Science.gov

Sample records for carbon 13 reactions

  1. 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.

  2. 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.

  3. Measurement of Differential Cross Sections of CARBON-12, 13(PROTON, PROTON)CARBON-12, 13 and CARBON-12, 13(PROTON, Neutron)nitrogen -12, 13 Reactions at Backward Angles

    NASA Astrophysics Data System (ADS)

    Yu, Zhou

    1993-01-01

    We performed the following: Measurement of 200 MeV ^{12,13}C(p,p)^{12,13 }C differential cross sections for protons emitted between 160^circ and 180^circ; Measurement of 200 MeV ^{12,13}C(p,n)^{12,13 }N differential cross sections for neutrons emitted between 160^circ and 180^circ; Comparison with Distorted Wave Impulse Approximation (DWIA) calculations and alteration of optical potential standard parameter set in DWIA calculations to better reproduce measured data at backward angles for the ^{12}C(p,p) reaction, and applying best parameter set found in ^{12}C(p,p) calculations to the DWIA calculations for ^{13}C(p,p) and ^{12}C(p,n) reactions; Measurement of charge-state population vs. target thickness for ^{13}C going through ^{12}C target; Development of a readout system for micro-strip silicon detectors. Our data shows that the standard DWIA calculations underestimate the cross sections for each of the four (p,N) reactions in the backward directions, and that a new potential needs to be introduced into DWIA theory in order to explain the refraction pattern in that angular region where DWIA failed to predict the existence of the refraction. We found that a greatly improved fit for the (p,p) reactions can be obtained by using a real central potential depth much shallower than standard and a real central potential diffuseness smaller than standard. It is seen that ^{13}C recoils charge state populations do not change when target thickness is reduced from a few hundred mug/cm^2 to a few mug/cm^2 and that calculations of Shima et al best fit the data. A readout system for micro-strip silicon detectors was developed, the system is low cost, low power, contains simple electronic circuitry and is easy to construct.

  4. Estimating evolution of δ13CH4 during methanization of cellulosic waste based on stoichiometric chemical reactions, microbial dynamics and stable carbon isotope fractionation.

    PubMed

    Vavilin, V A

    2012-04-01

    A change in δ(13)CH(4) during mesophilic methanization of cellulosic waste (paper and cardboard) was described using a mathematical model based on stoichiometric chemical reactions, microbial dynamics and the equation for the (13)C isotope accumulation in products including isotope fractionation. In this study, experimental data, previously obtained by Qu et al. (2009), was used to model metabolic pathways of cellulose transformation. A significant change in δ(13)CH(4) occurred in time during cellulosic waste methanization which was in accordance with the model. It was explained by the change in input of acetoclastic and hydrogenotrophic methanogenesis as well as by fractionation of stable carbon isotopes (13)C and (12)C which was much higher for hydrogenotrophic methanogenesis when compared to acetoclastic methanogenesis.

  5. 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

  6. Calibration of an analyzing magnet using the 12C(d, p0)13C nuclear reaction with a thick carbon target

    NASA Astrophysics Data System (ADS)

    Andrade, E.; Canto, C. E.; Rocha, M. F.

    2017-09-01

    The absolute energy of an ion beam produced by an accelerator is usually determined by an electrostatic or magnetic analyzer, which in turn must be calibrated. Various methods for accelerator energy calibration are extensively reported in the literature, like nuclear reaction resonances, neutron threshold, and time of flight, among others. This work reports on a simple method to calibrate the magnet associated to a vertical 5.5 MV Van de Graaff accelerator. The method is based on bombarding with deuteron beams a thick carbon target and measuring with a surface barrier detector the particle energy spectra produced. The analyzer magnetic field is measured for each spectrum and the beam energy is deduced by the best fit of the simulation of the spectrum with the SIMNRA code that includes 12C(d,p0)13C nuclear cross sections.

  7. A new mechanism of phosphoric acid digestion reaction and theoretical re-calibration on the carbonate 13C-18O clumped isotope thermometry

    NASA Astrophysics Data System (ADS)

    Tang, M.; Liu, Y.

    2016-12-01

    The carbonate 13C-18O clumped isotope thermometry has been widely used for surface temperature systems. However, the existing D47-T relationships calibrated by different groups are incompatible, generating substantial confusions in the community. Here we propose a new molecular-level mechanism of the kinetic isotope effect (KIE) produced in the phosphoric acid digestion reaction of carbonates. We will show why the previous mechanism won't work and why this new one is reasonable, especially based on experimental evidences. This new mechanism, which suggests that there are three parallel pathways undergoing for the phosphoric acid digestion process, can explain well the discrepancies of the D47-T relationships obtained by different groups at slightly different experimental conditions (Fig.1). Based on the new mechanism and sophisticated quantum chemistry calculations, we show that the clumped isotope enrichments (i.e., Δ*47) can be significantly different from those provided by Guo et al. (2009) if considering the change of individual contributions of the three parallel pathways. Consequently, if we use these new Δ*47 values to plot the D47-T figure under the absolute reference frame (ARF), all the calibration lines conducted at 90°C (e.g., Dennis et al. (2011)) will be relocated. They can be much closer to those calibration lines conducted at 25°C than before in the low temperature range (Fig.1). In another word, there may not be much difference between these two groups of calibration lines. However, we obtain a slope very close to those conducted at 90°C but with distinct difference to that of Ghosh et al. (2006). Finally, we provide molecular-level explanations on the changes of calibration lines if the experiments are conducted under slightly different conditions. We show why the temperature of phosphoric acid digestion, the reaction time and the amount of sample can affect the position of calibration line but not the slope of it. This new mechanism not only

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

    NASA Astrophysics Data System (ADS)

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

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

  9. 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. The carbon (formerly dark) reactions of photosynthesis.

    PubMed

    Buchanan, Bob B

    2016-05-01

    In this brief account, I describe the background for dividing photosynthesis into "light" and "dark" reactions and show how this concept changed to "light" and "carbon" reactions as science in the field advanced.

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

    SciTech Connect

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

    1986-05-01

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

  12. 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. © 2016 American Society of Plant Biologists. All rights reserved.

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

    PubMed

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

    2016-09-15

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

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

    SciTech Connect

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

    1992-07-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  17. Chemical Reactions 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.

  18. 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.

  19. Spatially-variable carbonation reactions in polycrystalline olivine

    NASA Astrophysics Data System (ADS)

    Wells, Rachel K.; Xiong, Wei; Sesti, Erika; Cui, Jinlei; Giammar, Daniel; Skemer, Philip; Hayes, Sophia E.; Conradi, Mark S.

    2017-05-01

    Carbon dioxide (CO2) injection into olivine-rich mafic and ultramafic rocks is expected to result in the precipitation of divalent metal carbonate minerals, permanently storing the CO2 underground. Previous experiments that used unconsolidated forsterite (Mg2SiO4) particles in experimental investigations of reactions with water and carbon dioxide have been useful for determining the identity, rates of formation, and spatial location of carbonate mineral reaction products. However there remains a need for information regarding the influence of the internal pore structure and grain boundary surfaces on the extent and locations of these reactions in dense aggregates. We conducted several experiments at 100 °C and 100 bar CO2 using sintered San Carlos olivine (Fo90) and pure forsterite (Fo100) cylinders, and we documented the type and spatial distribution of the reaction products. Timing of carbonation was measured using in-situ 13C NMR spectroscopy without removing the sample from the reactor. Ex-situ solid-state NMR spectroscopy, Raman spectroscopy, and electron microscopy were used to examine reacted samples and precipitates. Within 15 days, magnesite is observed only on the surface of Fo90. After 53 and 102 days of reaction, magnesite and amorphous silica are observed as a crust around the entire Fo100 cylinder and as isolated layers within the sample. The spatial transition from an amorphous silica layer to the host Fo100 indicates that the development of amorphous silica did not impede further forsterite dissolution. While earlier studies documented localized reactions at the grain scale, the development of distinct zones of magnesite and amorphous silica suggest that divalent metal cations are mobile during carbonation of olivine. Grain boundaries, pore structure, and geochemical gradients strongly influence the locations of silicate mineral dissolution and carbonate mineral precipitation even in the absence of advective transport or confinement. The clear

  20. Selectivity in the carbon-oxygen reaction

    NASA Astrophysics Data System (ADS)

    Skokova, Kristina A.

    The dependence of the carbon-oxygen reaction rate and the CO/COsb2 ratio on temperature, oxygen pressure, carbon crystallite size, concentration of surface C(O) complexes, and content of heteroatoms was studied. It was shown that the temperature dependence of the CO/COsb2 ratio obeys an Arrhenius-type relationship, but the pre-exponential factor and the activation energy depend on oxygen pressure and carbon nature. The Arrhenius parameters were found to be directly proportional to each other. This confirmed the importance of the compensation effect in carbon oxidation. It was explained by active site heterogeneity in carbon materials. For all experimental conditions, the CO/COsb2 ratio was lower for carbons with more ordered graphitic structure. It was shown that the CO/COsb2 ratio is inversely proportional to the surface coverage with reactive C(O) complexes. More ordered carbons were revealed to possess lower concentrations of stable complexes, higher surface coverages with reactive complexes and thus lower CO/COsb2 ratios. The influence of B and N heteroatoms on carbon reactivity and the CO/COsb2 ratio was studied. It was confirmed that B acts as an inhibitor of carbon oxidation due to the formation of a protective Bsb2Osb3 coating. The N presence in the carbon structure increases its rate of oxidation, maybe due to decreasing carbon crystallite dimensions. The CO/COsb2 ratio did not correlate with the N content in the carbon, but depended on the concentration of surface carbon-oxygen complexes. A new reaction mechanism is proposed. A key feature of the mechanism is that it takes into account the presence and mobility of oxygen atoms on the basal plane. It was shown with the aid of theoretical molecular orbital calculations that chemisorption on a pair of adjacent edge and basal sites is thermodynamically favorable as a parallel process to the generally accepted path of chemisorption on two edge carbon atoms. The former process can lead to the formation of a

  1. Catalyzed hydrolytic cleavage reaction of carbon-carbon bond

    SciTech Connect

    Ioffe, I.I.; Rubinskaya, E.V.

    1986-12-01

    The authors split the carbon-carbon bond for a series of simple and complex organic compounds in neutral aqueous solutions on a heterogeneous metal-containing catalyst, palladium on carbon. The experimental results are given. In each case, the catalytic effect was controlled by a blank experiment, without a catalyst, where there was no decomposition of the substrate. The occurrence of the heterogeneous-catalytic cleavage reaction of the carbon-carbon bonds in the molecules is indicated not only by their extensive conversion, but also by the almost complete depletion of the content of organic carbon, confirmed by a similar decrease in the chemical consumption of oxygen coefficient in the system, which is possible only in the complete decomposition of the organic compounds to gaseous products or with the formation of inappreciable amounts of low-molecular-weight water-soluble compounds.

  2. 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.

  3. Urea hydrolysis and calcium carbonate reaction fronts

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

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

  4. 1,3-Diferrocenyl-1,3-alkadienes in diene synthesis reactions

    SciTech Connect

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

    1987-11-10

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

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

    PubMed Central

    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

  6. Polymorphs calcium carbonate on temperature reaction

    SciTech Connect

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

    2014-09-03

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

  7. 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.

  8. 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.

  9. Acid-base bifunctional catalysis of silica-alumina-supported organic amines for carbon-carbon bond-forming reactions.

    PubMed

    Motokura, Ken; Tomita, Mitsuru; Tada, Mizuki; Iwasawa, Yasuhiro

    2008-01-01

    Acid-base bifunctional heterogeneous catalysts were prepared by the reaction of an acidic silica-alumina (SA) surface with silane-coupling reagents possessing amino functional groups. The obtained SA-supported amines (SA-NR2) were characterized by solid-state 13C and 29Si NMR spectroscopy, FT-IR spectroscopy, and elemental analysis. The solid-state NMR spectra revealed that the amines were immobilized by acid-base interactions at the SA surface. The interactions between the surface acidic sites and the immobilized basic amines were weaker than the interactions between the SA and free amines. The catalytic performances of the SA-NR2 catalysts for various carbon-carbon bond-forming reactions, such as cyano-ethoxycarbonylation, the Michael reaction, and the nitro-aldol reaction, were investigated and compared with those of homogeneous and other heterogeneous catalysts. The SA-NR2 catalysts showed much higher catalytic activities for the carbon-carbon bond-forming reactions than heterogeneous amine catalysts using other supports, such as SiO2 and Al2O3. On the other hand, homogeneous amines hardly promoted these reactions under similar reaction conditions, and the catalytic behavior of SA-NR2 was also different from that of MgO, which was employed as a typical heterogeneous base. An acid-base dual-activation mechanism for the carbon-carbon bond-forming reactions is proposed.

  10. Determination of the (13)C/(12)C Carbon Isotope Ratio in Carbonates and Bicarbonates by (13)C NMR Spectroscopy.

    PubMed

    Pironti, Concetta; Cucciniello, Raffaele; Camin, Federica; Tonon, Agostino; Motta, Oriana; Proto, Antonio

    2017-10-09

    This paper is the first study focused on the innovative application of (13)C NMR (nuclear magnetic resonance) spectroscopy to determine the bulk (13)C/(12)C carbon isotope ratio, at natural abundance, in inorganic carbonates and bicarbonates. In the past, (13)C NMR spectroscopy (irm-(13)C NMR) was mainly used to measure isotope ratio monitoring with the potential of conducting (13)C position-specific isotope analysis of organic molecules with high precision. The reliability of the newly developed methodology for the determination of stable carbon isotope ratio was evaluated in comparison with the method chosen in the past for these measurements, i.e., isotope ratio mass spectrometry (IRMS), with very encouraging results. We determined the (13)C/(12)C ratio of carbonates and bicarbonates (∼50-100 mg) with a precision on the order of 1‰ in the presence of a relaxation agent, such as Cr(acac)3, and CH3(13)COONa as an internal standard. The method was first applied to soluble inorganic carbonates and bicarbonates and then extended to insoluble carbonates by converting them to Na2CO3, following a simple procedure and without observing isotopic fractionation. Here, we demonstrate that (13)C NMR spectroscopy can also be successfully adopted to characterize the (13)C/(12)C isotope ratio in inorganic carbonates and bicarbonates with applications in different fields, such as cultural heritage and geological studies.

  11. 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.

  12. 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.

  13. 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)

  14. 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)

  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. An improved 13C-tracer method for the study of lignin structure and reactions : differential 13C-NMR

    Treesearch

    Noritsugu Terashima; Dmitry Evtuguin; Carlos Pascoal Neto; Jim Parkas; Magnus Paulsson; Ulla Westermark; Sally Ralph; John Ralph

    2003-01-01

    The technique of selective 13C-enrichment of specific carbons in lignin combined with 13C-NMR differential spectrometry between spectra of 13C-enriched and unenriched lignins (Ä13C-NMR) provides definitive information on the structure of the lignin macromolecule. Improvements were made on, (1) specific 13C-enrichment of almost all carbons involved in inter-unit bonds...

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

    PubMed

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

    2015-01-06

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

  18. 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

  19. How to identify carbonate rock reactions in concrete

    SciTech Connect

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

    2004-11-15

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

  20. 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.

  1. Infrared laser spectroscopy of the linear C13 carbon cluster

    NASA Technical Reports Server (NTRS)

    Giesen, T. F.; Van Orden, A.; Hwang, H. J.; Fellers, R. S.; Provencal, R. A.; Saykally, R. J.

    1994-01-01

    The infrared absorption spectrum of a linear, 13-atom carbon cluster (C13) has been observed by using a supersonic cluster beam-diode laser spectrometer. Seventy-six rovibrational transitions were measured near 1809 wave numbers and assigned to an antisymmetric stretching fundamental in the 1 sigma g+ ground state of C13. This definitive structural characterization of a carbon cluster in the intermediate size range between C10 and C20 is in apparent conflict with theoretical calculations, which predict that clusters of this size should exist as planar monocyclic rings.

  2. Infrared laser spectroscopy of the linear C13 carbon cluster

    NASA Technical Reports Server (NTRS)

    Giesen, T. F.; Van Orden, A.; Hwang, H. J.; Fellers, R. S.; Provencal, R. A.; Saykally, R. J.

    1994-01-01

    The infrared absorption spectrum of a linear, 13-atom carbon cluster (C13) has been observed by using a supersonic cluster beam-diode laser spectrometer. Seventy-six rovibrational transitions were measured near 1809 wave numbers and assigned to an antisymmetric stretching fundamental in the 1 sigma g+ ground state of C13. This definitive structural characterization of a carbon cluster in the intermediate size range between C10 and C20 is in apparent conflict with theoretical calculations, which predict that clusters of this size should exist as planar monocyclic rings.

  3. 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.

  4. 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.

  5. Organic carbonates as alternative solvents for palladium-catalyzed substitution reactions.

    PubMed

    Schäffner, Benjamin; Holz, Jens; Verevkin, Sergey P; Börner, Armin

    2008-01-01

    Organic carbonates, such as propylene carbonate, butylene carbonate, and diethyl carbonate, were tested in the Pd-catalyzed asymmetric allylic substitution reactions of rac-1,3-diphenyl-3-acetoxy-prop-1-ene with dimethyl malonate or benzylamine as nucleophiles. Bidentate diphosphanes were used as chiral ligands. The application of monodentate phosphanes capable of self-assembling with the metal was likewise tested. In the substitution reaction with dimethyl malonate, enantioselectivities up to 98% were achieved. In the amination reaction, the chiral product was obtained with up to 83% ee. The results confirm that these "green solvents" can be advantageously used for this catalytic transformation as an alternative to those solvents usually employed which run some risk of being harmful to the environment.

  6. Oceanic Uptake of Fossil Fuel CO2: Carbon-13 Evidence.

    PubMed

    Quay, P D; Tilbrook, B; Wong, C S

    1992-04-03

    The delta(13)C value of the dissolved inorganic carbon in the surface waters of the Pacific Ocean has decreased by about 0.4 per mil between 1970 and 1990. This decrease has resulted from the uptake of atmospheric CO(2) derived from fossil fuel combustion and deforestation. The net amounts of CO(2) taken up by the oceans and released from the biosphere between 1970 and 1990 have been determined from the changes in three measured values: the concentration of atmospheric CO(2), the delta(13)C of atmospheric CO(2) and the delta(13)C value of dissolved inorganic carbon in the ocean. The calculated average net oceanic CO(2) uptake is 2.1 gigatons of carbon per year. This amount implies that the ocean is the dominant net sink for anthropogenically produced CO(2) and that there has been no significant net CO(2) released from the biosphere during the last 20 years.

  7. Adventures with carbons 11, 12, 13 and 14.

    PubMed

    Benson, Andrew Alm

    2011-10-01

    I provide here a glimpse of my involvement with different isotopes of carbon. In my 65 years of synthetic work with C-12, I had experience working with C-11 (one year, 1942-1943), C-13 (one year, 1999) and C-14 (67 years, 1943-2009). I have also included a postscript dealing with my 1951 communication on the 5-carbon intermediate in photosynthesis. © Springer Science+Business Media B.V. 2011

  8. 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.

  9. Carbon-Carbon Bond Cleavage Reaction: Synthesis of Multisubstituted Pyrazolo[1,5-a]pyrimidines.

    PubMed

    Saikia, Pallabi; Gogoi, Sanjib; Boruah, Romesh C

    2015-07-02

    A new carbon-carbon bond cleavage reaction was developed for the efficient synthesis of multisubstituted pyrazolo[1,5-a]pyrimidines. This base induced reaction of 1,3,5-trisubstituted pentane-1,5-diones and substituted pyrazoles afforded good yields of the pyrazolo[1,5-a]pyrimidines.

  10. 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

  11. Vibrationally Excited Carbon Monoxide Produced via a Chemical Reaction Between Carbon Vapor and Oxygen

    NASA Astrophysics Data System (ADS)

    Jans, Elijah R.; Eckert, Zakari; Frederickson, Kraig; Rich, Bill; Adamovich, Igor V.

    2017-06-01

    Measurements of the vibrational distribution function of carbon monoxide produced via a reaction between carbon vapor and molecular oxygen has shown a total population inversion on vibrational levels 4-7. Carbon vapor, produced using an arc discharge to sublimate graphite, is mixed with an argon oxygen flow. The excited carbon monoxide is vibrationally populated up to level v=14, at low temperatures, T=400-450 K, in a collision-dominated environment, 15-20 Torr, with total population inversions between v=4-7. The average vibrational energy per CO molecule formed by the reaction is 0.6-1.2 eV/molecule, which corresponds to 10-20% of the reaction enthalpy. Kinetic modeling of the flow reactor, including state specific vibrational processes, was performed to infer the vibrational distribution of the products of the reaction. The results show viability of developing of a new chemical CO laser from the reaction of carbon vapor and oxygen.

  12. A novel method for concurrent measurements of dissolved inorganic carbon concentration and its carbon isotope composition δ13C

    NASA Astrophysics Data System (ADS)

    Huang, K.; Cai, W. J.; Kim-Hak, D.; Jonsson, B. F.

    2016-02-01

    The concentration of dissolved inorganic carbon ([DIC]) and its stable carbon isotopic composition (δ13C) in the surface ocean are key to studying the important processes in the carbon cycle, e.g., photosynthesis and respiration, calcification, water mass mixing, and, in particularly, the Suess effect as well as the penetration of anthropogenic carbon into the surface ocean and the subsequent ocean acidification. Real-time, shipboard measurements of these properties are highly desired. Here we present a new method that concurrently measures [DIC] and δ13C of DIC in the surface ocean. The method couples sample acidification and delivery techniques (Apollo Scitech) with a cavity ring-down spectrometer (CRDS, Picarro), and works automatically to analyzer samples at the throughput of 8 minutes/sample. In each sampling cycle, a syringe pump withdraws a fixed volume of phosphoric acid and seawater sample, and injects them slowly into a reaction chamber where they were mixed. In the meantime, the CO2 evolved from the acidified sample is purged by a CO2-free gas flow into a CRDS carbon isotope analyzer for measurements of the CO2 concentration and δ13C-CO2. The concurrent injection, acidification, and purging yield a broad, flat peak of CO2 which is precisely and frequently measured by the CRDS analyzer. [DIC] and δ13C can then be calculated by integrating the concentration and δ13C of the CO2 peak. The precision of the [DIC] and δ13C is <0.15% (3 mmol kg-1 when [DIC] = 2000 μmol kg-1), and <0.1‰, relatively. The system is automated to run continuously onboard a research vessel as well as discrete samples in a lab environment.

  13. Interfacial enhancement of carbon fiber composites by generation 1-3 dendritic hexamethylenetetramine functionalization

    NASA Astrophysics Data System (ADS)

    Ma, Lichun; Meng, Linghui; Fan, Dapeng; He, Jinmei; Yu, Jiali; Qi, Meiwei; Chen, Zhongwu; Huang, Yudong

    2014-03-01

    PAN-based carbon fibers (CF) were functionalized with generation (n) 1-3 dendritic hexamethylenetetramine (HMTA) (denoted as CF-Gn-HMTA, n = 1, 2 and 3) in an attempt to improve the interfacial properties between carbon fibers and epoxy matrix. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), dynamic contact angle analysis (DCA), interfacial shear strength (IFSS) and single fiber tensile testing were carried out to investigate the functionalization process of carbon fibers and the interfacial properties of the composites. Experimental results showed that generation (n) 1-3 dendritic hexamethylenetetramine was grafted uniformly on the fiber surface through the chemical reaction, and then it increased significantly the fiber surface polarity and roughness. The surface energy and IFSS of carbon fibers increased obviously after the graft CF-G3-HMTA, by 147.6% and 81%, respectively. Generation (n) 1-3 dendritic hexamethylenetetramine enhanced effectively the interfacial adhesion of the composites by improving resin wettability, increasing chemical bonding and mechanical interlocking, and the interfacial adhesion increased with dendritic generation number. Moreover, the grafting of generation (n) 1-3 dendritic hexamethylenetetramine on the carbon fiber surface improved the fiber tensile strength, which is beneficial to the in-plane properties of the resulting composites.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  16. Carbon 13 exchanges between the atmosphere and biosphere

    NASA Astrophysics Data System (ADS)

    Fung, I.; Field, C. B.; Berry, J. A.; Thompson, M. V.; Randerson, J. T.; MalmströM, C. M.; Vitousek, P. M.; Collatz, G. James; Sellers, P. J.; Randall, D. A.; Denning, A. S.; Badeck, F.; John, J.

    1997-12-01

    We present a detailed investigation of the gross 12C and 13C exchanges between the atmosphere and biosphere and their influence on the δ13C variations in the atmosphere. The photosynthetic discrimination Δ against 13C is derived from a biophysical model coupled to a general circulation model [Sellers et al., 1996a], where stomatal conductance and carbon assimilation are determined simultaneously with the ambient climate. The δ13C of the respired carbon is calculated by a biogeochemical model [Potter et al., 1993; Randerson et al., 1996] as the sum of the contributions from compartments with varying ages. The global flux-weighted mean photosynthetic discrimination is 12-16‰, which is lower than previous estimates. Factors that lower the discrimination are reduced stomatal conductance and C4 photosynthesis. The decreasing atmospheric δ13C causes an isotopic disequilibrium between the outgoing and incoming fluxes; the disequilibrium is ˜0.33‰ for 1988. The disequilibrium is higher than previous estimates because it accounts for the lifetime of trees and for the ages rather than turnover times of the biospheric pools. The atmospheric δ13C signature resulting from the biospheric fluxes is investigated using a three-dimensional atmospheric tracer model. The isotopic disequilibrium alone produces a hemispheric difference of ˜0.02‰ in atmospheric δ13C, comparable to the signal from a hypothetical carbon sink of 0.5 Gt C yr-1 into the midlatitude northern hemisphere biosphere. However, the rectifier effect, due to the seasonal covariation of CO2 fluxes and height of the atmospheric boundary layer, yields a background δ13C gradient of the opposite sign. These effects nearly cancel thus favoring a stronger net biospheric uptake than without the background CO2 gradient. Our analysis of the globally averaged carbon budget for the decade of the 1980s indicates that the biospheric uptake of fossil fuel CO2 is likely to be greater than the oceanic uptake; the

  17. 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.

  18. 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.

  19. 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.

  20. HIGH TEMPERATURE POLYMERS FROM 1,3-DIPOLAR ADDITION REACTIONS.

    DTIC Science & Technology

    indazole with nitrobenzene as the reaction solvent has...phenylhydrazide chloride has been prepared. The reaction of this compound with ethynyl benzene in the presence of triethylamine yields 1,1’,5,5’- tetraphenyl-3,3...corresponding heterocycles. The polymerization reaction of 4,4’ oxydi benzoylphenyl- hydrazide chloride with p-diethynyl benzene afforded poly (1,1’,5,5’-tetraphenyl-3,3’- (oxydi-p-phenylene) -dipyrazole).

  1. 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

  2. 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.

  3. 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

  4. 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.

  5. Cobalt carbonate hydroxide superstructures for oxygen evolution reactions.

    PubMed

    Zhang, Simin; Ni, Bing; Li, Haoyi; Lin, Haifeng; Zhu, Huihui; Wang, Haiqing; Wang, Xun

    2017-07-13

    A novel three-dimensional (3D) superstructure of cobalt hydroxide carbonate assembled from nanoneedles has been synthesized via a facile hydrothermal method. Furthermore, we tested the electrocatalytic oxygen evolution reaction performance, which demonstrated that the superstructure exhibited high catalytic activity, achieving 10 mA cm(-2) at a low overpotential of merely 240 mV.

  6. 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.

  7. HIGH TEMPERATURE POLYMERS FROM 1,3-DIPOLAR ADDITION REACTIONS.

    DTIC Science & Technology

    reaction of benzoylphenylhydrazide chloride and m-divinylbenzene in the presence of triethylamine was prepared. The polymerization reaction of p...phenylene-3,3’-disydnone with p-benzoquinone afforded poly(2,4,6,8-tetrahydro-4,8-dioxo-2,6-p-phenylenepyrazolo (3,4-f) indazole ) which had good thermal...stability and an inherent viscosity of 0.6. The polymerization reaction of terephthaloyl phenylhydrazide chloride with m-divinylbenzene gave poly(1,1

  8. 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.

  9. Thermodynamics behind carbon nanotube growth via endothermic catalytic decomposition reaction.

    PubMed

    Harutyunyan, Avetik R; Kuznetsov, Oleg A; Brooks, Christopher J; Mora, Elena; Chen, Gugang

    2009-02-24

    Carbon filaments can be grown using hydrocarbons with either exothermic or endothermic catalytic decomposition enthalpies. By in situ monitoring the evolution of the reaction enthalpy during nanotube synthesis via methane gas, we found that although the decomposition reaction of methane is endothermic an exothermic process is superimposed which accompanies the nanotube growth. Analysis shows that the main contributor in this liberated heat is the radiative heat transfer from the surroundings, along with dehydrogenation reaction of in situ formed secondary hydrocarbons on the catalyst surface and the carbon hydrogenation/oxidation processes. This finding implies that nanotube growth process enthalpy is exothermic, and particularly, it extends the commonly accepted temperature gradient driven growth mechanism to the growth via hydrocarbons with endothermic decomposition enthalpy.

  10. 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.

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

    SciTech Connect

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

    2014-06-26

    Upgrading of 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 lower 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.

  12. 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.

  13. Preparation and Rate Capability of Carbon Coated LiNi1/3Co1/3Mn1/3O2 as Cathode Material in Lithium Ion Batteries.

    PubMed

    Yang, Chaofan; Zhang, Xiaosong; Huang, Mengyi; Huang, Junjie; Fang, Zebo

    2017-04-12

    LiNi1/3Co1/3Mn1/3O2 (NCM) is regarded as a promising material for next-generation lithium ion batteries due to the high capacity, but its practical applications are limited by the poor electronic conductivity. Here, a one-step method is used to prepare carbon coated LiNi1/3Co1/3Mn1/3O2 (NCM/C) by applying active carbon as reaction matrix. TEM shows LiNi1/3Co1/3Mn1/3O2 particles are homogeneously coated by carbon with a thickness about 10 nm. NCM/C delivers the discharge capacity of 191.2 mAh g(-1) at 0.5 C (85 mA g(-1)) with a columbic efficiency of 91.1%. At 40 C (6800 mA g(-1)), the discharge capacity of NCM/C is 54.6 mAh g(-1), whereas NCM prepared through sol-gel route only delivers 13.2 mAh g(-1). After 100 charge and discharge cycles at 1 C (170 mA g(-1)) the capacity retention is 90.3% for NCM/C, whereas it is only 72.4% for NCM. The superior charge/discharge performance of NCM/C owes much to the carbon coating layer, which is not only helpful to increase the electronic conductivity but also contributive to inhibit the side reactions between LiNi1/3Co1/3Mn1/3O2 and the liquid electrolyte.

  14. 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.

  15. Syntheses of carbon-13 labeled protoporphyrin-IX for spectroscopic studies of heme proteins

    SciTech Connect

    Fujinari, E.M.

    1985-01-01

    The development of various methodologies for synthesis of selectively tailored protoporphyrin-IX dimethyl ester are presented. The iron(II) complex of protoporphyrin-IX is the heme, the prosthetic group for Hb, Mb, cytochromes and peroxidases. The significance of this research is to provide direct means to establish definitive carbon-13 NMR assignments of heme proteins in order to study not only the structure-function relationships, but also protein dynamics of these vital systems. Carbon-13 labeling at the beta-vinyl position was first achieved by ozonolysis of protoporphyrin-IX dimethyl ester. Column LC method were used to first isolate 2,4-diformyldeuteroporphyrin-IX dimethyl ester. Concomitantly, monofomyl-monovinyl porphyrins were obtained as a mixture of two isomers. This mixture was separated by MPLC or prep HPLC to afford the isomerically pure products, Spirographis porphyrin dimethyl ester and Iso-Spirographis porphyrin dimethyl ester. A Wittig reaction to each of these porphyrins with /sup 13/C-methyltriphenylphosphonium iodide gave 2,4-bis(/sup 13/C/sub 2/)-vinyl protoporphyrin-IX dimethyl ester, 2-(/sup 13/C/sub 2/)-vinyl protoporphyrin-IX dimethyl ester, and the 4-(/sup 13/C/sub 2/)-vinyl protoporphyrin-IX dimethyl ester, respectively.

  16. The telomerisation of 1,3-butadiene and carbon dioxide: process development and optimisation in a continuous miniplant.

    PubMed

    Behr, Arno; Becker, Marc

    2006-10-14

    The telomerisation of 1,3-butadiene and carbon dioxide is one of the first homogeneously catalyzed reactions using carbon dioxide as a C1-building block. In this article we describe the process development for a miniplant applying this telomerisation in a continuous scale. Through repeated optimisation of the plant setup combined with parallel laboratory batch experiments the overall space-time-yield of the plant was enhanced significantly.

  17. Glycerol carbonate in Ferrier reaction: Access to new enantiopure building blocks to develop glycoglycerolipid analogues.

    PubMed

    da Costa, Pollyanna Leite Ferreira; Melo, Valentina Nascimento; Guimarães, Bruna Martins; Schuler, Marie; Pimenta, Vanessa; Rollin, Patrick; Tatibouët, Arnaud; de Oliveira, Ronaldo Nascimento

    2016-12-21

    Glycerol carbonate and tri-O-acetyl-D-glucal were used for the synthesis of glycero-functionalized carbohydrates. Ferrier reaction between the two partners afforded the O-glucoside in 84% yield. Spontaneous crystallization yielded 28% of a pure diastereoisomer with the S configuration as determined by X-ray crystallography. Then, the azido-glycerosugar was prepared in two steps: ring opening of the cyclic carbonate with sodium azide and per-acetylation with an excellent yield of 94%. A library of glycoconjugates were prepared using a 1,3-dipolar cycloaddition in yields ranging from 64 to 99%. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Hydrogenation, purification, and unzipping of carbon nanotubes by reaction with molecular hydrogen: road to graphane nanoribbons.

    PubMed

    Talyzin, Alexandr V; Luzan, Serhiy; Anoshkin, Ilya V; Nasibulin, Albert G; Jiang, Hua; Kauppinen, Esko I; Mikoushkin, Valery M; Shnitov, Vladimir V; Marchenko, Dmitry E; Noréus, Dag

    2011-06-28

    Reaction of single-walled carbon nanotubes (SWNTs) with hydrogen gas was studied in a temperature interval of 400-550 °C and at hydrogen pressure of 50 bar. Hydrogenation of nanotubes was observed for samples treated at 400-450 °C with about 1/3 of carbon atoms forming covalent C-H bonds, whereas hydrogen treatment at higher temperatures (550 °C) occurs as an etching. Unzipping of some SWNTs into graphene nanoribbons is observed as a result of hydrogenation at 400-550 °C. Annealing in hydrogen gas at elevated conditions for prolonged periods of time (72 h) is demonstrated to result also in nanotube opening, purification of nanotubes from amorphous carbon, and removal of carbon coatings from Fe catalyst particles, which allows their complete elimination by acid treatment.

  19. Reaction of Calcium Silicates with Carbon Dioxide and Water

    DTIC Science & Technology

    1979-09-26

    for Ca3SiO5 to 22.9 kcal/mole for CaSiO3 . The reaction products were calcium carbonate (CaCO3) and a calcium silicate hydrate of variable...Ca3SiO5, beta-Ca2SiO4, and gamma-Ca2SiO4 if free water is present. Aragonite forms in the absence of free H2O and in the carbonation of CaSiO3 . The

  20. 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.

  1. Free-radical reactions of 2-ethoxy-1,3-oxathiolane

    SciTech Connect

    Taganliev, A.; Pastushenko, E.V.; Rakhmankulov, D.L.; Rol'nik, L.Z.; Zlotskii, S.S.

    1986-01-01

    Homolytic reactions of 2-ethoxy-1,3-oxathiolane in the presence of benzoyl peroxide and tert-butyl peroxide in chlorobenzene have been studied. The principal reaction products are diethyl monothiocarbonate and 1,3-oxathiolane-2-one. The yields and ratios of the products are temperature-dependent.

  2. Cavitation-induced reactions in high-pressure carbon dioxide.

    PubMed

    Kuijpers, M W A; van Eck, D; Kemmere, M F; Keurentjes, J T F

    2002-12-06

    The feasibility of ultrasound-induced in situ radical formation in liquid carbon dioxide was demonstrated. The required threshold pressure for cavitation could be exceeded at a relatively low acoustic intensity, as the high vapor pressure of CO2 counteracts the hydrostatic pressure. With the use of a dynamic bubble model, the formation of hot spots upon bubble collapse was predicted. Cavitation-induced radical formation was used for the polymerization of methyl methacrylate in CO2, yielding high-molecular-weight polymers. These results show that sonochemical reactions can be performed in dense-phase fluids, which allows the environmentally benign CO2 to replace conventional organic solvents in many reaction systems.

  3. 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.

  4. Coupled Serpentinsation and Carbonation Reaction in Ultrabasic Minerals

    NASA Astrophysics Data System (ADS)

    Dufaud, F.; Martinez, I.; Shilobreeva, S.; Fiquet, G.

    2006-12-01

    Because of its significant atmospheric abundance compared with the other greenhouse gases, CO2 is by far the most important. One of the options to reduce the anthropogenic CO2 emission into the atmosphere is the mineral storage: the process that converts gaseous CO2 into a geologically stable phase, such as a carbonate. Such reactions, however, are characterized by slow kinetics, which have to be measured since it could be the most limiting factor of geochemical storage of CO2. We have carried out carbonation experiments on olivine, serpentine and orthopyroxene under various conditions in an hydraulic press (1-1.7kbar and 400-500°C). Powders (100-200μm grain size) of these minerals were kept in contact with oxalic acid used as a source of CO2 in platinum capsules and reacted at high pressure and temperature. Experiments conducted under such conditions provide large carbonation rates. The amounts of carbonate formed were measured by decarbonation of the reacted material. Chemical and carbon isotopic mass balance calculations were also done in order to provide precise monitoring of carbonation rates. Mineralogical study of the reacted samples using both SEM (Scanning Electron Microscopy) and TEM (Transmission Electron Microscopy) allowed the identification of the dissolution/precipitation carbonation mechanisms and the observation of nanometer sized magnesite crystals, systematically associated to protoserpentine phases. Strong differences in carbonate textures and carbonation rates were measured as a function of the initial mineral, water fugacity and NaCl concentrations. Similarities and differences of these results with experiments carried out under usual CO2 storage conditions in basic and ultrabasic rock will be discussed.

  5. Radical scavenging reaction kinetics with multiwalled carbon nanotubes

    PubMed Central

    Tsuruoka, Shuji; Matsumoto, Hidetoshi; Koyama, Kenichi; Akiba, Eiji; Yanagisawa, Takashi; Cassee, Flemming R.; Saito, Naoto; Usui, Yuki; Kobayashi, Shinsuke; Porter, Dale W.; Castranova, Vincent; Endo, Morinobu

    2016-01-01

    Progress in the development of carbon nanotubes (CNTs) has stimulated great interest among industries providing new applications. Meanwhile, toxicological evaluations on nanomaterials are advancing leading to a predictive exposure limit for CNTs, which implies the possibility of designing safer CNTs. To pursue safety by design, the redox potential in reactions with CNTs has been contemplated recently. However, the chemical reactivity of CNTs has not been explored kinetically, so that there is no scheme to express a redox reaction with CNTs, though it has been investigated and reported. In addition, the reactivity of CNTs is discussed with regard to impurities that consist of transition metals in CNTs, which obfuscates the contribution of CNTs to the reaction. The present work aimed at modeling CNT scavenging in aqueous solution using a kinetic approach and a simple first-order reaction scheme. The results show that CNTs follow the redox reaction assumption in a simple chemical system. As a result, the reaction with multiwalled CNTs is semi-quantitatively denoted as redox potential, which suggests that their biological reactions may also be evaluated using a redox potential scheme. PMID:27030782

  6. Ozone reaction with carbon nanostructures. 2: The reaction of ozone with milled graphite and different carbon black grades.

    PubMed

    Cataldo, Franco

    2007-01-01

    Synthetic graphite particles 0.2 microns in diameter react with O3 at room temperature with evolution of CO2. Graphite is less reactive with ozone than carbon blacks having different surface area ranging from 120 to 8 m2/g, but graphite reactivity is comparable to that shown by powdered solid C60 and C70 fullerenes. The kinetic rate constant derived from the ozone consumption k appears in relation with the rate of CO2 evolution suggesting a very simple reaction stoichiometry at the early stages. The reaction between ozone and graphite or carbon blacks essentially involves two stages: the gasification of the surface to CO2 and its functionalization with oxygenated chemical groups, mainly as COOH but also other oxygenated chemical moieties. The pseudofirst order kinetics appears adequate to describe the heterogeneous reaction between ozone and the selected carbon materials. The discussion of the results is focused on the role played by fullerene-like carbon nanostructures, present in graphene sheets to explain the observed gasification rates and surface functionalization.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. Model description of photonuclear 13C(γ, p)12B activation detection of carbon

    NASA Astrophysics Data System (ADS)

    Dzhilavyan, L. Z.; Pokotilovski, Yu. N.

    2017-09-01

    A model description of the activation detection of carbon with the use of registering 12B-activity produced in a graphite target by a beam of electrons with an energy of 50 MeV due to the photonuclear reaction 13C(γ, p) is presented. This description is carried out with consideration for the influence of the main background process related to the generation of potoneutrons under radiation and secondary background γ' quanta caused by them. A satisfactory agreement with experimental results is obtained taking into account the incompleteness of data on the conditions of these experiments.

  14. Functionalization of Carbon Nanotubes via Electrophilic Substitution Reaction in Polyphosphoric Acid

    DTIC Science & Technology

    2006-07-26

    1 Title of proposed research: Functionalization of Carbon Nanotubes via Electrophilic Substitution Reaction in Polyphosphoric Acid Proposer: Jong...Choi, J.-Y.; Tan, L.-S.; Baek, J.-B. “Functionalization of carbon nanotubes via electrophilic substitution reaction in polyphosphoric acid” AFOSR...2006 4. TITLE AND SUBTITLE Functionalization of carbon nanotubes via electrophilic substitution reaction in polyphosphoric acid 5a. CONTRACT

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

    NASA Astrophysics Data System (ADS)

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

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

  16. 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...

  17. 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...

  18. 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.

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

    DOEpatents

    Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

    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.

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

    DOEpatents

    Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

    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.

  1. 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

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

    PubMed

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

    2011-07-01

    The preparation and application of overbased nanodetergents with excess alkaline calcium carbonate is a good example of nanotechnology in practice. The phase transformation of calcium carbonate is of extensive concern since CaCO(3) serves both as an important industrial filling material and as the most abundant biomineral in nature. Industrially valuable overbased nanodetergents have been prepared based on calcium salts of heavy alkylbenzene sulfonate by a one-step process under ambient pressure, the carbonation reaction has been monitored by the instantaneous temperature changes and total base number (TBN). A number of analytical techniques such as TGA, DLS, SLS, TEM, FTIR, and XRD have been utilized to explore the carbonation reaction process and phase transformation mechanism of calcium carbonate. An enhanced understanding on the phase transformation of calcium carbonate involved in calcium sulfonate nanodetergents has been achieved and it has been unambiguously demonstrated that amorphous calcium carbonate (ACC) transforms into the vaterite polymorph rather than calcite, which would be of crucial importance for the preparation and quality control of lubricant additives and greases. Our results also show that a certain amount of residual Ca(OH)(2) prevents the phase transformation from ACC to crystalline polymorphs. Moreover, a vaterite nanodetergent has been prepared for the first time with low viscosity, high base number, and uniform particle size, nevertheless a notable improvement on its thermal stability is required for potential applications. Copyright © 2011 Elsevier Inc. All rights reserved.

  3. Pd-catalyzed reaction of allyl carbonate with polyols: the role of CO2 in transesterification versus etherification of glycerol.

    PubMed

    Gordillo, Alvaro; Lloyd-Jones, Guy C

    2012-02-27

    An intermolecular Pd/PPh(3)-catalyzed transesterification of diallyl carbonate with glycerol to generate glycerol carbonate has been developed. Analysis of the reaction kinetics in THF indicates a first-order dependence on Pd and diallyl carbonate, that the Pd bears two phosphines during the turnover limiting event, and that increasing the glycerol concentration inhibits reaction, possibly via change in the polarity of the medium. (13)C isotopic labeling studies demonstrate that the Pd-catalyzed transesterification requires at least one allyl carbonate moiety and that there is rapid equilibrium of the allyl carbonate with CO(2) in solution, even when present only at low concentrations. A mechanism that is consistent with these results involves oxidative addition of the allyl carbonate to Pd followed by reversible decarboxylation, with the intermediate η(1)- and η(3)-allyl Pd alkoxides mediating direct and indirect transesterification reactions with the glycerol. Using this model, successful simulations of the kinetics of reactions conducted under atmospheres of N(2) or CO(2) could be achieved, including switching in selectivity between etherification and transesterification in the early stages of reaction. Reactions with the higher polyols threitol and erythritol are also efficient, generating the terminal (1,2) monocarbonates with high selectivity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Targeted Control of Permeability Using Carbonate Dissolution/Precipitation Reactions

    NASA Astrophysics Data System (ADS)

    Clarens, A. F.; Tao, Z.; Plattenberger, D.

    2016-12-01

    Targeted mineral precipitation reactions are a promising approach for controlling fluid flow in the deep subsurface. Here we studied the potential to use calcium and magnesium bearing silicates as cation donors that would react with aqueous phase CO2 under reservoir conditions to form solid carbonate precipitates. Preliminary experiments in high pressure and temperature columns suggest that these reactions can effectively lower the permeability of a porous media. Wollastonite (CaSiO3) was used as the model silicate, injected as solid particles into the pore space of a packed column, which was then subsequently flooded with CO2(aq). The reactions occur spontaneously, leveraging the favorable kinetics that occur at the high temperature and pressure conditions characteristic of the deep subsurface, to form solid phase calcium carbonate (CaCO3) and amorphous silica (SiO2) within the pore space. Both x-ray tomography imaging of reacted columns and electron microscopy imaging of thin sections were used to characterize where dissolution/precipitation occurred within the porous media. The spatial distribution of the products was closely tied to the flow rate and the duration of the experiment. The SiO2 product precipitated in close spatial proximity to the CaSiO3 reactant. The CaCO3 product, which is sensitive to the low pH and high pCO2 brine, precipitated out of solution further down the column as Ca2+ ions moved with the brine. The permeability of the columns decreased by several orders of magnitude after injecting the CaSiO3 particles. Following carbonation, the permeability decreased even further as precipitates filled flow paths within the pore network. A pore network model was developed to help understand the interplay between precipitation kinetics and flow in altering the permeability of the porous media. The effect of particle concentration and size, pore size, reaction time, and pCO2, are explored on pore/fracture aperture and reaction extent. To provide better

  5. δ13C Analysis of Dissolved Organic Carbon in Eastern Canadian Coastal Waters

    NASA Astrophysics Data System (ADS)

    Gelinas, Y.; Barber, A.

    2016-12-01

    The application of carbon stable isotope analysis on dissolved organic carbon13C-DOC) from natural seawater samples has been limited owing to the difficulty of such analysis, with order of magnitude differences between interfering ions and analyte concentrations. High temperature catalytic oxidation allows for the separation of interferences from the organic carbon by precipitation on quartz chips upstream from the oxidation catalyst. Unlike wet chemical oxidation, where salts inhibit the oxidation of organic matter to CO2 via side reactions between the salt anions and the persulfate oxidizing agent, high temperature combustion ensures complete organic matter oxidation in a stream of O2. Using a programmable chemical trap to switch carrier gasses from O2 to He, the OI 1030C combustion unit can be coupled to and IRMS, allowing for the analysis of low DOC content saline waters with relatively high throughput. The analytical limitations and large water volumes traditionally required for these types of analyses have prevented any large-scale δ13C-DOC studies. Here we present DOC concentrations and δ13C-DOC signatures for surface and bottom waters obtained along Canada's East Coast. Included in the study are samples from the Esquiman channel (between Newfoundland and Labrador), Lake Melville, the Saglek and Nachvak Fjords, the Hudson Strait and finally covering the salinity gradient across the Gulf of the St. Lawrence, the St. Lawrence Estuary and the Saguenay Fjord. Measured δ13C-DOC signatures ranged from predominantly marine values of -21.3 ± 0.6 ‰ (vs. VPDB) off the coast of Newfoundland to predominantly terrestrial signatures of -25.8 ± 0.1‰ in Lake Melville. Overall, proper blank subtraction using the isotope mass balance equation and four replicate injections are crucial for the collection of meaningful high quality δ13C-DOC signatures on natural abundance, seawater samples.

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

    NASA Astrophysics Data System (ADS)

    Meisinger, Philipp; Wittlich, Christian

    2014-05-01

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

  7. Development of Decarboxylative Cyanation Reactions for C-13/C-14 Carboxylic Acid Labeling Using an Electrophilic Cyanating Reagent.

    PubMed

    Song, Fengbin; Salter, Rhys; Chen, Lu

    2017-04-07

    Degradation-reconstruction approaches for isotope labeling synthesis have been known for their remarkable efficiency, but applications are scarce due to some fundamental limitations of the chemistries developed to date. The decarboxylative cyanation reaction, as a degradation-reconstruction approach, is especially useful in rapid carboxylic acid carbon isotope labeling, however development toward its application as a widespread technique has stalled at the early stages due to numerous limitations which include somewhat narrow applicability. Employing the electrophilic cyanating reagent N-cyano-N-phenyl-p-toluenesulfonamide (NCTS) as the cyano source, efficient decarboxylative cyanation chemistry has been developed for aryl and alkyl carboxylic acids respectively with two rationally designed reaction pathways. The reactions provided good yields of nitrile products from carboxylic acids, with complete retention of isotopic purity from the [(13)CN]-NCTS used. The reaction conditions are relatively mild requiring no oxidant and no excess toxic heavy metal and the reagent [(13/14)CN]-NCTS is a stable, easy-to-handle crystalline solid that can be prepared quickly and effectively from the readily available [(13/14)C]-KCN. The following work describes this novel and efficient method for alkyl and aryl carboxylic acid isotopic labeling using a single reagent.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. Derivatization reactions of carbamate pesticides in supercritical carbon dioxide.

    PubMed

    King, Jerry W; Zhang, Zhouyao

    2002-09-01

    Supercritical fluid carbon dioxide (SC-CO(2)) has been used to dissolve derivatizing agents (e.g. heptafluorobutyric anhydride, HFBA, and pyridine), which also act as a modifier in the fluid phase, for simultaneous extraction and derivatization of carbamates from the sample matrix. The derivatized carbamate pesticides (carbaryl, 3-hydroxycarbofuran, carbofuran, aldicarb, methiocarb) were then analyzed by GC-ECD or GC-MS with excellent sensitivity. Extraction and conversion of the carbamates was complete, as indicated by HPLC with post-column hydrolysis and o-phthalaldehyde derivatization then fluorescence detection. GC-MS (ion trap) was also used to confirm the formation of the carbamate derivatives. Compared with the same HFBA reaction in an organic solvent the derivatization reaction time was considerably shorter in SC-CO(2.) The described approach, combining both extraction and derivatization, simplifies the analysis of carbamate pesticides and eliminates the use of organic solvents associated with the derivatization step.

  13. Three-carbon Dowd-Beckwith ring expansion reaction versus intramolecular 1,5-hydrogen transfer reaction: a theoretical study.

    PubMed

    Ardura, Diego; Sordo, Tomás L

    2005-11-11

    [Reaction: see text]. The evolution of the primary radicals formed by addition of AIBN/HSnBu3 to methyl 1-(3-iodopropyl)-5-oxocyclopentanecarboxylate, methyl (1R,2R)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate, and methyl (1R,2S)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate in benzene has been theoretically investigated by ROMP2/6-311++G(2d,2p)//UB3LYP/6-31G(d,p) calculations taking into account the effect of solvent through a PCM-UAHF model. According to the theoretical results, for methyl 1-(3-iodopropyl)-5-oxocyclopentanecarboxylate and methyl (1R,2S)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate the major product is the cyclooctane derivative from the three-carbon ring expansion, whereas for methyl (1R,2R)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate the major product is that corresponding to the 1,5-H transposition in agreement with the experimental findings. This different behavior is a consequence of several factors determining the relative energy barriers. The methyl substituent destabilizes the ring expansion process for methyl (1R,2R)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate because of steric repulsion but favors it in the case of the beta-trans-substituted substrate because it makes possible the evolution of the system along more favorable conformations. The methyl group also favors the 1,5-H transposition rendering the transposed product a tertiary radical. The second stage of the ring expansion process is stabilized by resonance.

  14. Picosecond laser spectroscopy of photocycloaddition reaction of 9-cyanoanthracene-1,3-diene systems and photodecomposition reaction of the cycloadducts

    NASA Astrophysics Data System (ADS)

    Okada, Tadashi; Kida, Kenji; Mataga, Noboru

    1982-04-01

    Transient absorption spectra of singlet biradical in addition to exciplex have been observed in the course of the photocycloaddition reaction of 9-cyanoanthracene (CNA) with 2,5-dimethyl-2,4-hexadiene (DMHD) while no intermediate was detected in CNA-1,3-cyclohexadiene (CHD). The cycloadduct with CHD shows an efficient adiabatic photodissociation into 1CNA ≠ and CHD immediately after excitation.

  15. Theoretical cross section calculations of medical 13N and 18F radioisotope using alpha induced reaction

    NASA Astrophysics Data System (ADS)

    Kılınç, F.; Karpuz, N.; ćetin, B.

    2017-02-01

    In medical physics, radionuclides are needed to diagnose functional disorders of organs and to diagnose and treat many diseases. Nuclear reactions are significant for the productions of radionuclides. It is important to analyze the cross sections for much different energy. In this study, reactional cross sections calculations on 13N, 18F radioisotopes are with TALYS 1.6 nuclear reaction simulation code. Cross sections calculated and experimental data taken from EXFOR library were compared

  16. Reactions of Atomic Carbon with Butene Isomers: Implications for Molecular Growth in Carbon-Rich Environments

    DOE PAGES

    Bourgalais, J.; Spencer, Michael; Osborn, David L.; ...

    2016-10-31

    We carried out the product detection studies of C(3P) atom reactions with butene (C4H8) isomers (but-1-ene, cis-but-2-ene, trans-but-2-ene) in a flow tube reactor at 353 K and 4 Torr under multiple collision conditions. Ground state carbon atoms are generated by 248 nm laser photolysis of tetrabromomethane, CBr4, in a buffer of helium. Thermalized reaction products are detected using synchrotron tunable VUV photoionization and time-of-flight mass spectrometry. The temporal profiles of the detected ions are used to discriminate products from side or secondary reactions. Furthermore, for the C(3P) + trans-but-2-ene and C(3P) + cis-but-2-ene reactions, various isomers of C4H5 and C5H7more » are identified as reaction products formed via CH3 and H elimination. Assuming equal ionization cross sections for all C4H5 and C5H7 isomers, C4H5:C5H7 branching ratios of 0.63:1 and 0.60:1 are derived for the C(3P) + trans-but-2-ene and the C(3P) + cis-but-2-ene reactions, respectively. For the C(3P) + but-1-ene reaction, two reaction channels are observed: the H-elimination channel, leading to the formation of the ethylpropargyl isomer, and the C3H3 + C2H5 channel. Assuming equal ionization cross sections for ethylpropargyl and C3H3 radicals, a branching ratio of 1:0.95 for the C3H3 + C2H5 and H + ethylpropargyl channels is derived. Finally, the experimental results are compared to previous H atom branching ratios and used to propose the most likely mechanisms for the reaction of ground state carbon atoms with butene isomers.« less

  17. Reactions of Atomic Carbon with Butene Isomers: Implications for Molecular Growth in Carbon-Rich Environments

    NASA Astrophysics Data System (ADS)

    Bourgalais, J.; Spencer, Michael; Osborn, David L.; Goulay, F.; Le Picard, S. D.

    2016-10-01

    Product detection studies of C(3P) atom reactions with butene (C4H8) isomers (but-1-ene, cis-but-2-ene, trans-but-2-ene) are carried out in a flow tube reactor at 353 K and 4 Torr under multiple collision conditions. Ground state carbon atoms are generated by 248 nm laser photolysis of tetrabromomethane, CBr4, in a buffer of helium. Thermalized reaction products are detected using synchrotron tunable VUV photoionization and time-of-flight mass spectrometry. The temporal profiles of the detected ions are used to discriminate products from side or secondary reactions. For the C(3P) + trans-but-2-ene and C(3P) + cis-but-2-ene reactions, various isomers of C4H5 and C5H7 are identified as reaction products formed via CH3 and H elimination. Assuming equal ionization cross sections for all C4H5 and C5H7 isomers, C4H5:C5H7 branching ratios of 0.63:1 and 0.60:1 are derived for the C(3P) + trans-but-2-ene and the C(3P) + cis-but-2-ene reactions, respectively. For the C(3P) + but-1ene reaction, two reaction channels are observed: the H-elimination channel, leading to the formation of the ethylpropargyl isomer, and the C3H3 + C2H5 channel. Assuming equal ionization cross sections for ethylpropargyl and C3H3 radicals, a branching ratio of 1:0.95 for the C3H3 + C2H5 and H + ethylpropargyl channels is derived. The experimental results are compared to previous H atom branching ratios and used to propose the most likely mechanisms for the reaction of ground state carbon atoms with butene isomers.

  18. 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.

  19. Reaction cross sections for. nu. sup 13 C r arrow e sup minus sup 13 N and. nu. sup 13 C r arrow. nu. prime sup 13 C sup * for low energy neutrinos

    SciTech Connect

    Fukugita, M. ); Kohyama, Y.; Kubodera, K.; Kuramoto, T. )

    1990-04-01

    Cross sections for {nu}+{sup 13}C reactions are calculated both for charged- and neutral-current reactions in order to estimate the efficiency of a {sup 13}C target as a solar neutrino detector. The relevant transition matrix elements are obtained using the semiphenomenological effective-operator approach for {ital p}-shell nuclei.

  20. Carbon-13 nuclear-magnetic-resonance spectroscopy of Forssman hapten.

    PubMed Central

    Koerner, T A; Cary, L W; Li, S C; Li, Y T

    1981-01-01

    The 13C n.m.r. spectrum of Forssman hapten was obtained at 25.16 MHz in [3H] chloroform/[2H] methanol (1:1, v/v), using purified glycosphinogolipid from canine intestinal mucosa (glycolipid I). All amide, olefin, anomeric, intersaccharide glycosidic ether, amide linkage, methyl and many methylene resonances were resolved and assigned. Analysis of the anomeric region reveals the following pentaglycosylceramide structure as originally proposed [Siddiqui & Hakomori (1971) J. Biol. Chem. 246, 5766-5769]: GalNAc (alpha 1 leads to 3) GalNAc (beta 1 leads to 3) Gal (alpha 1 leads to 4) Gal (beta 1 leads to 1) ceramide. Analysis of the amide, olefin and methylene regions reveals no alpha-hydroxy fatty acyl group and less than or equal to 6 mol% unsaturated fatty acyl groups are present. Chemical-shift assignments are reported for the anomeric and glycosidic ether carbon atoms of intersaccharide-linked alpha-galactose and N-acetyl-alpha-galactosamine residues. Two rules are proposed for the assignment of the anomeric form of 1 leads to 3 and 1 leads to 4 linkages of galactose and N-acetylgalactosamine residues present in the glycone of glyco-conjugates. The present study emphasizes the importance of the anomeric "window" (80-120 p.p.m.) in studies of glycone structure. PMID:7316971

  1. Monomeric metal aqua complexes in the interlayer space of montmorillonites as strong Lewis acid catalysts for heterogeneous carbon-carbon bond-forming reactions.

    PubMed

    Kawabata, Tomonori; Kato, Masaki; Mizugaki, Tomoo; Ebitani, Kohki; Kaneda, Kiyotomi

    2004-12-17

    Montmorillonite-enwrapped copper and scandium catalysts (Cu(2+)- and Sc(3+)-monts) were easily prepared by treating Na(+)-mont with the aqueous solution of the copper nitrate and scandium triflate, respectively. The resulting Cu(2+)- and Sc(3+)-monts showed outstanding catalytic activities for a variety of carbon-carbon bond-forming reactions, such as the Michael reaction, the Sakurai-Hosomi allylation, and the Diels-Alder reaction, under solvent-free or aqueous conditions. The remarkable activity of the mont catalysts is attributable to the negatively charged silicate layers that are capable of stabilizing metal cations. Furthermore, these catalysts were reusable without any appreciable loss in activity and selectivity. The Cu(2+)-mont-catalyzed Michael reaction proceeds via a ternary complex in which both the 1,3-dicarbonyl compound and the enone are coordinated to a Lewis acid Cu(2+) center.

  2. Trichloramine Removal with Activated Carbon Is Governed by Two Reductive Reactions: A Theoretical Approach with Diffusion-Reaction Models.

    PubMed

    Matsushita, Taku; Matsui, Yoshihiko; Ikekame, Shohei; Sakuma, Miki; Shirasaki, Nobutaka

    2017-04-06

    Mechanisms underlying trichloramine removal with activated carbon treatment were proven by batch experiments and theoretical analysis with diffusion-reaction models. The observed values of trichloramine and free chlorine were explained only by the model in which (1) both trichloramine and free chlorine were involved as reactants, (2) the removals of reactants were affected both by the intraparticle diffusion and by the reaction with activated carbon, and (3) trichloramine decomposition was governed by two distinct reductive reactions. One reductive reaction was expressed as a first-order reaction: the reductive reaction of trichloramine with the basal plane of PAC, which consists of graphene sheets. The other reaction was expressed as a second-order reaction: the reductive reaction of trichloramine with active functional groups located on the edge of the basal plane. Free chlorine competitively reacted with both the basal plane and the active functional groups. The fact that the model prediction succeeded even in experiments with different activated carbon doses, with different initial trichloramine concentrations, and with different sizes of activated carbon particles clearly proved that the mechanisms described in the model were reasonable for explaining trichloramine removal with activated carbon treatment.

  3. Measurement and importance of dissolved organic carbon. Chapter 13

    Treesearch

    Randall Kolka; Peter Weishampel; Mats. Froberg

    2008-01-01

    The flux of dissolved organic carbon (DOC) from an ecosystem can be a significant component of carbon (C) budgets especially in watersheds containing wetlands. Although internal ecosystem cycling of DOC is generally greater than the fluxes to ground or surface waters, it is the transport out of the system that is a main research focus for carbon accounting. In...

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

    PubMed

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

    1970-01-30

    The water content of the breccia is 150 to 455 ppm, with a deltaD from-580 to -870 per mil. Hydrogen gas content is 40 to 53 ppm with a deltaD of -830 to -970 per mil. The CO(2) is 290 to 418 ppm with delta (13)C = + 2.3 to + 5.1 per mil and delta(18)O = 14.2 to 19.1 per mil. Non-CO(2) carbon is 22 to 100 ppm, delta(13)C = -6.4 to -23.2 per mil. Lunar dust is 810 ppm H(2)O (D = 80 ppm) and 188 ppm total carbon(delta(13)C = -17.6 per mil). The (18)O analyses of whole rocks range from 5.8 to 6.2 per mil. The temperature of crystallization of type B rocks is 1100 degrees to 1300 degrees C, based on the oxygen isotope fractionation between coexisting plagioclase and ilmenite.

  5. 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.

  6. Fluorous oxime palladacycle: a precatalyst for carbon-carbon coupling reactions in aqueous and organic medium.

    PubMed

    Susanto, Woen; Chu, Chi-Yuan; Ang, Wei Jie; Chou, Tzyy-Chao; Lo, Lee-Chiang; Lam, Yulin

    2012-03-16

    To facilitate precatalyst recovery and reuse, we have developed a fluorous, oxime-based palladacycle 1 and demonstrated that it is a very efficient and versatile precatalyst for a wide range of carbon-carbon bond formation reactions (Suzuki-Miyaura, Sonogashira, Stille, Heck, Glaser-type, and Kumada) in either aqueous or organic medium under microwave irradiation. Palladacycle 1 could be recovered through F-SPE in various coupling reactions with recovery ranging from 84 to 95% for the first cycle. Inductively coupled plasma optical emission spectrometry (ICP-OES) analyses of the Pd content in the crude product from each class of transformation indicated extremely low levels of leaching and the palladacycle could be reused four to five times without significant loss of activity.

  7. Silver(I)-Catalyzed Enantioselective [3+2]-Cycloaddition Reaction of α-Silylimines: A Facile Route to Quaternary-Carbon-Rich Scaffolds.

    PubMed

    Kesava-Reddy, Naredla; Golz, Christopher; Strohmann, Carsten; Kumar, Kamal

    2016-12-19

    A silver-catalyzed highly enantioselective 1,3-dipolar cycloaddition reaction of α-silylimines with pyrone-based trisubstituted olefins was developed affording bi- and tricyclic α-quaternary-carbon-rich pyrano-pyrrolidines in excellent yields. The tricyclic benzopyrone adducts thus obtained were efficiently transformed into highly complex tetracyclic scaffolds supporting four consecutive stereogenic centers with three quaternary carbons.

  8. [Carbon isotope (13C/12C) effect of photorespiration in photosynthetic organisms. Evidence for existence, probable mechanism].

    PubMed

    Ivlev, A A

    2002-01-01

    Experimental evidence in favor of the new phenomenon predicted for photosynthesizing organisms, the fractionation of carbon isotopes in photorespiration is presented. A possible mechanism of this process is discussed. The fractionation of carbon in isotopes photorespiration occurs in the oxygenase phase of the functioning of ribulosebisphosphate carboxylase/oxygenase (rubisco), the key enzyme of photosynthesis, which is capable to act as carboxylase and oxygenase. Which function of the enzyme is active depends on CO2/O2 concentration ratio, which periodically changes in a cell. The key reaction in the mechanism of carbon isotope fractionation in photorespiration is glycine decarboxylation, which results in the splitting and removal from the cell of CO2 enriched with 12C and the accumulation of 13C photorespiratory carbon flow. The coupling of photorespiration and CO2 photoassimilation gives rise to two isotopically different carbon flows, which fill up separate carbohydrate pools, which are the sources of carbon in the following syntheses in the dark phase of photosynthesis. This enables one to identify, from the carbon isotope ratio of metabolites, their involvement in the photorespiratory and assimilatory carbon flows, to investigate the pathways of carbon metabolism, and to estimate more thoroughly the biosynthetic role of photorespiration.

  9. 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.

  10. Carbon-13 labelling shows no effect of ocean acidification on carbon transfer in Mediterranean plankton communities

    NASA Astrophysics Data System (ADS)

    Maugendre, L.; Gattuso, J.-P.; de Kluijver, A.; Soetaert, K.; van Oevelen, D.; Middelburg, J. J.; Gazeau, F.

    2017-02-01

    Despite an increasing number of experiments, no consensus has emerged on the effect of ocean acidification on plankton communities and carbon flow. During two experiments, performed in the Bay of Calvi (France, Corsica; summer 2012) and the Bay of Villefranche (France; winter 2013), nine off-shore mesocosms (∼50 m3) were deployed among which three served as controls and six were enriched with CO2 to reach partial pressure of CO2 (pCO2) levels from 450 to 1350 μatm and 350-1250 μatm in the Bay of Calvi and the Bay of Villefranche, respectively. In each mesocosm, inorganic 13C was added in order to follow carbon transfer from inorganic via bulk particulate organic carbon and phytoplankton to bacteria by means of biomarkers as well as to zooplankton and settling particles. Despite very low plankton biomasses, labelled carbon was clearly transferred through plankton communities. Incorporation rates in the various plankton compartments suggested a slow-growing community based on regenerated production in the Bay of Calvi while in the Bay of Villefranche, fast-growing species were clearly dominating community production at the start with a shift toward slow-growing species during the experiment due to nutrient limitation. Both bulk and group-specific productions rates did not respond to increasing pCO2 levels. These experiments were the first conducted in the Mediterranean Sea under low nutrient concentrations and phytoplankton biomasses and suggest that ocean acidification may not significantly impact plankton carbon flows in low nutrient low chlorophyll (LNLC) areas.

  11. Crystal Morphology and 13Carbon/12Carbon Composition of Solid Oxalate in Cacti 1

    PubMed Central

    Rivera, E. R.; Smith, B. N.

    1979-01-01

    Morphology, crystal structure, and carbon isotopic composition of calcium oxalate from representative species from the family Cactaceae were determined using scanning electron microscopy, x-ray diffraction, and isotope ratio mass spectrometry. Crystals from one species in the Opuntieae tribe of the Cactaceae were druses with acute points composed of the monohydrate form of calcium oxalate (whewellite). Crystals from three species in the Cereeae tribe were the dihydrate form of calcium oxalate (weddellite) forming druses made up of tetragonal and isodiametric crystallites. The oxalate was relatively enriched in 13C isotope (-7.3 to - 8.7 ‰) compared with woody fibers (-13.3 to 14.1 ‰) from the same plants. Images PMID:16661115

  12. 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...

  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. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    DOEpatents

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

    2016-11-01

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

  16. "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

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

    PubMed

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

    2015-06-04

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

  18. 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.

  19. 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.

  20. Reactions of Atomic Carbon with Butene Isomers: Implications for Molecular Growth in Carbon-Rich Environments

    SciTech Connect

    Bourgalais, J.; Spencer, Michael; Osborn, David L.; Goulay, F.; Le Picard, S. D.

    2016-10-31

    We carried out the product detection studies of C(3P) atom reactions with butene (C4H8) isomers (but-1-ene, cis-but-2-ene, trans-but-2-ene) in a flow tube reactor at 353 K and 4 Torr under multiple collision conditions. Ground state carbon atoms are generated by 248 nm laser photolysis of tetrabromomethane, CBr4, in a buffer of helium. Thermalized reaction products are detected using synchrotron tunable VUV photoionization and time-of-flight mass spectrometry. The temporal profiles of the detected ions are used to discriminate products from side or secondary reactions. Furthermore, for the C(3P) + trans-but-2-ene and C(3P) + cis-but-2-ene reactions, various isomers of C4H5 and C5H7 are identified as reaction products formed via CH3 and H elimination. Assuming equal ionization cross sections for all C4H5 and C5H7 isomers, C4H5:C5H7 branching ratios of 0.63:1 and 0.60:1 are derived for the C(3P) + trans-but-2-ene and the C(3P) + cis-but-2-ene reactions, respectively. For the C(3P) + but-1-ene reaction, two reaction channels are observed: the H-elimination channel, leading to the formation of the ethylpropargyl isomer, and the C3H3 + C2H5 channel. Assuming equal ionization cross sections for ethylpropargyl and C3H3 radicals, a branching ratio of 1:0.95 for the C3H3 + C2H5 and H + ethylpropargyl channels is derived. Finally, the experimental results are compared to previous H atom branching ratios and used to propose the most likely mechanisms for the reaction of ground state carbon atoms with butene isomers.

  1. 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.

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

    PubMed

    Choudhury, Partha P; Welker, Mark E

    2015-09-16

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

  3. Direct catalytic asymmetric aldol reactions of thioamides: toward a stereocontrolled synthesis of 1,3-polyols.

    PubMed

    Iwata, Mitsutaka; Yazaki, Ryo; Suzuki, Yuta; Kumagai, Naoya; Shibasaki, Masakatsu

    2009-12-30

    A direct catalytic asymmetric aldol reaction of thioamides with a soft Lewis acid/hard Brønsted base cooperative catalytic system comprising (R,R)-Ph-BPE/[Cu(CH(3)CN)(4)]PF(6)/LiOAr is described. Highly chemoselective deprotonative activation of thioamides allows for a direct aldol reaction of alpha-nonbranched aliphatic aldehydes, which are susceptible to self-condensation. Facile reduction of the thioamide functionality and a catalyst-controlled second aldol reaction provides 1,3-diols in a highly stereoselective manner.

  4. Chiral phosphoric acid catalyzed enantioselective 1,3-dipolar cycloaddition reaction of azlactones.

    PubMed

    Zhang, Zhenhua; Sun, Wangsheng; Zhu, Gongming; Yang, Junxian; Zhang, Ming; Hong, Liang; Wang, Rui

    2016-01-25

    The first chiral phosphoric acid catalyzed highly diastereo- and enantioselective 1,3-dipolar cycloaddition reaction of azlactones and methyleneindolinones was disclosed. By using a BINOL-derived chiral phosphoric acid as the catalyst, azlactones were activated as chiral anti N-protonated 1,3-dipoles to react with methyleneindolinones to yield biologically important 3,3'-pyrrolidonyl spirooxindole scaffolds in high yields, with good-to-excellent diastereo- and enantioselectivity.

  5. 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.

  6. 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

  7. Study on Utilization of Carboxyl Group Decorated Carbon Nanotubes and Carbonation Reaction for Improving Strengths and Microstructures of Cement Paste

    PubMed Central

    Yan, Xiantong; Cui, Hongzhi; Qin, Qinghua; Tang, Waiching; Zhou, Xiangming

    2016-01-01

    Carbon nanotubes (CNTs) have excellent mechanical properties and can be used to reinforce cement-based materials. On the other hand, the reaction product of carbonation with hydroxides in hydrated cement paste can reduce the porosity of cement-based materials. In this study, a novel method to improve the strength of cement paste was developed through a synergy of carbon nanotubes decorated with carboxyl group and carbonation reactions. The experimental results showed that the carboxyl group (–COOH) of decorated carbon nanotubes and the surfactant can control the morphology of the calcium carbonate crystal of carbonation products in hydrated cement paste. The spindle-like calcium carbonate crystals showed great morphological differences from those observed in the conventional carbonation of cement paste. The spindle-like calcium carbonate crystals can serve as fiber-like reinforcements to reinforce the cement paste. By the synergy of the carbon nanotubes and carbonation reactions, the compressive and flexural strengths of cement paste were significantly improved and increased by 14% and 55%, respectively, when compared to those of plain cement paste. PMID:28335281

  8. Study on Utilization of Carboxyl Group Decorated Carbon Nanotubes and Carbonation Reaction for Improving Strengths and Microstructures of Cement Paste.

    PubMed

    Yan, Xiantong; Cui, Hongzhi; Qin, Qinghua; Tang, Waiching; Zhou, Xiangming

    2016-08-19

    Carbon nanotubes (CNTs) have excellent mechanical properties and can be used to reinforce cement-based materials. On the other hand, the reaction product of carbonation with hydroxides in hydrated cement paste can reduce the porosity of cement-based materials. In this study, a novel method to improve the strength of cement paste was developed through a synergy of carbon nanotubes decorated with carboxyl group and carbonation reactions. The experimental results showed that the carboxyl group (-COOH) of decorated carbon nanotubes and the surfactant can control the morphology of the calcium carbonate crystal of carbonation products in hydrated cement paste. The spindle-like calcium carbonate crystals showed great morphological differences from those observed in the conventional carbonation of cement paste. The spindle-like calcium carbonate crystals can serve as fiber-like reinforcements to reinforce the cement paste. By the synergy of the carbon nanotubes and carbonation reactions, the compressive and flexural strengths of cement paste were significantly improved and increased by 14% and 55%, respectively, when compared to those of plain cement paste.

  9. Biosynthesis of curdlan from culture media containing 13C-labeled glucose as the carbon source.

    PubMed

    Kai, A; Ishino, T; Arashida, T; Hatanaka, K; Akaike, T; Matsuzaki, K; Kaneko, Y; Mimura, T

    1993-02-24

    13C-Labeled curdlans were biosynthesized by Agrobacterium sp. (ATCC 31749) from culture media containing D-(1-13C)glucose, D-(6-13C)glucose, or D-(2-13C)glucose as the carbon source, and their structures were analyzed by 13C NMR spectroscopy. The labeling was mainly found in the original position, that is, C-1, C-6, or C-2, indicating direct polymerization of introduced glucose. In addition, C-3 in curdlan obtained from D-(1-13C)glucose, C-1 in curdlan obtained from D-(6-13C)glucose, and C-1 and C-3 in curdlan obtained from D-(2-13)glucose were labeled. From analysis of this labeling, the biosynthesis of curdlan was interpreted as involving five routes: (1) direct synthesis from glucose; (2) rearrangement (1-13C-->3-13C); and (3) isomerization (6-13C-->1-13C) of cleaved trioses by the Embden-Meyerhof pathway, followed by neogenesis of glucose and formation of curdlan; (4) from fructose 6-phosphate formed in the pentose cycle (2-13C-->1-13C, 3-13C); and (5) neogenesis of glucose from fragments produced in various pathways of glycolysis. The 13C-labeling at C-6 and C-2 in the starting glucoses is well preserved in the C-6 carbon and the C-1 to C-3 carbons, respectively, in the curdlan produced.

  10. The carbon mainframe structure of cis-trans-1,3-difluoroacetone

    NASA Astrophysics Data System (ADS)

    Grubbs, G. S.

    2017-01-01

    The carbon-13 backbone structure of 1,3-difluoroacetone has been obtained and reported for the first time. This was achieved through the collection of singly substituted 13C isotopologue rotational spectra at each carbon position. The rotational constants for each isotopologue have been determined and are reported for the first time. Kraitchman coordinates and second moment analysis verify the structure determined by previous literature studies and are presented.

  11. Carbon-carbon bond formation involving reactions of alkynes with group 9 metals (Ir, Rh, Co): preparation of conjugated olefins.

    PubMed

    Chin, Chong Shik; Won, Gyongshik; Chong, Daesung; Kim, Mieock; Lee, Hyungeui

    2002-04-01

    Stable alkynyl complexes of iridium(III) (L(n)Ir-triple bond-R) that are prepared from the reactions of terminal alkynes readily undergo the intramolecular C-C bond-forming reactions between the alkynyl and adjacent hydrocarbyl ligands to yield conjugated olefins. These reactions are initiated by electrophiles (H(+), Me(+)) that attack the beta carbon of the alkynyl ligand to increase the electrophilicity of the alpha carbon of the alkynyl ligand. The C-C bond is then formed between the alpha carbons of the alkynyl and adjacent hydrocarbyl ligands.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. Carbon and Chlorine Isotope Fractionation Patterns Associated with Different Engineered Chloroform Transformation Reactions.

    PubMed

    Torrentó, Clara; Palau, Jordi; Rodríguez-Fernández, Diana; Heckel, Benjamin; Meyer, Armin; Domènech, Cristina; Rosell, Mònica; Soler, Albert; Elsner, Martin; Hunkeler, Daniel

    2017-06-06

    To use compound-specific isotope analysis for confidently assessing organic contaminant attenuation in the environment, isotope fractionation patterns associated with different transformation mechanisms must first be explored in laboratory experiments. To deliver this information for the common groundwater contaminant chloroform (CF), this study investigated for the first time both carbon and chlorine isotope fractionation for three different engineered reactions: oxidative C-H bond cleavage using heat-activated persulfate, transformation under alkaline conditions (pH ∼ 12) and reductive C-Cl bond cleavage by cast zerovalent iron, Fe(0). Carbon and chlorine isotope fractionation values were -8 ± 1‰ and -0.44 ± 0.06‰ for oxidation, -57 ± 5‰ and -4.4 ± 0.4‰ for alkaline hydrolysis (pH 11.84 ± 0.03), and -33 ± 11‰ and -3 ± 1‰ for dechlorination, respectively. Carbon and chlorine apparent kinetic isotope effects (AKIEs) were in general agreement with expected mechanisms (C-H bond cleavage in oxidation by persulfate, C-Cl bond cleavage in Fe(0)-mediated reductive dechlorination and E1CB elimination mechanism during alkaline hydrolysis) where a secondary AKIECl (1.00045 ± 0.00004) was observed for oxidation. The different dual carbon-chlorine (Δδ(13)C vs Δδ(37)Cl) isotope patterns for oxidation by thermally activated persulfate and alkaline hydrolysis (17 ± 2 and 13.0 ± 0.8, respectively) vs reductive dechlorination by Fe(0) (8 ± 2) establish a base to identify and quantify these CF degradation mechanisms in the field.

  18. A Low Energy Measurement of the 13C(α,n) Reaction

    NASA Astrophysics Data System (ADS)

    Toomey, Rebecca; Febbraro, Michael; Pain, Steven; Cizewski, Jolie

    2016-09-01

    The slow neutron capture process (s process) is a key mechanism in heavy-element synthesis, reaching up to 209Bi. The s process creates elements along the line of beta-stability via neutron capture and beta decay in a low neutron flux environment in AGB stars. The dominant source of neutrons for the s process is the 13C(α,n) reaction. At the low energies occurring in these stellar conditions, this reaction cross section is very low, making direct measurement of the reaction rate difficult. Currently the state-of-the-art measurements using high-efficiency moderated neutron counter detectors have constrained this cross section down to approximately 300 keV - still well above stellar conditions, therefore requiring extrapolation of the S factor into the Gamow window ( 140-230 keV). This talk will focus on the motivation and preparation for low-energy measurements of the 13C(α,n) reaction using a neutron spectroscopic technique with the aim of reducing uncertainties in current measurements, and also attempt measurements at lower energies. Background measurements and the characterisation of the experimental set up from the measurement of 13C(α,n) at higher energies at the University of Notre Dame will be presented. This work is supported in part by the U.S. Department of Energy and National Science Foundation.

  19. 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.

  20. 1,3-Dipolar Cycloaddition Reactions of Azomethine Ylides with Carbonyl Dipolarophiles Yielding Oxazolidine Derivatives.

    PubMed

    Meyer, Adam G; Ryan, John H

    2016-07-23

    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.

  1. 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.

  2. Analyses of cocondensation of melamine and urea through carbon 13 enriched formaldehyde with carbon 13 nuclear magnetic resonance spectroscopy

    Treesearch

    Tomita Bunchiro; Chung-Yun Hse

    1995-01-01

    The urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, and melamine-urea-formaldehyde (MUF) cocondensed resins were synthesized using the labeling method with 13C enriched formaldehyde unde neutral conditions and their 13C-NMR (nuclear magnetic resonance) spectra were analyzed. The remarkable down-field...

  3. Analysis on cocondensation of melamine and urea through carbon 13 enriched formaldehyde with carbon 13 nuclear magnetic resonance spectroscopy

    Treesearch

    Bunichiro Tomita; Chung-Yun Hse

    1995-01-01

    The urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, and melamine-urea-formaldehyde (MUF) cocondensed resins were synthesized using the labeling method of 13C enriched formaldehyde udner neutral conditions and their 13C-NMR (nuclear magnetic resonance) spectra were analyzed. The remarkable down-field shifts...

  4. 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

  5. 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)

  6. Reaction of carbon and water as catalyzed by nickel and iron surfaces

    SciTech Connect

    Kelemen, S.R.

    1986-01-01

    The individual steps of the reaction of carbon and water to produce CO and H/sub 2/ were quantified on nickel and iron surfaces using temperature-programmed reaction spectroscopy (TPRS), Auger electron spectroscopy (AES), Ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). Surface graphite and carbide, two metastable surface carbon forms, were prepared by dehydrogenation of C/sub 2/H/sub 2/ and served as reactant carbon. UPS of the graphite monolayer in contact with the metal yielded a valence electronic structure that could be interpreted in terms of the bulk band structure of graphite. The CO formation step is rate limiting in the uncatalyzed H/sub 2/O gasification reaction of graphite. The nickel surface in contact with graphitic carbon lowers the barrier for the CO formation step. The catalytic action occurs directly without isolated prior breaking of carbon-carbon bonds. The estimated activation energy for the direct reaction was 44 kcal/mole. The fully carbided surfaces of Ni and Fe were active for H/sub 2/O dissociation with an estimated activation energy between 5.0 and 10.0 kcal/mole. A different catalytic reaction cycle involving carbon-carbon bond breaking followed by oxidation of the carbide is energetically more demanding. The activation energy for direct carbon-carbon bond breaking was estimated between 65-70 kcal/mole on both nickel and iron. Following this demanding step, the reaction between carbidic carbon and oxygen proceeded on nickel and iron with estimated activation energies of 31 and 39 kcal/mole, respectively. This indirect carbide reaction cycle changed the energetics of the steam gasification of carbon.

  7. 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.

  8. 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.

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

    PubMed

    Han, Chong; Liu, Yongchun; He, Hong

    2013-04-02

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

  10. Staphylococcus aureus Peptidoglycan Tertiary Structure from Carbon-13 Spin Diffusion

    PubMed Central

    Sharif, Shasad; Singh, Manmilan; Kim, Sung Joon; Schaefer, Jacob

    2009-01-01

    The cell-wall peptidoglycan of Staphylococcus aureus is a heterogeneous, highly cross-linked polymer of unknown tertiary structure. We have partially characterized this structure by measuring spin diffusion from 13C labels in pentaglycyl cross-linking segments to natural-abundance 13C in the surrounding intact cell walls. The measurements were performed using a version of centerband-only detection of exchange (CODEX). The cell walls were isolated from S. aureus grown in media containing [1-13C]glycine. The CODEX spin diffusion rates established that the pentaglycyl bridge of one peptidoglycan repeat unit of S. aureus is within 5 Å of the glycan chain of another repeat unit. This surprising proximity is interpreted in terms of a model for the peptidoglycan lattice in which all peptide stems in a plane perpendicular to the glycan mainchain are parallel to one another. PMID:19419167

  11. 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.

  12. Graphitic mesoporous carbon based on aromatic polycondensation as catalyst support for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Liu, Peng; Kong, Jiangrong; Liu, Yaru; Liu, Qicheng; Zhu, Hongze

    2015-03-01

    Mesoporous carbon is constructed by monolithic polyaromatic mesophase deriving from the hexane insoluble of coal-tar pitch. This carbon material exhibits spherical morphology and layered crystallite, and thereby can be graphitized at 900 °C without destroying the mesoporous structure. Electrochemical measurements indicate that graphitic mesoporous carbon (GMC) support not only improves the activity of Pt electrocatalyst to oxygen reduction reaction (ORR), but also shows higher corrosion resistance than commercial XC-72 carbon black in the acid cathode environment.

  13. Study on the Alkylation Reactions of N(7)-Unsubstituted 1,3-Diazaoxindoles.

    PubMed

    Kókai, Eszter; Halász, Judit; Dancsó, András; Nagy, József; Simig, Gyula; Volk, Balázs

    2017-05-19

    The chemistry of the 5,7-dihydro-6H-pyrrolo[2,3-d]pyrimidin-6-one (1,3-diazaoxindole) compound family, possessing a drug-like scaffold, is unexplored. In this study, the alkylation reactions of N(7)-unsubstituted 5-isopropyl-1,3-diazaoxindoles bearing various substituents at the C(2) position have been investigated. The starting compounds were synthesized from the C(5)-unsubstituted parent compounds by condensation with acetone and subsequent catalytic reduction of the 5-isopropylidene moiety. Alkylation of the thus obtained 5-isopropyl derivatives with methyl iodide or benzyl bromide in the presence of a large excess of sodium hydroxide led to 5,7-disubstituted derivatives. Use of butyllithium as the base rendered alkylation in the C(5) position possible with reasonable selectivity, without affecting the N(7) atom. During the study on the alkylation reactions, some interesting by-products were also isolated and characterized.

  14. Calibration of the carbon isotope composition (δ13C) of benthic foraminifera

    NASA Astrophysics Data System (ADS)

    Schmittner, Andreas; Bostock, Helen C.; Cartapanis, Olivier; Curry, William B.; Filipsson, Helena L.; Galbraith, Eric D.; Gottschalk, Julia; Herguera, Juan Carlos; Hoogakker, Babette; Jaccard, Samuel L.; Lisiecki, Lorraine E.; Lund, David C.; Martínez-Méndez, Gema; Lynch-Stieglitz, Jean; Mackensen, Andreas; Michel, Elisabeth; Mix, Alan C.; Oppo, Delia W.; Peterson, Carlye D.; Repschläger, Janne; Sikes, Elisabeth L.; Spero, Howard J.; Waelbroeck, Claire

    2017-06-01

    The carbon isotope composition (δ13C) of seawater provides valuable insight on ocean circulation, air-sea exchange, the biological pump, and the global carbon cycle and is reflected by the δ13C of foraminifera tests. Here more than 1700 δ13C observations of the benthic foraminifera genus Cibicides from late Holocene sediments (δ13CCibnat) are compiled and compared with newly updated estimates of the natural (preindustrial) water column δ13C of dissolved inorganic carbon13CDICnat) as part of the international Ocean Circulation and Carbon Cycling (OC3) project. Using selection criteria based on the spatial distance between samples, we find high correlation between δ13CCibnat and δ13CDICnat, confirming earlier work. Regression analyses indicate significant carbonate ion (-2.6 ± 0.4) × 10-3‰/(μmol kg-1) [CO32-] and pressure (-4.9 ± 1.7) × 10-5‰ m-1 (depth) effects, which we use to propose a new global calibration for predicting δ13CDICnat from δ13CCibnat. This calibration is shown to remove some systematic regional biases and decrease errors compared with the one-to-one relationship (δ13CDICnat = δ13CCibnat). However, these effects and the error reductions are relatively small, which suggests that most conclusions from previous studies using a one-to-one relationship remain robust. The remaining standard error of the regression is generally σ ≅ 0.25‰, with larger values found in the southeast Atlantic and Antarctic (σ ≅ 0.4‰) and for species other than Cibicides wuellerstorfi. Discussion of species effects and possible sources of the remaining errors may aid future attempts to improve the use of the benthic δ13C record.

  15. 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.

  16. 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.

  17. Bioactivity and mechanical properties of cellulose/carbonate hydroxyapatite composites prepared in situ through mechanochemical reaction.

    PubMed

    Yoshida, Akihiko; Miyazaki, Toshiki; Ashizuka, Masahiro; Ishida, Eiichi

    2006-10-01

    Organic-inorganic composites, prepared from bone-bonding bioactive ceramics and organic polymers, are useful for novel bone substitutes having mechanical properties analogous to natural bone. We synthesized composites from cellulose and carbonate hydroxyapatite (CHAp) in situ through mechanochemical reaction. They contained B-type CHAp analogous to bone apatite. They showed a bending strengths of 10-13 MPa and Young's modulus of 1.5-2.2 GPa. We predicted their microstructure by comparing the measured density with the theoretical one. Cellulose was assumed to be distributed in the pore of CHAp at low cellulose content, and in grain boundaries of CHAp at high cellulose content. The composites formed calcium phosphate on their surfaces in simulated body fluid, meaning that they have a potential to be bioactive.

  18. Isotopic multiplets in the carbon-13 NMR spectra of aniline derivatives and nucleosides with partially deuterated amino groups: effects of intra- and intermolecular hydrogen bonding

    SciTech Connect

    Reuben, J.

    1987-01-21

    In aniline derivatives, the carbon-13 resonances of atoms bearing partially deuterated amino groups, as well as the resonances of vicinal carbon atoms, appear as multiplets. This phenomenon, which is due to upfield deuterium isotope effects on carbon-13 chemical shifts, is observed under conditions of slow hydrogen exchange (e.g., in Me/sub 2/SO solutions). The effects are larger for groups engaged in intramolecular hydrogen bonds. Empirical expressions are presented that relate isotope effects with amino proton chemical shifts and hydrogen bond energies. Isotopic multiplets are also observed in the carbon-13 NMR spectra of partially deuterated nucleosides. The multiplet structure is altered upon formation of base pairs. These results are interpreted in terms of hydrogen exchange reactions involving uridine (or thymidine) hydrogen-bonded dimers or changes in hydrogen bond energies upon formation of guanosine-cytidine complexes. Estimates are given for the energies of individual hydrogen bonds in Watson-Crick base pairs.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  20. The CH + CO reaction: Rate coefficient for carbon atom exchange at 294 K

    SciTech Connect

    Anderson, S.M.; McCurdy, K.E.; Kolb, C.E. )

    1989-02-09

    A fast-flow reactor equipped with isotope-specific laser-excited fluorescence detection of CH radicals has been used to study carbon atom exchange in the reaction between CH and CO at 294 K and 2 Torr of total pressure. The rate coefficient for exchange, k{sub 3} = (2.1 {times} 0.3) {times} 10{sup {minus}12} cm{sup 3} s{sup {minus}1}, is about an order of magnitude larger than the bimolecular rate for the addition reaction, k{sub 2} = (2.7 {plus minus} 0.4) {times} 10{sup {minus}13}. High-pressure limiting bimolecular and low-pressure termolecular recombination rate coefficients of 1.1 {times} 10{sup {minus}10} cm{sup 3} s{sup {minus}1} and 4.9 {times} 10{sup {minus}30} cm{sup 6} s{sup {minus}1} are derived. The results are discussed in the context of previous work on the title reaction and on the chemistry of singlet CH{sub 2}.

  1. 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.

  2. Effect of nasogastric administration of sodium bicarbonate on carbon 13 isotopic enrichment of carbon dioxide in serum of horses.

    PubMed

    Hinchcliff, Kenneth W; Sams, Richard A

    2004-03-01

    To determine the effect of administration of commercially available sodium bicarbonate (NaHCO3) on carbon 13 (13C) isotopic enrichment of carbon dioxide (CO2) in serum of horses. 7 healthy Thoroughbreds. Sodium bicarbonate (450 g) was administered via nasogastric intubation to horses. Horses had been fed a diet obtained from the same source and had access to water from the same source for 3 months before the study. Blood samples were collected immediately before and at 2, 4, 6, and 24 hours after administration of NaHCO3. The concentration of total CO2 in serum was measured by use of a commercial analyzer. The 13C enrichment of bicarbonate in serum was estimated by measurement of 13C enrichment of CO2 released by acidification of the serum. The 13C enrichment of commercially available NaHCO3 was also determined and compared with that of CO2 in serum of horses before administration of NaHCO3. Commercially available NaHCO3 had a 13C enrichment significantly different from that of carbon dioxide in serum of horses before treatment. Administration of NaHCO3 increased the concentration of total CO2 from pretreatment values. The 13C enrichment of CO2 in serum was only transiently and minimally affected after administration of NaHCO3. Administration of NaHCO3 was not detected by measuring 13C enrichment of CO2 in serum of horses.

  3. Feasibility study of the 13C(α, n)16O reaction at LUNA

    NASA Astrophysics Data System (ADS)

    Kochanek, I.; Boeltzig, A.; Ciani, G. F.

    2017-03-01

    The 13C(α, n)16O reaction determines the dominant neutron source of the sprocess in thermally pulsing, low-mass, asymptotic giant branch (TP-AGB) stars. The temperature during the s-process in the 13C pocket of 90×106 K corresponds to a Gamow window of 140-230 keV. Since this energy is far below the Coulomb barrier, the cross section of this reaction is extremely small and its rate can only be extrapolated from the measurements at higher energies. At present, the cross section at Gamow peak is uncertain by almost one order of magnitude. An experimental campaign aimed at measuring low energy cross section in 13C(α n)16O is scheduled at the underground LUNA-400 accelerator in Gran Sasso Laboratory, Italy. The unique underground location of this facility offers significant improvement in sensitivity compared with previous investigations. It will allow to establish the interference pattern of the resonances and the absolute scale of this reaction.

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

    PubMed

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

    2015-05-07

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    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.

  6. 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

  7. 13C-NOESY-HSQC with Split Carbon Evolution for Increased Resolution with Uniformly Labeled Proteins

    NASA Astrophysics Data System (ADS)

    Baur, Matthias; Gemmecker, Gerd; Kessler, Horst

    1998-06-01

    Two new pulse sequences are presented for the recording of 2D13C-HSQC and 3D13C-NOESY-HSQC experiments, containing two consecutive carbon evolution periods. The two periods are separated by az-filter which creates a clean CxHz-quantum state for evolution in the second period. Each period is incremented (in anon-constant-time fashion) only to the extent that the defocusing of carbon inphase magnetization throughJ-coupling with neighboring carbons remains insignificant. Therefore,13C homonuclearJ-couplings are rendered ineffective, reducing the loss of signal and peak splitting commonly associated with long13C evolution times. The two periods are incremented according to a special acquisition protocol employing a13C-13C gradient echo to yield a data set analogous to one obtained by evolution over the added duration of both periods. The spectra recorded with the new technique on uniformly13C-labeled proteins at twice the evolution time of the standard13C-HSQC experiment display a nearly twofold enhancement of resolution in the carbon domain, while maintaining a good sensitivity even in the case of large proteins. Applied to the IIAManprotein ofE. coli(31 kDa), the13C-HSQC experiment recorded with a carbon evolution time of 2 × 8 ms showed a 36% decrease in linewidths compared to the standard13C-HSQC experiment, and theS/Nratio of representative cross-peaks was reduced to 40%. This reduction reflects mostly the typical loss of intensity observed when recording with an increased resolution. The13C-NOESY-HSQC experiment derived from the13C-HSQC experiment yielded additional NOE restraints between resonances which previously had been unresolved.

  8. 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.

  9. Hydroxyl radical and ozone initiated photochemical reactions of 1,3-butadiene

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoyu; Jeffries, Harvey E.; Sexton, Kenneth G.

    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 the biogenic emissions in US). In this paper, samples from both hydroxyl- and ozone-initiated photooxidation of 1,3-butadiene were analyzed by derivatization with O- (2,3,4,5,6-pentafluorobenzyl)-hydroxylamine followed by separation and detection by gas chromatography/ion trap mass spectrometry to detect and identify carbonyl compounds. The following carbonyls were observed: formaldehyde, acrolein, glycolaldehyde, glycidaldehyde, 3-hydroxy-propanaldehyde, hydroxy acetone, and malonaldehyde, which can be classified into three categories: epoxy carbonyls, hydroxyl carbonyls, and di-carbonyls. Three non-carbonyls, furan, 1,3-buatdiene monoxide, and 1,3-butadiene diepoxide, were also found. To confirm their identities, both commercially available and synthesized standards were used. To investigate the mechanism of 1,3-butadiene, separate batch reactor experiments for acrolein and 1,3-butadiene monoxide were carried out. Time series samples for several products were also taken. When necessary, computational chemistry methods were also employed. Based on these results, various schemes for the reaction mechanism are proposed.

  10. Reaction of ketones with 1,4-diaza-1,3-diene zirconium and hafnium complexes: First example of a 1,3-dipolar cycloaddition reaction of 1,4-diaza-1,3-diene complexes of early transition metals

    SciTech Connect

    Scholz, J.; Goerls, H.

    1996-07-17

    The chemical preparation of M[O(R)PhCH(CH{double_bond}N(tBu))N(tBu)]{sub 2} (M = Zr, R = Me (4a), R = Ph (4b) and M = Hf, R = Me (5a), R = Ph (5b)) complexes is described. The reaction can be described as a 1,3-dipolar cycloaddition of C{double_bond}O across the M-N-C portion of Zr and Hf 1,4-diaza-1,3-diene complexes. The crystal structures of 4a and 5b are reported.

  11. 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  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. Analyses of cocondensation of melamine and urea through formaldehyde with carbon 13 nuclear magnetic resonance spectroscopy

    Treesearch

    Tomita Bunchiro; Chung-Yun Hse

    1995-01-01

    The 13C-NMR (carbon 13 nuclear magnetic resonance) spectra of urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, and melamine-urea-formaldehyde (MUF) cocondensed resins synthesized under various conditions were taken with a frequency of 75 MHz. The main purpose was to investigate whether or not the occurrences of cocondensation...

  14. Analysis of cocondensation of melamine and urea through formaldehyde with carbon 13 nuclear magnetic resonance spectroscopy

    Treesearch

    Bunichiro Tomita; Chung-Yun Hse

    1995-01-01

    The 13C-NMR (carbon 13 nuclear magnetic resonance) spectra of urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, and melamine-urea-formaldehyde (MUF) cocondensed resins synthesized under various conditions were taken with a frequency of 75 MHz. The main purpose was to investigate whether or not the occurrences of cocondensation...

  15. Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.

    PubMed

    Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng

    2014-08-01

    The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable.

  16. 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.

  17. 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

  18. Straightforward access to pyrazines, piperazinones, and quinoxalines by reactions of 1,2-diaza-1,3-butadienes with 1,2-diamines under solution, solvent-free, or solid-phase conditions.

    PubMed

    Aparicio, Domitila; Attanasi, Orazio A; Filippone, Paolino; Ignacio, Roberto; Lillini, Samuele; Mantellini, Fabio; Palacios, Francisco; de Los Santos, Jesús M

    2006-08-04

    The preparation of tetrahydropyrazines, dihydropyrazines, pyrazines, piperazinones, and quinoxalines by 1,4-addition of 1,2-diamines to 1,2-diaza-1,3-butadienes bearing carboxylate, carboxamide, or phosphorylated groups at the terminal carbon and subsequent internal heterocyclization is described. The solvent-free reaction of carboxylated 1,2-diaza-1,3-butadienes with the same reagents affords piperazinones, while phosphorylated 1,2-diaza-1,3-butadienes yield phosphorylated pyrazines. The solid-phase reaction of polymer-bound 1,2-diaza-1,3-butadienes with 1,2-diamines produces pyrazines.

  19. 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.

  20. 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.

  1. Enhanced biosynthetically directed fractional carbon-13 enrichment of proteins for backbone NMR Assignments

    PubMed Central

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

    2015-01-01

    Routes to carbon-13 enrichment of bacterially expressed proteins include achieving uniform or positionally selective (e.g. ILV-Me, or 13C′, etc.) enrichment. We consider the potential for biosynthetically directed fractional enrichment (e.g. carbon-13 incorporation in the protein less than 100%) for performing routine n-(D)dimensional NMR spectroscopy of proteins. First, we demonstrate an approach to fractional isotope addition where the initial growth media containing natural abundance glucose is replenished at induction with a small amount (e.g. 10%w/w u-13C-glucose) of enriched nutrient. The approach considered here is to add 10% (e.g. 200 mg for a 2 g/L culture) u-13C-glucose at the induction time (OD600=0.8), resulting in a protein with enhanced 13C incorporation that gives almost the same NMR signal levels as an exact 20% 13C sample. Second, whereas fractional enrichment is used for obtaining stereospecific methyl assignments, we find that 13C incorporation levels no greater than 20%w/w yield 13C and 13C-13C spin pair incorporation sufficient to conduct typical 3D-bioNMR backbone experiments on moderate instrumentation (600 MHz, RT probe). Typical 3D-bioNMR experiments of a fractionally enriched protein yield expected backbone connectivities, and did not show amino acid biases in this work, with one exception. When adding 10% u-13C glucose to expression media at induction, there is poor preservation of 13Cα-13Cβ spin pairs in the amino acids ILV, leading to the absence of Cβ signals in HNCACB spectra for ILV, a potentially useful editing effect. Enhanced fractional carbon-13 enrichment provides lower-cost routes to high throughput protein NMR studies, and makes modern protein NMR more cost-accessible. PMID:26256059

  2. Organocatalytic azomethine imine-olefin click reaction: high-yielding stereoselective synthesis of spiroindane-1,3-dione-pyrazolidinones.

    PubMed

    Ramachary, Dhevalapally B; Prabhakar Reddy, T; Suresh Kumar, A

    2016-07-06

    In search of developing new useful "click reactions", herein we report the organocatalytic azomethine imine-olefin [3 + 2]-cycloaddition as a new click reaction for the synthesis of drug-like spiroindane-1,3-dione-pyrazolidinones from indane-1,3-diones, aldehydes and N,N-cyclic azomethine imines through amino acid-catalysis. The scope of this new click reaction is demonstrated using many examples with high reactivity, selectivity and yields.

  3. Spark combustion reactor for 13-carbon isotope enrichment analysis of gases

    NASA Astrophysics Data System (ADS)

    May, Michael; Gray, Michael; Kuo, John E.; Tan, C. T.

    2003-04-01

    A novel spark combustion reactor was designed, built, and utilized for quantitative 13-carbon isotope determination of highly enriched permanent gases. The analytical methodology developed is straightforward and begins by loading the reactor with hydrocarbon and oxygen using a steel gas manifold. High voltage is applied to the platinum electrode spark plug incorporated into the reactor, which rapidly converts hydrocarbon to carbon dioxide (and other products). Carbon dioxide species are then quantitated by quadrupole mass spectrometry. The primary reactor consists of a three-way stainless steel tee, plus the following components connected to threaded ports: (1) a platinum electrode spark plug sealed with a Viton O ring, (2) a steel gas storage cylinder, and (3) a manual bellows valve terminated with a VCO type connector. Making use of the spark combustion reactor, the 13-carbon fraction of highly enriched 13CH4 was measured to be ⩾99.5 at. % 13C. This portable, static reactor permits determination of the 13C/12C isotope fraction for permanent gases utilizing mass spectrometric detection. The analytical system presented is relatively rapid (due to spark ignition), straightforward, and flexible (applicable to hydrocarbon gases using various gas detectors). Its limitation in performance for 13C isotope work is probably due to carbon embedded in the reactor interior.

  4. Does the differential photodissociation and chemical fractionation reaction of 13CO affect the column density estimates?

    NASA Astrophysics Data System (ADS)

    Szücs, László; Glover, Simon

    2013-07-01

    Carbon monoxide (CO) and its isotopes are frequently used as a tracer of column density in studies of the dense interstellar medium. The most abundant CO isotope, 12CO, is usually optically thick in intermediate and high density regions and so provides only a lower limit for the column density. In these regions, less abundant isotopes are used, such as 13CO. To relate observations of 13CO to the 12CO column density, a constant 12CO/13CO isotopic ratio is often adopted. In this work, we examine the impact of two effects -- selective photodissociation of 13CO and chemical fractionation -- on the 12CO/13CO isotopic ratio, with the aid of numerical simulations. Our simulations follow the coupled chemical, thermal and dynamical evolution of isolated molecular clouds in several different environments. We post-process our simulation results with line radiative transfer and produce maps of the emergent 13CO emission. We compare emission maps produced assuming a constant isotopic ratio with ones produced using the results from a more self-consistent calculation, and also compare the column density maps derived from the emission maps. We find that at low and high column densities, the column density estimates that we obtain with the approximation of constant isotopic ratio agree well with those derived from the self-consistent model. At intermediate column densities, 10^12 cm^-2 < N(13CO)< 10^15 cm^-2, the approximate model under-predicts the column density by a factor of a few, but we show that we can correct for this, and hence obtain accurate column density estimates, via application of a simple correction factor.

  5. Ring-opening reactions of cyclic acetals and 1,3-oxazolidines with halosilane equivalents.

    PubMed

    Iwata, Arihiro; Tang, Heqing; Kunai, Atsutaka; Ohshita, Joji; Yamamoto, Yasushi; Matui, Chinami

    2002-07-26

    Reactions of acetal and 1,3-oxazolidine rings were examined using two kinds of iodosilane equivalent reagents, a 1:2 mixture of Me3SiNEt2 and MeI (reagent 1a) and a 1:1 mixture of Et3SiH and MeI containing a catalytic amount of PdCl2 (reagent 1b). In the reactions of alkanone ethylene acetals with reagent 1a, a C-O bond in the acetal ring readily cleaved to give 2-(trimethylsiloxy)ethyl enol ethers. Similarly, the C-O bond of 1,3-oxazolidine rings cleaved to give ring-opened imine or enamine derivatives. The reactions of aromatic ketone ethylene acetals and cyclohexanone trimethylene acetal led to deprotection of the acetal unit to liberate free ketones. With reagent 1b, cycloalkanone ethylene acetal afforded a dimeric product with 2-iodoethyl alkenoate moieties, while aromatic ketone ethylene or trimethylene acetals produced deprotected ketones.

  6. Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes.

    PubMed

    Camasso, Nicole M; Sanford, Melanie S

    2015-03-13

    Homogeneous nickel catalysis is used for the synthesis of pharmaceuticals, natural products, and polymers. These reactions generally proceed via nickel intermediates in the Ni(0), Ni(I), Ni(II), and/or Ni(III) oxidation states. In contrast, Ni(IV) intermediates are rarely accessible. We report herein the design, synthesis, and characterization of a series of organometallic Ni(IV) complexes, accessed by the reaction of Ni(II) precursors with the widely used oxidant S-(trifluoromethyl)dibenzothiophenium triflate. These Ni(IV) complexes undergo highly selective carbon(sp(3))-oxygen, carbon(sp(3))-nitrogen, and carbon(sp(3))-sulfur coupling reactions with exogenous nucleophiles. The observed reactivity has the potential for direct applications in the development of nickel-catalyzed carbon-heteroatom coupling reactions.

  7. 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.

  8. 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

  9. 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.

  10. 1,3-Dipolar cycloaddition-decarboxylation reactions of an azomethine ylide with isatoic anhydrides: formation of novel benzodiazepinones.

    PubMed

    D'Souza, Asha M; Spiccia, Nadia; Basutto, Jose; Jokisz, Pawel; Wong, Leon S-M; Meyer, Adam G; Holmes, Andrew B; White, Jonathan M; Ryan, John H

    2011-02-04

    A nonstabilized azomethine ylide reacts with a wide range of substituted isatoic anhydrides to afford novel 1,3-benzodiazepin-5-one derivatives, which are generally isolated in high yield. The transformations involve 1,3-dipolar cycloaddition reactions of the ylide with the anhydrides to give transient, and in a representative case spectroscopically observable, oxazolidine intermediates that undergo ring-opening-decarboxylation-ring-closing reaction cascades to yield the 1,3-benzodiazepin-5-one products.

  11. Carbon dioxide evolution in a Belousov-Zhabotinsky type oscillating reaction with acetonedicarboxylic acid.

    PubMed

    Sevcík, Peter; Misicák, Daniel; Adamcíková, L'ubica

    2007-10-11

    Oscillations in the platinum redox potential during the reaction of bromate ions with acetonedicarboxylic acid catalyzed by Mn(II) ions were observed. The volume of gaseous carbon dioxide produced was measured. A nonoscillatory course was found both at the slow and rapid stirring rates for carbon dioxide evolution. The perturbation experiments suggest supersaturation during the Belousov-Zhabotinsky reaction with acetonedicarboxylic acid. Possible reasons for such observations are discussed.

  12. 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.

  13. 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.

  14. Chemical exchange spectroscopy based on carbon-13 NMR. Applications to enzymology and protein folding

    NASA Astrophysics Data System (ADS)

    Alexandrescu, Andrei T.; Loh, Stewart N.; Markley, John L.

    We explore how 13C-based two-dimensional chemical exchange spectroscopy (EXSY) can be used to investigate exchange processes that are slow on the NMR time scale. Results are shown for the mutarotase-catalyzed α →← β isomerization of [1- 13C]glucose using experiments that detect carbon spins: homonuclear 13C exchange spectroscopy [ 13C { 13C} EXSY] and heteronuclear exchange spectroscopy [ 13C { 1H} EXSY]; and inverse experiments that select for proton spins attached to 13C: 1H- 13C single-bond correlation exchange spectroscopy [ 1H { 13C} SBC-EXSY] and 13C-filtered 1H exchange spectroscopy [ 1H{ 1H}- 13Cƒ- EXSY] . The main advantage of 13C-based exchange experiments is the simplification of complex spectra afforded by incorporation of selective labels. The inherent power of this approach is illustrated with a 1H { 13C} SBC-EXSY spectrum showing the native →← denatured interconversion of [ 13Cδ1] Trp-staphylococcal nuclease. Certain 13C-based EXSY experiments are useful for discriminating exchange connectivities from dipole-dipole connectivities.

  15. 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.

  16. A DFT study on the reaction pathways for carbon-carbon bond-forming reactions between propargylic alcohols and alkenes or ketones catalyzed by thiolate-bridged diruthenium complexes.

    PubMed

    Sakata, Ken; Miyake, Yoshihiro; Nishibayashi, Yoshiaki

    2009-01-05

    The reaction pathways of two types of the carbon-carbon bond-forming reactions catalyzed by thiolate-bridged diruthenium complexes have been investigated by density-functional-theory calculations. It is clarified that both carbon-carbon bond-forming reactions proceed through a ruthenium-allenylidene complex as a common reactive intermediate. The attack of pi electrons on propene or the vinyl alcohol on the ruthenium-allenylidene complex is the first step of the reaction pathways. The reaction pathways are different after the attack of nucleophiles on the ruthenium-alkynyl complex. In the reaction with propene, the carbon-carbon bond-forming reaction proceeds through a stepwise process, whereas in the reaction with vinyl alcohol, it proceeds through a concerted process. The interactions between the ruthenium-allenylidene complex and propene or vinyl alcohol have been investigated by applying a simple way of looking at orbital interactions.

  17. From graphite to porous carbon containing nanoparticles through chemical reactions

    SciTech Connect

    Hung, C.C.; Corbin, J.

    1996-12-31

    Porous carbon containing large quantities of separated individual nanoparticles (2--100 nm) was produced. The chemical process includes fluorination or oxygenation of graphite, and then exposing the product (graphite fluoride or graphite oxide) to metal chlorides. The nanoparticles were metal halides or metal oxides, which could contain dopants if they were added during the synthesis process. The chlorides used in this research include those of Pd, Zn, Al and Li. Depending on the synthesis process, the carbon pores could be either filled with the nanoparticles, resulting in near-zero surface area and high metal concentration, or partially filled with nanoparticles, resulting in large surface areas. In this report, near zero surface areas were observed for a product of LiCl in carbon, and a surface area of 75 m{sup 2}/g was observed for the product of {gamma}-Al{sub 2}O{sub 3} in carbon. Heating these products in 1 atm air allowed the nanoparticles to become fused together in the form of metal oxide while the carbon was oxidized, producing metal oxides which have the same shape as the carbon precursors (fibers, fabrics, or powder) and large surface areas. These products are potentially useful in the area of batteries, high temperature gas sensors, and catalysts.

  18. Attaching molecules to chlorinated and brominated amorphous carbon substrates via Grignard reactions

    PubMed Central

    Lockett, Matthew R.; Smith, Lloyd M.

    2009-01-01

    Amorphous carbon thin films are an attractive material as they provide a chemically robust surface that has been utilized in biomolecule array, biosensor, and bioelectronic applications. These thin films are particularly versatile as they are deposited at room temperature making them readily integrated with other materials and devices. Here we present an alternative means of functionalizing carbon substrates based on Grignard chemistry. First, the amorphous carbon substrates are halogenated with a solution-based, radical-initiated halogenation reaction using PX5 (X = Br or Cl). Next, the halogenated surfaces are modified via the formation of a carbon-carbon bond between the surface and the Grignard reagents employed. An alkyl-, perfluoroalkyl-, and a poly(ethylene glycol)-Grignard reagent were chosen to show the utility of this reaction scheme in functionalizing carbon surfaces to withstand oxidation and provide a hydrophobic and/or biocompatible substrate. PMID:19708232

  19. Carbon dioxide and related heterocumulenes at zinc and lithium cations: bioinspired reactions and principles.

    PubMed

    Schenk, Stephan; Notni, Johannes; Köhn, Uwe; Wermann, Kurt; Anders, Ernst

    2006-09-21

    This Perspective starts with the discussion of the properties of an interesting metalloenzyme (carbonic anhydrase, CA) that performs extremely successfully the activation of carbon dioxide. Conclusions from that are important for many synthetic procedures and include experimental and theoretical investigation (DFT calculations) of such metal mediated processes in the condensed and in the gas phase in which the zinc cation plays a dominant role. This is extended to the bio-analogue activation of further heterocumulenes such as COS, an important atmospheric trace gas, and CS(2). Novel metal complexes which serve as useful catalysts for the reactions (copolymerisations and cyclisation) of CO(2) and oxiranes are discussed subject to the inclusion of recently published DFT calculations. We continue with the discussion of the very general aspect of the insertion of CO(2) into metal-nitrogen bonds (formation of carbamates). This again is closely related to many biological or bio-analogue processes. We describe the synthesis and mechanistic aspects of characteristic metal carbamates of a wide variety of metals and include a discussion of the mechanistic aspects, especially for the formation of Mg(2+) and Li(+) carbamates and the formation of related cyclic products after addition of the heterocumulenes CO(2), Ph-NCO or CS(2) to novel ligands, the 4H-pyridin-1-ides which finally result in the formation of e.g. 1,3-thiazole-5(2H)-thiones.

  20. Modeling of CO2 Adsorption on Activated Carbon and 13X Zeolite via Vacuum Swing Adsorption

    NASA Astrophysics Data System (ADS)

    Zarghampoor, M. H.; Mozaffarian, M.; Soleimani, M.; Takht Ravanchi, M.

    2017-06-01

    Due to carbon dioxide role in global warming, low CO2 emission limits have been established in recent years. This has led to a variety of studies on CO2 removal approaches. In this study, a VSA cycle consisting of two packed beds is considered for CO2 removal from flue gas. An atmospheric stream containing 20 CO2 and 80 N2 is fed to the beds at 50°C. Two adsorbents, namely Zeolite 13X and activated carbon were selected to compare their performance. Due to the monolayer adsorption of CO2 and N2 on these adsorbents, the Toth isotherm was used for equilibrium adsorption estimation. A quasi-second order model was considered for the mass transfer rate prediction due to low CO2 concentration. The modeling results showed that the average absolute deviation for equilibrium adsorption capacity prediction was 2, and the CO2 breakthrough time curve was predicted with less than 2.5 deviation. Based on the results, the VSA cycle time for zeolite 13X bed will be 3.5 times of the activated carbon bed. Another advantage of Zeolite 13X is that in each process cycle, 80 of adsorbent will be used, while only 74 of activated carbon in beds is used. The advantage of activated carbon bed is its better regeneration capability, since the activated carbon will be regenerated 5 more than zeolite 13X at a vacuum pressure of 0.02bar.

  1. 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.

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

    PubMed

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

    2014-09-12

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

  3. Carbon nitride nanocrystals having cubic structure using pulsed laser induced liquid-solid interfacial reaction

    NASA Astrophysics Data System (ADS)

    Yang, G. W.; Wang, J. B.

    Carbon nitride nanocrystals were prepared using a pulsed laser induced liquid-solid interfacial reaction and transmission electron microscopy, while high resolution electron microscopy characterized their morphology and structure. It is important that the cubic-C3N4 phase was observed. The formation mechanism of the carbon nitride nanocrystals is also discussed.

  4. Growth and Destruction of PAH Molecules in Reactions with Carbon Atoms

    NASA Astrophysics Data System (ADS)

    Krasnokutski, Serge A.; Huisken, Friedrich; Jäger, Cornelia; Henning, Thomas

    2017-02-01

    A very high abundance of atomic carbon in the interstellar medium (ISM), and the high reactivity of these species toward different hydrocarbon molecules including benzene, raise questions regarding the stability of polycyclic aromatic hydrocarbon (PAH) molecules in space. To test the efficiency of destruction of PAH molecules via reactions with atomic carbon, we performed a set of laboratory and computational studies of the reactions of naphthalene, anthracene, and coronene molecules with carbon atoms in the ground state. The reactions were investigated in liquid helium droplets at T = 0.37 K and by quantum chemical computations. Our studies suggest that all small and all large catacondensed PAHs react barrierlessly with atomic carbon, and therefore should be efficiently destroyed by such reactions in a broad temperature range. At the same time, large compact pericondensed PAHs should be more inert toward such a reaction. In addition, taking into account their higher photostability, much higher abundances of pericondensed PAHs should be expected in various astrophysical environments. The barrierless reactions between carbon atoms and small PAHs also suggest that, in the ISM, these reactions could lead to the bottom-up formation of PAH molecules.

  5. Pathways of electrophilic aromatic substitution reactions catalyzed by group 13 trihalides: An ab initio study

    NASA Astrophysics Data System (ADS)

    Volkov, Alexey N.; Timoshkin, Alexey Y.; Suvorov, Andrew V.

    An ab initio study of the two possible pathways of ectrophilic aromatic substitution reaction catalyzed by monomeric and dimeric forms of group 13 metal halides has been performed. Optimized geometries of π, σ-complexes and corresponding transition states have been obtained at second-order Møller-Plesset/ LANL2DZ(d)+ level of theory. It is found that operation of the dimeric pathway is more favorable both thermodynamically and kinetically. Thus, it is expected that catalytical activity of the metal halide will be greatly increased if the stoichiometric ratio 2:1 is employed. Obtained results are in qualitative agreement with available experimental data.

  6. 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.

  7. Evaluating North Sea carbon sources using radiogenic (224Ra and 228Ra) and stable carbon isotope (DI13C) tracers

    NASA Astrophysics Data System (ADS)

    Burt, William; Thomas, Helmuth; Hagens, Mathilde; Brenner, Heiko; Paetsch, Johannes; Clargo, Nikki

    2015-04-01

    In the North Sea, much uncertainty still exists regarding the role of boundary fluxes (e.g. benthic input from sediments or lateral inputs from the coastline) in the overall biogeochemical cycling of the system. The stable carbon isotope signature of dissolved inorganic carbon13C-DIC) is a common tool for following transformations of carbon in the water column and identifying carbon sources and sinks. Here, analyses of the first basin-wide observations of δ13C-DIC reveal that a balance between biological production and respiration, as well as a freshwater input near the European continental coast, predominantly control surface distributions in the North Sea. A strong relationship between the biological component of DIC (DICbio) and δ13C-DIC is then used to quantify the metabolic DIC flux associated with changes in the carbon isotopic signature. Correlations are also found between δ13C-DIC and naturally-occurring Radium isotopes (224Ra and 228Ra), which have well-identified sources from the seafloor and coastal boundaries. The relationship between δ13C-DIC and the longer-lived 228Ra isotope (half-life = 5.8 years) is used to derive a metabolic DIC flux from the European continental coastline. 228Ra is also shown to be a highly effective tracer of North Sea total alkalinity (TA) compared to the more conventional use of salinity as a tracer. Coastal alkalinity inputs are calculated using relationships with 228Ra, and ratios of DIC and TA suggest denitrification as the main metabolic pathway for the formation of these coastal inputs. Finally, coastal TA inputs are translated into inputs of protons to quantify their impact on the buffering capacity of the Southern North Sea.

  8. The role of carbon in the photocatalytic reaction of carbon/TiO2 photocatalysts

    NASA Astrophysics Data System (ADS)

    Teng, Feng; Zhang, Guozhi; Wang, Youqing; Gao, Caitian; Chen, Lulu; Zhang, Peng; Zhang, Zhenxing; Xie, Erqing

    2014-11-01

    The carbon/TiO2 nanocomposites were fabricated by a simple one-step carbonization method with different polymers as precursors. Due to the dehydration carbonation effect of polymers, carbon was formed inside and outside of the TiO2 nanoparticles. The photo-degradation study of rhodamine B was carried out under UV-vis light irradiation, and the photocatalytic activities of carbon/TiO2 nanocomposites are affected severely by the state of carbon, including dopants and coatings. The results show that the carbon on the surface plays more important role in the photocatalytic process.

  9. 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

  10. 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.

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

    PubMed

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

    2010-10-28

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

  12. 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.

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

    PubMed

    Darensbourg, Donald J; Yarbrough, Jason C

    2002-06-05

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

  14. Carbon-13 in black sea waters and implications for the origin of hydrogen sulfide.

    PubMed

    Deuser, W G

    1970-06-26

    A combination of measurements of carbon-13 and the hydrogen sulfide content in Black Sea waters with available data on the total carbon dioxide in these waters indicates that the contribution of organic sulfur to the hydrogen sulfide lies between 3 and 5 percent and increases with depth. Likely causes for the increase are increasing productivity or upward movement of the anoxic zone during the facts last 2000 year.

  15. Test plan for reactions between spent fuel and J-13 well water under unsaturated conditions

    SciTech Connect

    Finn, P.A.; Wronkiewicz, D.J.; Hoh, J.C.; Emery, J.W.; Hafenrichter, L.D.; Bates, J.K.

    1993-01-01

    The Yucca Mountain Site Characterization Project is evaluating the long-term performance of a high-level nuclear waste form, spent fuel from commercial reactors. Permanent disposal of the spent fuel is possible in a potential repository to be located in the volcanic tuff beds near Yucca Mountain, Nevada. During the post-containment period the spent fuel could be exposed to water condensation since of the cladding is assumed to fail during this time. Spent fuel leach (SFL) tests are designed to simulate and monitor the release of radionuclides from the spent fuel under this condition. This Test Plan addresses the anticipated conditions whereby spent fuel is contacted by small amounts of water that trickle through the spent fuel container. Two complentary test plans are presented, one to examine the reaction of spent fuel and J-13 well water under unsaturated conditions and the second to examine the reaction of unirradiated UO{sub 2} pellets and J-13 well water under unsaturated conditions. The former test plan examines the importance of the water content, the oxygen content as affected by radiolysis, the fuel burnup, fuel surface area, and temperature. The latter test plant examines the effect of the non-presence of Teflon in the test vessel.

  16. Metabolism of Methanol in Plant Cells. Carbon-13 Nuclear Magnetic Resonance Studies

    PubMed Central

    Gout, Elizabeth; Aubert, Serge; Bligny, Richard; Rébeillé, Fabrice; Nonomura, Arthur R.; Benson, Andrew A.; Douce, Roland

    2000-01-01

    Using 13C-NMR, we demonstrate that [13C]methanol readily entered sycamore (Acer pseudoplatanus L.) cells to be slowly metabolized to [3-13C]serine, [13CH3]methionine, and [13CH3]phosphatidylcholine. We conclude that the assimilation of [13C]methanol occurs through the formation of 13CH3H4Pte-glutamate (Glu)n and S-adenosyl-methionine, because feeding plant cells with [3-13CH3]serine, the direct precursor of 13CH2H4Pte-Glun, can perfectly mimic [13CH3]methanol for folate-mediated single-carbon metabolism. On the other hand, the metabolism of [13C]methanol in plant cells revealed assimilation of label into a new cellular product that was identified as [13CH3]methyl-β-d-glucopyranoside. The de novo synthesis of methyl-β-d-glucopyranoside induced by methanol did not require the formation of 13CH3H4Pte-Glun and was very likely catalyzed by a “transglycosylation” process. PMID:10806245

  17. Using a Natural Analogue to Investigate Chemical Reactions Associated with Carbon Dioxide Sequestration

    NASA Astrophysics Data System (ADS)

    Navarre-Sitchler, A.; Kaszuba, J.; Thyne, G.

    2008-12-01

    Capture and storage of carbon dioxide in deep underground geologic formations (geologic carbon sequestration) is currently the most advanced technology for reducing or mitigating anthropogenic carbon dioxide emissions. There are a number of scientific challenges associated with injection and storage of large amounts of CO2 in geologic formations. Understanding the chemical reactions that can occur among reservoir rocks, aqueous fluids, and supercritical carbon dioxide ± other gasses is one of these challenges. Natural analogues to CO2 sequestration are systems where carbon dioxide has been stored over geologic time scales. By studying these analogues we can determine important chemical reactions between the host rock and stored gases. The Moxa Arch is a structural feature located in the southern end of the greater Green River Basin, Wyoming. Carbon dioxide and methane were emplaced in Paleozoic rocks, including the 1000 feet thick Mississippian age Madison Limestone, of the Moxa Arch through natural processes. Concentrations of carbon dioxide in the emplaced gas in these formations vary in the region of the Moxa Arch from 70-95% and are as low as ~ 15% in gas producing areas outside of the Moxa Arch. Methane, hydrogen sulfide and helium comprise the balance of the gas compositons. Geochemical reaction path and reactive transport models based upon the mineralogy of 12 core samples collected from three wells completed in the Madison Limestone near the Moxa Arch will be presented. These models help identify potential geochemical reactions between reservoir minerals and stored gasses.

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Diffusion Reaction of Carbon Monoxide in the Human Lung

    NASA Astrophysics Data System (ADS)

    Kang, M.-Y.; Guénard, H.; Sapoval, B.

    2017-08-01

    The capture of CO, a standard lung function test, results from diffusion-reaction processes of CO with hemoglobin inside red blood cells (RBCs). In its current understanding, suggested by Roughton and Forster in 1957, the capture is represented by two independent resistances in series, one for diffusion from the gas to the RBC periphery, the second for internal diffusion reaction. Numerical studies in 3D model structures described here contradict the independence hypothesis. This results from two different theoretical reasons: (i) The RBC peripheries are not equi-concentrations; (ii) diffusion times in series are not additive.

  5. 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.

  6. A spontaneous combustion reaction for synthesizing Pt hollow capsules using colloidal carbon spheres as templates.

    PubMed

    Yang, Ruizhi; Li, Hong; Qiu, Xinping; Chen, Liquan

    2006-05-15

    Here we report a spontaneous combustion reaction in synthesizing Pt hollow capsules. In brief, Pt nanoparticles were loaded on the surface of colloidal carbon spheres by wet-chemical impregnation. When Pt-loaded carbon spheres were taken out of an argon-filled tube furnace at room temperature and exposed to air, they underwent spontaneous combustion. The internal carbon spheres templates were removed to leave nanostructured Pt hollow capsules. There are at least two critical conditions for the occurrence of the spontaneous combustion: the Pt particle size is below 5.8 nm, and the hydrogen content in the carbon spheres is above 2.570 wt %. Such a reaction is interesting for the preparation of metal hollow spheres and is also relevant with respect to removal of accumulated carbon on catalysts and for soot oxidation at room temperature.

  7. Sulfate, Methane, Alkalinity, Calcium and Carbon Isotope (δ13C) Profiles as an Indicator of Upward Methane Flux

    NASA Astrophysics Data System (ADS)

    Chatterjee, S.; Bhatnagar, G.; Chapman, W. G.; Dickens, G. R.; Dugan, B.; Hirasaki, G. J.

    2009-12-01

    The upward flux of methane is an important determinant for the amount of hydrate that may potentially be present in the sediments. One approach to measure methane flux is to relate sulfate methane transition (SMT) depth to the methane flux via anaerobic oxidation of methane (AOM) reaction (Borowski et al., 1996; Dickens and Snyder, 2009). However, numerous prominent authors such as Kastner argue that consumption of pore water sulfate in shallow sediments is a result of oxidation of particulate organic carbon (POC) as opposed to methane. Another contradictory argument between these two groups is based on the carbon isotopic composition (δ13C) of dissolved inorganic carbon (DIC) across the SMT. The articles in Fire in the ice by Kastner et al. (2008) and Dickens and Snyder (2009) focus on these two important arguments in the gas hydrate community and warrant more detailed modeling to help resolve the questions raised by these two groups. We examine the two hypotheses by the two groups and reconcile their interpretations using Bhatnagar’s 1-D model (2008). This model computes methane and sulfate mass balances with both advective and diffusive fluxes. In addition to the mass balances, sulfate consumption reactions following the two pathways (i.e. POC driven and anaerobic oxidation of methane) have been included in the current model. Setting the model parameters to represent zero net flux, and thus assuming a closed system, we are able to justify Kastner’s interpretations. Bicarbonate (DIC) or alkalinity, Ca2+ (for calculating carbonate precipitation), and δ13C in DIC profiles are computed in addition to the sulfate and methane profiles along depth to provide an understanding of the contribution due to the deep bicarbonate flux. This deep flux of bicarbonate profile would validate Dickens’ interpretations and justify the dominance of the AOM reaction for consumption of sulfate in shallow sediments. This model serves as a tool to interpret methane flux with the

  8. 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.

  9. 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).

  10. Confinement effects on chemical reactions in nanostructured carbon materials

    NASA Astrophysics Data System (ADS)

    George, Aaron; Kostov, Milen; Buongiorno Nardelli, Marco

    2005-03-01

    Chemical reactions are frequently carried out in nano-structured media, such as micellar or colloidal solutions, nano-porous media, hydrogels or organogels, or in systems involving nano-particles. Nanostructured environments have been shown to enhance reaction rates through a variety of catalytic effects, such as high surface area, interactions with the nano-structure or confinement. In this work, we have used state-of-the-art electronic structure techniques to study the prototypical example of the hydrogen-producing reaction of formaldehyde dissociation (H2CO -> H2 + CO) within various configurations of a graphitic pore. Using the Nudged Elastic Band (NEB) method for transition states analysis, we have found that the activation energy of the dissociation can be influenced by the presence of a graphitic pore. In particular, while a graphene surface reduces the activation barrier for the reaction, this catalytic effect is enhanced by the presence of two planar sheets, which mimic the geometry of a nano-pore. These findings will be discussed in terms of the charge transfer and/or polarization mechanism associated with the catalytic process.

  11. Silylated Derivatives Retain Carbon and Alter Expected 13C-Tracer Enrichments Using Continuous Flow-Combustion-Isotope Ratio Mass Spectrometry

    PubMed Central

    Shinebarger, Steven R.; Haisch, Michael; Matthews, Dwight E.

    2008-01-01

    Continuous-flow inlets from oxidation reactors are commonly used systems for biological sample introduction into isotope ratio mass spectrometers (IRMS) to measure 13C enrichment above natural abundance. Because the samples must be volatile enough to pass through a gas chromatograph, silylated derivatization reactions are commonly used to modify biological molecules to add the necessary volatility. Addition of a t-butyldimethylsilyl (TBDMS) group is a common derivatization approach. However, we have found that samples do not produce the expected increment in measured 13C abundance as the TBDMS derivatives. We have made measurements of 13C enrichment of leucine and glutamate standards of known 13C enrichment using derivatives without silicon (N-acetyl n-propyl ester), with silicon (TBDMS), and an intermediate case. The measurements of 13C in amino acids derivatized without silicon were as expected. The 13C enrichment measurements using the TBDMS derivative were higher than expected, but could be corrected to produce the expected 13C enrichment measurement by IRMS if one carbon was removed per silicon. We postulate that the silicon in the derivative forms silicon carbide compounds in the heated cupric oxide reactor, rather than forming silicon dioxide. Doing so reduces the amount of CO2 formed from the carbon in the sample. Silylated derivatives retain carbon with the silicon and must be used carefully and with correction factors to measure 13C enrichments by continuous-flow IRMS. PMID:12510745

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

    PubMed

    Ichikawa, Kazuhiko

    2007-01-01

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

  13. 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

  14. Heat of reaction measurements for hydrothermal carbonization of biomass.

    PubMed

    Funke, Axel; Ziegler, Felix

    2011-08-01

    This paper presents a set of calorimetric measurements with the aim of better understanding the calorific nature of hydrothermal carbonization. Presented values so far show an inadequately high scatter to do so, preventing a well funded assessment of the energetic feasibility of this process. The heat released during hydrothermal carbonization at 240°C measured with the applied differential calorimetry setup is -1.06MJ/kg(glucose,daf) with a standard deviation of 14%, -1.07MJ/kg(cellulose,daf) with a standard deviation of 9%, and -0.76MJ/kg(wood,daf) with a standard deviation of 32%. These results are in good agreement with the theoretically derived maximum heat release. Despite the comparably high experimental standard deviation of these results, their accuracy is considerably higher than previously published results.

  15. 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.

  16. A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals.

    PubMed

    Khaled, Fethi; Giri, Binod Raj; Szőri, Milán; Mai, Tam V-T; Huynh, Lam K; Farooq, Aamir

    2017-03-08

    The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning's augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

  17. Reaction Of Single-Wall Carbon Nanotubes With Radicals

    NASA Astrophysics Data System (ADS)

    Lobach, A. S.; Solomentsev, V. V.; Obraztsova, E. D.; Shchegolikhin, A. N.; Sokolov, V. I.

    2004-09-01

    A method for functionalizing the sidewalls of HiPco SWNT via interaction with carbon- and metal-centered radicals is presented. A number of methods: UV-vis-NIR spectroscopy, thermogravimetric analysis, TEM and Raman spectroscopy provided a direct evidence of a chemical attachment of functional groups to the tubes. Functionalization was shown to be reversible: a thermal treatment led to the recovering of pristine structure of SWNT.

  18. High-resolution proton and carbon-13 NMR of membranes: why sonicate

    SciTech Connect

    Oldfield, E.; Bowers, J.L.; Forbes, J.

    1987-11-03

    The authors have obtained high-field (11.7-T) proton and carbon-13 Fourier transform (FT) nuclear magnetic resonance (NMR) spectra of egg lecithin and egg lecithin-chloresterol (1:1) multibilayers, using magic-angle sample spinning (MASS) techniques, and sonicated egg lecithin and egg lecithin-cholesterol (1:1) vesicles, using conventional FT NMR methods. Resolution of the proton and carbon-13 MASS NMR spectra of the pure egg lecithin samples is essentially identical with that of sonicated samples, but spectra of the unsonicated lipid, using MASS, can be obtained very much faster than with the more dilute, sonicated systems. With the 1:1 lecithin-cholesterol system, proton MASS NMR spectra are virtually identical with conventional FT spectra of sonicated samples, while the /sup 13/C NMR, the authors demonstrate that most /sup 13/C nuclei in the cholesterol moiety can be monitored, even though these same nuclei are essentially invisible, i.e., are severely broadened, in the corresponding sonicated systems. In addition, /sup 13/C MASS NMR spectra can again be recorded much faster than with sonicated samples, due to concentration effects. Taken together, these results strongly suggest there will seldom be need in the future to resort to ultransonic disruption of lipid bilayer membranes in order to obtain high-resolution proton or carbon-13 NMR spectra.

  19. 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.

  20. Carbon and electron fluxes during the electricity driven 1,3-propanediol biosynthesis from glycerol.

    PubMed

    Zhou, Mi; Chen, Jingwen; Freguia, Stefano; Rabaey, Korneel; Keller, Jürg

    2013-10-01

    1,3-Propanediol (1,3-PDO) can be produced biologically through glycerol fermentation. While such a process typically involves a pure culture system, particularly for crude glycerol, there would be operational advantages if a mixed population could be used. However, in the latter case the yield is typically low. Here, we use electrical current as the driving force for a mixed population fermenting glycerol in the cathode of a microbial bioelectrochemical system (BES). The carbon and electron flows were monitored by a titration and off-gas analysis (TOGA) sensor, and the syntrophic interactions in the BES were also investigated. Results show that on a carbon yield basis, current enhanced 1,3-PDO production from 24.8% (without current) to 50.1% (with a polarized biocathode at -0.9 V versus standard hydrogen electrode, SHE). Flux analysis indicated that the reductive current can be integrated into glycerol metabolism to enhance 1,3-PDO yield and that glycerol metabolism was redirected from propionate fermentation to 1,3-PDO production. A polarization of -0.6 V (vs SHE) resulted in more fermentative hydrogen production (from 2.7% to 8.0% on electron basis). 1,3-PDO production was also enhanced with hydrogen supply (37.7% on carbon basis), by suppressing hydrogen fermentation. Moreover, interspecies hydrogen transfer encouraged hydrogenotrophic methanogenesis, which was also accelerated by the cathodic polarization.

  1. 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

  2. [Distribution of carbon isotopes ((13)C/(12)C) in cells and temporal organization of cellular processes].

    PubMed

    Ivlev, A A

    1991-01-01

    Recent studies on fractionation of carbon isotopes in biological systems are reviewed. It follows that direct experimental proofs have been obtained that 1) basic fractionation of carbon isotopes in the cell is related to isotope effect in pyruvate decarboxylation; 2) fractionation of carbon isotopes in the above reaction in vivo proceeds with exhausting substrate pool. The latter provides natural relationship between metabolites isotope distribution and sequence of their synthesis in the cell cycle, or with the temporal organization of cellular metabolism. The non-steady and periodic pattern of pyruvate decarboxylation due to the exhausting substrate pool well agrees with the existing notions on reciprocal oscillations in the cell glycolytic chain. Experimental data are presented corroborating indirectly the existence of oscillations in bacterial cells. Earlier proposed model of the mechanism of carbon isotope fractionation based on the above principles can be used for analysing changes in isotopic characteristics of the organisms and interpreting their relations with metabolic processes.

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

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 1,3-Benzenedimethanamine, polymers...-Benzenedimethanamine, polymers with epichlorohydrin-polyethylene glycol reaction products. (a) Chemical substance and..., polymers with epichlorohydrin-polyethylene glycol reaction products (PMN P-03-645; CAS No. 652968-34-8) is...

  4. 40 CFR 721.10472 - 1,3-Benzenedimethanamine, polymers with epichlorohydrin-polyethylene glycol reaction products.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 1,3-Benzenedimethanamine, polymers...-Benzenedimethanamine, polymers with epichlorohydrin-polyethylene glycol reaction products. (a) Chemical substance and..., polymers with epichlorohydrin-polyethylene glycol reaction products (PMN P-03-645; CAS No. 652968-34-8) is...

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

    PubMed

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

    2014-04-14

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

  6. Production of N-13 ammonia using a solid graphite target and the {sup 12}C (d,n) {sup 13}N nuclear reaction

    SciTech Connect

    Dence, C.S.; Welch, M.J.; Hughey, B.J.; Shefer, R.E.; Klinkowstein, R.E.

    1994-12-31

    With the appearance of new low energy accelerators dedicated to the production of short-lived isotopes, comes new approaches to the production of radiopharmaceuticals. The nuclear reaction {sup 12}C(d,n){sup 13}N was chosen for this study because of its low energy threshold (0.33 MeV) and therefore compatibility with these low energy accelerators. Low porosity graphite was chosen as the target material; irradiated graphite has been used since 1940 to extract N-13 for biological studies (4-8) but in most cases the activity was obtained as N-13 nitrogen. Kjeldahl digestion and microwave irradiation have also been applied to obtain N-13 ammonia. The authors studied the extraction of N-13 nitrogen from a solid graphite target after deuteron beam irradiation and heated in an atmosphere of pure oxygen, the authors identified the species formed and converted them to N-13 ammonia.

  7. Characterization, preparation, and reaction mechanism of hemp stem based activated carbon

    NASA Astrophysics Data System (ADS)

    Zhang, Ji; Gao, Jianmin; Chen, Yao; Hao, Xinmin; Jin, Xiaojuan

    In this study, hemp stem was used to prepare high surface area activated carbon (AC) by KOH activation. The structure, characterization, thermal and structure analysis on reaction mechanisms of AC were investigated via N2 adsorption-desorption isotherm, Fourier transform infrared (FTIR) spectroscopy and thermogravimetric-mass (TG-MS) spectrometry. Results show that when the impregnation ratio is 4.5:1 (KOH/char), the activation temperature is 800 °C, and the activation time is 1.5 h, AC has the highest specific surface area of 2388 m2·g-1 and exhibits narrow pore size distributions with maxima in the micropore areas. The reaction mechanism of AC from hemp stems by KOH activation is as follows: In the first carbonization stage, it is primarily because of the substitution, scission, and oxidization reactions of methylene. Then in the second activation stage, it is mainly related to polycyclic reactions, reactions between carbon and KOH, and reactions between intermediate potassium oxide species and carbon.

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

    PubMed

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

    2014-01-21

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

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

    PubMed

    Huijgen, Wouter J J; Comans, Rob N J

    2006-04-15

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

  10. 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.

  11. 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.

  12. The ^12C(^7Li,^6Li)^13C Transfer Reaction

    NASA Astrophysics Data System (ADS)

    Bartosz, E. E.; Keeley, N.; Kemper, K. W.

    2001-04-01

    We present the first complete set of analysing powers, including all third rank ones, for a ^7Li induced transfer reaction. Data were obtained for transfers to the 1/2^-, 1/2^+ and 5/2^+ states of ^13C at 0.0, 3.09 and 3.85 MeV excitation energies respectively, induced by a 34 MeV polarised ^7Li beam. This experiment was motivated by the complete failure of previous DWBA and CCBA calculations to describe transfers to the 1/2^+ state (K.W. Kemper, et al./, Phys. Rev. C 38, 2664 (1988).). Extensive coupled-discretised-continuum-channels (CDCC) calculations using cluster-folding (CF) model form-factors have been carried out and show that the failure to describe the 1/2^+ data is not a result of a dynamical effect.

  13. 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.

  14. 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.

  15. 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.

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

    PubMed

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

    2012-10-04

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

  17. 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.

  18. Cluster Emission in 13C + 12C and 12C + 12C Reactions at ~ 6 Mev/nucleon

    NASA Astrophysics Data System (ADS)

    Rana, T. K.; Bhattacharya, C.; Kundu, S.; Banerjee, K.; Bhattacharya, S.; Mukherjee, G.; Ghosh, T. K.; Meena, J. K.; Dhara, P.; Biswas, M.; Pai, H.; Mahata, K.; Kumar, Suresh; Ramachandran, K.; Rout, P. C.; Pandit, S. K.; Nanal, V.; Pillay, R. G.

    Cluster state formation viz. the population of unbound 8Be and the Hoyle state of 12C produced in the reactions 12C(77 MeV) + 12C and 13C(75 MeV) + 12C have been studied using resonance particle spectroscopy. It was observed that there is a large difference in the cluster state formation in these two reactions and the yield of neutron rich isotopes of different fragments is more in the 13C + 12C compared to 12C + 12C reactions at 6 MeV/u.

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

    PubMed

    Haarstad, Ketil; Mæhlum, Trond

    2013-01-01

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

  20. 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

  1. 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.

  2. 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 supported

  3. 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

  4. Carbon monoxide gas sensing using zinc oxide deposited by successive ionic layer adhesion and reaction

    NASA Astrophysics Data System (ADS)

    Florido, E. A.; Dagaas, N. A. C.

    2017-05-01

    This study was aimed to determine the carbon monoxide (CO) gas sensing capability of zinc oxide (ZnO) film fabricated by successive ionic layer adsorption and reaction (SILAR) on glass substrate. Films consisting of a mixture of flower-like clusters of ZnO nanorods and nanowires were observed using scanning electron microscopy (SEM). Current-voltage characterization of the samples showed an average resistivity of 13.0 Ω-m. Carbon monoxide gas was synthesized by mixing the required amount of formic acid and excess sulfuric acid to produce CO gas concentrations of 100, 200, 300, 400, and 500 parts per million (ppm) v/v with five trials for each concentration. Two sets of data were obtained. One set consisted of the voltage response of the single film sensor while the other set were obtained from the double film sensor. The voltage response for the single film sensor and the double film sensor showed an average sensitivity of 0.0038 volts per ppm and 0.0024 volts per ppm, respectively. The concentration the single film can detect with a 2V output is 526 ppm while the double film sensor can detect up to 833 ppm with a 2V output. This shows that using the double film sensor is advantageous compared to single film sensor, because of its higher concentration range due to the larger surface area for the gas to interact. Moreover, the measured average resistance for the single film sensor was 10 MΩ while for the double film sensor the average resistance was 5 MΩ.

  5. Direct formation of ring-fused 1,3-thiazine-2,4-dithiones from aromatic o-amino carboxylic acids: observation of a carbon disulfide mediated thionation.

    PubMed

    Ottersbach, Philipp A; Elsinghorst, Paul W; Häcker, Hans-Georg; Gütschow, Michael

    2010-08-20

    A facile synthesis of 2H-3,1-benzothiazine-2,4(1H)-dithiones (trithioisatoic anhydrides) or 2H-naphtho[2,3-d][1,3]thiazine-2,4(1H)-dithione solely from anthranilic acids or 3-amino-2-naphthoic acid and carbon disulfide, performed at room temperature in 1,4-dioxane in the presence of Et(3)N, is reported. Corresponding 2-alkylsulfanyl derivatives were obtained in one-pot reactions under the same conditions after addition of alkyl halides. The mechanism of the thiazine cyclization was investigated using (13)C-labeled carbon disulfide to reveal that carbon disulfide was incorporated into the heterocycle and additionally acted as a thionation reagent.

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

    SciTech Connect

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

    2011-05-01

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

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

    SciTech Connect

    Pol, Vilas G.; Thackeray, Michael M.

    2010-01-01

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

  8. Carbon nanotube inner phase chemistry: the Cl- exchange SN2 reaction.

    PubMed

    Halls, Mathew D; Raghavachari, Krishnan

    2005-10-01

    Density functional calculations have been carried out to investigate the nature of the inner phase of a (6,6) carbon nanotube, using the Cl(-) exchange S(N)2 reaction as an indicator. Inside the carbon nanotube the classical barrier height increases by 6.6 kcal/mol due to the nanotube polarizability. This suggests that the inner phase environment can be considered a form of solid solvation, offering the possibility of obtaining altered guest properties and reactivity through dielectric stabilization.

  9. 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Unsteady flow of carbon nanotubes with chemical reaction and Cattaneo-Christov heat flux model

    NASA Astrophysics Data System (ADS)

    Hayat, Tasawar; Kiran, Asmara; Imtiaz, Maria; Alsaedi, Ahmed

    Present analysis examines boundary layer flow of carbon nanotubes over a curved stretching surface. Instead of classical Fourier law we employed Cattaneo-Christov heat flux theory. The heterogeneous reaction taking place on the wall surface are given by isothermal cubic autocatalytic kinetics. The homogeneous reaction occurring in the ambient fluid are governed by first order kinetics. Appropriate transformations are employed to obtain system of nonlinear ordinary differential equations. Convergent series solution are obtained. Single and multi wall carbon nanotubes are used. Water is taken as a base fluid. Fluid flow, temperature, concentration, skin friction coefficient and Nusselt number are examined and analyzed for different involved parameters.

  11. 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.

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

    SciTech Connect

    Dave, Bhasker B.

    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, DO1/2CO, estimated by the cyclic voltammetry concurred with that calculated by the EIS technique. The temperature dependence of the exchange current density and the product DO1/2CO were examined and the apparent activation energies were determined to be about 122 and 175 kJ/ mol, respectively.

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  14. Reaction kinetics of CO2 carbonation with Mg-rich minerals.

    PubMed

    Kwon, Soonchul; Fan, Maohong; Dacosta, Herbert F M; Russell, Armistead G; Tsouris, Costas

    2011-07-07

    Due to their low price, wide availability, and stability of the resulting carbonates, Mg-rich minerals are promising materials for carbonating CO(2). Direct carbonation of CO(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(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(2)SiO(4)), a representative compound in Mg-rich minerals, was used to study CO(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(2) is obtained from experimental data. The Arrhenius form of CO(2) carbonation with Mg(2)SiO(4) is established based on changes in the rate constants of the chosen deactivation model as a function of temperature.

  15. Surface reactions of carbon dioxide at the adsorbed water-iron oxide interface.

    PubMed

    Baltrusaitis, Jonas; Grassian, Vicki H

    2005-06-30

    Despite the fact that carbon dioxide is an abundant atmospheric gas with profound environmental implications, there is little information on the reaction of carbon dioxide at the adsorbed water-oxide interface. In this study, the chemistry of carbon dioxide at the adsorbed water-iron oxide interface is investigated with FTIR spectroscopy. As shown here, the thin water layer on the iron oxide surface plays an important role in the surface chemistry of carbon dioxide. In particular, adsorbed water enhances CO(2) uptake, undergoes isotope exchange with CO(2) in O(18)-labeled experiments, and influences the chemical nature of the predominant adsorbed product on the surface from bicarbonate to carbonate. The resultant thin water film is acidic in nature from the reaction of CO(2). The IR spectrum recorded of adsorbed carbonate at the adsorbed water-iron oxide interface is remarkably similar to that at the bulk liquid water-iron oxide interface. Since reactions in thin water films estimated to be approximately 2 layers will play a role in a number of environmental processes, it is essential to understand the chemistry of these "wet" interfaces with atmospheric gases.

  16. Coincidence Analyzing-Power Measurements of the Reaction Carbon

    NASA Astrophysics Data System (ADS)

    Lyndon, Christopher Robinson

    Analyzing-power measurements A_sp {n}{coinc}, A_sp {s}{coinc}, and A_sp {l}{coinc} are presented for the reaction ^{12}C( vec p ,p^'gamma) ^{12}C^{* } (15.11 MeV). A polarized proton beam at 318 MeV was used and data were taken for 3 mutually perpendicular directions of polarization. A scintillator hodoscope was used for scattered proton detection and 4 BGO detectors for the 15.11 MeV gamma-ray. Data are presented for 8 azimuthal directions of the scattered proton around the beam direction, and for the polar angles averaged between 3.3^circ and 11.2^circ. The data are compared with non-relativistic calculations (DW81) and relativistic calculations with explicit treatment of exchange (DREX). The average size of the asymmetries measured is comparable to these predictions but does not agree closely with either prediction.

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

    DOEpatents

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

    2004-01-13

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

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

    DOEpatents

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

    2002-11-12

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

  19. Kinetics and mechanism of the catalytic reaction between alcohols and dimethyl carbonate

    NASA Astrophysics Data System (ADS)

    Koledina, K. F.; Koledin, S. N.; Shchadneva, N. A.; Gubaidullin, I. M.

    2017-03-01

    The mechanism of the reaction between alcohols and dimethyl carbonate, catalyzed by dicobalt octacarbonyl Co2(CO)8, is studied by means of mathematical modeling. Kinetic models for possible schemes of chemical transformations are constructed at different initial concentrations of the catalyst. Based on a comparative analysis of activation energies of possible stages of chemical transformations, possible reaction pathways are determined and an appropriate mechanism is selected.

  20. Interference effects between /sup 17/O states populated in the /sup 13/C(/sup 6/Li,d)/sup 17/O*. --> cap alpha. +/sup 13/C reaction

    SciTech Connect

    Cardella, G.; Cunsolo, A.; Foti, A.; Imme, G.; Pappalardo, G.; Raciti, G.; Rizzo, F.; Alamanos, N.; Berthier, B.; Saunier, N.

    1987-12-01

    An analysis of the /sup 13/C(/sup 6/Li,d..cap alpha..)/sup 13/C reaction in the collinear (theta/sub d/ = 0/sup 0/) and noncollinear (theta/sub d/ = 10/sup 0/,8/sup 0/) geometry is made for two peaks observed in the deuteron energy spectrum and corresponding to excitation energies of 16.1 and 13.6 MeV in the /sup 17/O nucleus. It is shown that the reaction proceeds via a direct alpha-transfer process which populates doublets of interfering /sup 17/O levels. Spins, weights, and parities of these levels are obtained by means of a least square procedure.

  1. 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.

  2. 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.

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

    SciTech Connect

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

    1999-09-01

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

  4. Elemental quantitation of carbon via production of polyatomic anions in gas chromatography-plasma assisted reaction chemical ionization mass spectrometry.

    PubMed

    Haferl, Peter J; Zheng, Kunyu; Wang, Haopeng; Jorabchi, Kaveh

    2017-06-01

    Elemental mass spectrometry offers quantitation and isotopic analysis without the need for compound-specific standards. We have recently introduced plasma assisted reaction chemical ionization (PARCI) as an efficient elemental ionization method for halogens. Here, we report a new ionization chemistry in PARCI for facile quantitation of elemental carbon in gas chromatography eluates. We demonstrate that in-plasma reactions of organic compounds followed by afterglow ionization lead to formation of polyatomic anions (CN(-), OCN(-), and CO3(-)), among which CN(-) offers the best analytical sensitivity with a detection limit of ~25 pg (21 pg/s) carbon on column. Using a mixture of pesticides with wide variations in structures and heteroatom content, we demonstrate that CN(-) ion response is quantitatively correlated with the carbon concentration over two orders of magnitude (r (2) = 0.985). We show that the novel GC-PARCI-MS method provides recoveries within 80-120% using a single standard for all analytes, highlighting the strength of elemental quantitation. Further, the ability of GC-PARCI-MS to identify (13)C-tagged molecules without a priori knowledge of chemical formulas of analytes is demonstrated. Graphical abstract ᅟ.

  5. Tracing carbon monoxide uptake by Clostridium ljungdahlii during ethanol fermentation using (13)C-enrichment technique.

    PubMed

    Yun, Seok-In; Gang, Seong-Joo; Ro, Hee-Myong; Lee, Min-Jin; Choi, Woo-Jung; Hong, Seong-Gu; Kang, Kwon-Kyoo

    2013-05-01

    Conversion of synthesis gas (CO and H2) to ethanol can be an alternative, promising technology to produce biofuels from renewable biomass. To distinguish microbial utilization of carbon source between fructose and synthesis gas CO and to evaluate biological production of ethanol from CO, we adopted the (13)C-enrichment of the CO substrate and hypothesized that the residual increase in δ(13)C of the cell biomass would reflect the increased contribution of (13)C-enriched CO. Addition of synthesis gas to live culture medium for ethanol fermentation by Clostridum ljungdahlii increased the microbial growth and ethanol production. Despite the high (13)C-enrichment in CO (99 atom % (13)C), however, microbial δ(13)C increased relatively small compared to the microbial growth. The uptake efficiency of CO estimated using the isotope mass balance equation was also very low: 0.0014 % for the low CO and 0.0016 % for the high CO treatment. Furthermore, the fast production of ethanol in the early stage indicated that the presence of sugar in fermentation medium would limit the utilization of CO as a carbon source by C. ljungdahlii.

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

    PubMed

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

    2002-04-10

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

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

    PubMed

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

    2015-07-20

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

  8. 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.

  9. Mapping carbon fate during bleaching in a model cnidarian symbiosis: the application of (13) C metabolomics.

    PubMed

    Hillyer, Katie E; Dias, Daniel A; Lutz, Adrian; Roessner, Ute; Davy, Simon K

    2017-03-08

    Coral bleaching is a major threat to the persistence of coral reefs. Yet we lack detailed knowledge of the metabolic interactions that determine symbiosis function and bleaching-induced change. We mapped autotrophic carbon fate within the free metabolite pools of both partners of a model cnidarian-dinoflagellate symbiosis (Aiptasia-Symbiodinium) during exposure to thermal stress via the stable isotope tracer ((13) C bicarbonate), coupled to GC-MS. Symbiont photodamage and pronounced bleaching coincided with substantial increases in the turnover of non(13) C-labelled pools in the dinoflagellate (lipid and starch store catabolism). However, (13) C enrichment of multiple compounds associated with ongoing carbon fixation and de novo biosynthesis pathways was maintained (glucose, fatty acid and lipogenesis intermediates). Minimal change was also observed in host pools of (13) C-enriched glucose (a major symbiont-derived mobile product). However, host pathways downstream showed altered carbon fate and/or pool composition, with accumulation of compatible solutes and nonenzymic antioxidant precursors. In hospite symbionts continue to provide mobile products to the host, but at a significant cost to themselves, necessitating the mobilization of energy stores. These data highlight the need to further elucidate the role of metabolic interactions between symbiotic partners, during the process of thermal acclimation and coral bleaching.

  10. Organic carbon isotope ratios (δ13C) of Arctic Amerasian Continental shelf sediments

    NASA Astrophysics Data System (ADS)

    Naidu, A. S.; Cooper, L. W.; Finney, B. P.; Macdonald, R. W.; Alexander, C.; Semiletov, I. P.

    2000-09-01

    Organic matter origins are inferred from carbon isotope ratios (δ13C) in recent continental shelf sediments and major rivers from 465 locations from the north Bering-Chukchi-East Siberian-Beaufort Sea, Arctic Amerasia. Generally, there is a cross-shelf increase in δ13C, which is due to progressive increased contribution seaward of marine-derived organic carbon to surface sediments. This conclusion is supported by the correlations between sediment δ13C, OC/N, and δ15N. The sources of total organic carbon (TOC) to the Amerasian margin sediments are primarily from marine water-column phytoplankton and terrigenous C3 plants constituted of tundra taiga and angiosperms. In contrast to more temperate regions, the source of TOC from terrigenous C4 and CAM plants to the study area is probably insignificant because these plants do not exist in the northern high latitudes. The input of carbon to the northern Alaskan shelf sediments from nearshore kelp community (Laminaria solidungula) is generally insignificant as indicated by the absence of high sediment δ13C values (-16.5 to -13.6‰) which are typical of the macrophytes. Our study suggests that the isotopic composition of sediment TOC has potential application in reconstructing temporal changes in delivery and accumulation of organic matter resulting from glacial-interglacial changes in sea level and environments. Furthermore, recycling and advection of the extensive deposits of terrestrially derived organic matter from land, or the wide Amerasian margin, could be a mechanism for elevating total CO2 and pCO2 in the Arctic Basin halocline.

  11. Using Isotope Ratio Infrared Spectrometer to determine δ13C and δ18O of carbonate samples

    NASA Astrophysics Data System (ADS)

    Smajgl, Danijela; Stöbener, Nils; Mandic, Magda

    2017-04-01

    The isotopic composition of calcifying organisms is a key tool for reconstruction past seawater temperature and water chemistry. Therefore stable carbon and oxygen isotopes (δ13C and δ18O) in carbonates have been widely used for reconstruction of paleoenvironments. Precise and accurate determination of isotopic composition of carbon (13C) and oxygen (18O) from carbonate sample with proper referencing and data evaluation algorithm presents a challenge for scientists. Mass spectrometry was the only widely used technique for this kind of analysis, but recent advances make laser based spectroscopy a viable alternative. The Thermo Scientific Delta Ray Isotope Ratio Infrared Spectrometer (IRIS) analyzer with the Universal Reference Interface (URI) Connect is one of those alternatives and with TELEDYNE Cetac ASX-7100 autosampler extends the traditional offerings with a system of high precision and throughput of samples. To establish precision and accuracy of measurements and also to develop optimal sample preparation method for measurements with Delta Ray IRIS and URI Connect, IAEA reference materials were used. Preparation is similar to a Gas Bench II method. Carbonate material is added into the vials, flushed with CO2 free synthetic air and acidified with few droplets of 104% H3PO4. Sample amount used for analysis can be as low as 200 μg. Samples are measured after acidification and equilibration time of one hour at 70°C. The CO2 gas generated by reaction is flushed into the variable volume inside the URI Connect through the Nafion based built-in water trap. For this step, carrier gas (CO2 free air) is used to flush the gas from the vial into the variable volume with a maximum volume of 100 ml. A small amount of the sample is then used for automatic concentration determination present in the variable volume. The Thermo Scientific Qtegra Software automatically adjusts any additional dilution of the sample to achieve the desired concentration (usually 400 ppm) in the

  12. The impact of carbon-13 and deuterium on relative quantification of proteins using stable isotope diethyl labeling.

    PubMed

    Koehler, Christian J; Arntzen, Magnus Ø; Thiede, Bernd

    2015-05-15

    Stable isotopic labeling techniques are useful for quantitative proteomics. A cost-effective and convenient method for diethylation by reductive amination was established. The impact using either carbon-13 or deuterium on quantification accuracy and precision was investigated using diethylation. We established an effective approach for stable isotope labeling by diethylation of amino groups of peptides. The approach was validated using matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) and nanospray liquid chromatography/electrospray ionization (nanoLC/ESI)-ion trap/orbitrap for mass spectrometric analysis as well as MaxQuant for quantitative data analysis. Reaction conditions with low reagent costs, high yields and minor side reactions were established for diethylation. Furthermore, we showed that diethylation can be applied to up to sixplex labeling. For duplex experiments, we compared diethylation in the analysis of the proteome of HeLa cells using acetaldehyde-(13) C(2)/(12) C(2) and acetaldehyde-(2) H(4)/(1) H(4). Equal numbers of proteins could be identified and quantified; however, (13) C(4)/(12) C(4) -diethylation revealed a lower variance of quantitative peptide ratios within proteins resulting in a higher precision of quantified proteins and less falsely regulated proteins. The results were compared with dimethylation showing minor effects because of the lower number of deuteriums. The described approach for diethylation of primary amines is a cost-effective and accurate method for up to sixplex relative quantification of proteomes. (13) C(4)/(12) C(4) -diethylation enables duplex quantification based on chemical labeling without using deuterium which reduces identification of false-negatives and increases the quality of the quantification results. Copyright © 2015 John Wiley & Sons, Ltd.

  13. The reaction of SRL 202 glass in J-13 and DIW

    SciTech Connect

    Ebert, W.L.; Bates, J.K.; Buck, E.C.

    1992-12-31

    Static leach tests were performed in both 304L stainless steel and Teflon vessels using a synthetic high-level waste glass with either deionized water (DIW) or a tuff groundwater solution as the leachant to assess the effects of the vessel and the initial leachant composition on the extent and nature of the glass reaction. The tests were performed using monolith samples at 340 m{sup {minus}1} and crushed samplesat 2000 m{sup {minus}1} for times up to 1 year. The results show less silicon is released from the glass into the groundwater solution than into DIW at both high and low glass surface area/leachant volume ratios (SAN), but the alkali metal and boron releases are not affected by the leachant used. Tests performed in a stainless steel vessel resulted in slightly lower leachate pH values, but similar reaction rates to those performed in a Teflon vessel, as measured by the boron release. Blank tests with DIW or EJ-13 in the vessels showed the Teflon vessels to release small amounts of fluoride (1 to 2 ppm) and to acidify the DIW slightly (4.0 < pH < 5.6). The pH values of blank tests with EJ- 1 3 increased from 8.2 to about 8.6 in steel and to about 9.2 in Teflon vessels. The slightly higher pH values attained in Teflon vessels are attributed to outgassing of CO{sub 2} during the test.

  14. 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.

  15. 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.

  16. 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.

  17. Characterisation of Dissolved Organic Carbon by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Materić, Dušan; Peacock, Mike; Kent, Matthew; Cook, Sarah; Gauci, Vincent; Röckmann, Thomas; Holzinger, Rupert

    2017-04-01

    Dissolved organic carbon (DOC) is an integral component of the global carbon cycle. DOC represents an important terrestrial carbon loss as it is broken down both biologically and photochemically, resulting in the release of carbon dioxide (CO2) to the atmosphere. The magnitude of this carbon loss can be affected by land management (e.g. drainage). Furthermore, DOC affects autotrophic and heterotrophic processes in aquatic ecosystems, and, when chlorinated during water treatment, can lead to the release of harmful trihalomethanes. Numerous methods have been used to characterise DOC. The most accessible of these use absorbance and fluorescence properties to make inferences about chemical composition, whilst high-performance size exclusion chromatography can be used to determine apparent molecular weight. XAD fractionation has been extensively used to separate out hydrophilic and hydrophobic components. Thermochemolysis or pyrolysis Gas Chromatography - Mass Spectrometry (GC-MS) give information on molecular properties of DOC, and 13C NMR spectroscopy can provide an insight into the degree of aromaticity. Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. So far, PTR-MS has been used in various environmental applications such as real-time monitoring of volatile organic compounds (VOCs) emitted from natural and anthropogenic sources, chemical composition measurements of aerosols etc. However, as the method is not compatible with water, it has not been used for analysis of organic traces present in natural water samples. The aim of this work was to develop a method based on thermal desorption PTR-MS to analyse water samples in order to characterise chemical composition of dissolved organic carbon. We developed a clean low-pressure evaporation/sublimation system to remove water from samples and thermal desorption system to introduce

  18. Theoretical studies on the regioselectivity of iridium-catalyzed 1,3-dipolar azide-alkyne cycloaddition reactions.

    PubMed

    Luo, Qiong; Jia, Guochen; Sun, Jianwei; Lin, Zhenyang

    2014-12-19

    Iridium-catalyzed cycloaddition of thioalkynes and bromoalkynes with azides have been investigated with the aid of density functional theory (DFT) calculations at the M06 level of theory. Our investigation focused on the different regioselectivity observed for the reactions of the two classes of alkynes. The DFT results have shown that the mechanisms of cycloaddition reactions using thioalkynes and bromoalkynes as substrates are similar yet different. The reactions of thioalkynes occur via a metallabicyclic Ir-carbene intermediate formed through alkyne-azide oxidative coupling via attack of the azide terminal nitrogen toward the β alkyne carbon, whose carbene ligand is stabilized by an alkylthio/arylthio substituent. Reductive elimination from the intermediate leads to the formation of the experimentally observed 5-sulfenyltriazole. In the reactions of bromoalkynes RC≡CBr, the reaction mechanism involves the initial formation of a six-membered-ring metallacycle intermediate in the oxidative coupling step. The six-membered-ring intermediate then undergoes isomerization via migrating the terminal azide nitrogen from the β carbon to the α carbon to form a much less stable metallabicyclic Ir-carbene species from which reductive elimination gives 4-bromotriazole.

  19. The oxidation of carbon monoxide on polycrystalline rhodium under knudsen conditions. II. Reaction with nitrogen monoxide

    NASA Astrophysics Data System (ADS)

    Lintz, Hans-Günther; Weisker, Tilman

    1985-09-01

    The reaction between carbon monoxide and nitrogen monoxide on a polycrystalline rhodium ribbon under stationary conditions is followed by mass spectrometry. In the temperature range 300 to 1100 K the ratio of the partial pressures of the reactants varies between 0.1 < pNO/ pCO < 100 at values of the total pressure in the reactor from 10 -4 to 10 -5 Torr. The results can be interpreted qualitatively by a simple elementary reaction sequence. Simulation using literature values of the kinetic constants leads to semi-quantitative agreement with experimental results. No isothermal oscillations of the reaction rate could be observed under the stated conditions.

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

    PubMed

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

    2015-06-15

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

  1. 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.

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

    SciTech Connect

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

    2005-10-16

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

  4. 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.

  5. Computational methods to calculate accurate activation and reaction energies of 1,3-dipolar cycloadditions of 24 1,3-dipoles.

    PubMed

    Lan, Yu; Zou, Lufeng; Cao, Yang; Houk, K N

    2011-12-01

    Theoretical calculations were performed on the 1,3-dipolar cycloaddition reactions of 24 1,3-dipoles with ethylene and acetylene. The 24 1,3-dipoles are of the formula X≡Y(+)-Z(-) (where X is HC or N, Y is N, and Z is CH(2), NH, or O) or X═Y(+)-Z(-) (where X and Z are CH(2), NH, or O and Y is NH, O, or S). The high-accuracy G3B3 method was employed as the reference. CBS-QB3, CCSD(T)//B3LYP, SCS-MP2//B3LYP, B3LYP, M06-2X, and B97-D methods were benchmarked to assess their accuracies and to determine an accurate method that is practical for large systems. Several basis sets were also evaluated. Compared to the G3B3 method, CBS-QB3 and CCSD(T)/maug-cc-pV(T+d)Z//B3LYP methods give similar results for both activation and reaction enthalpies (mean average deviation, MAD, < 1.5 kcal/mol). SCS-MP2//B3LYP and M06-2X give small errors for the activation enthalpies (MAD < 1.5 kcal/mol), while B3LYP has MAD = 2.3 kcal/mol. SCS-MP2//B3LYP and B3LYP give the reasonable reaction enthalpies (MAD < 5.0 kcal/mol). The B3LYP functional also gives good results for most 1,3-dipoles (MAD = 1.9 kcal/mol for 17 common 1,3-dipoles), but the activation and reaction enthalpies for ozone and sulfur dioxide are difficult to calculate by any of the density functional methods.

  6. 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.

  7. 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.

  8. 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.

  9. Aluminium coordination complexes in copolymerization reactions of carbon dioxide and epoxides.

    PubMed

    Ikpo, Nduka; Flogeras, Jenna C; Kerton, Francesca M

    2013-07-07

    Al complexes are widely used in a range of polymerization reactions (ROP of cyclic esters and cationic polymerization of alkenes). Since the discovery in 1978 that an Al porphyrin complex could copolymerize propylene oxide with carbon dioxide, Al coordination compounds have been studied extensively as catalysts for epoxide-carbon dioxide copolymerizations. The most widely studied catalysts are Al porphyrin and Al salen derivatives. This is partially due to their ability to act as mechanistic models for more reactive, paramagnetic Cr catalysts. However, this in depth mechanistic understanding could be employed to design more active Al catalysts themselves, which would be beneficial given the wide availability of this metal. Polymerization data (% CO3 linkages, M(n), M(w)/M(n) and TON) for these complexes are presented and mechanisms discussed. In most cases, especially those employing square-based pyramidal Al complexes, co-catalysts are required to obtain high levels of carbon dioxide incorporation. However, in some cases, the use of co-catalysts inhibits the copolymerization reaction. Lewis acidic Al phenolate complexes have been used as activators in CHO-carbon dioxide copolymerizations to increase TOF and this has recently led to the development of asymmetric copolymerization reactions. Given the ready availability of Al, the robustness of many complexes (e.g. use in immortal polymerizations) and opportunity to prepare block copolymers and other designer materials, Al complexes for copolymerization of carbon dioxide are surely worth a second look.

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

    PubMed

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

    2012-05-01

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

  11. Carbon sequestration via reaction with basaltic rocks: Geochemical modeling and experimental results

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

    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. 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.

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

    SciTech Connect

    Bowers, J.L.; Oldfield, E.

    1988-07-12

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

  14. Background levels of carbon-13 reduced in breath and stool by new infant formula.

    PubMed

    Boutton, T W; Hopkinson, J M; Benton, D A; Klein, P D

    1988-01-01

    Studies of the absorption and bioavailability of nutrients naturally enriched with 13C require accurate measurements of small increases of 13C in respiratory CO2 and stool carbon. The sensitivity of these measurements would be increased if the natural background of 13C in these excreta were reduced. We have developed a 13C-depleted infant formula based on lactose, whey, and casein from New Zealand cows that consume only C3 vegetation naturally low in 13C. This formula, designated CNRC3, was produced by a commercial infant formula manufacturer and was comparable with a 60:40 whey/casein product. To test the ability of the formula to reduce baseline levels of 13C in infant excreta, 10 formula-fed infants 28-60 days old and free of metabolic disorders were enrolled in the 9-day study. Two stool samples were collected daily. Infants received their usual formula on days 1 and 2 and were switched to CNRC3 formula for days 3-9. On days 2 and 9, seven breath samples were collected at 30-min intervals with a face mask. Breath and stool samples were analyzed for 13C content by gas isotope ratio mass spectrometry. Infants consuming their commercial formula had breath delta 13C values of -21.1 +/- 0.6% over the 3-h collection period; stool values were -22.9 +/- 0.4%. After 7 days on the CNRC3 formula, delta 13C values of breath declined by 5.6% to -26.7 +/- 0.7%; stool values declined by 3.0% to -25.6 +/- 0.5%. The reduced background of 13C achieved by the CNRC3 formula can improve resolution of excess 13C from naturally enriched substrates in infant breath by approximately 50% and in stool by approximately 30%.

  15. 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

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

    PubMed Central

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

    2014-01-01

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

  17. Synergy among manganese, nitrogen and carbon to improve the catalytic activity for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Kang, Jian; Wang, Hui; Ji, Shan; Key, Julian; Wang, Rongfang

    2014-04-01

    A highly active electrocatalyst for oxygen reduction reaction, manganese modified glycine derivative-carbon (Mn-CNx), is synthesized by a two-step carbonizing process. X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy are used to characterize structure and morphology of the catalysts. Electrochemical tests show that Mn-CNx has higher catalytic activity for oxygen reduction reaction than CNx derived glycine and Mn modified Vulcan carbon. Moreover, the half-wave potential of Mn-CNx is only 12 mV lower than that of commercial Pt/C. Mn-CNx also has excellent durability to methanol crossover in alkaline solution, and thus provides a promising low cost, non-precious metal cathode catalyst for fuel cells.

  18. Pt loaded carbon aerogel catalyst for catalytic exchange reactions between water and hydrogen gas

    NASA Astrophysics Data System (ADS)

    Singh, Rashmi; Singh, Ashish; Kohli, D. K.; Singh, M. K.; Gupta, P. K.

    2013-06-01

    We report development and characterization of platinum doped carbon aerogel catalyst for catalytic exchange reactions between water and hydrogen gas. The carbon aerogel with uniformly dispersed platinum nanoparticles was prepared by adding platinum precursor during the sol-gel process. Thereafter colloidal PTFE was mixed with the platinum doped carbon aerogel powder and coated on Dixon rings to obtain hydrophobic catalyst with required mechanical strength. Detailed studies have been carried out to observe the effect of physical characteristics of the catalyst powder (surface area and pore size of aerogels, Pt cluster size and its valence state etc) and the different coating parameters (PTFE to Pt-CA ratio and Pt loading on Dixon ring) on volume transfer rate (Ky.a) for H/D reaction. Ky.a values of ˜0.8 m3 (STP).s-1. m-3 were obtained for Pt loading of 7% and Pt cluster size of 3 nm at atmospheric pressure.

  19. 13C NMR investigations of the metallic state of Li intercalated carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Schmid, M.; Goze-Bac, C.; Mehring, M.; Roth, S.; Bernier, P.

    2003-10-01

    13C Nuclear Magnetic Resonance measurements were performed on pristine and lithium intercalated single wall carbon nanotubes (SWNT). We investigated the NMR signatures by means of static and high resolution Magic Angle Spinning experiments. This allows us to measure in detail the modifications of the lineshape with the Li concentration. Our results can be explained in terms of charge transfer and changes of the metallic state with an increasing density of states at the Fermi level compared to the pristine SWNT.

  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. 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.

  2. 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.

  3. Formal (2 + 2 + 2) cycloaddition of molecular oxygen, 1,3-diketone, and olefin. Synthesis and reactions of cyclic peroxides

    SciTech Connect

    Yoshida, Junichi; Nakatani, Shogo; Sakaguchi, Kazuhiko; Isoe, Sachihiko )

    1989-07-07

    Formal (2 + 2 + 2) cycloaddition of molecular oxygen, 1,3-diketones, and olefins took place by electrochemical oxidation. A catalytic amount of electricity was sufficient for the reaction, and an electroinitiated radical chain mechanism was proposed. The reaction was also initiated by a radical initiator. The resulting cyclic peroxides reacted with acids and some reducing agents such as ferrous sulfate, thiourea, and copper(I) chloride to give oxygen-oxygen bond cleavage products.

  4. 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.

  5. Paternò-Büchi reaction between aromatic carbonyl compounds and 1-(3-furyl)alkanols.

    PubMed

    D'Auria, Maurizio; Emanuele, Lucia; Racioppi, Rocco; Valente, Anna

    2008-01-01

    The photochemical reaction between aromatic carbonyl compounds and 3-furylmethanol derivatives occurs with high regioselectivity. In most of the experiments formation of oxetanes occurs at the hydroxyalkylated double bond. With chiral 1-(3-furyl)alkanols the reaction occurs with good-high stereoselectivity. In the case of 1-(3-furyl)-benzyl alcohol the stereoselectivity can be explained on the basis of the conformers of the reagent, assuming the formation of a complex between the carbonyl compound and the hydroxyl group.

  6. Cluster Based Reaction Probabilities for Boron with Oxygen, Hydrogen, Water, Nitrogen, Nitrous Oxide, Carbon Dioxide, Carbon Monoxide, Methane, Tetrafluoromethane, and Silane

    DTIC Science & Technology

    1989-10-28

    measured for reactions of boron cluster ions with the gases in question. We present both total reaction probabilities and also the branching fractions...Water, Nitrogen, Nitrous Oxide, Carbon Dioxide, Carbon Monoxide, Methane, Tetrafluoromethane , and Silane Paul A. Hintz, Stephen A. Ruatta, and Scott...detailed study of boron cluster ion reaction dynamics, we have tried to present our cross section measurements in a form most useful to combustion

  7. 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.

  8. 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.

  9. Evaluation of Carbon Interstitial in C-ion Implanted ZnO Bulk Single Crystals by a Nuclear Reaction Analysis Study: An Origin of Low Resistivity

    SciTech Connect

    Izawa, Y.; Matsumoto, K.; Oga, T.; Kuriyama, K.; Kushida, K.; Kinomura, A.

    2011-12-23

    Nuclear reaction analysis (NRA) of carbon-implanted ZnO bulk single crystals (carbon concentration: 1.5x10{sup 20} cm{sup -3}), in conjunction with the channeling technique, using the {sup 12}C(d,p){sup 13}C and {sup 16}O(d,p){sup 17}O reactions shows the presence of the interstitial carbon (C{sub i}) and the occupancy of substitute sites of oxygen atoms. These results suggest that the variation in resistivity from the order of 10{sup 4} {Omega}cm(for un-implanted samples) to that of 10 {Omega}cm (for as-implanted ones) is attributed to the C{sub i} and/or its complex defects, which would act as a shallow donor in ZnO.

  10. 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

  11. 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.

  12. CH 1 Introduction to Chemistry. Study Guide to Minicourse I - 13 Chemical Reaction Principles.

    ERIC Educational Resources Information Center

    Schlenker, Richard

    Provided is a study guide for an introductory minicourse to the principles of chemical reactions. This written text is designed to accompany a series of audio tapes and 35mm slides which the student studies at his own pace. The course presents chemical kinetics, reaction mechanisms, reaction rates, and equilibrium. (SL)

  13. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  14. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

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

  15. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

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

  16. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

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

  17. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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

  18. Multicomponent synthesis of spiropyrrolidine analogues derived from vinylindole/indazole by a 1,3-dipolar cycloaddition reaction

    PubMed Central

    Narayanarao, Manjunatha; Koodlur, Lokesh; Revanasiddappa, Vijayakumar G; Gopal, Subramanya

    2016-01-01

    A new series of spiropyrrolidine compounds containing indole/indazole moieties as side chains have been accomplished via a one-pot multicomponent synthesis. The method uses the 1,3-dipolar cycloaddition reaction between N-alkylvinylindole/indazole and azomethine ylides, prepared in situ from cyclic/acyclic amino acids. The 1,3-dipolar cycloaddition proceeds efficiently under thermal conditions to afford the regio- and stereospecific cyclic adducts. PMID:28144362

  19. Dechlorination of chloropicrin and 1,3-dichloropropene by hydrogen sulfide species: redox and nucleophilic substitution reactions.

    PubMed

    Zheng, Wei; Yates, Scott R; Papiernik, Sharon K; Guo, Mingxin; Gan, Jianying

    2006-03-22

    The chlorinated fumigants chloropicrin (trichloronitromethane) and 1,3-dichloropropene (1,3-D) are extensively used in agricultural production for the control of soilborne pests. The reaction of these two fumigants with hydrogen sulfide species (H2S and HS-) was examined in well-defined anoxic aqueous solutions. Chloropicrin underwent an extremely rapid redox reaction in the hydrogen sulfide solution. Transformation products indicated reductive dechlorination of chloropicrin by hydrogen sulfide species to produce dichloro- and chloronitromethane. The transformation of chloropicrin in hydrogen sulfide solution significantly increased with increasing pH, indicating that H2S is less reactive toward chloropicrin than HS- is. For both 1,3-D isomers, kinetics and transformation products analysis revealed that the reaction between 1,3-D and hydrogen sulfide species is an S(N)2 nucleophilic substitution process, in which the chlorine at C3 of 1,3-D is substituted by the sulfur nucleophile to form corresponding mercaptans. The 50% disappearance time (DT50) of 1,3-D decreased with increasing hydrogen sulfide species concentration at a constant pH. Transformation of 1,3-D was more rapid at high pH, suggesting that the reactivity of hydrogen sulfide species in the experimental system stems primarily from HS-. Because of the relatively low smell threshold values and potential environmental persistence of organic sulfur products yielded by the reaction of 1,3-D and HS-, the effects of reduced sulfide species should be considered in the development of alternative fumigation practices, especially in the integrated application of sulfur-containing fertilizers.

  20. Multicomponent synthesis of spiropyrrolidine analogues derived from vinylindole/indazole by a 1,3-dipolar cycloaddition reaction.

    PubMed

    Narayanarao, Manjunatha; Koodlur, Lokesh; Revanasiddappa, Vijayakumar G; Gopal, Subramanya; Kamila, Susmita

    2016-01-01

    A new series of spiropyrrolidine compounds containing indole/indazole moieties as side chains have been accomplished via a one-pot multicomponent synthesis. The method uses the 1,3-dipolar cycloaddition reaction between N-alkylvinylindole/indazole and azomethine ylides, prepared in situ from cyclic/acyclic amino acids. The 1,3-dipolar cycloaddition proceeds efficiently under thermal conditions to afford the regio- and stereospecific cyclic adducts.

  1. 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.

  2. Polybromocyclopentadienes in the diene synthesis reaction. VI. The reactivity of hexabromo- and 5,5-dimethoxytetrabromo-1,3-cyclopentadienes in the diene synthesis reaction with bismaleimides

    SciTech Connect

    Mustafaev, A.M.; Guseinov, M.M.; Gasanova, K.M.; Gadzhieva, S.T.

    1987-10-10

    The adducts from the diene condensation of hexabromo- and 5,5-dimethoxytetrabromo-1,3-cyclopentadienes with bismaleimides were obtained and characterized. The reactivity of hexabromo- and 5,5-dimethoxytetrabromo-1,3-cyclopentadienes in the diene synthesis reactions with bismaleimides and with the monoadducts 1,4,5,6,7,7-hexabromo- and 1,4,5,6-tetrabromo-7,7-dimethoxybicyclo-(2.2.1)-hept-5-ene-2,3-dicarboximides was studied. In these reactions hexabromo-1,3-cyclopentadiene acts as diene-acceptor, while 5,5-dimethoxytetrabromo-1,3-cyclopentadiene acts as diene-donor. It is suggested that the reactivity of the addends in the investigated reaction series depends not only on their donor-acceptor characteristics but also on the localization energy. The IR spectra of the adducts were recorded in Vaseline oil on a UR-20 spectrophotometer. The PMR spectra were measured on a Tesla BS-487B instrument at 80 MHz with DMFA-d/sub 7/ as solvent and TMS as internal standard.

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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

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

  4. 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.

  5. (13)C-Labeling the carbon-fixation pathway of a highly efficient artificial photosynthetic system.

    PubMed

    Liu, Chong; Nangle, Shannon N; Colón, Brendan C; Silver, Pamela A; Nocera, Daniel G

    2017-03-15

    Interfacing the CO2-fixing microorganism, Ralstonia eutropha, to the energy derived from hydrogen produced by water splitting is a viable approach to achieving renewable CO2 reduction at high efficiencies. We employ (13)C-labeling to report on the nature of CO2 reduction in the inorganic water splitting|R. eutropha hybrid system. Accumulated biomass in a reactor under a (13)C-enriched CO2 atmosphere may be sampled at different time points during CO2 reduction. Converting the sampled biomass into gaseous CO2 allows the (13)C/(12)C ratio to be determined by gas chromatography-mass spectrometry. After 2 hours of inoculation and the initiation of water splitting, the microbes adapted and began to convert CO2 into biomass. The observed time evolution of the (13)C/(12)C ratio in accumulated biomass is consistent with a Monod model for carbon fixation. Carbon dioxide produced by catabolism was found to be minimal. This rapid response of the bacteria to a hydrogen input and to subsequent CO2 reduction at high efficiency are beneficial to achieving artificial photosynthesis for the storage of renewable energy.

  6. 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.

  7. The oceanic carbon cycle implicated in the d13Ccarb and the d13Corg variations from the terminal Ediacaran to the Early Cambrian

    NASA Astrophysics Data System (ADS)

    Ishikawa, T.; Ueno, Y.; Komiya, T.; Shu, D.; Li, Y.; Yoshida, N.; Maruyama, S.

    2009-04-01

    The terminal Neoproterozoic and its transition into the Cambrian witnessed major evolutionary and geochemical changes (e.g. Knoll, 1994). Evolutionary features include extinction and subsequent radiation events (e.g. Brasier, 1994; Knoll, 1994; Knoll and Carroll, 1999; Shu 2008). Geochemical changes comprise secular variations of the global carbon cycle expressed as variations of the d13C isotope records. A representative d13C curve for inorganic carbon (d13Ccarb) across the Precambrian/Cambrian boundary (Pc/C boundary) shows the existence of large fluctuations (e.g. Kirschvink et al., 1991; Narbonne et al., 1994; Kaufman et al., 1995; Amthor et al., 2003; Maloof et al., 2005, Ishikawa et al., 2008). This indicates a significant change of the oceanic carbon cycle at that time. On the other hand, the d13C values for total organic carbon (d13Corg) have rarely been reported together with the d13Ccarb across the boundary. Therefore, the precise relation between the d13Ccarb and the d13Corg and the global carbon cycle at the Pc/C boundary are still ambiguous. This work presents a first high-resolution d13Corg chemostratigraphy of drill core samples across the Pc/C boundary in the Three Gorges area, South China. Based on the results, this work additionally proposes variations of the sizes of the oceanic carbon reservoirs by a calculation of the carbon cycle model at the Pc/C boundary. The Three Gorges section extends from the uppermost Ediacaran dolostone (Dengying Formation), through the lowermost Early Cambrian muddy limestone (Yanjiahe Formation) to the middle Early Cambrian calcareous black shale (Shuijingtuo Formation). The ^13Corg values exhibit relatively invariant values averaging at -31 permil. By comparison between the d13Ccarb and d13Corg, we recognize two different terms in this period. The first term from the Pc/C boundary to the early Nemakit-Daldynian (ND) is characterized by the decoupling of d13Corg and d13Ccarb, stable d13Corg and the significant

  8. 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

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  11. Carbon 13 chemical shift tensors in aromatic compounds. 3. Phenanthrene and triphenylene

    SciTech Connect

    Soderquist, A.; Hughes, C.D.; Horton, W.J.; Facelli, J.C.; Grant, D.M.

    1992-04-08

    Measurements of the principal values of the {sup 13}C chemical shift tensor are presented for the three carbons in triphenylene and for three different {alpha} carbons in phenanthrene. The measurements in triphenylene were made in natural abundance samples at room temperature, while the phenanthrene tensors were obtained from selectively labeled compounds (99% {sup 13}C) at low temperatures ({approx} 25 K). The principal values of the shift tensors were oriented in the molecular frame using ab initio LORG calculations. The steric compression at C{sub 4} in phenanthrene and in corresponding positions in triphenylene is manifested in sizable upfield shift in the {sigma} 33 component relative to the corresponding {sigma} 33 values at C{sub 1} and C{sub 9} in phenanthrene. The upfield shift in {sigma} 33 is mainly responsible for the well-known upfield shift of the isotropic chemical shifts of such sterically perturbed carbons. In phenanthrene c{sub 9} exhibits a unique {sigma} 22 value reflecting the greater localization of {pi}-electrons in the c{sub 9}-C{sub 10} bond. This localization of the {pi}-electrons at the C{sub 9}-C{sub 10} bond in the central ring of phenanthrene also corresponds with the most likely ordering of electrons described by the various Kekule structures in phenanthrene. The analysis of the {sup 13}C chemical shieldings of the bridgehead carbons in the triphenylene provides significant experimental information on bonding between rings in polycyclic aromatic compounds. 39 refs., 8 fig., 3 tab.

  12. 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.

  13. 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.

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

    PubMed

    Mohammed, Fiaz S; Kitchens, Christopher L

    2015-12-23

    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.

  15. Fungal carbon sources in a pine forest: evidence from a 13C-labeled global change experiment

    Treesearch

    Erik A. Hobbie; Kirsten S. Hofmockel; Linda T.A. Van Diepen; Erik A. Lilleskov; Andrew P. Oiumette; Adrien C. Finzi

    2014-01-01

    We used natural abundance 13C:12C (δ13C) and 8 yr of labeling with 13C-depleted CO2 in a Pinus taeda Free Air CO2 Enrichment (FACE) experiment to investigate carbon sources of saprotrophic fungi, ectomycorrhizal...

  16. 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

  17. 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.

  18. Fabrication of carbonate apatite blocks from set gypsum based on dissolution-precipitation reaction in phosphate-carbonate mixed solution.

    PubMed

    Nomura, Shunsuke; Tsuru, Kanji; Maruta, Michito; Matsuya, Shigeki; Takahashi, Ichiro; Ishikawa, Kunio

    2014-01-01

    Carbonate apatite (CO3Ap), fabricated by dissolution-precipitation reaction based on an appropriate precursor, is expected to be replaced by bone according to bone remodeling cycle. One of the precursor candidates is gypsum because it shows self-setting ability, which then enables it to be shaped and molded. The aim of this study, therefore, was to fabricate CO3Ap blocks from set gypsum. Set gypsum was immersed in a mixed solution of 0.4 mol/L disodium hydrogen phosphate (Na2HPO4) and 0.4 mol/L sodium hydrogen carbonate (NaHCO3) at 80-200°C for 6-48 h. Powder X-ray diffraction patterns and Fourier transform infrared spectra showed that CO3Ap block was fabricated by dissolution-precipitation reaction in Na2HPO4-NaHCO3 solution using set gypsum in 48 h when the temperature was 100°C or higher. Conversion rate to CO3Ap increased with treatment temperature. CO3Ap block containing a larger amount of carbonate was obtained when treated at lower temperature.

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  1. Whole-stream 13C tracer addition reveals distinct fates of newly fixed carbon.

    PubMed

    Hotchkiss, Erin R; Hall, Robert O

    2015-02-01

    Many estimates of freshwater carbon (C) fluxes focus on inputs, processing, and storage of terrestrial C; yet inland waters have high rates of internally fixed (autochthonous) C production. Some fraction of newly fixed C may be released as biologically available, dissolved organic C (DOC) and stimulate microbial-driven biogeochemical cycles soon after fixation, but the fate of autochthonous C is difficult to measure directly. Tracing newly fixed C can increase our understanding of fluxes and fate of autochthonous C in the context of freshwater food webs and C cycling. We traced autochthonous C fixation and fate using a dissolved inorganic C stable isotope addition (13C(DIC)). We added 13C(DIC) to North Fork French Creek, Wyoming, USA during two days in August. We monitored changes in 13C pools, fluxes, and storage for 44 d after the addition. Two-compartment flux models were used to quantify net release of newly fixed 13C(DOC) and 13C(DIC) into the water column. We compared net 13C fixation with tracer 13C(DIC) removal and gross primary production (GPP) to account for the mass of tracer fixed, released, lost to the atmosphere, and exported downstream. Much of the fixed C turned over rapidly and did not enter longer-term storage pools. Net C fixed was 70% of GPP measured with O2. Algae likely released the remaining 30% via 13C(DOC) exudation and respiration of newly fixed C. Primary producers released 13C(DOC) at rates of up to 16% per day during the 13C addition, but exudation of new labile C declined to near zero by day 6. DIC production from newly fixed C accounted for 21% of ecosystem respiration the day after the 13C addition. All measured organic C (OC) pools were enriched with 13C 1 d after the tracer addition. 20% of fixed 13C remained in benthic OC by day 44, and average residence time of autochthonous C in benthic OC was 62 d. Newly fixed C had two distinct fates: short-term (< 1 week) exudation and respiration or longer-term storage and downstream export

  2. 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

  3. The 13C(α,n) reaction and its role as a neutron source for the s process

    NASA Astrophysics Data System (ADS)

    Heil, M.; Detwiler, R.; Azuma, R. E.; Couture, A.; Daly, J.; Görres, J.; Käppeler, F.; Reifarth, R.; Tischhauser, P.; Ugalde, C.; Wiescher, M.

    2008-08-01

    The 13C(α,n)16O reaction constitutes the dominant neutron source for the main s process, which operates at a thermal energy of kT=8 keV. Since the cross section at stellar energies is very small, the reaction rate cannot be directly determined and has to be extrapolated from cross section results obtained at higher energies. To remove various discrepancies in the normalization of previous data sets and to subsequently improve the reliability of the extrapolation, we performed measurements of the 13C(α,n)16O reaction in the energy range Ec.m.=320-700 keV. In addition, the double differential scattering cross section 13C(α,α)13C was measured in the energy range Elab=2.6-6.2 MeV for 28 angles. These data were used to constrain possible contributions from background resonances for a reliable extrapolation with the multichannel R-matrix code SAMMY. As a result, the uncertainties were significantly reduced, and a reaction rate of (4.6±1.0)×10-14 cm3/moles at kT=8 keV (T=0.1×109 K) was determined.

  4. Asymmetric three-component domino reaction: an original access to chiral nonracemic 1,3-thiazin-2-ones.

    PubMed

    Peudru, Flavie; Le Cavelier, Fabien; Lohier, Jean-François; Gulea, Mihaela; Reboul, Vincent

    2013-11-15

    A new asymmetric three-component domino process, based on a diastereoselective hetero-Diels-Alder reaction, involving an aldehyde, an alkene, and a chiral thiocarbamate was developed. The chiral auxiliary is directly removed during this process, leading to enantioenriched 2H-1,3-thiazin-2-ones with up to 96% ee.

  5. 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...

  6. 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...

  7. 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

  8. 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

  9. Characterization of milled woods lignins and dehydrogenative polymerization products from monolignol by carbon-13 NMR spectroscopy

    SciTech Connect

    Chen, C.L.

    1996-10-01

    Milled wood lignins and dehydrogenative polymerization products from monolignol will be characterized by using {sup 13}C NMR spectroscopy. The techniques include (1) routine qualitative method, (2) quantitative method using inverse gated decoupling (IGD) pulse sequence, (3) distortionless enhancement by polarization transfer (DEPT) pulse sequence, (4) quantitative determination of phenolic, primal and secondary alcohol hydroxyl groups, and finally (5) used of {sup 13}C specifically labelled compound to monitor biosynthesis of lignin as well as modification reaction of technical lignins. Several appropriate examples will be used to discuss advantages and disadvantages of aforementioned methods. Advantages in combination of chemical methods and {sup 13}C NMR spectroscopy for characterization of lignin preparations will be also discussed.

  10. A VUV photoionization study of the multichannel reaction of phenyl radicals with 1,3-butadiene under combustion relevant conditions.

    PubMed

    Golan, Amir; Ahmed, Musahid; Mebel, Alexander M; Kaiser, Ralf I

    2013-01-07

    We studied the reaction of phenyl radicals (C(6)H(5)) with 1,3-butadiene (H(2)CCHCHCH(2)) exploiting a high temperature chemical reactor under combustion-like conditions (300 Torr, 873 K). The reaction products were probed in a supersonic beam by utilizing VUV radiation from the Advanced Light Source and by recording the experimental PIE curves at mass-to-charge ratios of m/z = 130 (C(10)H(10)(+)), 116 (C(9)H(8)(+)), and 104 (C(8)H(8)(+)). Our data suggest that the atomic hydrogen (H), methyl (CH(3)), and vinyl (C(2)H(3)) losses are open with estimated branching ratios of about 86 ± 4%, 8 ± 2%, and 6 ± 2%, respectively. The isomer distributions were probed further by fitting the experimentally recorded PIE curves with a linear combination of the PIE curves of individual C(10)H(10), C(9)H(8), and C(8)H(8) isomers. These fits indicate the formation of three C(10)H(10) isomers (trans-1,3-butadienylbenzene, 1,4-dihydronaphthalene, 1-methylindene), three C(9)H(8) isomers (indene, phenylallene, 1-phenyl-1-methylacetylene), and a C(8)H(8) isomer (styrene). A comparison with results from recent crossed molecular beam studies of the 1,3-butadiene-phenyl radical reaction and electronic structure calculations suggests that trans-1,3-butadienylbenzene (130 amu), 1,4-dihydronaphthalene (130 amu), and styrene (104 amu) are reaction products formed as a consequence of a bimolecular reaction between the phenyl radical and 1,3-butadiene. 1-Methylindene (130 amu), indene (116 amu), phenylallene (116 amu), and 1-phenyl-1-methylacetylene (116 amu) are synthesized upon reaction of the phenyl radical with three C(4)H(6) isomers: 1,2-butadiene (H(2)CCCH(CH(3))), 1-butyne (HCCC(2)H(5)), and 2-butyne (CH(3)CCCH(3)); these C(4)H(6) isomers can be formed from 1,3-butadiene via hydrogen atom assisted isomerization reactions or via thermal rearrangements of 1,3-butadiene involving hydrogen shifts in the high temperature chemical reactor.

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

    PubMed

    Petrov, Viacheslav A; Marshall, Will

    2013-01-01

    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.

  12. 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.

  13. 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.

  14. Regiocomplementary cycloaddition reactions of boryl- and silylbenzynes with 1,3-dipoles: selective synthesis of benzo-fused azole derivatives.

    PubMed

    Ikawa, Takashi; Takagi, Akira; Goto, Masahiko; Aoyama, Yuya; Ishikawa, Yoshinobu; Itoh, Yuji; Fujii, Satoshi; Tokiwa, Hiroaki; Akai, Shuji

    2013-04-05

    Benzo-fused nitrogen-containing heterocycles are abundant in biologically active compounds. One of the most important methods for preparing such heterocycles is the (3 + 2) cycloaddition reaction of benzynes with 1,3-dipolar compounds. However, the reactions of unsymmetrically substituted benzynes generally show low selectivity and hence yield mixtures of two regioisomers. In this paper, we describe the synthesis of both regioisomers of multisubstituted benzo-fused azole derivatives such as benzotriazoles, 1H-indazoles, and benzo[d]isoxazoles through the regiocomplementary (3 + 2) cycloaddition reactions of 3-boryl- and 3-silylbenzynes with 1,3-dipoles. The improved generation of 3-borylbenzynes from new precursors was one of the most important results of this work, which produced the successful (3 + 2) cycloaddition reactions with exclusive and proximal selectivities. On the other hand, similar reactions of 3-silylbenzynes selectively afforded distal cycloadducts. Analysis of the reaction pathways of these amazing regioselectivities by density functional theory calculations revealed that the (3 + 2) cycloadditions of borylbenzynes are controlled by the electrostatic effect of the boryl group, while those of silylbenzynes are controlled mainly by the steric effect of the bulky silyl groups that produced electrostatically unfavorable adducts via anomalous transition states.

  15. A study of the incorporation reaction of lithium into V6O13 in a rechargeable lithium battery

    NASA Astrophysics Data System (ADS)

    Wang, Dequan; Liao, Zhenjiang; Feng, Xikang; Liu, Dangjun

    1989-05-01

    Practical C- and AA-size ambient temperature, rechargeable Li/V6O13 cells have been constructed using pure V6O13, prepared in the laboratory, as cathode active material. X-ray diffraction pattern d values of V6O13 prepared in this study are the same as those given by JCPDS, and cathodes of this material have performed satisfactorily. Cathodic discharge products of test cells have been analyzed by XRD and ESR. New expanded diffraction lines have been discovered in XRD patterns. From XRD and ESR results, it is considered that the incorporation of lithium into V6O13 is the main reduction reaction in the V6O13 cathodic process.

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

    PubMed

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

    2006-11-10

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

  17. Carbon cycle dynamics following the end-Triassic mass extinction: Constraints from paired δ13Ccarb and δ13Corg records

    NASA Astrophysics Data System (ADS)

    Bachan, Aviv; van de Schootbrugge, Bas; Fiebig, Jens; McRoberts, Christopher A.; Ciarapica, Gloria; Payne, Jonathan L.

    2012-09-01

    Constraining the carbon isotopic changes associated with the end-Triassic mass extinction is key to understanding the causes of the extinction and dynamics of recovery from it. Yet the pattern and timing of δ13C variation surrounding the extinction remain poorly constrained. Here we present close to 1000 new δ13C measurements from six newly sampled sections in Italy. We observe a sharp negative excursion in δ13Ccarb coincident with the disappearance of the Triassic fauna, and two positive excursions above it. The negative δ13Ccarb excursion in these sections does not occur in δ13Corg suggesting a possible diagenetic origin. In contrast, the interval of elevated δ13C occurs in both carbonate and organic carbon, suggesting that it is likely to be a primary feature. The positive excursions in the Lombardy Basin (southern Alps) and Mt. Cefalo (southern Apennines) appear to be time correlative on the basis of their position above the disappearance of characteristically Triassic biota. However, it is less certain that they are time correlative with positive excursions in other sections worldwide, as few options exist that honor both bio- and chemostratigraphy. Nonetheless, similarity to other events that are interpreted as global, as well as carbon cycle considerations, suggest that the isotopic enrichment is best interpreted to reflect a shift in the isotope composition of the global surface carbon reservoir. Our data indicate that perturbation of the global carbon cycle was not confined to the immediate vicinity of the extinction interval, but rather persisted for substantial length of geologic time afterwards.

  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

    2015-04-08

    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.

  19. Preparation of Diaminedicarboxyplatinum (II) Functionalized Single-Wall Carbon Nanotube via Bingel Reaction as a Novel Cytotoxic Agent

    PubMed Central

    Irannejad, Saeed; Amini, Mohsen; Modanlookordi, Mona; Shokrzadeh, Mohammad; Irannejad, Hamid

    2016-01-01

    Carbon nanotubes have unique properties like high stability, high surface to mass ratio and so on which make them suitable for medicinal purpose applications. Treatment of cancer by organoplatinum agents like Cisplatin has become unresponsive in most cases due to low distribution of drug in biological fluids, inability of drug to cross cellular membranes and low stability in biological environments. Recently, carbon nanotubes (CNT) have stimulated much interest to overcome these limitations. ‎‎ Herein, we report the preparation of single-wall carbon nanotube functionalized by diaminedicarboxyplatinum (II) as an analogy of SWCNT-based Carboplatin. Functionalization was started by cyclopropanation through Bingel reaction and by use of diethylmalonate to yield cyclopropane-1,1-dicarboxy ethyl ester. Final product was obtained by hydrolysis of ester group and then chelation of platinum (IV) by dicarboxylate groups on the surface of SWCNT. Raman and Fourier transform -Infrared ‎spectroscopy (IR), ‎Thermogravimetric ‎analysis ‎(TGA) and energy dispers‎ive X-ray‎spectroscopy ‎(EDAX) truly showed and confirmed the presence of the platinum (II) complex on the side wall of SWCNT. Cytotoxicity evaluation of the functionalized-SWCNTs on HeLa cells showed its higher anticancer ability than Cisplatin as indicated by IC50 value of 13 µg/mL. PMID:28243271

  20. 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

  1. Substituent effects on the nitrogen-15 and carbon-13 shieldings of some N-arylguanidinium chlorides.

    PubMed

    Botto, R E; Schwartz, J H; Roberts, J D

    1980-01-01

    The (13)C and (15)N chemical shifts of five N-arylguanidinium chlorides carrying polar substituents, ranging in character from 4-methoxy to 4-nitro groups, have been determined by NMR spectroscopy at the natural-abundance level of (13)C and (15)N in dimethyl sulfoxide solution. Comparison of the (13)C shifts of these salts with those of monosubstituted benzenes shows that the guanidinium group induces an average downfield shift of -5.8 ppm of the resonance of the aryl carbon to which it is attached (C1), an average upfield shift of +4.2 ppm for C2 and C6, and a small upfield shift of +1.9 ppm for C4. The shifts of C3 and C5 are small and erratic relative to the corresponding carbons in monosubstituted benzenes. The (15)N resonances of the guanidinium nitrogens are quite sensitive to electric effects resulting from substitution of polar groups at C4. The (15)N shift of the [unk]NAr nitrogen relative to that of the salts suggests that the predominant tautomer for N-arylguanidines is (H(2)N)(2)C[unk]NAr. The (15)N shifts of the (NH(2))(2) nitrogens correlate rather well with sigma(p) (-) parameters, whereas the shifts of the -NHAr nitrogens seem to correlate only with R values derived from the sigma(p) (-) substituent constants.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  3. Isoprene/methyl acrylate Diels-Alder reaction in supercritical carbon dioxide

    SciTech Connect

    Lin, B.; Akgerman, A.

    1999-12-01

    The Diels-Alder reaction between isoprene and methyl acrylate was carried out in supercritical carbon dioxide in the temperature range 110--140 C and the pressure range 95.2--176.9 atm in a 300 cm{sup 3} autoclave. The high-pressure phase behavior of the reaction mixture in the vicinity of its critical region was determined in a mixed vessel with a sight window to ensure that all the experiments were performed in the supercritical single-phase region. Kinetic data were obtained at different temperatures, pressures, and reaction times. It was observed that in the vicinity of the critical point the reaction rate constant decreases with increasing pressure. It was also determined that the reaction selectivity does not change with operating conditions. Transition-state theory was used to explain the effect of pressure on reaction rate and product selectivity. Additional experiments were conducted at constant temperature but different phase behaviors (two-phase region, liquid phase, supercritical phase) by adjusting the initial composition and pressure. It was shown that the highest reaction rate is in the supercritical region.

  4. 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.

  5. Racing Carbon Atoms. Atomic Motion Reaction Coordinates and Structural Effects on Newtonian Kinetic Isotope Effects

    PubMed Central

    Andujar-De Sanctis, Ivonne L.

    2012-01-01

    Intramolecular 13C kinetic isotope effects were determined for the dimerization of methacrolein. Trajectory studies accurately predict the isotope effects and support an origin in Newton’s second law of motion, with no involvement of zero-point energy or transition state recrossing. Atomic motion reaction coordinate diagrams are introduced as a way to qualitatively understand the selectivity. PMID:23025278

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

    PubMed

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

    2012-10-19

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

  7. Temporal mapping of photochemical reactions and molecular excited states with carbon specificity.

    PubMed

    Wang, K; Murahari, P; Yokoyama, K; Lord, J S; Pratt, F L; He, J; Schulz, L; Willis, M; Anthony, J E; Morley, N A; Nuccio, L; Misquitta, A; Dunstan, D J; Shimomura, K; Watanabe, I; Zhang, S; Heathcote, P; Drew, A J

    2017-04-01

    Photochemical reactions are essential to a large number of important industrial and biological processes. A method for monitoring photochemical reaction kinetics and the dynamics of molecular excitations with spatial resolution within the active molecule would allow a rigorous exploration of the pathway and mechanism of photophysical and photochemical processes. Here we demonstrate that laser-excited muon pump-probe spin spectroscopy (photo-μSR) can temporally and spatially map these processes with a spatial resolution at the single-carbon level in a molecule with a pentacene backbone. The observed time-dependent light-induced changes of an avoided level crossing resonance demonstrate that the photochemical reactivity of a specific carbon atom is modified as a result of the presence of the excited state wavefunction. This demonstrates the sensitivity and potential of this technique in probing molecular excitations and photochemistry.

  8. Asymmetric Synthesis of α-Trifluoromethyl Pyrrolidines through Organocatalyzed 1,3-Dipolar Cycloaddition Reaction.

    PubMed

    Dong, Zhenghao; Zhu, Yuanyuan; Li, Boyu; Wang, Cui; Yan, Wenjin; Wang, Kairong; Wang, Rui

    2017-02-28

    The optically active α-trifluoromethyl pyrrolidines have been achieved through organocatalyzed 1, 3-dipolar cycloaddition reaction firstly. With diphenyl- prolinol trimethylsilyl ether as catalyst and in the presence of 3, 5-dinitrobenzoic acid, the reaction of trifluoroethylamine-derived ketimine with 2-enals gave α-trifluoro-methyl pyrrolidines bearing three contiguous stereogenic centers in excellent diastereoselectivies, stereoselectivities and yields.

  9. Expression of MMP-13 in osteoblast cells and rat tibia after exposure to gamma rays or accelerated carbon ions.

    PubMed

    Sawajiri, M; Takinami, S; Uchida, T; Nomura, Y; Mizoe, J; Banik, S; Tanimoto, K

    2007-06-01

    In past research, we found that carbon ion irradiation increased bone volume in rats, and a significant amount of cartilage remained inside the carbon ion-irradiated trabeculae. The amounts of matrix metalloproteinase 13 (MMP-13) mRNA in osteoblast-like MC3T3-E1 cells tended to decrease after carbon ion irradiation. The level of MMP-13 mRNA in non-irradiated cells was stable during the experimental period, but in gamma ray-irradiated cells it tended to increase. When localization of MMP-13 in locally irradiated experimental rats was investigated, it was found in the marginal trabeculae in both non-irradiated and gamma ray-irradiated animals. MMP-13 was detected in osteoid and neogenetic bone in the trabeculae surface. The trabeculae in carbon ion-irradiated bone remained cartilaginous. Carbon ion-irradiated rats exhibited weak expression of MMP-13 around the cartilage inside the trabeculae. We conclude that carbon ion irradiation reduced expression of MMP-13, thus suppressing both chondrocyte maturation and cartilage resorption. Increases in hyperplasia of the bone trabeculae and of bone volume were caused by ongoing bone addition and calcification in the absence of sufficient cartilage resorption.

  10. Kinetics of the catalytic reaction of 2,2-di-(chloromethyl)-1,3-propanediol with thionyl chloride

    SciTech Connect

    Bolotov, A.A.; V'yunov, K.A.

    1989-01-10

    The aim of this work was to determine the partial rate constants for the catalytic formation of 4,4-di(chloromethyl)trimethylene sulfite and to establish the controlling stage of the complex process. The choice of DMFA as catalyst during investigation of the quantitative relationships governing the substitution of the hydroxyl group by the chlorine atom was based on the fact that the reaction with triethylamine and pyridine takes place in a more complicated manner; the initially formed triethylamine and pyridine hydrochlorides accelerate substitution, i.e., autocatalysts by the reaction products is observed. The slowest stage of the complex catalytic process in the reaction of 2,2-di(chloromethyl)-1,3-propanediol with thionyl chloride in the presence of dimethylformamide is the reaction of the alcohol-catalyst donor-acceptor complex with the thionyl chloride.

  11. [Involvement of carbonate/bicarbonate ions in the superoxide-generating reaction of adrenaline autoxidation].

    PubMed

    Sirota, T V

    2015-01-01

    An important role of carbonate/bicarbonate ions has been recognized in the superoxide generating reaction of adrenaline autooxidation in an alkaline buffer (a model of quinoid adrenaline oxidation in the body). It is suggested that these ions are directly involved not only in formation of superoxide anion radical (О(2)(-)) but also other radicals derived from the carbonate/bicarbonate buffer. Using various buffers it was shown that the rate of accumulation of adrenochrome, the end product of adrenaline oxidation, and the rate of О(2)(-)· formation depend on concentration of carbonate/bicarbonate ions in the buffer and that these ions significantly accelerate adrenaline autooxidation thus demonstrating prooxidant properties. The detectable amount of diformazan, the product of nitro blue tetrazolium (NBT) reduction, was significantly higher than the amount of adrenochrome formed; taking into consideration the literature data on О(2)(-)· detection by NBT it is suggested that adrenaline autooxidation is accompanied by one-electron reduction not only of oxygen dissolved in the buffer and responsible for superoxide formation but possible carbon dioxide also dissolved in the buffer as well as carbonate/bicarbonate buffer components leading to formation of corresponding radicals. The plots of the dependence of the inhibition of adrenochrome and diformazan formation on the superoxide dismutase concentration have shown that not only superoxide radicals are formed during adrenaline autooxidation. Since carbonate/bicarbonate ions are known to be universally present in the living nature, their involvement in free radical processes proceeding in the organism is discussed.

  12. Synthesis of 2D Nitrogen-Doped Mesoporous Carbon Catalyst for Oxygen Reduction Reaction

    PubMed Central

    Yu, Zhipeng; Piao, Jinhua; Liang, Zhenxing

    2017-01-01

    2D nitrogen-doped mesoporous carbon (NMC) is synthesized by using a mesoporous silica film as hard template, which is then investigated as a non-precious metal catalyst for the oxygen reduction reaction (ORR). The effect of the synthesis conditions on the silica template and carbon is extensively investigated. In this work, we employ dual templates—viz. graphene oxide and triblock copolymer F127—to control the textural features of a 2D silica film. The silica is then used as a template to direct the synthesis of a 2D nitrogen-doped mesoporous carbon. The resultant nitrogen-doped mesoporous carbon is characterized by transmission electron microscopy (TEM), nitrogen ad/desorption isotherms, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and rotating disk electrode measurements (RDE). The electrochemical test reveals that the obtained 2D-film carbon catalyst yields a highly electrochemically active surface area and superior electrocatalytic activity for the ORR compared to the 3D-particle. The superior activity can be firstly attributed to the difference in the specific surface area of the two catalysts. More importantly, the 2D-film morphology makes more active sites accessible to the reactive species, resulting in a much higher utilization efficiency and consequently better activity. Finally, it is noted that all the carbon catalysts exhibit a higher ORR activity than a commercial Pt catalyst, and are promising for use in fuel cells. PMID:28772558

  13. 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.

  14. Controlled Molybdenum Disulfide Assembly inside Carbon Nanofiber by Boudouard Reaction Inspired Selective Carbon Oxidation.

    PubMed

    Nam, Dae-Hyun; Kang, Ho-Young; Jo, Jun-Hyun; Kim, Byung Kyu; Na, Sekwon; Sim, Uk; Ahn, In-Kyoung; Yi, Kyung-Woo; Nam, Ki Tae; Joo, Young-Chang

    2017-03-01

    Vertical stacking and lateral growth of molybdenum disulfide (MoS2 ) are controlled with remarkable precision, and MoS2 nanotubes are directly converted from nanofibers. Predictive synthesis is enabled by identifying the specific thermodynamic region where the Boudouard reaction becomes favored. It reveals how the chemical potential of each species in the MoSCO system can predict phase behaviors.

  15. 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

  16. Environmental Transmission Electron Microscopy Study of Diesel Carbon Soot Combustion under Simulated Catalytic-Reaction Conditions.

    PubMed

    Mori, Kohsuke; Watanabe, Keitaro; Sato, Takeshi; Yamashita, Hiromi

    2015-05-18

    Environmental transmission electron microscopy (ETEM) is used to monitor the catalytic combustion of diesel carbon soot upon exposure to molecular oxygen at elevated temperatures by using a gas-injection specimen heating holder. The reaction conditions simulated in the ETEM experiments reconstruct real conditions effectively. This study demonstrated for the first time that soot combustion occurs at the soot-catalyst interface for both Ag/CeO2 and Cu/BaO/La2 O3 catalysts.

  17. Design and reactions of a carbon Lewis base/boron Lewis acid frustrated Lewis pair.

    PubMed

    Möricke, Jennifer; Wibbeling, Birgit; Daniliuc, Constantin G; Kehr, Gerald; Erker, Gerhard

    2017-08-28

    The conjugated dienamine 4 selectively adds Piers' borane [HB(C6F5)2] to give the enamine/borane system 5, which features a boratirane structure by internal enamine carbon Lewis base to boron Lewis acid interaction. Compound 5 behaves as a C/B frustrated Lewis pair and undergoes typical addition reactions to benzaldehyde, several nitriles and to sulfur dioxide.This article is part of the themed issue 'Frustrated Lewis pair chemistry'. © 2017 The Author(s).

  18. Proton-decoupled, Overhauser-enhanced, spatially localized carbon-13 spectroscopy in humans

    SciTech Connect

    Bottomley, P.A.; Hardy, C.J.; Roemer, P.B.; Mueller, O.M. )

    1989-12-01

    Spatially localized, natural abundance, carbon (13C) NMR spectroscopy has been combined with proton (1H) decoupling and nuclear Overhauser enhancement to improve 13C sensitivity up to five-fold in the human leg, liver, and heart. Broadhand-decoupled 13C spectra were acquired in 1 s to 17 min with a conventional 1.5-T imaging/spectroscopy system, an auxiliary 1H decoupler, an air-cooled dual-coil coplanar surface probe, and both depth-resolved surface coil spectroscopy (DRESS) and one-dimensional phase-encoding gradient NMR pulse sequences. The surface coil probe comprised circular and figure-eight-shaped coils to eliminate problems with mutual coupling of coils at high decoupling power levels applied during 13C reception. Peak decoupler RF power deposition in tissue was computed numerically from electromagnetic theory assuming a semi-infinite plane of uniform biological conductor. Peak values at the surface were calculated at 4 to 6 W/kg in any gram of tissue for each watt of decoupler power input excluding all coil and cable losses, warning of potential local RF heating problems in these and related experiments. The average power deposition was about 9 mW/kg per watt input, which should present no systemic hazard. At 3 W input, human 13C spectra were decoupled to a depth of about 5 cm while some Overhauser enhancement was sustained up to about 3 cm depth, without ill effect. The observation of glycogen in localized natural abundance 13C spectra of heart and muscle suggests that metabolites in the citric acid cycle should be observable noninvasively using 13C-labeled substrates.

  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. 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

  2. Hetero-Diels-Alder reaction of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with arylsulfonylcyanides. Synthesis and antimicrobial activity of 4-hydroxy-2-(arylsulfonyl)pyridines.

    PubMed

    Hussain, Ibrar; Yawer, Mirza Arfan; Lalk, Michael; Lindequist, Ulrike; Villinger, Alexander; Fischer, Christine; Langer, Peter

    2008-12-01

    Hetero-Diels-Alder reactions of 1,3-bis(silyloxy)-1,3-butadienes with arylsulfonylcyanides afforded a variety of 4-hydroxy-2-(arylsulfonyl)pyridines. Several derivatives show antimicrobial activity against Gram-positive bacteria.

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

    PubMed

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

    2016-09-16

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

  4. Gold-catalyzed reactions of propargylic esters with vinylazides for the synthesis of Z- or E-configured buta-1,3-dien-2-yl esters.

    PubMed

    Wagh, Sachin Bhausaheb; Liu, Rai-Shung

    2015-10-28

    Gold-catalyzed synthesis of buta-1,3-dien-2-yl esters by the reaction of propargyl esters with vinylazides is described; the reaction mechanism is postulated to involve a vinyl attack of vinylazides at alkenyl gold carbenes.

  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. 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.

  7. Carbon Dioxide Utilization by the Five-Membered Ring Products of Cyclometalation Reactions

    PubMed Central

    Omae, Iwao

    2016-01-01

    In carbon dioxide utilization by cyclometalated five-membered ring products, the following compounds are used in four types of applications: 1. 2-Phenylpyrazole iridium compounds, pincer phosphine iridium compounds and 2-phenylimidazoline iridium compounds are used as catalysts for both formic acid production from CO2 and H2, and hydrogen production from the formic acid. This formic acid can be a useful agent for H2 production and storage for fuel cell electric vehicles. 2. Other chemicals, e.g., dimethyl carbonate, methane, methanol and CO, are produced with dimethylaminomethylphenyltin compounds, pincer phosphine iridium compounds, pincer phosphine nickel compound and ruthenium carbene compound or 2-phenylpyridine iridium compounds, and phenylbenzothiazole iridium compounds as the catalysts for the reactions with CO2. 3. The five-membered ring intermediates of cyclometalation reactions with the conventional substrates react with carbon dioxide to afford their many types of carboxylic acid derivatives. 4. Carbon dioxide is easily immobilized at room temperature with immobilizing agents such as pincer phosphine nickel compounds, pincer phosphine palladium compounds, pincer N,N-dimethylaminomethyltin compounds and tris(2-pyridylthio)methane zinc compounds. PMID:28503084

  8. Stable carbon isotope fractionation during trichloroethene degradation in magnetite-catalyzed Fenton-like reaction

    NASA Astrophysics Data System (ADS)

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Liu, Cunfu; Yu, Tingting; Li, Xiaoqian

    2013-02-01

    Mineral-catalyzed Fenton-like oxidation of chlorinated ethylenes is an attractive technique for in situ soil and groundwater remediation. Stable carbon isotope enrichment factors associated with magnetite-catalyzed Fenton-like oxidation of trichloroethylene (TCE) have been determined, to study the possibility of applying stable carbon isotope analysis as a technique to assess the efficacy of remediation implemented by Fenton-like oxidation. The carbon enrichment factors (ɛ values) ranged from - 2.7‰ to - 3.6‰ with a mean value of - 3.3 ± 0.3‰, and only small differences were observed for different initial reactive conditions. The ɛ values were robust and reproducible, and were relatively insensitive to a number of environmental factors such as ratios of reactants and PCE co-contamination, which can reduce the uncertainty associated with application of isotope enrichment factors for quantification of in situ remediation by Fenton-like reaction. ɛ values for Fenton-like oxidation of TCE were intermediate in those previously reported for aerobic biological processes (ɛ = - 1.1 to - 20.7‰). Thus, field-derived ɛ values that are more negative than those for Fenton-like oxidation, may indicate the occurrence of aerobic biodegradation at contaminated sites undergoing in situ remediation with Fenton-like reaction. However, stable carbon isotope analysis is unable to determine whether there is the occurrence of biodegradation processes if field-derived ɛ values are less negative than those for Fenton-like oxidation.

  9. 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.

  10. In-beam measurements of 13C+12C fusion reaction cross section at energies around and below Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Stefanescu, I.; Chilug, A.; Tudor, D.; Trache, L.; Straticiuc, M.; Burducea, I.; Focsa, I. M.; Ghita, D. G.; Zhang, N.; Tang, X.; Chen, H.

    2017-06-01

    The reaction cross section of the 12C+12C system is difficult to measure because of the presence of the resonances in the Gamow energy window. It has been proved that the 13C+12C reaction is a good alternative to study the behavior of the reaction cross section at energies relevant for astrophysics. We have measured it with activation and online techniques. During online measurements we were interested to determine the relative contributions of the open channels of the 13C+12C reaction. These determinations are necessary to evaluate the total fusion reaction cross section. Therefore, we have measured the γ-ray yields of proton, neutron and alpha particle evaporation channels from the resulting 25Mg compound nucleus using prompt γ-rays measurements. This complements the activation method. The irradiations took place at the 3 MV Tandetron Accelerator at IFIN-HH [1], Bucharest and the prompt gamma-rays were measured using a hyper-pure germanium detector with 100% relative efficiency, shielded with lead bricks. The energy range for the irradiation was from 4.6 up to 11 MeV (in laboratory frame), in steps of 0.2 MeV and the online measurements were performed from 6.4 up to 11 MeV.

  11. 13C-Depleted carbon microparticles in >3700-Ma sea-floor sedimentary rocks from west greenland

    PubMed

    Rosing

    1999-01-29

    Turbiditic and pelagic sedimentary rocks from the Isua supracrustal belt in west Greenland [more than 3700 million years ago (Ma)] contain reduced carbon that is likely biogenic. The carbon is present as 2- to 5-micrometer graphite globules and has an isotopic composition of delta13C that is about -19 per mil (Pee Dee belemnite standard). These data and the mode of occurrence indicate that the reduced carbon represents biogenic detritus, which was perhaps derived from planktonic organisms.

  12. What do carbonate δ13C variations tell us about the evolution of the marine environmental conditions vs. life?

    NASA Astrophysics Data System (ADS)

    Ridgwell, A.

    2016-12-01

    Each end of the Proterozoic Eon (2500-542 Ma) sees the occurrence of extended intervals in which unusually large (compared to the Dullville record of the Phanerozoic) fluctuations in the carbon isotopic (δ13C) values recorded in marine carbonates. These variations presumably must reflect fundamental changes occurring in the global carbon cycle (although some point to diagenesis as the elephant in the outcrop), yet the nature of these, and their relationship to e.g. extreme climatic fluctuations and occurrence of quasi global scale ice ages, is unknown. Here I outline a new interpretation that is in theory able to account for much of the observed Proterozoic δ13C variability and potentially linking it to transitions in the oxidation state of the surficial Earth via changes in ocean pH. I illustrate how this all works by considering the evolution of global carbon cycling in the immediate aftermath of Marinoan glaciation, in an Earth system model (`cGENIE'), elucidating the process that together account for the enigmatic cap carbonate δ13C (negative excursion) signature. If even partially correct, such an interpretation of Proterozoic carbonate δ13C variability suggests an even more unstable and variable evolution of redox state than previously thought and sheds a new light on the utility of carbonate δ13C as a proxy.

  13. 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.

  14. Dissolution and secondary mineral precipitation in basalts due to reactions with carbonic acid

    NASA Astrophysics Data System (ADS)

    Kanakiya, Shreya; Adam, Ludmila; Esteban, Lionel; Rowe, Michael C.; Shane, Phil

    2017-06-01

    One of the leading hydrothermal alteration processes in volcanic environments is when rock-forming minerals with high concentrations of iron, magnesium, and calcium react with CO2 and water to form carbonate minerals. This is used to the advantage of geologic sequestration of anthropogenic CO2. Here we experimentally investigate how mineral carbonation processes alter the rock microstructure due to CO2-water-rock interactions. In order to characterize these changes, CO2-water-rock alteration in Auckland Volcanic Field young basalts (less than 0.3 Ma) is studied before and after a 140 day reaction period. We investigate how whole core basalts with similar geochemistry but different porosity, permeability, pore geometry, and volcanic glass content alter due to CO2-water-rock reactions. Ankerite and aluminosilicate minerals precipitate as secondary phases in the pore space. However, rock dissolution mechanisms are found to dominate this secondary mineral precipitation resulting in an increase in porosity and decrease in rigidity of all samples. The basalt with the highest initial porosity and volcanic glass volume shows the most secondary mineral precipitation. At the same time, this sample exhibits the greatest increase in porosity and permeability, and a decrease in rock rigidity post reaction. For the measured samples, we observe a correlation between volcanic glass volume and rock porosity increase due to rock-fluid reactions. We believe this study can help understand the dynamic rock-fluid interactions when monitoring field scale CO2 sequestration projects in basalts.

  15. 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

    2015-04-07

    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.

  16. 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.

  17. 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

  18. A tandem reaction initiated by 1,4-addition of bis(iodozincio)methane for 1,3-diketone formation.

    PubMed

    Sada, Mutsumi; Matsubara, Seijiro

    2010-01-20

    Treatment of an gamma-acyloxy-alpha,beta-unsaturated ketone with bis(iodozincio)methane leads to a novel tandem reaction consisting of three steps: (1) 1,4-addition of the dizinc reagent to the enone, which affords the corresponding zinc enolate of the beta-zinciomethylated ketone; (2) intramolecular nucleophilic attack by the enolate on the ester group; and (3) Grob-type fragmentation of the adduct, accompanied by elimination of the zinc alkoxide of allyl alcohol. The overall reaction gives 1,3-diketones efficiently.

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

    PubMed Central

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

    2011-01-01

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

  20. 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

  1. 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.

  2. Production of Various Carbon Nanoclusters by Impact Reaction Using Light-Gas Gun as Simulation of Asteroid Collisions in Space

    NASA Astrophysics Data System (ADS)

    Mieno, Tetsu; Hasegawa, Sunao; Mitsuishi, Kazutaka

    2011-12-01

    An impact production of carbon nanoclusters is carried out in nitrogen gas using a two-stage light-gas gun. A small polycarbonate ball (or a stainless steel ball) is injected at about 6.5 km/s into a pressurized target chamber to collide with an aluminum target (or a hexane + aluminum target) in 1 atm of nitrogen gas. We can confirm the production of many types of carbon nanoclusters such as aluminum-encapsulated carbon nanoparticles, carbon nanotubes, and balloonlike nanocarbons. Therefore, it is expected that many types of carbon nanoclusters are produced by impact reactions of asteroids in space, when such reactions take place in a carbon-rich atmosphere. Particularly on Titan satellite, a large number of carbon clusters produced by impacts of asteroids are expected to be stored.

  3. Reactions of Criegee Intermediates with Non-Water Greenhouse Gases: Implications for Metal Free Chemical Fixation of Carbon Dioxide.

    PubMed

    Kumar, Manoj; Francisco, Joseph S

    2017-09-07

    High-level theoretical calculations suggest that a Criegee intermediate preferably interacts with carbon dioxide compared to two other greenhouse gases, nitrous oxide and methane. The results also suggest that the interaction between Criegee intermediates and carbon dioxide involves a cycloaddition reaction, which results in the formation of a cyclic carbonate-type adduct with a barrier of 6.0-14.0 kcal/mol. These results are in contrast to a previous assumption that the reaction occurs barrierlessly. The subsequent decomposition of the cyclic adduct into formic acid and carbon dioxide follows both concerted and stepwise mechanisms. The latter mechanism has been overlooked previously. Under formic acid catalysis, the concerted decomposition of the cyclic carbonate may be favored under tropospheric conditions. Considering that there is a strong nexus between carbon dioxide levels in the atmosphere and global warming, the high reactivity of Criegee intermediates could be utilized for designing efficient carbon capture technologies.

  4. 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.

  5. Indirect study of the {sup 13}C({alpha},n){sup 16}O reaction via the {sup 13}C({sup 7}Li,t){sup 17}O transfer reaction

    SciTech Connect

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

    2008-04-15

    The {sup 13}C({alpha},n){sup 16}O reaction is considered the main neutron source for the s process in low mass asymptotic giant branch (AGB) stars. In the Gamow peak, the cross section sensitively depends on the 1/2{sup +} subthreshold state of {sup 17}O (E{sub x}=6.356 MeV). In this work, we determined the astrophysical S factor through an evaluation of the {alpha} spectroscopic factor and the corresponding asymptotic normalization factor (ANC) of the 6.356 MeV state using the transfer reaction {sup 13}C({sup 7}Li,t){sup 17}O at two different incident energies. Our result confirms that the contribution of the 1/2{sup +} state is dominant at astrophysical energies. Our reaction rate at T=0.09 GK is slightly lower than the value adopted in the Nuclear Astrophysics Compilation of REaction rates (NACRE), but two times larger than the one obtained in a recent ANC measurement.

  6. Characterization of sewage sludge organic matter using solid-state carbon-13 nuclear magnetic resonance spectroscopy.

    PubMed

    Smernik, Ronald J; Oliver, Ian W; Merrington, Graham

    2003-01-01

    Six sewage sludges from five sewage treatment plants in Australia were characterized using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Spectra were acquired both before and after removal of mineral components through treatment with hydrofluoric acid (HF). Carbon mass balance indicated that little organic matter was lost on HF treatment, which significantly improved NMR sensitivity and spectral resolution, and decreased acquisition time and hence cost of NMR analysis. Two NMR techniques were used, the standard cross polarization (CP) technique and Bloch decay (BD). The BD technique had not been applied previously to the analysis of sewage sludge. For each sludge sample, both before and after HF treatment, the BD spectrum contained significantly more alkyl carbon. Spin counting, another technique applied to sewage sludge here for the first time, showed that the BD spectra of the HF-treated sludges were quantitative, while approximately 30% of the CP NMR signal went undetected. The discrepancy between CP and BD spectra was attributed to the presence of alkyl carbon with such high molecular mobility that the efficiency of cross polarization is affected. This study shows that sewage sludge organic matter is significantly different in chemistry to soil organic matter and has implications for the application of sewage sludge to agricultural land.

  7. Promotion of Electrocatalytic Hydrogen Evolution Reaction on Nitrogen-Doped Carbon Nanosheets with Secondary Heteroatoms.

    PubMed

    Qu, Konggang; Zheng, Yao; Zhang, Xianxi; Davey, Ken; Dai, Sheng; Qiao, Shi Zhang

    2017-07-25

    Dual heteroatom-doped carbon materials are efficient electrocatalysts via a synergistic effect. With nitrogen as the primary dopant, boron, sulfur, and phosphorus can be used as secondary elements for co-doped carbons. However, evaluation and analysis of the promotional effect of B, P, and S to N-doped carbons has not been widely researched. Here we report a robust platform that is constructed through polydopamine to prepare N,B-, N,P-, and N,S-co-doped carbon nanosheets, characterized by similar N species content and efficient B, P, and S doping. Systematic investigation reveals S to have the greatest promotional effect in hydrogen evolution reactions (HER) followed by P and that B decreases the activity of N-doped carbons. Experimental and theoretical analyses show the secondary heteroatom promotional effect is impacted by the intrinsic structures and extrinsic surface areas of both materials, i.e., electronic structures exclusively determine the catalytic activity of active sites, while large surface areas optimize apparent HER performance.

  8. 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.

  9. The curved 14C vs. δ13C relationship in dissolved inorganic carbon: A useful tool for groundwater age- and geochemical interpretations

    USGS Publications Warehouse

    Han, Liang-Feng; Plummer, Niel; Aggarwal, Pradeep

    2014-01-01

    Determination of the 14C content of dissolved inorganic carbon (DIC) is useful for dating of groundwater. However, in addition to radioactive decay, the 14C content in DIC (14CDIC) can be affected by many geochemical and physical processes and numerous models have been proposed to refine radiocarbon ages of DIC in groundwater systems. Changes in the δ13C content of DIC (δ13CDIC) often can be used to deduce the processes that affect the carbon isotopic composition of DIC and the 14C value during the chemical evolution of groundwater. This paper shows that a curved relationship of 14CDIC vs. δ13CDIC will be observed for groundwater systems if (1) the change in δ13C value in DIC is caused by a first-order or pseudo-first-order process, e.g. isotopic exchange between DIC and solid carbonate, (2) the reaction/process progresses with the ageing of the groundwater, i.e. with decay of 14C in DIC, and (3) the magnitude of the rate of change in δ13C of DIC is comparable with that of 14C decay. In this paper, we use a lumped parameter method to derive a model based on the curved relationship between 14CDICand δ13CDIC. The derived model, if used for isotopic exchange between DIC and solid carbonate, is identical to that derived by Gonfiantini and Zuppi (2003). The curved relationship of 14CDIC vs. δ13CDIC can be applied to interpret the age of the DIC in groundwater. Results of age calculations using the method discussed in this paper are compared with those obtained by using other methods that calculate the age of DIC based on adjusted initial radiocarbon values for individual samples. This paper shows that in addition to groundwater age interpretation, the lumped parameter method presented here also provides a useful tool for geochemical interpretations, e.g. estimation of apparent rates of geochemical reactions and revealing the complexity of the geochemical environment.

  10. Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model

    NASA Astrophysics Data System (ADS)

    Hansen, Maximilian; Scholz, Denis; Froeschmann, Marie-Louise; Schöne, Bernd R.; Spötl, Christoph

    2017-08-01

    Speleothem stable carbon isotope (δ13C) records provide important paleoclimate and paleo-environmental information. However, the interpretation of these records in terms of past climate or environmental change remains challenging because of various processes affecting the δ13C signals. A process that has only been sparsely discussed so far is carbon isotope exchange between the gaseous CO2 of the cave atmosphere and the dissolved inorganic carbon (DIC) contained in the thin solution film on the speleothem, which may be particularly important for strongly ventilated caves. Here we present a novel, complete reaction diffusion model describing carbon isotope exchange between gaseous CO2 and the DIC in thin solution films. The model considers all parameters affecting carbon isotope exchange, such as diffusion into, out of and within the film, the chemical reactions occurring within the film as well as the dependence of diffusion and the reaction rates on isotopic mass and temperature. To verify the model, we conducted laboratory experiments under completely controlled, cave-analogue conditions at three different temperatures (10, 20, 30 °C). We exposed thin (≈0.1 mm) films of a NaHCO3 solution with four different concentrations (1, 2, 5 and 10 mmol/l, respectively) to a nitrogen atmosphere containing a specific amount of CO2 (1000 and 3000 ppmV). The experimentally observed temporal evolution of the pH and δ13C values of the DIC is in good agreement with the model predictions. The carbon isotope exchange times in our experiments range from ca. 200 to ca. 16,000 s and strongly depend on temperature, film thickness, atmospheric pCO2 and the concentration of DIC. For low pCO2 (between 500 and 1000 ppmV, as for strongly ventilated caves), our time constants are substantially lower than those derived in a previous study, suggesting a potentially stronger influence of carbon isotope exchange on speleothem δ13C values. However, this process should only have an

  11. Synthesis of 3-hydroxy-5-alkoxyhomophthalates by domino '2 : 1-coupling/intramolecular aldol condensation' reactions of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with tetraalkoxymethanes.

    PubMed

    Lubbe, Mathias; Langer, Peter

    2010-02-21

    The first domino '2 : 1 condensation/intramolecular aldol' reactions of 1,3-bis(trimethylsilyloxy)-1,3-butadiene with tetraalkoxymethanes provide a convenient approach to 3-hydroxy-5-alkoxyhomophthalates. These products, which contain one free and one protected hydroxyl group, can be functionalized by palladium(0)-catalyzed cross-coupling reactions.

  12. Thermal 1,3-dipolar cycloaddition reaction of azomethine imines with active esters.

    PubMed

    He, Liwenze; Liu, Lin; Han, Runfeng; Zhang, Weiwei; Xie, Xingang; She, Xuegong

    2016-07-12

    An efficient method for the 1,3-dipolar cycloaddition of azomethine imines with active esters under thermal conditions has been described in good to high yields. This method offers a straightforward pathway to synthesize bioactive pyrazolidinones.

  13. Anhydrous TEMPO-H: reactions of a good hydrogen atom donor with low-valent carbon centres.

    PubMed

    Giffin, Nick A; Makramalla, Miller; Hendsbee, Arthur D; Robertson, Katherine N; Sherren, Cody; Pye, Cory C; Masuda, Jason D; Clyburne, Jason A C

    2011-05-21

    In this paper, we report a novel synthesis of anhydrous 1-hydroxy-2,2,6,6-tetramethyl-piperidine (TEMPO-H). An X-ray crystal structure and full characterization of the compound are included. Compared to hydrated TEMPO-H, its anhydrous form exhibits improved stability and a differing chemical reactivity. The reactions of anhydrous TEMPO-H with a variety of low-valent carbon centres are described. For example, anhydrous TEMPO-H was reacted with 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), an unsaturated NHC. Crystals of [CHNC(6)H(2)(CH(3))(3)](2)C···HO(NC(5)H(6)(CH(3))(4)), IMes···TEMPO-H, were isolated and a crystal structure determined. The experimental structure is compared to the results of theoretical calculations on the hydrogen-bonded dimer. Anhydrous TEMPO-H was also reacted with the saturated NHC, 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr), giving the product [CH(2)Ni-Pr(2)C(6)H(3)](2)CH···O(NC(5)H(6)(CH(3))(4)). In contrast, the reaction of hydrated TEMPO-H with 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene gave small amounts of the hydrolysis product, N-(2,6-diisopropylphenyl)-N-[2-(2,6-diisopropylphenylamino)ethyl]formamide. Finally, anhydrous TEMPO-H was reacted with (triphenylphosphoranylidene)ketene to generate Ph(3)PC(H)C(=O)O(NC(5)H(6)(CH(3))(4)). A full characterization of the product, including an X-ray crystal structure, is described.

  14. 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-...

  15. 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-...

  16. Experimental and computational studies on interrupted Nazarov reactions: exploration of umpolung reactivity at the α-carbon of cyclopentanones.

    PubMed

    Wu, Yen-Ku; Dunbar, Christine R; McDonald, Robert; Ferguson, Michael J; West, F G

    2014-10-22

    A set of densely substituted, α-functionalized cyclopentanones can be generated by a two-component, domino reaction sequence entailing the Nazarov electrocyclization of divinyl ketones and nucleophilic addition of the resulting 2-oxidocyclopentenyl cations by selected trapping modalities. Bypassing the typical eliminative termination, Nazarov oxyallyl species can react with carbon π-nucleophiles through cycloadditions (or formal cycloadditions), in which bridged bicyclic systems are established, or nucleophilic trappings whereby one terminal carbon of the oxyallyl intermediate is subjected to carbon-carbon bond formation. A detailed investigation of reaction parameters to explicitly control the course of the "interrupted" Nazarov reactions is described. This methodology allows for facile installation of α-quaternary centers bearing allyl, alkynyl, and heteroaryl groups in an umpolung fashion. In addition, the trapping event of a Nazarov intermediate with furan was studied by DFT computations, in conjunction with experimental data, offering a rationale for the observed reaction pattern and diastereoselectivity.

  17. The significance of monoisotopic and carbon-13 isobars for the identification of a 19-component dodecapeptide library by positive ion electrospray Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Ramjit, H G; Kruppa, G H; Spier, J P; Ross, C W; Garsky, V M

    2000-01-01

    Harnessing the ultra high resolution capabilities of Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and positive ion electrospray, we have demonstrated the significance and utility of cumulative mass defect high resolution mass separation stable isotope distribution, exact mass measurement and elemental formula as a means of simultaneously identifying 19 components of the dodecapeptide library Ac-ANKISYQS[X]STE-NH(2). With an instrument resolution of 275 000 (average), isobaric multiplets attributed to monoisotopic and carbon-13 components of peptides: Ac approximately SLS approximately NH(2); Ac approximately SNS approximately NH(2); Ac approximately SOS approximately NH(2); Ac approximately SDS approximately NH(2); within the mass window of 1380-1385 Da, and Ac approximately SQS approximately NH(2); Ac approximately SKS approximately NH(2); Ac approximately SES approximately NH(2); Ac approximately SMS approximately NH(2), within the mass window 1395-1400 Da, were mass resolved, accurately mass measured and identified from the computed molecular formulas. This experimental procedure enabled the separation of monoisotopic and carbon-13 isobars yielding enhanced selectivity and specificity and serves to illustrate the significance of monoisotopic and carbon-13 isobars in final product analysis. Chromatographic separation (HPLC) was of limited utility except for monitoring the overall extent of reaction and apparent product distribution. Positive ion electrospray-FTICR-MS and fast atom bombardment (FAB) MS were used to assess final product quality and apparent component distribution.

  18. 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.

  19. 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.

  20. Improving heterologous production of phenylpropanoids in Saccharomyces cerevisiae by tackling an unwanted side reaction of Tsc13, an endogenous double-bond reductase.

    PubMed

    Lehka, Beata Joanna; Eichenberger, Michael; Bjørn-Yoshimoto, Walden Emil; Vanegas, Katherina Garcia; Buijs, Nicolaas; Jensen, Niels Bjerg; Dyekjær, Jane Dannow; Jenssen, Håvard; Simon, Ernesto; Naesby, Michael

    2017-01-01

    Phenylpropanoids, such as flavonoids and stilbenoids, are of great commercial interest, and their production in Saccharomyces cerevisiae is a very promising strategy. However, to achieve commercially viable production, each step of the process must be optimised. We looked at carbon loss, known to occur in the heterologous flavonoid pathway in yeast, and identified an endogenous enzyme, the enoyl reductase Tsc13, which turned out to be responsible for the accumulation of phloretic acid via reduction of p-coumaroyl-CoA. Tsc13 is an essential enzyme involved in fatty acid synthesis and cannot be deleted. Hence, two approaches were adopted in an attempt to reduce the side activity without disrupting the natural function: site saturation mutagenesis identified a number of amino acid changes which slightly increased flavonoid production but without reducing the formation of the side product. Conversely, the complementation of TSC13 by a plant gene homologue essentially eliminated the unwanted side reaction, while retaining the productivity of phenylpropanoids in a simulated fed batch fermentation. © FEMS 2016.

  1. Apportioning carbon sources of authigenic carbonate of extremely 13C-depleted foraminifera from the western North Pacific sediments: Implication from the coupled 13C and 14C isotopic mass balance approach

    NASA Astrophysics Data System (ADS)

    Uchida, M.; Ohkushi, K.; Ahagon, N.; Kimoto, K.; Inagaki, F.; Shibata, Y.

    2005-12-01

    Recently, Uchida et al. (G-cubed, 2004) and Ohkushi et al. (G-cubed, 2005) interprete /delta 13C variations of planktonic and benthic foraminifera found in Last Glacial sediments in off Shimokita Peninsula and Tokachi as evidence for periodic releases of methane, arising from the dissociation of methane hydrate, and its subsequent oxidation in bottom- and/or surface-water environments. According to recent observations of anomalous bottom-simulating reflections, northwest Pacific marginal sediments around Japan main islands bear large abundances of methane hydrate. In this study, analyzed piston cores (42° 21.42' N, 144° 13.36' E) at a water depth 1066-m was retrieved from the off Tokachi continental slope in the Oyashio current region, where recently is found to bear immense amounts of methane hydrate. The piston core covered past 22 ka with high-resolution. Here we showed that carbon isotope signals indicated that planktonic and benthic foraminifera in several glacial sediment layers in the core were highly depleted in13 C; both the planktonic and benthic foraminiferal /delta 13C values ranged from about -10/permil to -2/permil. Most foraminiferal tests in these horizons were brown as a result of postdepositional alteration. Foraminiferal oxygen isotopes fluctuated abnormally in the glacial sediment layers, showing small (about 0.5/permil) positive shifts relative to normal glacial values. We attributed the positive shifts to authigenic carbonate formation in the foraminiferal tests. In order to decipher the relation between foraminifera carbon isotopic signal and methane release from the seafloor, we have apportioned carbon sources (methane from methane hydrate or not) of foraminiferal carbon isotopic anomalies using dual mass balance isotopic model (14C/ 12C and 13C/ 12C). It has been suggested that sulfate-dependent anaerobic methane oxidation (AOM) dominates carbon oxidation and attendant authigenic carbonate precipitation to foraminifera. To this assumption

  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. Intrinsic relationship between enhanced oxygen reduction reaction activity and nanoscale work function of doped carbons.

    PubMed

    Cheon, Jae Yeong; Kim, Jong Hun; Kim, Jae Hyung; Goddeti, Kalyan C; Park, Jeong Young; Joo, Sang Hoon

    2014-06-25

    Nanostructured carbon materials doped with a variety of heteroatoms have shown promising electrocatalytic activity in the oxygen reduction reaction (ORR). However, understanding of the working principles that underpin the superior ORR activity observed with doped nanocarbons is still limited to predictions based on theoretical calculations. Herein, we demonstrate, for the first time, that the enhanced ORR activity in doped nanocarbons can be correlated with the variation in their nanoscale work function. A series of doped ordered mesoporous carbons (OMCs) were prepared using N, S, and O as dopants; the triple-doped, N,S,O-OMC displayed superior ORR activity and four-electron selectivity compared to the dual-doped (N,O-OMC and S,O-OMC) and the monodoped (O-OMC) OMCs. Significantly, the work functions of these heteroatom-doped OMCs, measured by Kelvin probe force microscopy, display a strong correlation with the activity and reaction kinetics for the ORR. This unprecedented experimental insight can be used to provide an explanation for the enhanced ORR activity of heteroatom-doped carbon materials.

  4. 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

  5. NMR method for measuring carbon-13 isotopic enrichment of metabolites in complex solutions.

    PubMed

    Lewis, Ian A; Karsten, Ryan H; Norton, Mark E; Tonelli, Marco; Westler, William M; Markley, John L

    2010-06-01

    Isotope-based methods are commonly used for metabolic flux analysis and metabolite quantification in biological extracts. Nuclear magnetic resonance (NMR) spectroscopy is a powerful analytical tool for these studies because NMR can unambiguously identify compounds and accurately measure (13)C enrichment. We have developed a new pulse sequence, isotope-edited total correlation spectroscopy (ITOCSY), that filters two-dimensional (1)H-(1)H NMR spectra from (12)C- and (13)C-containing molecules into separate, quantitatively equivalent spectra. The ITOCSY spectra of labeled and unlabeled molecules are directly comparable and can be assigned using existing bioinformatics tools. In this study, we evaluate ITOCSY using synthetic mixtures of standards and extracts from Escherichia coli . We show that ITOCSY has low technical error (6.6% for metabolites ranging from 0.34 to 6.2 mM) and can detect molecules at concentrations less than 10 muM. We propose ITOCSY as a practical NMR strategy for metabolic flux analysis, isotope dilution experiments, and other methods that rely on carbon-13 labeling.

  6. NMR Method for Measuring Carbon-13 Isotopic Enrichment of Metabolites in Complex Solutions

    PubMed Central

    2010-01-01

    Isotope-based methods are commonly used for metabolic flux analysis and metabolite quantification in biological extracts. Nuclear magnetic resonance (NMR) spectroscopy is a powerful analytical tool for these studies because NMR can unambiguously identify compounds and accurately measure 13C enrichment. We have developed a new pulse sequence, isotope-edited total correlation spectroscopy (ITOCSY), that filters two-dimensional 1H−1H NMR spectra from 12C- and 13C-containing molecules into separate, quantitatively equivalent spectra. The ITOCSY spectra of labeled and unlabeled molecules are directly comparable and can be assigned using existing bioinformatics tools. In this study, we evaluate ITOCSY using synthetic mixtures of standards and extracts from Escherichia coli. We show that ITOCSY has low technical error (6.6% for metabolites ranging from 0.34 to 6.2 mM) and can detect molecules at concentrations less than 10 μM. We propose ITOCSY as a practical NMR strategy for metabolic flux analysis, isotope dilution experiments, and other methods that rely on carbon-13 labeling. PMID:20459129

  7. The composition of primary carbonate melts and their evolution through wallrock reaction in the mantle

    NASA Astrophysics Data System (ADS)

    Dalton, John A.; Wood, Bernard J.

    1993-10-01

    We have experimentally determined the composition of near-soldus melts from depleted natural Iherzolite at pressures greater than 25 kbar. The melts are carbontitic with low alkali contents and Ca/(Ca + Mg) ratios of 0.72-0.74. Primary carbonate melts from fertile mantle are more sodic with Ca/(Ca + Mg + Fe + Na) of 0.52 and Na/(Na + Ca + Mg + Fe) up to 0.15. The melt compositions are similar to many natural magnesio-carbonatites, but differ substantially from the more abundant calcio-carbonatites. Experimentally we find that calcio-carbonatites are produced by wallrock reaction of primary melts with harzburgite at pressures of less than 25 kbar. At 15 kbar we have obtained a Ca/(Ca + Mg + Fe + Na) ratio of up to 0.87 and very low Na contents generated by this process. Values of Ca/(Ca + Mg + Fe + Na) up to 0.95 are possible at lower pressures. Low pressure wallrock reaction of primary carbonate melt with fertile Iherzolite produces melts richer in Na2CO3, corresponding to possible parental magmas of natrocarbonatite. Wallrock reaction at low pressures transforms the bulk peridotite composition from that of a harzburgite or Iherzolite to wehrlite. Examples of such carbonatite metasomatism are now widely documented. Our experiments show that the calcium content of olivine and the jadeite content of clinopyroxene may be used to constrain the Ca and Na contents respectively of the cabonatite melt responsible for metasomatism.

  8. 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.

  9. 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.

  10. 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

  11. Prediction of carbon-13 NMR chemical shift of alkanes with rooted path vector.

    PubMed

    Zhou, L P; Sun, L L; Yu, Y; Lu, W; Li, Z L

    2006-11-01

    Systematic studies were further made on graph theory in quantitative structure-spectrum relationships (QSSR) for various areas of spectroscopies. Chemical shifts (CS) in alkanes for carbon-13 nuclear magnetic resonance (13C NMR) were well correlated with a set of novel molecular graph indices, called the rooted path vector of various lengths, as several multivariate regression equations as following:CS=3.022+5.336P1+7.356P2-1.648P3+0.83859P4+0.210P5-0.138P6-0.506P7+2.486P8-1.669P9; n=402, m=9, R=0.944, RCV=0.9413, S.D.=3.333, F=358.343, U=35833.211, Q=4355.422 for all types (primary, secondly, tertiary, quaternary as well as methane) of carbon atoms CS=0.983+6.811P1+7.584P2-2.029P3+0.809P4+0.106P5+0.043P6-0.124P7+1.715P8-1.101P9; n=374, m=9, R=0.975, RCV=0.9737, S.D.=2.303, F=773.372, U=36912.109, Q=1930.363 for primary, secondly, tertiary (including methane) carbon atoms; and CS=27.819+2.351P2+0.549P3-0.440P4+0.170P5-0.050P6; n=27, m=5, R=0.992, RCV=0.9674, S.D.=0.324, F=265.418, U=138.891, Q=2.198 for quaternary carbon atoms, respectively. Quite good estimation and prediction results were obtained from the quantitative molecular modeling and the performance of multiple linear regression (MLR) equations were tested to work well through cross-validation (CV) with the leave-one-out (LOO) procedure.

  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. 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.

  14. Analysis of cocondensation of melamine and urea through carbon 13 enriched formaldehyde with C-13 nuclear magnetic resonance spectroscopy

    Treesearch

    Bunichiro Tomita; Chung-Yun Hse

    1995-01-01

    The urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, and melamine-ureaformaldehyde (MUF) cocondensed resins were synthesized using the labeling method with 13C enriched formaldehyde under neutral conditions and their 13C-NMR (nuclear magnetic resonance) spectra were analyzed. The remarkable down-field...

  15. User`s input manual for quasi-steady sodium/water reaction analysis computer program SWAC-13E

    SciTech Connect

    Shin, Y W; Choi, U S; Nelson, S O

    1985-08-01

    SWAC-13E is a quasi-steady two-phase flow analysis code for liquid sodium and hydrogen mixtures in an LMFBR intermediate heat transport system and pressure relief system following large-leak sodium/water reactions in a steam generator. SWAC-13E complements the SWAAM-II and SWAAM-LT codes developed by ANL. SWAC-13E was received from Power Reactor and Nuclear Fuel Development Corporation (PNC) of Japan through an international agreement on the exchange of breeder reactor technology between the US Department of Energy and PNC. SWAC-13E was originally written for the Japanese computer system FACOM, and was converted to run on an IBM system at ANL. Input data needed for execution of the SWAC-13E code are described, following the understanding gained through execution of the code for several example problems. The coding changes involved in the conversion are also described. This report is intended to serve as the first document for use of the IBM version of SWAC-13E. Users are referred to various other documents for details of the code capabilities, theoretical basis, and other pertinent information needed in use of the code.

  16. 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

  17. Polyaddition of Azide-Containing Norbornene-Based Monomer through Strain-Promoted 1,3-Dipolar Cycloaddition Reaction.

    PubMed

    Zhang, Xiaojuan; Zhang, Qian; Wu, Yuzhen; Feng, Chao; Xie, Chao; Fan, Xiaodong; Li, Pengfei

    2016-08-01

    The azide-alkyne "click" reaction has been well known in the past decade, however, another kind of 1,3-dipolar cycloaddition, the azide-alkene reaction is not fully explored in polymer science to date. This contribution reports, for the first time, the discovery of a polyaddition of norbornene based monomer (NC11N3 ) containing both strained double bond and azide moieties. The reaction product is characterized by Fourier transform infrared spectroscopy (FTIR), NMR, gel permeation chromatography (GPC), and mass spectrometry (MS), which confirmed the mechanism that is through cycloaddition of azide to strained double bond on norbornene ring to form triazoline linkage. The reaction can proceed at room temperature as indicated by the increase of molecular weight and viscosity during storage. Monomer, dimer, trimer, tetramer, etc., and species with loss of N2 due to lability of triazoline moiety are identified in the mixture of reaction product. As a unique feature, elimination of N2 in the five-membered ring of triazoline affords a chance to form highly reactive materials, such as with aziridine, which can be a very powerful tool in chemical functionalizations, and find promising applications in reactive polymer resin industries.

  18. The confined space inside carbon nanotubes can dictate the stereo- and regioselectivity of Diels-Alder reactions.

    PubMed

    Smith, Nicole M; Iyer, K Swaminathan; Corry, Ben

    2014-04-21

    Chemical reactions inside carbon nanotubes can yield unusual outcomes. Molecular dynamics simulations show that within the confined space of carbon nanotubes, the 1,4-exo adduct of a Diels-Alder cycloaddition may be produced instead of the 9,10-adduct, which is favoured in bulk. The likely product is highly dependent on the nanotube radius and reactant size.

  19. Nitrogen-rich mesoporous carbon derived from melamine with high electrocatalytic performance for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Wang, Rongfang; Zhou, Tiaobao; Li, Hao; Wang, Hui; Feng, Hanqing; Goh, Jonathan; Ji, Shan

    2014-09-01

    Melamine-derived N-doped mesoporous carbon (MNMC) is synthesized by the pyrolysis of lysine and melamineunder at nitrogen atmosphere using ferric chloride as a dopant and SiO2 nanoparticles as hard templates to form mesoporous architecture. The N content in the bulk of carbon materials is as high as 11.3% and ca. 40.6% of N is in the form of pyridinic-N. The surface area of MNMC is ca. 650 m2 g-1 with a pore size distribution in the range of 2.2-34.5 nm. Compared to commercial Pt/C (20 wt%), MNMC exhibits much better electrocatalytic activity, better durability, and higher methanol tolerance for oxygen reduction reaction (ORR) in alkaline medium. Particularly, the onset ORR potential and half-wave ORR potential of MNMC are 1.059 and 0.871 V vs. RHE respectively, which are higher than those of commercial Pt/C.

  20. Ammonia-treated Ordered Mesoporous Carbons as Catalytic Materials for Oxygen Reduction Reaction

    SciTech Connect

    Wang, Xiqing; Lee, Je Seung; Zhu, Qing; Liu, Jun; Wang, Yong; Dai, Sheng

    2010-04-13

    Polymer electrolyte membrane fuel cells (PEMFCs) have been considered as promising alternative power sources for many mobile and stationary applications. Compared to the fast hydrogen oxidation at the anode, the sluggish oxygen reduction reaction (ORR) at the cathode requires high-performance catalysts. Currently, platium (Pt) nanoparticles supported on high surface area carbons remain the best catalysts for ORR. However, both instability and high cost of Pt-based catalysts represent two main obstacles limiting the commercial applications of PEMFCs. The instability of supported Pt catalysts is mainly due to the corrosion of carbon support under operation conditions and the agglomation and detachment of Pt particles, leading to a decrease in catalytic surface areas. Development of corrosion resistant supports and enhancement of the interactions between Pt and supports are two strategies to improve the cathode long-term activity.

  1. Effect of Co in the efficiency of the methanol electrooxidation reaction on carbon supported Pt

    NASA Astrophysics Data System (ADS)

    Hernández-Fernández, P.; Montiel, M.; Ocón, P.; Fierro, J. L. G.; Wang, H.; Abruña, H. D.; Rojas, S.

    The effect of Co addition to carbon nanotubes supported Pt in the methanol oxidation reaction has been investigated by means of differential electrochemical mass spectrometry (DEMS). It has been observed that the CO 2 efficiency increases in carbon nanotubes supported PtCo compared to its homologous Pt catalysts, especially at potentials lower than 0.55 V. Despite of this, the Faradaic current reached by the bimetallic catalysts in the methanol electrooxidation was lower than those recorded on the monometallic samples. This is because Co addition difficult finding enough Pt vicinal sites for methanol dehydrogenation. On the other hand, it has been found that alloying Pt with Co, shifts down the d-band center of the larger element, so the strength of the interaction with adsorbates decreases. Consequently, it will be easier to oxidize CO ad on the bimetallic surface. Furthermore, the necessary -OH ad species for the CO ad oxidation to CO 2 will be provided by the CNTs themselves.

  2. 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.

  3. Carbon-13 Chemical-Shift Tensors in Polycyclic Aromatic Compounds: Fluoranthene and Decacyclene

    SciTech Connect

    Barich, Dewey H.; Hu, Jian Zhi; Pugmire, Ronald J.; Grant, David M.

    2002-06-18

    The measurement of 13C chemical-shift tensors (CSTs) of polycyclic aromatic hydrocarbons (PAHs) has received considerable attention in recent years.1-7 Challenges to measuring CSTs in aromatic microcrystalline powders include spectral complexity due to the spinning sideband patterns, the relatively close isotropic chemical shifts of the various carbons in the molecule (typically 120-140 ppm), and coincidental overlap of equivalent molecular positions in crystallographically inequivalent sites. Spectral complexity is reduced in this work by application of the FIREMAT experiment, a two-dimensional (2D) magic angle turning (MAT) experiment that isolates individual sideband patterns associated with different isotropic chemical shifts.8 Recent advances in such methods have made possible the isolation of several dozen sideband patterns from a composite spectrum.

  4. 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.

  5. 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 ...

  6. 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 ...

  7. Reactions of carbon dioxide with bis(trimethylsilyl)amino derivatives of lanthanides

    SciTech Connect

    Rad'kov, Yu.F.; Fedorova, E.A.; Khorshev, S.Ya.; Kalinina, G.S.; Bochkarev, M.N.; Razuvaev, G.A.

    1986-08-10

    The aminolanthanides ((Me/sub 3/Si)/sub 2/N)/sub x/Ln (Ln = Pr, Nd, Sm, Eu, Yb; x = 2, 3) under normal conditions take up 2 or 3 moles of carbon dioxide. The reactions are accompanied by secondary processes, leading to the formation of Me/sub 3/SiNCO, (Me/sub 3/Si)/sub 2/O, Me/sub 3/SiNCNSiMe/sub 3/, and an unidentified substance containing coordinated CO/sub 2/. A general scheme is proposed for the process

  8. Stepwise quenching of exciton fluorescence in carbon nanotubes by single-molecule reactions.

    PubMed

    Cognet, Laurent; Tsyboulski, Dmitri A; Rocha, John-David R; Doyle, Condell D; Tour, James M; Weisman, R Bruce

    2007-06-08

    Single-molecule chemical reactions with individual single-walled carbon nanotubes were observed through near-infrared photoluminescence microscopy. The emission intensity within distinct submicrometer segments of single nanotubes changed in discrete steps after exposure to acid, base, or diazonium reactants. The steps were uncorrelated in space and time and reflected the quenching of mobile excitons at localized sites of reversible or irreversible chemical attack. Analysis of step amplitudes revealed an exciton diffusional range of about 90 nanometers, independent of nanotube structure. Each exciton visited about 10,000 atomic sites during its lifetime, providing highly efficient sensing of local chemical and physical perturbations.

  9. 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.

  10. Continuous reactions in supercritical carbon dioxide: problems, solutions and possible ways forward.

    PubMed

    Han, Xue; Poliakoff, Martyn

    2012-02-21

    This Tutorial Review focuses on supercritical carbon dioxide (scCO(2)), and discusses some of the problems that have frustrated its wide use on an industrial scale. It gives some recent examples where strategies have been developed to reduce the energy requirements, including sequential reactions and gas-expanded liquids. It then describes a number of cases where scCO(2) offers real chemical advantages over more conventional solvents, for example by controlled phase separation, tunable selectivity, oxidation and on-line analysis and self-optimisation. Overall, this review indicates where scCO(2) could deliver value in the future.

  11. {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.

  12. Using ordered carbon nanomaterials for shedding light on the mechanism of the cathodic oxygen reduction reaction.

    PubMed

    Ruvinskiy, Pavel S; Bonnefont, Antoine; Pham-Huu, Cuong; Savinova, Elena R

    2011-07-19

    Insufficient understanding of the mechanism of the cathodic oxygen reduction reaction puts constraints on the improvement of the efficiency of polymer electrolyte fuel cells (PEMFCs). We apply ordered catalytic layers based on vertically aligned carbon nanofilaments and combine experimental rotating ring-disk studies with mathematical modeling for shedding light on the mechanism of the oxygen reduction reaction on Pt nanoparticles. Based on the experimental and simulation evidence we propose a dual path ORR mechanism which comprises a "direct 4e(-)" and a "series 2e(-) + 2e(-)" pathway and explains switching between the two. For the first time we show that below 0.8 V the "direct" path may be discarded and the ORR predominantly occurs via H(2)O(2) mediated pathway, while in the potential interval between ca. 0.8 V and the onset of the ORR the "direct" path is dominating.

  13. Concerning the Role of Supercritical Carbon Dioxide in SN 1 Reactions.

    PubMed

    Qiao, Yun X; Theyssen, Nils; Eifert, Tobias; Liauw, Marcel A; Franciò, Giancarlo; Schenk, Karolin; Leitner, Walter; Reetz, Manfred T

    2017-03-17

    A series of SN 1-type reactions has been studied under various conditions to clarify the role of supercritical carbon dioxide (scCO2 ) as reaction medium for this kind of transformations. The application of scCO2 did not result in higher yields in any of the experiments in comparison to those under neat conditions or in the presence of other inert compressed gases. High-pressure UV/Vis spectroscopic measurements were carried out to quantify the degree of carbocation formation of a highly SN 1-active alkyl halide as a function of the applied solvent. No measureable concentration of carbocations could be detected in scCO2 , just like in other low polarity solvents. Taken together, these results do not support the previously claimed activating effect via enhanced SN 1 ionization due to the quadrupolar moment of the supercritical fluid. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  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.

  15. 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.

  16. 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.

  17. 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.

  18. 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, tw