Convert Graphene Sheets to Boron Nitride and Boron Nitride-carbon Sheets via a Carbon-substitution Reaction

    SciTech Connect

    W Han; H Yu; Z Liu

    2011-12-31

    Here we discuss our synthesis of highly crystalline pure boron nitride (BN) and BN-carbon (BN-C) sheets by using graphene sheets as templates via a carbon-substitution reaction. Typically, these sheets are several micrometers wide and have a few layers. The composition ratios of BN-C sheets can be controlled by the post-treatment (remove carbon by oxidation) temperature. We also observed pure BN and BN-C nanoribbons. We characterized the BN-C sheets via Raman spectroscopy and density functional theory calculations. The results reveal that BN-C sheets with an armchair C-BN chain, and embedded C2 or C6 units in BN-dominated regions energetically are the most favorable.

  4. Convert Graphene Sheets to Boron Nitride and Boron Nitride-Carbon Sheets via a Carbon-Substitution-Reaction

    SciTech Connect

    Han, W.; Yu, H.-G.; Liu. Z.

    2011-05-16

    Here we discuss our synthesis of highly crystalline pure boron nitride (BN) and BN-carbon (BN-C) sheets by using graphene sheets as templates via a carbon-substitution reaction. Typically, these sheets are several micrometers wide and have a few layers. The composition ratios of BN-C sheets can be controlled by the post-treatment (remove carbon by oxidation) temperature. We also observed pure BN and BN-C nanoribbons. We characterized the BN-C sheets via Raman spectroscopy and density functional theory calculations. The results reveal that BN-C sheets with an armchair C-BN chain, and embedded C{sub 2} or C{sub 6} units in BN-dominated regions energetically are the most favorable.

  5. CARBON-13 NMR OR SOLID STATE HYDROCARBONS AND RELATED SUBSTANCES-FINAL REPORT

    SciTech Connect

    Grant, David M.

    2007-08-16

    CARBON-13 NMR OR SOLID STATE HYDROCARBONS AND RELATED SUBSTANCES-FINAL REPORT Abstract: During recent years we have been engaged in SSNMR (Solid State NMR) structural studies of unusual tetracyanoethylene compounds with unusually long bonds between four carbons centered on two electrons. The chemical shift tensors reflect these unusual atomic arrangements. Quantum chemistry predicts the strange tensor shifts. The three dimensional molecular structure may be determined in this manner. Despite significant advances in structural determination from powder diffraction data, NMR shift tensors argument the structural accuracy and also suggest initial trial structures. Mixtures of polymorphs are difficult to analyze with diffraction methods whereas the SSNMR methods are able to characterize such mixtures in one another’s presence. Spectroscopic developments in our laboratory include SSNMR INADEQUATE and FIREMAT methods. We have used these methods to study the 13C and 15N NMR explosive CL-20.

  6. Effects of the size of nano-copper catalysts and reaction temperature on the morphology of carbon fibers

    SciTech Connect

    Zhang Qian; Yu Liyan; Cui Zuolin

    2008-03-04

    In this study, carbon fibers with different morphologies, including coiled carbon nanofibers and straight carbon fibers, were obtained by the chemical vapor deposition using a Cu-catalytic pyrolysis of acetylene at 250 deg. C. The influences of nano-copper catalyst particle size and the reaction temperature on the morphology of carbon fibers were investigated. Under the same reaction condition, coiled carbon nanofibers generally were synthesized using nano-copper catalyst with smaller particles size, and bigger copper particles are apt to produce straight carbon fibers. With decreasing of reaction temperature to 200 deg. C, straight carbon fibers were obtained, instead of coiled carbon nanofibers at 250 deg. C. The product was characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray powder diffraction (XRD)

  7. 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

  8. 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

  9. 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

  10. 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. PMID:16853637

  11. 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.

  12. Astrophysical Reaction Rate for the Neutron-Generator Reaction {sup 13}C({alpha},n){sup 16}O in Asymptotic Giant Branch Stars

    SciTech Connect

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

    2006-11-10

    The reaction {sup 13}C({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{sup +} 6.356 MeV subthreshold resonance in {sup 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 ({sup 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.

  13. 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.

  14. 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.

  15. 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.

  16. Thermal cyclization of phenylallenes that contain ortho-1,3-dioxolan-2-yl groups: new cascade reactions initiated by 1,5-hydride shifts of acetalic H atoms.

    PubMed

    Alajarin, Mateo; Bonillo, Baltasar; Marin-Luna, Marta; Sanchez-Andrada, Pilar; Vidal, Angel

    2013-11-18

    A series of 2-(1,3-dioxolan-2-yl)phenylallenes that contained a range of substituents (alkyl, aryl, phosphinyl, alkoxycarbonyl, sulfonyl) at the cumulenic C3 position were prepared by using a diverse range of synthetic strategies and converted into their respective 1-(2-hydroxy)-ethoxy-2-substituted naphthalenes by smooth thermal activation in toluene solution. Electron-withdrawing groups at the C3 position accelerated these tandem processes, which consisted of 1) an initial hydride-like [1,5]-H shift of the acetalic H atom onto the central cumulene carbon atom; 2) a subsequent 6π-electrocyclic ring-closure of the resulting reactive ortho-xylylenes; and 3) a final aromatization step with concomitant ring-opening of the 1,3-dioxolane fragment. If the 1,3-dioxolane ring of the starting allenes was replaced by a dimethoxymethyl group, the reactions led to mixtures of two disubstituted naphthalenes, which were formed by the migration of either the acetalic H atom or the methoxy group, with the latter migration occurring to a lesser extent. Two of the final 1,2-disubstituted naphthalenes were converted into their corresponding naphtho-fused dioxaphosphepine or dioxepinone through an intramolecular transesterification reaction. A DFT computational study accounted for the beneficial influence of the 1,3-dioxolane fragment on the carbon atom from which the H-shift took place and also of the electron-withdrawing substituents on the allene terminus. Remarkably, in the processes that contained a sulfonyl substituent, the conrotatory 6π-electrocyclization step was of lower activation energy than the alternative disrotatory mode. PMID:24123192

  17. Inverting 13CO2 for Terrestrial Carbon Fractionation in North America

    NASA Astrophysics Data System (ADS)

    Alden, C. B.; White, J. W.; Miller, J. B.

    2011-12-01

    The stable isotope of Carbon, 13C, has been used globally to partition ocean from terrestrial CO2 fluxes, and regionally as an indicator of C3 plant discrimination and the relative abundances of C3 and C4 vegetation. In North America, the spatial and temporal density of atmospheric observations enables, for the first time, inversions of land surface fluxes of CO2 and the δ13C signature of those fluxes (multiplied together: isofluxes). We optimize North American isofluxes in a traditional Bayesian Inversion, and divide by CO2 fluxes optimized in an offline inversion. We are left with estimates of the isotopic signature of photosynthesis and related error. We generate influence functions (i.e. influence of surface fluxes on measurements made "downwind") with FLEXPART, driven by National Centers for Environmental Prediction Global Forecast System meteorology. Prior isofluxes (CarbonTracker 2010 posterior net ecosystem exchange multiplied by biosphere δ13C from SiB) are of 3-hour, 1x1 degree resolution. Unoptimized fire and fossil fuel emissions are also from the CarbonTracker system, and background CO2 and δ13C values are taken from NOAA/ESRL marine boundary layer and aircraft data. We invert for isofluxes using quasi-daily observations from tall towers in Park Falls, Wisconsin (WLEF), Argyle, Maine (AMT), and Moody, Texas (WKT). At these sites the air is thought to be influenced predominately by corn production, C3 vegetation, and savannah vegetation, respectively. By investigating areas with varying degrees of C3 and C4 vegetation influences, and by examining multiple years of data from each site, in conjunction with crop yield and climate data, we propose to disentangle the competing influences of agriculture, drought, and other climatic stressors on spatial and temporal variability in atmospheric δ13C.

  18. DFT study of zigzag (n, 0) single-walled carbon nanotubes: (13)C NMR chemical shifts.

    PubMed

    Kupka, Teobald; Stachów, Michal; Stobiński, Leszek; Kaminský, Jakub

    2016-06-01

    (13)C NMR chemical shifts of selected finite-size models of pristine zigzag single walled carbon nanotubes (SWCNTs) with a diameter of ∼0.4-0.8nm and length up to 2.2nm were studied theoretically. Results for finite SWCNTs models containing 1, 4 and 10 adjacent bamboo-type units were compared with data obtained for infinite tubes in order to estimate the reliability of small finite models in predicting magnetic properties of real-size nanotubes and to assess their tube-length dependence. SWCNTs were fully optimized using unrestricted density functional theory (DFT-UB3LYP/6-31G*). Cyclacenes, as the shortest models of open-ended zigzag SWCNTs, with systematically varying diameter were calculated as well. GIAO NMR calculations on the SWCNT and cyclacene models were performed using the BHandH density functional combined with relatively small STO-3Gmag basis set, developed by Leszczyński and coworkers for accurate description of magnetic properties. Regular changes of carbon (13)C chemical shifts along the tube axis of real size (6, 0) and (9, 0) zigzag carbon nanotubes were shown. The (13)C NMR shifts according to increasing diameter calculated for zigzag (n, 0, n=5-10) cyclacenes followed the trends observed for zigzag (n, 0) SWCNTs. The results for 4-units long SWCNTs match reasonably well with the data obtained for infinite zigzag (n, 0) SWCNTs, especially to those with bigger diameter (n=8-15). The presence of rim hydrogens obviously affects theoretical (13)C chemical shieldings and shifts in cyclacenes and thus cyclacenes can provide only approximate estimation of (13)C NMR parameters of real-size SWCNTs. The NMR properties predicted for the longest 10-units long models of SWCNTs reliably correspond to results obtained for infinite nanotubes. They were thus able to accurately predict also recently reported experimental chemical shift of chiral (6, 5) SWCNT. PMID:27155813

  19. 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

  20. Reduced Reactivity of Amines against Nucleophilic Substitution via Reversible Reaction with Carbon Dioxide.

    PubMed

    Mohammed, Fiaz S; Kitchens, Christopher L

    2015-01-01

    The reversible reaction of carbon dioxide (CO₂) with primary amines to form alkyl-ammonium carbamates is demonstrated in this work to reduce amine reactivity against nucleophilic substitution reactions with benzophenone and phenyl isocyanate. The reversible formation of carbamates has been recently exploited for a number of unique applications including the formation of reversible ionic liquids and surfactants. For these applications, reduced reactivity of the carbamate is imperative, particularly for applications in reactions and separations. In this work, carbamate formation resulted in a 67% reduction in yield for urea synthesis and 55% reduction for imine synthesis. Furthermore, the amine reactivity can be recovered upon reversal of the carbamate reaction, demonstrating reversibility. The strong nucleophilic properties of amines often require protection/de-protection schemes during bi-functional coupling reactions. This typically requires three separate reaction steps to achieve a single transformation, which is the motivation behind Green Chemistry Principle #8: Reduce Derivatives. Based upon the reduced reactivity, there is potential to employ the reversible carbamate reaction as an alternative method for amine protection in the presence of competing reactions. For the context of this work, CO₂ is envisioned as a green protecting agent to suppress formation of n-phenyl benzophenoneimine and various n-phenyl-n-alky ureas. PMID:26703563

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

    NASA Astrophysics Data System (ADS)

    Lehmeier, C. A.; Ballantyne, F., IV; Min, K.; Billings, S. A.

    2015-10-01

    Understanding how carbon dioxide (CO2) flux from soils feeds back to climate warming depends in part on our ability to quantify the efficiency with which microorganisms convert soil 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 soil organic substrates. However, the diversity of organic substrates' δ13C and the challenges of measuring microbial C use efficiency (CUE) in soils fundamentally limit our ability to project soil, and thus 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 soil microorganism growing at a constant rate. Specific respiration rate increased by 250 % between 13 and 26.5 °C, decreasing CUE from 77 to 56 %. 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 soil C fluxes.

  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. 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

  4. [Analysis of the association between cellulose and lignin by carbon 13 tracer method].

    PubMed

    Xiang, Song-ming; Xie, Yi-min; Yang, Hai-tao; Yao, Lan

    2013-09-01

    In order to further understand the association between cellulose and lignin in gymnosperm plant, carbohydrate part of the lignin-carbohydrate complexes was analyzed. Cellulose precursor, i.e., (6(-13) C) uridine diphoshphate glucose, was synthesized, and injected into a living ginkgo tree with lignin inhibitor AOPP and exogenous lignin precursor. The results from the determination of 13C abundance indicate that the deposition of cellulose in the cell wall is very fast and effective in the primary wall. The analysis of high resolution solid nuclear magnetic 13C NMR spectra confirms that the bonds between C5 position of glucose units in cellulose and alpha-carbons of lignin side chain are benzyl ether linkage. PMID:24369658

  5. Effect of Fiber Surface Structure on Interfacial Reaction between Carbon Fiber and Aluminium

    NASA Astrophysics Data System (ADS)

    Chang, Kuang-Chih; Matsugi, Kazuhiro; Sasaki, Gen; Yanagisawa, Osamu

    Surface structure of carbon fiber and interfacial reaction between fiber and aluminium in carbon fiber reinforced aluminium composites were investigated by high-resolution transmission electron microscopy. Low and high graphitized carbon fiber reinforced pure aluminium composites were prepared by ultrasonic liquid infiltration. Vapor grown carbon nano fiber (VGCF) reinforced pure aluminium composites were prepared by hot-pressing. Heteroatoms, which existed abundantly in the surface of low graphitized carbon fiber, caused carbon lamellar structure in the fiber surface pronounced curvature. VGCF surface structure appeared regular and linear graphitic lamellae. Low graphitized fiber reinforced pure aluminium composites revealed serious interfacial reaction produced crystalline aluminium carbides (Al4C3), compared to composites reinforced by high graphitized fiber. On the other hand, Al4C3 crystalline reactants were not found at the interface of VGCF reinforced pure aluminium composites, but formation of interlayer was observed. In order to promote Al4C3 growth, carbon fiber reinforced composites were heat-treated at 573K and 873K for 1.8ks. Al4C3 interfacial phases in low and high graphitized fiber reinforced aluminium composites grew with the rise in the temperature. The heat-treatment resulted in the formation of non-crystalline Al4C3 interlayer by energy dispersive X-ray spectroscopy analysis of electron microscopy. At high temperature, Al4C3 was not grew and increased merely at the interface between carbon fiber and pure aluminium matrix, and moreover, the formation of new Al4C3 crystal occurred in this interlayer.

  6. 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.

  7. Concurrent Formation of Carbon-Carbon Bonds and Functionalized Graphene by Oxidative Carbon-Hydrogen Coupling Reaction.

    PubMed

    Morioku, Kumika; Morimoto, Naoki; Takeuchi, Yasuo; Nishina, Yuta

    2016-01-01

    Oxidative C-H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C-C bond formation via C-H transformation and production of functionalized graphene. PMID:27181191

  8. Kinetic study of carbon dioxide reaction with tertiary amines in aqueous solutions

    SciTech Connect

    Barth, D.; Tondre, C.; Lappai, G.; Delpuech, J.J.

    1981-11-26

    Reaction kinetics of CO/sub 2/ with triethanolamine (TEA) and methyldiethanolamine (MDEA) in aqueous solution have been studied by using a stopped-flow technique with pH detection. Rate constants are obtained from the comparison of experimental and theoretical curves giving the optical density as a function of time. At concentrations of CO/sub 2/ well below the saturation limit, the results are consistent with the hydration reactions of the CO/sub 2/ molecules either with neutral water molecules or with hydroxide ions, depending upon the pH, itself governed by the ionization equilibrium of the dissolved amine. Moreover, a specific (catalytic) reaction, first order with respect to both carbon dioxide and amine (rate constant, 2.85 M/sup -1/ s/sup -1/ at 25/sup 0/C), has been shown to contribute significantly to the reaction rate in the case of the first amine (TEA) only.

  9. 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

  10. Ignition phenomena and reaction mechanisms of the self-propagating high-temperature synthesis reaction in the titanium-carbon-aluminum system

    SciTech Connect

    Lee, W.C.; Chung, S.L.

    1997-01-01

    The effect of the addition of aluminum on the ignition and self-propagating high-temperature synthesis (SHS) reaction between titanium and carbon was experimentally investigated. Although TiC was the only product compound in the final product, the reaction between titanium and aluminum was believed to occur before the ignition of the reaction between titanium and carbon, as evidenced by a hump that appeared in the temperature profile during heating. The ignition temperature of the reaction between titanium and carbon was significantly decreased by the addition of aluminum. This was explained by the fact that the aluminum provides an easier route for reactant mass transfer, thus significantly increasing the reaction rate of the reaction between titanium and carbon. As the temperature was increased to beyond the melting point of aluminum during heating, aluminum melted and titanium dissolved into it. As the temperature was increased to beyond the melting point of aluminum during heating, aluminum melted and titanium dissolved into it. As the temperature was increased further (>1,050 C), the titanium-containing aluminum spread over the carbon particles. Ignition is believed to have occurred by the reaction of titanium and carbon at the interface by the diffusion of titanium through the aluminum melt to the interface. The rate of heating and the density of the reactant compact also affected the ignition temperature. These were explained by their influence on the extent of the capillary spreading of the titanium-containing aluminum melt on the carbon particles or by the formation of a TiAl{sub x} layer at the interface between the aluminum melt and the titanium particles. Fracture surfaces of the product showed three different types of morphology. A possible reaction mechanism was proposed that describes the ignition process and explains the formation of each type of product.

  11. 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

  12. 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.

  13. Carbon transfer from the host to Tuber melanosporum mycorrhizas and ascocarps followed using a 13C pulse-labeling technique.

    PubMed

    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 (13)CO2. The transfer of (13)C 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 (13)C and transferred it slowly to the mycorrhizas. The mycorrhizas first formed a carbon sink and accumulated (13)C prior to ascocarp development. Then, the mycorrhizas transferred (13)C to the ascocarps to provide constitutive carbon (1.7 mg of (13)C 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. 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

  15. Carbon-protected bimetallic carbide nanoparticles for a highly efficient alkaline hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Liu, Yipu; Li, Guo-Dong; Yuan, Long; Ge, Lei; Ding, Hong; Wang, Dejun; Zou, Xiaoxin

    2015-02-01

    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.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

  16. 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

  17. Fabrication and characterization of reaction bonded silicon carbide/carbon nanotube composites

    NASA Astrophysics Data System (ADS)

    Thostenson, Erik T.; Karandikar, Prashant G.; Chou, Tsu-Wei

    2005-11-01

    Carbon nanotubes have generated considerable excitement in the scientific and engineering communities because of their exceptional mechanical and physical properties observed at the nanoscale. Carbon nanotubes possess exceptionally high stiffness and strength combined with high electrical and thermal conductivities. These novel material properties have stimulated considerable research in the development of nanotube-reinforced composites (Thostenson et al 2001 Compos. Sci. Technol. 61 1899, Thostenson et al 2005 Compos. Sci. Technol. 65 491). In this research, novel reaction bonded silicon carbide nanocomposites were fabricated using melt infiltration of silicon. A series of multi-walled carbon nanotube-reinforced ceramic matrix composites (NT-CMCs) were fabricated and the structure and properties were characterized. Here we show that carbon nanotubes are present in the as-fabricated NT-CMCs after reaction bonding at temperatures above 1400 °C. Characterization results reveal that a very small volume content of carbon nanotubes, as low as 0.3 volume %, results in a 75% reduction in electrical resistivity of the ceramic composites. A 96% decrease in electrical resistivity was observed for the ceramics with the highest nanotube volume fraction of 2.1%.

  18. 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

  19. 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.

  20. 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

  1. Carbon-oxygen bond strength as a control of reaction kinetics: Phenol on Mo(110)

    NASA Astrophysics Data System (ADS)

    Serafin, J. G.; Friend, C. M.

    The reaction of phenol on Mo(110) has been studied using temperature programmed reaction and X-ray photoelectron spectroscopies. After desorption of multilayers and a weakly bound molecular species, decomposition produces the only reaction products observed: gaseous dihydrogen, surface carbon and surface oxygen. The OH bond cleaves first at temperatures below 360 K to form surface phenoxide (C 6H 5O-), followed by CH bond activation commencing at 370 K. CO bonds are cleaved in the temperature range of 370 to 450 K. After annealing to 300 K, multiple species are detected on the surface by X-ray photoelectron spectroscopy. The cleavage of CH bonds in the same temperature regime as CO bonds is thought to lead to selective decomposition of phenol on Mo(110). The reaction of phenol is contrasted to that of a sulfur-containing analogue, benzenethiol, on the Mo(110) surface. The stability of the phenoxide intermediate with respect to carbon-heteroatom bond cleavage is greater than that of the corresponding phenyl thiolate formed from benzenethiol. Comparison of the reaction of phenol and benzenethiol demonstrates the importance of C X ( X = O, S) bond strength in determining the reactivity and selectivity of these molecules.

  2. Carbon-oxygen bond strength as a control of reaction kinetics: Phenol on Mo(110)

    NASA Astrophysics Data System (ADS)

    Serafin, J. G.; Friend, C. M.

    1989-03-01

    The reaction of phenol on Mo(110) has been studied using temperature programmed reaction and X-ray photoelectron spectroscopies. After desorption of multilayers and a weakly bound molecular species, decomposition produces the only reaction products observed: gaseous dihydrogen, surface carbon and surface oxygen. The O-H bond cleaves first at temperatures below 360 K to form surface phenoxide (C 6H 5O-), followed by C-H bond activation commencing at 370 K. C-O bonds are cleaved in the temperature range of 370 to 450 K. After annealing to 300 K, multiple species are detected on the surface by X-ray photoelectron spectroscopy. The cleavage of C-H bonds in the same temperature regime as C-O bonds is thought to lead to selective decomposition of phenol on Mo(110). The reaction of phenol is contrasted to that of a sulfur-containing analogue, benzenethiol, on the Mo(110) surface. The stability of the phenoxide intermediate with respect to carbon-heteroatom bond cleavage is greater than that of the corresponding phenyl thiolate formed from benzenethiol. Comparison of the reaction of phenol and benzenethiol demonstrates the importance of C- X ( X = O, S) bond strength in determining the reactivity and selectivity of these molecules.

  3. Reaction cross sections on carbon for neutron energies from 11. 5 to 19 MeV

    SciTech Connect

    Antolkovic, B. ); Dietze, G.; Klein, H. )

    1991-01-01

    This paper reports on neutron-induced reaction cross sections for carbon measured in the 11.5- to 19-MeV energy range. The response of an NE-213 scintillation detector is measured in steps of at least 0.5 MeV for monoenergetic neutrons, applying suitable time-of-flight techniques, and compared with Monte Carlo simulations. The total cross sections of all reactions with charged particles (except carbon recoil protons) in the exit channel are determined with respect to the n-p scattering cross section. In addition, the {sup 12}C(n,n{prime}3{alpha}) reaction is investigated for neutron energies of 11.9, 12.9, 14.0, 14.8, 17.0, and 19.0 MeV using the nuclear emulsion technique. As it is kinematically complete, this measurement yields the total and partial cross sections for the various channels of the {sup 12}C(n,n{prime}3{alpha}) reaction. The experimental data show deviations of up to {plus minus}25% from those recommended in ENDF/B-V, while a recent evaluation by Axton is partially confirmed. Reasonable agreement is found with most of the recent scattering experiments; thus, this data set represents a valuable constraint for further evaluations. The analysis performed, however, has shown that additional data from some partial reaction cross sections are needed.

  4. 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

  5. Reaction studies of hot silicon, germanium and carbon atoms: Progress report, February 1, 1985-July 31, 1987

    SciTech Connect

    Gaspar, P.P.

    1987-08-01

    The experimental approach toward attaining the goals of this research program is briefly outlined, and the progress made in the 1985 to 1987 period is reviewed in sections entitled: (1) reactions of recoiling silicon atoms; (2) reactions of recoiling carbon atoms; and (3) reactions of thermally evaporated germanium atoms.

  6. 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.

  7. 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

  8. S-Factor measurement of the 12C(p,γ)13N reaction in inverse kinematics

    NASA Astrophysics Data System (ADS)

    Stöckel, Klaus; Reinhardt, Tobias P.; Akhmadaliev, S.; Bemmerer, D.; Gohl, St.; Reinicke, S.; Schmidt, K.; Serfling, M.; Szücs, T.; Takács, M. P.; Wagner, L.; Zuber, K.

    2015-05-01

    Hydrogen rich solid targets have been developed and produced to investigate the 12C(p, γ)13N reaction in inverse kinematics. The SRIM simulation software has been used to determine the parameters for ion implantation in various materials. Nuclear Resonant Reacton Analysis (NRRA) with the resonant reaction 15N(p, αγ)12C has been carried out to measure the hydrogen content of the produced targets. Measurements of the produced targets at the energy range from Ecm = 577 keV down to Ecm = 191 keV, were performed at the 3-MV Tandetron of Helmholtz-Zentrum Dresden-Rossendorf (HZDR).

  9. DFT investigations for the reaction mechanism of dimethyl carbonate synthesis on Pd(II)/β zeolites.

    PubMed

    Shen, Yongli; Meng, Qingsen; Huang, Shouying; Gong, Jinlong; Ma, Xinbin

    2013-08-21

    Density functional theory (DFT) calculations have been used to investigate the oxidative carbonylation of methanol on Pd(II)/β zeolite. Activation energies for all the elementary steps involved in the commonly accepted mechanism, including the formation of dimethyl carbonate, methyl formate and dimethoxymethane, are presented. Upon conducting the calculations, we identify that the Pd(2+) cation bonded with four O atoms of the zeolite framework acts as the active site of the catalyst. Molecularly adsorbed methanol starts to react with oxygen molecules to produce a methanediol intermediate (CH2(OH)2) and O atom. Then, another methanol can react with the O atom to produce the (CH3O)(OH)-Pd(II)/β zeolite species. (CH3O)(OH)-Pd(II)/β zeolite can further react with carbon monoxide or methanol to give monomethyl carbonate or di-methoxide species ((CH3O)2-Pd(II)/β zeolite). Dimethyl carbonate can form via two distinct reaction pathways: (I) methanol reacts with monomethyl carbonate or (II) carbon monoxide inserts into di-methoxide. Our calculation results show the activation energy of reaction (I) is too high to be achieved. The methanediol intermediate is unstable and can decompose to formaldehyde and H2O immediately. Formaldehyde can either react with an O atom or methanol to form formic acid or a CH3OCH2OH intermediate. Both of them can react with methanol to form the secondary products (methyl formate or dimethoxymethane). Upon conducting calculations, we confirmed that the activation energies for the formation of methyl formate and dimethoxymethane are higher than that of dimethyl carbonate. All these conformations were characterized at the same calculation level. PMID:23824280

  10. 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.

  11. Carbon-13 and proton nuclear magnetic resonance spectroscopy of water-soluble porphyrins and metalloporphyrins.

    PubMed

    Goff, H M; Morgan, L O

    1978-07-01

    Carbon-13 and proton nuclear magnetic resonance (NMR) spectra have been recorded for porphyrins, zinc porphyrins, and iron(III) porphyrin complexes in aqueous media. Spectra of porphyrin-c and hemin-c confirm the structure with thioether linkages at positions alpha to the porphyrin ring. The pattern of NMR isotropic shifts has implications regarding electron transfer in cytochrome-c. Free-base porphyrin-c and meso-substituted porphyrins have been examined for pyrrole nitrogen-hydrogen tautomerism and possible aggregation in aqueous solution. Zinc porphyrin 13C NMR spectra were recorded in order to provide diamagnetic references for paramagnetic iron(III) derivatives. Low-spin iron(III) porphyrin-biscyano complexes in aqueous solution exhibit NMR isotropic shift patterns similar to those previously observed for related compounds in non-aqueous media. The first 13C NMR spectra are reported for mu-oxo-bridged iron(III) porphyrin dimers. A partially resolved spectrum of a high-spin iron(III) porphyrin has also been obtained. Patterns of 13C and proton isotropic shifts are compared, and unpaired spin delocalization mechanisms for 13C resonances are discussed in a qualitative manner. PMID:687673

  12. 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

  13. Linear heterocyclic aromatic fluorescence compounds having various donor-acceptor spacers prepared by the combination of carbon-carbon bond and carbon-nitrogen bond cross-coupling reactions.

    PubMed

    Hu, Bin; Fu, Shu-Jun; Xu, Feng; Tao, Tao; Zhu, Hao-Yu; Cao, Kou-Sen; Huang, Wei; You, Xiao-Zeng

    2011-06-01

    A family of novel linear 1,10-phenanthroline-based (A-D-A-D-A) and oligothiophene-based (A-D-D-D-(D)-A) heterocyclic aromatic fluorescence compounds having N-containing imidazole and pyridine tails with effective π-conjugated systems, prepared by the combination of carbon-carbon (C-C) bond and carbon-nitrogen (C-N) bond cross-coupling reactions, is described. They have molecular lengths of more than 2.30 nm in the cases of 4, 6, 9, and 26, various D-A spacers, and certain N-coordination sites (phen, imidazole, and pyridine). X-ray single-crystal structures of 13 compounds reveal a variety of trans and cis configurations with different dihedral angles between adjacent aromatic heterocycles. Synthetic, computational, and spectral studies have been made to reveal the differences between cross-coupling approaches on the C-C bond and C-N bond formation as well as band gaps and energy levels and optical and electrochemical properties for related compounds. The influences of introducing a β-methyl group to the thiophene ring on reaction activity, solubility, and conformation of related compounds have also been discussed. PMID:21513323

  14. Paleoclimate Reconstruction From the d13C Organic and d13C Carbonate Proxies in Triassic Paleosols and Sediments, Ischigualasto Basin Argentina

    NASA Astrophysics Data System (ADS)

    Moore, K. A.; Tabor, N. J.; Montañez, I. P.; Currie, B.; Shipman, T.

    2001-12-01

    Stable carbon isotopes of organic matter and paleosol carbonate from the Triassic Ischigualasto Formation, Argentina are used as a proxy of paleoatmospheric pCO2 and d13CO2. Carbon and Oxygen isotope values were determined for over 100 Triassic pedogenic carbonate nodules and associated organic matter. The d13C of carbonate ranges from -3.29 per mil to -10.56 per mil. The d13C of organic matter ranges from -21.07 per mil to -24.24 per mil. The Hydrogen and Oxygen indices and TOC values indicate that the best preserved organic matter samples yield the most negative d13C values. Reconstructed pCO2 levels were around 1000 ppm V in the early to mid- Triassic and increased to around 2000 ppm V later in the Triassic. This maximum is followed by a fall in pCO2 in the late Triassic. This previously undocumented rapid change in paleo-CO2 levels likely accompanied the evolution of mammal-like reptiles to true dinosaurs as well as rapid climate change.

  15. The stable-carbon kinetic isotope effects of the reactions of isoprene, methacrolein, and methyl vinyl ketone with ozone in the gas phase

    NASA Astrophysics Data System (ADS)

    Iannone, Richard; Koppmann, Ralf; Rudolph, Jochen

    The stable-carbon kinetic isotope effects (KIEs) for the gas-phase reactions of isoprene, methacrolein (MACR), and methyl vinyl ketone (MVK) with ozone were studied in a 25 L reaction chamber at 298 ± 2 K and ambient pressure. The time dependence of both the stable-carbon isotope ratios and the concentrations was determined using a gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) system. The volatile organic compounds (VOCs) used in the KIE experiments had natural-abundance isotopic composition thus KIE data obtained from these experiments can be directly applied to atmospheric studies of isoprene chemistry. All 13C/ 12C KIEs reported herein are as per mille ɛ values, where ɛ = (KIE - 1) × 1000‰, and KIE = k12/ k13. The following average stable-carbon KIEs were obtained: (8.40 ± 0.11)‰ (isoprene), (8.38 ± 0.42)‰ (MACR), and (8.01 ± 0.07)‰ (MVK). The stable-carbon KIE values of three 1-alkenes, which were used as reference compounds for relative rate experiments, were also determined: (5.48 ± 0.09)‰ (1-heptene), (4.67 ± 0.17)‰ (1-octene), and (4.59 ± 0.56)‰ (1-nonene). The ɛ values for the reactions of isoprene and 1-heptene with ozone agree with measurements in a previous study [Iannone, R., Anderson, R.S., Rudolph, J., Huang, L., Ernst, D., 2003. The carbon kinetic isotope effects of ozone-alkene reactions in the gas-phase and the impact of ozone reactions on the stable carbon isotope ratio of alkenes in the atmosphere. Geophysical Research Letters 30, 1684, doi: 10.1029/2003GL017221.], but the values presented here have a substantially improved accuracy. The ɛ values for 1-octene and 1-nonene reactions with ozone have not been measured before and closely follow the 1/ NC dependence (where NC represents the number of carbon atoms in the alkene) derived in the aforementioned study. MACR and MVK had ɛ values that were somewhat below the expected range of values predicted by the 1/ NC dependence found for alkenes.

  16. Reactions of the inner surface of carbon nanotubes and nanoprotrusion processes imaged at the atomic scale

    NASA Astrophysics Data System (ADS)

    Chamberlain, Thomas W.; Meyer, Jannik C.; Biskupek, Johannes; Leschner, Jens; Santana, Adriano; Besley, Nicholas A.; Bichoutskaia, Elena; Kaiser, Ute; Khlobystov, Andrei N.

    2011-09-01

    Although the outer surface of single-walled carbon nanotubes (atomically thin cylinders of carbon) can be involved in a wide range of chemical reactions, it is generally thought that the interior surface of nanotubes is unreactive. In this study, we show that in the presence of catalytically active atoms of rhenium inserted into nanotubes, the nanotube sidewall can be engaged in chemical reactions from the inside. Aberration-corrected high-resolution transmission electron microscopy operated at 80 keV allows visualization of the formation of nanometre-sized hollow protrusions on the nanotube sidewall at the atomic level in real time at ambient temperature. Our direct observations and theoretical modelling demonstrate that the nanoprotrusions are formed in three stages: (i) metal-assisted deformation and rupture of the nanotube sidewall, (ii) the fast formation of a metastable asymmetric nanoprotrusion with an open edge and (iii) a slow symmetrization process that leads to a stable closed nanoprotrusion.

  17. Reactions of the inner surface of carbon nanotubes and nanoprotrusion processes imaged at the atomic scale.

    PubMed

    Chamberlain, Thomas W; Meyer, Jannik C; Biskupek, Johannes; Leschner, Jens; Santana, Adriano; Besley, Nicholas A; Bichoutskaia, Elena; Kaiser, Ute; Khlobystov, Andrei N

    2011-09-01

    Although the outer surface of single-walled carbon nanotubes (atomically thin cylinders of carbon) can be involved in a wide range of chemical reactions, it is generally thought that the interior surface of nanotubes is unreactive. In this study, we show that in the presence of catalytically active atoms of rhenium inserted into nanotubes, the nanotube sidewall can be engaged in chemical reactions from the inside. Aberration-corrected high-resolution transmission electron microscopy operated at 80 keV allows visualization of the formation of nanometre-sized hollow protrusions on the nanotube sidewall at the atomic level in real time at ambient temperature. Our direct observations and theoretical modelling demonstrate that the nanoprotrusions are formed in three stages: (i) metal-assisted deformation and rupture of the nanotube sidewall, (ii) the fast formation of a metastable asymmetric nanoprotrusion with an open edge and (iii) a slow symmetrization process that leads to a stable closed nanoprotrusion. PMID:21860464

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. Aspartate beta-decarboxylase from Alcaligenes faecalis: carbon-13 kinetic isotope effect and deuterium exchange experiments

    SciTech Connect

    Rosenberg, R.M.; O'Leary, M.H.

    1985-03-26

    The authors have measured the /sup 13/C kinetic isotope effect at pH 4.0, 5.0, 6.0, and 6.5 and in D/sub 2/O at pH 5.0 and the rate of D-H exchange of the alpha and beta protons of aspartic acid in D/sub 2/O at pH 5.0 for the reaction catalyzed by the enzyme aspartate beta-decarboxylase from Alcaligenes faecalis. The /sup 13/C kinetic isotope effect, with a value of 1.0099 +/- 0.0002 at pH 5.0, is less than the intrinsic isotope effect for the decarboxylation step, indicating that the decarboxylation step is not entirely rate limiting. The authors have been able to estimate probable values of the relative free energies of the transition states of the enzymatic reaction up to and including the decarboxylation step from the /sup 13/C kinetic isotope effect and the rate of D-H exchange of alpha-H. The pH dependence of the kinetic isotope effect reflects the pKa of the pyridine nitrogen of the coenzyme pyridoxal 5'-phosphate but not that of the imine nitrogen. A mechanism is proposed for the exchange of aspartate beta-H that is consistent with the stereochemistry suggested earlier.

  4. 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. PMID:25611887

  5. 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

  6. Electroactive carbon nanoforms: a comparative study via sequential arylation and click chemistry reactions

    NASA Astrophysics Data System (ADS)

    Mateos-Gil, Jaime; Rodríguez-Pérez, Laura; Moreno Oliva, María; Katsukis, Georgios; Romero-Nieto, Carlos; Herranz, M. Ángeles; Guldi, Dirk M.; Martín, Nazario

    2014-12-01

    The reactivity of several carbon nanoforms (CNFs), single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs) and graphene, has been investigated through a combination of arylation and click chemistry CuI-mediated azide-alkyne cycloaddition (CuAAC) reactions. The approach is based on the incorporation of electroactive π-extended tetrathiafulvalene (exTTF) units into the triazole linkers to modulate the electronic properties of the obtained conjugates. The introduction of strain, by bending the planar graphene sheet into a 3D carbon framework, is responsible for the singular reactivity observed in carbon nanotubes. The formed nanoconjugates were fully characterized by analytical, spectroscopic, and microscopic techniques (TGA, FTIR, Raman, UV-Vis-NIR, cyclic voltammetry, TEM and XPS). In the case of SWCNT conjugates, where the functionalization degree is higher, a series of steady-state and time resolved spectroscopy experiments revealed a photoinduced electron transfer from the exTTF unit to the electron-accepting SWCNT.The reactivity of several carbon nanoforms (CNFs), single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs) and graphene, has been investigated through a combination of arylation and click chemistry CuI-mediated azide-alkyne cycloaddition (CuAAC) reactions. The approach is based on the incorporation of electroactive π-extended tetrathiafulvalene (exTTF) units into the triazole linkers to modulate the electronic properties of the obtained conjugates. The introduction of strain, by bending the planar graphene sheet into a 3D carbon framework, is responsible for the singular reactivity observed in carbon nanotubes. The formed nanoconjugates were fully characterized by analytical, spectroscopic, and microscopic techniques (TGA, FTIR, Raman, UV-Vis-NIR, cyclic voltammetry, TEM and XPS). In the case of SWCNT conjugates, where the functionalization degree is higher, a series of steady-state and time resolved

  7. 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

  8. Matrix isolation study of the ozonolysis of 1,3- and 1,4-cyclohexadiene: identification of novel reaction pathways.

    PubMed

    Pinelo, Laura; Gudmundsdottir, Anna D; Ault, Bruce S

    2013-05-23

    The ozonolysis reactions of 1,3- and 1,4-cyclohexadiene have been studied using a combination of matrix isolation, infrared spectroscopy, and theoretical calculations. Experimental and theoretical results demonstrate that these reactions predominantly do not follow the long-accepted Criegee mechanism. Rather, the reaction of O3 with 1,4-cyclohexadiene leads to the essentially barrierless formation of benzene, C6H6, and H2O3. These two species are then trapped in the same argon matrix cage and weakly interact to form a molecular complex. There is also evidence for the formation of a small amount of the primary ozonide as a minor product, formed through a transition state that is slightly higher in energy. The reaction of O3 with 1,3-cyclohexadiene follows two pathways, one of which is the Criegee mechanism through a low energy transition state leading to formation of the primary ozonide. In addition, with a similar barrier, ozone abstracts a single hydrogen from C5 while adding to C1, forming a hydroperoxy intermediate. This study presents two of the rare cases in which the Criegee mechanism is not the dominant pathway for the ozonolysis of an alkene as well as the first evidence for dehydrogenation of an alkene by ozone. PMID:23638640

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. 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

  14. Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

    NASA Astrophysics Data System (ADS)

    Hockaday, W. C.; Masiello, C. A.; Randerson, J. T.; Smernik, R. J.; Baldock, J. A.; Chadwick, O. A.; Harden, J. W.

    2009-06-01

    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 Cox. 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

  15. 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

  16. 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

  17. 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.

  18. Effects of alloying elements on carbon dioxide corrosion in 13% to 20% chromium-containing steels

    SciTech Connect

    Hara, T.; Asahi, H.; Kawakami, A.; Takahashi, A.

    2000-04-01

    Effects of alloying elements on corrosion rates were investigated for 13% to 20% chromium-containing steels in wet carbon dioxide (CO{sub 2}) environments without wet hydrogen sulfide (H{sub 2}S) gas at 150 C to 200 C. Results showed that a reduction in carbon content and an increase in chromium, molybdenum, and nickel content improved CO{sub 2} corrosion resistance. However, corrosion rate was independent of nitrogen content. The combined additions of nickel and copper greatly improved CO{sub 2} corrosion resistance. To satisfy the criteria in which the corrosion rates became < 0.1 mm/y, the nickel content should have been > 1% and copper > 0.5% at 10 C. This level of alloying corresponded to the reduction of the Cr + 1.6% Mo index value by {approximately}6%. In the case at 200 C, nickel content was required at > 4%, and copper content at > 1%. The reason for the improvement of CO{sub 2} corrosion resistance is thought to be the combined additions of nickel and copper that made the corrosion film more stable and more protective. The equation to be satisfied with a corrosion rate < 0.1 mm/y at 180 C in 0.02% C-containing steels was indicated as Cr + 1.6% Mo {ge} 19% (copper-free steels) and Cr + 1.6% Mo {ge} 13% (combined additions of nickel and copper).

  19. Dynamic nuclear polarization of biocompatible (13)C-enriched carbonates for in vivo pH imaging.

    PubMed

    Korenchan, D E; Flavell, R R; Baligand, C; Sriram, R; Neumann, K; Sukumar, S; VanBrocklin, H; Vigneron, D B; Wilson, D M; Kurhanewicz, J

    2016-02-18

    A hyperpolarization technique using carbonate precursors of biocompatible molecules was found to yield high concentrations of hyperpolarized (13)C bicarbonate in solution. This approach enabled large signal gains for low-toxicity hyperpolarized (13)C pH imaging in a phantom and in vivo in a murine model of prostate cancer. PMID:26792559

  20. SUBSTITUENT EFFECTS AND ADDITIVITY IN THE CARBON-13 NUCLEAR MAGNETIC RESONANCE SPECTRA OF CHLORINATED NAPHTHALENES AND THEIR CHLORINATED NAPHTHOL METABOLITES

    EPA Science Inventory

    Carbon-13 and proton nuclear magnetic resonance spectra were obtained for 12 chlorinated naphthalenes and six chlorinated naphthols, some of which are metabolites of the naphthalenes. The validity of the use of additivity of chlorine and hydroxyl substituent effects to predict 13...

  1. Measurement of the sup 12 C( p ,. pi. sup 0 ) sup 13 N reaction by recoil detection

    SciTech Connect

    Homolka, J.; Schott, W.; Wagner, W.; Wilhelm, W. ); Saber, M.; Segel, R.E. ); Bent, R.D.; Fatyga, M.; Pollock, R.E. ); Kienle, P. ); Rehm, K.E. )

    1992-03-01

    Differential cross sections for the neutral pion production reaction {sup 12}C({ital p},{pi}{sup 0}){sup 13}N{sub g.s.} have been measured at 153.5, 166.1, 186.0, and 204.0 MeV bombarding energy using recoil detection. The shape of the angular distribution agrees well with that of the mirror reaction {sup 12}C({ital p},{pi}{sup +}){sup 13}C{sub g.s.}. Isospin invariance predicts for the ratio of the cross sections {sigma}({ital p},{pi}{sup +})/{sigma}({ital p},{pi}{sup 0})=2. At 153.5, 166.1, and 186.0, MeV, where ({ital p},{pi}{sup +}) cross sections have been reported previously by other groups at the same reduced pion momentum {eta}={ital p}{sub {pi}}/{ital m}{sub {pi}}{ital c}=0.34,0.55,0.78, the ratio of the total cross sections is 2.02{plus minus}0.14, 3.14{plus minus}0.12, and 2.12{plus minus}0.16, respectively. The ({ital p},{pi}{sup 0}) cross sections at 166 MeV is therefore 1.57{plus minus}0.06 times larger than expected. For {ital T}{sub {ital p}}{lt}160 MeV, the experimental cross sections are larger than predicted by a phase space and Coulomb barrier penetration calculation that fits the higher-energy data. Differential cross sections were also obtained for the {sup 12}C({ital p},{pi}{sup {minus}}){sup 13}O reaction, and upper limits set for differential cross sections for radiative capture to the ground state of {sup 13}N.

  2. 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

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. Synthesis of empagliflozin, a novel and selective sodium-glucose co-transporter-2 inhibitor, labeled with carbon-14 and carbon-13.

    PubMed

    Hrapchak, Matt; Latli, Bachir; Wang, Xiao-Jun; Lee, Heewon; Campbell, Scot; Song, Jinhua J; Senanayake, Chris H

    2014-10-01

    Empagliflozin, (2S,3R,4R,5S,6R)-2-[4-chloro-3-[[4-[(3S)-oxolan-3-yl]oxyphenyl]methyl]phenyl]-6-(hydroxymethyl)oxane-3,4,5-triol was recently approved by the FDA for the treatment of chronic type 2 diabetes mellitus. Herein, we report the synthesis of carbon-13 and carbon-14 labeled empagliflozin. Carbon-13 labeled empagliflozin was prepared in five steps and in 34% overall chemical yield starting from the commercially available α-D-glucose-[(13)C6]. For the radiosynthesis, the carbon-14 atom was introduced in three different positions of the molecule. In the first synthesis, Carbon-14 D-(+)-gluconic acid δ-lactone was used to prepare specifically labeled empagliflozin in carbon-1 of the sugar moiety in four steps and in 19% overall radiochemical yield. Carbon-14 labeled empagliflozin with the radioactive atom in the benzylic position was obtained in eight steps and in 7% overall radiochemical yield. In the last synthesis carbon-14 uniformly labeled phenol was used to give [(14)C]empagliflozin in eight steps and in 18% overall radiochemical yield. In all these radiosyntheses, the specific activities of the final compounds were higher than 53 mCi/mmol, and the radiochemical purities were above 98.5%. PMID:25332189

  8. Diagnosis of Helicobacter pylori by carbon-13 urea breath test using a portable mass spectrometer

    PubMed Central

    Sreekumar, J; France, N; Taylor, S; Matthews, T; Turner, P; Bliss, P; Watson, AJM

    2015-01-01

    Context: In the non-invasive detection of markers of disease, mass spectrometry is able to detect small quantities of volatile markers in exhaled air. However, the problem of size, expense and immobility of conventional mass spectrometry equipment has restricted its use. Now, a smaller, less expensive, portable quadrupole mass spectrometer system has been developed. Helicobacter pylori has been implicated in the development of chronic gastritis, gastric and duodenal ulcers and gastric cancer. Objectives: To compare the results obtained from the presence of H. pylori by a carbon-13 urea test using a portable quadrupole mass spectrometer system with those from a fixed mass spectrometer in a hospital-based clinical trial. Methods: Following ethical approval, 45 patients attending a gastroenterology clinic at the Royal Liverpool University Hospital exhaled a breath sample into a Tedlar gas sampling bag. They then drank an orange juice containing urea radiolabelled with carbon and 30 min later gave a second breath sample. The carbon-13 content of both samples was measured using both quadrupole mass spectrometer systems. If the post-drink level exceeded the pre-drink level by 3% or more, a positive diagnosis for the presence of H. pylori was made. Results: The findings were compared to the results using conventional isotope ratio mass spectrometry using a laboratory-based magnetic sector instrument off-site. The results showed agreement in 39 of the 45 patients. Conclusions: This study suggests that a portable quadrupole mass spectrometer is a potential alternative to the conventional centralised testing equipment. Future development of the portable quadrupole mass spectrometer to reduce further its size and cost is indicated, together with further work to validate this new equipment and to enhance its use in mass spectrometry diagnosis of other medical conditions. PMID:26770764

  9. 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-...

  10. Evidence for 13-carbon enrichment in oxalic acid via iron catalyzed photolysis in aqueous phase

    NASA Astrophysics Data System (ADS)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka

    2012-02-01

    To investigate the effect of photochemical aging on the stable carbon isotopic ratio (δ13C) of oxalic acid (OxA), a dominant organic species in atmospheric aerosols, we conducted a laboratory photolysis of OxA under H2O2-Fe3+(Fe2+)-UV system in aqueous phase and measured δ13C of remaining OxA. Our results showed that a significant photolysis of OxA occurred with OH radical but the isotopic fractionation of OxA was insignificant. In contrast, in the presence of Fe3+ (Fe2+), we found a significant enrichment of 13C in remaining OxA. We also found that kinetic isotope effect (KIE) of OxA largely depends on photochemical age (irradiation time) and concentration ratios of OxA to iron; 3.20 ± 0.49‰ (2.18 ± 1.18‰) and 21.62 ± 5.41‰ in 90 min and 180 min irradiation, in which OxA and Fe3+ (Fe2+) ratios were 50:1 and 200:1, respectively. The enrichment of 13C in remaining OxA was more significant during the photolysis catalyzed by Fe3+ (7‰) than by Fe2+ (3‰) in 90 min irradiation when OxA and iron ratios are the same (50:1). This study provides a laboratory evidence for the isotopic enrichment of 13C in OxA with photochemical aging. This approach is useful for better interpretation of atmospheric isotopic measurements in terms of the extent of atmospheric processing of aerosols.

  11. 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

  12. /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.

  13. Determination of the Reaction Coordinate for a Key Conformational Fluctuation in Human Carbonic Anhydrase II.

    PubMed

    Paul, Sanjib; Taraphder, Srabani

    2015-08-27

    During the reversible hydration of carbon dioxide into bicarbonate by the enzyme human carbonic anhydrase II, the rate-determining step of proton transfer across the active site has been suggested to involve side chain rotation of the residue His-64 shuttling an excess proton in and out of the active site. In the present article, we have determined the reaction coordinate for this catalytically important conformational transition starting from a set of 32 order parameters (or candidate collective variables). Following the original work by Peters and Trout (J. Chem. Phys. 2006, 125, 054108), unbiased dynamical transition paths connecting the two major side chain conformations are harvested using an aimless shooting algorithm, and the reaction coordinate is determined using the method of forward-trajectory likelihood maximization. Several different models are tested involving a single order parameter or linear combinations of several of them chosen from the preselected set. An optimum reaction coordinate, identified using a Bayesian information criterion, is found to be a linear combination of 4 order parameters. This reaction coordinate is subsequently utilized to explore the associated free energy profile and diffusive barrier crossing dynamics. To the best of our knowledge, previous instances of this calculation include only alanine dipeptide and photoactive yellow protein (125 residues) in explicit water solvent. The present work is the first report of a quantitative determination of the reaction coordinate for conformational transition in a protein having as many as 259 residues in the presence of explicit water and sampled near the free energy barrier for about 1 μs. PMID:26135039

  14. Reactions of hydroxyl radical with humic substances: bleaching, mineralization, and production of bioavailable carbon substrates.

    PubMed

    Goldstone, J V; Pullin, M J; Bertilsson, S; Voelker, B M

    2002-02-01

    In this study, we examine the role of the hydroxyl (OH*) radical as a mechanism for the photodecomposition of chromophoric dissolved organic matter (CDOM) in sunlit surface waters. Using gamma-radiolysis of water, OH* was generated in solutions of standard humic substances in quantities comparable to those produced on time scales of days in sunlit surface waters. The second-order rate coefficients of OH* reaction with Suwannee River fulvic (SRFA; 2.7 x 10(4) s(-1) (mg of C/L)(-1)) and humic acids (SRHA; 1.9 x 10(4) s(-1) (mg of C/L)(-1)) are comparable to those observed for DOM in natural water samples and DOM isolates from other sources but decrease slightly with increasing OH* doses. OH* reactions with humic substances produced dissolved inorganic carbon (DIC) with a high efficiency of approximately 0.3 mol of CO2/mol of OH*. This efficiency stayed approximately constant from early phases of oxidation until complete mineralization of the DOM. Production rates of low molecular weight (LMW) acids including acetic, formic, malonic, and oxalic acids by reaction of SRFA and SRHA with OH* were measured using HPLC. Ratios of production rates of these acids to rates of DIC production for SRHA and for SRFA were similar to those observed upon photolysis of natural water samples. Bioassays indicated that OH* reactions with humic substances do not result in measurable formation of bioavailable carbon substrates other than the LMW acids. Bleaching of humic chromophores by OH* was relatively slow. Our results indicate that OH* reactions with humic substances are not likely to contribute significantly to observed rates of DOM photomineralization and LMW acid production in sunlit waters. They are also not likely to be a significant mechanism of photobleaching except in waters with very high OH* photoformation rates. PMID:11871550

  15. Studies of individual carbon sites of azurin from Pseudomonas aeruginosa by natural-abundance carbon-13 nuclear magnetic resonance spectroscopy.

    PubMed

    Ugurbil, K; Norton, R S; Allerhand, A; Bersohn, R

    1977-03-01

    The environments of the aromatic residues (and of the single arginine residue) of azurin from Pseudomonas aeruginosa are investigated by means of natural-abundance 13C Fourier transform NMR spectroscopy. In the case of the diamagnetic Cu(I) azurin, all 17 nonprotonated aromatic carbons (and Czota of Arg-79) yield narrow resonances. Furthermore, a single-carbon amide carbonyl resonance with an unusual chemical shift (peak chi) is observed. The pH dependence of chemical shifts is used to identify the resonances of Cgamma of titrating histidines, and of Cgamma and Czota of the two tyrosines. The resonances of Cgamma and Cdelta2 of the single tryptophan residue (and Czota of Arg-79) are also identified. The pKa values of the two tyrosines are different from each other and higher than typical values of "solvent-exposed" tyrosine residues. Two of the four histidine residues do not titrate (in the pH range 4 to 11). The resonance of Cgamma of one histidine exhibits a pH titration with fast proton exchange behavior and a pKa of 7.5 +/- 0.2. The direction of the titration shift indicates that the imidazole form of this histidine is the Ndelta1-H tautomer. The Cgamma resonance of the other titrating histidine exhibits slow exchange behavior with a pKa of about 7. The imidazole form of this histidine is the Nepsilon2-H tautomer. When going to the paramagnetic Cu(II) protein, only 11 of the 19 carbons mentioned above yield resonances that are narrow enough to be detected. Also, some of the observed resonances exhibit significant paramagnetic broadening. A comparison of spectra of fully reduced azurin, mixtures of reduced and oxidized azurin, and fully oxidized azurin yields the following information. (i) Peak chi arises from an amide group that probably is coordinated to the copper. (ii) The two nontitrating histidine residues are probably copper ligands, with Ndelta1 coordinated to the metal. (iii) The side chains of Arg-79 and the two tyrosine residues are not coordinated to

  16. 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 ...

  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. Carbon incorporation effects and reaction mechanism of FeOCl cathode materials for chloride ion batteries

    NASA Astrophysics Data System (ADS)

    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.

  19. Surface reactions as carbon removal mechanism in deposition of silicon dioxide films at atmospheric pressure

    SciTech Connect

    Reuter, R.; Ellerweg, D.; Keudell, A. von; Benedikt, J.

    2011-03-14

    The deposition of thin SiO{sub x}C{sub y}H{sub z} or SiO{sub x}H{sub y} films by means of an atmospheric pressure microplasma jet with helium/hexamethyldisiloxane (HMDSO)/O{sub 2} mixtures and the surface reactions involving oxygen have been studied. It is shown, that the carbon content in the film can be controlled by choosing the right O{sub 2}/HMDSO ratio in the gas mixture. The microplasma jet geometry and localization of the deposition at a spot of few square millimeters allows studying the role of oxygen in the deposition process. This is done by alternating application of He/HMDSO plasma and He/O{sub 2} plasma to the same deposition area, here achieved by a treatment of a rotating substrate by two jets with above mentioned gas mixtures. It is shown that carbon-free SiO{sub x}H{sub y} film can be deposited in this way and that surface reaction with oxygen is the main loss mechanism of carbon from the film.

  20. 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

  1. 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

  2. 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.

  3. 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

  4. Overcoming Barriers to the Remediation of Carbon Tetrachloride through Manipulation of Competing Reaction Mechanisms

    SciTech Connect

    Tratnyek, Paul G.; Amonette, James E.; Bylaska, Eric J. and Szecsody, James E.

    2004-06-01

    Most approaches that have been proposed for the remediation of groundwater contaminated with carbon tetrachloride (CCl4) produce chloroform (CHCl3) as the major product and methylene chloride (CH2Cl2) as a minor product. Both of these products are nearly as persistent and problematic as the parent compound, but competing reaction pathways produce the more desirable products carbon monoxide (CO) and/or formate (HCOO-). Results scattered throughout the chemical and environmental engineering literature show that the branching between these reaction pathways is highly variable, but the controlling factors have not been identified. If we understood the fundamental chemistry that controls the branching among these, and related, product-formation pathways, we could improve the applicability of a host of remediation technologies (both chemical and biological) to the large plumes of CCl4 that contaminate DOE sites across the country. This project will provide the first complete characterization of the mechanisms and kinetics of competing degradation reactions of CCl4 through laboratory experiments in simple model systems closely coordinated with theoretical modeling studies. The results provide strategies for maximizing the yield of desirable products from CCl4 degradation, and the most promising of these will be tested in column model systems using real site waters and matrix materials.

  5. 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

  6. {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.

  7. 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. PMID:26095823

  8. On the Reaction of FNO2 with CH3, t-butyl, and C13H21

    NASA Technical Reports Server (NTRS)

    Thuemmel, H. T.; Bauschlicher, Charles W., Jr.; Arnold, James O. (Technical Monitor)

    1996-01-01

    Theoretical studies are reported for the reaction of FN02 with the radicals CH3, t-butyl, and C13H21, which are templates for the radical site of a hydrogenated diamond surface. All structures axe fully optimized using density functional theory (DFT) based on the B3LYP functional. Calibration calculations axe performed for CH3 + FNO2 using the coupled cluster approach, the the internally contracted multireference configuration. interaction method, and second order perturbation theory based upon complete active space SCF (CASSCF) reference wave function. These calibration calculations support the B3LYP approach for the calculation of bond energies, but show the B3LYP barrier is too low. Combining the calibration calculations with the larger clusters yields our best estimate of a barrier of about 10 kcal/mol. for the reaction of FNO2 with a radical site on hydrogenated diamond.

  9. 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.

  10. Spot-free catalysis using gold carbon nanotube & gold graphene composites for hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Sai Siddhardha, R. S.; Lakshminarayanan, V.; Ramamurthy, Sai Sathish

    2015-08-01

    Hydrogen has been proposed as the green fuel of the future in the wake of depleting fossil fuels. Recently, carbon paste electrodes (CPE) modified with nanomaterials as electrocatalysts have drawn wide attention for hydrogen evolution reaction (HER) in acid medium. The CPEs are advantageous owing to their chemical stability and ease of fabrication. Their applications for HER without any modification, however, are hampered on account of large hydrogen overpotential associated with carbon surface. In the present study, CPE has been modified with novel gold composites as electro-catalysts for HER in acid medium. The nanocomposites have shown ∼100 fold increased current density than unmodified CPE at -0.3 V. Most strikingly for the first time, this study has quantitatively brought out the difference in catalysis between surfactant capped and pristine gold nanoparticles in terms of their application as spot-free catalysts towards hydrogen gas production by electrochemical route.

  11. 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

  12. Two dimensional N-containing carbon materials for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Feng, Yexin; Hu, Zhenpeng; Zhang, Lixin

    2013-03-01

    Seeking Pt replacement catalysts for cathode oxygen reduction reaction (ORR) is very important for the application of some new energy technologies like fuel cells and lithium-air batteries. N-doped graphene and carbon nitride sheets are two kinds of promising materials. For the N-doped graphene, it is found that nitrogen clusters other than isolated substitutionals are the active sites for oxygen reduction. Clusters with three or four N atoms are found to be the most active. Codoping boron (or Fe, Co) can effectively stabilize these high energy clusters while keep the cluster's high activity. For the carbon nitride sheets, in the C:N ratio range of 2.0-3.0, they are stable enough and can potentially catalyze the oxygen reduction as efficiently as Pt. It is revealed that the concentration of nitrogen can tune the Fermi level of the material and thus the catalytic property. The catalytic sites are located at those carbon atoms with special configurations rather than the nitrogen atoms. These results are helpful in designing N-containing carbon materials for ORR.

  13. 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.

  14. Covalent grafting of carbon nanotubes with a biomimetic heme model compound to enhance oxygen reduction reactions.

    PubMed

    Wei, Ping-Jie; Yu, Guo-Qiang; Naruta, Yoshinori; Liu, Jin-Gang

    2014-06-23

    The oxygen reduction reaction (ORR) is one of the most important reactions in both life processes and energy conversion systems. The replacement of noble-metal Pt-based ORR electrocatalysts by nonprecious-metal catalysts is crucial for the large-scale commercialization of automotive fuel cells. Inspired by the mechanisms of dioxygen activation by metalloenzymes, herein we report a structurally well-defined, bio-inspired ORR catalyst that consists of a biomimetic model compound-an axial imidazole-coordinated porphyrin-covalently attached to multiwalled carbon nanotubes. Without pyrolysis, this bio-inspired electrocatalyst demonstrates superior ORR activity and stability compared to those of the state-of-the-art Pt/C catalyst in both acidic and alkaline solutions, thus making it a promising alternative as an ORR electrocatalyst for application in fuel-cell technology. PMID:24842193

  15. 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.

  16. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Nandan, Ravi; Nanda, Karuna Kar

    2015-06-01

    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-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.

  17. Reaction pathways in the coadsorption of carbon monoxide and nitric oxide at caesium surfaces

    NASA Astrophysics Data System (ADS)

    Carley, A. F.; Roberts, M. W.; Santra, A. K.

    2002-09-01

    The reactivity of caesium surfaces to nitric oxide, carbon monoxide and mixtures of NO and CO at low temperatures (90-220 K) has been studied by X-ray photoelectron spectroscopy. Reaction pathways for CO-NO mixtures are controlled by oxygen transients generated by the dissociative chemisorption of NO emphasising the limitations of evidence that might be deduced from the reactivity of the individual molecules, CO on its own not being adsorbed at a caesium surface. Spectroscopic evidence for the formation of CO 2δ- , CO 3, and NO 2 species is discussed.

  18. Photochemically Induced Dynamic Nuclear Polarization Observed by Solid-State NMR in a Uniformly (13)C-Isotope-Labeled Photosynthetic Reaction Center.

    PubMed

    Paul, Shubhajit; Bode, Bela E; Matysik, Jörg; Alia, A

    2015-10-29

    A sample of solubilized and quinone-depleted reaction centers from the purple bacterium Rhodobacter (R.) sphaeroides wild type has been prepared entirely (13)C and (15)N isotope labeled at all positions of the protein as well as of the cofactors. In this sample, the occurrence of the solid-state photo-CIDNP (photochemically induced dynamic nuclear polarization) effect has been probed by (13)C solid-state magic-angle spinning NMR under illumination. Under continuous illumination, signal intensities are modified by the three-spin mixing (TSM) mechanism. Time-resolved illumination experiments reveal the occurrence of light-induced nuclear polarization on the time scale of hundreds of microseconds, initially dominated by the transient polarization of the singlet branch of the radical-pair mechanism. A first kinetic analysis shows that the lifetime of the polarization from the singlet branch, indicated by the enhanced absorptive intensities of the signals from aliphatic carbons, is significantly extended. Upon arrival of the polarization from the triplet decay branch, emissive polarization caused by the TSM mechanism is observed. Also, this arrival is significantly delayed. The decay of TSM polarization occurs in two steps, assigned to intra- and intermolecular spin diffusion. PMID:26110356

  19. 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

  20. Synthesis of Pyrroloquinones via a CAN Mediated Oxidative Free Radical Reaction of 1,3-Dicarbonyl Compounds with Aminoquinones

    PubMed Central

    Nguyen, Thao; Nadkarni, Dwayaja; Dutta, Shilpa; Xu, Su; Kim, Sanghun; Murugesan, Srinivasan; Velu, Sadanandan

    2015-01-01

    Pyrroloquinone ring systems are important structural units present in many biologically active molecules including a number of marine alkaloids. For example, they are found in a series of marine metabolites, such as tsitsikammamines, zyzzyanones, wakayin, and terreusinone. Several of these alkaloids have exhibited antimicrobial, antimalarial, antifungal, antitumor, and photoprotecting activities. Synthesis of pyrroloquinone unit is the key step in the synthesis of many of these important organic molecules. Here, we present a ceric (IV) ammonium nitrate (CAN) mediated oxidative free radical cyclization reaction of 1,3-dicarbonyl compounds with aminoquinones as a facile methodology for making various substituted pyrroloquinones. 1,3-dicarbonyl compounds used in this study are ethyl acetoacetate, acetylacetone, benzoyl acetone, and N,N-dimethyl acetoacetamide. The aminoquinones used in this study are 2-(benzylamino)naphthalene-1,4-dione and 6-(benzylamino)-1-tosyl-1H-indole-4,7-dione. The yields of the synthesized pyrroloquinones ranged from 23–91%. PMID:25705550

  1. Benzyl alcohol oxidation in supercritical carbon dioxide: spectroscopic insight into phase behaviour and reaction mechanism.

    PubMed

    Caravati, Matteo; Grunwaldt, Jan-Dierk; Baiker, Alfons

    2005-01-21

    Selective oxidation of benzyl alcohol to benzaldehyde with molecular oxygen over an alumina-supported palladium catalyst was performed with high rate at about 95% selectivity in supercritical carbon dioxide. The experiments in a continuous flow fixed-bed reactor showed that the pressure has a strong influence on the reaction rate. A marked increase of the rate (turnover frequency) from 900 h(-1) to 1800 h(-1) was observed when increasing the pressure from 140 to 150 bar. Video monitoring of the bulk fluid phase behavior and the simultaneous investigation by transmission and attenuated total reflection (ATR) infrared spectroscopy at two positions of the view cell showed that the sharp increase in activity is correlated to a transition from a biphasic to a monophasic reaction mixture. In the single phase region, both oxygen and benzyl alcohol are dissolved in the supercritical CO2 phase, which leads to a reduction of the mass transport resistances (both in the external fluid film and in the catalyst pores) and thus to the high reaction rate measured in the catalytic experiments. The phase transition could be effectively and easily monitored by transmission and ATR-IR spectroscopy despite the small concentration of the dense liquid like phase. Deposition of the Pd/Al2O3 catalyst on the ATR-crystal at the bottom of the view cell allowed to gain insight into the chemical changes and mass transfer processes occurring in the solid/liquid interface region during reaction. Analyzing the shift of the upsilon2 bending mode of CO2 gave information on the fluid composition in and outside the catalyst pores. Moreover, the catalytic reaction could be investigated in situ in this spectroscopic batch reactor cell by monitoring simultaneously the reaction progress, the phase behaviour and the catalytic interface. PMID:19785149

  2. 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.

  3. 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.

  4. Use of laser spectroscopy to measure the 13C/12C and 18O/16O compositions of carbonate minerals.

    PubMed

    Barker, Shaun L L; Dipple, Gregory M; Dong, Feng; Baer, Douglas S

    2011-03-15

    The stable carbon and oxygen isotope compositions of carbonate minerals are utilized throughout the earth and environmental sciences for various purposes. Here, we demonstrate the first application of a prototype instrument, based on off-axis integrated cavity output laser spectroscopy, to measure the carbon and oxygen isotope composition of CO(2) gas evolved from the acidification of carbonate minerals. The carbon and oxygen isotope ratios were recorded from absorption spectra of (12)C(16)O(16)O, (13)C(16)O(16)O, and (12)C(16)O(18)O in the near-infrared wavelength region. The instrument was calibrated using CaCO(3) minerals with known δ(13)C(VPDB) and δ(18)O(VSMOW) values, which had been previously calibrated by isotope ratio mass spectrometry relative to the international isotopic standards NBS 18 and NBS 19. Individual analyses are demonstrated to have internal precision (1 SE) of better than 0.15‰ for δ(13)C and 0.6‰ for δ(18)O. Analysis of four carbonate standards of known isotopic composition over 2 months, determined using the original instrumental calibration, indicates that analyses are accurate to better than 0.5‰ for both δ(13)C and δ(18)O without application of standard-sample-standard corrections. PMID:21341717

  5. 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.

  6. 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

  7. Contribution of rice straw carbon to CH4 emission from rice paddies using 13C-enriched rice straw

    NASA Astrophysics Data System (ADS)

    Watanabe, Akira; Yoshida, Mariko; Kimura, Makoto

    1998-04-01

    It is generally recognized that the application of rice straw (RS) increases CH4 emission from rice paddies. To estimate the contribution of RS carbon to CH4 emission, a pot experiment was conducted using 13C-enriched RS. The percentage contributions of RS carbon to CH4 emission throughout the rice growth period were 10±1, 32±3, and 43±3% for the treatments with RS applied at the rates of 2, 4, and 6 g kg-1 soil, respectively. The increase in the rate of application of RS increased CH4 emission derived from both RS carbon and other carbon sources. The percentage contribution of RS carbon to CH4 emission was larger in the earlier period (maximum 96%) when the decomposition rate of RS was larger. After RS decomposition had slowed, CH4 emission derived from RS carbon decreased. However, the δ13C values of CH4 emitted from the pots with 13C-enriched RS applied at rates of 4 and 6 g kg-1 soil were significantly higher than those from the pots with natural RS until the harvesting stage. An increased atom-13C% of roots of rice plants growing in the pots with 6 g kg-1 of 13C-enriched RS at around the maximum tiller number stage and a decrease during the following 2 months suggested that rice plants assimilated RS carbon once and then released a portion of it. This supply of RS carbon from roots may be one of the sources of CH4 in the late period of rice growth.

  8. 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

  9. 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.

  10. Synthesis of a water-soluble analog of 6-methyl-3-N-alkyl catechol labeled with carbon 13: NMR approach to the reactivity of poison ivy/oak sensitizers toward proteins.

    PubMed

    Goetz, G; Meschkat, E; Lepoittevin, J P

    1999-04-19

    A 13-C labeled water soluble derivative of alkylcatechol was synthesized and reacted with human serum albumin in phosphate buffer at pH 7.4 in air to allow a slow oxidation of the catechol into orthoquinone. The formation of several adducts was evidenced by a combination of 13C and 1H-13C correlation NMR. Although some adducts could result from a classical o-quinone formation - Michael type addition, our results suggest that a second pathway, involving a direct reaction of a carbon centered radical with proteins could be an important mechanism in the formation of modified proteins. PMID:10328301

  11. 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

  12. Silver(I)-Catalyzed Three-Component Reaction of Propargylic Alcohols, Carbon Dioxide and Monohydric Alcohols: Thermodynamically Feasible Access to β-Oxopropyl Carbonates.

    PubMed

    Zhou, Zhi-Hua; Song, Qing-Wen; Xie, Jia-Ning; Ma, Ran; He, Liang-Nian

    2016-07-20

    A silver(I)-catalyzed three-component reaction of propargylic alcohols, CO2 , and monohydric alcohols was successfully developed for the synthesis of β-oxopropyl carbonates. As such, a series of β-oxopropyl carbonates were exclusively produced in excellent yields (up to 98 %), even under atmospheric pressure of CO2 . The silver catalyst works efficiently for both the carboxylative cyclization of propargylic alcohols with CO2 and subsequent transesterification of α-alkylidene cyclic carbonates with monohydric alcohols; thus this tandem process performs smoothly under mild conditions. This work provides a versatile and thermodynamically favorable approach to dissymmetric dialkyl carbonates. PMID:27237704

  13. /sup 13/C and /sup 61/Ni isotope substitutions confirm the presence of a nickel(III)-carbon species in acetogenic CO dehydrogenases

    SciTech Connect

    Ragsdale, S.W.; Ljungdahl, L.G.; DerVartanian, D.V.

    1983-09-15

    The nickel-containing CO dehydrogenase from Acetobacterium woodii and Clostridium thermoaceticum were studied by EPR spectroscopy in order to define the components involved in the EPR spectrum obtained by reaction of the enzymes with the substrate, CO. Using isotopic substitution techniques, these experiments unequivocally establish that a nickel-carbon species is involved in the g=2.08, 2.02 EPR signal. Comparing the /sup 61/Ni- and /sup 59/Ni-substituted enzymes, the g=2.08 component of the resonance was found to be mainly due to nickel with a smaller contribution by the carbon species. Reaction of the CO dehydrogenase with (/sup 13/C)CO versus (/sup 12/C)CO showed that a carbon species, formed from CO, was the major contributor to the g=2.02 EPR signal. In addition, the oxidized CO dehydrogenase was found to exhibit a Ni(III) EPR signal analogous to that of the hydrogenase from the methanogenic and sulfate-reducing bacteria. 19 references, 3 figures.

  14. 13C and 61Ni isotope substitutions confirm the presence of a nickel (III)-carbon species in acetogenic CO dehydrogenases.

    PubMed

    Ragsdale, S W; Ljungdahl, L G; DerVartanian, D V

    1983-09-15

    The nickel-containing CO dehydrogenases from Acetobacterium woodii and Clostridium thermoaceticum were studied by EPR spectroscopy in order to define the components involved in the EPR spectrum obtained by reaction of the enzymes with the substrate, CO. Using isotopic substitution techniques, these experiments unequivocally establish that a nickel-carbon species is involved in the g = 2.08, 2.02 EPR signal. Comparing the 61Ni- and 59Ni-substituted enzymes, the g = 2.08 component of the resonance was found to be mainly due to nickel with a smaller contribution by the carbon species. Reaction of the CO dehydrogenase with [13C]CO versus [12C]CO showed that a carbon species, formed from CO, was the major contributor to the g = 2.02 EPR signal. In addition, the oxidized CO dehydrogenase was found to exhibit a Ni (III) EPR signal analogous to that of the hydrogenases from the methanogenic and sulfate-reducing bacteria. PMID:6312988

  15. Reaction of Topopah Spring tuff with J-13 water: a geochemical modeling approach using the EQ3/6 reaction path code

    SciTech Connect

    Delany, J.M.

    1985-11-25

    EQ3/6 geochemical modeling code package was used to investigate the interaction of the Topopah Spring Tuff and J-13 water at high temperatures. EQ3/6 input parameters were obtained from the results of laboratory experiments using USW G-1 core and J-13 water. Laboratory experiments were run at 150 and 250{sup 0}C for 66 days using both wafer-size and crushed tuff. EQ3/6 modeling reproduced results of the 150{sup 0}C experiments except for a small increase in the concentration of potassium that occurs in the first few days of the experiments. At 250{sup 0}C, the EQ3/6 modeling reproduced the major water/rock reactions except for a small increase in potassium, similar to that noted above, and an overall increase in aluminum. The increase in potassium concentration cannot be explained at this time, but the increase in A1 concentration is believed to be caused by the lack of thermodynamic data in the EQ3/6 data base for dachiardite, a zeolite observed as a run product at 250{sup 0}C. The ability to reproduce the majority of the experimental rock/water interactions at 150{sup 0}C validates the use of EQ3/6 as a geochemical modeling tool that can be used to theoretically investigate physical/chemical environments in support of the Waste Package Task of NNWSI.

  16. Investigation into the role of the boudouard reaction in self-reducing iron oxide and carbon briquettes

    NASA Astrophysics Data System (ADS)

    Moon, Jeremy; Sahajwalla, Veena

    2006-04-01

    With increasing impetus to utilize more waste byproducts from ironmaking processes, a greater understanding of processes that utilize these wastes is required. In this article, the kinetics of reaction of briquettes consisting of ultrafine iron oxide and carbon are examined representing a progression in the understanding of methods to utilize fine iron oxide and carbon resulting from all stages of processing. More specifically, this article examines the role of the Boudouard reaction and its level of control in such reaction systems for the temperature range of 1000 °C to 1200 °C. Various techniques were used to examine this role, including investigating the effect of the surface area of the carbon used, the effect of a known Boudouard reaction catalyst, and the effect of temperature.

  17. Cu-N dopants boost electron transfer and photooxidation reactions of carbon dots.

    PubMed

    Wu, Wenting; Zhan, Liying; Fan, Weiyu; Song, Jizhong; Li, Xiaoming; Li, Zhongtao; Wang, Ruiqin; Zhang, Jinqiang; Zheng, Jingtang; Wu, Mingbo; Zeng, Haibo

    2015-05-26

    The broadband light-absorption ability of carbon dots (CDs) has inspired their application in photocatalysis, however this has been impeded by poor electron transfer inside the CDs. Herein, we report the preparation of Cu-N-doped CDs (Cu-CDs) and investigate both the doping-promoted electron transfer and the performance of the CDs in photooxidation reactions. The Cu-N doping was achieved through a one-step pyrolytic synthesis of CDs with Na2 [Cu(EDTA)] as precursor. As confirmed by ESR, FTIR, and X-ray photoelectron spectroscopies, the Cu species chelates with the carbon matrix through Cu-N complexes. As a result of the Cu-N doping, the electron-accepting and -donating abilities were enhanced 2.5 and 1.5 times, and the electric conductivity was also increased to 171.8 μs cm(-1) . As a result of these enhanced properties, the photocatalytic efficiency of CDs in the photooxidation reaction of 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate is improved 3.5-fold after CD doping. PMID:25881689

  18. 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

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Cost-effectiveness of the Carbon-13 Urea Breath Test for the Detection of Helicobacter Pylori

    PubMed Central

    Masucci, L; Blackhouse, G; Goeree, R

    2013-01-01

    Objectives This analysis aimed to evaluate the cost-effectiveness of various testing strategies for Helicobacter pylori in patients with uninvestigated dyspepsia and to calculate the budgetary impact of these tests for the province of Ontario. Data Sources Data on the sensitivity and specificity were obtained from the clinical evidence-based analysis. Resource items were obtained from expert opinion, and costs were applied on the basis of published sources as well as expert opinion. Review Methods A decision analytic model was constructed to compare the costs and outcomes (false-positive results, false-negative results, and misdiagnoses avoided) of the carbon-13 (13C) urea breath test (UBT), enzyme-linked immunosorbent assay (ELISA) serology test, and a 2-step strategy of an ELISA serology test and a confirmatory 13C UBT based on the sensitivity and specificity of the tests and prevalence estimates. Results The 2-step strategy is more costly and more effective than the ELISA serology test and results in $210 per misdiagnosis case avoided. The 13C UBT is dominated by the 2-step strategy, i.e., it is more costly and less effective. The budget impact analysis indicates that it will cost $7.9 million more to test a volume of 129,307 patients with the 13C UBT than with ELISA serology, and $4.7 million more to test these patients with the 2-step strategy. Limitations The clinical studies that were pooled varied in the technique used to perform the breath test and in reference standards used to make comparisons with the breath test. However, these parameters were varied in a sensitivity analysis. The economic model was designed to consider intermediate outcomes only (i.e., misdiagnosed cases) and was not a complete model with final patient outcomes (e.g., quality-adjusted life years). Conclusions Results indicate that the 2-step strategy could be economically attractive for the testing of H. pylori. However, testing with the 2-step strategy will cost the Ministry of

  5. Curbing the greenhouse effect by carbon dioxide adsorption with zeolite 13X

    SciTech Connect

    Konduru, N.; Lindner, P.; Assaf-Anad, N.M.

    2007-12-15

    The removal of carbon dioxide (CO{sub 2}) from industrial emissions has become essential in the fight against climate change. In this study, we employed Zeolite 13X for the capture and recovery of CO{sub 2} in a flow through system where the adsorbent was subjected to five adsorption-desorption cycles. The influent stream contained 1.5% CO{sub 2} at standard conditions. The adsorbent bed was 1 in. in length and 1 in.3/8 in dia., and was packed with 10 g of the zeolite. Temperature swing adsorption (TSA) was employed as the regeneration method through heating to approximately 135{sup o}C with helium as the purge gas. The adsorbent capacity at 90% saturation was found to decrease from 78 to 60g CO{sub 2}/kg{sub Zeolite13X} after the fifth cycle. The CO{sub 2} capture ratio or the mass of CO{sub 2} adsorbed to the total mass that entered the system decreased from 63% to only 61% after the fifth cycle. The CO{sub 2} recovery efficiency ranged from 82 to 93% during desorption, and the CO{sub 2} relative recovery, i.e., CO{sub 2} desorbed for the nth cycle to CO{sub 2} adsorbed for the first cycle, ranged from 88 to 68%. The service life of the adsorbent was determined to be equal to eleven cycles at a useful capacity of 40g CO{sub 2}/kg{sub Zeolite13X}.

  6. 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.

  7. Controls on the δ 13C of dissolved inorganic carbon in marine pore waters: An integrated case study of isotope exchange during syndepositional recrystallization of biogenic carbonate sediments (South Florida Platform, USA)

    NASA Astrophysics Data System (ADS)

    Walter, Lynn M.; Ku, Timothy C. W.; Muehlenbachs, Karlis; Patterson, William P.; Bonnell, Linda

    2007-06-01

    VPDB). Pore water δ 13C (DIC) values thus require inputs from inorganic C that exceed those from organic C, even though less than 25% of the DIC can be accounted for by the amount of net carbonate dissolution indicated by Ca 2+/Cl - ratios. Incubation experiments attain DIC concentrations in excess of 20 mM during closed system SO 42- reduction, but δ 13C (DIC) values remain buffered between -4‰ and -6‰. Exchange of 12C for 13C during carbonate recrystallization in pore waters is required to reconcile the significant imbalance between mass and isotope budgets. Past work and data presented here for Sr 2+/Ca 2+ in pore waters show that recrystallization of biogenic aragonites and high-Mg calcites from South Florida platform sediments can occur without significant mineralogic change. Although these phases are metastable relative to lower Mg-calcite, the drive for recrystallization does not appear to be mineralogic stabilization. Instead, the high surface areas of many biogenic carbonates from algal and foraminiferal sources (about 2 m 2 g -1) contribute excess surface free energy that is released by recrystallization to larger crystallites of the same mineralogy. Studies of carbonate dissolution and precipitation kinetics have firmly established that high ratios of solid surface area: solution volume causes reaction of CO 2 with grain surfaces to become the rate-limiting step. Thus, in sediment-pore water systems containing carbonates with high specific surface areas, pore water δ 13C (DIC) may be buffered either by the value of the bulk CaCO 3, producing δ 13C (DIC) values approaching +2‰, or by the relatively large fractionation factor between CO 2 and solid CaCO 3 ( Δ˜-8‰), producing δ 13C (DIC) values that approach -6‰ VPBD. The observed magnitude of isotopic exchange between organic and inorganic carbon pools during the earliest stages of sedimentation has ramifications for the interpretation of the C isotopic record of marine carbonate rocks and

  8. Investigation of chemical and electrochemical reactions mechanisms in a direct carbon fuel cell using olive wood charcoal as sustainable fuel

    NASA Astrophysics Data System (ADS)

    Elleuch, Amal; Halouani, Kamel; Li, Yongdan

    2015-05-01

    Direct carbon fuel cell (DCFC) is a high temperature fuel cell using solid carbon as fuel. The use of environmentally friendly carbon material constitutes a promising option for the DCFC future. In this context, this paper focuses on the use of biomass-derived charcoal renewable fuel. A practical investigation of Tunisian olive wood charcoal (OW-C) in planar DCFCs is conducted and good power density (105 mW cm-2) and higher current density (550 mA cm-2) are obtained at 700 °C. Analytical and predictive techniques are performed to explore the relationships between fuel properties and DCFC chemical and electrochemical mechanisms. High carbon content, carbon-oxygen groups and disordered structure, are the key parameters allowing the achieved good performance. Relatively complex chain reactions are predicted to explain the gas evolution within the anode. CO, H2 and CH4 participation in the anodic reaction is proved.

  9. 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

  10. 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

  11. 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.

  12. 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

  13. 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

  14. 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

  15. 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

  16. Historical oceanographic events reflected in13C/12C ratio of total organic carbon in laminated Santa Barbara Basin Sediment

    NASA Astrophysics Data System (ADS)

    Schimmelmann, Arndt; Tegner, Mia J.

    1991-06-01

    An 1844-1987 time series of carbon stable isotope ratios from dated sedimentary total organic carbon (TOC) from the center of the Santa Barbara Basin (SBB) is compared with historical climate and oceanographic records. Four isotopically distinct biogeochemical sources of TOC are important: phytoplankton-derived marine biomass, macroalgal biomass from kelp forests, terrigenous biomass (mainly flushed into the SBB via river discharge), and redeposited fossil organic carbon. The significance of the latter two sources is largely limited to a few unusual flood and oil spill events, whereas the combination of 13C-depleted phytoplankton and 13C-enriched macroalgal biomass appears to be responsible for most of the isotopic variance of the marine coastal biomass as recorded in sedimentary TOC. The isotopic response of marine organic carbon in sediments records strong El Niño-Southern Oscillation (ENSO) and the frequently associated severe storm and wave events in SBB varved sediments. The plausible major isotopic mechanisms are (1) increased physical liberation of 13C-enriched kelp carbon from locally abundant giant kelp (Macrocystis spp.) forests during times of physical and environmental stress, and (2) decreased productivity of 13C-depleted phytoplankton during ENSO events.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. Shrimp-shell derived carbon nanodots as carbon and nitrogen sources to fabricate three-dimensional N-doped porous carbon electrocatalysts for the oxygen reduction reaction.

    PubMed

    Liu, Rongrong; Zhang, Haimin; Liu, Shengwen; Zhang, Xian; Wu, Tianxing; Ge, Xiao; Zang, Yipeng; Zhao, Huijun; Wang, Guozhong

    2016-02-01

    Development of cheap, abundant and metal-free N-doped carbon materials as high efficiency oxygen reduction electrocatalysts is crucial for their practical applications in future fuel cell devices. Here, three-dimensional (3D) N-doped porous carbon (NPC) materials have been successfully developed by a simple template-assisted (e.g., SiO2 spheres) high temperature pyrolysis approach using shrimp-shell derived N-doped carbon nanodots (N-CNs) as carbon and nitrogen sources obtained through a facile hydrothermal method. The shrimp-shell derived N-CNs with a product yield of ∼ 5% possess rich surface O- and N-containing functional groups and small nanodot sizes of 1.5-5.0 nm, which are mixed with surface acidification treated SiO2 spheres with an average diameter of ∼ 200 nm in aqueous solution to form a N-CNs@SiO2 composite subjected to a thermal evaporation treatment. The resultant N-CNs@SiO2 composite is further thermally treated in a N2 atmosphere at different pyrolysis temperatures, followed by acid etching, to obtain 3D N-doped porous carbon (NPC) materials. As electrocatalysts for oxygen reduction reaction (ORR) in alkaline media, the experimental results demonstrate that 3D NPC obtained at 800 °C (NPC-800) with a surface area of 360.2 m(2) g(-1) exhibits the best ORR catalytic activity with an onset potential of -0.06 V, a half wave potential of -0.21 V and a large limiting current density of 5.3 mA cm(-2) (at -0.4 V, vs. Ag/AgCl) among all NPC materials investigated, comparable to that of the commercial Pt/C catalyst with an onset potential of -0.03 V, a half wave potential of -0.17 V and a limiting current density of 5.5 mA cm(-2) at -0.4 V. Such a 3D porous carbon ORR electrocatalyst also displays superior durability and high methanol tolerance in alkaline media, apparently better than the commercial Pt/C catalyst. The findings of this work would be valuable for the development of low-cost and abundant N-doped carbon materials from biomass as high

  7. Sr-isotopic constraints on brine-mineral reactions in Geological Carbon Storage: Results from an EOR Experiment

    NASA Astrophysics Data System (ADS)

    Chapman, H.; Kampman, N.; Dubacq, B.; Galy, A.; Bickle, M. J.; Ballentine, C. J.; Zhou, Z.; Crius Team

    2011-12-01

    Reactions between CO2-charged brines and minerals in reservoirs used for geological carbon storage may either enhance the storage of CO2 by precipitating carbonate minerals and increasing dissolution of CO2 in brines or allow migration of CO2 by corroding cap rocks. However the nature and rates of such reactions are too poorly constrained for reliable modelling of the impact of the reactions. This study attempts to infer the nature and rates of such reactions by sampling brines during a phase of CO2 injection for enhanced oil recovery in a small oil field. The interpretation of the fluid-mineral reactions from changes in the water chemistry is complicated by the previous history of the field and re-injection of produced water prior to injection of CO2. Anion (Cl, F, Br, I) and stable isotope ratios (δ18O, D/H) primarily track fluid sources and fluid mixing. Cation concentrations and Sr-isotopic compositions reflect both mixing of injected waters and fluid mineral reactions (Fig. 1). The variations in Sr-isotopic ratios are interpreted to reflect the relative inputs from dissolution of unradiogenic carbonate minerals and radiogenic silicate minerals. It is notable that Sr-isotopic ratios decrease after CO2 breakthrough as Sr concentrations continue to rise implying, increased carbonate dissolution although increases in Na, K and Si also require dissolution of silicate minerals.

  8. 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.

  9. 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

  10. A new approach to carbon-carbon bond formation: Development of aerobic Pd-catalyzed reductive coupling reactions of organometallic reagents and styrenes

    PubMed Central

    Gligorich, Keith M.; Iwai, Yasumasa; Cummings, Sarah A.; Sigman, Matthew S.

    2009-01-01

    Alkenes are attractive starting materials for organic synthesis and the development of new selective functionalization reactions are desired. Previously, our laboratory discovered a unique Pd-catalyzed hydroalkoxylation reaction of styrenes containing a phenol. Based upon deuterium labeling experiments, a mechanism involving an aerobic alcohol oxidation coupled to alkene functionalization was proposed. These results inspired the development of a new Pd-catalyzed reductive coupling reaction of alkenes and organometallic reagents that generates a new carbon-carbon bond. Optimization of the conditions for the coupling of both organostannanes and organoboronic esters is described and the initial scope of the transformation is presented. Additionally, several mechanistic experiments are outlined and support the rationale for the development of the reaction based upon coupling alcohol oxidation to alkene functionalization. PMID:20161306

  11. Single-carbon catabolism in acetogens: analysis of carbon flow in Acetobacterium woodii and Butyribacterium methylotrophicum by fermentation and 13C nuclear magnetic resonance measurement.

    PubMed Central

    Kerby, R; Niemczura, W; Zeikus, J G

    1983-01-01

    The catabolism of methanol, formate, or carbon monoxide to acetate or butyrate or both was examined in two acetogenic bacteria. Butyribacterium methylotrophicum simultaneously transformed methanol and formate mainly to butyrate with concomitant H2 and CO2 production and consumption. In contrast, methanol plus CO was primarily converted to acetate, and only slight amounts of CO2 were produced. In vivo 13C nuclear magnetic resonance analysis of [13C]methanol transformation by B. methylotrophicum indicated that methanol was predominantly incorporated into the methyl of acetate. 13CO2 was produced and then consumed, and butyrate was formed from the condensation of two acetate precursors. The analysis of the position of acetate labeled by a given 13C single-carbon substrate when B. methylotrophicum or Acetobacterium woodii was grown in the presence of a second one-carbon substrate indicated two trends: when methanol was consumed, CO, CO2, or formate predominantly labeled the acetate carboxyl; when CO was consumed, CO2 and formate were principally funneled into the acetate methyl group, and CO remained a better carboxyl precursor. These data suggest a model of acetate synthesis via the combined operation of two readily reversible single-carbon pathways which are linked by CO2. PMID:6411684

  12. Single-carbon catabolism in acetogens: analysis of carbon flow in Acetobacterium woodii and Butyribacterium methylotrophicum by fermentation and 13C nuclear magnetic resonance measurement.

    PubMed

    Kerby, R; Niemczura, W; Zeikus, J G

    1983-09-01

    The catabolism of methanol, formate, or carbon monoxide to acetate or butyrate or both was examined in two acetogenic bacteria. Butyribacterium methylotrophicum simultaneously transformed methanol and formate mainly to butyrate with concomitant H2 and CO2 production and consumption. In contrast, methanol plus CO was primarily converted to acetate, and only slight amounts of CO2 were produced. In vivo 13C nuclear magnetic resonance analysis of [13C]methanol transformation by B. methylotrophicum indicated that methanol was predominantly incorporated into the methyl of acetate. 13CO2 was produced and then consumed, and butyrate was formed from the condensation of two acetate precursors. The analysis of the position of acetate labeled by a given 13C single-carbon substrate when B. methylotrophicum or Acetobacterium woodii was grown in the presence of a second one-carbon substrate indicated two trends: when methanol was consumed, CO, CO2, or formate predominantly labeled the acetate carboxyl; when CO was consumed, CO2 and formate were principally funneled into the acetate methyl group, and CO remained a better carboxyl precursor. These data suggest a model of acetate synthesis via the combined operation of two readily reversible single-carbon pathways which are linked by CO2. PMID:6411684

  13. 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

  14. Studies of individual carbon sites of proteins in solution by natural abundance carbon 13 nuclear magnetic resonance spectroscopy. Strategies for assignments.

    PubMed

    Oldfield, E; Norton, R S; Allerhand, A

    1975-08-25

    Natural abundance 13C Fourier transform NMR spectra (at 15.18 MHz, in 20-mm sample tubes) of aqueous native proteins yield numerous narrow single carbon resonances of nonprotonated aromatic carbons. Techniques for the assignment of these resonances are presented. Each technique is applied to one or more of the following proteins: ferricytochrome c from horse heart and Candida krusei, ferrocytochrome c and cyanoferricytochrome c from horse heart, lysozyme from hen egg white, cyanoferrimyoglobins from horse and sperm whale skeletal muscle, and carbon monoxide myoglobin from horse. In all of the protein spectra we have examined, methine aromatic carbons give rise to broad bands. Studies of the narrow resonances of nonprotonated aromatic carbons of proteins are facilitated by removal of these broad bands by means of the convolution-difference method, preferably from spectra recorded under conditions of noise-modulated off-resonance proton decoupling. We present a summary of the chemical shift ranges for the various types of nonprotonated aromatic carbons of amino acid residues and hemes of diamagnetic proteins, based on our results for hen egg white lysozyme, horse heart ferrocytochrome c, horse carbon monoxide myoglobin, and carbon monoxide hemoglobins from various species... PMID:169240

  15. Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and Cℓ2 in solid para-hydrogen

    NASA Astrophysics Data System (ADS)

    Bahou, Mohammed; Wu, Jen-Yu; Tanaka, Keiichi; Lee, Yuan-Pern

    2012-08-01

    The reactions of chlorine and hydrogen atoms with trans-1,3-butadiene in solid para-hydrogen (p-H2) were investigated with infrared (IR) absorption spectra. When a p-H2 matrix containing Cℓ2 and trans-1,3-butadiene was irradiated with ultraviolet light at 365 nm, intense lines at 650.3, 809.0, 962.2, 1240.6 cm-1, and several weaker ones due to the trans-1-chloromethylallyl radical, •(CH2CHCH)CH2Cℓ, appeared. Observed wavenumbers and relative intensities agree with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3PW91/6-311++g(2d, 2p) method. That the Cℓ atom adds primarily to the terminal carbon atom of trans-1,3-butadiene is in agreement with the path of minimum energy predicted theoretically, but in contrast to the reaction of Cℓ + propene in solid p-H2 [J. Amicangelo and Y.-P. Lee, J. Phys. Chem. Lett. 1, 2956 (2010)], 10.1021/jz101119b in which the addition of Cℓ to the central C atom is favored, likely through steric effects in a p-H2 matrix. A second set of lines, intense at 781.6, 957.9, 1433.6, 2968.8, 3023.5, 3107.3 cm-1, were observed when the UV-irradiated Cℓ2/trans-1,3-butadiene/p-H2 matrix was further irradiated with IR light from a SiC source. These lines are assigned to the trans-1-methylallyl radical, •(CH2CHCH)CH3, produced from reaction of 1,3-butadiene with a H atom resulted from the reaction of Cℓ atoms with solid p-H2 exposed to IR radiation.

  16. Carbonate deposition and benthic δ 13C in the subarctic Pacific: implications for changes of the oceanic carbonate system during the past 750,000 years

    NASA Astrophysics Data System (ADS)

    Zahn, Rainer; Rushdi, Ahmed; Pisias, Nicklas G.; Bornhold, Brian D.; Blaise, Bertrand; Karlin, Robert

    1991-04-01

    Carbonate deposition at two core sites in the subarctic Pacific (48°N, 133°W; 2.9 km and 3.7 km water depth) follows the standard Pacific carbonate cycles, with glacial values being increased over interglacial values. Benthic δ 13C follows the global trend; that is, glacial values are more negative than interglacial values. Comparison with the benthic δ 13C record of North Atlantic DSDP Site 552 (56°N, 23°W; 2.3 km water depth) shows the North Pacific records to be nearly in phase with and continuously more negative relative to the North Atlantic record. This suggests that concentrations of ∑CO 2(org) were permanently higher in the North Pacific than in the North Atlantic during the past 750,000 years conceivably supporting the hypothesis that there was no deep-water forming in the late Pleistocene North Pacific. Whereas one would expect that the North Pacific deep waters were continuously more corrosive to carbonates than deep waters in the North Atlantic, carbonate deposition at the deep North Pacific core sites is enhanced during glacial periods, and occasionally higher than at shallow North Atlantic Site 552 even though Site 552 was probably above lysocline-depth during most of the late Pleistocene. This apparent paradox can be resolved only by invoking an increase in alkalinity in the glacial North Pacific which would have increased the degree of carbonate ion saturation and thereby improved the state of carbonate preservation.

  17. Hydroalumination of Ketenimines and Subsequent Reactions with Heterocumulenes: Synthesis of Unsaturated Amide Derivatives and 1,3-Diimines.

    PubMed

    Jin, Xing; Willeke, Matthias; Lucchesi, Ralph; Daniliuc, Constantin-Gabriel; Fröhlich, Roland; Wibbeling, Birgit; Uhl, Werner; Würthwein, Ernst-Ulrich

    2015-06-19

    The series of differently substituted ketenimines 1 was hydroluminated using di-iso-butyl aluminum hydride. For the sterically congested ketenimine 1a, preferred hydroalumination of the C═N-bond was proven by X-ray crystallography (compound 5a). In situ treatment of the hydroaluminated ketenimines 5 with various heterocumulenes like carbodiimides, isocycanates, isothiocyanates and ketenimines as electrophiles and subsequent hydrolytic workup resulted in novel enamine derived amide species in case of N-attack (sterically less hindered ketenimines) under formation of a new C-N-bond or in 1,3-diimines by C-C-bond-formation in case of bulky substituents at the ketenimine-nitrogen atom. Furthermore, domino reactions with more than 1 equiv of the electrophile or by subsequent addition of two different electrophiles are possible and lead to polyfunctional amide derivatives of the biuret type which are otherwise not easily accessible. PMID:26031425

  18. Simplified single sample 13Carbon urea breath test for Helicobacter pylori: comparison with histology, culture, and ELISA serology.

    PubMed Central

    Logan, R P; Polson, R J; Misiewicz, J J; Rao, G; Karim, N Q; Newell, D; Johnson, P; Wadsworth, J; Walker, M M; Baron, J H

    1991-01-01

    There is no ideal method for detecting Helicobacter pylori. The 'standard' 13Carbon urea breath test (13C-UBT), which involves collecting eight to 15 breath samples and subsequent costly analysis, was modified by pooling 21 samples of expired breath taken at five minute intervals for 40 minutes into a collecting bag, from which a single 20 ml aliquot was taken and analysed by mass spectrometry. This test was evaluated on 50 patients after routine upper gastrointestinal endoscopy, and results were compared with those from the standard 13C-UBT, bacteriology, ELISA serology, and histology--the latter being taken as the gold standard. H pylori were seen in 34 of 50 (68%) patients (in three it was detected in biopsy specimens from the corpus alone). The modified 13C-UBT was positive (pooled excretion delta 13CO2 greater than 5 per mil) in 31 patients and negative in 19 (three false negative results), specificity was 100% (standard 13C-UBT 94%) and sensitivity 92% (standard 13C-UBT 93%). The modified 13C-UBT had a coefficient of variation within subjects of 3.7%. For the ELISA serology and culture the specificities were both 100%, but the sensitivities were 82% and 68% respectively. The 13C-UBT results correlated with the grade of histological gastritis. The modified 13C-UBT is simpler, cheaper, more reproducible, and provides an easy non-invasive method for the detection of H pylori. PMID:1773948

  19. Improved characterization of the botanical origin of sugar by carbon-13 SNIF-NMR applied to ethanol.

    PubMed

    Thomas, Freddy; Randet, Celia; Gilbert, Alexis; Silvestre, Virginie; Jamin, Eric; Akoka, Serge; Remaud, Gerald; Segebarth, Nicolas; Guillou, Claude

    2010-11-24

    Until now, no analytical method, not even isotopic ones, had been able to differentiate between sugars coming from C4-metabolism plants (cane, maize, etc.) and some crassulacean acid metabolism plants (e.g., pineapple, agave) because in both cases the isotope distributions of the overall carbon-13/carbon-12 and site-specific deuterium/hydrogen isotope ratios are very similar. Following recent advances in the field of quantitative isotopic carbon-13 NMR measurements, a procedure for the analysis of the positional carbon-13/carbon-12 isotope ratios of ethanol derived from the sugars of pineapples and agave using the site-specific natural isotopic fractionation-nuclear magnetic resonance (SNIF-NMR) method is presented. It is shown that reproducible results can be obtained when appropriate analytical conditions are used. When applied to pineapple juice, this new method demonstrates a unique ability to detect cane and maize sugar, which are major potential adulterants, with a detection limit in the order of 15% of the total sugars, which provides an efficient mean of controlling the authenticity of juices made from this specific fruit. When applied to tequila products, this new method demonstrates a unique ability to unambiguously differentiate authentic 100% agave tequila, as well as misto tequila (made from at least 51% agave), from products made from a larger proportion of cane or maize sugar and therefore not complying with the legal definition of tequila. PMID:21028824

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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

  5. 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)

  6. 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

  7. 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.

  8. Numerical modeling of SHS reaction wave propagating speed using various thermal conductivity values for titanium and carbon mixture

    SciTech Connect

    Cui, T.; Azad, G.S.; Huque, Z.

    1996-12-01

    A numerical model was developed to predict the propagation speed of a Self-Propagating High-Temperature Synthesis (SHS) reaction wave along a vertical cylindrical reactant compact made from a mixture of titanium and carbon powders. Various thermal conductivity values are used corresponding to the supply mole ratio of titanium and carbon powder mixture and initial sample density. These values are obtained experimentally in the laboratory. Results are also obtained for variation of particle sizes in the mixture. The reaction kinetics employed are Aleksandrov (1987) kinetic model and Kanury (1989). The prediction results are compared with Huque`s (1993) earlier work.

  9. 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

  10. 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

  11. 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.

  12. 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

  13. 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

  14. 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.

  15. 13C nuclear magnetic resonance study of five- and six-coordinated carbon in nonclassical organometallic compounds: Dimeric trialkyl-, tricyclopropyl-, and triarylaluminums and some nido and closo carboranes*

    PubMed Central

    Olah, George A.; Prakash, G. K. Surya; Liang, Gao; Henold, Kenneth L.; Haigh, Gary B.

    1977-01-01

    A 13C nuclear magnetic resonance spectroscopic study of dimeric trimethyl-, triethyl-, tricyclopropyl-, and triarylaluminums is reported. The five-coordinated bridging carbons are found consistently more shielded than the terminal carbons, in accordance with the increased p-character of the former. The nature of bridging two-electron three-centered Al—C—Al bonds is discussed. 13C nuclear magnetic resonance shifts of several nido and closo carboranes containing five and six coordinated carbons and their 13C-1H spin-spin coupling constants were also obtained. The relationship between the carbon chemical shifts and coordination number of the carbon atom is discussed. There is approximately a 20- to 40-ppm shielding of the 13C chemical shifts of five- and six-coordinated carbons, compared with those of four valent carbons, with a simultaneous general increase of JC-H coupling constants. PMID:16592469

  16. 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

  17. Theoretical study of addition reactions of carbene, silylene, and germylene to carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Chu, Ying-Ying; Su, Ming-Der

    2004-08-01

    A theoretical study of the mechanism of the reaction of a single-walled carbon nanotube (SWCNT) with carbene (H 2C), silylene (H 2Si), and germylene (H 2Ge) has been carried out using a two-layered ONIOM(B3LYP/6-311G ∗:PM3) approach. The main findings are as follows: (1) The computational results based on the method used in this work are in good agreement with recent theoretical findings [Angew. Chem. Int. Ed. 41 (2002) 1853]. That is, SWCNTs with H 2C, H 2Si, and H 2Ge addends favor opened structures rather than three-membered rings. (2) The greater the atomic number of the carbene center, the larger the activation energy and the less exothermic (or the more endothermic) the cycloaddition reaction becomes. Therefore, addition to the C dbnd C bond of a SWCNT is more difficult the heavier the carbene center. (3) The theoretical observations suggest that the singlet-triplet splitting of a carbene can be used as a guide to its reactivity during the SWCNT cycloaddition process.

  18. 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

  19. 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.

  20. 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

  1. 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

  2. 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

  3. 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

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. Carbon Isotope Fractionation Between CO Gas and CO Ice with Implications for 12C/13C of the Interstellar Medium and the Early Solar System

    NASA Astrophysics Data System (ADS)

    Young, E. D.; Schauble, E. A.

    2011-03-01

    A model for carbon-isotope fractionation between CO ice and gas is presented. The model includes a self-consistent portrayal of the kinetics of partitioning of 12C and 13C between CO ice and gas. Ice-gas carbon exchange may be a primary control for 12C/13C.

  12. 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.

  13. Analysis of carbon-oxygen reactions by use of a square-input response technique and {sup 18}O isotope

    SciTech Connect

    Miura, Kouichi; Nakagawa, Hiroyuki

    1996-12-31

    Carbon gasification reaction has been investigated for decades including the pioneering works of Walker and his co-workers, but its mechanism has not been completely elucidated. The concept of the active surface area (ASA) was proposed by them, and its importance has been recognized. However, since ASA was measured by O{sub 2} chemisorption at below 300{degrees}C where carbon loss through gasification is negligible, it does not reflect the actual gasification situation. To overcome this weak point, measurements of ASA in a batch reactor and the so-called transient kinetic (TK) method were proposed. Ahmed and Back successfully measured the chemisorbed oxygen during the gasification using a batch reactor, and proposed a new mechanistic sequence for carbon-oxygen reaction which stresses the importance of the reaction between the gaseous oxygen and the chemisorbed oxygen. Radovic et al. proposed the concept of the reactive surface area (RSA), and reported excellent proportionality between the CO{sub 2} gasification rate and the RSA estimated by the TK and the TPD methods. Kapte