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Sample records for alkane oxidation rate

  1. Millisecond Oxidation of Alkanes

    SciTech Connect

    Scott Han

    2011-09-30

    This project was undertaken in response to the Department of Energy's call to research and develop technologies 'that will reduce energy consumption, enhance economic competitiveness, and reduce environmental impacts of the domestic chemical industry.' The current technology at the time for producing 140 billion pounds per year of propylene from naphtha and Liquified Petroleum Gas (LPG) relied on energy- and capital-intensive steam crackers and Fluidized Catalytic Cracking (FCC) units. The propylene is isolated from the product stream in a costly separation step and subsequently converted to acrylic acid and other derivatives in separate production facilities. This project proposed a Short Contact Time Reactor (SCTR)-based catalytic oxydehydrogenation process that could convert propane to propylene and acrylic acid in a cost-effective and energy-efficient fashion. Full implementation of this technology could lead to sizeable energy, economic and environmental benefits for the U. S. chemical industry by providing up to 45 trillion BTUs/year, cost savings of $1.8 billion/year and a combined 35 million pounds/year reduction in environmental pollutants such as COx, NOx, and SOx. Midway through the project term, the program directive changed, which approval from the DOE and its review panel, from direct propane oxidation to acrylic acid at millisecond contact times to a two-step process for making acrylic acid from propane. The first step was the primary focus, namely the conversion of propane to propylene in high yields assisted by the presence of CO2. The product stream from step one was then to be fed directly into a commercially practiced propylene-to-acrylic acid tandem reactor system.

  2. Rubredoxins Involved in Alkane Oxidation

    PubMed Central

    van Beilen, Jan B.; Neuenschwander, Martin; Smits, Theo H. M.; Roth, Christian; Balada, Stefanie B.; Witholt, Bernard

    2002-01-01

    Rubredoxins (Rds) are essential electron transfer components of bacterial membrane-bound alkane hydroxylase systems. Several Rd genes associated with alkane hydroxylase or Rd reductase genes were cloned from gram-positive and gram-negative organisms able to grow on n-alkanes (Alk-Rds). Complementation tests in an Escherichia coli recombinant containing all Pseudomonas putida GPo1 genes necessary for growth on alkanes except Rd 2 (AlkG) and sequence comparisons showed that the Alk-Rds can be divided in AlkG1- and AlkG2-type Rds. All alkane-degrading strains contain AlkG2-type Rds, which are able to replace the GPo1 Rd 2 in n-octane hydroxylation. Most strains also contain AlkG1-type Rds, which do not complement the deletion mutant but are highly conserved among gram-positive and gram-negative bacteria. Common to most Rds are the two iron-binding CXXCG motifs. All Alk-Rds possess four negatively charged residues that are not conserved in other Rds. The AlkG1-type Rds can be distinguished from the AlkG2-type Rds by the insertion of an arginine downstream of the second CXXCG motif. In addition, the glycines in the two CXXCG motifs are usually replaced by other amino acids. Mutagenesis of residues conserved in either the AlkG1- or the AlkG2-type Rds, but not between both types, shows that AlkG1 is unable to transfer electrons to the alkane hydroxylase mainly due to the insertion of the arginine, whereas the exchange of the glycines in the two CXXCG motifs only has a limited effect. PMID:11872724

  3. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, P.E. Jr.; Lyons, J.E.

    1994-01-18

    Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or [beta]-pyrrolic positions.

  4. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1994-01-01

    Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or .beta.-pyrrolic positions.

  5. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1992-01-01

    Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been replaced with one or more nitro groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

  6. Regulation of alkane oxidation in Pseudomonas putida.

    PubMed Central

    Grund, A; Shapiro, J; Fennewald, M; Bacha, P; Leahy, J; Markbreiter, K; Nieder, M; Toepfer, M

    1975-01-01

    We have studied the appearance of whole-cell oxidizing activity for n-alkanes and their oxidation products in strains of Pseudomonas putida carrying the OCT plasmid. Our results indicate that the OCT plasmid codes for inducible alkane-hydroxylating and primary alcohol-dehydrogenating activities and that the chromosome codes for constitutive oxidizing activities for primary alcohols, aliphatic aldehydes, and fatty acids. Mutant isolation confirms the presence of an alcohol dehydrogenase locus on the OCT plasmid and indicated the presence of multiple alcohol and aldehyde dehydrogenase loci on the P. putida chromosome. Induction tests with various compounds indicate that inducer recognition has specificity for chain length and can be affected by the degree of oxidation of the carbon chain. Some inducers are neither growth nor respiration substrates. Growth tests with and without a gratuitous inducer indicate that undecane is not a growth substrate because it does not induce alkane hydroxylase activity. Using a growth test for determining induction of the plasmid alcohol dehydrogenase it is possible to show that heptane induces this activity in hydroxylase-negative mutants. This suggests that unoxidized alkane molecules are the physiological inducers of both plasmid activities. PMID:1150626

  7. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

    Kung, Harold H.; Chaar, Mohamed A.

    1988-01-01

    Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M.sub.3 (VO.sub.4).sub.2 and MV.sub.2 O.sub.6, M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

  8. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

    Kung, H.H.; Chaar, M.A.

    1988-10-11

    Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M[sub 3](VO[sub 4])[sub 2] and MV[sub 2]O[sub 6], M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

  9. Oxidation Products of Semi-volatile Alkanes by Hydroxyl Radicals

    NASA Astrophysics Data System (ADS)

    Zhang, H.; Worton, D. R.; Nah, T.; Goldstein, A. H.; Wilson, K. R.

    2013-12-01

    Alkanes are ubiquitous in the atmosphere and are important components that influence atmospheric chemistry. Semi-volatile alkanes are partitioned between the gas- and the particle-phases and can be readily oxidized in both phases. Previous studies have demonstrated that reaction rates and the products of OH oxidation are very different for organic compounds in the gas- and particle phases. In the present study, n-octadecane (C18H38), n-eicosane (C20H42), n-docosane (C22H46), n-tricosane (C24H50), and n-pentadecylcyclohexane (C21H42) were chosen as model compounds for semi-volatile alkanes to examine their OH-initiated oxidation reactions in a flow tube reactor. OH exposure was varied in the experiments, equivalent to oxidation of up to one week in the atmosphere. Oxidation products were collected on filters and analyzed using two-dimensional gas chromatography coupled to a high-resolution time-of-flight electron impact ionization and vacuum ultraviolet photoionization mass spectrometer. Most of the oxygenated higher molecular weight isomers were separated and quantified. Our results suggest that aerosol samples formed in the n-octadecane experiment were more oxidized than the other model compounds (i.e., functionalization products with three oxygen atoms per molecule compared to two oxygen atoms per molecule) at similar OH exposures and aerosol mass loadings. This is likely due to the concentration of n-octadecane in the gas phase where oxidation is more rapid. We find that the first-generation gas-phase oxidation products quickly partition to the particle phase after which higher-generation oxidation likely occurs in the particle phase. Interestingly, functionalized carbonyl isomers for the normal alkanes were only observed on the 4 carbon positions closest to the molecule end in all cases, which is in contrast to structure-reactivity relationship (SRR) predictions for gas-phase reactions. For n-octadecane, the concentrations of first-generation functionalization

  10. Geomicrobiological linkages between short-chain alkane consumption and sulfate reduction rates in seep sediments.

    PubMed

    Bose, Arpita; Rogers, Daniel R; Adams, Melissa M; Joye, Samantha B; Girguis, Peter R

    2013-01-01

    Marine hydrocarbon seeps are ecosystems that are rich in methane, and, in some cases, short-chain (C2-C5) and longer alkanes. C2-C4 alkanes such as ethane, propane, and butane can be significant components of seeping fluids. Some sulfate-reducing microbes oxidize short-chain alkanes anaerobically, and may play an important role in both the competition for sulfate and the local carbon budget. To better understand the anaerobic oxidation of short-chain n-alkanes coupled with sulfate-reduction, hydrocarbon-rich sediments from the Gulf of Mexico (GoM) were amended with artificial, sulfate-replete seawater and one of four n-alkanes (C1-C4) then incubated under strict anaerobic conditions. Measured rates of alkane oxidation and sulfate reduction closely follow stoichiometric predictions that assume the complete oxidation of alkanes to CO2 (though other sinks for alkane carbon likely exist). Changes in the δ(13)C of all the alkanes in the reactors show enrichment over the course of the incubation, with the C3 and C4 incubations showing the greatest enrichment (4.4 and 4.5‰, respectively). The concurrent depletion in the δ(13)C of dissolved inorganic carbon (DIC) implies a transfer of carbon from the alkane to the DIC pool (-3.5 and -6.7‰ for C3 and C4 incubations, respectively). Microbial community analyses reveal that certain members of the class Deltaproteobacteria are selectively enriched as the incubations degrade C1-C4 alkanes. Phylogenetic analyses indicate that distinct phylotypes are enriched in the ethane reactors, while phylotypes in the propane and butane reactors align with previously identified C3-C4 alkane-oxidizing sulfate-reducers. These data further constrain the potential influence of alkane oxidation on sulfate reduction rates (SRRs) in cold hydrocarbon-rich sediments, provide insight into their contribution to local carbon cycling, and illustrate the extent to which short-chain alkanes can serve as electron donors and govern microbial community

  11. Geomicrobiological linkages between short-chain alkane consumption and sulfate reduction rates in seep sediments

    PubMed Central

    Bose, Arpita; Rogers, Daniel R.; Adams, Melissa M.; Joye, Samantha B.; Girguis, Peter R.

    2013-01-01

    Marine hydrocarbon seeps are ecosystems that are rich in methane, and, in some cases, short-chain (C2–C5) and longer alkanes. C2–C4 alkanes such as ethane, propane, and butane can be significant components of seeping fluids. Some sulfate-reducing microbes oxidize short-chain alkanes anaerobically, and may play an important role in both the competition for sulfate and the local carbon budget. To better understand the anaerobic oxidation of short-chain n-alkanes coupled with sulfate-reduction, hydrocarbon-rich sediments from the Gulf of Mexico (GoM) were amended with artificial, sulfate-replete seawater and one of four n-alkanes (C1–C4) then incubated under strict anaerobic conditions. Measured rates of alkane oxidation and sulfate reduction closely follow stoichiometric predictions that assume the complete oxidation of alkanes to CO2 (though other sinks for alkane carbon likely exist). Changes in the δ13C of all the alkanes in the reactors show enrichment over the course of the incubation, with the C3 and C4 incubations showing the greatest enrichment (4.4 and 4.5‰, respectively). The concurrent depletion in the δ13C of dissolved inorganic carbon (DIC) implies a transfer of carbon from the alkane to the DIC pool (−3.5 and −6.7‰ for C3 and C4 incubations, respectively). Microbial community analyses reveal that certain members of the class Deltaproteobacteria are selectively enriched as the incubations degrade C1–C4 alkanes. Phylogenetic analyses indicate that distinct phylotypes are enriched in the ethane reactors, while phylotypes in the propane and butane reactors align with previously identified C3–C4 alkane-oxidizing sulfate-reducers. These data further constrain the potential influence of alkane oxidation on sulfate reduction rates (SRRs) in cold hydrocarbon-rich sediments, provide insight into their contribution to local carbon cycling, and illustrate the extent to which short-chain alkanes can serve as electron donors and govern microbial

  12. DITERMINAL OXIDATION OF LONG-CHAIN ALKANES BY BACTERIA1

    PubMed Central

    Kester, A. S.; Foster, J. W.

    1963-01-01

    Kester, A. S. (The University of Texas, Austin) and J. W. Foster. Diterminal oxidation of long-chain alkanes by bacteria. J. Bacteriol. 85:859–869. 1963.—A corynebacterial organism capable of growing in mineral salts with individual pure alkanes as carbon sources produces a series of acids from the C10-C14 alkanes. They have been isolated in pure form and identified as monoic, ω-hydroxy monoic, and dioic acids containing the same number of carbon atoms as the substrate alkane. Oxidation took place at both terminal methyl groups—“diterminal oxidation.” Appropriate labeling experiments indicate that omega oxidation of fatty acids occurs in this organism and that an oxygenation with O2 occurs. Images PMID:14044955

  13. Catalytic oxidation of light alkanes in presence of a base

    DOEpatents

    Bhinde, Manoj V.; Bierl, Thomas W.

    1998-01-01

    The presence of a base in the reaction mixture in a metal-ligand catalyzed partial oxidation of alkanes results in sustained catalyst activity, and in greater percent conversion as compared with oxidation in the absence of base, while maintaining satisfactory selectivity for the desired oxidation, for example the oxidation of isobutane to isobutanol.

  14. Catalytic oxidation of light alkanes in presence of a base

    DOEpatents

    Bhinde, M.V.; Bierl, T.W.

    1998-03-03

    The presence of a base in the reaction mixture in a metal-ligand catalyzed partial oxidation of alkanes results in sustained catalyst activity, and in greater percent conversion as compared with oxidation in the absence of base, while maintaining satisfactory selectivity for the desired oxidation, for example the oxidation of isobutane to isobutanol. 1 fig.

  15. Site isolation in vanadium phosphorus oxide alkane oxidation

    SciTech Connect

    Thompson, M R; Ebner, J R

    1991-06-01

    Single crystal X-ray diffraction studies of vanadyl pyrophosphate indicate that at least two polytypical structures exists for this active and selective alkane oxidation catalyst. The crystal structures of these materials differ with respect to the symmetry and direction of columns of vanadyl groups within the unit cell. Single crystals of vanadyl pyrophosphate have been generated at extreme temperatures not often experienced by microcrystalline catalysts. The crystallography of the system suggests that other crystalline modifications or disordered phases might also exist. Zeroth-order models of crystal surface termination of vanadyl pyrophosphate have been constructed which conceptually illustrate the ability of vanadyl pyrophosphate to accommodate varying amounts of surface phosphorus parallel to (1,0,0), (0,1,0) and (0,2,4). Pyrophosphate termination of surfaces parallel to (1,0,0) likely results in the isolation of clusters of reactive centers and limits overoxidation of the alkane substrate. 23 refs., 6 figs.

  16. Anaerobic oxidation of short-chain alkanes in hydrothermal sediments: potential influences on sulfur cycling and microbial diversity

    SciTech Connect

    Adams, MM; Hoarfrost, AL; Bose, A; Joye, SB; Girguis, PR

    2013-05-14

    Short-chain alkanes play a substantial role in carbon and sulfur cycling at hydrocarbon-rich environments globally, yet few studies have examined the metabolism of ethane (C-2), propane (C-3), and butane (C-4) in anoxic sediments in contrast to methane (C-1). In hydrothermal vent systems, short-chain alkanes are formed over relatively short geological time scales via thermogenic processes and often exist at high concentrations. The sediment-covered hydrothermal vent systems at Middle Valley (MV Juan de Fuca Ridge) are an ideal site for investigating the anaerobic oxidation of C-1-C-4 alkanes, given the elevated temperatures and dissolved hydrocarbon species characteristic of these metalliferous sediments. We examined whether MV microbial communities oxidized C-1-C-4 alkanes under mesophilic to thermophilic sulfate-reducing conditions. Here we present data from discrete temperature (25, 55, and 75 degrees C) anaerobic batch reactor incubations of MV sediments supplemented with individual alkanes. Co-registered alkane consumption and sulfate reduction (SR) measurements provide clear evidence for C-1-C-4 alkane oxidation linked to SR over time and across temperatures. In these anaerobic batch reactor sediments, 16S ribosomal RNA pyrosequencing revealed that Deltaproteobacteria, particularly a novel sulfate-reducing lineage, were the likely phylotypes mediating the oxidation of C-2-C-4 alkanes. Maximum C-1-C-4 alkane oxidation rates occurred at 55 degrees C, which reflects the mid-core sediment temperature profile and corroborates previous studies of rate maxima for the anaerobic oxidation of methane (AOM). Of the alkanes investigated, C-3 was oxidized at the highest rate over time, then C-4, C-2, and C-1, respectively. The implications of these results are discussed with respect to the potential competition between the anaerobic oxidation of C-2-C(4)alkanes with AOM for available oxidants and the influence on the fate of C-1 derived from these hydrothermal systems.

  17. Anaerobic oxidation of short-chain alkanes in hydrothermal sediments: potential influences on sulfur cycling and microbial diversity.

    PubMed

    Adams, Melissa M; Hoarfrost, Adrienne L; Bose, Arpita; Joye, Samantha B; Girguis, Peter R

    2013-01-01

    Short-chain alkanes play a substantial role in carbon and sulfur cycling at hydrocarbon-rich environments globally, yet few studies have examined the metabolism of ethane (C2), propane (C3), and butane (C4) in anoxic sediments in contrast to methane (C1). In hydrothermal vent systems, short-chain alkanes are formed over relatively short geological time scales via thermogenic processes and often exist at high concentrations. The sediment-covered hydrothermal vent systems at Middle Valley (MV, Juan de Fuca Ridge) are an ideal site for investigating the anaerobic oxidation of C1-C4 alkanes, given the elevated temperatures and dissolved hydrocarbon species characteristic of these metalliferous sediments. We examined whether MV microbial communities oxidized C1-C4 alkanes under mesophilic to thermophilic sulfate-reducing conditions. Here we present data from discrete temperature (25, 55, and 75°C) anaerobic batch reactor incubations of MV sediments supplemented with individual alkanes. Co-registered alkane consumption and sulfate reduction (SR) measurements provide clear evidence for C1-C4 alkane oxidation linked to SR over time and across temperatures. In these anaerobic batch reactor sediments, 16S ribosomal RNA pyrosequencing revealed that Deltaproteobacteria, particularly a novel sulfate-reducing lineage, were the likely phylotypes mediating the oxidation of C2-C4 alkanes. Maximum C1-C4 alkane oxidation rates occurred at 55°C, which reflects the mid-core sediment temperature profile and corroborates previous studies of rate maxima for the anaerobic oxidation of methane (AOM). Of the alkanes investigated, C3 was oxidized at the highest rate over time, then C4, C2, and C1, respectively. The implications of these results are discussed with respect to the potential competition between the anaerobic oxidation of C2-C4alkanes with AOM for available oxidants and the influence on the fate of C1 derived from these hydrothermal systems.

  18. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, P.E. Jr.; Lyons, J.E.

    1995-01-17

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or [beta]-pyrrolic positions.

  19. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, P.E. Jr.; Lyons, J.E.

    1993-05-18

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso- and/or [beta]-pyrrolic positions.

  20. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1995-01-01

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

  1. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1993-01-01

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

  2. Cyano- and polycyanometalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1992-01-01

    Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been substituted with one or more cyano groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

  3. Modeling SOA production from the oxidation of intermediate volatility alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-12-01

    Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapour pressure. This process was investigated using the explicit oxidation model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere). Results for the C8-C24 n-alkane series show the expected trends, i.e. (i) SOA yield grows with the carbon backbone of the parent hydrocarbon, (ii) SOA yields decreases with the decreasing pre-existing organic aerosol concentration, (iii) the number of generations required to describe SOA production increases when the pre-existing organic aerosol concentration decreases. Most SOA contributors were found to be not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA). Branched alkanes are more prone to fragment in the early stage of the oxidation than their corresponding linear analogues. Fragmentation is expected to alter both the yield and the mean oxidation state of the SOA. Here, GECKO-A is applied to generate highly detailed oxidation schemes for various series of branched and cyclised alkanes. Branching and cyclisation effects on SOA yields and oxidation states will be examined.

  4. Modeling of Alkane Oxidation Using Constituents and Species

    NASA Technical Reports Server (NTRS)

    Bellan, Jasette; Harstad, Kenneth G.

    2010-01-01

    It is currently not possible to perform simulations of turbulent reactive flows due in particular to complex chemistry, which may contain thousands of reactions and hundreds of species. This complex chemistry results in additional differential equations, making the numerical solution of the equation set computationally prohibitive. Reducing the chemical kinetics mathematical description is one of several important goals in turbulent reactive flow modeling. A chemical kinetics reduction model is proposed for alkane oxidation in air that is based on a parallel methodology to that used in turbulence modeling in the context of the Large Eddy Simulation. The objective of kinetic modeling is to predict the heat release and temperature evolution. This kinetic mechanism is valid over a pressure range from atmospheric to 60 bar, temperatures from 600 K to 2,500 K, and equivalence ratios from 0.125 to 8. This range encompasses diesel, HCCI, and gas-turbine engines, including cold ignition. A computationally efficient kinetic reduction has been proposed for alkanes that has been illustrated for n-heptane using the LLNL heptane mechanism. This model is consistent with turbulence modeling in that scales were first categorized into either those modeled or those computed as progress variables. Species were identified as being either light or heavy. The heavy species were decomposed into defined 13 constituents, and their total molar density was shown to evolve in a quasi-steady manner. The light species behave either in a quasi-steady or unsteady manner. The modeled scales are the total constituent molar density, Nc, and the molar density of the quasi-steady light species. The progress variables are the total constituent molar density rate evolution and the molar densities of the unsteady light species. The unsteady equations for the light species contain contributions of the type gain/loss rates from the heavy species that are modeled consistent with the developed mathematical

  5. In Vivo Evolution of Butane Oxidation by Terminal Alkane Hydroxylases AlkB and CYP153A6▿ †

    PubMed Central

    Koch, Daniel J.; Chen, Mike M.; van Beilen, Jan B.; Arnold, Frances H.

    2009-01-01

    Enzymes of the AlkB and CYP153 families catalyze the first step in the catabolism of medium-chain-length alkanes, selective oxidation of the alkane to the 1-alkanol, and enable their host organisms to utilize alkanes as carbon sources. Small, gaseous alkanes, however, are converted to alkanols by evolutionarily unrelated methane monooxygenases. Propane and butane can be oxidized by CYP enzymes engineered in the laboratory, but these produce predominantly the 2-alkanols. Here we report the in vivo-directed evolution of two medium-chain-length terminal alkane hydroxylases, the integral membrane di-iron enzyme AlkB from Pseudomonas putida GPo1 and the class II-type soluble CYP153A6 from Mycobacterium sp. strain HXN-1500, to enhance their activity on small alkanes. We established a P. putida evolution system that enables selection for terminal alkane hydroxylase activity and used it to select propane- and butane-oxidizing enzymes based on enhanced growth complementation of an adapted P. putida GPo12(pGEc47ΔB) strain. The resulting enzymes exhibited higher rates of 1-butanol production from butane and maintained their preference for terminal hydroxylation. This in vivo evolution system could be useful for directed evolution of enzymes that function efficiently to hydroxylate small alkanes in engineered hosts. PMID:19011057

  6. Rate of Hydrolysis of Tertiary Halogeno Alkanes

    ERIC Educational Resources Information Center

    Pritchard, D. R.

    1978-01-01

    Describes an experiment to measure the relative rate of hydrolysis of the 2-x-2 methylpropanes, where x is bromo, chloro or iodo. The results are plotted on a graph from which the relative rate of hydrolysis can be deduced. (Author/GA)

  7. Rate of Hydrolysis of Tertiary Halogeno Alkanes

    ERIC Educational Resources Information Center

    Pritchard, D. R.

    1978-01-01

    Describes an experiment to measure the relative rate of hydrolysis of the 2-x-2 methylpropanes, where x is bromo, chloro or iodo. The results are plotted on a graph from which the relative rate of hydrolysis can be deduced. (Author/GA)

  8. Radiation induced oxidation of liquid alkanes as a polymer model

    NASA Astrophysics Data System (ADS)

    Soebianto, Yanti S.; Katsumura, Yosuke; Ishigure, Kenkichi; Kubo, Junichi; Hamakawa, Satoshi; Kudoh, Hisaaki; Seguchi, Tadao

    1996-10-01

    Radiation induced oxidation of liquid n-hexadecane ( n-C 16H 34) and squalene (C 30H 62) as a polymer model has been investigated by the measurements of the gas evolution and O 2 uptake, and analyses of the oxidation products. Low O 2 uptake [G(-O 2 ≈ 6.0] in liquid alkanes, indicates in solid oxidation reaction does not exhibit chain kinetics, which is a big contrast to the process observed in solid, G(-O 2) ≫ 10. H 2 is the main gas product. More than 90% of the consumed O 2 are converted into the oxidation products in liquid phase, mainly carboxylic acids, which is also a big contrast to the results of the radiolysis of liquid cyclohexane in the presence of O 2 and thermal oxidation of hexadecene at elevated temperatures, where ketones and alcohols are major products at the initial stage. In the presence of aromatic additives, energy and charge transfer to the additives taking place despite the presence of O 2 reduce the H 2 evolution and the acid formation in parallel. Although hydroaromatic compounds act as an energy and charge scavenger, the are selectively oxidized through the donation of hydrogen in cyclic alkyl part attached to the phenyl ring, leading to large O 2 uptake and corresponding ketone formation. From the comparison of the G-values of the O 2 uptake, it was found that the oxidation reactions of liquid alkanes reflect well the oxidation of amorphous part in polymers.

  9. Anaerobic oxidation of short-chain alkanes in hydrothermal sediments: potential influences on sulfur cycling and microbial diversity

    PubMed Central

    Adams, Melissa M.; Hoarfrost, Adrienne L.; Bose, Arpita; Joye, Samantha B.; Girguis, Peter R.

    2013-01-01

    Short-chain alkanes play a substantial role in carbon and sulfur cycling at hydrocarbon-rich environments globally, yet few studies have examined the metabolism of ethane (C2), propane (C3), and butane (C4) in anoxic sediments in contrast to methane (C1). In hydrothermal vent systems, short-chain alkanes are formed over relatively short geological time scales via thermogenic processes and often exist at high concentrations. The sediment-covered hydrothermal vent systems at Middle Valley (MV, Juan de Fuca Ridge) are an ideal site for investigating the anaerobic oxidation of C1–C4 alkanes, given the elevated temperatures and dissolved hydrocarbon species characteristic of these metalliferous sediments. We examined whether MV microbial communities oxidized C1–C4 alkanes under mesophilic to thermophilic sulfate-reducing conditions. Here we present data from discrete temperature (25, 55, and 75°C) anaerobic batch reactor incubations of MV sediments supplemented with individual alkanes. Co-registered alkane consumption and sulfate reduction (SR) measurements provide clear evidence for C1–C4 alkane oxidation linked to SR over time and across temperatures. In these anaerobic batch reactor sediments, 16S ribosomal RNA pyrosequencing revealed that Deltaproteobacteria, particularly a novel sulfate-reducing lineage, were the likely phylotypes mediating the oxidation of C2–C4 alkanes. Maximum C1–C4 alkane oxidation rates occurred at 55°C, which reflects the mid-core sediment temperature profile and corroborates previous studies of rate maxima for the anaerobic oxidation of methane (AOM). Of the alkanes investigated, C3 was oxidized at the highest rate over time, then C4, C2, and C1, respectively. The implications of these results are discussed with respect to the potential competition between the anaerobic oxidation of C2–C4alkanes with AOM for available oxidants and the influence on the fate of C1 derived from these hydrothermal systems. PMID:23717305

  10. Melting of thin films of alkanes on magnesium oxide

    NASA Astrophysics Data System (ADS)

    Arnold, T.; Barbour, A.; Chanaa, S.; Cook, R. E.; Fernandez-Canato, D.; Landry, P.; Seydel, T.; Yaron, P.; Larese, J. Z.

    2009-02-01

    Recent incoherent neutron scattering investigations of the dynamics of thin alkane films adsorbed on the Magnesium Oxide (100) surface are reported. There are marked differences in the behaviour of these films, as a function of temperature and coverage, compared to similar measurements on graphite. In particular, it has previously been shown that adsorbed multilayer films on graphite exhibit an interfacial solid monolayer that coexists with bulk-like liquid, well above the bulk melting point. In contrast, these studies show that the alkane films on MgO exhibit no such stabilization of the solid layer closest to the substrate as a function of the film thickness, even though the monolayer crystal structures are remarkably similar. These studies are supported by extensive thermodynamic data, a growing body of structural data from neutron diffraction and state of the art computer modelling

  11. Microbial Oxidation of Gaseous Hydrocarbons: Production of Secondary Alcohols from Corresponding n-Alkanes by Methane-Utilizing Bacteria

    PubMed Central

    Patel, Ramesh N.; Hou, C. T.; Laskin, A. I.; Felix, A.; Derelanko, P.

    1980-01-01

    Over 20 new strains of methane-utilizing bacteria were isolated from lake water and soil samples. Cell suspensions of these and of other known strains of methane-utilizing bacteria oxidized n-alkanes (propane, butane, pentane, hexane) to their corresponding secondary alcohols (2-propanol, 2-butanol, 2-pentanol, 2-hexanol). The product secondary alcohols accumulated extracellularly. The rate of production of secondary alcohols varied with the organism used for oxidation. The average rate of 2-propanol, 2-butanol, 2-pentanol, and 2-hexanol production was 1.5, 1.0, 0.15, and 0.08 μmol/h per 5.0 mg of protein in cell suspensions, respectively. Secondary alcohols were slowly oxidized further to the corresponding methylketones. Primary alcohols and aldehydes were also detected in low amounts (rate of production were 0.05 to 0.08 μmol/h per 5.0 mg of protein in cell suspensions) as products of n-alkane (propane and butane) oxidation. However, primary alcohols and aldehydes were rapidly metabolized further by cell suspensions. Methanol-grown cells of methane-utilizing bacteria did not oxidize n-alkanes to their corresponding secondary alcohols, indicating that the enzymatic system required for oxidation of n-alkanes was induced only during growth on methane. The optimal conditions for in vivo secondary alcohol formation from n-alkanes were investigated in Methylosinus sp. (CRL-15). The rate of 2-propanol and 2-butanol production was linear for the 40-min incubation period and increased directly with cell protein concentration up to 12 mg/ml. The optimal temperature and pH for the production of 2-propanol and 2-butanol were 40°C and pH 7.0. Metalchelating agents inhibited the production of secondary alcohols. The activities for the hydroxylation of n-alkanes in various methylotrophic bacteria were localized in the cell-free particulate fractions precipitated by centrifugation between 10,000 and 40,000 × g. Both oxygen and reduced nicotinamide adenine dinucleotide were

  12. Identity and mechanisms of alkane-oxidizing metalloenzymes from deep-sea hydrothermal vents

    PubMed Central

    Bertrand, Erin M.; Keddis, Ramaydalis; Groves, John T.; Vetriani, Costantino; Austin, Rachel Narehood

    2013-01-01

    Six aerobic alkanotrophs (organism that can metabolize alkanes as their sole carbon source) isolated from deep-sea hydrothermal vents were characterized using the radical clock substrate norcarane to determine the metalloenzyme and reaction mechanism used to oxidize alkanes. The organisms studied were Alcanivorax sp. strains EPR7 and MAR14, Marinobacter sp. strain EPR21, Nocardioides sp. strains EPR26w, EPR28w, and Parvibaculum hydrocarbonoclasticum strain EPR92. Each organism was able to grow on n-alkanes as the sole carbon source and therefore must express genes encoding an alkane-oxidizing enzyme. Results from the oxidation of the radical-clock diagnostic substrate norcarane demonstrated that five of the six organisms (EPR7, MAR14, EPR21, EPR26w, and EPR28w) used an alkane hydroxylase functionally similar to AlkB to catalyze the oxidation of medium-chain alkanes, while the sixth organism (EPR92) used an alkane-oxidizing cytochrome P450 (CYP)-like protein to catalyze the oxidation. DNA sequencing indicated that EPR7 and EPR21 possess genes encoding AlkB proteins, while sequencing results from EPR92 confirmed the presence of a gene encoding CYP-like alkane hydroxylase, consistent with the results from the norcarane experiments. PMID:23825470

  13. Identity and mechanisms of alkane-oxidizing metalloenzymes from deep-sea hydrothermal vents.

    PubMed

    Bertrand, Erin M; Keddis, Ramaydalis; Groves, John T; Vetriani, Costantino; Austin, Rachel Narehood

    2013-01-01

    Six aerobic alkanotrophs (organism that can metabolize alkanes as their sole carbon source) isolated from deep-sea hydrothermal vents were characterized using the radical clock substrate norcarane to determine the metalloenzyme and reaction mechanism used to oxidize alkanes. The organisms studied were Alcanivorax sp. strains EPR7 and MAR14, Marinobacter sp. strain EPR21, Nocardioides sp. strains EPR26w, EPR28w, and Parvibaculum hydrocarbonoclasticum strain EPR92. Each organism was able to grow on n-alkanes as the sole carbon source and therefore must express genes encoding an alkane-oxidizing enzyme. Results from the oxidation of the radical-clock diagnostic substrate norcarane demonstrated that five of the six organisms (EPR7, MAR14, EPR21, EPR26w, and EPR28w) used an alkane hydroxylase functionally similar to AlkB to catalyze the oxidation of medium-chain alkanes, while the sixth organism (EPR92) used an alkane-oxidizing cytochrome P450 (CYP)-like protein to catalyze the oxidation. DNA sequencing indicated that EPR7 and EPR21 possess genes encoding AlkB proteins, while sequencing results from EPR92 confirmed the presence of a gene encoding CYP-like alkane hydroxylase, consistent with the results from the norcarane experiments.

  14. Oxidation of Alkanes to Internal Monoalkenes by a Nocardia1

    PubMed Central

    Abbott, Bernard J.; Casida, L. E.

    1968-01-01

    A suspension of glucose-grown resting cells of Nocardia salmonicolor PSU-N-18 oxidized hexadecane to a mixture of internal monohexadecenes. The latter exhibited a cis configuration, and the mixture consisted of the following: 7-hexadecene, 80%; 8-hexadecene, 18%; and 6-hexadecene, 2%. Alkanes other than hexadecane also were unsaturated by the resting cells, and the composition of the monoalkenes resulting from octadecane dehydrogenation was 9-octadecene, 91%; 8-octadecene, 2 to 3%; 7-octadecene, 1 to 2%; and 6- and 5-octadecenes, trace amounts. Only minute quantities of unsaturated hydrocarbons accumulated during growth on hexadecane and during resting-cell incubation of hexadecane-grown cells with hexadecane. The dehydrogenation of hydrocarbons did not appear to be related to the formation of unsaturated fatty acids. It is postulated that double bond insertion may represent an early step in a new pathway of aliphatic hydrocarbon degradation. PMID:5686017

  15. N-Alkane oxidation enzymes of a pseudomonad.

    PubMed Central

    Parekh, V R; Traxler, R W; Sobek, J M

    1977-01-01

    A nicotinamide adenine dinucleotide (NAD)-dependent n-alkane dehydrogenase and an NAD phosphate (reduced form)-dependent alkane hydroxylase have been purified from cell-free extracts of Pseudomonas sp. strain 196Aa grown anaerobically on n-alkane. The n-alkane dehydrogenase (fraction R-3), obtained as a single peak from Bio-Gel P-60, showed an overall 135-fold purification and was demonstrated by infrared spectroscopy and gas chromatography to convert n-decane to 1-decene. The alkene hydroxylase activity in the S-3 fraction, purified 167 times from diethylaminoethyl-cellulose, was shown by the same methodology to convert decene to decanol. Commercial ferredoxin has been shown to increase the alkane dehydrogenase activity. An NAD-, flavine adenine dinucleotide-, and iron-dependent alcohol dehydrogenase was demonstrated in the R-3 fraction. A mechanism for the anaerobic conversion of n-alkane to fatty acid has been proposed. PMID:869535

  16. Physiological function of the Pseudomonas putida PpG6 (Pseudomonas oleovorans) alkane hydroxylase: monoterminal oxidation of alkanes and fatty acids.

    PubMed Central

    Nieder, M; Shapiro, J

    1975-01-01

    Pseudomonas putida PpG6 is able to utilize purified n-alkanes of six to ten carbon atoms for growth. It can also grow on the primary terminal oxidation products of these alkanes and on 1-dodecanol but not on the corresponding 2-ketones or 1,6-hexanediol, adipic acid, or pimelic acid. Revertible point mutants can be isolated which have simultaneously lost the ability to grow on all five n-alkane growth substrates but which can still grow on octanol or nonanol. An acetate-negative mutant defective in isocitrate lysase activity is unable to grow on even-numbered alkanes and fatty acids. Analysis of double mutants defective in acetate and propionate or in acetate and glutarate metabolism shows that alkane carbon is assimilated only via acetyl-coenzyme A and propionyl-coenzyme A. These results support the following conclusions: (i) The n-alkane growth specificity of P. putida PpG6 is due to the substrate specificity of whole-cell alkane hydroxylation; (ii) there is a single alkane hydroxylase enzyme complex; (iii) the physiological role of this complex is to initiate the monoterminal oxidation of alkane chains; and (iv) straight-chain fatty acids from butyric through nonanoic are degraded exclusively by beta-oxidation from the carboxyl end of the molecule. PMID:804473

  17. The genome sequence of Desulfatibacillum alkenivorans AK-01: a blueprint for anaerobic alkane oxidation.

    PubMed

    Callaghan, A V; Morris, B E L; Pereira, I A C; McInerney, M J; Austin, R N; Groves, J T; Kukor, J J; Suflita, J M; Young, L Y; Zylstra, G J; Wawrik, B

    2012-01-01

    Desulfatibacillum alkenivorans AK-01 serves as a model organism for anaerobic alkane biodegradation because of its distinctive biochemistry and metabolic versatility. The D. alkenivorans genome provides a blueprint for understanding the genetic systems involved in alkane metabolism including substrate activation, CoA ligation, carbon-skeleton rearrangement and decarboxylation. Genomic analysis suggested a route to regenerate the fumarate needed for alkane activation via methylmalonyl-CoA and predicted the capability for syntrophic alkane metabolism, which was experimentally verified. Pathways involved in the oxidation of alkanes, alcohols, organic acids and n-saturated fatty acids coupled to sulfate reduction and the ability to grow chemolithoautotrophically were predicted. A complement of genes for motility and oxygen detoxification suggests that D. alkenivorans may be physiologically adapted to a wide range of environmental conditions. The D. alkenivorans genome serves as a platform for further study of anaerobic, hydrocarbon-oxidizing microorganisms and their roles in bioremediation, energy recovery and global carbon cycling.

  18. Alkane oxidation with porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.; Bhinde, M.V.

    1998-06-23

    Transition metal complexes of meso-haloalkylporphyrins are disclosed, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. 7 figs.

  19. Alkane oxidation with porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

    1998-01-01

    Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides.

  20. Relative rate studies of the reactions of chlorine atoms with simple alkanes and the chlorinated methanes

    SciTech Connect

    Wingen, L.; Lee, J.J.; Neavyn, R.

    1995-12-01

    The reactions of chlorine atoms with organics are of interest because atomic chlorine is a potential tropospheric oxidant. Relative rate constants for the reaction of pairs of simple alkanes (ethane/propane, ethane/n-butane, and isobutane/n-butane) and the chlorinated methanes (chloromethane, dichloromethane, and chloroform relative to methane) were measured, using the photolysis of Cl{sub 2} as the source of chlorine atoms and following the loss of the organics by GC-FID. The ratios of the relative rate constants were in excellent agreement with the literature except for ethane/n-butane, where our results are approximately 20% lower than recently published values, and for chloroform/methane, where our value is approximately 50% higher than the values recommended by JPL and JPCRD. Our results will be compard to previously published relative rate studies as well as to the results of absolute rate constant studies, and the differences will be discussed.

  1. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOEpatents

    Crabtree, R.H.; Brown, S.H.

    1989-10-17

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  2. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOEpatents

    Crabtree, Robert H.; Brown, Stephen H.

    1989-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  3. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-08-01

    The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

  4. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-06-01

    The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

  5. Monocarboxylic acids from oxidation of acyclic isoprenoid alkanes by Mycobacterium fortuitum

    NASA Technical Reports Server (NTRS)

    Cox, R. E.; Maxwell, J. R.; Myers, R. N.

    1976-01-01

    Mycobacterium fortuitum utilizes certain stereoisomeric mixtures of individual multimethyl branched alkanes as sole carbon source, including 2,6(R), 10(S), 14(RS)-tetramethylhexadecane; 2,6(R), 10(S), 14(RS)-tetramethylheptadecane; 2,6(RS), 10(RS)-trimethyltetradecane, and 2,6(R), 10(S)-trimethylpentadecane. Products of oxidation isolated from the bacterial lipids were acids derived predominantly from oxidation of the isopropyl terminus of each alkane, except in the case of 2,6(RS), 10(RS)-trimethyltetradecane. With the latter, acids from oxidation at either terminus were detected in comparable proportions.

  6. Monocarboxylic acids from oxidation of acyclic isoprenoid alkanes by Mycobacterium fortuitum

    NASA Technical Reports Server (NTRS)

    Cox, R. E.; Maxwell, J. R.; Myers, R. N.

    1976-01-01

    Mycobacterium fortuitum utilizes certain stereoisomeric mixtures of individual multimethyl branched alkanes as sole carbon source, including 2,6(R), 10(S), 14(RS)-tetramethylhexadecane; 2,6(R), 10(S), 14(RS)-tetramethylheptadecane; 2,6(RS), 10(RS)-trimethyltetradecane, and 2,6(R), 10(S)-trimethylpentadecane. Products of oxidation isolated from the bacterial lipids were acids derived predominantly from oxidation of the isopropyl terminus of each alkane, except in the case of 2,6(RS), 10(RS)-trimethyltetradecane. With the latter, acids from oxidation at either terminus were detected in comparable proportions.

  7. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... with mixed metal oxides (generic). 721.10148 Section 721.10148 Protection of Environment ENVIRONMENTAL... mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  8. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... with mixed metal oxides (generic). 721.10148 Section 721.10148 Protection of Environment ENVIRONMENTAL... mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  9. Light alkane conversion processes - Suprabiotic catalyst systems for selective oxidation of light alkane gases to fuel oxygenates.

    SciTech Connect

    Lyons, J.E.

    1992-07-01

    The objective of the work presented in this paper is to develop new, efficient catalysts for the selective transformation of the light alkanes in natural gas to alcohols for use as liquid transportation fuels, fuel precursors and chemical products. There currently exists no DIRECT one-step catalytic air-oxidation process to convert these substrates to alcohols. Such a one-step route would represent superior useful technology for the utilization of natural gas and similar refinery-derived light hydrocarbon streams. Processes for converting natural gas or its components (methane, ethane, propane, and the butanes) to alcohols for use as motor fuels, fuel additives or fuel precursors will not only add a valuable alternative to crude oil but will produce a clean-burning, high octane alternative to conventional gasoline.

  10. Light alkane conversion processes - Suprabiotic catalyst systems for selective oxidation of light alkane gases to fuel oxygenates

    SciTech Connect

    Lyons, J.E.

    1992-01-01

    The objective of the work presented in this paper is to develop new, efficient catalysts for the selective transformation of the light alkanes in natural gas to alcohols for use as liquid transportation fuels, fuel precursors and chemical products. There currently exists no DIRECT one-step catalytic air-oxidation process to convert these substrates to alcohols. Such a one-step route would represent superior useful technology for the utilization of natural gas and similar refinery-derived light hydrocarbon streams. Processes for converting natural gas or its components (methane, ethane, propane, and the butanes) to alcohols for use as motor fuels, fuel additives or fuel precursors will not only add a valuable alternative to crude oil but will produce a clean-burning, high octane alternative to conventional gasoline.

  11. Geochemical Tracers and Rates of Short-Chain Alkane Production in Gulf of Mexico Cold Seep Sediments

    NASA Astrophysics Data System (ADS)

    Sibert, R.; Bernard, B. B.; Brooks, J. M.; Hunter, K.; Joye, S. B.

    2014-12-01

    The organic-rich cold seep sediments in the deep Gulf of Mexico commonly contain mixtures of light hydrocarbon gases either dissolved in pore fluids, adsorbed to sediment particles, trapped in methane ice, or as free gas. The dominant component in these natural gas mixtures is typically methane (C1), but ethane (C2) and propane (C3) are nearly always present in trace or major amounts. The ratio of C1:C2:C3 varies but C2 and C3 are typically present at single digit percent levels, whereas methane usually dominates at >80%. Methane production proceeds by at least two well-studied mechanisms: either 1) by thermocatalytic cracking of fossil organic matter, or 2) as a direct product of microbial metabolism, methanogenesis. In contrast, ethane and propane production in deep-sea sediments has been historically attributed only to thermocatalytic processes. However, limited data suggests production of C2/C3 compounds through the activity of archaea. Such studies of microbial- driven dynamics of C2/C3 gases (i.e. 'alkanogenesis') in cold seep sediments are rare. Furthermore, the identities of potential substrates are poorly constrained and no attempt has been made to quantify production rates of C2/C3 gases. However, carbon isotopic data on ethane and propane from deep cores from the Gulf of Mexico suggest alkanogenesis at depth in the sediment column and alkane oxidation in uppermost oxidant-rich sediments. Here, we present the results of a series of incubation experiments using sediment slurries culled from GC600, one of the most prolific natural oil and gas seeps in the Gulf of Mexico. Rates of both alkane production and oxidation were measured under a variety of conditions to assess the net rates of alkane production and elucidate the driving microbiological mechanisms and controls on the central processes of >C1 alkane cycling in cold seep sediments. Microbial processes are important both in terms of alkane production and oxidation, raising many questions as to the

  12. Activated aluminum oxide selectively retaining long chain n-alkanes. Part I, description of the retention properties.

    PubMed

    Fiselier, Katell; Fiorini, Dennis; Grob, Koni

    2009-02-16

    Aluminum oxide activated by heating to 350-400 degrees C retains n-alkanes with more than about 20 carbon atoms, whereas iso-alkanes largely pass the column non-retained. Retention of n-alkanes is strong with n-pentane or n-hexane as mobile phase, but weak or negligible with cyclohexane or iso-octane. It is strongly reduced with increasing column temperature. Even small amounts of polar components, such as modifiers or impurities in the mobile phase, cause the retention of n-alkanes to irreversibly collapse. Since n-alkanes are not more polar than iso-alkanes and long chain n-alkanes not more polar than those of shorter chains, retention by a mechanism based on steric properties is assumed. The sensitivity to deactivation by polar components indicates that polar components and n-alkanes are retained by the same sites. The capacity for retaining n-alkanes is low, with the effect that the retention of n-alkanes depends on the load with retained paraffins. These retention properties are useful for the pre-separation of hydrocarbons in the context of the analysis of mineral oil paraffins in foodstuffs and tissue, where plant n-alkanes, typically ranging from C(23) to C(33), may severely disturb the analysis (subject of Part II).

  13. Di(hydroperoxy)alkane Adducts of Phosphine Oxides: Safe, Solid, Stoichiometric, and Soluble Oxidizing Agents.

    PubMed

    Bluemel, Janet; Ahn, Shin Hye; Bhuvanesh, Nattamai

    2017-08-29

    The di(hydroperoxy)alkane adducts of phosphine oxides Ph3PO*(HOO)2CMe2 (1), Cy3PO*(HOO)2CMe2 (2), Ph3PO*(HOO)2CMeEt (3), Cy3PO*(HOO)2CMeEt (4), Cy3PO*(HOO)2CEt2 (5), Cy3PO*(HOO)2C(CH2)5 (6), and Cy3PO*(HOO)2CMePh (7), (Ph2P(O)CH2CH2P(O)Ph2)*((HOO)2CEt2)2 (8), and Ph2P(O)CH2P(O)Ph2*(HOO)2CMe2 (9), are synthesized and fully characterized by 1H, 13C, and 31P NMR and IR spectroscopy. Single crystal X-ray structures are reported for 3-9. Different one-pot synthetic pathways, starting from R3P, R3PO, R3PO*H2O, and R3PO*H2O2 are explored and discussed and a mechanism for the formation of the di(hydroperoxy)alkane adducts of phosphine oxides is suggested. The longevity of the adducts is tested by monitoring the oxidation of Ph3P with quantitative NMR. The solubilities of the adducts in organic solvents are presented, and their applicability as stoichiometric oxidizing agents for the selective oxidation of sulfides to sulfoxides is reported. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Fe-Catalyzed Oxidation Reactions of Olefins, Alkanes, and Alcohols: Involvement of Oxo- and Peroxo Complexes

    NASA Astrophysics Data System (ADS)

    Schröder, Kristin; Junge, Kathrin; Bitterlich, Bianca; Beller, Matthias

    In this review, recent developments of iron-catalyzed oxidations of olefins (epoxidation), alkanes, arenes, and alcohols are summarized. Special focus is given on the ligand systems and the catalytic performance of the iron complexes. In addition, the mechanistic involvement of high-valent iron-oxo species is discussed.

  15. Thermal non-oxidative aromatization of light alkanes catalyzed by gallium nitride.

    PubMed

    Li, Lu; Mu, Xiaoyue; Liu, Wenbo; Kong, Xianghua; Fan, Shizhao; Mi, Zetian; Li, Chao-Jun

    2014-12-15

    The thermal catalytic activity of GaN in non-oxidative alkane dehydroaromatization has been discovered for the first time. The origin of the catalytic activity was studied experimentally and theoretically. Commercially available GaN powders with a wurtzite crystal structure showed superior stability and reactivity for converting light alkanes, including methane, propane, n-butane, n-hexane and cyclohexane into benzene at an elevated temperature with high selectivity. The catalyst is highly robust and can be used repeatedly without noticeable deactivation.

  16. Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

    DOEpatents

    Lin, Manhua; Wang, Xiang; Yeom, Younghoon

    2015-09-29

    A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase is dispersed.

  17. Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

    DOEpatents

    Lin, Manhua; Wang, Xiang; Yeom, Younghoon

    2015-03-17

    A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase id dispersed.

  18. Alkane Oxidation by a Particulate Preparation from Candida

    PubMed Central

    Liu, Chao-Min; Johnson, Marvin J.

    1971-01-01

    The oxidation of decane by a cell-free particulate preparation from Candida intermedia was studied. Decane is oxidized to decanoate via decanol and decanaldehyde. Oxidation of decane to decanol requires molecular oxygen. Decanol is oxidized to decanaldehyde by a nicotinamide adenine dinucleotide-linked dehydrogenase differing greatly in specificity from ordinary yeast alcohol dehydrogenase. Decanaldehyde is oxidized to decanoate by a nicotinamide adenine dinucleotide-linked dehydrogenase that oxidizes long-chain aldehydes but not short-chain aldehydes. The enzymes that oxidize decane, decanol, and decanaldehyde are all induced when decane is present in the medium. These enzymes are apparently located in the cell membrane. PMID:4326743

  19. Integrated two-liquid phase bioconversion and product-recovery processes for the oxidation of alkanes: Process design and economic evaluation

    SciTech Connect

    Mathys, R.G.; Schmid, A.; Witholt, B.

    1999-08-20

    Pseudomonas oleovorans and recombinant strains containing the alkane oxidation genes can product alkane oxidation genes can produce alkane oxidation products in two-liquid phase bioreactor systems. In these bioprocesses the cells, which grow in the aqueous phase, oxidize apolar, non-water soluble substrates. The apolar products typically accumulate in the emulsified apolar phase. The authors have studied both the bioconversion systems and several downstream processing systems to separate and purify alkanols from these two-liquid phase media. Based on the information generated in these studies, the authors have now designed bioconversion and downstream processing systems for the production of 1-alkanols from n-alkanes on a 10 kiloton/yr scale, taking the conversion of n-octane to 1-octanol as a model system. Here, the authors describe overall designs of fed-batch and continuous-fermentation processes for the oxidation of octane to 1-octanol by Pseudomonas oleovoran, and the authors discuss the economics of these processes. The overall performance of each of these two systems has been modeled with Aspen software. Although the continuous process is about 10% more expensive than the fed-batch process, improvements to reduce overall cost can be achieved more easily for continuous than for fed-batch fermentation by decreasing the dilution rate while maintaining near constant productivity. Improvements relevant to both processes can be achieved by increasing the biocatalyst performance, which results in improved overall efficiency, decreased capital investment, and hence, decreased production cost.

  20. Kinetic features and industrial prospects of the selective oxidative cracking of light alkanes

    NASA Astrophysics Data System (ADS)

    Arutyunov, V. S.; Savchenko, V. I.; Sedov, I. V.; Nikitin, A. V.; Magomedov, R. N.; Proshina, A. Yu

    2017-01-01

    The results of kinetic investigations of selective oxidative cracking of light alkanes are analyzed and integrated. This process attracts researchers' attention owing to possible opportunities for designing new industrial processes based on light hydrocarbon feed. Particular attention is paid to ethane for which comprehensive and adequate models of oxidative conversion suitable for detailed analysis of the process kinetics have already been developed. The prospects for the practical application of methane homologues present in natural and associated gases in the selective oxidative cracking are discussed. The bibliography includes 85 references.

  1. Oxidation of Light Alkanes Using Photocatalytic Thin Films

    DTIC Science & Technology

    2006-01-01

    Methods 4.2.1 Catalyst Preparation and Characterization All catalysts were prepared using sol - gel methods [26]. Binary oxides were mixed...chemical vapor deposition, sputtering, sol - gel , etc.). The versatility of TiO2 has led to numerous applications discussed in thousands of literature...Catalyst Preparation The mixed-oxide catalyst material used in this study was prepared using a sol - gel method [11] in which titania and zirconia sols

  2. Flow reactor studies of non-equilibrium plasma-assisted oxidation of n-alkanes.

    PubMed

    Tsolas, Nicholas; Lee, Jong Guen; Yetter, Richard A

    2015-08-13

    The oxidation of n-alkanes (C1-C7) has been studied with and without the effects of a nanosecond, non-equilibrium plasma discharge at 1 atm pressure from 420 to 1250 K. Experiments have been performed under nearly isothermal conditions in a flow reactor, where reactive mixtures are diluted in Ar to minimize temperature changes from chemical reactions. Sample extraction performed at the exit of the reactor captures product and intermediate species and stores them in a multi-position valve for subsequent identification and quantification using gas chromatography. By fixing the flow rate in the reactor and varying the temperature, reactivity maps for the oxidation of fuels are achieved. Considering all the fuels studied, fuel consumption under the effects of the plasma is shown to have been enhanced significantly, particularly for the low-temperature regime (T<800 K). In fact, multiple transitions in the rates of fuel consumption are observed depending on fuel with the emergence of a negative-temperature-coefficient regime. For all fuels, the temperature for the transition into the high-temperature chemistry is lowered as a consequence of the plasma being able to increase the rate of fuel consumption. Using a phenomenological interpretation of the intermediate species formed, it can be shown that the active particles produced from the plasma enhance alkyl radical formation at all temperatures and enable low-temperature chain branching for fuels C3 and greater. The significance of this result demonstrates that the plasma provides an opportunity for low-temperature chain branching to occur at reduced pressures, which is typically observed at elevated pressures in thermal induced systems.

  3. Copper-Catalyzed Oxidative Dehydrogenative Carboxylation of Unactivated Alkanes to Allylic Esters via Alkenes

    PubMed Central

    2015-01-01

    We report copper-catalyzed oxidative dehydrogenative carboxylation (ODC) of unactivated alkanes with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV–vis) revealed that the resting state of the catalyst is [(BPI)Cu(O2CPh)] (1-O2CPh), formed from [(BPI)Cu(PPh3)2], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of 1-O2CPh with alkyl radicals and radical probes imply that C–H bond cleavage occurs by a tert-butoxy radical. In addition, the deuterium kinetic isotope effect from reactions of cyclohexane and d12-cyclohexane in separate vessels showed that the turnover-limiting step for the ODC of cyclohexane is C–H bond cleavage. To understand the origin of the difference in products formed from copper-catalyzed amidation and copper-catalyzed ODC, reactions of an alkyl radical with a series of copper–carboxylate, copper–amidate, and copper–imidate complexes were performed. The results of competition experiments revealed that the relative rate of reaction of alkyl radicals with the copper complexes follows the trend Cu(II)–amidate > Cu(II)–imidate > Cu(II)–benzoate. Consistent with this trend, Cu(II)–amidates and Cu(II)–benzoates containing more electron-rich aryl groups on the benzamidate and benzoate react faster with the alkyl radical than do those with more electron-poor aryl groups on these ligands to produce the corresponding products. These data on the ODC of cyclohexane led to preliminary investigation of copper-catalyzed oxidative dehydrogenative amination of cyclohexane to generate a mixture of N-alkyl and N-allylic products. PMID:25389772

  4. Electron Microscopy in the Catalysis of Alkane Oxidation, Environmental Control, and Alternative Energy Sources

    NASA Astrophysics Data System (ADS)

    Gai, Pratibha L.; Calvino, Jose J.

    2005-08-01

    The key role of electron microscopy in understanding and creating advanced catalyst materials and processes in selective alkane oxidation, environmental control, and alternative energy sources is reviewed. In many technological processes, catalysts are increasingly nanoscale heterogeneous materials. With growing regulatory guidelines requiring efficient and environmentally compatible catalytic processes, it is crucial to have a fundamental understanding of the catalyst nanostructure and modes of operation under reaction conditions to design novel catalysts and processes. The review highlights the pioneering development and applications of atomic resolution in situ-environmental transmission electron microscopy (ETEM) for probing dynamic catalysis directly at the atomic level, high-resolution electron microscopy, and analytical spectroscopic methods in the development of alkane catalyzation, environmental protection, and new energy sources.

  5. Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics.

    PubMed

    Wang, Vincent C-C; Maji, Suman; Chen, Peter P-Y; Lee, Hung Kay; Yu, Steve S-F; Chan, Sunney I

    2017-02-16

    Methane monooxygenases (MMOs) mediate the facile conversion of methane into methanol in methanotrophic bacteria with high efficiency under ambient conditions. Because the selective oxidation of methane is extremely challenging, there is considerable interest in understanding how these enzymes carry out this difficult chemistry. The impetus of these efforts is to learn from the microbes to develop a biomimetic catalyst to accomplish the same chemical transformation. Here, we review the progress made over the past two to three decades toward delineating the structures and functions of the catalytic sites in two MMOs: soluble methane monooxygenase (sMMO) and particulate methane monooxygenase (pMMO). sMMO is a water-soluble three-component protein complex consisting of a hydroxylase with a nonheme diiron catalytic site; pMMO is a membrane-bound metalloenzyme with a unique tricopper cluster as the site of hydroxylation. The metal cluster in each of these MMOs harnesses O2 to functionalize the C-H bond using different chemistry. We highlight some of the common basic principles that they share. Finally, the development of functional models of the catalytic sites of MMOs is described. These efforts have culminated in the first successful biomimetic catalyst capable of efficient methane oxidation without overoxidation at room temperature.

  6. Hydrogen isotope composition of leaf wax n-alkanes in Arabidopsis lines with different transpiration rates

    NASA Astrophysics Data System (ADS)

    Pedentchouk, N.; Lawson, T.; Eley, Y.; McAusland, L.

    2012-04-01

    Stable isotopic compositions of oxygen and hydrogen are used widely to investigate modern and ancient water cycles. The D/H composition of organic compounds derived from terrestrial plants has recently attracted significant attention as a proxy for palaeohydrology. However, the role of various plant physiological and biochemical factors in controlling the D/H signature of leaf wax lipids in extant plants remains unclear. The focus of this study is to investigate the effect of plant transpiration on the D/H composition of n-alkanes in terrestrial plants. This experiment includes 4 varieties of Arabidopsis thaliana that differ with respect to stomatal density and stomatal geometry. All 4 varieties were grown indoors under identical temperature, relative humidity, light and watering regimes and then sampled for leaf wax and leaf water stable isotopic measurements. During growth, stomatal conductance to carbon dioxide and water vapour were also determined. We found that the plants varied significantly in terms of their transpiration rates. Transpiration rates were significantly higher in Arabidopsis ost1 and ost1-1 varieties (2.4 and 3.2 mmol m-2 s-1, respectively) than in Arabidopsis RbohD and Col-0 (1.5 and 1.4). However, hydrogen isotope measurements of n-alkanes extracted from leaf waxes revealed a very different pattern. Varieties ost1, ost1-1, and RbohD have very similar deltaD values of n-C29 alkane (-125, -128, and -127 per mil), whereas the deltaD value of Col-0 is more negative (-137 per mil). The initial results of this work suggest that plant transpiration is decoupled from the D/H composition of n-alkanes. In other words, physical processes that affect water vapour movement between the plant and its environment apparently cannot account for the stable hydrogen isotope composition of organic compounds that comprise leaf waxes. Additional, perhaps biochemical, processes that affect hydrogen isotope fractionation during photosynthesis might need to be invoked

  7. Anaerobic oxidation of long-chain n-alkanes by the hyperthermophilic sulfate-reducing archaeon, Archaeoglobus fulgidus.

    PubMed

    Khelifi, Nadia; Amin Ali, Oulfat; Roche, Philippe; Grossi, Vincent; Brochier-Armanet, Céline; Valette, Odile; Ollivier, Bernard; Dolla, Alain; Hirschler-Réa, Agnès

    2014-11-01

    The thermophilic sulfate-reducing archaeon Archaeoglobus fulgidus strain VC-16 (DSM 4304), which is known to oxidize fatty acids and n-alkenes, was shown to oxidize saturated hydrocarbons (n-alkanes in the range C10-C21) with thiosulfate or sulfate as a terminal electron acceptor. The amount of n-hexadecane degradation observed was in stoichiometric agreement with the theoretically expected amount of thiosulfate reduction. One of the pathways used by anaerobic microorganisms to activate alkanes is addition to fumarate that involves alkylsuccinate synthase as a key enzyme. A search for genes encoding homologous enzymes in A. fulgidus identified the pflD gene (locus-tag AF1449) that was previously annotated as a pyruvate formate lyase. A phylogenetic analysis revealed that this gene is of bacterial origin and was likely acquired by A. fulgidus from a bacterial donor through a horizontal gene transfer. Based on three-dimensional modeling of the corresponding protein and molecular dynamic simulations, we hypothesize an alkylsuccinate synthase activity for this gene product. The pflD gene expression was upregulated during the growth of A. fulgidus on an n-alkane (C16) compared with growth on a fatty acid. Our results suggest that anaerobic alkane degradation in A. fulgidus may involve the gene pflD in alkane activation through addition to fumarate. These findings highlight the possible importance of hydrocarbon oxidation at high temperatures by A. fulgidus in hydrothermal vents and the deep biosphere.

  8. Anaerobic oxidation of long-chain n-alkanes by the hyperthermophilic sulfate-reducing archaeon, Archaeoglobus fulgidus

    PubMed Central

    Khelifi, Nadia; Amin Ali, Oulfat; Roche, Philippe; Grossi, Vincent; Brochier-Armanet, Céline; Valette, Odile; Ollivier, Bernard; Dolla, Alain; Hirschler-Réa, Agnès

    2014-01-01

    The thermophilic sulfate-reducing archaeon Archaeoglobus fulgidus strain VC-16 (DSM 4304), which is known to oxidize fatty acids and n-alkenes, was shown to oxidize saturated hydrocarbons (n-alkanes in the range C10–C21) with thiosulfate or sulfate as a terminal electron acceptor. The amount of n-hexadecane degradation observed was in stoichiometric agreement with the theoretically expected amount of thiosulfate reduction. One of the pathways used by anaerobic microorganisms to activate alkanes is addition to fumarate that involves alkylsuccinate synthase as a key enzyme. A search for genes encoding homologous enzymes in A. fulgidus identified the pflD gene (locus-tag AF1449) that was previously annotated as a pyruvate formate lyase. A phylogenetic analysis revealed that this gene is of bacterial origin and was likely acquired by A. fulgidus from a bacterial donor through a horizontal gene transfer. Based on three-dimensional modeling of the corresponding protein and molecular dynamic simulations, we hypothesize an alkylsuccinate synthase activity for this gene product. The pflD gene expression was upregulated during the growth of A. fulgidus on an n-alkane (C16) compared with growth on a fatty acid. Our results suggest that anaerobic alkane degradation in A. fulgidus may involve the gene pflD in alkane activation through addition to fumarate. These findings highlight the possible importance of hydrocarbon oxidation at high temperatures by A. fulgidus in hydrothermal vents and the deep biosphere. PMID:24763368

  9. Steric modifications tune the regioselectivity of the alkane oxidation catalyzed by non-heme iron complexes.

    PubMed

    He, Yu; Gorden, John D; Goldsmith, Christian R

    2011-12-19

    Iron complexes with the tetradentate N-donor ligand N,N'-di(phenylmethyl)-N,N'-bis(2-pyridinylmethyl)-1,2-cyclohexanediamine (bbpc) are reported. Despite the benzyl groups present on the amines, the iron compounds catalyze the oxygenation of cyclohexane to an extent similar to those employing less sterically encumbered ligands. The catalytic activity is strongly dependent on the counterion, with the highest activity and the strongest preference for alkane hydroxylation correlating to the most weakly coordinating anion, SbF(6)(-). The selectivity for the alcohol product over the ketone is amplified when acetic acid is present as an additive. When hydrocarbon substrates with both secondary and tertiary carbons are oxidized by H(2)O(2), the catalyst directs oxidation toward the secondary carbons to a greater degree than other previously reported iron-containing homogeneous catalysts.

  10. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Acryloxy alkanoic alkane derivative... Significant New Uses for Specific Chemical Substances § 721.10148 Acryloxy alkanoic alkane derivative with...) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  11. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Acryloxy alkanoic alkane derivative... Significant New Uses for Specific Chemical Substances § 721.10148 Acryloxy alkanoic alkane derivative with...) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  12. Clay minerals and metal oxides strongly influence the structure of alkane-degrading microbial communities during soil maturation.

    PubMed

    Steinbach, Annelie; Schulz, Stefanie; Giebler, Julia; Schulz, Stephan; Pronk, Geertje J; Kögel-Knabner, Ingrid; Harms, Hauke; Wick, Lukas Y; Schloter, Michael

    2015-07-01

    Clay minerals, charcoal and metal oxides are essential parts of the soil matrix and strongly influence the formation of biogeochemical interfaces in soil. We investigated the role of these parental materials for the development of functional microbial guilds using the example of alkane-degrading bacteria harbouring the alkane monooxygenase gene (alkB) in artificial mixtures composed of different minerals and charcoal, sterile manure and a microbial inoculum extracted from an agricultural soil. We followed changes in abundance and community structure of alkane-degrading microbial communities after 3 and 12 months of soil maturation and in response to a subsequent 2-week plant litter addition. During maturation we observed an overall increasing divergence in community composition. The impact of metal oxides on alkane-degrading community structure increased during soil maturation, whereas the charcoal impact decreased from 3 to 12 months. Among the clay minerals illite influenced the community structure of alkB-harbouring bacteria significantly, but not montmorillonite. The litter application induced strong community shifts in soils, maturated for 12 months, towards functional guilds typical for younger maturation stages pointing to a resilience of the alkane-degradation function potentially fostered by an extant 'seed bank'.

  13. Clay minerals and metal oxides strongly influence the structure of alkane-degrading microbial communities during soil maturation

    PubMed Central

    Steinbach, Annelie; Schulz, Stefanie; Giebler, Julia; Schulz, Stephan; Pronk, Geertje J; Kögel-Knabner, Ingrid; Harms, Hauke; Wick, Lukas Y; Schloter, Michael

    2015-01-01

    Clay minerals, charcoal and metal oxides are essential parts of the soil matrix and strongly influence the formation of biogeochemical interfaces in soil. We investigated the role of these parental materials for the development of functional microbial guilds using the example of alkane-degrading bacteria harbouring the alkane monooxygenase gene (alkB) in artificial mixtures composed of different minerals and charcoal, sterile manure and a microbial inoculum extracted from an agricultural soil. We followed changes in abundance and community structure of alkane-degrading microbial communities after 3 and 12 months of soil maturation and in response to a subsequent 2-week plant litter addition. During maturation we observed an overall increasing divergence in community composition. The impact of metal oxides on alkane-degrading community structure increased during soil maturation, whereas the charcoal impact decreased from 3 to 12 months. Among the clay minerals illite influenced the community structure of alkB-harbouring bacteria significantly, but not montmorillonite. The litter application induced strong community shifts in soils, maturated for 12 months, towards functional guilds typical for younger maturation stages pointing to a resilience of the alkane-degradation function potentially fostered by an extant ‘seed bank'. PMID:25535940

  14. Method for oxidizing alkanes using novel porphyrins synthesized from dipyrromethanes and aldehydes

    DOEpatents

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.

    1999-01-01

    The invention comprises a method for the oxidation of alkanes to alcohols and for decomposition of hydroperoxides to alcohols utilizing new compositions of matter, which are metal complexes of porphyrins. Preferred complexes have hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. Other preferred complexes are ones in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also disclosed.

  15. A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane

    NASA Technical Reports Server (NTRS)

    Harstad, Kenneth G.; Bellan, Josette

    2011-01-01

    The reduction of elementary or skeletal oxidation kinetics to a subgroup of tractable reactions for inclusion in turbulent combustion codes has been the subject of numerous studies. The skeletal mechanism is obtained from the elementary mechanism by removing from it reactions that are considered negligible for the intent of the specific study considered. As of now, there are many chemical reduction methodologies. A methodology for deriving a reduced kinetic mechanism for alkane oxidation is described and applied to n-heptane. The model is based on partitioning the species of the skeletal kinetic mechanism into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement of the species ensemble. For modeling purposes, the heavy species are mathematically decomposed into constituents, which are similar but not identical to groups in the group additivity theory. From analysis of the LLNL (Lawrence Livermore National Laboratory) skeletal mechanism in conjunction with CHEMKIN II, it is shown that a similarity variable can be formed such that the appropriately non-dimensionalized global constituent molar density exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures that is of interest for predicting n-heptane oxidation. Furthermore, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable. The light species ensemble is partitioned into quasi-steady and unsteady species. The reduced model is based on concepts consistent with those of Large Eddy Simulation (LES) in which functional forms are used to replace the small scales eliminated through filtering of the governing equations; in LES, these small scales are unimportant as far as the overwhelming part of dynamic energy is concerned. Here, the scales thought unimportant for recovering the thermodynamic energy are removed. The concept is tested by

  16. Designing safer chemicals: Predicting the rates of metabolism of halogenated alkanes

    SciTech Connect

    Yin, H.; Anders, M.W.; Higgins, L.

    1995-11-21

    A computational model is presented that can be used as a tool in the design of safer chemicals. This model predicts that rate of hydrogen-atom abstraction by cytochrome P450 enzymes. Excellent correlations between biotransformation rates and the calculated activation energies ({Delta}H{sub act}) of the cytochrome P450-mediated hydrogen-atom abstractions were obtained for the in vitro biotransformation of six halogenated alkanes (1-fluoro-1,1,1,2,2-tetrachloroethane, 1,1,1,2-tetrafluoro-2-chloroethane, 1,1,1,2,2-pentafluoroethane, and 2-bromo-2-chloro-1,1,1-trifluoroethane) with both rat and human enzyme preparations: (rate, human CYP2E1) = 44.99 - 1.79 ({Delta}H{sub act}), r{sup 2} = 0.86; In (rate, human Cyp2E1)= 46399 -1.77 ({Delta}H{sub act}), r{sup 2} = 0.97 (rates are in nmol of product per min per nmol of cytochrome P450 and energies are in kcal/mol). Correlations were also obtained for five inhalation anesthetics (enflurane, sevoflurane, desflurane, methoxyflurane, and isoflurane) for both in vivo and in vitro data have been shown to agree in any species. The model presented herein provides an archetype for the methodology that may be used in the future design of safer chemicals, particularly hydrochlorofluorocarbons and inhalation anesthetics. 41 refs., 1 fig., 2 tabs.

  17. Oxidation of alcohols and activated alkanes with Lewis acid-activated TEMPO.

    PubMed

    Nguyen, Thuy-Ai D; Wright, Ashley M; Page, Joshua S; Wu, Guang; Hayton, Trevor W

    2014-11-03

    The reactivity of MCl3(η(1)-TEMPO) (M = Fe, 1; Al, 2; TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) with a variety of alcohols, including 3,4-dimethoxybenzyl alcohol, 1-phenyl-2-phenoxyethanol, and 1,2-diphenyl-2-methoxyethanol, was investigated using NMR spectroscopy and mass spectrometry. Complex 1 was effective in cleanly converting these substrates to the corresponding aldehyde or ketone. Complex 2 was also able to oxidize these substrates; however, in a few instances the products of overoxidation were also observed. Oxidation of activated alkanes, such as xanthene, by 1 or 2 suggests that the reactions proceed via an initial 1-electron concerted proton-electron transfer (CPET) event. Finally, reaction of TEMPO with FeBr3 in Et2O results in the formation of a mixture of FeBr3(η(1)-TEMPOH) (23) and [FeBr2(η(1)-TEMPOH)]2(μ-O) (24), via oxidation of the solvent, Et2O.

  18. OH-initiated heterogeneous oxidation of cholestane: a model system for understanding the photochemical aging of cyclic alkane aerosols.

    PubMed

    Zhang, Haofei; Ruehl, Christopher R; Chan, Arthur W H; Nah, Theodora; Worton, David R; Isaacman, Gabriel; Goldstein, Allen H; Wilson, Kevin R

    2013-11-27

    Aerosols containing aliphatic hydrocarbons play a substantial role in the urban atmosphere. Cyclic alkanes constitute a large fraction of aliphatic hydrocarbon emissions originating from incomplete combustion of diesel fuel and motor oil. In the present study, cholestane (C27H48) is used as a model system to examine the OH-initiated heterogeneous oxidation pathways of cyclic alkanes in a photochemical flow tube reactor. Oxidation products are collected on filters and analyzed by a novel soft ionization two-dimensional gas chromatography/mass spectrometry technique. The analysis reveals that the first-generation functionalization products (cholestanones, cholestanals, and cholestanols) are the dominant reaction products that account for up to 70% by mass of the total speciated compounds. The ratio of first-generation carbonyls to alcohols is near unity at every oxidation level. Among the cholestanones/cholestanals, 55% are found to have the carbonyl group on the rings of the androstane skeleton, while 74% of cholestanols have the hydroxyl group on the rings. Particle-phase oxidation products with carbon numbers less than 27 (i.e., "fragmentation products") and higher-generation functionalization products are much less abundant. Carbon bond cleavage was found to occur only on the side chain. Tertiary-carbon alkoxy radicals are suggested to play an important role in governing both the distribution of functionalization products (via alkoxy radical isomerization and reaction with oxygen) and the fragmentation products (via alkoxy radical decomposition). These results provide new insights into the oxidation mechanism of cyclic alkanes.

  19. Additional chain-branching pathways in the low-temperature oxidation of branched alkanes

    DOE PAGES

    Wang, Zhandong; Zhang, Lidong; Moshammer, Kai; ...

    2015-12-31

    Chain-branching reactions represent a general motif in chemistry, encountered in atmospheric chemistry, combustion, polymerization, and photochemistry; the nature and amount of radicals generated by chain-branching are decisive for the reaction progress, its energy signature, and the time towards its completion. In this study, experimental evidence for two new types of chain-branching reactions is presented, based upon detection of highly oxidized multifunctional molecules (HOM) formed during the gas-phase low-temperature oxidation of a branched alkane under conditions relevant to combustion. The oxidation of 2,5-dimethylhexane (DMH) in a jet-stirred reactor (JSR) was studied using synchrotron vacuum ultra-violet photoionization molecular beam mass spectrometry (SVUV-PI-MBMS).more » Specifically, species with four and five oxygen atoms were probed, having molecular formulas of C8H14O4 (e.g., diketo-hydroperoxide/keto-hydroperoxy cyclic ether) and C8H16O5 (e.g., keto-dihydroperoxide/dihydroperoxy cyclic ether), respectively. The formation of C8H16O5 species involves alternative isomerization of OOQOOH radicals via intramolecular H-atom migration, followed by third O2 addition, intramolecular isomerization, and OH release; C8H14O4 species are proposed to result from subsequent reactions of C8H16O5 species. The mechanistic pathways involving these species are related to those proposed as a source of low-volatility highly oxygenated species in Earth's troposphere. At the higher temperatures relevant to auto-ignition, they can result in a net increase of hydroxyl radical production, so these are additional radical chain-branching pathways for ignition. Furthermore, the results presented herein extend the conceptual basis of reaction mechanisms used to predict the reaction behavior of ignition, and have implications on atmospheric gas-phase chemistry and the oxidative stability of organic substances.« less

  20. Application of the homogeneous oxidation of alkanes: Synthesis and characterization of metal complexes of a linked aryloxide

    NASA Astrophysics Data System (ADS)

    Gordon, Benjamin Willis Franklin

    Methane is the main component of natural gas, largely left behind due to cost of transportation. There are vast stores of natural gas outweighing the known reserves of liquid petroleum. A chemical process by which methane can be transformed into a usable transportable product is very important. The selective transformation of methane into a transportable product, such as methanol or formaldehyde, would be a large step forward in utilizing a vast resource. Research on transforming methane selectively has been met with several obstacles based on poor conversion and selectivity. Several methods exist for transforming methane to methanol or formaldehyde through heterogeneous metal catalyzed oxidation. Currently, these metal catalyzed processes are energy intensive and result in low conversion and selectivity. Methanol, the desired product, tends to react preferentially. In many cases, methanol is transformed to another product at a fast rate before recovery. This work describes new techniques for preventing the over oxidation using a homogeneous catalyst system under mild temperature conditions and employing solvents that react with methanol. The solvent effectively removes methanol in a reversible process protecting it from further oxidation. The selective oxidation of higher weight alkanes, such as propane and butane, is also discussed where unusual primary carbon selectivity is observed. The transition metal atoms, tantalum and niobium, have received attention for the interesting chemical reactions, such as metathesis and living polymerization, that they are known to mediate. Aryloxide complexes of these metals undergo unusual chemical transformations especially in the presence of bulky ligand substituents. This work describes the synthesis and characterization of tantalum and niobium complexes of a linked aryloxide ligand. The metal complexes of this ligand are unusual and this dissertation provides the foundation for important future studies of the complexes of

  1. Quaternary Branched Alkanes: A Geologic Proxy for Biological Sulfur Oxidation in Pleistocene Coastal Sediments of California

    NASA Astrophysics Data System (ADS)

    Zinniker, D. A.; Green Nylen, N.; Moldowan, J. M.; Denisevich, P.; Ingle, J. C.

    2003-12-01

    Branched alkanes with quaternary substituted carbon atoms (QBAs) have been identified in two Pleistocene sedimentary sequences exposed along the California coastline. While these compounds have yet to be isolated from cultured microorganisms, a growing body of evidence points towards their origin as membrane components of colorless sulfur oxidizing bacteria (Kenig et al., 2002). This evidence includes an association with sulfide minerals, an association with environments or paleoenvironments with sharp sulfide:oxygen gradients, a positive correlation with the bacterial lipid diploptene, and (in this study) a positive correlation between the abundance of QBAs and the abundance of elemental sulfur in organic extracts. The wide distribution of QBAs in modern environments (deep sea hydrothermal systems, Arctic shelf sediments, and sediment traps from an oligotrophic marine site) may implicate chemoautotrophic and/or chemoorganotrophic members of the epsilon Proteobacteria as the source of QBAs. Sediments of the neritic to nonmarine Merced Formation near San Francisco and the bathyal to neritic Rio Dell Formation north of Cape Mendocino have been found to contain QBAs - predominantly 5,5-diethylalkanes and 2,2-dimethylalkanes. 5,5-diethylalkanes were identified by comparison of their spectra and elution time with published reports. 2,2-dimethylalkanes were identified through the chemical synthesis of authentic standards. In both sedimentary sequences, QBAs vary in abundance by more than two orders of magnitude over glacial-interglacial cycles. This variation appears to be crudely correlated with the abundance of elemental sulfur. In the Rio Dell Formation QBAs show an inverse correlation with the neritic benthic foraminifer biofacies as well as trace and macrofossil assemblages indicative of higher benthic oxygen concentrations. The occurrence of QBAs in shelf deposits of the lower Merced Formation supports previous interpretations that suggest a restricted basin

  2. Perspective: what is known, and not known, about the connections between alkane oxidation and metal uptake in alkanotrophs in the marine environment.

    PubMed

    Austin, Rachel Narehood; Kenney, Grace E; Rosenzweig, Amy C

    2014-06-01

    Should iron and copper be added to the environment to stimulate the natural bioremediation of marine oil spills? The key enzymes that catalyze the oxidation of alkanes require either iron or copper, and the concentration of these ions in seawater is vanishingly low. Nevertheless, the dependence of alkane oxidation activity on external metal concentrations remains unclear. This perspective will summarize what is known about the co-regulation of alkane oxidation and metal acquisition and pose a series of critical questions to which, for the most part, we do not yet have answers. The paucity of answers points to the need for additional studies to illuminate the cellular biology connecting microbial growth on alkanes to the acquisition of metal ions.

  3. Stereoselective Alkane Oxidation with meta-Chloroperoxybenzoic Acid (MCPBA) Catalyzed by Organometallic Cobalt Complexes.

    PubMed

    Shul'pin, Georgiy B; Loginov, Dmitriy A; Shul'pina, Lidia S; Ikonnikov, Nikolay S; Idrisov, Vladislav O; Vinogradov, Mikhail M; Osipov, Sergey N; Nelyubina, Yulia V; Tyubaeva, Polina M

    2016-11-22

    hydroperoxides are not formed in this oxidation. It can be thus concluded that the interaction of the alkanes with MCPBA occurs without the formation of free radicals. The complexes catalyze oxidation of alcohols with tert-butylhydroperoxide (TBHP). For example, tert-BuOOH efficiently oxidizes 1-phenylethanol to acetophenone in 98% yield if compound 1 is used as a catalyst.

  4. Additional chain-branching pathways in the low-temperature oxidation of branched alkanes

    SciTech Connect

    Wang, Zhandong; Zhang, Lidong; Moshammer, Kai; Popolan-Vaida, Denisia M.; Shankar, Vijai Shankar Bhavani; Lucassen, Arnas; Hemken, Christian; Taatjes, Craig A.; Leone, Stephen R.; Kohse-Hoinghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Sarathy, S. Mani

    2015-12-31

    Chain-branching reactions represent a general motif in chemistry, encountered in atmospheric chemistry, combustion, polymerization, and photochemistry; the nature and amount of radicals generated by chain-branching are decisive for the reaction progress, its energy signature, and the time towards its completion. In this study, experimental evidence for two new types of chain-branching reactions is presented, based upon detection of highly oxidized multifunctional molecules (HOM) formed during the gas-phase low-temperature oxidation of a branched alkane under conditions relevant to combustion. The oxidation of 2,5-dimethylhexane (DMH) in a jet-stirred reactor (JSR) was studied using synchrotron vacuum ultra-violet photoionization molecular beam mass spectrometry (SVUV-PI-MBMS). Specifically, species with four and five oxygen atoms were probed, having molecular formulas of C8H14O4 (e.g., diketo-hydroperoxide/keto-hydroperoxy cyclic ether) and C8H16O5 (e.g., keto-dihydroperoxide/dihydroperoxy cyclic ether), respectively. The formation of C8H16O5 species involves alternative isomerization of OOQOOH radicals via intramolecular H-atom migration, followed by third O2 addition, intramolecular isomerization, and OH release; C8H14O4 species are proposed to result from subsequent reactions of C8H16O5 species. The mechanistic pathways involving these species are related to those proposed as a source of low-volatility highly oxygenated species in Earth's troposphere. At the higher temperatures relevant to auto-ignition, they can result in a net increase of hydroxyl radical production, so these are additional radical chain-branching pathways for ignition. Furthermore, the results presented herein extend the conceptual basis of reaction mechanisms used to predict the reaction behavior of ignition, and have

  5. Oxidation of Methyl tert-Butyl Ether by Alkane Hydroxylase in Dicyclopropylketone-Induced and n-Octane-Grown Pseudomonas putida GPo1

    PubMed Central

    Smith, Christy A.; Hyman, Michael R.

    2004-01-01

    The alkane hydroxylase enzyme system in Pseudomonas putida GPo1 has previously been reported to be unreactive toward the gasoline oxygenate methyl tert-butyl ether (MTBE). We have reexamined this finding by using cells of strain GPo1 grown in rich medium containing dicyclopropylketone (DCPK), a potent gratuitous inducer of alkane hydroxylase activity. Cells grown with DCPK oxidized MTBE and generated stoichiometric quantities of tert-butyl alcohol (TBA). Cells grown in the presence of DCPK also oxidized tert-amyl methyl ether but did not appear to oxidize either TBA, ethyl tert-butyl ether, or tert-amyl alcohol. Evidence linking MTBE oxidation to alkane hydroxylase activity was obtained through several approaches. First, no TBA production from MTBE was observed with cells of strain GPo1 grown on rich medium without DCPK. Second, no TBA production from MTBE was observed in DCPK-treated cells of P. putida GPo12, a strain that lacks the alkane-hydroxylase-encoding OCT plasmid. Third, all n-alkanes that support the growth of strain GPo1 inhibited MTBE oxidation by DCPK-treated cells. Fourth, two non-growth-supporting n-alkanes (propane and n-butane) inhibited MTBE oxidation in a saturable, concentration-dependent process. Fifth, 1,7-octadiyne, a putative mechanism-based inactivator of alkane hydroxylase, fully inhibited TBA production from MTBE. Sixth, MTBE-oxidizing activity was also observed in n-octane-grown cells. Kinetic studies with strain GPo1 grown on n-octane or rich medium with DCPK suggest that MTBE-oxidizing activity may have previously gone undetected in n-octane-grown cells because of the unusually high Ks value (20 to 40 mM) for MTBE. PMID:15294784

  6. Oxidation of methyl tert-butyl ether by alkane hydroxylase in dicyclopropylketone-induced and n-octane-grown Pseudomonas putida GPo1.

    PubMed

    Smith, Christy A; Hyman, Michael R

    2004-08-01

    The alkane hydroxylase enzyme system in Pseudomonas putida GPo1 has previously been reported to be unreactive toward the gasoline oxygenate methyl tert-butyl ether (MTBE). We have reexamined this finding by using cells of strain GPo1 grown in rich medium containing dicyclopropylketone (DCPK), a potent gratuitous inducer of alkane hydroxylase activity. Cells grown with DCPK oxidized MTBE and generated stoichiometric quantities of tert-butyl alcohol (TBA). Cells grown in the presence of DCPK also oxidized tert-amyl methyl ether but did not appear to oxidize either TBA, ethyl tert-butyl ether, or tert-amyl alcohol. Evidence linking MTBE oxidation to alkane hydroxylase activity was obtained through several approaches. First, no TBA production from MTBE was observed with cells of strain GPo1 grown on rich medium without DCPK. Second, no TBA production from MTBE was observed in DCPK-treated cells of P. putida GPo12, a strain that lacks the alkane-hydroxylase-encoding OCT plasmid. Third, all n-alkanes that support the growth of strain GPo1 inhibited MTBE oxidation by DCPK-treated cells. Fourth, two non-growth-supporting n-alkanes (propane and n-butane) inhibited MTBE oxidation in a saturable, concentration-dependent process. Fifth, 1,7-octadiyne, a putative mechanism-based inactivator of alkane hydroxylase, fully inhibited TBA production from MTBE. Sixth, MTBE-oxidizing activity was also observed in n-octane-grown cells. Kinetic studies with strain GPo1 grown on n-octane or rich medium with DCPK suggest that MTBE-oxidizing activity may have previously gone undetected in n-octane-grown cells because of the unusually high K(s) value (20 to 40 mM) for MTBE.

  7. Efficient catalytic oxidation of alkanes by Lewis acid/[Os(VI)(N)Cl4]- using peroxides as terminal oxidants. Evidence for a metal-based active intermediate.

    PubMed

    Yiu, Shek-Man; Man, Wai-Lun; Lau, Tai-Chu

    2008-08-13

    The oxidation of alkanes by various peroxides ((t)BuOOH, H2O2, PhCH2C(CH3)2OOH) is efficiently catalyzed by [Os(VI)(N)Cl4](-)/Lewis acid (FeCl3 or Sc(OTf)3) in CH2Cl2/CH3CO2H to give alcohols and ketones. Oxidations occur rapidly at ambient conditions, and excellent yields and turnover numbers of over 7500 and 1000 can be achieved in the oxidation of cyclohexane with (t)BuOOH and H2O2, respectively. In particular, this catalytic system can utilize PhCH2C(CH3)2OOH (MPPH) efficiently as the terminal oxidant; good yields of cyclohexanol and cyclohexanone (>70%) and MPPOH (>90%) are obtained in the oxidation of cyclohexane. This suggests that the mechanism does not involve alkoxy radicals derived from homolytic cleavage of MPPH but is consistent with heterolytic cleavage of MPPH to produce a metal-based active intermediate. The following evidence also shows that no free alkyl radicals are produced in the catalytic oxidation of alkanes: (1) The product yields and distributions are only slightly affected by the presence of O2. (2) Addition of BrCCl3 does not affect the yields of cyclohexanol and cyclohexanone in the oxidation of cyclohexane. (3) A complete retention of stereochemistry occurs in the hydroxylation of cis- and trans-1,2-dimethylcyclohexane. The proposed mechanism involves initial O-atom transfer from ROOH to [Os(VI)(N)Cl4](-)/Lewis acid to generate [Os(VIII)(N)(O)Cl4](-)/Lewis acid, which then oxidizes alkanes via H-atom abstraction.

  8. Revisiting the Kinetics and Thermodynamics of the Low-Temperature Oxidation Pathways of Alkanes: A Case Study of the Three Pentane Isomers.

    PubMed

    Bugler, John; Somers, Kieran P; Silke, Emma J; Curran, Henry J

    2015-07-16

    This paper describes our developing understanding of low-temperature oxidation kinetics. We have investigated the ignition of the three pentane isomers in a rapid compression machine over a wide range of temperatures and pressures, including conditions of negative temperature coefficient behavior. The pentane isomers are small alkanes, yet have structures that are complex enough to allow for the application of their kinetic and thermochemical rules to larger molecules. Updates to the thermochemistry of the species important in the low-temperature oxidation of hydrocarbons have been made based on a thorough literature review. An evaluation of recent quantum-chemically derived rate coefficients from the literature pertinent to important low-temperature oxidation reaction classes has been performed, and new rate rules are recommended for these classes. Several reaction classes have also been included to determine their importance with regard to simulation results, and we have found that they should be included when developing future chemical kinetic mechanisms. A comparison of the model simulations with pressure-time histories from experiments in a rapid compression machine shows very good agreement for both ignition delay time and pressure rise for both the first- and second-stage ignition events. We show that revisions to both the thermochemistry and the kinetics are required in order to replicate experiments well. A broader validation of the models with ignition delay times from shock tubes and a rapid compression machine is presented in an accompanying paper. The results of this study enhance our understanding of the combustion of straight- and branched-chained alkanes.

  9. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation

    NASA Astrophysics Data System (ADS)

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2016-02-01

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas-wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas-wall mass transfer, the vapor pressure of the species and the duration of the experiments. This work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.

  10. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation

    NASA Astrophysics Data System (ADS)

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2015-09-01

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool which explicitly represents SOA formation and gas/wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas/wall mass transfer, the vapor pressure of the species and the duration of the experiments. This work suggests that SOA yields inferred from chamber experiments could be underestimated up to 0.35 yield unit due to the loss of organic vapors to chamber walls.

  11. Transitions from functionalization to fragmentation reactions of laboratory secondary organic aerosol (SOA) generated from the OH oxidation of alkane precursors.

    PubMed

    Lambe, Andrew T; Onasch, Timothy B; Croasdale, David R; Wright, Justin P; Martin, Alexander T; Franklin, Jonathan P; Massoli, Paola; Kroll, Jesse H; Canagaratna, Manjula R; Brune, William H; Worsnop, Douglas R; Davidovits, Paul

    2012-05-15

    Functionalization (oxygen addition) and fragmentation (carbon loss) reactions governing secondary organic aerosol (SOA) formation from the OH oxidation of alkane precursors were studied in a flow reactor in the absence of NO(x). SOA precursors were n-decane (n-C10), n-pentadecane (n-C15), n-heptadecane (n-C17), tricyclo[5.2.1.0(2,6)]decane (JP-10), and vapors of diesel fuel and Southern Louisiana crude oil. Aerosol mass spectra were measured with a high-resolution time-of-flight aerosol mass spectrometer, from which normalized SOA yields, hydrogen-to-carbon (H/C) and oxygen-to-carbon (O/C) ratios, and C(x)H(y)+, C(x)H(y)O+, and C(x)H(y)O(2)+ ion abundances were extracted as a function of OH exposure. Normalized SOA yield curves exhibited an increase followed by a decrease as a function of OH exposure, with maximum yields at O/C ratios ranging from 0.29 to 0.74. The decrease in SOA yield correlates with an increase in oxygen content and decrease in carbon content, consistent with transitions from functionalization to fragmentation. For a subset of alkane precursors (n-C10, n-C15, and JP-10), maximum SOA yields were estimated to be 0.39, 0.69, and 1.1. In addition, maximum SOA yields correspond with a maximum in the C(x)H(y)O+ relative abundance. Measured correlations between OH exposure, O/C ratio, and H/C ratio may enable identification of alkane precursor contributions to ambient SOA.

  12. OXIDATION OF ALKANES WITH AIR USING IRON AND MANGANESE CATALYSTS. AN OVERALL GREEN CHEMISTRY APPROACH INCLUDING THE USE OF ALTERNATIVE SOLVENT SYSTEMS GENERATED BY PARIS II

    EPA Science Inventory

    The selective oxidation of alkanes is an industrially important process that is often plagued by low conversions and the formation of unwanted by-products. Research being conducted at the USEPA, implements a Green chemistry approach which is utilized to improve these difficult o...

  13. Isolation and characterization of a novel oxygenase that catalyzes the first step of n-alkane oxidation in Acinetobacter sp. strain M-1.

    PubMed Central

    Maeng, J H; Sakai, Y; Tani, Y; Kato, N

    1996-01-01

    In the Finnerty pathway for n-alkane, oxidation in Acinetobacter sp., n-alkanes are postulated to be attacked by a dioxygenase and the product, n-alkyl hydroperoxide, is further metabolized to the corresponding aldehyde via the peroxy acid [W. R. Finnerty, P. 184-188, in A. H. Applewhite (ed.), Proceedings of the World Conference on Biotechnology for the Fats and Oil Industry, 1988]. However, no biochemical evidence regarding the first-step reaction is available. In this study, we found a novel n-alkane-oxidizing enzyme that requires only molecular oxygen, i.e., not NAD(P)H, in our isolate, Acinetobacter sp. strain M-1, and purified it to apparent homogeneity by gel electrophoresis. The purified enzyme is a homodimeric protein with a molecular mass of 134 kDa, contains 1 mol of flavin adenine dinucleotide per mol of subunit, and requires CU2+ for its activity. The enzyme uses n-alkanes ranging in length from 10 to 30 carbon atoms and is also active toward n-alkenes (C12 to C20) and some aromatic compounds with substituted alkyl groups but not toward a branched alkane, alcohol, or aldehyde. Transient accumulation of n-alkyl hydroperoxide was detected in the course of the reaction, and no oxygen radical scavengers affected the enzyme activity. From these properties, the enzyme is most probably a dioxygenase that catalyzes the introduction of two atoms of oxygen to the substrate, leading to the formation of the corresponding n-alkyl hydroperoxide. The enzymatic evidence strongly supports the existence of an n-alkane oxidation pathway, which is initiated by a dioxygenase reaction, in Acinetobacter spp. PMID:8682768

  14. Antioxidant, electrochemical, thermal, antimicrobial and alkane oxidation properties of tridentate Schiff base ligands and their metal complexes

    NASA Astrophysics Data System (ADS)

    Ceyhan, Gökhan; Çelik, Cumali; Uruş, Serhan; Demirtaş, İbrahim; Elmastaş, Mahfuz; Tümer, Mehmet

    2011-10-01

    In this study, two Schiff base ligands (HL 1 and HL 2) and their Cu(II), Co(II), Ni(II), Pd(II) and Ru(III) metal complexes were synthesized and characterized by the analytical and spectroscopic methods. Alkane oxidation activities of the metal complexes were studied on cyclohexane as substrate. The ligands and their metal complexes were evaluated for their antimicrobial activity against Corynebacterium xerosis, Bacillus brevis, Bacillus megaterium, Bacillus cereus, Mycobacterium smegmatis, Staphylococcus aureus, Micrococcus luteus and Enterococcus faecalis (as Gram-positive bacteria) and Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Yersinia enterocolitica, Klebsiella fragilis, Saccharomyces cerevisiae, and Candida albicans (as Gram-negative bacteria). The antioxidant properties of the Schiff base ligands were evaluated in a series of in vitro tests: 1,1-diphenyl-2-picrylhydrazyl (DPPH rad ) free radical scavenging and reducing power activity of superoxide anion radical generated non-enzymatic systems. Electrochemical and thermal properties of the compounds were investigated.

  15. Rate constants for OH with selected large alkanes: shock-tube measurements and an improved group scheme.

    PubMed

    Sivaramakrishnan, R; Michael, J V

    2009-04-30

    1.649 exp(80 K/T) cm3 molecule-1 s-1 (224-1308 K)kOH+n-hexane)3.959 x 10(-18)T2.218 exp(443 K/T) cm3 molecule-1 s-1 (292-1299 K)kOH+2,3-DMB)2.287 x 10(-17)T1.958 exp(365 K/ T) cm3 molecule-1 s-1 (220-1292 K). The experimental data and the evaluations obtained for these five larger alkanes in the present work were used along with prior data/evaluations obtained in this laboratory for H abstractions by OH from a series of smaller alkanes (C(3)-C(5)) to devise rate rules for abstractions from various types of primary, secondary, and tertiary H atoms. Specifically, the current scheme was applied with good success to H abstractions by OH from a series of n-alkanes (n-octane through n-hexadecane). The total rate constants using this group scheme for reactions of OH with selected large alkanes are given as three-parameter fits in this article. The rate constants for the various abstraction channels in any large n-alkane can also be obtained using the groups listed in this article. The present group scheme serves to reduce the uncertainties in rate constants for OH + alkane reactions.

  16. Rate constants for OH with selected large alkanes : shock-tube measurements and an improved group scheme.

    SciTech Connect

    Sivaramakrishnan, R.; Michael, J. V.; Chemical Sciences and Engineering Division

    2009-04-30

    } molecule{sup -1} s{sup -1} (241-1287 K); k{sub OH+2,2,3,3-TMB} = 6.835 x 10{sup -17}T{sup 1.886} exp(-365 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (290-1180 K); k{sub OH+n-pentane} = 2.495 x 10{sup -16}T{sup 1.649} exp(80 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (224-1308 K); k{sub OH+n-hexane} = 3.959 x 10{sup -18}T{sup 2.218} exp(443 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (292-1299 K); and k{sub OH+2,3-DMB} = 2.287 x 10{sup -17}T{sup 1.958} exp(365 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (220-1292 K). The experimental data and the evaluations obtained for these five larger alkanes in the present work were used along with prior data/evaluations obtained in this laboratory for H abstractions by OH from a series of smaller alkanes (C{sub 3}?C{sub 5}) to devise rate rules for abstractions from various types of primary, secondary, and tertiary H atoms. Specifically, the current scheme was applied with good success to H abstractions by OH from a series of n-alkanes (n-octane through n-hexadecane). The total rate constants using this group scheme for reactions of OH with selected large alkanes are given as three-parameter fits in this article. The rate constants for the various abstraction channels in any large n-alkane can also be obtained using the groups listed in this article. The present group scheme serves to reduce the uncertainties in rate constants for OH + alkane reactions.

  17. A new approach to the non-oxidative conversion of gaseous alkanes in a barrier discharge and features of the reaction mechanism

    NASA Astrophysics Data System (ADS)

    Kudryashov, S.; Ryabov, A.; Shchyogoleva, G.

    2016-01-01

    A new approach to the non-oxidative conversion of C1-C4 alkanes into gaseous and liquid products in a barrier discharge is proposed. It consists in inhibiting the formation of deposits on the reactor electrode surfaces due to the addition of distilled water into the flow of hydrocarbon gases. The energy consumption on hydrocarbon conversion decreases from methane to n-butane from ~46 to 35 eV molecule-1. The main gaseous products of the conversion of light alkanes are hydrogen and C2-C4 hydrocarbons. The liquid reaction products contain C5+ alkanes with a predominantly isomeric structure. The results of modeling the kinetics of chemical reactions show that an increase in the molecular weight of the reaction products is mainly due to processes involving CH2 radical and the recombination of alkyl radicals.

  18. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: Explicit modeling of SOA formation from alkane and alkene oxidation

    DOE PAGES

    La, Y. S.; Camredon, M.; Ziemann, P. J.; ...

    2016-02-08

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas–wall partitioning. The model was compared with 41 smog chambermore » experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas–wall mass transfer, the vapor pressure of the species and the duration of the experiments. Furthermore, this work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.« less

  19. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: Explicit modeling of SOA formation from alkane and alkene oxidation

    SciTech Connect

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2016-02-08

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas–wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas–wall mass transfer, the vapor pressure of the species and the duration of the experiments. Furthermore, this work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.

  20. Mass spectra of cyclic ethers formed in the low-temperature oxidation of a series of n-alkanes

    PubMed Central

    Herbinet, Olivier; Bax, Sarah; Glaude, Pierre-Alexandre; Carré, Vincent; Battin-Leclerc, Frédérique

    2013-01-01

    Cyclic ethers are important intermediate species formed during the low-temperature oxidation of hydrocarbons. Along with ketones and aldehydes, they could consequently represent a significant part of the heavy oxygenated pollutants observed in the exhaust gas of engines. Apart a few of them such as ethylene oxide and tetrahydrofuran, cyclic ethers have not been much studied and very few of them are available for calibration and identification. Electron impact mass spectra are available for very few of them, making their detection in the exhaust emissions of combustion processes very difficult. The main goal of this study was to complete the existing set of mass spectra for this class of molecules. Thus cyclic ethers have been analyzed in the exhaust gases of a jet-stirred reactor in which the low-temperature oxidation of a series of n-alkanes was taking place. Analyzes were performed by gas chromatography coupled to mass spectrometry and to MS/MS. The second goal of this study was to derive some rules for the fragmentation of cyclic ethers in electron impact mass spectrometry and allow the identification of these species when no mass spectrum is available. PMID:24092947

  1. Identification and use of an alkane transporter plug-in for applications in biocatalysis and whole-cell biosensing of alkanes.

    PubMed

    Grant, Chris; Deszcz, Dawid; Wei, Yu-Chia; Martínez-Torres, Rubéns Julio; Morris, Phattaraporn; Folliard, Thomas; Sreenivasan, Rakesh; Ward, John; Dalby, Paul; Woodley, John M; Baganz, Frank

    2014-07-28

    Effective application of whole-cell devices in synthetic biology and biocatalysis will always require consideration of the uptake of molecules of interest into the cell. Here we demonstrate that the AlkL protein from Pseudomonas putida GPo1 is an alkane import protein capable of industrially relevant rates of uptake of C7-C16 n-alkanes. Without alkL expression, native E.coli n-alkane uptake was the rate-limiting step in both the whole-cell bioconversion of C7-C16 n-alkanes and in the activation of a whole-cell alkane biosensor by C10 and C11 alkanes. By coexpression of alkL as a transporter plug-in, specific yields improved by up to 100-fold for bioxidation of >C12 alkanes to fatty alcohols and acids. The alkL protein was shown to be toxic to the host when overexpressed but when expressed from a vector capable of controlled induction, yields of alkane oxidation were improved a further 10-fold (8 g/L and 1.7 g/g of total oxidized products). Further testing of activity on n-octane with the controlled expression vector revealed the highest reported rates of 120 μmol/min/g and 1 g/L/h total oxidized products. This is the first time AlkL has been shown to directly facilitate enhanced uptake of C10-C16 alkanes and represents the highest reported gain in product yields resulting from its use.

  2. Identification and use of an alkane transporter plug-in for applications in biocatalysis and whole-cell biosensing of alkanes

    NASA Astrophysics Data System (ADS)

    Grant, Chris; Deszcz, Dawid; Wei, Yu-Chia; Martínez-Torres, Rubéns Julio; Morris, Phattaraporn; Folliard, Thomas; Sreenivasan, Rakesh; Ward, John; Dalby, Paul; Woodley, John M.; Baganz, Frank

    2014-07-01

    Effective application of whole-cell devices in synthetic biology and biocatalysis will always require consideration of the uptake of molecules of interest into the cell. Here we demonstrate that the AlkL protein from Pseudomonas putida GPo1 is an alkane import protein capable of industrially relevant rates of uptake of C7-C16 n-alkanes. Without alkL expression, native E.coli n-alkane uptake was the rate-limiting step in both the whole-cell bioconversion of C7-C16 n-alkanes and in the activation of a whole-cell alkane biosensor by C10 and C11 alkanes. By coexpression of alkL as a transporter plug-in, specific yields improved by up to 100-fold for bioxidation of >C12 alkanes to fatty alcohols and acids. The alkL protein was shown to be toxic to the host when overexpressed but when expressed from a vector capable of controlled induction, yields of alkane oxidation were improved a further 10-fold (8 g/L and 1.7 g/g of total oxidized products). Further testing of activity on n-octane with the controlled expression vector revealed the highest reported rates of 120 μmol/min/g and 1 g/L/h total oxidized products. This is the first time AlkL has been shown to directly facilitate enhanced uptake of C10-C16 alkanes and represents the highest reported gain in product yields resulting from its use.

  3. Identification and use of an alkane transporter plug-in for applications in biocatalysis and whole-cell biosensing of alkanes

    PubMed Central

    Grant, Chris; Deszcz, Dawid; Wei, Yu-Chia; Martínez-Torres, Rubéns Julio; Morris, Phattaraporn; Folliard, Thomas; Sreenivasan, Rakesh; Ward, John; Dalby, Paul; Woodley, John M.; Baganz, Frank

    2014-01-01

    Effective application of whole-cell devices in synthetic biology and biocatalysis will always require consideration of the uptake of molecules of interest into the cell. Here we demonstrate that the AlkL protein from Pseudomonas putida GPo1 is an alkane import protein capable of industrially relevant rates of uptake of C7-C16 n-alkanes. Without alkL expression, native E.coli n-alkane uptake was the rate-limiting step in both the whole-cell bioconversion of C7-C16 n-alkanes and in the activation of a whole-cell alkane biosensor by C10 and C11 alkanes. By coexpression of alkL as a transporter plug-in, specific yields improved by up to 100-fold for bioxidation of >C12 alkanes to fatty alcohols and acids. The alkL protein was shown to be toxic to the host when overexpressed but when expressed from a vector capable of controlled induction, yields of alkane oxidation were improved a further 10-fold (8 g/L and 1.7 g/g of total oxidized products). Further testing of activity on n-octane with the controlled expression vector revealed the highest reported rates of 120 μmol/min/g and 1 g/L/h total oxidized products. This is the first time AlkL has been shown to directly facilitate enhanced uptake of C10-C16 alkanes and represents the highest reported gain in product yields resulting from its use. PMID:25068650

  4. Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

    NASA Technical Reports Server (NTRS)

    DeMore, W.; Bayes, K.

    1998-01-01

    Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.

  5. Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

    NASA Technical Reports Server (NTRS)

    DeMore, W.; Bayes, K.

    1998-01-01

    Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.

  6. Catalytic oxidation of alkanes by iron bispidine complexes and dioxygen: oxygen activation versus autoxidation.

    PubMed

    Comba, Peter; Lee, Yong-Min; Nam, Wonwoo; Waleska, Arkadius

    2014-01-14

    Organic substrates (specifically cis-1,2-dimethylcyclohexane, DMCH) are oxidized by O2 in the presence of iron(II)-bispidine complexes. It is shown that this oxidation reaction is not based on O2 activation by the nonheme iron catalysts as in Nature but due to a radical-based initiation, followed by a radical- and ferryl-based catalytic reaction.

  7. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... with mixed metal oxides (generic). 721.10148 Section 721.10148 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES... mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting....

  8. Employing a new 12-connected topological open-framework copper borovanadate as an effective heterogeneous catalyst for oxidation of benzyl-alkanes.

    PubMed

    Feng, Yuquan; Ding, Chenghua; Fan, Huitao; Zhong, Zhiguo; Qiu, Dongfang; Shi, Hengzhen

    2015-11-21

    A new 12-connected topological open-framework copper borovanadate with a unique B/V ratio (20/12) and a -B3O7(OH)-Na(μ-OH)[B(OH)2]-B3O7(OH)- connection mode has been hydrothermally obtained and characterized. It not only features the first 3-D copper(II) borovanadate which possesses the largest ratio of TM(2+) and borovanadate anion, but also displays highly catalytic activities for the oxidation of benzyl-alkanes.

  9. CYP63A2, a catalytically versatile fungal P450 monooxygenase capable of oxidizing higher-molecular-weight polycyclic aromatic hydrocarbons, alkylphenols, and alkanes.

    PubMed

    Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E; Yadav, Jagjit S

    2013-04-01

    Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills).

  10. CYP63A2, a Catalytically Versatile Fungal P450 Monooxygenase Capable of Oxidizing Higher-Molecular-Weight Polycyclic Aromatic Hydrocarbons, Alkylphenols, and Alkanes

    PubMed Central

    Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E.

    2013-01-01

    Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills). PMID:23416995

  11. Ruthenium tetraoxide oxidations of alkanes: DFT calculations of barrier heights and kinetic isotope effects.

    PubMed

    Drees, Markus; Strassner, Thomas

    2006-03-03

    The oxidation of C-H and C-C bonds by metal-oxo compounds is of general interest. We studied the RuO4-mediated catalytic oxidation of several cycloalkanes such as adamantane and cis- and trans-decalin as well as methane. B3LYP/6-31G(d) calculations on the experimentally proposed (3+2) mechanism are in good agreement with known experimental results. Comparison of experimental and theoretical kinetic isotope effects confirms the proposed mechanism. Besides RuO4, we also looked at RuO4(OH)- as a potential active species to account for ruthenium tetraoxide oxidations under strong basic conditions.

  12. Surface electronic structure and isomerization reactions of alkanes on some transition metal oxides

    NASA Astrophysics Data System (ADS)

    Katrib, A.; Logie, V.; Saurel, N.; Wehrer, P.; Hilaire, L.; Maire, G.

    1997-04-01

    XP spectra of some reduced transition metal oxides are presented. Different number of free nd,( n + 1)s valence electrons in each case could be observed by the presence of a certain density of states (DOS) at the Fermi-level in the valence band (VB) energy region of the XP spectrum. Catalytic isomerization reactions of 2-methylpentane yielding 3-methylpentane and n-hexane at 350°C have been observed on these reduced valence surface states. The bifunctionel mechanism in terms of metallic and acidic sites required for such reactions is proposed by considering the metallic properties of the rutile deformed structure through the C-axis in the case of MoO 2 and WO 2, while the oxygen atom(s) in the lattice structure exhibit Brönsted acidic properties. On the other hand, highly reduced or clean surfaces of these transition metals yield hydrogenolysis catalytic reactions for the same reactant with methane as the major product. In all cases, the exposure of the lower valence oxidation states of bulk transition metal oxides to air results in the surface partial oxidation to the stable oxides such as MoO 3, WO 3, V 2O 5 and Nb 2O 5.

  13. Understanding the factors affecting the activation of alkane by Cp'Rh(CO)2 (Cp' = Cp or Cp*).

    PubMed

    George, Michael W; Hall, Michael B; Jina, Omar S; Portius, Peter; Sun, Xue-Zhong; Towrie, Michael; Wu, Hong; Yang, Xinzheng; Zaric, Snezana D

    2010-11-23

    Fast time-resolved infrared spectroscopic measurements have allowed precise determination of the rates of activation of alkanes by Cp'Rh(CO) (Cp(') = η(5)-C(5)H(5) or η(5)-C(5)Me(5)). We have monitored the kinetics of C─H activation in solution at room temperature and determined how the change in rate of oxidative cleavage varies from methane to decane. The lifetime of CpRh(CO)(alkane) shows a nearly linear behavior with respect to the length of the alkane chain, whereas the related Cp*Rh(CO)(alkane) has clear oscillatory behavior upon changing the alkane. Coupled cluster and density functional theory calculations on these complexes, transition states, and intermediates provide the insight into the mechanism and barriers in order to develop a kinetic simulation of the experimental results. The observed behavior is a subtle interplay between the rates of activation and migration. Unexpectedly, the calculations predict that the most rapid process in these Cp'Rh(CO)(alkane) systems is the 1,3-migration along the alkane chain. The linear behavior in the observed lifetime of CpRh(CO)(alkane) results from a mechanism in which the next most rapid process is the activation of primary C─H bonds (─CH(3) groups), while the third key step in this system is 1,2-migration with a slightly slower rate. The oscillatory behavior in the lifetime of Cp*Rh(CO)(alkane) with respect to the alkane's chain length follows from subtle interplay between more rapid migrations and less rapid primary C─H activation, with respect to CpRh(CO)(alkane), especially when the CH(3) group is near a gauche turn. This interplay results in the activation being controlled by the percentage of alkane conformers.

  14. Expression of an alkane monooxygenase (alkB) gene and methyl tert-butyl ether co-metabolic oxidation in Pseudomonas citronellolis.

    PubMed

    Bravo, Ana Luisa; Sigala, Juan Carlos; Le Borgne, Sylvie; Morales, Marcia

    2015-04-01

    Pseudomonas citronellolis UAM-Ps1 co-metabolically transforms methyl tert-butyl ether (MTBE) to tert-butyl alcohol with n-pentane (2.6 mM), n-octane (1.5 mM) or dicyclopropylketone (DCPK) (4.4 mM), a gratuitous inducer of alkane hydroxylase (AlkB) activity. The reverse transcription quantitative real-time PCR was used to quantify the alkane monooxygenase (alkB) gene expression. The alkB gene was expressed in the presence of n-alkanes and DCPK and MTBE oxidation occurred only in cultures when alkB was transcribed. A correlation between the number of alkB transcripts and MTBE consumption was found (ΜΤΒΕ consumption in μmol = 1.44e(-13) x DNA copies, R(2) = 0.99) when MTBE (0.84 mM) was added. Furthermore, alkB was cloned and expressed into Escherichia coli and the recombinant AlkB had a molecular weight of 42 kDa. This is the first report where the expression of alkB is related to the co-metabolic oxidation of MTBE.

  15. Homogeneous catalysis in the oxidative functionalization of alkanes in protic media

    NASA Astrophysics Data System (ADS)

    Chepaikin, E. G.

    2011-04-01

    Examples of the activation of saturated hydrocarbons and dioxygen as well as oxidative functionalization of saturated hydrocarbons involving the C-H and C-C bonds in the presence of metal complexes in protic media are considered. The mechanisms of processes are analyzed. Attention is focused on the transformations of methane and C2-C4 hydrocarbons as the natural and associated gas components.

  16. Selective oxidation of alkanes and/or alkenes to valuable oxygenates

    DOEpatents

    Lin, Manhua; Pillai, Krishnan S.

    2011-02-15

    A catalyst, its method of preparation and its use for producing at least one of methacrolein and methacrylic acid, for example, by subjecting isobutane or isobutylene or a mixture thereof to a vapor phase catalytic oxidation in the presence of air or oxygen. In the case where isobutane alone is subjected to a vapor phase catalytic oxidation in the presence of air or oxygen, the product is at least one of isobutylene, methacrolein and methacrylic acid. The catalyst comprises a compound having the formula A.sub.aB.sub.bX.sub.xY.sub.yZ.sub.zO.sub.o wherein A is one or more elements selected from the group of Mo, W and Zr, B is one or more elements selected from the group of Bi, Sb, Se, and Te, X is one or more elements selected from the group of Al, Bi, Ca, Ce, Co, Fe, Ga, Mg, Ni, Nb, Sn, W and Zn, Y is one or more elements selected from the group of Ag, Au, B, Cr, Cs, Cu, K, La, Li, Mg, Mn, Na, Nb, Ni, P, Pb, Rb, Re, Ru, Sn, Te, Ti, V and Zr, and Z is one or more element from the X or Y groups or from the following: As, Ba, Pd, Pt, Sr, or mixtures thereof, and wherein a=1, 0.05oxidation state of the other elements.

  17. Comprehensive chemical kinetic modeling of the oxidation of C8 and larger n-alkanes and 2-methylalkanes

    SciTech Connect

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M; Togbe, C; Dagaut, P; Wang, H; Oehlschlaeger, M; NIemann, U; Seshadri, K; Veloo, P S; Ji, C; Egolfopoulos, F; Lu, T

    2011-03-16

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed and reduced chemical kinetic mechanism for singly methylated iso-alkanes (i.e., 2-methylalkanes) ranging from C{sub 8} to C{sub 20}. The mechanism also includes an updated version of our previously published C{sub 8} to C{sub 16} n-alkanes model. The complete detailed mechanism contains approximately 7,200 species 31,400 reactions. The proposed model is validated against new experimental data from a variety of fundamental combustion devices including premixed and nonpremixed flames, perfectly stirred reactors and shock tubes. This new model is used to show how the presence of a methyl branch affects important combustion properties such as laminar flame propagation, ignition, and species formation.

  18. Alkane-Based Urethane Potting Compounds

    NASA Technical Reports Server (NTRS)

    Morris, D. E.

    1986-01-01

    New low viscosity urethanes easily mixed, molded, and outgassed. Alkane-based urethanes resist hydrolysis and oxidation and have excellent dielectric properties. Low-viscosity alkane-based urethane prepolymer prepared by one-step reaction of either isophorone diisocyanate or methyl-bis (4-cyclohexyl isocyanate) with hydrogenated, hydroxy-terminated polybutadiene (HTPBD).

  19. Copper(II) Coordination Polymers Self-Assembled from Aminoalcohols and Pyromellitic Acid: Highly Active Precatalysts for the Mild Water-Promoted Oxidation of Alkanes.

    PubMed

    Fernandes, Tiago A; Santos, Carla I M; André, Vânia; Kłak, Julia; Kirillova, Marina V; Kirillov, Alexander M

    2016-01-04

    Three novel water-soluble 2D copper(II) coordination polymers-[{Cu2(μ2-dmea)2(H2O)}2(μ4-pma)]n·4nH2O (1), [{Cu2(μ2-Hedea)2}2(μ4-pma)]n·4nH2O (2), and [{Cu(bea)(Hbea)}4(μ4-pma)]n·2nH2O (3)-were generated by an aqueous medium self-assembly method from copper(II) nitrate, pyromellitic acid (H4pma), and different aminoalcohols [N,N-dimethylethanolamine (Hdmea), N-ethyldiethanolamine (H2edea), and N-benzylethanolamine (Hbea)]. Compounds 2 and 3 represent the first coordination polymers derived from H2edea and Hbea. All the products were characterized by infrared (IR), electron paramagnetic resonance (EPR), and ultraviolet-visible light (UV-vis) spectroscopy, electrospray ionization-mass spectroscopy (ESI-MS(±)), thermogravimetric and elemental analysis, and single-crystal X-ray diffraction (XRD), which revealed that their two-dimensional (2D) metal-organic networks are composed of distinct dicopper(II) or monocopper(II) aminoalcoholate units and μ4-pyromellitate spacers. From the topological viewpoint, the underlying 2D nets of 1-3 can be classified as uninodal 4-connected layers with the sql topology. The structures of 1 and 2 are further extended by multiple intermolecular hydrogen bonds, resulting in three-dimensional (3D) hydrogen-bonded networks with rare or unique topologies. The obtained compounds also act as highly efficient precatalysts for the mild homogeneous oxidation, by aqueous H2O2 in acidic MeCN/H2O medium, of various cycloalkanes to the corresponding alcohols and ketones. Overall product yields up to 45% (based on cycloalkane) were attained and the effects of various reaction parameters were investigated, including the type of precatalyst and acid promoter, influence of water, and substrate scope. Although water usually strongly inhibits the alkane oxidations, a very pronounced promoting behavior of H2O was detected when using the precatalyst 1, resulting in a 15-fold growth of an initial reaction rate in the cyclohexane oxidation on

  20. Millisecond Oxidation of Alkanes

    SciTech Connect

    2004-09-01

    This factsheet describes a project whose goal is to commercialize a production process for propylene and acrylic acid from propane using a catalytic auto-thermal oxydehydrogenation process operating at short contact times.

  1. [Hydrocarbon-Oxidizing potential and the genes for n-alkane biodegradation in a new acidophilic mycobacterial association from sulfur blocks].

    PubMed

    Ivanova, I E; Sukhacheva, M V; Kanat'eva, A Yu; Kravchenko, I K; Kurganov, A A

    2014-01-01

    Capacity of AG(S10), a new aerobic acidophilic (growing within the pH range from 1.3 to 4.5 with the optimum at 2.0-2.5) bacterial association from sulfur blocks of the Astrakhan gas-processing complex (AGC), for oxidation of hydrocarbons of various chemical structure was investigated. A broad spectrum of normal (C10-C21) and iso-alkanes, toluene, naphthalene, andphenanthrene, as well as isoprenoids resistant to microbial degradation, pristane and phytane (components of paraffin oil), and 2,2,4,4,6,8,8,-heptamethylnonane, a branched hydrocarbon, were biodegraded under acidic conditions. Microbiological investigation revealed the dominance of mycobacteria in the AGS10 association, which was confirmed by analysis of the 16S rRNA gene clone library. In the phylogenetic tree, the 16S rRNA sequences formed a branch within the cluster of slow-growing mycobacteria, with 98% homology to the closest species Mycobacterium florentinum. Genomic DNA of AG(S10) culture grown on C14-C17 n-alkanes at pH 2.5 was found to contain the genes of two hydroxylase families, alkB and Cyp 153, indicating their combined involvement in hydrocarbon biodegradation. The high hydrocarbon-oxidizing potential of the AGS10 bacterial association, indicated that further search for the genes responsible for degradation of various hydrocarbons in acidophilic mycobacteria could be promising.

  2. Chemical kinetic modeling of the oxidation of large alkane fuels: n-octane and iso-octane

    SciTech Connect

    Axelsson, E.I.; Brezinsky, K.; Dryer, F.L.; Pitz, W.J.; Westbrook, C.K.

    1986-01-13

    The development of detailed chemical kinetic reaction mechanisms for oxidation of n-octane and iso-octane is described, with emphasis on the factors which are specific to many large hydrocarbon fuel molecules. Elements which are of particular importance are found to include site-specific abstraction of H atoms, radical isomerization of alkyl radicals by internal H atom abstraction, and rapid ..beta..-scission of the alkyl radicals. These features, combined with distinctions in the types of intermediate olefin species produced, are used to explain the significant differences in the rate of oxidation between n-octane and iso-octane. 24 refs., 3 figs., 1 tab.

  3. The quantitative significance of Syntrophaceae and syntrophic partnerships in methanogenic degradation of crude oil alkanes.

    PubMed

    Gray, N D; Sherry, A; Grant, R J; Rowan, A K; Hubert, C R J; Callbeck, C M; Aitken, C M; Jones, D M; Adams, J J; Larter, S R; Head, I M

    2011-11-01

    Libraries of 16S rRNA genes cloned from methanogenic oil degrading microcosms amended with North Sea crude oil and inoculated with estuarine sediment indicated that bacteria from the genera Smithella (Deltaproteobacteria, Syntrophaceace) and Marinobacter sp. (Gammaproteobacteria) were enriched during degradation. Growth yields and doubling times (36 days for both Smithella and Marinobacter) were determined using qPCR and quantitative data on alkanes, which were the predominant hydrocarbons degraded. The growth yield of the Smithella sp. [0.020 g(cell-C)/g(alkane-C)], assuming it utilized all alkanes removed was consistent with yields of bacteria that degrade hydrocarbons and other organic compounds in methanogenic consortia. Over 450 days of incubation predominance and exponential growth of Smithella was coincident with alkane removal and exponential accumulation of methane. This growth is consistent with Smithella's occurrence in near surface anoxic hydrocarbon degrading systems and their complete oxidation of crude oil alkanes to acetate and/or hydrogen in syntrophic partnership with methanogens in such systems. The calculated growth yield of the Marinobacter sp., assuming it grew on alkanes, was [0.0005 g(cell-C)/g(alkane-C)] suggesting that it played a minor role in alkane degradation. The dominant methanogens were hydrogenotrophs (Methanocalculus spp. from the Methanomicrobiales). Enrichment of hydrogen-oxidizing methanogens relative to acetoclastic methanogens was consistent with syntrophic acetate oxidation measured in methanogenic crude oil degrading enrichment cultures. qPCR of the Methanomicrobiales indicated growth characteristics consistent with measured rates of methane production and growth in partnership with Smithella.

  4. The quantitative significance of Syntrophaceae and syntrophic partnerships in methanogenic degradation of crude oil alkanes

    PubMed Central

    Gray, N D; Sherry, A; Grant, R J; Rowan, A K; Hubert, C R J; Callbeck, C M; Aitken, C M; Jones, D M; Adams, J J; Larter, S R; Head, I M

    2011-01-01

    Libraries of 16S rRNA genes cloned from methanogenic oil degrading microcosms amended with North Sea crude oil and inoculated with estuarine sediment indicated that bacteria from the genera Smithella (Deltaproteobacteria, Syntrophaceace) and Marinobacter sp. (Gammaproteobacteria) were enriched during degradation. Growth yields and doubling times (36 days for both Smithella and Marinobacter) were determined using qPCR and quantitative data on alkanes, which were the predominant hydrocarbons degraded. The growth yield of the Smithella sp. [0.020 g(cell-C)/g(alkane-C)], assuming it utilized all alkanes removed was consistent with yields of bacteria that degrade hydrocarbons and other organic compounds in methanogenic consortia. Over 450 days of incubation predominance and exponential growth of Smithella was coincident with alkane removal and exponential accumulation of methane. This growth is consistent with Smithella's occurrence in near surface anoxic hydrocarbon degrading systems and their complete oxidation of crude oil alkanes to acetate and/or hydrogen in syntrophic partnership with methanogens in such systems. The calculated growth yield of the Marinobacter sp., assuming it grew on alkanes, was [0.0005 g(cell-C)/g(alkane-C)] suggesting that it played a minor role in alkane degradation. The dominant methanogens were hydrogenotrophs (Methanocalculus spp. from the Methanomicrobiales). Enrichment of hydrogen-oxidizing methanogens relative to acetoclastic methanogens was consistent with syntrophic acetate oxidation measured in methanogenic crude oil degrading enrichment cultures. qPCR of the Methanomicrobiales indicated growth characteristics consistent with measured rates of methane production and growth in partnership with Smithella. PMID:21914097

  5. A green and efficient photocatalytic route for the highly-selective oxidation of saturated alpha-carbon C-H bonds in aromatic alkanes over flower-like Bi2WO6.

    PubMed

    Liu, Ying; Chen, Lang; Yuan, Qing; He, Jie; Au, Chak-Tong; Yin, Shuang-Feng

    2016-01-21

    A green and efficient route for the highly-selective oxidation of saturated alpha-carbon C-H bonds in aromatic alkanes under visible-light irradiation and solvent-free conditions is developed using flower-like Bi2WO6 microspheres as catalysts.

  6. Understanding the factors affecting the activation of alkane by Cp′Rh(CO)2 (Cp′ = Cp or Cp*)

    PubMed Central

    George, Michael W.; Hall, Michael B.; Jina, Omar S.; Portius, Peter; Sun, Xue-Zhong; Towrie, Michael; Wu, Hong; Yang, Xinzheng; Zarić, Snežana D.

    2010-01-01

    Fast time-resolved infrared spectroscopic measurements have allowed precise determination of the rates of activation of alkanes by Cp′Rh(CO) (Cp′ = η5-C5H5 or η5-C5Me5). We have monitored the kinetics of C─H activation in solution at room temperature and determined how the change in rate of oxidative cleavage varies from methane to decane. The lifetime of CpRh(CO)(alkane) shows a nearly linear behavior with respect to the length of the alkane chain, whereas the related Cp*Rh(CO)(alkane) has clear oscillatory behavior upon changing the alkane. Coupled cluster and density functional theory calculations on these complexes, transition states, and intermediates provide the insight into the mechanism and barriers in order to develop a kinetic simulation of the experimental results. The observed behavior is a subtle interplay between the rates of activation and migration. Unexpectedly, the calculations predict that the most rapid process in these Cp′Rh(CO)(alkane) systems is the 1,3-migration along the alkane chain. The linear behavior in the observed lifetime of CpRh(CO)(alkane) results from a mechanism in which the next most rapid process is the activation of primary C─H bonds (─CH3 groups), while the third key step in this system is 1,2-migration with a slightly slower rate. The oscillatory behavior in the lifetime of Cp*Rh(CO)(alkane) with respect to the alkane’s chain length follows from subtle interplay between more rapid migrations and less rapid primary C─H activation, with respect to CpRh(CO)(alkane), especially when the CH3 group is near a gauche turn. This interplay results in the activation being controlled by the percentage of alkane conformers. PMID:21048088

  7. Multiple alkane hydroxylase systems in a marine alkane degrader, Alcanivorax dieselolei B-5.

    PubMed

    Liu, Chenli; Wang, Wanpeng; Wu, Yehui; Zhou, Zhongwen; Lai, Qiliang; Shao, Zongze

    2011-05-01

    Alcanivorax dieselolei strain B-5 is a marine bacterium that can utilize a broad range of n-alkanes (C(5) -C(36) ) as sole carbon source. However, the mechanisms responsible for this trait remain to be established. Here we report on the characterization of four alkane hydroxylases from A. dieselolei, including two homologues of AlkB (AlkB1 and AlkB2), a CYP153 homologue (P450), as well as an AlmA-like (AlmA) alkane hydroxylase. Heterologous expression of alkB1, alkB2, p450 and almA in Pseudomonas putida GPo12 (pGEc47ΔB) or P. fluorescens KOB2Δ1 verified their functions in alkane oxidation. Quantitative real-time RT-PCR analysis showed that these genes could be induced by alkanes ranging from C(8) to C(36) . Notably, the expression of the p450 and almA genes was only upregulated in the presence of medium-chain (C(8) -C(16) ) or long-chain (C(22) -C(36) ) n-alkanes, respectively; while alkB1 and alkB2 responded to both medium- and long-chain n-alkanes (C(12) -C(26) ). Moreover, branched alkanes (pristane and phytane) significantly elevated alkB1 and almA expression levels. Our findings demonstrate that the multiple alkane hydroxylase systems ensure the utilization of substrates of a broad chain length range.

  8. Oxidation of alkane and alkene moieties with biologically inspired nonheme iron catalysts and hydrogen peroxide: from free radicals to stereoselective transformations.

    PubMed

    Olivo, Giorgio; Cussó, Olaf; Borrell, Margarida; Costas, Miquel

    2017-04-01

    The selective oxidation of hydrocarbons is a challenging reaction for synthetic chemists, but common in nature. Iron oxygenases activate the O-O bond of dioxygen to perform oxidation of alkane and alkenes moieties with outstanding levels of regio-, chemo- and stereoselectivity. Along a bioinspired approach, iron coordination complexes which mimic structural and reactivity aspects of the active sites of nonheme iron oxygenases have been explored as oxidation catalysts. This review describes the evolution of this research field, from the early attempts to reproduce the basic reactivity of nonheme iron oxygenases to the development of effective iron oxidation catalysts. The work covers exclusively nonheme iron complexes which rely on H2O2 or O2 as terminal oxidants. First, it delineates the key steps and the essential catalyst design principles required to activate the peroxide bond at nonheme iron centers without (or at least minimizing) the release of free-diffusing radicals. It follows with a critical description of the mechanistic pathways which govern the reaction between iron complexes and H2O2 to generate the oxidizing species. Eventually, the work presents a state-of-the-art report on the use of these catalysts in aliphatic C-H oxidation, olefin epoxidation and alkene syn-dihydroxylation, under substrate-limiting conditions. A special focus is given on the main strategies elaborated to tune catalyst activity and selectivity by modification of its structure. The work is concluded by a concise discussion on the essential progresses of these oxidation catalysts together with the challenges that remain still to be tackled.

  9. Deposition rates of oxidized iron on Mars

    NASA Technical Reports Server (NTRS)

    Burns, R. G.

    1993-01-01

    The reddened oxidized surface of Mars is indicative of temporal interactions between the Martian atmosphere and its surface. During the evolution of the Martian regolith, primary ferromagnesian silicate and sulfide minerals in basaltic rocks apparently have been oxidized to secondary ferric-bearing assemblages. To evaluate how and when such oxidized deposits were formed on Mars, information about the mechanisms and rates of chemical weathering of Fe(2+)-bearing minerals has been determined. In this paper, mechanisms and rates of deposition of ferric oxide phases on the Martian surface are discussed.

  10. Laboratory evolution of a soluble, self-sufficient, highly active alkane hydroxylase.

    PubMed

    Glieder, Anton; Farinas, Edgardo T; Arnold, Frances H

    2002-11-01

    We have converted cytochrome P450 BM-3 from Bacillus megaterium (P450 BM-3), a medium-chain (C12-C18) fatty acid monooxygenase, into a highly efficient catalyst for the conversion of alkanes to alcohols. The evolved P450 BM-3 exhibits higher turnover rates than any reported biocatalyst for the selective oxidation of hydrocarbons of small to medium chain length (C3-C8). Unlike naturally occurring alkane hydroxylases, the best known of which are the large complexes of methane monooxygenase (MMO) and membrane-associated non-heme iron alkane monooxygenase (AlkB), the evolved enzyme is monomeric, soluble, and requires no additional proteins for catalysis. The evolved alkane hydroxylase was found to be even more active on fatty acids than wild-type BM-3, which was already one of the most efficient fatty acid monooxgenases known. A broad range of substrates including the gaseous alkane propane induces the low to high spin shift that activates the enzyme. This catalyst for alkane hydroxylation at room temperature opens new opportunities for clean, selective hydrocarbon activation for chemical synthesis and bioremediation.

  11. Structural insights into diversity and n-alkane biodegradation mechanisms of alkane hydroxylases

    PubMed Central

    Ji, Yurui; Mao, Guannan; Wang, Yingying; Bartlam, Mark

    2013-01-01

    Environmental microbes utilize four degradation pathways for the oxidation of n-alkanes. Although the enzymes degrading n-alkanes in different microbes may vary, enzymes functioning in the first step in the aerobic degradation of alkanes all belong to the alkane hydroxylases. Alkane hydroxylases are a class of enzymes that insert oxygen atoms derived from molecular oxygen into different sites of the alkane terminus (or termini) depending on the type of enzymes. In this review, we summarize the different types of alkane hydroxylases, their degrading steps, and compare typical enzymes from various classes with regard to their three-dimensional structures, in order to provide insights into how the enzymes mediate their different roles in the degradation of n-alkanes and what determines their different substrate ranges. Through the above analyzes, the degrading mechanisms of enzymes can be elucidated and molecular biological methods can be utilized to expand their catalytic roles in the petrochemical industry or in bioremediation of oil-contaminated environments. PMID:23519435

  12. Dinuclear manganese complexes containing chiral 1,4,7-triazacyclononane-derived ligands and their catalytic potential for the oxidation of olefins, alkanes, and alcohols.

    PubMed

    Romakh, Vladimir B; Therrien, Bruno; Süss-Fink, Georg; Shul'pin, Georgiy B

    2007-02-19

    Five new 1,4,7-triazacyclononane-derived compounds, sodium 3-(4,7-dimethyl-1,4,7-triazacyclononan-1-yl)propionate (Na[LMe2R']) as well as the enantiopure derivatives (S)-1-(2-methylbutyl)-4,7-dimethyl-1,4,7-triazacyclononane (S-LMe2R''), SS-trans-2,5,8-trimethyl-2,5,8-triazabicyclo[7.4.01,9]tridecane (SS-LBMe3), (S)-1-(2-hydroxypropyl)-4,7-dimethyl-1,4,7-triazacyclononane (S-LMe2R), and (R)-1-(2-hydroxypropyl)-4,7-dimethyl-1,4,7-triazacyclononane (R-LMe2R), have been synthesized. Reaction of manganese dichloride with the chiral macrocycles S-LMe2R and R-LMe2R in aqueous ethanol gives, upon oxidation with hydrogen peroxide, the brown dinuclear Mn(III)-Mn(IV) complexes which are enantiomers, [Mn2(S-LMe2R)2(mu-O)2]3+ (S,S-1) and [Mn2(R-LMe2R)2(mu-O)2]3+ (R,R-1). The single-crystal X-ray structure analyses of [S,S-1][PF6]3.0.5(CH3)2CO and [R,R-1][PF6]3.0.5(CH3)2CO show both enantiomers to contain Mn(III) and Mn(IV) centers, each of which being coordinated to three nitrogen atoms of a triazacyclononane ligand and each of which being bridged by two oxo and by two chiral hydroxypropyl pendent arms of the macrocycle. The enantiomeric complexes S,S-1 and R,R-1 were found to catalyze the oxidation of olefins, alkanes, and alcohols with hydrogen peroxide. In the epoxidation of indene the enantiomeric excess values attain 13%. The bond selectivities of the oxidation of linear and branched alkanes suggest the crucial step in this process to be the attack of a sterically hindered high-valent manganese-oxo species on the C-H bond.

  13. Microbial biosynthesis of alkanes.

    PubMed

    Schirmer, Andreas; Rude, Mathew A; Li, Xuezhi; Popova, Emanuela; del Cardayre, Stephen B

    2010-07-30

    Alkanes, the major constituents of gasoline, diesel, and jet fuel, are naturally produced by diverse species; however, the genetics and biochemistry behind this biology have remained elusive. Here we describe the discovery of an alkane biosynthesis pathway from cyanobacteria. The pathway consists of an acyl-acyl carrier protein reductase and an aldehyde decarbonylase, which together convert intermediates of fatty acid metabolism to alkanes and alkenes. The aldehyde decarbonylase is related to the broadly functional nonheme diiron enzymes. Heterologous expression of the alkane operon in Escherichia coli leads to the production and secretion of C13 to C17 mixtures of alkanes and alkenes. These genes and enzymes can now be leveraged for the simple and direct conversion of renewable raw materials to fungible hydrocarbon fuels.

  14. Hydrocarbon Metabolism by Brevibacterium erythrogenes: Normal and Branched Alkanes1

    PubMed Central

    Pirnik, M. P.; Atlas, R. M.; Bartha, R.

    1974-01-01

    Branched- and straight-chain alkanes are metabolized by Brevibacterium erythrogenes by means of two distinct pathways. Normal alkanes (e.g., n-pentadecane) are degraded, after terminal oxidation, by the beta-oxidation system operational in fatty acid catabolism. Branched alkanes like pristane (2,6,10,14-tetramethylpentadecane) and 2-methylundecane are degraded as dicarboxylic acids, which also undergo beta-oxidation. Pristane-derived intermediates are observed to accumulate, with time, as a series of dicarboxylic acids. This dicarboxylic acid pathway is not observed in the presence of normal alkanes. Release of 14CO2 from [1-14C]pristane is delayed, or entirely inhibited, in the presence of n-hexadecane, whereas CO2 release from n-hexadecane remains unaffected. These results suggest an inducible dicarboxylic acid pathway for degradation of branched-chain alkanes. PMID:4852318

  15. Hydrocracking and hydroisomerization of long-chain alkanes and polyolefins over metal-promoted anion-modified transition metal oxides

    SciTech Connect

    Venkatesh, Koppampatti R.; Hu, Jianli; Tierney, John W.; Wender, Irving

    1996-12-01

    A method is described for cracking a feedstock by contacting the feedstock with a metal-promoted anion-modified metal oxide catalyst in the presence of hydrogen gas. The metal oxide of the catalyst is one or more of ZrO{sub 2}, HfO{sub 2}, TiO{sub 2} and SnO{sub 2}, and the feedstock is principally chains of at least 20 carbon atoms. The metal-promoted anion-modified metal oxide catalyst contains one or more of Pt, Ni, Pd, Rh, Ir, Ru, (Mn and Fe) or mixtures of them present between about 0.2% to about 15% by weight of the catalyst. The metal-promoted anion-modified metal oxide catalyst contains one or more of SO{sub 4}, WO{sub 3}, or mixtures of them present between about 0.5% to about 20% by weight of the catalyst.

  16. Hydrocracking and hydroisomerization of long-chain alkanes and polyolefins over metal-promoted anion-modified transition metal oxides

    DOEpatents

    Venkatesh, Koppampatti R.; Hu, Jianli; Tierney, John W.; Wender, Irving

    2001-01-01

    A method of cracking a feedstock by contacting the feedstock with a metal-promoted anion-modified metal oxide catalyst in the presence of hydrogen gas. The metal oxide of the catalyst is one or more of ZrO.sub.2, HfO.sub.2, TiO.sub.2 and SnO.sub.2, and the feedstock is principally chains of at least 20 carbon atoms. The metal-promoted anion-modified metal oxide catalyst contains one or more of Pt, Ni, Pd, Rh, Ir, Ru, (Mn & Fe) or mixtures of them present between about 0.2% to about 15% by weight of the catalyst. The metal-promoted anion-modified metal oxide catalyst contains one or more of SO.sub.4, WO.sub.3, or mixtures of them present between about 0.5% to about 20% by weight of the catalyst.

  17. Catalytic conversion of light alkanes

    SciTech Connect

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  18. Biodegradation of variable-chain-length n-alkanes in Rhodococcus opacus R7 and the involvement of an alkane hydroxylase system in the metabolism.

    PubMed

    Zampolli, Jessica; Collina, Elena; Lasagni, Marina; Di Gennaro, Patrizia

    2014-01-01

    Rhodococcus opacus R7 is a Gram-positive bacterium isolated from a polycyclic aromatic hydrocarbon contaminated soil for its versatile metabolism; indeed the strain is able to grow on naphthalene, o-xylene, and several long- and medium-chain n-alkanes. In this work we determined the degradation of n-alkanes in Rhodococcus opacus R7 in presence of n-dodecane (C12), n-hexadecane (C16), n-eicosane (C20), n-tetracosane (C24) and the metabolic pathway in presence of C12. The consumption rate of C12 was 88%, of C16 was 69%, of C20 was 51% and of C24 it was 78%. The decrement of the degradation rate seems to be correlated to the length of the aliphatic chain of these hydrocarbons. On the basis of the metabolic intermediates determined by the R7 growth on C12, our data indicated that R. opacus R7 metabolizes medium-chain n-alkanes by the primary alcohol formation. This represents a difference in comparison with other Rhodococcus strains, in which a mixture of the two alcohols was observed. By GC-MSD analysis we also identified the monocarboxylic acid, confirming the terminal oxidation. Moreover, the alkB gene cluster from R. opacus R7 was isolated and its involvement in the n-alkane degradation system was investigated by the cloning of this genomic region into a shuttle-vector E. coli-Rhodococcus to evaluate the alkane hydroxylase activity. Our results showed an increased biodegradation of C12 in the recombinant strain R. erythropolis AP (pTipQT1-alkR7) in comparison with the wild type strain R. erythropolis AP. These data supported the involvement of the alkB gene cluster in the n-alkane degradation in the R7 strain.

  19. Biodegradation of variable-chain-length n-alkanes in Rhodococcus opacus R7 and the involvement of an alkane hydroxylase system in the metabolism

    PubMed Central

    2014-01-01

    Rhodococcus opacus R7 is a Gram-positive bacterium isolated from a polycyclic aromatic hydrocarbon contaminated soil for its versatile metabolism; indeed the strain is able to grow on naphthalene, o-xylene, and several long- and medium-chain n-alkanes. In this work we determined the degradation of n-alkanes in Rhodococcus opacus R7 in presence of n-dodecane (C12), n-hexadecane (C16), n-eicosane (C20), n-tetracosane (C24) and the metabolic pathway in presence of C12. The consumption rate of C12 was 88%, of C16 was 69%, of C20 was 51% and of C24 it was 78%. The decrement of the degradation rate seems to be correlated to the length of the aliphatic chain of these hydrocarbons. On the basis of the metabolic intermediates determined by the R7 growth on C12, our data indicated that R. opacus R7 metabolizes medium-chain n-alkanes by the primary alcohol formation. This represents a difference in comparison with other Rhodococcus strains, in which a mixture of the two alcohols was observed. By GC-MSD analysis we also identified the monocarboxylic acid, confirming the terminal oxidation. Moreover, the alkB gene cluster from R. opacus R7 was isolated and its involvement in the n-alkane degradation system was investigated by the cloning of this genomic region into a shuttle-vector E. coli-Rhodococcus to evaluate the alkane hydroxylase activity. Our results showed an increased biodegradation of C12 in the recombinant strain R. erythropolis AP (pTipQT1-alkR7) in comparison with the wild type strain R. erythropolis AP. These data supported the involvement of the alkB gene cluster in the n-alkane degradation in the R7 strain. PMID:25401074

  20. The anaerobic degradation of gaseous, nonmethane alkanes — From in situ processes to microorganisms

    PubMed Central

    Musat, Florin

    2015-01-01

    The short chain, gaseous alkanes ethane, propane, n- and iso-butane are released in significant amounts into the atmosphere, where they contribute to tropospheric chemistry and ozone formation. Biodegradation of gaseous alkanes by aerobic microorganisms, mostly bacteria and fungi isolated from terrestrial environments, has been known for several decades. The first indications for short chain alkane anaerobic degradation were provided by geochemical studies of deep-sea environments around hydrocarbon seeps, and included the uncoupling of the sulfate-reduction and anaerobic oxidation of methane rates, the consumption of gaseous alkanes in anoxic sediments, or the enrichment in 13C of gases in interstitial water vs. the source gas. Microorganisms able to degrade gaseous alkanes were recently obtained from deep-sea and terrestrial sediments around hydrocarbon seeps. Up to date, only sulfate-reducing pure or enriched cultures with ethane, propane and n-butane have been reported. The only pure culture presently available, strain BuS5, is affiliated to the Desulfosarcina–Desulfococcus cluster of the Deltaproteobacteria. Other phylotypes involved in gaseous alkane degradation have been identified based on stable-isotope labeling and whole-cell hybridization. Under anoxic conditions, propane and n-butane are activated similar to the higher alkanes, by homolytic cleavage of the C—H bond of a subterminal carbon atom, and addition of the ensuing radical to fumarate, yielding methylalkylsuccinates. An additional mechanism of activation at the terminal carbon atoms was demonstrated for propane, which could in principle be employed also for the activation of ethane. PMID:25904994

  1. Rate constant for OH with selected large alkanes : shock-tube measurements and an improved group scheme.

    SciTech Connect

    Sivaramakrishnan, R.; Michael, J. V.; Chemical Sciences and Engineering Division

    2009-04-06

    High-temperature rate constant experiments on OH with the five large (C{sub 5}-C{sub 8}) saturated hydrocarbons n-heptane, 2,2,3,3-tetramethylbutane (2,2,3,3-TMB), n-pentane, n-hexane, and 2,3-dimethylbutane (2,3-DMB) were performed with the reflected-shock-tube technique using multipass absorption spectrometric detection of OH radicals at 308 nm. Single-point determinations at {approx}1200 K on n-heptane, 2,2,3,3-TMB, n-hexane, and 2,3-DMB were previously reported by Cohen and co-workers; however, the present work substantially extends the database to both lower and higher temperature. The present experiments span a wide temperature range, 789-1308 K, and represent the first direct measurements of rate constants at T > 800 K for n-pentane. The present work utilized 48 optical passes corresponding to a total path length of {approx}4.2 m. As a result of this increased path length, the high OH concentration detection sensitivity permitted pseudo-first-order analyses for unambiguously measuring rate constants.

  2. Growth of Pseudomonas chloritidismutans AW-1(T) on n-alkanes with chlorate as electron acceptor.

    PubMed

    Mehboob, Farrakh; Junca, Howard; Schraa, Gosse; Stams, Alfons J M

    2009-06-01

    Microbial (per)chlorate reduction is a unique process in which molecular oxygen is formed during the dismutation of chlorite. The oxygen thus formed may be used to degrade hydrocarbons by means of oxygenases under seemingly anoxic conditions. Up to now, no bacterium has been described that grows on aliphatic hydrocarbons with chlorate. Here, we report that Pseudomonas chloritidismutans AW-1(T) grows on n-alkanes (ranging from C7 until C12) with chlorate as electron acceptor. Strain AW-1(T) also grows on the intermediates of the presumed n-alkane degradation pathway. The specific growth rates on n-decane and chlorate and n-decane and oxygen were 0.5 +/- 0.1 and 0.4 +/- 0.02 day(-1), respectively. The key enzymes chlorate reductase and chlorite dismutase were assayed and found to be present. The oxygen-dependent alkane oxidation was demonstrated in whole-cell suspensions. The strain degrades n-alkanes with oxygen and chlorate but not with nitrate, thus suggesting that the strain employs oxygenase-dependent pathways for the breakdown of n-alkanes.

  3. Oxidation rates of some heat resistant alloys

    SciTech Connect

    Kelly, J.C.; Wilson, J.D.

    1995-12-31

    Cyclic oxidation testing of several heat resistant alloys was carried out at 1,093 and 1,149 C for times up to 3,000 hours. The quantitative results, coupled with extensive service history for the established alloys, provide a useful guide to anticipated performance of newly developed grades. Maximum practical use temperature is to some extent a function of section size, thin sheet being more quickly depleted of elements used to form the protective scale. Metallurgical factors influencing oxidation rate include grain size as well as the alloying elements silicon, manganese, molybdenum and columbium. Some comparisons are made between laboratory results and service performance.

  4. Microbial Communities in Methane- and Short Chain Alkane-Rich Hydrothermal Sediments of Guaymas Basin

    PubMed Central

    Dowell, Frederick; Cardman, Zena; Dasarathy, Srishti; Kellermann, Matthias Y.; Lipp, Julius S.; Ruff, S. Emil; Biddle, Jennifer F.; McKay, Luke J.; MacGregor, Barbara J.; Lloyd, Karen G.; Albert, Daniel B.; Mendlovitz, Howard; Hinrichs, Kai-Uwe; Teske, Andreas

    2016-01-01

    The hydrothermal sediments of Guaymas Basin, an active spreading center in the Gulf of California (Mexico), are rich in porewater methane, short-chain alkanes, sulfate and sulfide, and provide a model system to explore habitat preferences of microorganisms, including sulfate-dependent, methane- and short chain alkane-oxidizing microbial communities. In this study, hot sediments (above 60°C) covered with sulfur-oxidizing microbial mats surrounding a hydrothermal mound (termed “Mat Mound”) were characterized by porewater geochemistry of methane, C2–C6 short-chain alkanes, sulfate, sulfide, sulfate reduction rate measurements, in situ temperature gradients, bacterial and archaeal 16S rRNA gene clone libraries and V6 tag pyrosequencing. The most abundantly detected groups in the Mat mound sediments include anaerobic methane-oxidizing archaea of the ANME-1 lineage and its sister clade ANME-1Guaymas, the uncultured bacterial groups SEEP-SRB2 within the Deltaproteobacteria and the separately branching HotSeep-1 Group; these uncultured bacteria are candidates for sulfate-reducing alkane oxidation and for sulfate-reducing syntrophy with ANME archaea. The archaeal dataset indicates distinct habitat preferences for ANME-1, ANME-1-Guaymas, and ANME-2 archaea in Guaymas Basin hydrothermal sediments. The bacterial groups SEEP-SRB2 and HotSeep-1 co-occur with ANME-1 and ANME-1Guaymas in hydrothermally active sediments underneath microbial mats in Guaymas Basin. We propose the working hypothesis that this mixed bacterial and archaeal community catalyzes the oxidation of both methane and short-chain alkanes, and constitutes a microbial community signature that is characteristic for hydrothermal and/or cold seep sediments containing both substrates. PMID:26858698

  5. Microbial Communities in Methane- and Short Chain Alkane-Rich Hydrothermal Sediments of Guaymas Basin.

    PubMed

    Dowell, Frederick; Cardman, Zena; Dasarathy, Srishti; Kellermann, Matthias Y; Lipp, Julius S; Ruff, S Emil; Biddle, Jennifer F; McKay, Luke J; MacGregor, Barbara J; Lloyd, Karen G; Albert, Daniel B; Mendlovitz, Howard; Hinrichs, Kai-Uwe; Teske, Andreas

    2016-01-01

    The hydrothermal sediments of Guaymas Basin, an active spreading center in the Gulf of California (Mexico), are rich in porewater methane, short-chain alkanes, sulfate and sulfide, and provide a model system to explore habitat preferences of microorganisms, including sulfate-dependent, methane- and short chain alkane-oxidizing microbial communities. In this study, hot sediments (above 60°C) covered with sulfur-oxidizing microbial mats surrounding a hydrothermal mound (termed "Mat Mound") were characterized by porewater geochemistry of methane, C2-C6 short-chain alkanes, sulfate, sulfide, sulfate reduction rate measurements, in situ temperature gradients, bacterial and archaeal 16S rRNA gene clone libraries and V6 tag pyrosequencing. The most abundantly detected groups in the Mat mound sediments include anaerobic methane-oxidizing archaea of the ANME-1 lineage and its sister clade ANME-1Guaymas, the uncultured bacterial groups SEEP-SRB2 within the Deltaproteobacteria and the separately branching HotSeep-1 Group; these uncultured bacteria are candidates for sulfate-reducing alkane oxidation and for sulfate-reducing syntrophy with ANME archaea. The archaeal dataset indicates distinct habitat preferences for ANME-1, ANME-1-Guaymas, and ANME-2 archaea in Guaymas Basin hydrothermal sediments. The bacterial groups SEEP-SRB2 and HotSeep-1 co-occur with ANME-1 and ANME-1Guaymas in hydrothermally active sediments underneath microbial mats in Guaymas Basin. We propose the working hypothesis that this mixed bacterial and archaeal community catalyzes the oxidation of both methane and short-chain alkanes, and constitutes a microbial community signature that is characteristic for hydrothermal and/or cold seep sediments containing both substrates.

  6. Atmospheric-pressure, liquid-phase, selective aerobic oxidation of alkanes catalysed by metal-organic frameworks.

    PubMed

    Dhakshinamoorthy, Amarajothi; Alvaro, Mercedes; Garcia, Hermenegildo

    2011-05-23

    Aerobic oxidation of cyclooctane to its corresponding ol/one mixture at atmospheric pressure and in the liquid phase is efficiently promoted by an Fe(BTC) (BTC=1,3,5-benzenetricarboxylate) metal-organic framework, incorporating N-hydroxyphthalimide and in several cases reaches a selectivity over 90% at 28% conversion. This catalytic system is further extended to other hydrocarbons, such as ethylbenzene and 1,2,3,4-tetrahydronaphthalene (tetralin), with high selectivity (>85%). This high selectivity in the product distribution arises from a radical reaction mechanism that occurs inside a hydrophobic cavity that preferentially adsorbs hydrocarbons over their corresponding alcohols. The system can be reused although there is a gradual decrease in turnover frequency, caused by minor changes in the crystal structure due to the formation of iron oxide nanoparticles. Given the sustainable nature of the oxidant and the mild conditions used, this discovery could serve to develop a new catalyst generation for the oxyfunctionalisation of hydrocarbon feedstocks with the real possibility of finding industrial application. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Rates of manganese oxidation in aqueous systems

    USGS Publications Warehouse

    Hem, J.D.

    1981-01-01

    The rate of crystal growth of Mn3O4 (hausmannite) and ??MnOOH (feitknechtite) in aerated aqueous manganous perchlorate systems, near 0.01 M in total manganese, was determined at pH levels ranging from 7.00 to 9.00 and at temperatures from 0.5 to 37.4??C. The process is autocatalytic, but becomes psuedo first-order in dissolved Mn2+ activity when the amount of precipitate surface is large compared to the amount of unreacted manganese. Reaction rates determined by titrations using an automated pH-stat were fitted to an equation for precipitate growth. The rates are proportional to surface area of oxide and degree of supersaturation with respect to Mn2+. The oxide obtained at the higher temperature was Mn3O4, but at 0.5?? C only ??MnOOH was formed. At intermediate temperatures, mixtures of these solids were formed. The rate of precipitation of hausmannite is strongly influenced by temperature, and that of feitknechtite much less so. The difference in activation energy may be related to differences in crystal structure of the oxides and the geometry of polymeric hydroxy ion precursors. ?? 1981.

  8. Metathesis of alkanes and related reactions.

    PubMed

    Basset, Jean-Marie; Copéret, Christophe; Soulivong, Daravong; Taoufik, Mostafa; Cazat, Jean Thivolle

    2010-02-16

    The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, ([triple bond]SiO)(2)TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of alumina-supported tungsten hydride, W(H)(3)/Al(2)O(3), which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis

  9. Tetranuclear iron(III) complexes of an octadentate pyridine-carboxylate ligand and their catalytic activity in alkane oxidation by hydrogen peroxide.

    PubMed

    Gutkina, Elena A; Trukhan, Vladimir M; Pierpont, Cortlandt G; Mkoyan, Shaen; Strelets, Vladimir V; Nordlander, Ebbe; Shteinman, Albert A

    2006-01-21

    oxidation catalysts. Catalytic reactions carried out with alkane substrate molecules and hydrogen peroxide predominantly gave alcohols. High stereospecificity in the oxidation of cis-1,2-dimethylcyclohexane supports the metal-based molecular mechanism of O-insertion into C-H bonds postulated for non-heme iron enzymes such as methane monooxygenase.

  10. Conversion of alkanes to organoseleniums and organotelluriums

    DOEpatents

    Periana, Roy A.; Konnick, Michael M.; Hashiguchi, Brian G.

    2016-11-29

    The invention provides processes and materials for the efficient and costeffective functionalization of alkanes and heteroalkanes, comprising contacting the alkane or heteroalkane and a soft oxidizing electrophile comprising Se(VI) or Te(VI), in an acidic medium, optionally further comprising an aprotic medium, which can be carried out at a temperature of less than 300 C. Isolation of the alkylselenium or alkyltellurium intermediate allows the subsequent conversion to products not necessarily compatible with the initial reaction conditions, such as amines, stannanes, organosulfur compounds, acyls, halocarbons, and olefins.

  11. The role of alkane coordination in CH bond cleavage at a Pt(II) center

    PubMed Central

    Chen, George S.; Labinger, Jay A.; Bercaw, John E.

    2007-01-01

    The rates of CH bond activation for various alkanes by [(N–N)Pt(Me)(TFEd3)]+ (N N = ArNC(Me)C(Me)NAr; Ar = 3,5-di-tert-butylphenyl; TFE-d3 = CF3CD2OD) were studied. Both linear and cyclic alkanes give the corresponding alkene-hydride cation [(N–N)Pt(H)(alkene)]+ via (i) rate determining alkane coordination to form a CH σ complex, (ii) oxidative cleavage of the coordinated CH bond to give a platinum(IV) alkyl-methyl-hydride intermediate, (iii) reductive coupling to generate a methane σ complex, (iv) dissociation of methane, and (v) β-H elimination to form the observed product. Second-order rate constants for cycloalkane activation (CnH2n), are proportional to the size of the ring (k ∼ n). For cyclohexane, the deuterium kinetic isotope effect (kH/kD) of 1.28 (5) is consistent with the proposed rate determining alkane coordination to form a CH σ complex. Statistical scrambling of the five hydrogens of the Pt-methyl and the coordinated methylene unit, via rapid, reversible steps ii and iii, and interchange of geminal CH bonds of the methane and cyclohexane CH σ adducts, is observed before loss of methane. PMID:17416678

  12. Efficent H[sub 2]O[sub 2] oxidation of alkanes and arenes to alkyl peroxides and phenols catalyzed by the system vanadate-pyrazine-2-carboxylic acid

    SciTech Connect

    Shul'pin, G.B.; Attanasio, D.; Suber, L. )

    1993-07-01

    H[sub 2]O[sub 2] oxidizes cyclohexane and other alkanes in CH[sub 3]CN at 20-70[degrees]C in the presence of the catalyst Bu[sub 4]NVO[sub 3]-pyrazine-2-carboxylic acid (ratio 1:4) to afford, after reduction with PPh[sub 3], the corresponding alcohol and carbonyl derivatives (the ratio decreases from 12 to 4 on raising the temperature from 20 to 70[degrees]C). The product yield reaches 46%, based on H[sub 2]O[sub 2], and the turnover number is ca. 1000. The oxidation appears to give predominantly alkyl peroxides, which are partially decomposed in the course of the reaction. Peroxides can be formed when alkyl radicals, generated from alkanes, and radical-like species react with O[sub 2] or abstract OOH groups from the vanadium complex. Benzene and its alkyl derivatives are oxidized to produce phenols as well as side-chain oxidation derivatives. 11 refs., 2 figs., 1 tab.

  13. Hysteresis-free high rate reactive sputtering of niobium oxide, tantalum oxide, and aluminum oxide

    SciTech Connect

    Särhammar, Erik Berg, Sören; Nyberg, Tomas

    2014-07-01

    This work reports on experimental studies of reactive sputtering from targets consisting of a metal and its oxide. The composition of the targets varied from pure metal to pure oxide of Al, Ta, and Nb. This combines features from both the metal target and oxide target in reactive sputtering. If a certain relation between the metal and oxide parts is chosen, it may be possible to obtain a high deposition rate, due to the metal part, and a hysteresis-free process, due to the oxide part. The aim of this work is to quantify the achievable boost in oxide deposition rate from a hysteresis-free process by using a target consisting of segments of a metal and its oxide. Such an increase has been previously demonstrated for Ti using a homogeneous substoichiometric target. The achievable gain in deposition rate depends on transformation mechanisms from oxide to suboxides due to preferential sputtering of oxygen. Such mechanisms are different for different materials and the achievable gain is therefore material dependent. For the investigated materials, the authors have demonstrated oxide deposition rates that are 1.5–10 times higher than what is possible from metal targets in compound mode. However, although the principle is demonstrated for oxides of Al, Ta, and Nb, a similar behavior is expected for most oxides.

  14. Rate constants and H atom branching ratios of the gas-phase reactions of methylidyne CH(X2Pi) radical with a series of alkanes.

    PubMed

    Loison, Jean-Christophe; Bergeat, Astrid; Caralp, Françoise; Hannachi, Yacine

    2006-12-21

    The reactions of the CH radical with several alkanes were studied, at room temperature, in a low-pressure fast-flow reactor. CH(X2Pi, v = 0) radicals were obtained from the reaction of CHBr(3) with potassium atoms. The overall rate constants at 300 K are (0.76 +/- 0.20) x 10(-10) [Fleurat-Lessard, P.; Rayez, J. C.; Bergeat, A.; Loison, J. C. Chem. Phys. 2002, 279, 87],1 (1.60 +/- 0.60) x 10(-10)[Galland, N.; Caralp, F.; Hannachi, Y.; Bergeat, A.; Loison, J.-C. J. Phys. Chem. A 2003, 107, 5419],2 (2.20 +/- 0.80) x 10(-10), (2.80 +/- 0.80) x 10(-10), (3.20 +/- 0.80) x 10(-10), (3.30 +/- 0.60) x 10(-10), and (3.60 +/- 0.80) x 10(-10) cm3 molecule(-1) s(-1), (errors refer to +/-2sigma) for methane, ethane, propane, n-butane, n-pentane, neo-pentane, and n-hexane respectively. The experimental overall rate constants correspond to those obtained using a simple classical capture theory. Absolute atomic hydrogen production was determined by V.U.V. resonance fluorescence, with H production from the CH + CH4 reaction being used as a reference. Observed H branching ratios were for CH4, 1.00[Fleurat-Lessard, P.; Rayez, J. C.; Bergeat, A.; Loison, J. C. Chem. Phys. 2002, 279, 87];1 C(2)H(6), 0.22 +/- 0.08 [Galland, N.; Caralp, F.; Hannachi, Y.; Bergeat, A.; Loison, J.-C. J. Phys. Chem. A 2003, 107, 5419];2 C(3)H(8), 0.19 +/- 0.07; C(4)H(10) (n-butane), 0.14 +/- 0.06; C(5)H(12) (n-pentane), 0.52 +/- 0.08; C(5)H(12) (neo-pentane), 0.51 +/- 0.08; C(5)H(12) (iso-pentane), 0.12 +/- 0.06; C(6)H(14) (n-hexane), 0.06 +/- 0.04.

  15. Kinetic study of asphaltene dissolution in amphiphile/alkane solutions

    SciTech Connect

    Permsukarome, P.; Chang, C.; Fogler, H.S.

    1997-09-01

    The kinetics of dissolution of pentane-insoluble solid asphaltene precipitates by amphiphile/alkane solutions were investigated using a differential reactor flow system. Two amphiphiles, dodecylbenzenesulfonic acid and nonylphenol, and five alkane solvents, ranging from hexane to hexadecane, were used. Results showed that the rate of asphaltene dissolution in amphiphile/alkane fluids could be approximated with a first-order kinetics with respect to the undissolved asphaltene mass in solution. The specific dissolution rate constant, k, varied with the concentration of amphiphiles, the type of alkane solvents, the temperature, and the fluid flow rate. The rate of asphaltene dissolution displayed a Langmuir-Hinshelwood kinetics with respect to the concentration of amphiphiles. Increasing the temperature of amphiphile/alkane fluids also enhanced the rate of asphaltene dissolution. The apparent activation energy for asphaltene dissolution was approximated to be 4--7 kcal/mol. The rate of asphaltene dissolution was also greater in amphiphile solutions containing lighter alkanes, such as hexane, with lower viscosities. These trends suggest that both surface reaction and mass transfer processes are important to the rate of asphaltene dissolution in amphiphile/alkane fluids.

  16. Product Repression of Alkane Monooxygenase Expression in Pseudomonas butanovora

    PubMed Central

    Doughty, D. M.; Sayavedra-Soto, L. A.; Arp, D. J.; Bottomley, P. J.

    2006-01-01

    Physiological and regulatory mechanisms that allow the alkane-oxidizing bacterium Pseudomonas butanovora to consume C2 to C8 alkane substrates via butane monooxygenase (BMO) were examined. Striking differences were observed in response to even- versus odd-chain-length alkanes. Propionate, the downstream product of propane oxidation and of the oxidation of other odd-chain-length alkanes following β-oxidation, was a potent repressor of BMO expression. The transcriptional activity of the BMO promoter was reduced with as little as 10 μM propionate, even in the presence of appropriate inducers. Propionate accumulated stoichiometrically when 1-propanol and propionaldehyde were added to butane- and ethane-grown cells, indicating that propionate catabolism was inactive during growth on even-chain-length alkanes. In contrast, propionate consumption was induced (about 80 nmol propionate consumed · min−1 · mg protein−1) following growth on the odd-chain-length alkanes, propane and pentane. The induction of propionate consumption could be brought on by the addition of propionate or pentanoate to the growth medium. In a reporter strain of P. butanovora in which the BMO promoter controls β-galactosidase expression, only even-chain-length alcohols (C2 to C8) induced β-galactosidase following growth on acetate or butyrate. In contrast, both even- and odd-chain-length alcohols (C3 to C7) were able to induce β-galactosidase following the induction of propionate consumption by propionate or pentanoate. PMID:16547046

  17. Matrix solid-phase dispersion with chitosan-zinc oxide nanoparticles combined with flotation-assisted dispersive liquid-liquid microextraction for the determination of 13 n-alkanes in soil samples.

    PubMed

    Khajeh, Mostafa; Yan, Hongyuan; Arefnejad, Esmat; Bohlooli, Mousa

    2014-11-01

    In this study, chitosan-zinc oxide nanoparticles were used as a sorbent of miniaturized matrix solid-phase dispersion combined with flotation-assisted dispersive liquid-liquid microextraction for the simultaneous determination of 13 n-alkanes such as C8 H18 and C20 H42 in soil samples. The solid samples were directly blended with the chitosan nanoparticles in the solid-phase dispersion method. The eluent of solid-phase dispersion was applied as the dispersive solvent for the following flotation-assisted dispersive liquid-liquid microextraction for further purification and enrichment of the target compounds prior to gas chromatography with flame ionization detection. Under the optimum conditions, good linearity with correlation coefficients in the range 0.9991 < r(2) < 0.9995 and low detection limits between 0.08 to 2.5 ng/g were achieved. The presented procedure combined the advantages of chitosan-zinc oxide nanoparticles, solid-phase dispersion and flotation-assisted dispersive liquid-liquid microextraction, and could be applied for the determination of n-alkanes in complicated soil samples with acceptable recoveries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Enhanced wet air oxidation : synergistic rate acceleration upon effluent recirculation

    Treesearch

    Matthew J. Birchmeier; Charles G. Hill; Carl J. Houtman; Rajai H. Atalla; Ira A. Weinstock

    2000-01-01

    Wet air oxidation (WAO) reactions of cellobiose, phenol, and syringic acid were carried out under mild conditions (155°C; 0.93MPa 02; soluble catalyst, Na5[PV2Mo10O40]). Initial oxidation rates were rapid but decreased to small values as less reactive oxidation products accumulated. Recalcitrant oxidation products were consumed more rapidly, however, if additional...

  19. Effects of Dichloroethene Isomers on the Induction and Activity of Butane Monooxygenase in the Alkane-Oxidizing Bacterium “Pseudomonas butanovora”

    PubMed Central

    Doughty, D. M.; Sayavedra-Soto, L. A.; Arp, D. J.; Bottomley, P. J.

    2005-01-01

    We examined cooxidation of three different dichloroethenes (1,1-DCE, 1,2-trans DCE, and 1,2-cis DCE) by butane monooxygenase (BMO) in the butane-utilizing bacterium “Pseudomonas butanovora.” Different organic acids were tested as exogenous reductant sources for this process. In addition, we determined if DCEs could serve as surrogate inducers of BMO gene expression. Lactic acid supported greater rates of oxidation of the three DCEs than the other organic acids tested. The impacts of lactic acid-supported DCE oxidation on BMO activity differed among the isomers. In intact cells, 50% of BMO activity was irreversibly lost after consumption of ∼20 nmol mg protein−1 of 1,1-DCE and 1,2-trans DCE in 0.5 and 5 min, respectively. In contrast, a comparable loss of activity required the oxidation of 120 nmol 1,2-cis DCE mg protein−1. Oxidation of similar amounts of each DCE isomer (∼20 nmol mg protein−1) produced different negative effects on lactic acid-dependent respiration. Despite 1,1-DCE being consumed 10 times faster than 1,2,-trans DCE, respiration declined at similar rates, suggesting that the product(s) of oxidation of 1,2-trans DCE was more toxic to respiration than 1,1-DCE. Lactate-grown “P. butanovora” did not express BMO activity but gained activity after exposure to butane, ethene, 1,2-cis DCE, or 1,2-trans DCE. The products of BMO activity, ethene oxide and 1-butanol, induced lacZ in a reporter strain containing lacZ fused to the BMO promoter, whereas butane, ethene, and 1,2-cis DCE did not. 1,2-trans DCE was unique among the BMO substrates tested in its ability to induce lacZ expression. PMID:16204521

  20. [Microbial communities and their ability to oxidize n-alkanes in the area of release of gas- and oil-containing fluids in Mid-Baikal (Cape Gorevoi Utes)].

    PubMed

    avlova, O N; Lomakina, A V; Gorshkov, A G; Suslova, M Iu; Likhoshvaĭ, A V; Zemskaia, T I

    2012-01-01

    The microbial community in the area of oil seep in Mid-Baikal (Cape Gorevoi Utes) was studied. The number of microorganisms that oxidize normal hydrocarbons, petroleum, and easily accessible organic matter in the water mass of the lake, bottom sediments, and bitumen structures was studied in 2005-2009. The high heterogeneity of the distribution of microorganisms associated with the deparaffination of oil in the areas of oil seeps was noted. The maximum concentrations of hydrocarbon-oxidizing microorganisms in the samples of bottom water above bitumen structures (up to 2200 +/- 175 CFU/ml) and in bitumen structures themselves (up to 170000 +/- 13000 CFU/g) were determined. A model experiment showed that in the conditions of low temperatures (4 degrees C) the degradation of the fraction of oil n-alkanes by the natural microbial community reaches 90% over a period of 60 days.

  1. Involvement of an alkane hydroxylase system of Gordonia sp. strain SoCg in degradation of solid n-alkanes.

    PubMed

    Lo Piccolo, Luca; De Pasquale, Claudio; Fodale, Roberta; Puglia, Anna Maria; Quatrini, Paola

    2011-02-01

    Enzymes involved in oxidation of long-chain n-alkanes are still not well known, especially those in gram-positive bacteria. This work describes the alkane degradation system of the n-alkane degrader actinobacterium Gordonia sp. strain SoCg, which is able to grow on n-alkanes from dodecane (C(12)) to hexatriacontane (C(36)) as the sole C source. SoCg harbors in its chromosome a single alk locus carrying six open reading frames (ORFs), which shows 78 to 79% identity with the alkane hydroxylase (AH)-encoding systems of other alkane-degrading actinobacteria. Quantitative reverse transcription-PCR showed that the genes encoding AlkB (alkane 1-monooxygenase), RubA3 (rubredoxin), RubA4 (rubredoxin), and RubB (rubredoxin reductase) were induced by both n-hexadecane and n-triacontane, which were chosen as representative long-chain liquid and solid n-alkane molecules, respectively. Biotransformation of n-hexadecane into the corresponding 1-hexadecanol was detected by solid-phase microextraction coupled with gas chromatography-mass spectrometry (SPME/GC-MS) analysis. The Gordonia SoCg alkB was heterologously expressed in Escherichia coli BL21 and in Streptomyces coelicolor M145, and both hosts acquired the ability to transform n-hexadecane into 1-hexadecanol, but the corresponding long-chain alcohol was never detected on n-triacontane. However, the recombinant S. coelicolor M145-AH, expressing the Gordonia alkB gene, was able to grow on n-triacontane as the sole C source. A SoCg alkB disruption mutant that is completely unable to grow on n-triacontane was obtained, demonstrating the role of an AlkB-type AH system in degradation of solid n-alkanes.

  2. Comparison of the Oxidation Rates of Some New Copper Alloys

    NASA Technical Reports Server (NTRS)

    Ogbuji, Linus U. J. Thomas; Humphrey, Donald L.

    2002-01-01

    Copper alloys were studied for oxidation resistance and mechanisms between 550 and 700 C, in reduced-oxygen environments expected in rocket engines, and their oxidation behaviors compared to that of pure copper. They included two dispersion-strengthened alloys (precipitation-strengthened and oxide-dispersion strengthened, respectively) and one solution-strengthened alloy. In all cases the main reaction was oxidation of Cu into Cu2O and CuO. The dispersion-strengthened alloys were superior to both Cu and the solution-strengthened alloy in oxidation resistance. However, factors retarding oxidation rates seemed to be different for the two dispersion-strengthened alloys.

  3. Degradation of alkanes by bacteria.

    PubMed

    Rojo, Fernando

    2009-10-01

    Pollution of soil and water environments by crude oil has been, and is still today, an important problem. Crude oil is a complex mixture of thousands of compounds. Among them, alkanes constitute the major fraction. Alkanes are saturated hydrocarbons of different sizes and structures. Although they are chemically very inert, most of them can be efficiently degraded by several microorganisms. This review summarizes current knowledge on how microorganisms degrade alkanes, focusing on the biochemical pathways used and on how the expression of pathway genes is regulated and integrated within cell physiology.

  4. Oxidation of dimethylselenide by δMnO2: oxidation product and factors affecting oxidation rate

    USGS Publications Warehouse

    Wang, Bronwen; Burau, Richard G.

    1995-01-01

    Volatile dimethylselenide (DMSe) was transformed to a nonvolatile Se compound in a ??-MnO2 suspension. The nonvolatile product was a single compound identified as dimethylselenoxide based on its mass spectra pattern. After 24 h, 100% of the DMSe added to a ??-MnO2 suspension was converted to nonpurgable Se as opposed to 20%, 18%, and 4% conversion for chromate, permanganate, and the filtrate from the suspension, respectively. Manganese was found in solution after reaction. These results imply that the reaction between manganese oxide and DMSe was a heterogeneous redox reaction involving solid phase ??-MnO2 and solution phase DMSe. Oxidation of DMSe to dimethylselenoxide [OSe(CH3)2] by a ??-MnO2 suspension appears to be first order with respect to ??-MnO2, to DMSe, and to hydrogen ion with an overall rate law of d[OSe(CH3)2 ]/dt = 95 M-2 min-1 [MnO2]1[DMSe]1[H+]1 for the MnO2 concentration range of 0.89 ?? 10-3 - 2.46 ?? 10-3 M, the DMSe concentration range of 3.9 ?? 10-7 - 15.5 ?? 10-7 M Se, and a hydrogen ion concentation range of 7.4 ?? 10-6 -9.5 ?? 10-8 M. A general surface site adsorption model is consistent with this rate equation if the uncharged |OMnOH is the surface adsorption site. DMSe acts as a Lewis base, and the manganese oxide surface acts as a Lewis acid. DMSe adsorption to |OMnOH can be viewed as a Lewis acid/ base complex between the largely p orbitals of the DMSe lone pair and the unoccupied eg orbitals on manganese oxide. For such a complex, frontier molecular orbital theory predicts electron transfer to occur via an inner-sphere complex between the DMSe and the manganese oxide. ?? 1995 American Chemical Society.

  5. Determining and quantifying specific sources of light alkane

    NASA Astrophysics Data System (ADS)

    Bill, M.; Conrad, M. E.

    2015-12-01

    Determining and quantifying specific sources of emission of methane (an important greenhouse gas) and light alkanes from abandoned gas and oil wells, hydraulic fracturing or associated with CO2 sequestration are a challenge in determining their contribution to the atmospheric greenhouse gas budget or to identify source of groundwater contamination. Here, we review organic biogeochemistry proprieties and isotopic fingerprinting of C1-C5 alkanes to address this problem. For instance, the concentration ratios of CH4 to C2-C5 alkanes can be used to distinguish between thermogenic and microbial generated CH4. Together C and H isotopes of CH4 are used to differentiate bacterial generated sources and thermogenic CH4 and may also identify processes such as alteration and source mixing. Carbon isotope ratios pattern of C1-C5 alkanes highlight sources and oxidation processes in the gas reservoirs. Stable carbon isotope measurements are a viable tool for monitoring the degradation progress of methane and light hydrocarbons. The carbon isotope ratios of the reactants and products are independent of the concentration and only depend on the relative progress of the particular reaction. Oxidation/degradation of light alkanes are typically associated with increasing ð13C values. Isotopic mass balances offer the possibility to independently determine the fractions coming from microbial versus thermogenic and would also permit differentiation of the isotope fractionations associated with degradation. Unlike conventional concentration measurements, this approach is constrained by the different isotopic signatures of various sources and sinks.

  6. Contribution of cyanobacterial alkane production to the ocean hydrocarbon cycle

    PubMed Central

    Lea-Smith, David J.; Biller, Steven J.; Davey, Matthew P.; Cotton, Charles A. R.; Perez Sepulveda, Blanca M.; Turchyn, Alexandra V.; Scanlan, David J.; Smith, Alison G.; Chisholm, Sallie W.; Howe, Christopher J.

    2015-01-01

    Hydrocarbons are ubiquitous in the ocean, where alkanes such as pentadecane and heptadecane can be found even in waters minimally polluted with crude oil. Populations of hydrocarbon-degrading bacteria, which are responsible for the turnover of these compounds, are also found throughout marine systems, including in unpolluted waters. These observations suggest the existence of an unknown and widespread source of hydrocarbons in the oceans. Here, we report that strains of the two most abundant marine cyanobacteria, Prochlorococcus and Synechococcus, produce and accumulate hydrocarbons, predominantly C15 and C17 alkanes, between 0.022 and 0.368% of dry cell weight. Based on global population sizes and turnover rates, we estimate that these species have the capacity to produce 2–540 pg alkanes per mL per day, which translates into a global ocean yield of ∼308–771 million tons of hydrocarbons annually. We also demonstrate that both obligate and facultative marine hydrocarbon-degrading bacteria can consume cyanobacterial alkanes, which likely prevents these hydrocarbons from accumulating in the environment. Our findings implicate cyanobacteria and hydrocarbon degraders as key players in a notable internal hydrocarbon cycle within the upper ocean, where alkanes are continually produced and subsequently consumed within days. Furthermore we show that cyanobacterial alkane production is likely sufficient to sustain populations of hydrocarbon-degrading bacteria, whose abundances can rapidly expand upon localized release of crude oil from natural seepage and human activities. PMID:26438854

  7. Contribution of cyanobacterial alkane production to the ocean hydrocarbon cycle.

    PubMed

    Lea-Smith, David J; Biller, Steven J; Davey, Matthew P; Cotton, Charles A R; Perez Sepulveda, Blanca M; Turchyn, Alexandra V; Scanlan, David J; Smith, Alison G; Chisholm, Sallie W; Howe, Christopher J

    2015-11-03

    Hydrocarbons are ubiquitous in the ocean, where alkanes such as pentadecane and heptadecane can be found even in waters minimally polluted with crude oil. Populations of hydrocarbon-degrading bacteria, which are responsible for the turnover of these compounds, are also found throughout marine systems, including in unpolluted waters. These observations suggest the existence of an unknown and widespread source of hydrocarbons in the oceans. Here, we report that strains of the two most abundant marine cyanobacteria, Prochlorococcus and Synechococcus, produce and accumulate hydrocarbons, predominantly C15 and C17 alkanes, between 0.022 and 0.368% of dry cell weight. Based on global population sizes and turnover rates, we estimate that these species have the capacity to produce 2-540 pg alkanes per mL per day, which translates into a global ocean yield of ∼ 308-771 million tons of hydrocarbons annually. We also demonstrate that both obligate and facultative marine hydrocarbon-degrading bacteria can consume cyanobacterial alkanes, which likely prevents these hydrocarbons from accumulating in the environment. Our findings implicate cyanobacteria and hydrocarbon degraders as key players in a notable internal hydrocarbon cycle within the upper ocean, where alkanes are continually produced and subsequently consumed within days. Furthermore we show that cyanobacterial alkane production is likely sufficient to sustain populations of hydrocarbon-degrading bacteria, whose abundances can rapidly expand upon localized release of crude oil from natural seepage and human activities.

  8. Oxidation rates of niobium and tantalum alloys at low pressures

    SciTech Connect

    DiStefano, J.R.; Hendricks, J.W. )

    1994-06-01

    Niobium and tantalum alloys have excellent properties for use in high-temperature, space-power applications, but must be protected from oxidation that would result from exposure to air in ground-evaluation tests. The oxygen-uptake/oxidation rates of three alloys, Nb-1Zr, PWC-11, and ASTAR-811C were measured at oxygen partial pressure of 10[sup [minus]6] and 10[sup [minus]7] torr at temperatures up to 1350 K. No visible oxide film was observed, and the oxidation rate was found to be linearly proportional to pressure and exponentially proportional to temperature. A thin molybdenum coating on Nb-1Zr was a barrier to low-pressure oxidation at 773 K. 13 refs., 6 figs., 7 tabs.

  9. Catalytic, mild, and selective oxyfunctionalization of linear alkanes: current challenges.

    PubMed

    Bordeaux, Mélanie; Galarneau, Anne; Drone, Jullien

    2012-10-22

    Selective catalysts for sustainable oxidation of alkanes are highly demanded because of the abundance of these molecules in the environment, the possibility to transform them into higher-value compounds, such as chemicals or synthetic fuels, and the fact that, kinetically speaking, this is a difficult reaction. Numerous chemical and biological catalysts have been developed in the lasts decades for this purpose, rendering the overview over this field of chemistry difficult. After giving a definition of the ideal catalyst for alkane oxyfunctionalization, this review aims to present the catalysts available today that are closest to ideal.

  10. Observation of a ferric hydroperoxide complex during the non-heme iron catalysed oxidation of alkenes and alkanes by O2.

    PubMed

    He, Yu; Goldsmith, Christian R

    2012-11-04

    A non-heme iron complex catalyses the oxidation of allylic, benzylic, and aliphatic C-H bonds by O(2). During this reactivity, a ferric hydroperoxide species is observed. The kinetic analysis of this complex's formation may suggest a ferric superoxo species as the initial metal-based oxidant.

  11. Alkane desaturation by concerted double hydrogen atom transfer to benzyne.

    PubMed

    Niu, Dawen; Willoughby, Patrick H; Woods, Brian P; Baire, Beeraiah; Hoye, Thomas R

    2013-09-26

    The removal of two vicinal hydrogen atoms from an alkane to produce an alkene is a challenge for synthetic chemists. In nature, desaturases and acetylenases are adept at achieving this essential oxidative functionalization reaction, for example during the biosynthesis of unsaturated fatty acids, eicosanoids, gibberellins and carotenoids. Alkane-to-alkene conversion almost always involves one or more chemical intermediates in a multistep reaction pathway; these may be either isolable species (such as alcohols or alkyl halides) or reactive intermediates (such as carbocations, alkyl radicals, or σ-alkyl-metal species). Here we report a desaturation reaction of simple, unactivated alkanes that is mechanistically unique. We show that benzynes are capable of the concerted removal of two vicinal hydrogen atoms from a hydrocarbon. The discovery of this exothermic, net redox process was enabled by the simple thermal generation of reactive benzyne intermediates through the hexadehydro-Diels-Alder cycloisomerization reaction of triyne substrates. We are not aware of any single-step, bimolecular reaction in which two hydrogen atoms are simultaneously transferred from a saturated alkane. Computational studies indicate a preferred geometry with eclipsed vicinal C-H bonds in the alkane donor.

  12. Selective conversion of {Mo132} Keplerate ion into 4-electron reduced crown-capped Keggin derivative [Te5Mo15O57](8-). A key intermediate to single-phase M1 multielement MoVTeO light-alkanes oxidation catalyst.

    PubMed

    Canioni, Romain; Marchal-Roch, Catherine; Leclerc-Laronze, Nathalie; Haouas, Mohamed; Taulèlle, Francis; Marrot, Jérôme; Paul, Sebastien; Lamonier, Carole; Paul, Jean-François; Loridant, Stéphane; Millet, Jean-Marc M; Cadot, Emmanuel

    2011-06-14

    {Mo(132)} Keplerate anion reacts with tellurites to give a soluble precursor to produce in hydrothermal conditions single-phase M1 MoVTeO light-alkanes oxidation catalyst. Characterization of this Te-containing intermediate by single-crystal X-ray diffraction, (125)Te NMR, UV-visible and redox titration reveals a molybdotellurite anion as a crown-capped Keggin derivative.

  13. Integrated process for preparing a carboxylic acid from an alkane

    SciTech Connect

    Benderly, Abraham; Chadda, Nitin; Sevon, Douglass

    2011-12-20

    The present invention relates to an integrated process for producing unsaturated carboxylic acids from the corresponding C.sub.2-C.sub.4 alkane. The process begins with performance of thermally integrated dehydrogenation reactions which convert a C.sub.2-C.sub.4 alkane to its corresponding C.sub.2-C.sub.4 alkene, and which involve exothermically converting a portion of an alkane to its corresponding alkene by oxidative dehydrogenation in an exothermic reaction zone, in the presence of oxygen and a suitable catalyst, and then feeding the products of the exothermic reaction zone to an endothermic reaction zone wherein at least a portion of the remaining unconverted alkane is endothermically dehydrogenated to form an additional quantity of the same corresponding alkene, in the presence of carbon dioxide and an other suitable catalyst. The alkene products of the thermally integrated dehydrogenation reactions are then provided to a catalytic vapor phase partial oxidation process for conversion of the alkene to the corresponding unsaturated carboxylic acid or nitrile. Unreacted alkene and carbon dioxide are recovered from the oxidation product stream and recycled back to the thermally integrated dehydrogenation reactions.

  14. Rates of oxidative weathering on the surface of Mars

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.

    1992-01-01

    Implicit in the mnemonic 'MSATT' (Mars surface and atmosphere through time) is that rates of surface processes on Mars through time should be investigated, including studies of the kinetics and mechanism of oxidative weathering reactions occurring in the Martian regolith. Such measurements are described. Two major elements analyzed in the Viking Lander XRF experiment that are most vulnerable to atmospheric oxidation are iron and sulfur. Originally, they occurred as Fe(2+)-bearing silicate and sulfide minerals in basaltic rocks on the surface of Mars. However, chemical weathering reactions through time have produced ferric- and sulfate-bearing assemblages now visible in the Martian regolith. Such observations raise several question about: (1) when the oxidative weathering reactions took place on Mars; (2) whether or not the oxidized regolith is a fossilized remnant of past weathering processes; (3) deducting chemical interactions of the ancient Martian atmosphere with its surface from surviving phases; (4) possible weathering reactions still occurring in the frozen regolith; and (5) the kinetics and mechanism of past and present-day oxidative reactions on Mars. These questions may be addressed experimentally by studying reaction rates of dissolution and oxidation of basaltic minerals, and by identifying reaction products forming on the mineral surfaces. Results for the oxidation of pyrrhotite and dissolved ferrous iron are reported.

  15. Metabolism of Hydrocarbons in n-Alkane-Utilizing Anaerobic Bacteria.

    PubMed

    Wilkes, Heinz; Buckel, Wolfgang; Golding, Bernard T; Rabus, Ralf

    2016-01-01

    The glycyl radical enzyme-catalyzed addition of n-alkanes to fumarate creates a C-C-bond between two concomitantly formed stereogenic carbon centers. The configurations of the two diastereoisomers of the product resulting from n-hexane activation by the n-alkane-utilizing denitrifying bacterium strain HxN1, i.e. (1-methylpentyl)succinate, were assigned as (2S,1'R) and (2R,1'R). Experiments with stereospecifically deuterated n-(2,5-2H2)hexanes revealed that exclusively the pro-S hydrogen atom is abstracted from C2 of the n-alkane by the enzyme and later transferred back to C3 of the alkylsuccinate formed. These results indicate that the alkylsuccinate-forming reaction proceeds with an inversion of configuration at the carbon atom (C2) of the n-alkane forming the new C-C-bond, and thus stereochemically resembles a SN2-type reaction. Therefore, the reaction may occur in a concerted manner, which may avoid the highly energetic hex-2-yl radical as an intermediate. The reaction is associated with a significant primary kinetic isotope effect (kH/kD ≥3) for hydrogen, indicating that the homolytic C-H-bond cleavage is involved in the first irreversible step of the reaction mechanism. The (1-methylalkyl)succinate synthases of n-alkane-utilizing anaerobic bacteria apparently have very broad substrate ranges enabling them to activate not only aliphatic but also alkyl-aromatic hydrocarbons. Thus, two denitrifiers and one sulfate reducer were shown to convert the nongrowth substrate toluene to benzylsuccinate and further to the dead-end product benzoyl-CoA. For this purpose, however, the modified β-oxidation pathway known from alkylbenzene-utilizing bacteria was not employed, but rather the pathway used for n-alkane degradation involving CoA ligation, carbon skeleton rearrangement and decarboxylation. Furthermore, various n-alkane- and alkylbenzene-utilizing denitrifiers and sulfate reducers were found to be capable of forming benzyl alcohols from diverse alkylbenzenes

  16. Regioselective alkane hydroxylation with a mutant AlkB enzyme

    DOEpatents

    Koch, Daniel J.; Arnold, Frances H.

    2012-11-13

    AlkB from Pseudomonas putida was engineered using in-vivo directed evolution to hydroxylate small chain alkanes. Mutant AlkB-BMO1 hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. Mutant AlkB-BMO2 similarly hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. These biocatalysts are highly active for small chain alkane substrates and their regioselectivity is retained in whole-cell biotransformations.

  17. Liquid-liquid interfaces of semifluorinated alkane diblock copolymers with water, alkanes, and perfluorinated alkanes.

    PubMed

    Pierce, Flint; Tsige, Mesfin; Perahia, Dvora; Grest, Gary S

    2008-12-18

    The liquid-liquid interface between semifluorinated alkane diblock copolymers of the form F3C(CF2)n-1-(CH2)m-1CH3 and water, protonated alkanes, and perfluorinated alkanes are studied by fully atomistic molecular dynamics simulations. A modified version of the OPLS-AA (Optimized Parameter for Liquid Simulation All-Atom) force field of Jorgensen et al. has been used to study the interfacial behavior of semifluorinated diblocks. Aqueous interfaces are found to be sharp, with correspondingly large values of the interfacial tension. Due to the reduced hydrophobicity of the protonated block compared to the fluorinated block, hydrogen enhancement is observed at the interface. Water dipoles in the interfacial region are found to be oriented nearly parallel to the liquid-liquid interface. A number of protonated alkanes and perfluorinated alkanes are found to be mutually miscible with the semifluorinated diblocks. For these liquids, interdiffusion follows the expected Fickian behavior, and concentration-dependent diffusivities are determined.

  18. Liquid-liquid interfaces of semifluorinated alkane diblock copolymers with water, alkanes, and perfluorinated alkanes.

    SciTech Connect

    Perahia, Dvora, Dr.; Pierce, Flint; Tsige, Mesfin; Grest, Gary Stephen, Dr.

    2008-08-01

    The liquid-liquid interface between semifluorinated alkane diblock copolymers of the form F3C(CF2)n-1-(CH2)m-1CH3 and water, protonated alkanes, and perfluorinated alkanes are studied by fully atomistic molecular dynamics simulations. A modified version of the OPLS-AA (Optimized Parameter for Liquid Simulation All-Atom) force field of Jorgensen et al. has been used to study the interfacial behavior of semifluorinated diblocks. Aqueous interfaces are found to be sharp, with correspondingly large values of the interfacial tension. Due to the reduced hydrophobicity of the protonated block compared to the fluorinated block, hydrogen enhancement is observed at the interface. Water dipoles in the interfacial region are found to be oriented nearly parallel to the liquid-liquid interface. A number of protonated alkanes and perfluorinated alkanes are found to be mutually miscible with the semifluorinated diblocks. For these liquids, interdiffusion follows the expected Fickian behavior, and concentration-dependent diffusivities are determined.

  19. Biochemistry of Short-Chain Alkanes (Tissue-Specific Biosynthesis of n-Heptane in Pinus jeffreyi).

    PubMed

    Savage, T. J.; Hamilton, B. S.; Croteau, R.

    1996-01-01

    Short-chain (C7-C11) alkanes accumulate as the volatile component of oleoresin (pitch) in several pine species native to western North America. To establish the tissue most amenable for use in detailed studies of short-chain alkane biosynthesis, we examined the tissue specificity of alkane accumulation and biosynthesis in Pinus jeffreyi Grev. & Balf. Short-chain alkane accumulation was highly tissue specific in both 2-year-old saplings and mature trees; heart-wood xylem accumulated alkanes up to 7.1 mg g-1 dry weight, whereas needles and other young green tissue contained oleoresin with monoterpenoid, rather than paraffinic, volatiles. These tissue-specific differences in oleoresin composition appear to be a result of tissue-specific rates of alkane and monoterpene biosynthesis; incubation of xylem tissue with [14C]sucrose resulted in accumulation of radiolabel in alkanes but not monoterpenes, whereas incubation of foliar tissue with 14CO2 resulted in the accumulation of radiolabel in monoterpenes but not alkanes. Furthermore, incubation of xylem sections with [14C]acetate resulted in incorporation of radiolabel into alkanes at rates up to 1.7 nmol h-1 g-1 fresh weight, a rate that exceeds most biosynthetic rates reported with other plant systems for the incorporation of this basic precursor into natural products. This suggests that P. jeffreyi may provide a suitable model for elucidating the enzymology and molecular biology of short-chain alkane biosynthesis.

  20. Biochemistry of Short-Chain Alkanes (Tissue-Specific Biosynthesis of n-Heptane in Pinus jeffreyi).

    PubMed Central

    Savage, T. J.; Hamilton, B. S.; Croteau, R.

    1996-01-01

    Short-chain (C7-C11) alkanes accumulate as the volatile component of oleoresin (pitch) in several pine species native to western North America. To establish the tissue most amenable for use in detailed studies of short-chain alkane biosynthesis, we examined the tissue specificity of alkane accumulation and biosynthesis in Pinus jeffreyi Grev. & Balf. Short-chain alkane accumulation was highly tissue specific in both 2-year-old saplings and mature trees; heart-wood xylem accumulated alkanes up to 7.1 mg g-1 dry weight, whereas needles and other young green tissue contained oleoresin with monoterpenoid, rather than paraffinic, volatiles. These tissue-specific differences in oleoresin composition appear to be a result of tissue-specific rates of alkane and monoterpene biosynthesis; incubation of xylem tissue with [14C]sucrose resulted in accumulation of radiolabel in alkanes but not monoterpenes, whereas incubation of foliar tissue with 14CO2 resulted in the accumulation of radiolabel in monoterpenes but not alkanes. Furthermore, incubation of xylem sections with [14C]acetate resulted in incorporation of radiolabel into alkanes at rates up to 1.7 nmol h-1 g-1 fresh weight, a rate that exceeds most biosynthetic rates reported with other plant systems for the incorporation of this basic precursor into natural products. This suggests that P. jeffreyi may provide a suitable model for elucidating the enzymology and molecular biology of short-chain alkane biosynthesis. PMID:12226177

  1. CYP63A2, a catalytically versatile fungal P450 monooxygenase capable of oxidizing higher-molecular-weight polycyclic aromatic hydrocarbons, alkylphenols, and alkanes

    EPA Science Inventory

    Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was fo...

  2. CYP63A2, a catalytically versatile fungal P450 monooxygenase capable of oxidizing higher-molecular-weight polycyclic aromatic hydrocarbons, alkylphenols, and alkanes

    EPA Science Inventory

    Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was fo...

  3. Rate Law Analysis of Water Oxidation on a Hematite Surface

    PubMed Central

    2015-01-01

    Water oxidation is a key chemical reaction, central to both biological photosynthesis and artificial solar fuel synthesis strategies. Despite recent progress on the structure of the natural catalytic site, and on inorganic catalyst function, determining the mechanistic details of this multiredox reaction remains a significant challenge. We report herein a rate law analysis of the order of water oxidation as a function of surface hole density on a hematite photoanode employing photoinduced absorption spectroscopy. Our study reveals a transition from a slow, first order reaction at low accumulated hole density to a faster, third order mechanism once the surface hole density is sufficient to enable the oxidation of nearest neighbor metal atoms. This study thus provides direct evidence for the multihole catalysis of water oxidation by hematite, and demonstrates the hole accumulation level required to achieve this, leading to key insights both for reaction mechanism and strategies to enhance function. PMID:25936408

  4. Rate law analysis of water oxidation on a hematite surface.

    PubMed

    Le Formal, Florian; Pastor, Ernest; Tilley, S David; Mesa, Camilo A; Pendlebury, Stephanie R; Grätzel, Michael; Durrant, James R

    2015-05-27

    Water oxidation is a key chemical reaction, central to both biological photosynthesis and artificial solar fuel synthesis strategies. Despite recent progress on the structure of the natural catalytic site, and on inorganic catalyst function, determining the mechanistic details of this multiredox reaction remains a significant challenge. We report herein a rate law analysis of the order of water oxidation as a function of surface hole density on a hematite photoanode employing photoinduced absorption spectroscopy. Our study reveals a transition from a slow, first order reaction at low accumulated hole density to a faster, third order mechanism once the surface hole density is sufficient to enable the oxidation of nearest neighbor metal atoms. This study thus provides direct evidence for the multihole catalysis of water oxidation by hematite, and demonstrates the hole accumulation level required to achieve this, leading to key insights both for reaction mechanism and strategies to enhance function.

  5. Cometabolism of Methyl tertiary Butyl Ether and Gaseous n-Alkanes by Pseudomonas mendocina KR-1 Grown on C5 to C8 n-Alkanes

    PubMed Central

    Smith, Christy A.; O'Reilly, Kirk T.; Hyman, Michael R.

    2003-01-01

    Pseudomonas mendocina KR-1 grew well on toluene, n-alkanes (C5 to C8), and 1° alcohols (C2 to C8) but not on other aromatics, gaseous n-alkanes (C1 to C4), isoalkanes (C4 to C6), 2° alcohols (C3 to C8), methyl tertiary butyl ether (MTBE), or tertiary butyl alcohol (TBA). Cells grown under carbon-limited conditions on n-alkanes in the presence of MTBE (42 μmol) oxidized up to 94% of the added MTBE to TBA. Less than 3% of the added MTBE was oxidized to TBA when cells were grown on either 1° alcohols, toluene, or dextrose in the presence of MTBE. Concentrated n-pentane-grown cells oxidized MTBE to TBA without a lag phase and without generating tertiary butyl formate (TBF) as an intermediate. Neither TBF nor TBA was consumed by n-pentane-grown cells, while formaldehyde, the expected C1 product of MTBE dealkylation, was rapidly consumed. Similar Ks values for MTBE were observed for cells grown on C5 to C8 n-alkanes (12.95 ± 2.04 mM), suggesting that the same enzyme oxidizes MTBE in cells grown on each n-alkane. All growth-supporting n-alkanes (C5 to C8) inhibited MTBE oxidation by resting n-pentane-grown cells. Propane (Ki = 53 μM) and n-butane (Ki = 16 μM) also inhibited MTBE oxidation, and both gases were also consumed by cells during growth on n-pentane. Cultures grown on C5 to C8 n-alkanes also exhibited up to twofold-higher levels of growth in the presence of propane or n-butane, whereas no growth stimulation was observed with methane, ethane, MTBE, TBA, or formaldehyde. The results are discussed in terms of their impacts on our understanding of MTBE biodegradation and cometabolism. PMID:14660389

  6. Carbon monoxide oxidation rates computed for automobile thermal reactor conditions

    NASA Technical Reports Server (NTRS)

    Brokaw, R. S.; Bittker, D. A.

    1972-01-01

    Carbon monoxide oxidation rates in thermal reactors for exhaust manifolds are computed by integrating differential equations for system of twenty-nine reversible chemical reactions. Reactors are noncatalytic replacements for conventional exhaust manifolds and are a system for reducing carbon monoxide and hydrocarbons in automobile exhausts.

  7. Nickel(II) complexes of pentadentate N5 ligands as catalysts for alkane hydroxylation by using m-CPBA as oxidant: a combined experimental and computational study.

    PubMed

    Sankaralingam, Muniyandi; Balamurugan, Mani; Palaniandavar, Mallayan; Vadivelu, Prabha; Suresh, Cherumuttathu H

    2014-09-01

    A new family of nickel(II) complexes of the type [Ni(L)(CH(3)CN)](BPh(4))(2), where L=N-methyl-N,N',N'-tris(pyrid-2-ylmethyl)-ethylenediamine (L1, 1), N-benzyl-N,N',N'-tris(pyrid-2-yl-methyl)-ethylenediamine (L2, 2), N-methyl-N,N'-bis(pyrid-2-ylmethyl)-N'-(6-methyl-pyrid-2-yl-methyl)-ethylenediamine (L3, 3), N-methyl-N,N'-bis(pyrid-2-ylmethyl)-N'-(quinolin-2-ylmethyl)-ethylenediamine (L4, 4), and N-methyl-N,N'-bis(pyrid-2-ylmethyl)-N'-imidazole-2-ylmethyl)-ethylenediamine (L5, 5), has been isolated and characterized by means of elemental analysis, mass spectrometry, UV/Vis spectroscopy, and electrochemistry. The single-crystal X-ray structure of [Ni(L(3))(CH(3)CN)](BPh(4))(2) reveals that the nickel(II) center is located in a distorted octahedral coordination geometry constituted by all the five nitrogen atoms of the pentadentate ligand and an acetonitrile molecule. In a dichloromethane/acetonitrile solvent mixture, all the complexes show ligand field bands in the visible region characteristic of an octahedral coordination geometry. They exhibit a one-electron oxidation corresponding to the Ni(II) /Ni(III) redox couple the potential of which depends upon the ligand donor functionalities. The new complexes catalyze the oxidation of cyclohexane in the presence of m-CPBA as oxidant up to a turnover number of 530 with good alcohol selectivity (A/K, 7.1-10.6, A=alcohol, K=ketone). Upon replacing the pyridylmethyl arm in [Ni(L1)(CH(3)CN)](BPh(4))(2) by the strongly σ-bonding but weakly π-bonding imidazolylmethyl arm as in [Ni(L5)(CH(3)CN)](BPh(4))(2) or the sterically demanding 6-methylpyridylmethyl ([Ni(L3)(CH(3)CN)](BPh(4))(2) and the quinolylmethyl arms ([Ni(L4)(CH(3)CN)](BPh(4))(2), both the catalytic activity and the selectivity decrease. DFT studies performed on cyclohexane oxidation by complexes 1 and 5 demonstrate the two spin-state reactivity for the high-spin [(N5)Ni(II)-O(.)] intermediate (ts1(hs), ts2(doublet)), which has a low-spin state located closely in

  8. Rate of Nitric Oxide Scavenging by hemoglobin bound to haptoglobin

    PubMed Central

    Azarov, Ivan; He, Xiaojun; Jeffers, Anne; Basu, Swati; Ucer, Burak; Hantgan, Roy R.; Levy, Andrew; Kim-Shapiro, Daniel B.

    2008-01-01

    Cell-free hemoglobin, released from the red cell, may play a major role in regulating the bioavailability of nitric oxide. The abundant serum protein haptoglobin, rapidly binds to free hemoglobin forming a stable complex accelerating its clearance. The haptoglobin gene is polymorphic with two classes of alleles denoted 1 and 2. We have previously demonstrated that the haptoglobin 1 protein-hemoglobin complex is cleared twice as fast as the haptoglobin 2 protein-hemoglobin complex. In this report we explored whether haptoglobin binding to hemoglobin reduces the rate of nitric oxide scavenging using time-resolved absorption spectroscopy. We found that both the haptoglobin 1 and haptoglobin 2 protein complexes react with nitric oxide at the same rate as unbound cell-free hemoglobin. To confirm these results we developed a novel assay where free hemoglobin and hemoglobin bound to haptoglobin competed in the reaction with NO. The relative rate of the NO reaction was then determined by examining the amount of reacted species using analytical ultracentrifugation. Since complexation of hemoglobin with haptoglobin does not reduce NO scavenging, we propose that the haptoglobin genotype may influence nitric oxide bioavailability by determining the clearance rate of the haptoglobin-hemoglobin complex. We provide computer simulations showing that a two-fold difference in the rate of uptake of the haptoglobin hemoglobin complex by macrophages significantly affects nitric oxide bioavailability thereby providing a plausible explanation for why there is more vasospasm after subarachnoid hemorrhage in individuals and transgenic mice homozygous for the Hp 2 allele. PMID:18364244

  9. Biodegradation of variable-chain-length alkanes at low temperatures by a psychrotrophic Rhodococcus sp.

    SciTech Connect

    Whyte, L.G.; Hawari, J.; Zhou, E.; Bourbonniere, L.; Greer, C.W.; Inniss, W.E.

    1998-07-01

    The psychrotroph Rhodococcus sp. strain Q15 was examined for its ability to degrade individual n-alkanes and diesel fuel at low temperatures, and its alkane catabolic pathway was investigated by biochemical and genetic techniques. At 0 and 5 C, Q15 mineralized the short-chain alkanes dodecane and hexadecane to a greater extent than that observed for the long-chain alkanes octacosane and dotriacontane. Q15 utilized a broad range of aliphatics (C{sub 10} to C{sub 21} alkanes, branched alkanes, and a substituted cyclohexane) present in diesel fuel at 5 C. Mineralization of hexadecane at 5 C was significantly greater in both hydrocarbon-contaminated and pristine soil microcosms seeded with Q15 cells than in uninoculated control soil microcosms. The detection of hexadecane and dodecane metabolic intermediates (1-hexadecanol and 2-hexadecanol and 1-do-decanol and 2-dodecanone, respectively) by solid-phase microextraction-gas chromatography-mass spectrometry and the utilization of potential metabolic intermediates indicated that Q15 oxidizes alkanes by both the terminal oxidation pathway and the subterminal oxidation pathway. Genetic characterization by PCR and nucleotide sequence analysis indicated that Q15 possesses an aliphatic aldehyde dehydrogenase gene highly homologous to the Rhodococcus erythropolis thcA gene. Rhodococcus sp. strain Q15 possessed two large plasmids of approximately 90 and 115 kb (shown to mediate Cd resistance) which were not required for alkane mineralization, although the 90-kb plasmid enhanced mineralization of some alkanes and growth on diesel oil at both 5 and 25 C.

  10. Biodegradation of Variable-Chain-Length Alkanes at Low Temperatures by a Psychrotrophic Rhodococcus sp.

    PubMed Central

    Whyte, Lyle G.; Hawari, Jalal; Zhou, Edward; Bourbonnière, Luc; Inniss, William E.; Greer, Charles W.

    1998-01-01

    The psychrotroph Rhodococcus sp. strain Q15 was examined for its ability to degrade individual n-alkanes and diesel fuel at low temperatures, and its alkane catabolic pathway was investigated by biochemical and genetic techniques. At 0 and 5°C, Q15 mineralized the short-chain alkanes dodecane and hexadecane to a greater extent than that observed for the long-chain alkanes octacosane and dotriacontane. Q15 utilized a broad range of aliphatics (C10 to C21 alkanes, branched alkanes, and a substituted cyclohexane) present in diesel fuel at 5°C. Mineralization of hexadecane at 5°C was significantly greater in both hydrocarbon-contaminated and pristine soil microcosms seeded with Q15 cells than in uninoculated control soil microcosms. The detection of hexadecane and dodecane metabolic intermediates (1-hexadecanol and 2-hexadecanol and 1-dodecanol and 2-dodecanone, respectively) by solid-phase microextraction–gas chromatography-mass spectrometry and the utilization of potential metabolic intermediates indicated that Q15 oxidizes alkanes by both the terminal oxidation pathway and the subterminal oxidation pathway. Genetic characterization by PCR and nucleotide sequence analysis indicated that Q15 possesses an aliphatic aldehyde dehydrogenase gene highly homologous to the Rhodococcus erythropolis thcA gene. Rhodococcus sp. strain Q15 possessed two large plasmids of approximately 90 and 115 kb (shown to mediate Cd resistance) which were not required for alkane mineralization, although the 90-kb plasmid enhanced mineralization of some alkanes and growth on diesel oil at both 5 and 25°C. PMID:9647833

  11. Theoretical study of the rhenium–alkane interaction in transition metal–alkane σ-complexes

    PubMed Central

    Cobar, Erika A.; Khaliullin, Rustam Z.; Bergman, Robert G.; Head-Gordon, Martin

    2007-01-01

    Metal–alkane binding energies have been calculated for [CpRe(CO)2](alkane) and [(CO)2M(C5H4)CC(C5H4)M(CO)2](alkane), where M = Re or Mn. Calculated binding energies were found to increase with the number of metal–alkane interaction sites. In all cases examined, the manganese–alkane binding energies were predicted to be significantly lower than those for the analogous rhenium–alkane complexes. The metal (Mn or Re)–alkane interaction was predicted to be primarily one of charge transfer, both from the alkane to the metal complex (70–80% of total charge transfer) and from the metal complex to the alkane (20–30% of the total charge transfer). PMID:17442751

  12. Theoretical study of the rhenium-alkane interaction in transition metal-alkane sigma-complexes.

    PubMed

    Cobar, Erika A; Khaliullin, Rustam Z; Bergman, Robert G; Head-Gordon, Martin

    2007-04-24

    Metal-alkane binding energies have been calculated for [CpRe(CO)2](alkane) and [(CO)2M(C5H4)C[triple bond]C(C5H4)M(CO)2](alkane), where M = Re or Mn. Calculated binding energies were found to increase with the number of metal-alkane interaction sites. In all cases examined, the manganese-alkane binding energies were predicted to be significantly lower than those for the analogous rhenium-alkane complexes. The metal (Mn or Re)-alkane interaction was predicted to be primarily one of charge transfer, both from the alkane to the metal complex (70-80% of total charge transfer) and from the metal complex to the alkane (20-30% of the total charge transfer).

  13. Co-metabolic conversion of toluene in anaerobic n-alkane-degrading bacteria.

    PubMed

    Rabus, Ralf; Jarling, René; Lahme, Sven; Kühner, Simon; Heider, Johann; Widdel, Friedrich; Wilkes, Heinz

    2011-09-01

    Diverse microorganisms have been described to degrade petroleum hydrocarbons anaerobically. Strains able to utilize n-alkanes do not grow with aromatic hydrocarbons, whereas strains able to utilize aromatic hydrocarbons do not grow with n-alkanes. To investigate this specificity in more detail, three anaerobic n-alkane degraders (two denitrifying, one sulfate-reducing) and eight anaerobic alkylbenzene degraders (five denitrifying, three sulfate-reducing) were incubated with mixtures of n-alkanes and toluene. Whereas the toluene degradationers formed only the characteristic toluene-derived benzylsuccinate and benzoate, but no n-alkane-derived metabolites, the n-alkane degraders formed toluene-derived benzylsuccinate, 4-phenylbutanoate, phenylacetate and benzoate besides the regular n-alkane-derived (1-methylalkyl)succinates and methyl-branched alkanoates. The co-metabolic conversion of toluene by anaerobic n-alkane degraders to the level of benzoate obviously follows the anaerobic n-alkane degradation pathway with C-skeleton rearrangement and decarboxylation rather than the β-oxidation pathway of anaerobic toluene metabolism. Hence, petroleum-derived aromatic metabolites detectable in anoxic environments may not be exclusively formed by genuine alkylbenzene degraders. In addition, the hitherto largely unexplored fate of fumarate hydrogen during the activation reactions was examined with (2,3-(2) H(2) )fumarate as co-substrate. Deuterium was completely exchanged with hydrogen at the substituted carbon atom (C-2) of the succinate adducts of n-alkanes, whereas it is retained in toluene-derived benzylsuccinate, regardless of the type of enzyme catalysing the fumarate addition reaction.

  14. Determining Oxidation Rates in Multi-component Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Sage, A. M.; Weitkamp, E. A.; Huff Hartz, K. E.; Robinson, A. L.; Donahue, N. M.

    2006-12-01

    Aerosol composition influences the kinetics of condensed-phase organic species, making extrapolation of rate constants from single-component systems to atmospherically-relevant mixtures difficult. Using a mixed-phase relative rate constants approach, we have overcome this difficulty, obtaining heterogeneous oxidation rate constants for each species in several multi-component organic mixtures. We have also derived a compound- specific uptake coefficient that relates these rate constants to previous uptake measurements. In the ozonolysis of model meat-cooking mixtures, we observe significant decay of saturated and unsaturated acids and sterols. By relating the observed decomposition of condensed-phase species to that of gas-phase standards, we track the evolution of effective rate constants for oleic acid and palmitoleic acid oxidation as the aerosol is chemically processed. Each decreases by nearly a factor of ten over the course of an experiment. Rate constants also depend strongly on aerosol composition, changing by more than an order of magnitude with increasing mixture complexity. To compare these results with previous results, we have derived a compound-specific uptake coefficient (γi' for condensed-phase species i), which describes the kinetics of reactive uptake in mixtures and can be meaningfully related to the traditional uptake coefficient. We express uptake in terms of the concentrations of condensed-phase species, and to do so accurately, we use alkanoic acids to correct the decay of reactive alkenoic acids for secondary chemistry. This correction is incorporated into the definition of γi', and in terms of γi', the standard uptake coefficient can be written as: γ=∑χiγi', where χi is the mass fraction of species i and the summation is over all oxidized species. By using condensed-phase decay to calculate the uptake, we have apportioned reactive uptake among responsible species. This provides information not only about the potential of a particle

  15. Rates of oxidative weathering on the surface of Mars

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.; Fisher, Duncan S.

    1993-01-01

    A model of acid weathering is proposed for the iron-rich basalts on Mars. Aqueous oxidation of iron sulfides released SO4(2-) and H(+) ions that initiated the dissolution of basaltic ferromagnesian silicates and released Fe(2+) ions. The Fe(2+) ions eventually underwent ferrolysis reactions and produced insoluble hydrous ferric oxide phases. Measurements of the time-dependence of acid weathering reactions show that pyrrhotite is rapidly converted to pyrite plus dissolved ferrous iron, the rate of pyrite formation decreasing with rising pH and lower temperatures. On Mars, oxidation rates of dissolved Fe(2+) ions in equatorial melt-waters in contact with the atmosphere are estimated to lie in the range 0.3-3.0 ppb Fe/yr over the pH range 2 to 6. Oxidation of Fe(2+) ions is estimated to be extremely slow in brine eutectic solutions that might be present on Mars and to be negligible in the frozen regolith.

  16. Modular and selective biosynthesis of gasoline-range alkanes.

    PubMed

    Sheppard, Micah J; Kunjapur, Aditya M; Prather, Kristala L J

    2016-01-01

    Typical renewable liquid fuel alternatives to gasoline are not entirely compatible with current infrastructure. We have engineered Escherichia coli to selectively produce alkanes found in gasoline (propane, butane, pentane, heptane, and nonane) from renewable substrates such as glucose or glycerol. Our modular pathway framework achieves carbon-chain extension by two different mechanisms. A fatty acid synthesis route is used to generate longer chains heptane and nonane, while a more energy efficient alternative, reverse-β-oxidation, is used for synthesis of propane, butane, and pentane. We demonstrate that both upstream (thiolase) and intermediate (thioesterase) reactions can act as control points for chain-length specificity. Specific free fatty acids are subsequently converted to alkanes using a broad-specificity carboxylic acid reductase and a cyanobacterial aldehyde decarbonylase (AD). The selectivity obtained by different module pairings provides a foundation for tuning alkane product distribution for desired fuel properties. Alternate ADs that have greater activity on shorter substrates improve observed alkane titer. However, even in an engineered host strain that significantly reduces endogenous conversion of aldehyde intermediates to alcohol byproducts, AD activity is observed to be limiting for all chain lengths. Given these insights, we discuss guiding principles for pathway selection and potential opportunities for pathway improvement. Copyright © 2015 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

  17. Enhanced production of n-alkanes in Escherichia coli by spatial organization of biosynthetic pathway enzymes.

    PubMed

    Rahmana, Ziaur; Sung, Bong Hyun; Yi, Ji-Yeun; Bui, Le Minh; Lee, Jun Hyoung; Kim, Sun Chang

    2014-12-20

    Alkanes chemically mimic hydrocarbons found in petroleum, and their demand as biofuels is steadily increasing. Biologically, n-alkanes are produced from fatty acyl-ACPs by acyl-ACP reductases (AARs) and aldehyde deformylating oxygenases (ADOs). One of the major impediments in n-alkane biosynthesis is the low catalytic turnover rates of ADOs. Here, we studied n-alkane biosynthesis in Escherichia coli using a chimeric ADO-AAR fusion protein or zinc finger protein-guided ADO/AAR assembly on DNA scaffolds to control their stoichiometric ratios and spatial arrangements. Bacterial production of n-alkanes with the ADO-AAR fusion protein was increased 4.8-fold (24 mg/L) over a control strain expressing ADO and AAR separately. Optimal n-alkane biosynthesis was achieved when the ADO:AAR binding site ratio on a DNA scaffold was 3:1, yielding an 8.8-fold increase (44 mg/L) over the control strain. Our findings indicate that the spatial organization of alkane-producing enzymes is critical for efficient n-alkane biosynthesis in E. coli.

  18. Measurements of in situ chemical ozone (oxidant) production rates

    NASA Astrophysics Data System (ADS)

    Huang, Hao; Faloon, Kate; Najera, Juan; Bloss, William

    2013-04-01

    Tropospheric ozone is a major air pollutant, harmful to human health, agricultural crops and vegetation, the main precursor to the atmospheric oxidants which initiate the degradation of most reactive gases emitted to the atmosphere, and an important greenhouse gas in its own right. The capacity to understand and predict tropospheric ozone levels is a key goal for atmospheric science - but one which is challenging, as ozone is formed in the atmosphere from the complex oxidation of VOCs in the presence of NOx and sunlight, on a timescale such that in situ chemical processes, deposition and transport all affect ozone levels. Known uncertainties in emissions, chemistry, dynamics and deposition affect the accuracy of predictions of current and future ozone levels, and hinder development of optimal air quality policies to mitigate against ozone exposure. Recently new approaches to directly measure the local chemical ozone production rate, bypassing the many uncertainties in emissions and chemical schemes, have been developed (Cazorla & Brune, AMT 2010). Here, we describe the development of an analogous Ozone Production Rate (OPR) approach: Air is sampled into parallel reactors, within which ozone formation either occurs as in the ambient atmosphere, or is suppressed. Comparisons of ozone levels exiting a pair of such reactors determines the net chemical oxidant production rate, after correction for perturbation of the NOx-O3 photochemical steady state, and when operated under conditions such that wall effects are minimised. We report preliminary measurements of local chemical ozone production made during the UK NERC ClearfLo (Clean Air for London) campaign at an urban background location in London in January and July 2012. The OPR system was used to measure the local chemical oxidant formation rate, which is compared with observed trends in O3 and NOx and the prevailing meteorology, and with the predictions of a detailed zero-dimensional atmospheric chemistry model

  19. Texture-dependent anaerobic microsites constrain soil carbon oxidation rates

    NASA Astrophysics Data System (ADS)

    Keiluweit, Marco; Fendorf, Scott

    2016-04-01

    Soil texture, which is a product of parent material, climate and other soil forming factors, is a predictor for long-term storage of soil organic carbon (SOC) storage in many soil ecosystems. Positive correlation between texture (particularly clay content) and SOC storage have long been attributed to protective associations between clay minerals and organic compounds that prevent microbial and enzymatic access - a mechanism commonly referred to as 'mineral protection'. Texture therefore acts as the primary proxy for mineral protection in terrestrial ecosystem models used to assess SOC storage and its sensitivity to global change impacts. Here we show that this protective effect of texture is not only due to mineral protection, but also to the formation of anaerobic microsites. Combining micro-scale laboratory experiments with field-scale observations, we find that oxygen diffusion limitations within clay-rich domains create anaerobic microsites within seemingly well-aerated soils, shifting microbial metabolism to less efficient anaerobic SOC oxidation pathways. Kinetic and thermodynamic constraints reduce SOC oxidation rates within these anaerobic microsites by an order of magnitude relative to aerobic rates, and caused the preservation of bioavailable, polymeric and reduced organic compounds. Lifting these metabolic constraints through increased soil aeration (e.g., through changes in precipitation patterns or land use) may stimulate microbial oxidation of this inherently bioavailable SOC pool. Models that attribute the effects of texture merely to 'mineral protection' may therefore underestimate the vulnerability of soil C to global change impacts.

  20. Alkane biohydroxylation: Interests, constraints and future developments.

    PubMed

    Soussan, Laurence; Pen, Nakry; Belleville, Marie-Pierre; Marcano, José Sanchez; Paolucci-Jeanjean, Delphine

    2016-03-20

    Alkanes constitute one of the vastest reserves of raw materials for the production of fine chemicals. This paper focuses on recent advances in alkane biohydroxylation, i.e. the bioactivation of alkanes into their corresponding alcohols. Enzyme and whole-cell biocatalysts have been reviewed. Process considerations to implement such biocatalysts in bioreactors at large scale by coupling the bioconversion with cofactor regeneration and product removal are also discussed.

  1. Reversible Interconversion between Alkanes, Alkenes, Alcohols and Ketones under Hydrothermal Conditions

    NASA Astrophysics Data System (ADS)

    Shipp, J.; Hartnett, H. E.; Gould, I. R.; Shock, E.; Williams, L. B.

    2011-12-01

    Many transformation reactions involving hydrocarbons that occur in deep sedimentary systems and determine petroleum compositions occur in the presence of H2O. Hydrothermal transformations of organic material are thought to provide carbon sources for microbes in deep ocean sediments. Hydrothermal conditions may also mimic the conditions where life developed on an early Earth. Nevertheless, much remains to be learned about the mechanisms of hydrothermal organic reactions, including ways in which various reactions are interrelated and how reactions compete with each other. It can be argued that metastable equilibrium states develop over geological timescales and at geochemically relevant temperatures, suggesting that reactions occur under thermodynamic rather than kinetic control. The extent to which reactions are reversible, and how product distributions are determined, are primary tests of the metastable equilibrium model. Seewald (2001, GCA 65, 1641-1664) showed that under hydrothermal conditions and in the presence of a redox buffer, simple alkanes and alkenes undergo oxidation, reduction, and hydration reactions. He proposed a reaction scheme where alkanes interconvert with alkenes, followed by stepwise hydration of alkenes to alcohols, oxidation to ketones, and finally conversion to carboxylic acids, which can undergo decarboxylation. Here we describe experiments that further develop the scope of these functional group interconversions, determine relative reaction kinetics, and provide insight into competing reactions. Hydrothermal experiments were performed at 300°C and 100 MPa in gold capsules for 12 to 144 hours. The reactant structures were based on cyclohexane with one and two methyl groups that served as regio- and stereochemical markers for the reactions. Starting with the alkanes, the observed products include the corresponding alkenes, alcohols, ketones and enones, in support of the Seewald reaction scheme. Our experiments add a branch to this scheme

  2. Short-chain alkane cycling in deep Gulf of Mexico cold-seep sediments

    NASA Astrophysics Data System (ADS)

    Sibert, R.; Joye, S. B.; Hunter, K.

    2015-12-01

    Mixtures of light hydrocarbon gases are common in deep Gulf of Mexico cold-seep sediments, and are typically dissolved in pore fluids, adsorbed to sediment particles, trapped in methane ice, or as free gas. The dominant component in these natural gas mixtures is usually methane (>80% C1), but ethane (C2) and propane (C3) are nearly always present in trace amounts (<1% total). The processes that control the concentration and isotopic signature of these gases in sediments are well explained for methane, but the controls for C2/C3 cycling are still a relative mystery. Methane production proceeds in deep anoxic sediments by either 1) thermocatalytic cracking of fossil organic matter, or 2) as a direct product of microbial metabolism, i.e. methanogenesis. In surface sediments, it appears that both microbial consumption and chemical deposition of methane (i.e. as methane clathrate) ensures that >95% of the methane produced at depth never reaches the water column. Production of C1 and C2 in deep-sea sediments has been historically attributed only to thermocatalytic processes, though limited data suggests production of C2/C3 compounds through the activity of archaea at depth. Furthermore, carbon isotopic data on ethane and propane from deep cores of Gulf of Mexico sediments suggest alkanogenesis at >3 m depth in the sediment column and alkane oxidation in uppermost oxidant-rich sediments. Additional studies have also isolated microorganisms capable of oxidizing ethane and propane in the laboratory, but field studies of microbial-driven dynamics of C2/C3 gases in cold-seep sediments are rare. Here, we present the results of a series of incubation experiments using sediment slurries culled from surface sediments from one of the most prolific natural oil and gas seeps in the Gulf of Mexico. Rates of alkane oxidation were measured under a variety of conditions to assess the surface-driven microbial controls on C2/C3 cycling in cold-seep environments. Such microbial processes

  3. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    SciTech Connect

    Grimes, Travis Shane; Mincher, Bruce Jay; Schmitt, Nicholas C

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  4. Magnesium Oxide Carbonation Rate Law in Saturated Brines

    NASA Astrophysics Data System (ADS)

    Nemer, M. B.; Allen, C.; Deng, H.

    2008-12-01

    Magnesium oxide (MgO) is the only engineered barrier certified by the EPA for emplacement in the Waste Isolation Pilot Plant (WIPP), a U.S. Department of Energy repository for transuranic waste in southeast New Mexico. MgO reduces actinide solubility by sequestering CO2 generated by the biodegradation of cellulosic, plastic, and rubber materials. Demonstration of the effectiveness of MgO is essential for WIPP recertification. In order to be an effective barrier, the rate of CO2 sequestration should be fast compared to the rate CO2 production, over the entire 10,000 year regulatory period. While much research has been conducted on the kinetics of magnesium oxide carbonation in waters with salinity up to that of sea water, we are not aware of any work on determining the carbonation rate law in saturated brines at low partial pressures of CO2 (PCO2 as low as 10-5.5 atm), which is important for performing safety assessments of bedded salt waste repositories. Using a Varian ion-trap gas- chromatograph/mass-spectrometer (GC/MS) we experimentally followed the CO2 sequestration kinetics of magnesium oxide in salt-saturated brines down to a PCO2 as low as 10-5.5 atm. This was performed in a closed reactor with a known initial PCO2. The results of this study show that carbonation is approximately first order in PCO2, in saturated brines. We believe that this method will benefit the study of the detailed kinetics of other similar processes.

  5. Enhanced Rates of Hydrogen Absorption Resulting from Oxidation of Pd and Internal Oxidation of Pd-Al Alloys

    SciTech Connect

    Shanahan, K.L.

    1999-08-20

    The goal of this research was the determination of the relative rates before and after internal oxidation of Pd--Al alloys and oxidation (Pd) and this is independent of whether heat transfer is the rate-limiting step for the internally oxidized Pd--Al alloys rather than a more fundamental step.

  6. Crystallization and prevention of supercooling of microencapsulated n-alkanes.

    PubMed

    Zhang, Xing-xiang; Fan, Yao-feng; Tao, Xiao-ming; Yick, Kit-lun

    2005-01-15

    Microencapsulated n-alkanes (n-octadecane, n-nonadecane, and n-eicosane) were synthesized by in situ polymerization using urea-melamine-formaldehyde polymer as shells. Microcapsules 5.0 and 10.0 wt% of 1-tetradecanol, paraffin, and 1-octadecanol were used as nucleating agents. The fabrication was characterized using Fourier transform infrared, light microscopy, and scanning electron microscopy. The crystallization and prevention of supercooling of the microcapsules are studied using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction. The crystal system of the microencapsulated n-alkane is the same as that of the bulk. The enthalpies of the microcapsules containing 70 wt% n-alkanes are approximately 160 J/g. The melting temperature of the n-alkanes in the microcapsule is the same as that in the bulk. There are multiple peaks on the DSC cooling curves that are attributed to liquid-rotator, rotator-crystal, and liquid-crystal transitions. The DSC cooling behavior of microencapsulated n-octadecane is affected by the average diameters. The measured maximum degree of supercooling of the microencapsulated n-octadecane is approximately 26.0 degrees C at a heating and cooling rate of 10.0 degrees C/min. The degree of supercooling of microencapsulated n-octadecane is decreased by adding 10.0 wt% of 1-octadecanol as a nucleating agent.

  7. Microbial Methane Oxidation Rates in Guandu Wetland of northern Taiwan

    NASA Astrophysics Data System (ADS)

    Yu, Zih-Huei; Wang, Pei-Ling; Lin, Li-Hung

    2016-04-01

    Wetland is one of the major sources of atmospheric methane. The exact magnitude of methane emission is essentially controlled by microbial processes. Besides of methanogenesis, methanotrophy oxidizes methane with the reduction of various electron acceptors under oxic or anoxic conditions. The interplay of these microbial activities determines the final methane flux under different circumstances. In a tidal wetland, the cyclic flooding and recession of tide render oxygen and sulfate the dominant electron acceptors for methane oxidation. However, the details have not been fully examined, especially for the linkage between potential methane oxidation rates and in situ condition. In this study, a sub-tropical wetland in northern Taiwan, Guandu, was chosen to examine the tidal effect on microbial methane regulation. Several sediment cores were retrieved during high tide and low tide period and their geochemical profiles were characterized to demonstrate in situ microbial activities. Incubation experiments were conducted to estimate potential aerobic and anaerobic methane oxidation rates in surface and core sediments. Sediment cores collected in high tide and low tide period showed different geochemical characteristics, owning to tidal inundation. Chloride and sulfate concentration were lower during low tide period. A spike of enhanced sulfate at middle depth intervals was sandwiched by two sulfate depleted zones above and underneath. Methane was accumulated significantly with two methane depletion zones nearly mirroring the sulfate spike zone identified. During the high tide period, sulfate decreased slightly with depth with methane production inhibited at shallow depths. However, a methane consumption zone still occurred near the surface. Potential aerobic methane oxidation rates were estimated between 0.7 to 1.1 μmole/g/d, showing no difference between the samples collected at high tide or low tide period. However, a lag phase was widely observed and the lag phase

  8. Reaction pathway for alkane dehydrocyclization

    SciTech Connect

    Shi, Buchang; Davis, B.H.

    1996-08-01

    Naphtha reforming to produce high octane gasoline is an important process. Many reaction mechanisms are involved in this process. For example, the study of the fundamentals of this process led to the concept of bi- or poly-functional catalysis. The results of this study provide additional mechanistic information about the dehydrocyclization of an n-alkane to produce aromatics. The reaction coordinate diagram advanced to account for the observation of irreversible adsorption should be modified to account for the present results. 32 refs., 1 fig.

  9. Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation.

    PubMed

    Andersen, M S; Larsen, F; Postma, D

    2001-10-15

    The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase in the incubation bags became depleted in O2 and enriched in CO2 and N2 and was interpreted as due to pyrite oxidation in combination with calcite dissolution. Sediment incubation provides a new method to estimate low rates of pyrite oxidation in unsaturated zone aquifer sediments. Oxidation rates of up to 9.4 x 10(-10) mol FeS2/g x s are measured, and the rates are only weakly correlated with the sediment pyrite content. The reactivity of pyrite, including the inhibition by FeOOH layers formed on its surface, apparently has a major effect on the rate of oxidation. The code PHREEQC 2.0 was used to calculate the reaction stoichiometry and partitioning of gases between the solution and the gas phase. Pyrite oxidation with concurrent calcite dissolution was found to be consistent with the experimental data while organic carbon oxidation was not. The reaction involves changes in the total volume of the gas phase. The reaction scheme predicts the volume of O2 gas consumed to be larger than of CO2 produced. In addition the solubility of CO2 in water is about 30 times larger than of O2 causing a further decrease in total gas volume. The change in total gas volume therefore also depends on the gas/water volume ratio and the lower the ratio the more pronounced the loss of volume will be. Under field conditions the change in total volume may amount up to 20% in the absence of calcite and over 10% in the presence of calcite. Such changes in gas volume during the oxidation of pyrite are expected to result in pressure gradients causing advective transport of gaseous oxygen.

  10. Distribution, activity and function of short-chain alkane degrading phylotypes in hydrothermal vent sediments

    NASA Astrophysics Data System (ADS)

    Adams, M. M.; Joye, S. B.; Hoarfrost, A.; Girguis, P. R.

    2012-12-01

    Global geochemical analyses suggest that C2-C4 short chain alkanes are a common component of the utilizable carbon pool in deep-sea sediments worldwide and have been found in diverse ecosystems. From a thermodynamic standpoint, the anaerobic microbial oxidation of these aliphatic hydrocarbons is more energetically yielding than the anaerobic oxidation of methane (AOM). Therefore, the preferential degradation of these hydrocarbons may compete with AOM for the use of oxidants such as sulfate, or other potential oxidants. Such processes could influence the fate of methane in the deep-sea. Sulfate-reducing bacteria (SRB) from hydrocarbon seep sediments of the Gulf of Mexico and Guaymas Basin have previously been enriched that anaerobically oxidize short chain alkanes to generate CO2 with the preferential utilization of 12C-enriched alkanes (Kniemeyer et al. 2007). Different temperature regimens along with multiple substrates were tested and a pure culture (deemed BuS5) was isolated from mesophilic enrichments with propane or n-butane as the sole carbon source. Through comparative sequence analysis, strain BuS5 was determined to cluster with the metabolically diverse Desulfosarcina / Desulfococcus cluster, which also contains the SRB found in consortia with anaerobic, methane-oxidizing archaea in seep sediments. Enrichments from a terrestrial, low temperature sulfidic hydrocarbon seep also corroborated that propane degradation occurred with most bacterial phylotypes surveyed belonging to the Deltaproteobacteria, particularly Desulfobacteraceae (Savage et al. 2011). To date, no microbes capable of ethane oxidation or anaerobic C2-C4 alkane oxidation at thermophilic temperature have been isolated. The sediment-covered, hydrothermal vent systems found at Middle Valley (Juan de Fuca Ridge, eastern Pacific Ocean) are a prime environment for investigating mesophilic to thermophilic anaerobic oxidation of short-chain alkanes, given the elevated temperatures and dissolved

  11. Hydrogen isotope exchange between n-alkanes and water under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Reeves, Eoghan P.; Seewald, Jeffrey S.; Sylva, Sean P.

    2012-01-01

    To investigate the extent of hydrogen isotope (2H and 1H) exchange between hydrocarbons and water under hydrothermal conditions, we performed experiments heating C1-C5n-alkanes in aqueous solutions of varying initial 2H/1H ratios in the presence of a pyrite-pyrrhotite-magnetite redox buffer at 323 °C and 35-36 MPa. Extensive and reversible incorporation of water-derived hydrogen into C2-C5n-alkanes was observed on timescales of months. In contrast, comparatively minor exchange was observed for CH4. Isotopic exchange is facilitated by reversible equilibration of n-alkanes and their corresponding n-alkenes with H2 derived from the disproportionation of water. Rates of δ2H variation in C3+n-alkanes decreased with time, a trend that is consistent with an asymptotic approach to steady state isotopic compositions regulated by alkane-water isotopic equilibrium. Substantially slower δ2H variation was observed for ethane relative to C3-C5n-alkanes, suggesting that the greater stability of C3+ alkenes and isomerization reactions may dramatically enhance rates of 2H/1H exchange in C3+n-alkanes. Thus, in reducing aqueous environments, reversible reaction of alkanes and their corresponding alkenes facilitates rapid 2H/1H exchange between water and alkyl-bound hydrogen on relatively short geological timescales at elevated temperatures and pressures. The proximity of some thermogenic and purported abiogenic alkane δ2H values to those predicted for equilibrium 2H/1H fractionation with ambient water suggests that this process may regulate the δ2H signatures of some naturally occurring hydrocarbons.

  12. Elimination of alkanes from off-gases using biotrickling filters containing two liquid phases

    SciTech Connect

    Groenestijn, J.W. van; Lake, M.E.

    1999-09-30

    Biological techniques are highly cost-effective for the treatment of off-gases containing low concentrations of pollutants. They may also be attractive for the elimination of higher concentrations of explosive hydrocarbons. Conventional techniques such as biofilters have low elimination capacities for hydrophobic compounds caused by a poor mass transfer from the gas to the aqueous phase. To overcome solubility problems, a novel biotrickling filter was developed and is characterized by the use of an organic solvent. In such a biotrickling filter, a mixture of an organic solvent and water is continuously trickled over a packed bed, while the polluted gas passes counter-current to the liquid. The microorganisms exist on the packing material and in the circulating liquid. The alkanes are absorbed in the oil phase of the liquid, transferred to the microorganisms and biodegraded. Laboratory-scale experiments at 20 l scale with hexane as a model pollutant and silicon oil as a solvent revealed that a 90% elimination efficiency can be reached at a volumetric loading rate of 100 g hexane per m{sup 3} and had a temperature of 29 C. The method described in this paper can be a cost-effective was to treat gases containing hexane, other alkanes or other strongly hydrophobic compounds. Biological co-oxidation of other biodegradable pollutants from the gas is to be expected.

  13. On droplet combustion of biodiesel fuel mixed with diesel/alkanes in microgravity condition

    SciTech Connect

    Pan, Kuo-Long; Li, Je-Wei; Chen, Chien-Pei; Wang, Ching-Hua

    2009-10-15

    The burning characteristics of a biodiesel droplet mixed with diesel or alkanes such as dodecane and hexadecane were experimentally studied in a reduced-gravity environment so as to create a spherically symmetrical flame without the influence of natural convection due to buoyancy. Small droplets on the order of 500 {mu}m in diameter were initially injected via a piezoelectric technique onto the cross point intersected by two thin carbon fibers; these were prepared inside a combustion chamber that was housed in a drag shield, which was freely dropped onto a foam cushion. It was found that, for single component droplets, the tendency to form a rigid soot shell was relatively small for biodiesel fuel as compared to that exhibited by the other tested fuels. The soot created drifted away readily, showing a puffing phenomenon; this could be related to the distinct molecular structure of biodiesel leading to unique soot layers that were more vulnerable to oxidative reactivity as compared to the soot generated by diesel or alkanes. The addition of biodiesel to these more traditional fuels also presented better performance with respect to annihilating the soot shell, particularly for diesel. The burning rate generally follows that of multi-component fuels, by some means in terms of a lever rule, whereas the mixture of biodiesel and dodecane exhibits a somewhat nonlinear relation with the added fraction of dodecane. This might be related to the formation of a soot shell. (author)

  14. Oxidation kinetics of zinc sulfide: determination of intrinsic rate constant

    SciTech Connect

    Prabhu, G.M.

    1983-06-01

    An initial reaction rate study was done with the help of a thermogravimetric technique. Energy dispersive x-ray analyses on partially oxidized zinc sulfide pellets with a sintered porosity of 72.4% indicated flat sulfur intensity profiles within pellets reacted below 560/sup 0/C, which suggested a homogeneous reaction mechanism. Therefore, reaction temperatures below 600/sup 0/C were chosen for the reaction rate studies. Initial reaction rate studies on 72.4, 58.2, and 34.0% porous, cylindrical zinc sulfide pellets and the corresponding Arrhenius plot suggested chemical control in the temperature range from 480 to 565/sup 0/C. The corresponding intrinsic rate constant is correlated as k = 3.45 x 10/sup 17/ exp (- 86051/RT) cm/s. The variation in sulfur intensity within sintered pellets having a porosity of 72.4% that were reacted at temperatures above 560/sup 0/C indicated that the pore diffusion resistance gradually became comparable to the chemical reaction resistance leading to a mixed control mechanism above 570/sup 0/C. The critical temperature at which this shift occurred, increased with pellet porosity.

  15. Maximal Fat Oxidation Rates in an Athletic Population.

    PubMed

    Randell, Rebecca K; Rollo, Ian; Roberts, Timothy J; Dalrymple, Kortney J; Jeukendrup, Asker E; Carter, James M

    2017-01-01

    The aim of this study was to describe maximal fat oxidation (MFO) rates in an athletic population. In total, 1121 athletes (933 males and 188 females), from a variety of sports and competitive level, undertook a graded exercise test on a treadmill in a fasted state (≥5 h fasted). Rates of fat oxidation were determined using indirect calorimetry. The average MFO was 0.59 ± 0.18 g·min, ranging from 0.17 to 1.27 g·min. Maximal rates occurred at an average exercise intensity of 49.3% ± 14.8% V˙O2max, ranging from 22.6% to 88.8% V˙O2max. In absolute terms, male athletes had significantly higher MFO compared with females (0.61 and 0.50 g·min, respectively, P < 0.001). Expressed relative to fat-free mass (FFM), MFO were higher in the females compared with males (MFO/FFM: 11.0 and 10.0 mg·kg·FFM·min, respectively, P < 0.001). Soccer players had the highest MFO/FFM (10.8 mg·kg·FFM·min), ranging from 4.1 to 20.5 mg·kg·FFM·min, whereas American Football players displayed the lowest rates of MFO/FFM (9.2 mg·kg·FFM·min). In all athletes, and when separated by sport, large individual variations in MFO rates were observed. Significant positive correlations were found between MFO (g·min) and the following variables: FFM, V˙O2max, FATMAX (the exercise intensity at which the MFO was observed), percent body fat, and duration of fasting. When taken together these variables account for 47% of the variation in MFO. MFO and FATMAX vary significantly between athletes participating in different sports but also in the same sport. Although variance in MFO can be explained to some extent by body composition and fitness status, more than 50% of the variance is not explained by these variables and remains unaccounted for.

  16. Rates of nitrous oxide production in the oxidation of hydroxylamine by iron(III)

    SciTech Connect

    Butler, J.H.; Gordon, L.I.

    1986-12-03

    The dependence of the rate of N/sub 2/O formation on the reactants and on pH in the oxidation of NH/sub 2/OH by Fe(III) has been investigated over a range of reactant concentrations, with emphasis on low concentrations of hydroxylamine. The production rate of N/sub 2/O was pseudo first order with respect to total iron, pseudo first order or less with respect to total hydroxylamine, and inversely proportional to (H/sup +/)/sup 2.5/. The reaction is highly sensitive to temperature. Of the competing reactions producing nitrogenous products other than N/sub 2/O, at least one is catalyzed by light. An empirical rate law, based on the total concentrations of the reactants, is presented, and a more general rate law, based on the concentrations of presumed reactive species, is derived.

  17. RNAi silencing of a cytochrome P450 monooxygenase disrupts the ability of a filamentous fungus, Graphium sp. to grow on short-chain gaseous alkanes and ethers

    USDA-ARS?s Scientific Manuscript database

    Graphium sp. (ATCC 58400), a filamentous fungus, is one of the few eukaryotes that grows on short-chain alkanes and ethers. In this study, we investigated the genetic underpinnings that enable this fungus to catalyze the first step in the alkane and ether oxidation pathway. A gene, CYP52L1, was iden...

  18. A study of the redox properties and methanol oxidation rates for molybdenum-based mixed oxides

    SciTech Connect

    Baldychev, Ivan; Javadekar, Ashay; Buttrey, Doug J.; Vohs, J. M.; Gorte, R. J.

    2011-01-14

    The equilibrium properties of bulk MgMoO4, Zr(MoO4)2, Al2(MoO4)3, SrMoO4, and Cr2(MoO4)3 have been characterized by coulometric titration at 873 K in order to understand the effect of the mixed-cation environment on the Mo6+–Mo4+ redox properties and how this in turn affects reactivity for methanol oxidation. The structures of the oxidized and reduced phases were also characterized by XRD. With SrMoO4, reduction resulted in the formation of SrMoO3; however, each of the other oxides underwent a reversible decomposition. MgMoO4 formed a mixture of crystalline MgO and Mg2Mo3O8; Zr(MoO4)2 reduced to MoO2 and a mixture of monoclinic and tetragonal ZrO2; and Cr2(MoO4)3 formed a new crystalline phase. For MgMoO4, Zr(MoO4)2, Al2(MoO4)3, and Cr2(MoO4)3, removal of one O/Mo occurred at a P(O2) of 10-6 atm, corresponding to a ΔG of oxidation of -100 kJ/mol-O2; however, the equilibrium between SrMoO4 and SrMoO3 occurred at 10-26 atm O2, corresponding to a ΔG of oxidation equal to -375 kJ/mol-O2. These thermodynamic properties differ significantly from oxidation of MoO2 to MoO3, for which ΔG is -220 kJ/mol-O2 at 873 K. All of the mixed oxides were essentially inactive for the selective oxidation of methanol, with specific rates that were much lower than that observed for MoO3.

  19. Nitric oxide diffusion rate is reduced in the aortic wall.

    PubMed

    Liu, Xiaoping; Srinivasan, Parthasarathy; Collard, Eric; Grajdeanu, Paula; Zweier, Jay L; Friedman, Avner

    2008-03-01

    Endogenous nitric oxide (NO) plays important physiological roles in the body. As a small diatomic molecule, NO has been assumed to freely diffuse in tissues with a diffusion rate similar to that in water. However, this assumption has not been tested experimentally. In this study, a modified Clark-type NO electrode attached with a customized aorta holder was used to directly measure the flux of NO diffusion across the aortic wall at 37 degrees C. Experiments were carefully designed for accurate measurements of the apparent NO diffusion coefficient D and the partition coefficient alpha in the aortic wall. A mathematical model was presented for analyzing experimental data. It was determined that alpha = 1.15 +/- 0.11 and D = 848 +/- 45 mum(2)/s (n = 12). The NO diffusion coefficient in the aortic wall is nearly fourfold smaller than the reported diffusion coefficient in solution at 37 degrees C, indicating that NO diffusion in the vascular wall is no longer free, but markedly dependent on the environment in the tissue where these NO molecules are. These results imply that the NO diffusion rate in the vascular wall may be upregulated and downregulated by certain physiological and/or pathophysiological processes affecting the composition of tissues.

  20. Anisotropic interpolation method of silicon carbide oxidation growth rates for three-dimensional simulation

    NASA Astrophysics Data System (ADS)

    Šimonka, Vito; Nawratil, Georg; Hössinger, Andreas; Weinbub, Josef; Selberherr, Siegfried

    2017-02-01

    We investigate anisotropical and geometrical aspects of hexagonal structures of Silicon Carbide and propose a direction dependent interpolation method for oxidation growth rates. We compute three-dimensional oxidation rates and perform one-, two-, and three-dimensional simulations for 4H- and 6H-Silicon Carbide thermal oxidation. The rates of oxidation are computed according to the four known growth rate values for the Si- (0 0 0 1) , a- (1 1 2 bar 0) , m- (1 1 bar 0 0) , and C-face (0 0 0 1 bar) . The simulations are based on the proposed interpolation method together with available thermal oxidation models. We additionally analyze the temperature dependence of Silicon Carbide oxidation rates for different crystal faces using Arrhenius plots. The proposed interpolation method is an essential step towards highly accurate three-dimensional oxide growth simulations which help to better understand the anisotropic nature and oxidation mechanism of Silicon Carbide.

  1. Fatty aldehyde dehydrogenase multigene family involved in the assimilation of n-alkanes in Yarrowia lipolytica.

    PubMed

    Iwama, Ryo; Kobayashi, Satoshi; Ohta, Akinori; Horiuchi, Hiroyuki; Fukuda, Ryouichi

    2014-11-28

    In the n-alkane assimilating yeast Yarrowia lipolytica, n-alkanes are oxidized to fatty acids via fatty alcohols and fatty aldehydes, after which they are utilized as carbon sources. Here, we show that four genes (HFD1-HFD4) encoding fatty aldehyde dehydrogenases (FALDHs) are involved in the metabolism of n-alkanes in Y. lipolytica. A mutant, in which all of four HFD genes are deleted (Δhfd1-4 strain), could not grow on n-alkanes of 12-18 carbons; however, the expression of one of those HFD genes restored its growth on n-alkanes. Production of Hfd2Ap or Hfd2Bp, translation products of transcript variants generated from HFD2 by the absence or presence of splicing, also supported the growth of the Δhfd1-4 strain on n-alkanes. The FALDH activity in the extract of the wild-type strain was increased when cells were incubated in the presence of n-decane, whereas this elevation in FALDH activity by n-decane was not observed in Δhfd1-4 strain extract. Substantial FALDH activities were detected in the extracts of Escherichia coli cells expressing the HFD genes. Fluorescent microscopic observation suggests that Hfd3p and Hfd2Bp are localized predominantly in the peroxisome, whereas Hfd1p and Hfd2Ap are localized in both the endoplasmic reticulum and the peroxisome. These results suggest that the HFD multigene family is responsible for the oxidation of fatty aldehydes to fatty acids in the metabolism of n-alkanes, and raise the possibility that Hfd proteins have diversified by gene multiplication and RNA splicing to efficiently assimilate or detoxify fatty aldehydes in Y. lipolytica. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

  2. Alkane hydroxylase gene (alkB) phylotype composition and diversity in northern Gulf of Mexico bacterioplankton

    PubMed Central

    Smith, Conor B.; Tolar, Bradley B.; Hollibaugh, James T.; King, Gary M.

    2013-01-01

    Natural and anthropogenic activities introduce alkanes into marine systems where they are degraded by alkane hydroxylases expressed by phylogenetically diverse bacteria. Partial sequences for alkB, one of the structural genes of alkane hydroxylase, have been used to assess the composition of alkane-degrading communities, and to determine their responses to hydrocarbon inputs. We present here the first spatially extensive analysis of alkB in bacterioplankton of the northern Gulf of Mexico (nGoM), a region that experiences numerous hydrocarbon inputs. We have analyzed 401 partial alkB gene sequences amplified from genomic extracts collected during March 2010 from 17 water column samples that included surface waters and bathypelagic depths. Previous analyses of 16S rRNA gene sequences for these and related samples have shown that nGoM bacterial community composition and structure stratify strongly with depth, with distinctly different communities above and below 100 m. Although we hypothesized that alkB gene sequences would exhibit a similar pattern, PCA analyses of operational protein units (OPU) indicated that community composition did not vary consistently with depth or other major physical-chemical variables. We observed 22 distinct OPUs, one of which was ubiquitous and accounted for 57% of all sequences. This OPU clustered with AlkB sequences from known hydrocarbon oxidizers (e.g., Alcanivorax and Marinobacter). Some OPUs could not be associated with known alkane degraders, however, and perhaps represent novel hydrocarbon-oxidizing populations or genes. These results indicate that the capacity for alkane hydrolysis occurs widely in the nGoM, but that alkane degrader diversity varies substantially among sites and responds differently than bulk communities to physical-chemical variables. PMID:24376439

  3. Modeling the influence of alkane molecular structure on secondary organic aerosol formation.

    PubMed

    Aumont, Bernard; Camredon, Marie; Mouchel-Vallon, Camille; La, Stéphanie; Ouzebidour, Farida; Valorso, Richard; Lee-Taylor, Julia; Madronich, Sasha

    2013-01-01

    Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapor pressure. Intermediate Volatility Organic Compounds (IVOC) emitted to the atmosphere are expected to be a substantial source of SOA. These emitted IVOC constitute a complex mixture including linear, branched and cyclic alkanes. The explicit gas-phase oxidation mechanisms are here generated for various linear and branched C10-C22 alkanes using the GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) and SOA formation is investigated for various homologous series. Simulation results show that both the size and the branching of the carbon skeleton are dominant factors driving the SOA yield. However, branching appears to be of secondary importance for the particle oxidation state and composition. The effect of alkane molecular structure on SOA yields appears to be consistent with recent laboratory observations. The simulated SOA composition shows, however, an unexpected major contribution from multifunctional organic nitrates. Most SOA contributors simulated for the oxidation of the various homologous series are far too reduced to be categorized as highly oxygenated organic aerosols (OOA). On a carbon basis, the OOA yields never exceeded 10% regardless of carbon chain length, molecular structure or ageing time. This version of the model appears clearly unable to explain a large production of OOA from alkane precursors.

  4. The air-water exchange of C{sub 15}-C{sub 31} n-alkanes in a precipitation-dominated seepage lake.

    SciTech Connect

    Doskey, P. V.; Environmental Research

    2000-01-01

    The air-water exchange of semivolatile n-alkanes in Crystal Lake, a small precipitation-dominated seepage lake in northern Wisconsin, was investigated with modeling and mass balance approaches. The results suggest that atmospheric deposition contributes approximately 80% of the allochthonous input of n-alkanes to Crystal Lake. Atmospheric deposition accounts for about 50% of the total annual input of n-alkanes to Crystal Lake, and an additional 30% is contributed by in situ production of planktonic n-alkanes ({Sigma}C{sub 15}, C{sub 17}, C{sub 19}). Contributions to the particle dry flux of terrestrial n-alkanes ({Sigma}C{sub 25}, C{sub 27}, C{sub 29}, C{sub 31}) by pine pollen dispersal and by dry deposition of particles containing leaf waxes are similar in magnitude and constitute about 60% of the atmospheric input, with particle wet deposition being responsible for the remainder. Approximately 30% of the atmospheric input of the n-alkanes occurs during a two-week episode of pine pollen dispersal in spring. Concentration gradients between gaseous n-alkanes in the atmosphere and dissolved n-alkanes in the water column of Crystal Lake favor volatilization of n-alkanes from the lake surface; however, distributions of dissolved n-alkanes are characteristic of bacteria, and therefore are contained in organic matter and not available for air-water exchange. The estimated net atmospheric input of terrestrial n-alkanes is about 20% less than the settling sediment flux. Additional allochthonous sources of the terrestrial n-alkanes might include diffuse surface runoff or episodes of coarse-particle deposition. The discrepancies in the results from the modeling and mass balance approaches indicate that direct measurements of air-water exchange rates and measurements of the seasonal variations of particle size distributions in air and rain would greatly improve our ability to quantify air-water exchange rates of n-alkanes.

  5. Supported organoiridium catalysts for alkane dehydrogenation

    SciTech Connect

    Baker, R. Thomas; Sattelberger, Alfred P.; Li, Hongbo

    2013-09-03

    Solid supported organoiridium catalysts, a process for preparing such solid supported organoiridium catalysts, and the use of such solid supported organoiridium catalysts in dehydrogenation reactions of alkanes is provided. The catalysts can be easily recovered and recycled.

  6. Separating and characterizing functional alkane degraders from crude-oil-contaminated sites via magnetic nanoparticle-mediated isolation.

    PubMed

    Wang, Xinzi; Zhao, Xiaohui; Li, Hanbing; Jia, Jianli; Liu, Yueqiao; Ejenavi, Odafe; Ding, Aizhong; Sun, Yujiao; Zhang, Dayi

    Uncultivable microorganisms account for over 99% of all species on the planet, but their functions are yet not well characterized. Though many cultivable degraders for n-alkanes have been intensively investigated, the roles of functional n-alkane degraders remain hidden in the natural environment. This study introduces the novel magnetic nanoparticle-mediated isolation (MMI) technology in Nigerian soils and successfully separates functional microbes belonging to the families Oxalobacteraceae and Moraxellaceae, which are dominant and responsible for alkane metabolism in situ. The alkR-type n-alkane monooxygenase genes, instead of alkA- or alkP-type, were the key functional genes involved in the n-alkane degradation process. Further physiological investigation via a BIOLOG PM plate revealed some carbon (Tween 20, Tween 40 and Tween 80) and nitrogen (tyramine, l-glutamine and d-aspartic acid) sources promoting microbial respiration and n-alkane degradation. With further addition of promoter carbon or nitrogen sources, the separated functional alkane degraders significantly improved n-alkane biodegradation rates. This suggests that MMI is a promising technology for separating functional microbes from complex microbiota, with deeper insight into their ecological functions and influencing factors. The technique also broadens the application of the BIOLOG PM plate for physiological research on functional yet uncultivable microorganisms.

  7. Soot Nanostructure And Its Impact Upon The O2 Oxidation Rate

    NASA Technical Reports Server (NTRS)

    Wal, Randy L. Vander; Tomasek, Aaron J.

    2003-01-01

    Studies of soot oxidation have ranged from in situ flame studies to shock tubes to flow reactors. Each of these systems possesses particular advantages and limitations related to temperature, time and chemical environments. Despite the aforementioned differences, these soot oxidation investigations share three striking features. First and foremost is the wide variation in the rates of oxidation. Reported oxidation rates vary by factors of +6 to - 20 relative to the Nagle Strickland-Constable (NSC) rate for graphite oxidation [3]. Rate variations are not surprising, as the temperatures, residence times, types of oxidants and methods of oxidation differ from study to study. Nevertheless, a valid explanation for rate differences of this magnitude has yet to be presented.

  8. Determination of dispersion parameters for oxidizing air and the oxidation rate of calcium sulfites in a pilot desulfurization plant

    SciTech Connect

    Burenkov, D.K.; Derevich, I.V.; Rzaev, A.I.

    1995-10-01

    In the effort to remove sulfur oxides from waste gases, the widest use is gained by desulfurization plants based on wet collection of sulfur dioxide in empty absorbers in which a limestone-gypsum suspension is sprayed, with gypsum being produced as a commodity product. Dispersion of oxidizing air in a model liquid and the oxidation rate of calcium sulfites in a suspension contained in the sump of a pilot desulfurization plant absorber are studied experimentally. Flow velocities, bubble trajectories, and oxidation rates were determined and are presented.

  9. RNAi silencing of a cytochrome P450 monoxygenase disrupts the ability of a filamentous fungus, Graphium sp., to grow on short-chain gaseous alkanes and ethers.

    PubMed

    Trippe, Kristin M; Wolpert, Thomas J; Hyman, Michael R; Ciuffetti, Lynda M

    2014-02-01

    Graphium sp. (ATCC 58400), a filamentous fungus, is one of the few eukaryotes that grows on short-chain alkanes and ethers. In this study, we investigated the genetic underpinnings that enable this fungus to catalyze the first step in the alkane and ether oxidation pathway. A gene, CYP52L1, was identified, cloned and functionally characterized as an alkane-oxidizing cytochrome P450 (GSPALK1). Analysis of CYP52L1 suggests that it is a member of the CYP52 cytochrome P450 family, which is comprised of medium- and long-chain alkane-oxidizing enzymes found in yeasts. However, phylogenetic analysis of GSPALK1 with other CYP52 members suggests they are not closely related. Post-transcriptional ds-RNA-mediated gene silencing of CYP52L1 severely reduced the ability of this fungus to oxidize alkanes and ethers, however, downstream metabolic steps in these pathways were unaffected. Collectively, the results of this study suggest that GSPALK1 is the enzyme that catalyzes the initial oxidation of alkanes and ethers but is not involved in the later steps of alkane or ether metabolism.

  10. A delicate balance of complexation vs. activation of alkanes interacting with [Re(Cp)(CO)(PF3)] studied with NMR and time-resolved IR spectroscopy

    PubMed Central

    Ball, Graham E.; Brookes, Christopher M.; Cowan, Alexander J.; Darwish, Tamim A.; George, Michael W.; Kawanami, Hajime K.; Portius, Peter; Rourke, Jonathan P.

    2007-01-01

    The organometallic alkane complexes Re(Cp)(CO)(PF3)(alkane) and Re(Cp)(CO)2(alkane) have been detected after the photolysis of Re(Cp)(CO)2(PF3) in alkane solvent. NMR and time-resolved IR experiments reveal that the species produced by the interaction of n-pentane with [Re(Cp)(CO)(PF3)] are an equilibrium mixture of Re(Cp)(CO)(PF3)(pentane) and Re(Cp)(CO)(PF3)(pentyl)H. The interaction of cyclopentane with [Re(Cp)(CO)(PF3)] most likely results in a similar equilibrium between cyclopentyl hydride and cyclopentane complexes. An increasing proportion of alkane complex is observed on going from n-pentane to cyclopentane to cyclohexane, where only a small amount, if any, of the cyclohexyl hydride form is present. In general, when [Re(Cp)(CO)(PF3)] reacts with alkanes, the products display a higher degree of oxidative cleavage in comparison with [Re(Cp)(CO)2], which favors alkane complexation without activation. Species with the formula Re(Cp)(CO)(PF3)(alkane) have higher thermal stability and lower reactivity toward CO than the analogous Re(Cp)(CO)2(alkane) complexes. PMID:17435163

  11. Solar photothermochemical alkane reverse combustion.

    PubMed

    Chanmanee, Wilaiwan; Islam, Mohammad Fakrul; Dennis, Brian H; MacDonnell, Frederick M

    2016-03-08

    A one-step, gas-phase photothermocatalytic process for the synthesis of hydrocarbons, including liquid alkanes, aromatics, and oxygenates, with carbon numbers (Cn) up to C13, from CO2 and water is demonstrated in a flow photoreactor operating at elevated temperatures (180-200 °C) and pressures (1-6 bar) using a 5% cobalt on TiO2 catalyst and under UV irradiation. A parametric study of temperature, pressure, and partial pressure ratio revealed that temperatures in excess of 160 °C are needed to obtain the higher Cn products in quantity and that the product distribution shifts toward higher Cn products with increasing pressure. In the best run so far, over 13% by mass of the products were C5+ hydrocarbons and some of these, i.e., octane, are drop-in replacements for existing liquid hydrocarbons fuels. Dioxygen was detected in yields ranging between 64% and 150%. In principle, this tandem photochemical-thermochemical process, fitted with a photocatalyst better matched to the solar spectrum, could provide a cheap and direct method to produce liquid hydrocarbons from CO2 and water via a solar process which uses concentrated sunlight for both photochemical excitation to generate high-energy intermediates and heat to drive important thermochemical carbon-chain-forming reactions.

  12. Solar photothermochemical alkane reverse combustion

    PubMed Central

    Chanmanee, Wilaiwan; Islam, Mohammad Fakrul; Dennis, Brian H.; MacDonnell, Frederick M.

    2016-01-01

    A one-step, gas-phase photothermocatalytic process for the synthesis of hydrocarbons, including liquid alkanes, aromatics, and oxygenates, with carbon numbers (Cn) up to C13, from CO2 and water is demonstrated in a flow photoreactor operating at elevated temperatures (180–200 °C) and pressures (1–6 bar) using a 5% cobalt on TiO2 catalyst and under UV irradiation. A parametric study of temperature, pressure, and partial pressure ratio revealed that temperatures in excess of 160 °C are needed to obtain the higher Cn products in quantity and that the product distribution shifts toward higher Cn products with increasing pressure. In the best run so far, over 13% by mass of the products were C5+ hydrocarbons and some of these, i.e., octane, are drop-in replacements for existing liquid hydrocarbons fuels. Dioxygen was detected in yields ranging between 64% and 150%. In principle, this tandem photochemical–thermochemical process, fitted with a photocatalyst better matched to the solar spectrum, could provide a cheap and direct method to produce liquid hydrocarbons from CO2 and water via a solar process which uses concentrated sunlight for both photochemical excitation to generate high-energy intermediates and heat to drive important thermochemical carbon-chain-forming reactions. PMID:26903631

  13. Pd Particle Size Effects on Methane Dissociation on MgO-supported Pd Nanoparticles and Desorption Kinetics of Small Alkane Molecules on MgO(100)

    NASA Astrophysics Data System (ADS)

    Tait, Steven L., Jr.; Dohnalek, Zdenek; Kay, Bruce D.; Campbell, Charles T.

    2004-03-01

    Oxide-supported Pd nanoparticle catalysts are active in a variety of reactions involving small alkanes, including low-temperature methane combustion. Temperature programmed desorption (TPD) was used to study the adsorption of small alkane molecules, C_nH_2n+2 (n=1-10), on the MgO(100) surface at low temperatures (24 K). Hydrocarbon molecules are deposited on the surface by a highly collimated molecular beam with a well-defined kinetic energy. The sample is heated at a controlled rate and desorption products are observed by QMS. Adsorption energy increases linearly with alkane chain length with a small y-intercept. Dissociative adsorption probability of methane on MgO-supported Pd particles (<5 nm dia.) is measured by titration of C fragments with molecular oxygen beam. Dissociation probability is observed to increase with decreasing Pd particle size. PNNL is a multiprogram National Laboratory operated for the U.S. Department of Energy by Battelle Memorial Institute under contract DE-AC06-76RLO 1830. SLT supported by a UW/PNNL Joint Institute for Nanotechnology fellowship.

  14. Secondary organic aerosol formation from intermediate-volatility organic compounds: cyclic, linear, and branched alkanes.

    PubMed

    Tkacik, Daniel S; Presto, Albert A; Donahue, Neil M; Robinson, Allen L

    2012-08-21

    Intermediate volatility organic compounds (IVOCs) are an important class of secondary organic aerosol (SOA) precursors that have not been traditionally included in chemical transport models. A challenge is that the vast majority of IVOCs cannot be speciated using traditional gas chromatography-based techniques; instead they are classified as an unresolved complex mixture (UCM) that is presumably made up of a complex mixture of branched and cyclic alkanes. To better understand SOA formation from IVOCs, a series of smog chamber experiments was conducted with different alkanes, including cyclic, branched, and linear compounds. The experiments focused on freshly formed SOA from hydroxyl (OH) radical-initiated reactions under high-NO(x) conditions at typical atmospheric organic aerosol concentrations (C(OA)). SOA yields from cyclic alkanes were comparable to yields from linear alkanes three to four carbons larger in size. For alkanes with equivalent carbon numbers, branched alkanes had the lowest SOA mass yields, ranging between 0.05 and 0.08 at a C(OA) of 15 μg m(-3). The SOA yield of branched alkanes also depends on the methyl branch position on the carbon backbone. High-resolution aerosol mass spectrometer data indicate that the SOA oxygen-to-carbon ratios were largely controlled by the carbon number of the precursor compound. Depending on the precursor size, the mass spectrum of SOA produced from IVOCs is similar to the semivolatile-oxygenated and hydrocarbon-like organic aerosol factors derived from ambient data. Using the new yield data, we estimated SOA formation potential from diesel exhaust and predict the contribution from UCM vapors to be nearly four times larger than the contribution from single-ring aromatics and comparable to that of polycyclic aromatic hydrocarbons after several hours of oxidation at typical atmospheric conditions. Therefore, SOA from IVOCs may be an important contributor to urban OA and should be included in SOA models; the yield data

  15. Evolution of an alkane-inducible biosensor for increased responsiveness to short-chain alkanes.

    PubMed

    Reed, Ben; Blazeck, John; Alper, Hal

    2012-04-15

    Synthetic alkane-inducible biosensors have applications as detectors for environmental hydrocarbon contamination and as novel inducible expression systems with low-cost inducers. Here, we have assembled and evolved an alkane-responsive biosensor with a fluorescence output signal in Escherichia coli by utilizing regulatory machinery from Pseudomonas putida's alkane metabolism. Within our system, the transcriptional regulator, AlkSp, is activated by the presence of alkanes and binds to the P(alkB) promoter, stimulating transcription of a Green Fluorescent Protein reporter. Through two successive rounds of directed evolution via error prone PCR and fluorescence activated cell sorting, we isolated alkS mutants enabling up to a 5 fold increase in fluorescence output signal in response to short-chain alkanes such as hexane and pentane. Further characterization of selected mutants demonstrated altered responsiveness to a wide range of linear alkanes (pentane to dodecane). Sequence analysis highlighted the S470T mutation as a likely candidate responsible for increased effectiveness of the AlkS protein for short-chain alkanes. This work represents the first evolution of a synthetic biosensor system for alkanes.

  16. Characterization of the medium- and long-chain n-alkanes degrading Pseudomonas aeruginosa strain SJTD-1 and its alkane hydroxylase genes.

    PubMed

    Liu, Huan; Xu, Jing; Liang, Rubing; Liu, Jianhua

    2014-01-01

    A gram-negative aliphatic hydrocarbon-degrading bacterium SJTD-1 isolated from oil-contaminated soil was identified as Pseudomonas aeruginosa by comparative analyses of the 16S rRNA sequence, phenotype, and physiological features. SJTD-1 could efficiently mineralize medium- and long-chain n-alkanes (C12-C30) as its sole carbon source within seven days, showing the most optimal growth on n-hexadecane, followed by n-octadecane, and n-eicosane. In 36 h, 500 mg/L of tetradecane, hexadecane, and octadecane were transformed completely; and 2 g/L n-hexadecane was degraded to undetectable levels within 72 h. Two putative alkane-degrading genes (gene 3623 and gene 4712) were characterized and our results indicated that their gene products were rate-limiting enzymes involved in the synergetic catabolism of C12-C16 alkanes. On the basis of bioinformatics and transcriptional analysis, two P450 monooxygenases, along with a putative AlmA-like oxygenase, were examined. Genetically defective mutants lacking the characteristic alkane hydroxylase failed to degrade n-octadecane, thereby suggesting a different catalytic mechanism for the microbial transformation of alkanes with chain lengths over C18.

  17. (19)F Oximetry with semifluorinated alkanes.

    PubMed

    Kegel, Stefan; Chacon-Caldera, Jorge; Tsagogiorgas, Charalambos; Theisinger, Bastian; Glatting, Gerhard; Schad, Lothar R

    2016-12-01

    This work examines the variation of longitudinal relaxation rate R1(= 1/T1) of the (19)F-CF3-resonance of semifluorinated alkanes (SFAs) with oxygen tension (pO2), temperature (T) and pH in vitro. Contrary to their related perfluorocarbons (PFCs), SFA are amphiphilic and facilitate stable emulsions, a prerequisite for clinical use. A linear relationship between R1 and pO2 was confirmed for the observed SFAs at different temperatures. Using a standard saturation recovery sequence, T1 has been successfully measured using fluorine (19)F-MRI with a self-constructed birdcage resonator at 9.4 T. A calibration curve to calculate pO2 depending on T and R1 was found for each SFA used. In contrast to the commonly used PFC, SFAs are less sensitive to changes in pO2, but more sensitive to changes in temperature. The influence of pH to R1 was found to be negligible.

  18. Comparison of the sputter rates of oxide films relative to the sputter rate of SiO{sub 2}

    SciTech Connect

    Baer, D. R.; Engelhard, M. H.; Lea, A. S.; Nachimuthu, P.; Droubay, T. C.; Kim, J.; Lee, B.; Mathews, C.; Opila, R. L.; Saraf, L. V.; Stickle, W. F.; Wallace, R. M.; Wright, B. S.

    2010-09-15

    There is a growing interest in knowing the sputter rates for a wide variety of oxides because of their increasing technological importance in many different applications. To support the needs of users of the Environmental Molecular Sciences Laboratory, a national scientific user facility, as well as our research programs, the authors made a series of measurements of the sputter rates from oxide films that have been grown by oxygen plasma-assisted molecular beam epitaxy, pulsed laser deposition, atomic layer deposition, electrochemical oxidation, or sputter deposition. The sputter rates for these oxide films were determined in comparison with those from thermally grown SiO{sub 2}, a common reference material for sputter rate determination. The film thicknesses and densities for most of these oxide films were measured using x-ray reflectivity. These oxide films were mounted in an x-ray photoelectron or Auger electron spectrometer for sputter rate measurements using argon ion sputtering. Although the primary objective of this work was to determine relative sputter rates at a fixed angle, the measurements also examined (i) the angle dependence of the relative sputter rates, (ii) the energy dependence of the relative sputter rates, and (iii) the extent of ion beam induced reduction for some oxides. Oxide films examined include SiO{sub 2}, Al{sub 2}O{sub 3}, CeO{sub 2}, Cr{sub 2}O{sub 3}, Fe{sub 2}O{sub 3}, HfO{sub 2}, In-Sn oxide, Ta{sub 2}O{sub 5}, TiO{sub 2} (anatase, rutile, and amorphous), and ZnO. The authors found that the sputter rates for the oxides can vary up to a factor of 2 (usually lower) from that observed for SiO{sub 2}. The ratios of sputter rates relative to those of SiO{sub 2} appear to be relatively independent of ion beam energy in the range of 1-4 kV and for incident angles <50 deg. As expected, the extent of ion beam induced reduction of the oxides varies with the sputter angle.

  19. Statistical analysis of oxidation rates for K Basin fuel in dry air

    SciTech Connect

    Trimble, D.J.

    1998-02-06

    Test data from oxidation of K Basin fuel (SNF) samples in dry air were reviewed, and linear reaction rates were derived on a time-average basis. The derived rates were compared to literature data for unirradiated uranium in dry air using rate law of the form log(rate) = a + b (I/T). The analyses found differences between the SNF data and the literature data. Oxidation rate below 150 C was higher for K Basin fuel than for unirradiated uranium.

  20. Relative rates of nitric oxide and nitrous oxide production by nitrifiers, denitrifiers, and nitrate respirers

    NASA Technical Reports Server (NTRS)

    Anderson, I. C.; Levine, J. S.

    1986-01-01

    An account is given of the atmospheric chemical and photochemical effects of biogenic nitric and nitrous oxide emissions. The magnitude of the biogenic emission of NO is noted to remain uncertain. Possible soil sources of NO and N2O encompass nitrification by autotropic and heterotropic nitrifiers, denitrification by nitrifiers and denitrifiers, nitrate respiration by fermenters, and chemodenitrification. Oxygen availability is the primary determinant of these organisms' relative rates of activity. The characteristics of this major influence are presently investigated in light of the effect of oxygen partial pressure on NO and N2O production by a wide variety of common soil-nitrifying, denitrifying, and nitrate-respiring bacteria under laboratory conditions. The results obtained indicate that aerobic soils are primary sources only when there is sufficient moisture to furnish anaerobic microsites for denitrification.

  1. Relative rates of nitric oxide and nitrous oxide production by nitrifiers, denitrifiers, and nitrate respirers

    NASA Technical Reports Server (NTRS)

    Anderson, I. C.; Levine, J. S.

    1986-01-01

    An account is given of the atmospheric chemical and photochemical effects of biogenic nitric and nitrous oxide emissions. The magnitude of the biogenic emission of NO is noted to remain uncertain. Possible soil sources of NO and N2O encompass nitrification by autotropic and heterotropic nitrifiers, denitrification by nitrifiers and denitrifiers, nitrate respiration by fermenters, and chemodenitrification. Oxygen availability is the primary determinant of these organisms' relative rates of activity. The characteristics of this major influence are presently investigated in light of the effect of oxygen partial pressure on NO and N2O production by a wide variety of common soil-nitrifying, denitrifying, and nitrate-respiring bacteria under laboratory conditions. The results obtained indicate that aerobic soils are primary sources only when there is sufficient moisture to furnish anaerobic microsites for denitrification.

  2. Fasting Hyperglycemia Predicts Lower Rates of Weight Gain by Increased Energy Expenditure and Fat Oxidation Rate

    PubMed Central

    Thearle, Marie S.; Bogardus, Clifton; Krakoff, Jonathan

    2015-01-01

    Context: Increased adiposity and insulin resistance are associated with hyperglycemia and previous studies have reported that higher glucoses are associated with lower rates of weight gain. One possible mechanism is via increased energy expenditure (EE). Objective: To assess the relationships between changes in EE during spontaneous weight gain and concomitant changes in glucose levels. Design and Participants: Body composition, metabolic, and glycemic data were available from nondiabetic Native Americans who underwent two measurements of 24-h EE during eucaloric feeding in a metabolic chamber (N = 144; time between measurements: 5.0 ± 3.3 years) or resting EE by ventilated hood system during the euglycemic-hyperinsulinemic clamp (N = 261; 4.5 ± 3.2 years). Long-term follow-up data (8.3 ± 4.3 years) for weight and body composition were available in 131 and 122 subjects, respectively. Main Outcome Measures: Twenty four hour EE and respiratory quotient (RQ), resting (RMR), and sleeping (SMR) metabolic rates, glucose, and insulin levels, basal glucose output (BGO). Results: Weight gain-associated increase in fasting plasma glucose (FPG) levels was accompanied with decreased 24-h RQ (partial R = −0.24, P = .002) and increased 24-h EE, RMR, SMR, and fat oxidation after accounting for changes in body composition (partial R: 0.12 to 0.19, all P ≤ .05). Upon weight gain, BGO tended to increase (P = .07), while insulin infusion induced a decrease in EE (P = .04). Higher baseline FPG predicted lower rates of future weight gain (partial R = −0.18, P = .04). Conclusions: Higher FPG after weight gain was associated with greater-than-expected increase in EE. The rise in BGO and the insulin-induced EE suppression at follow-up indicate that increased hepatic gluconeogenesis may be an important mediator of EE changes associated with weight gain. PMID:25559400

  3. Comparison of the Sputter Rates of Oxide Films Relative to the Sputter Rate of SiO2

    SciTech Connect

    Baer, Donald R.; Engelhard, Mark H.; Lea, Alan S.; Nachimuthu, Ponnusamy; Droubay, Timothy C.; Kim, J.; Lee, B.; Mathews, C.; Opila, R. L.; Saraf, Laxmikant V.; Stickle, William F.; Wallace, Robert; Wright, B. S.

    2010-09-02

    Because of the increasing technological importance of oxide films for a variety of applications, there is a growing interest in knowing the sputter rates for a wide variety of oxides. To support needs of users of the Environmental Molecular Sciences Laboratory (EMSL) User facility as well as our research programs, we have made a series of measurements of the sputter rates for oxide films that have been grown by oxygen plasma assisted molecular beam epitaxy (OPA-MBE), pulsed laser deposition (PLD), Atomic Layer Deposition (ALD), electrochemical oxidation, or sputter deposition. The sputter rates for these oxide films were determined in comparison to the sputter rates for thermally grown SiO2, a common sputter rate reference material. The film thicknesses and densities of these films were usually measured using x-ray reflectivity (XRR). These samples were mounted in an x-ray photoelectron spectroscopy (XPS) system or an Auger electron spectrometer for sputtering measurements using argon ion sputtering. Although the primary objective was to determine relative sputter rates at a fixed angle, the measurements were also used to determine: i) the angle dependence of the relative sputter rates; ii) the energy dependence of the relative sputter rates; and iii) the extent of ion beam reduction for the various oxides. Materials examined include: SiO2 (reference films), Al2O3, CeO2, Cr2O3, Fe2O3, HfO2, ITO (In-Sn-oxide) Ta2O5, TiO2 (anatase and rutile) and ZnO. We find that the sputter rates for the oxides can vary up to a factor of two (usually slower) from that observed for SiO2. The ratios of sputter rates to SiO2 appear to be relatively independent of ion beam energy for the range of 1kV to 4 kV and for incident angles of less than 50º. As expected, the ion beam reduction of the oxides varies with the sputter angle. These studies demonstrate that we can usually obtain sputter rate reproducibility better than 5% for similar oxide films.

  4. Biomimetic Oxidation Studies. 11. Alkane Functionalization in Aqueous Solution Utilizing in Situ Formed [Fe(2)O(eta(1)-H(2)O)(eta(1)-OAc)(TPA)(2)](3+), as an MMO Model Precatalyst, Embedded in Surface-Derivatized Silica and Contained in Micelles.

    PubMed

    Neimann, Karine; Neumann, Ronny; Rabion, Alain; Buchanan, Robert M.; Fish, Richard H.

    1999-07-26

    The biomimetic, methane monooxygenase enzyme (MMO) precatalyst, [Fe(2)O(eta(1)-H(2)O)(eta(1)-OAc)(TPA)(2)](3+) (TPA = tris[(2-pyridyl)methyl]amine), 1, formed in situ at pH 4.2 from [Fe(2)O(&mgr;-OAc)(TPA)(2)](3+), 2, was embedded in an amorphous silicate surface modified by a combination of hydrophilic poly(ethylene oxide) and hydrophobic poly(propylene oxide). The resulting catalytic assembly was found to be a biomimetic model for the MMO active site within a hydrophobic macroenvironment, allowing alkane functionalization with tert-butyl hydroperoxide (TBHP)/O(2) in an aqueous reaction medium (pH 4.2). For example, cyclohexane was oxidized to a mixture of cyclohexanone, cyclohexanol, and cyclohexyl-tert-butyl peroxide, in a ratio of approximately 3:1:2. The balance between poly(ethylene oxide) and poly(propylene oxide), tethered on the silica surface, was crucial for maximizing the catalytic activity. The silica-based catalytic assembly showed reactivity somewhat higher in comparison to an aqueous micelle system utilizing the surfactant, cetyltrimethylammonium hydrogen sulfate at its critical micelle concentration, in which functionalization of cyclohexane with TBHP/O(2) in the presence of 1 was also studied at pH 4.2 and was found to provide similar products: cyclohexanol, cyclohexanone, and cyclohexyl-tert-butyl peroxide, in a ratio of approximately 2:3:1. Moreover, the mechanism for both the silica-based catalytic assembly and the aqueous micelle system was found to occur via the Haber-Weiss process, in which redox chemistry between 1 and TBHP provides both the t-BuO(*)() and t-BuOO(*)()( )()radicals. The t-BuO(*)()( )()radical initiates the C-H functionalization reaction to form the carbon radical, followed by O(2) trapping, to provide cyclohexyl hydroperoxide, which produces the cyclohexanol and cyclohexanone in the presence of 1, whereas the coupling product emanates from t-BuOO(*)() and cyclohexyl radicals. A discussion concerning both approaches for

  5. Using the alkanes and long-chain alcohols of plant cuticular wax to estimate diet composition and the intakes of mixed forages in sheep consuming a known amount of alkane-labelled supplement.

    PubMed

    Dove, H; Charmley, E

    2008-10-01

    almost two-thirds of estimates based on (LCOH + alkanes) had lower error than those found with alkanes alone. The results confirm that supplements labelled with plant wax components can be used to estimate forage intake, and also show that the LCOH are useful markers for estimating diet composition. Intakes were also computed using a combination of natural LCOH concentrations in the diet and the daily dose rate of even-chain alkanes administered by intra-ruminal device. Differences between intakes so estimated and the measured intakes were closely related to the difference in faecal recovery between the LCOH/alkane pair used to estimate intake, by an amount close to that expected on theoretical grounds. It is concluded that the use of plant wax LCOH, especially in combination with alkanes, will result in improved estimates of diet composition and intake in grazing animals.

  6. Enhanced charge trapping in bipolar spacer oxides during low-dose-rate irradiation

    SciTech Connect

    Fleetwood, D.M.; Reber, R.A. Jr.; Winokur, P.S.; Kosier, S.L.; Schrimpf, R.D.; Nowlin, R.N.; Pease, R.L.; DeLaus, M.

    1994-03-01

    Thermally-stimulated-current and capacitance-voltage measurements reveal enhanced hole trapping in bipolar spacer-oxide capacitors irradiated at 0 V at low dose rates. Possible mechanisms and implications for bipolar low-rate response are discussed.

  7. RATES OF HYDROUS FERRIC OXIDE CRYSTALLIZATION AND THE INFLUENCE ON COPRECIPITATED ARSENATE

    EPA Science Inventory

    Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 ?C. Compa...

  8. RATES OF HYDROUS FERRIC OXIDE CRYSTALLIZATION AND THE INFLUENCE ON COPRECIPITATED ARSENATE

    EPA Science Inventory

    Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 ?C. Compa...

  9. Measurement and modeling of oxidation rate of hydrogen isotopic gases by soil.

    PubMed

    Ota, Masakazu; Yamazawa, Hiromi; Moriizumi, Jun; Iida, Takao

    2007-01-01

    Measurements of oxidation rate of hydrogen isotopic gases by soil were made to model HT oxidation rate by soil. Soil was sampled at a cultivated farmland and laboratory measurements of the oxidation rate of H(2) and D(2) gases simulating HT gas were carried out under controlled conditions of soil. The oxidation rate increased with increase of H(2) or D(2) concentration in air and nearly saturated at high concentration. The oxidation rate was low under extremely dry and wet soil conditions and was the highest at soil water content of 8-14 w/w%. The oxidation rate increased exponentially with increasing soil temperature and was the highest at 46 degrees C. Michaelis constant K(m) increased exponentially with increasing soil temperature. Oxidation rate of H(2) was generally higher than that of D(2), while K(m) of H(2) was generally lower than that of D(2). From these results, oxidation rate of HT was modeled as a product of the functions that represent dependency on each soil factor.

  10. Adaptation of the Hydrocarbonoclastic Bacterium Alcanivorax borkumensis SK2 to Alkanes and Toxic Organic Compounds: a Physiological and Transcriptomic Approach

    PubMed Central

    Naether, Daniela J.; Slawtschew, Slavtscho; Stasik, Sebastian; Engel, Maria; Olzog, Martin; Wick, Lukas Y.; Timmis, Kenneth N.

    2013-01-01

    The marine hydrocarbonoclastic bacterium Alcanivorax borkumensis is able to degrade mixtures of n-alkanes as they occur in marine oil spills. However, investigations of growth behavior and physiology of these bacteria when cultivated with n-alkanes of different chain lengths (C6 to C30) as the substrates are still lacking. Growth rates increased with increasing alkane chain length up to a maximum between C12 and C19, with no evident difference between even- and odd-numbered chain lengths, before decreasing with chain lengths greater than C19. Surface hydrophobicity of alkane-grown cells, assessed by determination of the water contact angles, showed a similar pattern, with maximum values associated with growth rates on alkanes with chain lengths between C11 and C19 and significantly lower values for cells grown on pyruvate. A. borkumensis was found to incorporate and modify the fatty acid intermediates generated by the corresponding n-alkane degradation pathway. Cells grown on distinct n-alkanes proved that A. borkumensis is able to not only incorporate but also modify fatty acid intermediates derived from the alkane degradation pathway. Comparing cells grown on pyruvate with those cultivated on hexadecane in terms of their tolerance toward two groups of toxic organic compounds, chlorophenols and alkanols, representing intensely studied organic compounds, revealed similar tolerances toward chlorophenols, whereas the toxicities of different n-alkanols were significantly reduced when hexadecane was used as a carbon source. As one adaptive mechanism of A. borkumensis to these toxic organic solvents, the activity of cis-trans isomerization of unsaturated fatty acids was proven. These findings could be verified by a detailed transcriptomic comparison between cultures grown on hexadecane and pyruvate and including solvent stress caused by the addition of 1-octanol as the most toxic intermediate of n-alkane degradation. PMID:23645199

  11. Adaptation of the hydrocarbonoclastic bacterium Alcanivorax borkumensis SK2 to alkanes and toxic organic compounds: a physiological and transcriptomic approach.

    PubMed

    Naether, Daniela J; Slawtschew, Slavtscho; Stasik, Sebastian; Engel, Maria; Olzog, Martin; Wick, Lukas Y; Timmis, Kenneth N; Heipieper, Hermann J

    2013-07-01

    The marine hydrocarbonoclastic bacterium Alcanivorax borkumensis is able to degrade mixtures of n-alkanes as they occur in marine oil spills. However, investigations of growth behavior and physiology of these bacteria when cultivated with n-alkanes of different chain lengths (C6 to C30) as the substrates are still lacking. Growth rates increased with increasing alkane chain length up to a maximum between C12 and C19, with no evident difference between even- and odd-numbered chain lengths, before decreasing with chain lengths greater than C19. Surface hydrophobicity of alkane-grown cells, assessed by determination of the water contact angles, showed a similar pattern, with maximum values associated with growth rates on alkanes with chain lengths between C11 and C19 and significantly lower values for cells grown on pyruvate. A. borkumensis was found to incorporate and modify the fatty acid intermediates generated by the corresponding n-alkane degradation pathway. Cells grown on distinct n-alkanes proved that A. borkumensis is able to not only incorporate but also modify fatty acid intermediates derived from the alkane degradation pathway. Comparing cells grown on pyruvate with those cultivated on hexadecane in terms of their tolerance toward two groups of toxic organic compounds, chlorophenols and alkanols, representing intensely studied organic compounds, revealed similar tolerances toward chlorophenols, whereas the toxicities of different n-alkanols were significantly reduced when hexadecane was used as a carbon source. As one adaptive mechanism of A. borkumensis to these toxic organic solvents, the activity of cis-trans isomerization of unsaturated fatty acids was proven. These findings could be verified by a detailed transcriptomic comparison between cultures grown on hexadecane and pyruvate and including solvent stress caused by the addition of 1-octanol as the most toxic intermediate of n-alkane degradation.

  12. Excess processing of oxidative damaged bases causes hypersensitivity to oxidative stress and low dose rate irradiation.

    PubMed

    Yoshikawa, Y; Yamasaki, A; Takatori, K; Suzuki, M; Kobayashi, J; Takao, M; Zhang-Akiyama, Q-M

    2015-10-01

    Ionizing radiations such as X-ray and γ-ray can directly or indirectly produce clustered or multiple damages in DNA. Previous studies have reported that overexpression of DNA glycosylases in Escherichia coli (E. coli) and human lymphoblast cells caused increased sensitivity to γ-ray and X-ray irradiation. However, the effects and the mechanisms of other radiation, such as low dose rate radiation, heavy-ion beams, or hydrogen peroxide (H2O2), are still poorly understood. In the present study, we constructed a stable HeLaS3 cell line overexpressing human 8-oxoguanine DNA N-glycosylase 1 (hOGG1) protein. We determined the survival of HeLaS3 and HeLaS3/hOGG1 cells exposed to UV, heavy-ion beams, γ-rays, and H2O2. The results showed that HeLaS3 cells overexpressing hOGG1 were more sensitive to γ-rays, OH(•), and H2O2, but not to UV or heavy-ion beams, than control HeLaS3. We further determined the levels of 8-oxoG foci and of chromosomal double-strand breaks (DSBs) by detecting γ-H2AX foci formation in DNA. The results demonstrated that both γ-rays and H2O2 induced 8-oxoguanine (8-oxoG) foci formation in HeLaS3 cells. hOGG1-overexpressing cells had increased amounts of γ-H2AX foci and decreased amounts of 8-oxoG foci compared with HeLaS3 control cells. These results suggest that excess hOGG1 removes the oxidatively damaged 8-oxoG in DNA more efficiently and therefore generates more DSBs. Micronucleus formation also supported this conclusion. Low dose-rate γ-ray effects were also investigated. We first found that overexpression of hOGG1 also caused increased sensitivity to low dose rate γ-ray irradiation. The rate of micronucleus formation supported the notion that low dose rate irradiation increased genome instability.

  13. A Finite Rate Chemical Analysis of Nitric Oxide Flow Contamination Effects on Scramjet Performance

    NASA Technical Reports Server (NTRS)

    Cabell, Karen F.; Rock, Kenneth E.

    2003-01-01

    The level of nitric oxide contamination in the test gas of the Langley Research Center Arc-Heated Scramjet Test Facility and the effect of the contamination on scramjet test engine performance were investigated analytically. A finite rate chemical analysis was performed to determine the levels of nitric oxide produced in the facility at conditions corresponding to Mach 6 to 8 flight simulations. Results indicate that nitric oxide levels range from one to three mole percent, corroborating previously obtained measurements. A three-stream combustor code with finite rate chemistry was used to investigate the effects of nitric oxide on scramjet performance. Results indicate that nitric oxide in the test gas causes a small increase in heat release and thrust performance for the test conditions investigated. However, a rate constant uncertainty analysis suggests that the effect of nitric oxide ranges from no net effect, to an increase of about 10 percent in thrust performance.

  14. Improved Alkane Production in Nitrogen-Fixing and Halotolerant Cyanobacteria via Abiotic Stresses and Genetic Manipulation of Alkane Synthetic Genes.

    PubMed

    Kageyama, Hakuto; Waditee-Sirisattha, Rungaroon; Sirisattha, Sophon; Tanaka, Yoshito; Mahakhant, Aparat; Takabe, Teruhiro

    2015-07-01

    Cyanobacteria possess the unique capacity to produce alkane. In this study, effects of nitrogen deficiency and salt stress on biosynthesis of alkanes were investigated in three kinds of cyanobacteria. Intracellular alkane accumulation was increased in nitrogen-fixing cyanobacterium Anabaena sp. PCC7120, but decreased in non-diazotrophic cyanobacterium Synechococcus elongatus PCC7942 and constant in a halotolerant cyanobacterium Aphanothece halophytica under nitrogen-deficient condition. We also found that salt stress increased alkane accumulation in Anabaena sp. PCC7120 and A. halophytica. The expression levels of two alkane synthetic genes were not upregulated significantly under nitrogen deficiency or salt stress in Anabaena sp. PCC7120. The transformant Anabaena sp. PCC7120 cells with additional alkane synthetic gene set from A. halophytica increased intracellular alkane accumulation level compared to control cells. These results provide a prospect to improve bioproduction of alkanes in nitrogen-fixing halotolerant cyanobacteria via abiotic stresses and genetic engineering.

  15. In situ detection of anaerobic alkane metabolites in subsurface environments

    PubMed Central

    Agrawal, Akhil; Gieg, Lisa M.

    2013-01-01

    Alkanes comprise a substantial fraction of crude oil and refined fuels. As such, they are prevalent within deep subsurface fossil fuel deposits and in shallow subsurface environments such as aquifers that are contaminated with hydrocarbons. These environments are typically anaerobic, and host diverse microbial communities that can potentially use alkanes as substrates. Anaerobic alkane biodegradation has been reported to occur under nitrate-reducing, sulfate-reducing, and methanogenic conditions. Elucidating the pathways of anaerobic alkane metabolism has been of interest in order to understand how microbes can be used to remediate contaminated sites. Alkane activation primarily occurs by addition to fumarate, yielding alkylsuccinates, unique anaerobic metabolites that can be used to indicate in situ anaerobic alkane metabolism. These metabolites have been detected in hydrocarbon-contaminated shallow aquifers, offering strong evidence for intrinsic anaerobic bioremediation. Recently, studies have also revealed that alkylsuccinates are present in oil and coal seam production waters, indicating that anaerobic microbial communities can utilize alkanes in these deeper subsurface environments. In many crude oil reservoirs, the in situ anaerobic metabolism of hydrocarbons such as alkanes may be contributing to modern-day detrimental effects such as oilfield souring, or may lead to more beneficial technologies such as enhanced energy recovery from mature oilfields. In this review, we briefly describe the key metabolic pathways for anaerobic alkane (including n-alkanes, isoalkanes, and cyclic alkanes) metabolism and highlight several field reports wherein alkylsuccinates have provided evidence for anaerobic in situ alkane metabolism in shallow and deep subsurface environments. PMID:23761789

  16. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated phenyl alkane. 721.536... Substances § 721.536 Halogenated phenyl alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated phenyl alkane (PMN P-89-867)...

  17. 40 CFR 721.10163 - Chloro fluoro alkane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Chloro fluoro alkane (generic). 721... Substances § 721.10163 Chloro fluoro alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as chloro fluoro alkane (PMN...

  18. 40 CFR 721.535 - Halogenated alkane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane (generic). 721.535... Substances § 721.535 Halogenated alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkane (PMN P-01-433) is...

  19. In situ detection of anaerobic alkane metabolites in subsurface environments.

    PubMed

    Agrawal, Akhil; Gieg, Lisa M

    2013-01-01

    Alkanes comprise a substantial fraction of crude oil and refined fuels. As such, they are prevalent within deep subsurface fossil fuel deposits and in shallow subsurface environments such as aquifers that are contaminated with hydrocarbons. These environments are typically anaerobic, and host diverse microbial communities that can potentially use alkanes as substrates. Anaerobic alkane biodegradation has been reported to occur under nitrate-reducing, sulfate-reducing, and methanogenic conditions. Elucidating the pathways of anaerobic alkane metabolism has been of interest in order to understand how microbes can be used to remediate contaminated sites. Alkane activation primarily occurs by addition to fumarate, yielding alkylsuccinates, unique anaerobic metabolites that can be used to indicate in situ anaerobic alkane metabolism. These metabolites have been detected in hydrocarbon-contaminated shallow aquifers, offering strong evidence for intrinsic anaerobic bioremediation. Recently, studies have also revealed that alkylsuccinates are present in oil and coal seam production waters, indicating that anaerobic microbial communities can utilize alkanes in these deeper subsurface environments. In many crude oil reservoirs, the in situ anaerobic metabolism of hydrocarbons such as alkanes may be contributing to modern-day detrimental effects such as oilfield souring, or may lead to more beneficial technologies such as enhanced energy recovery from mature oilfields. In this review, we briefly describe the key metabolic pathways for anaerobic alkane (including n-alkanes, isoalkanes, and cyclic alkanes) metabolism and highlight several field reports wherein alkylsuccinates have provided evidence for anaerobic in situ alkane metabolism in shallow and deep subsurface environments.

  20. Effects of fuel properties on the burning characteristics of collision-merged alkane/water droplets

    SciTech Connect

    Wang, C.H.; Pan, K.L.; Huang, W.C.; Wen, H.C.; Yang, J.Y.; Law, C.K.

    2008-04-15

    The combustion characteristics of freely falling droplets, individually generated by the merging of colliding alkane and water droplets, were experimentally investigated. The outcome of the collision droplets was first studied and then the subsequent burning processes such as the flame appearance, ignition and burning behaviors were recorded, through either visual observation or microphotography with the aid of stroboscopic lighting. If the merged droplets were exhibited in an insertive manner, while the water droplet inserted into the alkane droplet, these yield the burning behaviors prior to the end of flame were very much similar to that of pure alkane. The burning was ended with droplet extinction for lower-C alkane, and with either droplet ''flash vaporization'' or extinction for hexadecane. And if the merged droplets were in adhesive manner, for hexadecane with large water content, they either could not be ignited for the large merged droplets, or be ignited with a much prolonged ignition delay, followed by a soot-reducing flame and an ending of droplet extinction for the small merged droplets. ''Homogeneous'' explosion was not observed in any of the tests, and ''heterogeneous'' explosion, induced by trapped air bubbles, occasionally occurred for merged droplets with C-atom in alkane is higher than dodecane. And the sudden disappearance of droplet definitely decreased the burning time and thus enhanced the burning intensity. Besides, the fuel mass consumption rates were increased, even in the cases that having droplet extinction, because of the enlargement of the surface area due to the stuffing of water droplet. (author)

  1. Geologic seepage of methane and light alkanes in Los Angeles

    NASA Astrophysics Data System (ADS)

    Doezema, L. A.; Chang, K.; Baril, R.; Nwachuku, I.; Contreras, P.; Marquez, A.; Howard, D.

    2013-12-01

    Natural geologic seepage of methane from underground oil and natural gas reservoirs has been suggested to be an underreported part of the global methane budget. Other light alkanes are also given off in combination with the methane seepage, making it possible that geologic seepage is also a potentially significant global source of these light alkanes. This study reports C1-C5 findings from geologic seepage made in the Los Angeles region. Microseepage, invisible escape of gases, was measured primarily at Kenneth Hahn Regional Park, while macroseepage, the visible release of gases, was measured at the La Brea Tar Pits. Samples were collected using stainless steel canisters and flux chambers and were analyzed using gas chromatography with flame ionization detectors (GC-FID). Average microseepage flux rates of 0.95 μg m-2 h-1 for ethane and 0.51 μg m-2 h-1 were found for propane, while average macroseepage rates for methane, ethane, and propane were 664, 19.8, and 18.1 mg m-2 h-1 respectively. Relationships between microseepage flux rate and location of underground oil and natural deposit and earthquake fault lines are presented. Additionally, the relative importance of findings in context with global budgets and local air quality is discussed.

  2. Reflectance spectroscopy of organic compounds: 1. Alkanes

    USGS Publications Warehouse

    Clark, R.N.; Curchin, J.M.; Hoefen, T.M.; Swayze, G.A.

    2009-01-01

    Reflectance spectra of the organic compounds comprising the alkane series are presented from the ultraviolet to midinfrared, 0.35 to 15.5 /??m. Alkanes are hydrocarbon molecules containing only single carbon-carbon bonds, and are found naturally on the Earth and in the atmospheres of the giant planets and Saturn's moon, Titan. This paper presents the spectral properties of the alkanes as the first in a series of papers to build a spectral database of organic compounds for use in remote sensing studies. Applications range from mapping the environment on the Earth, to the search for organic molecules and life in the solar system and throughout the. universe. We show that the spectral reflectance properties of organic compounds are rich, with major diagnostic spectral features throughout the spectral range studied. Little to no spectral change was observed as a function of temperature and only small shifts and changes in the width of absorption bands were observed between liquids and solids, making remote detection of spectral properties throughout the solar system simpler. Some high molecular weight organic compounds contain single-bonded carbon chains and have spectra similar to alkanes even ' when they fall into other families. Small spectral differences are often present allowing discrimination among some compounds, further illustrating the need to catalog spectral properties for accurate remote sensing identification with spectroscopy.

  3. Revised charge equilibration potential for liquid alkanes.

    PubMed

    Davis, Joseph E; Warren, G Lee; Patel, Sandeep

    2008-07-17

    We present a revised liquid alkane force field based on the charge equilibration formalism for incorporating electrostatic nonadditive effects arising from local polarization. The model is a revision of earlier work by Patel and Brooks, specifically addressing deficiencies in the dihedral potential, electrostatic, and Lennard-Jones (van der Waals) parameters of the force field. We discuss refinement of the alkane backbone torsion potential to match high-level ab initio relative conformational energetics for pentane, hexane, and heptane. We further discuss refinement of the electrostatic and Lennard-Jones (van der Waals) parameters to reproduce the experimental polarizability, liquid density, and vaporization enthalpy of hexane. Finally, we calculate bulk liquid properties including densities, vaporization enthalpies, self-diffusion constants, isothermal compressibilities, constant pressure heat capacities, and NMR T 1 relaxation times for a series of linear alkanes ranging from hexane to pentadecane based on the current revised model. We also compute free energies of hydration for pentane, hexane, and heptane. The revised force field offers a significantly improved overall description of these properties relative to the original parametrization. The current alkane force field represents a platform for ongoing development of a CHARMM (Chemistry at Harvard Molecular Mechanics) polarizable force field for lipids and integral membrane proteins.

  4. Anaerobic biodegradation of longer-chain n-alkanes coupled to methane production in oil sands tailings.

    PubMed

    Siddique, Tariq; Penner, Tara; Semple, Kathleen; Foght, Julia M

    2011-07-01

    Extraction of bitumen from mined oil sands ores produces enormous volumes of tailings that are stored in settling basins (current inventory ≥ 840 million m(3)). Our previous studies revealed that certain hydrocarbons (short-chain n-alkanes [C(6)-C(10)] and monoaromatics [toluene, o-xylene, m-xylene]) in residual naphtha entrained in the tailings are biodegraded to CH(4) by a consortium of microorganisms. Here we show that higher molecular weight n-alkanes (C(14), C(16), and C(18)) are also degraded under methanogenic conditions in oil sands tailings, albeit after a lengthy lag (~180 d) before the onset of methanogenesis. Gas chromatographic analyses showed that the longer-chain n-alkanes each added at ~400 mg L(-1) were completely degraded by the resident microorganisms within ~440 d at ~20 °C. 16S rRNA gene sequence analysis of clone libraries implied that the predominant pathway of longer-chain n-alkane metabolism in tailings is through syntrophic oxidation of n-alkanes coupled with CO(2) reduction to CH(4). These studies demonstrating methanogenic biodegradation of longer-chain n-alkanes by microbes native to oil sands tailings may be important for effective management of tailings and greenhouse gas emissions from tailings ponds.

  5. Analysis of alkane-dependent methanogenic community derived from production water of a high-temperature petroleum reservoir.

    PubMed

    Mbadinga, Serge Maurice; Li, Kai-Ping; Zhou, Lei; Wang, Li-Ying; Yang, Shi-Zhong; Liu, Jin-Feng; Gu, Ji-Dong; Mu, Bo-Zhong

    2012-10-01

    Microbial assemblage in an n-alkanes-dependent thermophilic methanogenic enrichment cultures derived from production waters of a high-temperature petroleum reservoir was investigated in this study. Substantially higher amounts of methane were generated from the enrichment cultures incubated at 55 °C for 528 days with a mixture of long-chain n-alkanes (C(15)-C(20)). Stoichiometric estimation showed that alkanes-dependent methanogenesis accounted for about 19.8% of the total amount of methane expected. Hydrogen was occasionally detected together with methane in the gas phase of the cultures. Chemical analysis of the liquid cultures resulted only in low concentrations of acetate and formate. Phylogenetic analysis of the enrichment revealed the presence of several bacterial taxa related to Firmicutes, Thermodesulfobiaceae, Thermotogaceae, Nitrospiraceae, Dictyoglomaceae, Candidate division OP8 and others without close cultured representatives, and Archaea predominantly related to uncultured members in the order Archaeoglobales and CO(2)-reducing methanogens. Screening of genomic DNA retrieved from the alkanes-amended enrichment cultures also suggested the presence of new alkylsuccinate synthase alpha-subunit (assA) homologues. These findings suggest the presence of poorly characterized (putative) anaerobic n-alkanes degraders in the thermophilic methanogenic enrichment cultures. Our results indicate that methanogenesis of alkanes under thermophilic condition is likely to proceed via syntrophic acetate and/or formate oxidation linked with hydrogenotrophic methanogenesis.

  6. Activation of carbon-hydrogen bonds in alkanes and other organic molecules using organotransition metal complexes

    SciTech Connect

    Bergman, R.G.

    1991-10-01

    We have recently begun to investigate the interaction of C-H activating iridium and rhodium complexes with functionalized organic molecules, to determine the effect of functional groups on the process, as well as to investigate the propensity of Ir and Rh to insert into C-H versus other types of X-H bonds. Recent experiments have demonstrated that xenon liquefied at -70{degrees}C and 10 atm pressure serves as an inert solvent for the C-H oxidative addition reaction. We have been able to prepare and isolate, for the first time, C-H oxidative addition products formed from high-melting solid substrates such as naphthalene, adamantane, and even cubane; the latter case represents the first observation of C-H oxidative addition at a tertiary C-H bond. Liquid xenon has also allowed us to carry out more conveniently the C-H oxidative addition reactions of low-boiling gases that are difficult to liquefy, such as methane. Recently we have also been able to carry out analogous studies in the gas phase. Under these conditions, naked'' rather than solvated Cp*Rh(CO) is formed, and this species reacts with cyclohexane at nearly gas-kinetic rates. Under the conditions, collision between Cp*Rh(CO) and cyclohexane is the slowest step in the overall C-H activation process. In contrast, in solution association of solvent with free Cp*Rh(CO) is so rapid that the step involving C-H bond cleavage in the coordinated alkane complex becomes rate-determining. 3 refs., 5 figs.

  7. Activation of carbon-hydrogen bonds in alkanes and other organic molecules using organotransition metal complexes

    SciTech Connect

    Bergman, R.G.

    1991-10-01

    We have recently begun to investigate the interaction of C-H activating iridium and rhodium complexes with functionalized organic molecules, to determine the effect of functional groups on the process, as well as to investigate the propensity of Ir and Rh to insert into C-H versus other types of X-H bonds. Recent experiments have demonstrated that xenon liquefied at -70{degrees}C and 10 atm pressure serves as an inert solvent for the C-H oxidative addition reaction. We have been able to prepare and isolate, for the first time, C-H oxidative addition products formed from high-melting solid substrates such as naphthalene, adamantane, and even cubane; the latter case represents the first observation of C-H oxidative addition at a tertiary C-H bond. Liquid xenon has also allowed us to carry out more conveniently the C-H oxidative addition reactions of low-boiling gases that are difficult to liquefy, such as methane. Recently we have also been able to carry out analogous studies in the gas phase. Under these conditions, ``naked`` rather than solvated Cp*Rh(CO) is formed, and this species reacts with cyclohexane at nearly gas-kinetic rates. Under the conditions, collision between Cp*Rh(CO) and cyclohexane is the slowest step in the overall C-H activation process. In contrast, in solution association of solvent with free Cp*Rh(CO) is so rapid that the step involving C-H bond cleavage in the coordinated alkane complex becomes rate-determining. 3 refs., 5 figs.

  8. Hydrocarbons disposition, lipid content, and fatty acid composition in trout after long-term dietary exposure to n-alkanes

    SciTech Connect

    Cravedi, J.P.; Tulliez, J.E.

    1983-12-01

    Uptake, distribution, and storage of n-alkanes was studied in rainbow trout receiving a diet containing 1% normal paraffins in the C/sub 13/-C/sub 22/ range. After 3 months, the concentration of hydrocarbons deposited in the whole body reached a steady equilibrium value in the range 700-900 ppm. The most pronounced deposition occurred in the adipose tissue. The n-alkane pattern in the whole body exhibited a profile different from that of the alkane mixture ingested. The alkanes around C/sub 20/ were not retained to any great extent, but as the chain length decreased, the relative amount stored increased. In the liver a marked predominance of even-carbon chain length was observed while in whole fish and in other organs such a phenomenon did not occur. After 5 months, total lipids in the carcass were significantly lower in the test group than in the control group. At the end of the accumulation period, a significant enhancement in the proportion of odd- and even-chain saturated fatty acids from C/sub 14:0/ to C/sub 18:0/ was noted in carcasses of hydrocarbon-fed fish. Myristic, pentadecanoic, and heptadecanoic acids were also significantly more abundant in the liver and adipose tissue of contaminated fish. This increase is attributed to the terminal oxidation of the predominant n-alkanes in the diet into the corresponding fatty acids. During the depuration period, one-half of the trout in each group were fed a hydrocarbon-free diet, while the others were starved. After 2 months, both starved and fed trout had lost approximately 50% of the amount of total n-alkanes stored. The n-alkanes longer than C/sub 16/ were well retained, while short-chain alkane concentration decreased rapidly. 41 references.

  9. Adsorption of alkyltrimethylammonium bromides at water/alkane interfaces: competitive adsorption of alkanes and surfactants.

    PubMed

    Fainerman, V B; Mucic, N; Pradines, V; Aksenenko, E V; Miller, R

    2013-11-12

    The adsorption of members of the homologous series of alkyl trimethylammonium bromides (C(n)TAB) is studied at water/alkane interfaces by drop profile analysis tensiometry. The results are discussed in terms of a competitive adsorption process of alkane and surfactant molecules. A thermodynamic model, derived originally for the adsorption of surfactant mixtures, is adapted such that it describes a competitive adsorption of the surfactant molecules from the aqueous phase and alkane molecules from the oil phase. This new model involves the interspecies attraction coefficient, which mutually increases the adsorption activities of the alkane and C(n)TAB. The effects of the alkyl chain length n of C(n)TABs and the influence of the number of C atoms in the alkane chain are discussed, and the physical quantities are compared to those determined at the aqueous solution/air interface. The new theoretical model for aqueous solution/oil interfaces is also compared to a theory that does not consider the adsorption of alkane. The proposed new model demonstrates good agreement with the experimental data.

  10. Regioselective alkane hydroxylation with a mutant CYP153A6 enzyme

    SciTech Connect

    Koch, Daniel J.; Arnold, Frances H.

    2013-01-29

    Cytochrome P450 CYP153A6 from Myobacterium sp. strain HXN1500 was engineered using in-vivo directed evolution to hydroxylate small-chain alkanes regioselectively. Mutant CYP153A6-BMO1 selectively hydroxylates butane and pentane at the terminal carbon to form 1-butanol and 1-pentanol, respectively, at rates greater than wild-type CYP153A6 enzymes. This biocatalyst is highly active for small-chain alkane substrates and the regioselectivity is retained in whole-cell biotransformations.

  11. Distribution and rate of methane oxidation in sediments of the Florida everglades

    SciTech Connect

    King, G.M.; Roslev, P.; Skovgaard, H. )

    1990-09-01

    Rates of methane emission from intact cores were measured during anoxic dark and oxic light and dark incubations. Rates of methane oxidation were calculated on the basis of oxic incubations by using the anoxic emissions as an estimate of the maximum potential flux. This technique indicated that methane oxidation consumed up to 91% of the maximum potential flux in peat sediments but that oxidation was negligible in marl sediments. Oxygen microprofiles determined for intact cores were comparable to profiles measured in situ. Thus, the laboratory incubations appeared to provide a reasonable approximation of in situ activities. The magnitude of root-associated oxidation rates indicated that belowground plant surfaces may not markedly increase the total capacity for methane consumption. However, the data collectively support the notion that the distribution and activity of methane oxidation have a major impact on the magnitude of atmospheric fluxes from the Everglades.

  12. Modeling Low-Dose-Rate Effects in Irradiated Bipolar-Base Oxides

    SciTech Connect

    Cirba, C.R.; Fleetwood, D.M.; Graves, R.J.; Michez, A.; Milanowski, R.J.; Saigne, F.; Schrimpf, R.D.; Witczak, S.C.

    1998-10-26

    A physical model is developed to quantify the contribution of oxide-trapped charge to enhanced low-dose-rate gain degradation in bipolar junction transistors. Multiple-trapping simulations show that space charge limited transport is partially responsible for low-dose-rate enhancement. At low dose rates, more holes are trapped near the silicon-oxide interface than at high dose rates, resulting in larger midgap voltage shifts at lower dose rates. The additional trapped charge near the interface may cause an exponential increase in excess base current, and a resultant decrease in current gain for some NPN bipolar technologies.

  13. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    NASA Astrophysics Data System (ADS)

    Tsotsis, T. T.; Sane, R. C.

    1987-04-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  14. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    NASA Technical Reports Server (NTRS)

    Tsotsis, T. T.; Sane, R. C.

    1987-01-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  15. The long-chain alkane metabolism network of Alcanivorax dieselolei.

    PubMed

    Wang, Wanpeng; Shao, Zongze

    2014-12-12

    Alkane-degrading bacteria are ubiquitous in marine environments, but little is known about how alkane degradation is regulated. Here we investigate alkane sensing, chemotaxis, signal transduction, uptake and pathway regulation in Alcanivorax dieselolei. The outer membrane protein OmpS detects the presence of alkanes and triggers the expression of an alkane chemotaxis complex. The coupling protein CheW2 of the chemotaxis complex, which is induced only by long-chain (LC) alkanes, sends signals to trigger the expression of Cyo, which participates in modulating the expression of the negative regulator protein AlmR. This change in turn leads to the expression of ompT1 and almA, which drive the selective uptake and hydroxylation of LC alkanes, respectively. AlmA is confirmed as a hydroxylase of LC alkanes. Additional factors responsible for the metabolism of medium-chain-length alkanes are also identified, including CheW1, OmpT1 and OmpT2. These results provide new insights into alkane metabolism pathways from alkane sensing to degradation.

  16. Pulse radiolysis of alkanes: A time-resolved electron paramagnetic resonance study

    SciTech Connect

    Shkrob, I.A.; Trifunac, A.D.

    1994-02-14

    Time-resolved spin-echo-detected electron paramagnetic resonance (EPR) was applied to examine short-lived alkyl radicals formed in pulse radiolysis of liquid alkanes. It was found that the ratio of yields of penultimate and interior radicals in n-alkanes at the instant of their generation is temperature-independent and is ca. 1.25 times greater than the statistical quantity. This higher-than-statistical production of penultimate radicals indicates that the fast ion molecule reactions involving radical cations are a significant route of radical generation. The analysis of spin-echo kinetics in n-alkanes suggests that the alkyl radicals are emissively polarized in spur reactions. this initial polarization rapidly increases with shortening of the aliphatic chain. Another finding is that a long-chain structure of these radicals results in much higher rate of Heisenberg spin exchange relative to the recombination rate. The relative yields of hydrogen abstraction and fragmentation for various branched alkanes are estimated. It is concluded that the fragmentation occurs prior to the formation of radicals in an excited precursor species. Effects of phenolic and alkene additives in radiolysis of n-alkanes are examined. It is demonstrated that phenoxy radicals are produced in dissociative capture of electrons and alkane holes. Another route is a reaction of phenols with free hydrogen atoms. A rapid transfer of singlet correlation from the geminate radical ion pairs is responsible for unusual polarization patterns in the phenoxy and cyclohexadienyl radicals. The significance of these results in the context of cross-linking in polyethylene and higher paraffins is discussed. 56 refs.

  17. Physiochemical Characterization of Iodine (V) Oxide: Hydration Rates

    DTIC Science & Technology

    2014-12-15

    differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and powder X‐ray diffraction (PXRD). In addition, the hydration rates...and thermal gravimetric analysis (TGA) ........................................................4 2 Powder X‐ray patterns of various samples of...relative humidity for various amounts of time .................................8 4 Powder X‐ray diffraction recordings displaying the conversion of

  18. Photo- and thermal-oxidation studies on methyl and phenyl linoleate: anti-oxidant behaviour and rates of reaction.

    PubMed

    Chacón, J N; Gaggini, P; Sinclair, R S; Smith, F J

    2000-09-01

    Photo-peroxidation of methyl and phenyl linoleate in methanol solutions at 25 degrees C, in the presence of methylene blue or 5,10,15,20-tetra(4-pyridyl)-porphyrin (TPP) as sensitisers of singlet oxygen, was found to proceed at more than 30 times the rate of the same polyunsaturated fatty acid (PUFA) ester species undergoing thermal-peroxidation in the bulk phase at 50 degrees C. The addition of anti-oxidants such as butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) quench the thermal-oxidation effectively but appear to only partially inhibit the photosensitized peroxidation reactions. The kinetics of the overall peroxidation reactions were followed by ultraviolet spectroscopy, measurements of hydroperoxide concentration and by high performance liquid chromatography (HPLC). The photo-peroxidation reaction proceeds more rapidly in chloroform solution as the lifetime of singlet oxygen is shown to be over ten times longer in chloroform than methanol. The initial fast reaction kinetics of the photo-peroxidation reactions were evaluated using a pulsed laser technique to show that singlet oxygen reacts competitively with both the anti-oxidants and the polyunsaturated fatty acid ester. Second order kinetic rate constants (in the range 10(5)-10(7) dm(3) mol(-1) s(-1)) were evaluated for the reactivity of singlet oxygen with a range of anti-oxidants and a singlet oxygen quencher, and the results used to explain the effect of anti-oxidants at different concentrations on the rate of the linoleate photo-peroxidation reaction.

  19. Oolong tea increases metabolic rate and fat oxidation in men.

    PubMed

    Rumpler, W; Seale, J; Clevidence, B; Judd, J; Wiley, E; Yamamoto, S; Komatsu, T; Sawaki, T; Ishikura, Y; Hosoda, K

    2001-11-01

    According to traditional Chinese belief, oolong tea is effective in the control of body weight. Few controlled studies, however, have been conducted to measure the impact of tea on energy expenditure (EE) of humans. A randomized cross-over design was used to compare 24-h EE of 12 men consuming each of four treatments: 1) water, 2) full-strength tea (daily allotment brewed from 15 g of tea), 3) half-strength tea (brewed from 7.5 g tea) and 4) water containing 270 mg caffeine, equivalent to the concentration in the full-strength tea treatment. Subjects refrained from consuming caffeine or flavonoids for 4 d prior to the study. Tea was brewed each morning; beverages were consumed at room temperature as five 300 mL servings. Subjects received each treatment for 3 d; on the third day, EE was measured by indirect calorimetry in a room calorimeter. For the 3 d, subjects consumed a typical American diet. Energy content of the diet was tailored to each subject's needs as determined from a preliminary measure of 24-h EE by calorimetry. Relative to the water treatment, EE was significantly increased 2.9 and 3.4% for the full-strength tea and caffeinated water treatments, respectively. This increase over water alone represented an additional expenditure of 281 and 331 kJ/d for subjects treated with full-strength tea and caffeinated water, respectively. In addition, fat oxidation was significantly higher (12%) when subjects consumed the full-strength tea rather than water.

  20. Flash kinetics in liquefied noble gases: Studies of alkane activation and ligand dynamics at rhodium carbonyl centers, and a search for xenon-carbene adducts

    SciTech Connect

    Yeston, Jake Simon

    2001-01-01

    A general introduction is given to place the subsequent chapters in context for the nonspecialist. Results are presented from a low temperature infrared (IR) flash kinetic study of C-H bond activation via photoinduced reaction of Cp*Rh(CO)2 (1) with linear and cyclic alkanes in liquid krypton and liquid xenon solution. No reaction was observed with methane; for all other hydrocarbons studied, the rate law supports fragmentation of the overall reaction into an alkane binding step followed by an oxidative addition step. For the binding step, larger alkanes within each series (linear and cyclic) interact more strongly than smaller alkanes with the Rh center. The second step, oxidative addition of the C-H bond across Rh, exhibits very little variance in the series of linear alkanes, while in the cyclic series the rate decreases with increasing alkane size. Results are presented from an IR flash kinetic study of the photoinduced chemistry of Tp*Rh(CO)2 (5; Tp* = hydridotris(3,5-dimethylpyrazolyl)borato) in liquid xenon solution at –50 °C. IR spectra of the solution taken 2 μs after 308 nm photolysis exhibit two transient bands at 1972-1980 cm-1 and 1992-2000 cm-1, respectively. These bands were assigned to (η3-Tp*)Rh(CO)•Xe and (η2-Tp*)Rh(CO)•Xe solvates on the basis of companion studies using Bp*Rh(CO)2 (9; Bp* = dihydridobis(3,5-dimethyl pyrazolyl)borato). Preliminary kinetic data for reaction of 5 with cyclohexane in xenon solution indicate that both transient bands still appear and that their rates of decay correlate with formation of the product Tp*Rh(CO)(C6H11)(H). The preparation and reactivity of the new complex Bp*Rh(CO)(pyridine) (11) are described. The complex reacts with CH3I to yield the novel Rh carbene hydride complex HB(Me2pz)2Rh(H)(I)(C5H5N)(C(O)Me) (12), resulting from formal addition of CH

  1. Chemical weathering on Mars: Rate of oxidation of iron dissolved in brines

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.

    1993-01-01

    Salts believed to occur in Martian regolith imply that brines occur on Mars, which may have facilitated the oxidation of dissolved Fe(2+) ions after they were released during chemical weathering of basaltic ferromagnesian silicate and iron sulfide minerals. Calculations show that the rate of oxidation of Fe(2+) ions at -35 C in a 6M chloride-sulfate brine that might exist on Mars is about 10(exp 6) times slower that the oxidation rate of iron in ice-cold terrestrial seawater.

  2. Chemical weathering on Mars: Rate of oxidation of iron dissolved in brines

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.

    1993-01-01

    Salts believed to occur in Martian regolith imply that brines occur on Mars, which may have facilitated the oxidation of dissolved Fe(2+) ions after they were released during chemical weathering of basaltic ferromagnesian silicate and iron sulfide minerals. Calculations show that the rate of oxidation of Fe(2+) ions at -35 C in a 6M chloride-sulfate brine that might exist on Mars is about 10(exp 6) times slower that the oxidation rate of iron in ice-cold terrestrial seawater.

  3. Tetramer-dimer equilibrium of oxyhemoglobin mutants determined from auto-oxidation rates.

    PubMed Central

    Griffon, N.; Baudin, V.; Dieryck, W.; Dumoulin, A.; Pagnier, J.; Poyart, C.; Marden, M. C.

    1998-01-01

    One of the main difficulties with blood substitutes based on hemoglobin (Hb) solutions is the auto-oxidation of the hemes, a problem aggravated by the dimerization of Hb tetramers. We have employed a method to study the oxyHb tetramer-dimer equilibrium based on the rate of auto-oxidation as a function of protein concentration. The 16-fold difference in dimer and tetramer auto-oxidation rates (in 20 mM phosphate buffer at pH 7.0, 37 degrees C) was exploited to determine the fraction dimer. The results show a transition of the auto-oxidation rate from low to high protein concentrations, allowing the determination of the tetramer-dimer dissociation coefficient K4,2 = [Dimer] 2/[Tetramer]. A 14-fold increase in K4,2 was observed for addition of 10 mM of the allosteric effector inositol hexaphosphate (IHP). Recombinant hemoglobins (rHb) were genetically engineered to obtain Hb with a lower oxygen affinity than native Hb (Hb A). The rHb alpha2beta2 [(C7) F41Y/(G4) N102Y] shows a fivefold increase in K4,2 at pH 7.0, 37 degrees C. An atmosphere of pure oxygen is necessary in this case to insure fully oxygenated Hb. When this condition is satisfied, this method provides an efficient technique to characterize both the tetramer-dimer equilibrium and the auto-oxidation rates of various oxyHb. For low oxygen affinity Hb equilibrated under air, the presence of deoxy subunits accelerates the auto-oxidation. Although a full analysis is complicated, the auto-oxidation studies for air equilibrated samples are more relevant to the development of a blood substitute based on Hb solutions. The double mutants, rHb alpha2beta2 [(C7) F41Y/(G4) N102A] and rHb alpha2beta2 [(C7) F41Y/(E10) K66T], show a lower oxygen affinity and a higher rate of oxidation than Hb A. Simulations of the auto-oxidation rate versus Hb concentration indicate that very high protein concentrations are required to observe the tetramer auto-oxidation rate. Because the dimers oxidize much more rapidly, even a small

  4. Room temperature dehydrogenation of ethane, propane, linear alkanes C4-C8, and some cyclic alkanes by titanium-carbon multiple bonds.

    PubMed

    Crestani, Marco G; Hickey, Anne K; Gao, Xinfeng; Pinter, Balazs; Cavaliere, Vincent N; Ito, Jun-Ichi; Chen, Chun-Hsing; Mindiola, Daniel J

    2013-10-02

    The transient titanium neopentylidyne, [(PNP)Ti≡C(t)Bu] (A; PNP(-)≡N[2-P(i)Pr2-4-methylphenyl]2(-)), dehydrogenates ethane to ethylene at room temperature over 24 h, by sequential 1,2-CH bond addition and β-hydrogen abstraction to afford [(PNP)Ti(η(2)-H2C═CH2)(CH2(t)Bu)] (1). Intermediate A can also dehydrogenate propane to propene, albeit not cleanly, as well as linear and volatile alkanes C4-C6 to form isolable α-olefin complexes of the type, [(PNP)Ti(η(2)-H2C═CHR)(CH2(t)Bu)] (R = CH3 (2), CH2CH3 (3), (n)Pr (4), and (n)Bu (5)). Complexes 1-5 can be independently prepared from [(PNP)Ti═CH(t)Bu(OTf)] and the corresponding alkylating reagents, LiCH2CHR (R = H, CH3(unstable), CH2CH3, (n)Pr, and (n)Bu). Olefin complexes 1 and 3-5 have all been characterized by a diverse array of multinuclear NMR spectroscopic experiments including (1)H-(31)P HOESY, and in the case of the α-olefin adducts 2-5, formation of mixtures of two diastereomers (each with their corresponding pair of enantiomers) has been unequivocally established. The latter has been spectroscopically elucidated by NMR via C-H coupled and decoupled (1)H-(13)C multiplicity edited gHSQC, (1)H-(31)P HMBC, and dqfCOSY experiments. Heavier linear alkanes (C7 and C8) are also dehydrogenated by A to form [(PNP)Ti(η(2)-H2C═CH(n)Pentyl)(CH2(t)Bu)] (6) and [(PNP)Ti(η(2)-H2C═CH(n)Hexyl)(CH2(t)Bu)] (7), respectively, but these species are unstable but can exchange with ethylene (1 atm) to form 1 and the free α-olefin. Complex 1 exchanges with D2C═CD2 with concomitant release of H2C═CH2. In addition, deuterium incorporation is observed in the neopentyl ligand as a result of this process. Cyclohexane and methylcyclohexane can be also dehydrogenated by transient A, and in the case of cyclohexane, ethylene (1 atm) can trap the [(PNP)Ti(CH2(t)Bu)] fragment to form 1. Dehydrogenation of the alkane is not rate-determining since pentane and pentane-d12 can be dehydrogenated to 4 and 4-d12 with comparable

  5. A diffusionless transition in a normal alkane

    NASA Astrophysics Data System (ADS)

    Nene, Shailesh; Karhu, Eric; Flemming, Roberta L.; Hutter, Jeffrey L.

    2009-12-01

    The normal alkanes are an interesting class of material, both in terms of their intrinsic properties and because many biological materials contain hydrocarbon domains. The normal alkanes often exhibit complicated phase behavior, with phase diagrams containing multiple solid phases. We report here a study of a curious pattern of twinned domains seen in one phase of tricosane (C 23H 48), which we have studied by X-ray diffraction, as well as by optical and atomic force microscopy. This pattern is seen in the rotator R V phase, a monoclinic arrangement of tricosane molecules without orientational order. Transitions between this polymorph and the orthorhombic R I rotator phase lying at higher temperatures preserve features at the molecular level, and thus represent a diffusionless, martensitic-like transformation.

  6. Density functional steric analysis of linear and branched alkanes.

    PubMed

    Ess, Daniel H; Liu, Shubin; De Proft, Frank

    2010-12-16

    Branched alkane hydrocarbons are thermodynamically more stable than straight-chain linear alkanes. This thermodynamic stability is also manifest in alkane bond separation energies. To understand the physical differences between branched and linear alkanes, we have utilized a novel density functional theory (DFT) definition of steric energy based on the Weizäcker kinetic energy. Using the M06-2X functional, the total DFT energy was partitioned into a steric energy term (E(s)[ρ]), an electrostatic energy term (E(e)[ρ]), and a fermionic quantum energy term (E(q)[ρ]). This analysis revealed that branched alkanes have less (destabilizing) DFT steric energy than linear alkanes. The lower steric energy of branched alkanes is mitigated by an equal and opposite quantum energy term that contains the Pauli component of the kinetic energy and exchange-correlation energy. Because the steric and quantum energy terms cancel, this leaves the electrostatic energy term that favors alkane branching. Electrostatic effects, combined with correlation energy, explains why branched alkanes are more stable than linear alkanes.

  7. Density Functional Steric Analysis of Linear and Branched Alkanes

    SciTech Connect

    Ess, Daniel H.; Liu, Shubin; De Proft, Frank

    2010-11-18

    Branched alkane hydrocarbons are thermodynamically more stable than straight-chain linear alkanes. This thermodynamic stability is also manifest in alkane bond separation energies. To understand the physical differences between branched and linear alkanes, we have utilized a novel density functional theory (DFT) definition of steric energy based on the Weizäcker kinetic energy. Using the M06-2X functional, the total DFT energy was partitioned into a steric energy term (Ee[[ρ]), an electrostatic energy term (Ee[ρ]), and a fermionic quantum energy term (Eq[[ρ]). This analysis revealed that branched alkanes have less (destabilizing) DFT steric energy than linear alkanes. The lower steric energy of branched alkanes is mitigated by an equal and opposite quantum energy term that contains the Pauli component of the kinetic energy and exchange-correlation energy. Because the steric and quantum energy terms cancel, this leaves the electrostatic energy term that favors alkane branching. Electrostatic effects, combined with correlation energy, explains why branched alkanes are more stable than linear alkanes.

  8. Oxidation rate of graphitic matrix material in the kinetic regime for VHTR air ingress accident scenarios

    NASA Astrophysics Data System (ADS)

    Lee, Jo Jo; Ghosh, Tushar K.; Loyalka, Sudarshan K.

    2014-08-01

    Data on oxidation rates of matrix-grade graphite in the kinetically-controlled temperature regime of graphite oxidation are needed for safety analysis of High Temperature Gas Cooled Reactors and Very High Temperature Reactors. In this work, the oxidation rate of graphitic matrix material GKrS was measured thermogravimetrically for various oxygen concentrations and with temperatures from 873 to 1873 K. A semi-empirical Arrhenius rate equation was also developed for this temperature range. The activation energy of the graphitic material is found to be about 111.5 kJ/mol. The order of reaction was found to be about 0.89. The surface of oxidized GKrS was characterized by Scanning Electron Microscopy, Electron Dispersive Spectroscopy, Fourier Transform Infrared Spectroscopy and X-ray Photoelectron Spectroscopy.

  9. Parabola-like shaped pH-rate profile for phenols oxidation by aqueous permanganate.

    PubMed

    Du, Juanshan; Sun, Bo; Zhang, Jing; Guan, Xiaohong

    2012-08-21

    Oxidation of phenols by permanganate in the pH range of 5.0-9.0 generally exhibits a parabola-like shape with the maximum reaction rate obtained at pH close to phenols' pK(a). However, a monotonic increase or decrease is observed if phenols' pK(a) is beyond the pH range of 5.0-9.0. A proton transfer mechanism is proposed in which the undissociated phenol is directly oxidized by permanganate to generate products while a phenolate-permanganate adduct, intermediate, is formed between dissociated phenol and permanganate ion and this is the rate-limiting step for phenolates oxidation by permanganate. The intermediate combines with H(+) and then decomposes to products. Rate equations derived based on the steady-state approximation can well simulate the experimentally derived pH-rate profiles. Linear free energy relationships (LFERs) were established among the parameters obtained from the modeling, Hammett constants, and oxygen natural charges in phenols and phenolates. LFERs reveal that chlorine substituents have opposite influence on the susceptibility of phenols and phenolates to permanganate oxidation and phenolates are not necessarily more easily oxidized than their neutral counterparts. The chlorine substituents regulate the reaction rate of chlorophenolates with permanganate mainly by influencing the natural charges of the oxygen atoms of dissociated phenols while they influence the oxidation of undissociated chlorophenols by permanganate primarily by forming intramolecular hydrogen bonding with the phenolic group.

  10. Crystal structure of the TetR family repressor, AlkX, from Dietzia sp. DQ12-45-1b implicated in biodegradation of n-alkanes.

    PubMed

    Liang, Jie-Liang; Gao, Yuan; He, Zheng; Nie, Yong; Wang, Meng; JiangYang, Jing-Hong; Zhang, Xuejun C; Shu, Wen-Sheng; Wu, Xiao-Lei

    2017-08-18

    n-Alkanes are ubiquitous in nature and are widely used by microorganisms as carbon sources. Alkane hydroxylation by alkane monooxygenases is a critical step in the aerobic biodegradation of n-alkanes, which plays important roles in natural alkane attenuation and is used in industrial and environmental applications. The alkane oxidation operon, alkW1-alkX, in an alkane-degrading strain Dietzia sp. DQ12-45-1b, is negatively auto-regulated by the TetR family repressor, AlkX, via a product positive feedback mechanism. To predict the gene regulation mechanism, we determined the 3.1 Å crystal structure of an AlkX homodimer in a non-DNA-bound state. The structure showed traceable long electron density deep inside a hydrophobic cavity of each monomer along the long axis of the helix bundle, and further gas chromatography-mass spectrometry analysis of AlkX revealed that it contained the E.coli-derived long-chain fatty acid molecules as ligand. Moreover, an unusual structural feature of AlkX is an extra helix, α6' , forming a lid-like structure with α6 covering the inducer-binding pocket and occupying the space between the two symmetrical DNA-binding motifs in one dimer, indicating a distinct conformational transition mode in modulating DNA binding. Sequence alignment of AlkX homologs from Dietzia strains showed that the residues involved in DNA and inducer binding are highly conserved, suggesting that the regulation mechanisms of n-alkane hydroxylation is possibly a common characteristic of Dietzia strains.Importance With ubiquitous n-alkanes in nature, many bacteria from terrestrial and aquatic environments have evolved n-alkane oxidation functions. Alkane hydroxylation by alkane monooxygenases is a critical step in the aerobic biodegradation of n-alkanes, which plays important roles in natural alkane attenuation and petroleum-contaminating environment bioremediation. The gene regulation of the most common alkane hydroxylase AlkB has been studied widely in Gram

  11. Interfacial properties of semifluorinated alkane diblock copolymers

    NASA Astrophysics Data System (ADS)

    Pierce, Flint; Tsige, Mesfin; Borodin, Oleg; Perahia, Dvora; Grest, Gary S.

    2008-06-01

    The liquid-vapor interfacial properties of semifluorinated linear alkane diblock copolymers of the form F3C(CF2)n-1(CH2)m-1CH3 are studied by fully atomistic molecular dynamics simulations. The chemical composition and the conformation of the molecules at the interface are identified and correlated with the interfacial energies. A modified form of the Optimized Parameter for Liquid Simulation All-Atom (OPLS-AA) force field of Jorgensen and co-workers [J. Am. Chem. Soc. 106, 6638 (1984); 118, 11225 (1996); J. Phys. Chem. A 105, 4118 (2001)], which includes specific dihedral terms for H-F blocks-and corrections to the H-F nonbonded interaction, is used together with a new version of the exp-6 force field developed in this work. Both force fields yield good agreement with the available experimental liquid density and surface tension data as well as each other over significant temperature ranges and for a variety of chain lengths and compositions. The interfacial regions of semifluorinated alkanes are found to be rich in fluorinated groups compared to hydrogenated groups, an effect that decreases with increasing temperature but is independent of the fractional length of the fluorinated segments. The proliferation of fluorine at the surface substantially lowers the surface tension of the diblock copolymers, yielding values near those of perfluorinated alkanes and distinct from those of protonated alkanes of the same chain length. With decreasing temperatures within the liquid state, chains are found to preferentially align perpendicular to the interface, as previously seen.

  12. Stable Isotope Labeled n-Alkanes to Assess Digesta Passage Kinetics through the Digestive Tract of Ruminants

    PubMed Central

    Warner, Daniel; Ferreira, Luis M. M.; Breuer, Michel J. H.; Dijkstra, Jan; Pellikaan, Wilbert F.

    2013-01-01

    We describe the use of carbon stable isotope (13C) labeled n-alkanes as a potential internal tracer to assess passage kinetics of ingested nutrients in ruminants. Plant cuticular n-alkanes originating from intrinsically 13C labeled ryegrass plants were pulse dosed intraruminally in four rumen-cannulated lactating dairy cows receiving four contrasting ryegrass silage treatments that differed in nitrogen fertilization level (45 or 90 kg nitrogen ha−1) and maturity (early or late). Passage kinetics through the gastrointestinal tract were derived from the δ13C (i.e. the ratio 13C:12C) in apparently undigested fecal material. Isotopic enrichment was observed in a wide range of long-chain n-alkanes (C27–C36) and passage kinetics were determined for the most abundant C29, C31 and C33 n-alkanes, for which a sufficiently high response signal was detected by combustion isotope ratio mass spectrometry. Basal diet treatment and carbon chain length of n-alkanes did not affect fractional passage rates from the rumen (K1) among individual n-alkanes (3.71–3.95%/h). Peak concentration time and transit time showed a quantitatively small, significant (p≤0.002) increase with carbon chain length. K1 estimates were comparable to those of the 13C labeled digestible dry matter fraction (3.38%/h; r = 0.61 to 0.71; p≤0.012). A literature review has shown that n-alkanes are not fermented by microorganisms in the rumen and affirms no preferential depletion of 13C versus 12C. Our results suggest that 13C labeled n-alkanes can be used as nutrient passage tracers and support the reliability of the δ13C signature of digestible feed nutrients as a tool to measure nutrient-specific passage kinetics. PMID:24124493

  13. Seasonal Oxygen Dynamics in a Thermokarst Bog in Interior Alaska: Implications for Rates of Methane Oxidation

    NASA Astrophysics Data System (ADS)

    Neumann, R. B.; Moorberg, C.; Wong, A.; Waldrop, M. P.; Turetsky, M. R.

    2015-12-01

    Methane is a potent greenhouse gas, and wetlands represent the largest natural source of methane to the atmosphere. However, much of the methane generated in anoxic wetlands never gets emitted to the atmosphere; up to >90% of generated methane can get oxidized to carbon dioxide. Thus, oxidation is an important methane sink and changes in the rate of methane oxidation can affect wetland methane emissions. Most methane is aerobically oxidized at oxic-anoxic interfaces where rates of oxidation strongly depend on methane and oxygen concentrations. In wetlands, oxygen is often the limiting substrate. To improve understanding of belowground oxygen dynamics and its impact on methane oxidation, we deployed two planar optical oxygen sensors in a thermokarst bog in interior Alaska. Previous work at this site indicated that, similar to other sites, rates of methane oxidation decrease over the growing season. We used the sensors to track spatial and temporal patterns of oxygen concentrations over the growing season. We coupled these in-situ oxygen measurements with periodic oxygen injection experiments performed against the sensor to quantify belowground rates of oxygen consumption. We found that over the season, the thickness of the oxygenated water layer at the peatland surface decreased. Previous research has indicated that in sphagnum-dominated peatlands, like the one studied here, rates of methane oxidation are highest at or slightly below the water table. It is in these saturated but oxygenated locations that both methane and oxygen are available. Thus, a seasonal reduction in the thickness of the oxygenated water layer could restrict methane oxidation. The decrease in thickness of the oxygenated layer coincided with an increase in the rate of oxygen consumption during our oxygen injection experiments. The increase in oxygen consumption was not explained by temperature; we infer it was due to an increase in substrate availability for oxygen consuming reactions and

  14. Uranium Oxide Rate Summary for the Spent Nuclear Fuel (SNF) Project (OCRWM)

    SciTech Connect

    PAJUNEN, A.L.

    2000-09-20

    The purpose of this document is to summarize the uranium oxidation reaction rate information developed by the Hanford Spent Nuclear Fuel (SNF) Project and describe the basis for selecting reaction rate correlations used in system design. The selection basis considers the conditions of practical interest to the fuel removal processes and the reaction rate application during design studies. Since the reaction rate correlations are potentially used over a range of conditions, depending of the type of evaluation being performed, a method for transitioning between oxidation reactions is also documented. The document scope is limited to uranium oxidation reactions of primary interest to the SNF Project processes. The reactions influencing fuel removal processes, and supporting accident analyses, are: uranium-water vapor, uranium-liquid water, uranium-moist air, and uranium-dry air. The correlation selection basis will consider input from all available sources that indicate the oxidation rate of uranium fuel, including the literature data, confirmatory experimental studies, and fuel element observations. Trimble (2000) summarizes literature data and the results of laboratory scale experimental studies. This document combines the information in Trimble (2000) with larger scale reaction observations to describe uranium oxidation rate correlations applicable to conditions of interest to the SNF Project.

  15. Calcium bisulfite oxidation rate in the wet limestone-gypsum flue gas desulfurization process

    SciTech Connect

    Lancia, A.; Musmarra, D.

    1999-06-01

    In this paper oxidation of calcium bisulfite in aqueous solutions was studied, in connection with the limestone-gypsum flue gas desulfurization process. Experimental measurements of the oxidation rate were carried out in a laboratory scale stirred reactor with continuous feeding of both gas and liquid phase. A calcium bisulfite clear solution was used as liquid phase, and pure oxygen or mixtures of oxygen and nitrogen were used as gas phase. Experiments were carried out at T = 45 C varying the composition of the liquid phase and the oxygen partial pressure. Manganous sulfate was used as catalyst. The analysis of the experimental results showed that the kinetics of bisulfite oxidation in the presence of MnSO{sub 4} follow a parallel reaction mechanism, in which the overall reaction rate can be calculated as the sum between the uncatalyzed rate (3/2 order in bisulfite ion) and the catalyzed reaction rate (first order in manganous ion).

  16. Reflectometry-Ellipsometry Reveals Thickness, Growth Rate, and Phase Composition in Oxidation of Copper.

    PubMed

    Diaz Leon, Juan J; Fryauf, David M; Cormia, Robert D; Zhang, Min-Xian Max; Samuels, Kathryn; Williams, R Stanley; Kobayashi, Nobuhiko P

    2016-08-31

    The oxidation of copper is a complicated process. Copper oxide develops two stable phases at room temperature and standard pressure (RTSP): cuprous oxide (Cu2O) and cupric oxide (CuO). Both phases have different optical and electrical characteristics that make them interesting for applications such as solar cells or resistive switching devices. For a given application, it is necessary to selectively control oxide thickness and cupric/cuprous oxide phase volume fraction. The thickness and composition of a copper oxide film growing on the surface of copper widely depend on the characteristics of as-deposited copper. In this Research Article, two samples, copper films prepared by two different deposition techniques, electron-beam evaporation and sputtering, were studied. As the core part of the study, the formation of the oxidized copper was analyzed routinely over a period of 253 days using spectroscopic polarized reflectometry-spectroscopic ellipsometry (RE). An effective medium approximation (EMA) model was used to fit the RE data. The RE measurements were complemented and validated by using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and X-ray diffraction (XRD). Our results show that the two samples oxidized under identical laboratory ambient conditions (RTSP, 87% average relative humidity) developed unique oxide films following an inverse-logarithmic growth rate with thickness and composition different from each other over time. Discussion is focused on the ability of RE to simultaneously extract thickness (i.e., growth rate) and composition of copper oxide films and on plausible physical mechanisms responsible for unique oxidation habits observed in the two copper samples. It appears that extended surface characteristics (i.e., surface roughness and grain boundaries) and preferential crystalline orientation of as-deposited polycrystalline copper films control the growth kinetics of the copper oxide film. Analysis based on a noncontact

  17. The dose rate effect and the homogeneity of radio-oxidation of plastics

    NASA Astrophysics Data System (ADS)

    Plaček, V.; Bartoníček, B.

    2001-12-01

    The homogeneity of the radio-oxidation of plastics in different depths from the surface has been determined by measuring the thermo-oxidative stability (oxidative induction time - OIT) of irradiated samples. Two materials have been studied: a fire retarding EPR/EVA cable sheathing compound with the thickness of 4.4 mm and a high-density polyethylene (HDPE) (20 mm thick) which was studied for potential use as a material for radioactive waste disposal containers. Both materials have been irradiated using 60Co gamma-ray source at different dose rates in the interval from 8.5 to 8550 Gy/h. Irradiated samples have been cut into very thin slices and the thermo-oxidative stability (OIT) has been measured using differential scanning calorimeter. In this way the dependence of OIT values on the distance from the surface has been obtained for both samples and at applied dose rates.

  18. Catalytic conversion of light alkanes: Proof of concept stage

    SciTech Connect

    Lyons, J.E.

    1995-06-01

    During the stage at which this work ended, our program consisted of two phases which were running concurrently, a research phase and a proof-of-concept phase. The function of the research phase is to design synthesize and perform laboratory tests on new materials in order to enhance the catalytic properties of the suprabiotic systems generated in our laboratories. Increases in catalytic activity and process selectivity as well as extensions of structure-activity relationships are examined. The research phase is intended to provide the process development phases with catalysts having superior properties for light alkane oxidation. The second concurrent phase, is the proof-of-concept phase. In this phase process development of oxidations which have succeeded in the research phase are carried out in a pre-pilot PDU. At the conclusion of the cooperative agreement we were developing a process for the conversion of isobutane to (TBA), We have identified two routes for this transformation: a one-step route directly from isobutane to TBA, and a two-step route in which the isobutane is oxidized first to tert-butyl hydroperoxide and then transformed into TBA catalytically. This paper presents the results of these activities.

  19. Effect of UVA fluence rate on indicators of oxidative stress in human dermal fibroblasts.

    PubMed

    Hoerter, James D; Ward, Christopher S; Bale, Kyle D; Gizachew, Admasu N; Graham, Rachelle; Reynolds, Jaclyn; Ward, Melanie E; Choi, Chesca; Kagabo, Jean-Leonard; Sauer, Michael; Kuipers, Tara; Hotchkiss, Timothy; Banner, Nate; Chellson, Renee A; Ohaeri, Theresa; Gant, Langston; Vanderhill, Leah

    2008-02-19

    During the course of a day human skin is exposed to solar UV radiation that fluctuates in fluence rate within the UVA (290-315 nm) and UVB (315-400 nm) spectrum. Variables affecting the fluence rate reaching skin cells include differences in UVA and UVB penetrating ability, presence or absence of sunscreens, atmospheric conditions, and season and geographical location where the exposure occurs. Our study determined the effect of UVA fluence rate in solar-simulated (SSR) and tanning-bed radiation (TBR) on four indicators of oxidative stress---protein oxidation, glutathione, heme oxygenase-1, and reactive oxygen species--in human dermal fibroblasts after receiving equivalent UVA and UVB doses. Our results show that the higher UVA fluence rate in TBR increases the level of all four indicators of oxidative stress. In sequential exposures when cells are exposed first to SSR, the lower UVA fluence rate in SSR induces a protective response that protects against oxidative stress following a second exposure to a higher UVA fluence rate. Our studies underscore the important role of UVA fluence rate in determining how human skin cells respond to a given dose of radiation containing both UVA and UVB radiation.

  20. Regioselective functionalization of alkanes by sequential dehydrogenation-hydrozirconation.

    PubMed

    Kuninobu, Yoichiro; Ureshino, Tomonari; Yamamoto, Shun-ichi; Takai, Kazuhiko

    2010-08-07

    We have succeeded in formal regioselective functionalization of alkanes by iridium-catalyzed dehydrogenation, hydrozirconation of the resulting alkenes, and electrophilic reaction of the generated alkylzirconium intermediate.

  1. Expanding the alkane oxygenase toolbox: new enzymes and applications.

    PubMed

    van Beilen, Jan B; Funhoff, Enrico G

    2005-06-01

    As highly reduced hydrocarbons are abundant in the environment, enzymes that catalyze the terminal or subterminal oxygenation of alkanes are relatively easy to find. A number of these enzymes have been biochemically characterized in detail, because the potential of alkane hydroxylases to catalyze high added-value reactions is widely recognized. Nevertheless, the industrial application of these enzymes is restricted owing to the complex biochemistry, challenging process requirements, and the limited number of cloned and expressed enzymes. Rational and evolutionary engineering approaches have started to yield more robust and versatile enzyme systems, broadening the alkane oxygenase portfolio. In addition, metagenomic approaches provide access to many novel alkane oxygenase sequences.

  2. [Digestion of alkane yeast carbohydrates by the preruminant calf].

    PubMed

    Besle, J M; Lassalas, B; Thivend, P

    1980-01-01

    Four 15-day old preruminant calves were fitted with two single cannulae, one in the lower ileum and the other in the upper colon. They were fed (on dry-matter basis) a milk substitute containing 35 p. 100 of dried, defatted, micronized alkane yeast (Candida tropicalis). Yeast carbohydrate digestion was studied in the ileum, colon and feces of two calves at 48, 72 and 102 days of age (three periods), using 1 p. 100 of chromic oxide in the diet as a marker. During each period, samples were collected every 2 hours and then pooled to obtain a sample from each part of the digestive tract. The carbohydrates were separated into 40 degrees C water-soluble (neutral and non-neutral) and water-insoluble fractions (fig. 1), and the composition of each was determined by hydrolysis and ion-exchange chromatography. The alkane yeast contained almost 22 p. 100 (in DM) of carbohydrate (table 1), mainly composed of 7.5 p. 100 of non-soluble mannans and 10.1 p. 100 of glucans, both from the hull, and 0.3 p. 100 of soluble galactans. The total carbohydrate content (table 2) was high in the ileum (23 to 28 p. 100 of DM) and low in the feces (3 to 8 p. 100 of DM). At the end of the small intestine, the soluble fraction contained some mannans and galactans partly bonded with non-carbohydrate compounds, but mainly neutral glucans (fig. 2). The apparent digestibilities (table 3, fig. 3) varied between animals and increased with age (total yeast carbohydrates: calf: 0.53 to 0.75; calf 2: 0.62 to 0.85). Mannans were better digested than glucans (calf 2: 0.95 and 0.57, respectively, at 102 days); the galactans were completely digested.

  3. Nitrite reduction with hydrous ferric oxide and Fe(II): stoichiometry, rate, and mechanism.

    PubMed

    Tai, Yuan-Liang; Dempsey, Brian A

    2009-02-01

    Fe(II)/Fe(III) oxide is an important redox couple in environmental systems. Recent studies have revealed unique characteristics of Fe(II)/Fe(III) oxide and reactions with oxidizing or reducing agents. Nitrite was used as an oxidizing agent in this study in order to probe details of these reactions and hydrous ferric oxide (HFO) was used as the Fe(III) oxide phase. Abiotic nitrite reduction is a significant global producer of nitric oxide (a catalyst for production of tropospheric ozone) and nitrous oxide (a greenhouse gas and contributor to stratospheric ozone depletion). All experiments were conducted at pH 6.8 using a strictly anoxic environment with mass-balance measurements for Fe(II). Oxidation of Fe(II) was negligible in the absence of HFO. The reaction was fast in the presence of HFO and was described by d[Fe(II)]/dt=-k(overall)[Fe(II)(diss)][Fe(II)(solid-bound)][NO(2)(-)] (k(overall)=2.59x10(-7)microM(-2)min(-1)) for Fe(II)/Fe(III) molar ratios less than 0.30. The reaction was inhibited for higher Fe(II)/HFO ratios. The concentration of solid-bound Fe(II) was constant after an initial equilibration period and the reaction stopped when dissolved Fe(II) was depleted even though substantial solid-bound Fe(II) and nitrite remained. The results regarding rate-dependence and conservation of solid-bound Fe(II) and inhibition of reaction at high Fe(II)/Fe(III) ratios were similar to our earlier results for the Fe(II)/HFO/O(2) system [Park, B., Dempsey, B.A., 2005. Heterogeneous oxidation of Fe(II) on ferric oxide at neutral pH and a low partial pressure of O(2). Environmental Science and Technology 39(17), 6494-6500.].

  4. Characterization of a Novel Rieske-Type Alkane Monooxygenase System in Pusillimonas sp. Strain T7-7

    PubMed Central

    Li, Ping; Wang, Lei

    2013-01-01

    The cold-tolerant bacterium Pusillimonas sp. strain T7-7 is able to utilize diesel oils (C5 to C30 alkanes) as a sole carbon and energy source. In the present study, bioinformatics, proteomics, and real-time reverse transcriptase PCR approaches were used to identify the alkane hydroxylation system present in this bacterium. This system is composed of a Rieske-type monooxygenase, a ferredoxin, and an NADH-dependent reductase. The function of the monooxygenase, which consists of one large (46.711 kDa) and one small (15.355 kDa) subunit, was further studied using in vitro biochemical analysis and in vivo heterologous functional complementation tests. The purified large subunit of the monooxygenase was able to oxidize alkanes ranging from pentane (C5) to tetracosane (C24) using NADH as a cofactor, with greatest activity on the C15 substrate. The large subunit also showed activity on several alkane derivatives, including nitromethane and methane sulfonic acid, but it did not act on any aromatic hydrocarbons. The optimal reaction condition of the large subunit is pH 7.5 at 30°C. Fe2+ can enhance the activity of the enzyme evidently. This is the first time that an alkane monooxygenase system belonging to the Rieske non-heme iron oxygenase family has been identified in a bacterium. PMID:23417490

  5. Role of Cysteine Residues in the Structure, Stability, and Alkane Producing Activity of Cyanobacterial Aldehyde Deformylating Oxygenase

    PubMed Central

    Hayashi, Yuuki; Yasugi, Fumitaka; Arai, Munehito

    2015-01-01

    Aldehyde deformylating oxygenase (AD) is a key enzyme for alkane biosynthesis in cyanobacteria, and it can be used as a catalyst for alkane production in vitro and in vivo. However, three free Cys residues in AD may impair its catalytic activity by undesired disulfide bond formation and oxidation. To develop Cys-deficient mutants of AD, we examined the roles of the Cys residues in the structure, stability, and alkane producing activity of AD from Nostoc punctiforme PCC 73102 by systematic Cys-to-Ala/Ser mutagenesis. The C71A/S mutations reduced the hydrocarbon producing activity of AD and facilitated the formation of a dimer, indicating that the conserved Cys71, which is located in close proximity to the substrate-binding site, plays crucial roles in maintaining the activity, structure, and stability of AD. On the other hand, mutations at Cys107 and Cys117 did not affect the hydrocarbon producing activity of AD. Therefore, we propose that the C107A/C117A double mutant is preferable to wild type AD for alkane production and that the double mutant may be used as a pseudo-wild type protein for further improvement of the alkane producing activity of AD. PMID:25837679

  6. N2O production rate of an enriched ammonia-oxidising bacteria culture exponentially correlates to its ammonia oxidation rate.

    PubMed

    Law, Yingyu; Ni, Bing-Jie; Lant, Paul; Yuan, Zhiguo

    2012-06-15

    The relationship between the ammonia oxidation rate (AOR) and nitrous oxide production rate (N(2)OR) of an enriched ammonia-oxidising bacteria (AOB) culture was investigated. The AOB culture was enriched in a nitritation system fed with synthetic anaerobic digester liquor. The AOR was controlled by adjusting the dissolved oxygen (DO) and pH levels and also by varying the initial ammonium (NH(4)(+)) concentration in batch experiments. Tests were also performed directly on the parent reactor where a stepwise decrease/increase in DO was implemented to alter AOR. The experimental data indicated a clear exponential relationship between the biomass specific N(2)OR and AOR. Four metabolic models were used to analyse the experimental data. The metabolic model formulated based on aerobic N(2)O production from the decomposition of nitrosyl radical (NOH) predicted the exponential correlation observed experimentally. The experimental data could not be reproduced by models developed on the basis of N(2)O production through nitrite (NO(2)(-)) and nitric oxide (NO) reduction by AOB.

  7. Propane and n-Butane Oxidation by Pseudomonas putida GPo1

    PubMed Central

    Johnson, Erika L.; Hyman, Michael R.

    2006-01-01

    Propane and n-butane inhibit methyl tertiary butyl ether oxidation by n-alkane-grown Pseudomonas putida GPo1. Here we demonstrate that these gases are oxidized by this strain and support cell growth. Both gases induced alkane hydroxylase activity and appear to be oxidized by the same enzyme system used for the oxidation of n-octane. PMID:16391142

  8. Pseudosolubilized n-alkanes analysis and optimization of biosurfactants production by Pseudomonas sp. DG17.

    PubMed

    Hua, Fei; Wang, Hong Qi; Zhao, Yi Cun; Yang, Yan

    2015-05-01

    The pseudosolubilized medium-chain-length n-alkanes during biodegradation process, and optimization of medium composition and culture conditions for rhamnolipid production by Pseudomonas sp. DG17 using Plackett-Burman design and Box-Behnken design, were examined in this study. The results showed that pseudosolubilized concentration of C14 to C20 n-alkanes was higher than that of C24 to C26. After incubation for 120 h, pseudosolubilized C16H34 increased to 2.63 ± 0.21 mg. Meanwhile, biodegradation rates of n-alkanes decreased along with the increase of carbon chain length. Carbon-14 assay suggested that nonlabeled C14H30, C16H34, and C20H42 inhibited the biodegradation of (14)C n-octadecane, and Pseudomonas sp. DG17 utilized different alkanes simultaneously. Three significant variables (substrate concentration, salinity, and C/N) that could influence rhamnolipid production were screened by Plackett-Burman design. Results of Box-Behnken design suggested that rhamnolipid concentration could be achieved at 91.24 mg L(-1) (observed value) or 87.92 mg L(-1) (predicted value) with the optimal levels of concentration, salinity, and C/N of 400 mg L(-1), 1.5 %, and 45, respectively.

  9. Solvent isotope effects on alkane formation by cyanobacterial aldehyde deformylating oxygenase and their mechanistic implications.

    PubMed

    Waugh, Matthew W; Marsh, E Neil G

    2014-09-02

    The reaction catalyzed by cyanobacterial aldehyde deformylating oxygenase is of interest both because of its potential application to the production of biofuels and because of the highly unusual nature of the deformylation reaction it catalyzes. Whereas the proton in the product alkane derives ultimately from the solvent, the identity of the proton donor in the active site remains unclear. To investigate the proton transfer step, solvent isotope effect (SIE) studies were undertaken. The rate of alkane formation was found to be maximal at pH 6.8 and to be the same in D2O or H2O within experimental error, implying that proton transfer is not a kinetically significant step. However, when the ratio of protium to deuterium in the product alkane was measured as a function of the mole fraction of D2O, a (D2O)SIEobs of 2.19 ± 0.02 was observed. The SIE was invariant with the mole fraction of D2O, indicating the involvement of a single protic site in the reaction. We interpret this SIE as most likely arising from a reactant state equilibrium isotope effect on a proton donor with an inverse fractionation factor, for which Φ = 0.45. These observations are consistent with an iron-bound water molecule being the proton donor to the alkane in the reaction.

  10. Cool-flame Extinction During N-Alkane Droplet Combustion in Microgravity

    NASA Technical Reports Server (NTRS)

    Nayagam, Vedha; Dietrich, Daniel L.; Hicks, Michael C.; Williams, Forman A.

    2014-01-01

    Recent droplet combustion experiments onboard the International Space Station (ISS) have revealed that large n-alkane droplets can continue to burn quasi-steadily following radiative extinction in a low-temperature regime, characterized by negative-temperaturecoefficient (NTC) chemistry. In this study we report experimental observations of n-heptane, n-octane, and n-decane droplets of varying initial sizes burning in oxygen/nitrogen/carbon dioxide and oxygen/helium/nitrogen environments at 1.0, 0.7, and 0.5 atmospheric pressures. The oxygen concentration in these tests varied in the range of 14% to 25% by volume. Large n-alkane droplets exhibited quasi-steady low-temperature burning and extinction following radiative extinction of the visible flame while smaller droplets burned to completion or disruptively extinguished. A vapor-cloud formed in most cases slightly prior to or following the "cool flame" extinction. Results for droplet burning rates in both the hot-flame and cool-flame regimes as well as droplet extinction diameters at the end of each stage are presented. Time histories of radiant emission from the droplet captured using broadband radiometers are also presented. Remarkably the "cool flame" extinction diameters for all the three n-alkanes follow a trend reminiscent of the ignition delay times observed in previous studies. The similarities and differences among the n-alkanes during "cool flame" combustion are discussed using simplified theoretical models of the phenomenon

  11. Effect of Reacting Surface Density on the Overall Graphite Oxidation Rate

    SciTech Connect

    Chang H. Oh; Eung Kim; Jong Lim; Richard Schultz; David Petti

    2009-05-01

    Graphite oxidation in an air-ingress accident is presently a very important issue for the reactor safety of the very high temperature gas cooled-reactor (VHTR), the concept of the next generation nuclear plant (NGNP) because of its potential problems such as mechanical degradation of the supporting graphite in the lower plenum of the VHTR might lead to core collapse if the countermeasure is taken carefully. The oxidation process of graphite has known to be affected by various factors, including temperature, pressure, oxygen concentration, types of graphite, graphite shape and size, flow distribution, etc. However, our recent study reveals that the internal pore characteristics play very important roles in the overall graphite oxidation rate. One of the main issues regarding graphite oxidation is the potential core collapse problem that may occur following the degradation of graphite mechanical strength. In analyzing this phenomenon, it is very important to understand the relationship between the degree of oxidization and strength degradation. In addition, the change of oxidation rate by graphite oxidation degree characterization by burn-off (ratio of the oxidized graphite density to the original density) should be quantified because graphite strength degradation is followed by graphite density decrease, which highly affects oxidation rates and patterns. Because the density change is proportional to the internal pore surface area, they should be quantified in advance. In order to understand the above issues, the following experiments were performed: (1)Experiment on the fracture of the oxidized graphite and validation of the previous correlations, (2) Experiment on the change of oxidation rate using graphite density and data collection, (3) Measure the BET surface area of the graphite. The experiments were performed using H451 (Great Lakes Carbon Corporation) and IG-110 (Toyo Tanso Co., Ltd) graphite. The reason for the use of those graphite materials is because

  12. Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes

    DOE PAGES

    Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

    2016-11-01

    In order to gain a deeper mechanistic understanding of water oxidation by [(bda)Ru(L)2] catalysts (bdaH2 = [2,2'-bipyridine]-6,6'-dicarboxylic acid; L = pyridine-type ligand), a series of modified catalysts with one and two trifluoromethyl groups in the 4 position of the bda2– ligand was synthesized and studied using stopped-flow kinetics. The additional $-$CF3 groups increased the oxidation potentials for the catalysts and enhanced the rate of electrocatalytic water oxidation at low pH. Stopped-flow measurements of cerium(IV)-driven water oxidation at pH 1 revealed two distinct kinetic regimes depending on catalyst concentration. At relatively high catalyst concentration (ca. ≥10–4 M), the rate-determining step (RDS)more » was a proton-coupled oxidation of the catalyst by cerium(IV) with direct kinetic isotope effects (KIE > 1). At low catalyst concentration (ca. ≤10–6 M), the RDS was a bimolecular step with kH/kD ≈ 0.8. The results support a catalytic mechanism involving coupling of two catalyst molecules. The rate constants for both RDSs were determined for all six catalysts studied. The presence of $-$CF3 groups had inverse effects on the two steps, with the oxidation step being fastest for the unsubstituted complexes and the bimolecular step being faster for the most electron-deficient complexes. Finally, though the axial ligands studied here did not significantly affect the oxidation potentials of the catalysts, the nature of the ligand was found to be important not only in the bimolecular step but also in facilitating electron transfer from the metal center to the sacrificial oxidant.« less

  13. Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes

    SciTech Connect

    Shaffer, David W.; Xie, Yan; Szalda, David J.; Concepcion, Javier J.

    2016-11-01

    In order to gain a deeper mechanistic understanding of water oxidation by [(bda)Ru(L)2] catalysts (bdaH2 = [2,2'-bipyridine]-6,6'-dicarboxylic acid; L = pyridine-type ligand), a series of modified catalysts with one and two trifluoromethyl groups in the 4 position of the bda2– ligand was synthesized and studied using stopped-flow kinetics. The additional $-$CF3 groups increased the oxidation potentials for the catalysts and enhanced the rate of electrocatalytic water oxidation at low pH. Stopped-flow measurements of cerium(IV)-driven water oxidation at pH 1 revealed two distinct kinetic regimes depending on catalyst concentration. At relatively high catalyst concentration (ca. ≥10–4 M), the rate-determining step (RDS) was a proton-coupled oxidation of the catalyst by cerium(IV) with direct kinetic isotope effects (KIE > 1). At low catalyst concentration (ca. ≤10–6 M), the RDS was a bimolecular step with kH/kD ≈ 0.8. The results support a catalytic mechanism involving coupling of two catalyst molecules. The rate constants for both RDSs were determined for all six catalysts studied. The presence of $-$CF3 groups had inverse effects on the two steps, with the oxidation step being fastest for the unsubstituted complexes and the bimolecular step being faster for the most electron-deficient complexes. Finally, though the axial ligands studied here did not significantly affect the oxidation potentials of the catalysts, the nature of the ligand was found to be important not only in the bimolecular step but also in facilitating electron transfer from the metal center to the sacrificial oxidant.

  14. Measurement of oxidation rate of sulfite in rain water in Yokohama, Japan

    SciTech Connect

    Tanaka, S.; Yamanaka, K.; Hashimoto, Y.

    1986-04-01

    In recent years, the influences of acid rain such as the acidification of lake water, on bio-system by the heavy metals from effluent of soils with acid rain and also on the structural materials of buildings are seriously discussed. Sulfur and nitrogen that are contained in fossil fuels are released into the atmosphere by the fuel combustion as their oxides dissolve in rain drops as sulfite and nitrous ions, where they are further oxidized into sulfate and nitrate ions These ions lower the pH of rain water resulting so-called acid rain. Therefore, it is important to accurately determine these ions in rain water for the investigation of reality of acid rain. However, it is not easy to accurately determine these ions, especially for sulfite ions in rain water, since they are quickly oxidized by the catalytic action of metallic ions such as ferric and manganous ions. And light, temperature, pH of solution and also species and concentrations of dissolved metallic ions as catalysts, must be influential factors for the rate of oxidation of sulfite ions. In this paper, first, the rate of oxidation of sulfite ion in the test solutions by the catalytic reactions of metallic ions was examined, since the metallic ions is most influential in the oxidation of sulfite ion, and then the relations between the rate of oxidation of sulfite ion and the metallic ions were investigated for rain samples. The contribution of hydrogen ion that was produced by the oxidation of sulfite ion to sulfate was also examined for the change of pH values of rain water.

  15. Enhanced biodegradation of alkane hydrocarbons and crude oil by mixed strains and bacterial community analysis.

    PubMed

    Chen, Yu; Li, Chen; Zhou, Zhengxi; Wen, Jianping; You, Xueyi; Mao, Youzhi; Lu, Chunzhe; Huo, Guangxin; Jia, Xiaoqiang

    2014-04-01

    In this study, two strains, Acinetobacter sp. XM-02 and Pseudomonas sp. XM-01, were isolated from soil samples polluted by crude oil at Bohai offshore. The former one could degrade alkane hydrocarbons (crude oil and diesel, 1:4 (v/v)) and crude oil efficiently; the latter one failed to grow on alkane hydrocarbons but could produce rhamnolipid (a biosurfactant) with glycerol as sole carbon source. Compared with pure culture, mixed culture of the two strains showed higher capability in degrading alkane hydrocarbons and crude oil of which degradation rate were increased from 89.35 and 74.32 ± 4.09 to 97.41 and 87.29 ± 2.41 %, respectively. In the mixed culture, Acinetobacter sp. XM-02 grew fast with sufficient carbon source and produced intermediates which were subsequently utilized for the growth of Pseudomonas sp. XM-01 and then, rhamnolipid was produced by Pseudomonas sp. XM-01. Till the end of the process, Acinetobacter sp. XM-02 was inhibited by the rapid growth of Pseudomonas sp. XM-01. In addition, alkane hydrocarbon degradation rate of the mixed culture increased by 8.06 to 97.41 % compared with 87.29 % of the pure culture. The surface tension of medium dropping from 73.2 × 10(-3) to 28.6 × 10(-3) N/m. Based on newly found cooperation between the degrader and the coworking strain, rational investigations and optimal strategies to alkane hydrocarbons biodegradation were utilized for enhancing crude oil biodegradation.

  16. Structural and Kinetic Studies of Novel Cytochrome P450 Small-Alkane Hydroxylases

    SciTech Connect

    Arnold, Frances H.

    2012-02-27

    The goals of this project are to investigate (1) the kinetics and stabilities of engineered cytochrome P450 (P450) small alkane hydroxylases and their evolutionary intermediates, (2) the structural basis for catalytic proficiency on small alkanes of these engineered P450s, and (3) the changes in redox control resulting from protein engineering. To reach these goals, we have established new methods for determining the kinetics and stabilities of multicomponent P450s such as CYP153A6. Using these, we were able to determine that CYP153A6 is proficient for hydroxylation of alkanes as small as ethane, an activity that has never been observed previously in any natural P450. To elucidate the structures of the engineered P450s, we obtained x-ray diffraction data for two variants in the P450PMO (propane monooxygenase) lineage and a preliminary structure for the most evolved variant. This structure shows changes in the substrate binding regions of the enzyme and a reduction in active site volume that are consistent with the observed changes in substrate specificity from fatty acids in the native enzyme to small alkanes in P450PMO. We also constructed semi-rational designed libraries mutating only residues in the enzyme active site that in one round of mutagenesis and screening produced variants that achieved nearly half of the activity of the most evolved enzymes of the P450PMO lineage. Finally, we found that changes in redox properties of the laboratory-evolved P450 alkane hydroxylases did not reflect the improvement in their electron transfer efficiency. The heme redox potential remained constant throughout evolution, while activity increased and coupling efficiency improved from 10% to 90%. The lack of correlation between heme redox potential and enzyme activity and coupling efficiency led us to search for other enzyme properties that could be better predictors for activity towards small alkanes, specifically methane. We investigated the oxidation potential of the radical

  17. Rate law of Fe(II) oxidation under low O2 conditions

    NASA Astrophysics Data System (ADS)

    Kanzaki, Yoshiki; Murakami, Takashi

    2013-12-01

    Despite intensive studies on Fe(II) oxidation kinetics, the oxidation rate law has not been established under low O2 conditions. The importance of Fe(II) oxidation under low O2 conditions has been recently recognized; for instance, the Fe(II)/Fe(III) compositions of paleosols, ancient soils formed by weathering, can produce a quantitative pattern of the atmospheric oxygen increase during the Paleoproterozoic. The effects of partial pressure of atmospheric oxygen (PO2) on the Fe(II) oxidation rate were investigated to establish the Fe(II) oxidation rate - PO2 relationships under low O2 conditions. All oxidation experiments were carried out in a glove box by introducing Ar gas at ∼10-5-∼10-4 atm of PO2, pH 7.57-8.09 and 22 °C. Luminol chemiluminescence was adopted to measure low Fe(II) concentrations (down to ∼2 nM). Combining previous data under higher PO2 conditions (10-3-0.2 atm) with the present data, the rate law for Fe(II) oxidation over a wide range of PO2 (10-5-0.2 atm) was found to be written as: d[Fe(II)]/dt=-k[Fe(II)][[]2 where the exponent of [O2], x, and the rate constant, k, change from x = 0.98 (±0.04) and log k = 15.46 (±0.06) at ∼6 × 10-3-0.2 atm of PO2 to x = 0.58 (±0.02) and log k = 13.41 (±0.03) at 10-5-∼6 × 10-3 atm of PO2. The most plausible mechanism that explains the change in x under low O2 conditions is that, instead of O2, oxygen-derived oxidants, H2O2 and to some extent, O2rad -, dominate the oxidation reactions at <∼10-3 atm of PO2. The rate law found in the present study requires us to reconsider distributions of Fe redox species at low PO2 in natural environments, especially in paleoweathering profiles, and may provide a deeper understanding of the evolution of atmospheric oxygen in the Precambrian.

  18. Reduction of iron-oxide-carbon composites: part I. Estimation of the rate constants

    SciTech Connect

    Halder, S.; Fruehan, R.J.

    2008-12-15

    A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO{sub 2} and wustite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wustite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wustite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wustite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (> 1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

  19. Rate of oxidative modification of cytochrome c by hydrogen peroxide is modulated by Hofmeister anions.

    PubMed

    Tomášková, Nataša; Varinská, Lenka; Sedlák, Erik

    2010-09-01

    Cytochrome c (cyt c) and other heme proteins are oxidatively modified in the presence of hydrogen peroxide in a concentration- and time-dependent manner. Cyt c modification has been monitored by several spectral probes by absorption spectroscopy (at wavelengths 410 nm, 530 nm), and circular dichroism (222, 268, 288 and 417 nm). Kinetics monitored with these spectral probes indicates that the oxidative modification of cyt c: i) proceeds in the order: heme --> aromatic amino acids --> secondary structure, and ii) the rate of the oxidative modification is proportional to the protein flexibility. The flexibility of cyt c was modulated by anions of Hofmeister series (sulfate, chloride, perchlorate) (Varhac et al. 2009). A minimalist scheme of the interaction of cyt c with hydrogen peroxide can be described by two steps: 1) interaction of hydrogen peroxide with heme iron forming the postulated ferryl intermediate, 2a) oxidation of another molecule of hydrogen peroxide and 2b) parallel oxidation of close amino acid residue(s) and/or heme. The catalase activity of cyt c is independent from the presence of Hofmeister anions, which indicates that both steps (1 and 2a) in the catalase reaction are independent from the flexibility of the heme region of the protein matrix. On the other hand, the flexibility of the polypeptide chain of the protein modulates the rate of parallel oxidative modification of the heme and amino acid residues.

  20. Metabolism of n-alkanes and their incorporation into lipids in the rainbow trout

    SciTech Connect

    Cravedi, J.P.; Tulliez, J.

    1986-02-01

    The metabolic utilization by fish of n-alkanes was investigated in Salmo gairdneri R. receiving per os a single dose of (14C)heptadecane. This alkane was largely absorbed and radioactivity in the intestinal content was entirely in heptadecane. No elimination of the hydrocarbon was observed in urine. One week after dosing, ca. 50% of the ingested radioactivity was stored in the carcass and two-thirds of this radioactivity was due to heptadecane. The highest concentration of 14C was found in adipose tissue and liver, in which 77 and 22%, respectively, of the radioactivity originated from hydrocarbon. The rest was omega-oxidized to heptadecanoic acid. This fatty acid was incorporated into neutral lipids (mainly as free fatty acid) and phospholipids.

  1. The Optical Properties of a Polished Uranium Surface and its Epitaxial Oxide, and the Rate of Oxide Growth Determined by Spectrophotometry

    SciTech Connect

    Siekhaus, W; Nelson, A

    2005-12-05

    Wide-band reflectrometry and ellipsometry have been used to determine the optical properties n and k of freshly polished uranium and of the epitaxial oxide layer, and also the rate of oxide growth in air. Results for uranium metal as well as for epitaxial oxide are compared with single wavelength ellipsometry literature values.

  2. Effect of temperature and oxidation rate on carbon-isotope fractionation during methane oxidation by landfill cover materials.

    PubMed

    Chanton, Jeffrey P; Powelson, David K; Abichou, Tarek; Fields, Dana; Green, Roger

    2008-11-01

    The quantification of methane oxidation is one of the major uncertainties in estimating CH4 emissions from landfills. Stable isotope methods provide a useful field approach for the quantification of methane oxidation in landfill cover soils. The approach relies upon the difference between the isotopic composition of oxidized gas at the location of interest and anaerobic zone CH4 and knowledge of alpha(ox), a term that describes the isotopic fractionation of the methanotrophic bacteria in their discrimination against (13)CH4. Natural variability in alpha(0x) in different landfill soils and the effect of temperature and other environmental factors on this parameter are not well defined. Therefore, standard determinations of alpha(ox), batch incubations of landfill cover soils with CH4, were conducted to determine alpha(ox) under a variety of conditions. When these results were combined with those of previous landfill incubation studies, the average alpha(ox) at 25 degrees C was 1.022 +/- 0.0015. alpha(ox) decreased with increasing temperature (-0.00039 alpha(ox) degrees C(-1)) overthe temperature range of 3-35 degrees C. alpha(ox) was found to be higher when determined after CH4-free storage and declined following CH4 pretreatment. alpha(ox) declined nonlinearly with increasing methane oxidation rate, Vmax.

  3. Experimental evaluation of the effects of quench rate and quartz surface area on homogeneous mercury oxidation

    SciTech Connect

    Andrew Fry; Brydger Cauch; Geoffrey D. Silcox; JoAnn S. Lighty; Constance L. Senior

    2007-07-01

    This paper presents a mercury oxidation data set suitable for validation of fundamental kinetic models of mercury chemistry and for mechanism development. Experimental facilities include a mercury reactor fitted with a 300-W, quartz-glass burner and a quartz reaction chamber. While operated with a temperature profile representative of a typical boiler, a residence time of 6 s was achieved. Participating reacting species (chlorine, mercury) were introduced through the burner to produce a radical pool representative of real combustion systems. Speciated mercury measurements were performed using a Tekran 2537A Analyzer coupled with a conditioning system. Homogeneous mercury reactions involving chlorine have been investigated under two different temperature profiles producing quench rates of -210 K/s and -440 K/s. The larger quench rate produced 52% greater total oxidation than the lower quench at chlorine concentrations of 200 ppm. The effect of reactor surface area on oxidation was also investigated. The quartz surfaces interacted with mercury only in the presence of chlorine and their overall effect was to weakly inhibit oxidation. The extent of oxidation was predicted using a detailed kinetic model. The model predicted the effects of quench rate and chlorine concentration shown in experimentation. 12 refs., 5 figs., 3 tabs.

  4. Process for the oxidation of materials in water at supercritical temperatures utilizing reaction rate enhancers

    SciTech Connect

    Swallow, K.C.; Killilea, W.R.; Hong, G.T.; Bourhis, A.L.

    1993-08-03

    A method is described for substantially completely oxidizing combustible materials in which an aqueous stream bearing the combustible materials is reacted in the presence of an oxidant comprising diatomic oxygen and at a temperature greater than the critical temperature of water and at a pressure greater than about 25 bar, within a reactor for a period of less than about 5 minutes to produce a reaction product stream, wherein the reaction is initiated in the presence of a rate enhancer comprising at least one oxidizing agent in addition to said oxidant selected from the group consisting of ozone, hydrogen peroxide, salts containing persulfate, salts containing permanganate, nitric acid, salts containing nitrate, oxyacids of chlorine and their corresponding salts, hypochlorous acid, salts containing hypochlorite, chlorous acid, salts containing chlorite, chloric acid, salts containing chlorate, perchloric acid, and salts containing perchlorate.

  5. Arbuscular mycorrhizal wheat inoculation promotes alkane and polycyclic aromatic hydrocarbon biodegradation: Microcosm experiment on aged-contaminated soil.

    PubMed

    Ingrid, Lenoir; Lounès-Hadj Sahraoui, Anissa; Frédéric, Laruelle; Yolande, Dalpé; Joël, Fontaine

    2016-06-01

    Very few studies reported the potential of arbuscular mycorrhizal symbiosis to dissipate hydrocarbons in aged polluted soils. The present work aims to study the efficiency of arbuscular mycorrhizal colonized wheat plants in the dissipation of alkanes and polycyclic aromatic hydrocarbons (PAHs). Our results demonstrated that the inoculation of wheat with Rhizophagus irregularis allowed a better dissipation of PAHs and alkanes after 16 weeks of culture by comparison to non-inoculated condition. These dissipations observed in the inoculated soil resulted from several processes: (i) a light adsorption on roots (0.5% for PAHs), (ii) a bioaccumulation in roots (5.7% for PAHs and 6.6% for alkanes), (iii) a transfer in shoots (0.4 for PAHs and 0.5% for alkanes) and mainly a biodegradation. Whereas PAHs and alkanes degradation rates were respectively estimated to 12 and 47% with non-inoculated wheat, their degradation rates reached 18 and 48% with inoculated wheat. The mycorrhizal inoculation induced an increase of Gram-positive and Gram-negative bacteria by 56 and 37% compared to the non-inoculated wheat. Moreover, an increase of peroxidase activity was assessed in mycorrhizal roots. Taken together, our findings suggested that mycorrhization led to a better hydrocarbon biodegradation in the aged-contaminated soil thanks to a stimulation of telluric bacteria and hydrocarbon metabolization in mycorrhizal roots.

  6. Iridium dihydroxybipyridine complexes show that ligand deprotonation dramatically speeds rates of catalytic water oxidation.

    PubMed

    DePasquale, Joseph; Nieto, Ismael; Reuther, Lauren E; Herbst-Gervasoni, Corey J; Paul, Jared J; Mochalin, Vadym; Zeller, Matthias; Thomas, Christine M; Addison, Anthony W; Papish, Elizabeth T

    2013-08-19

    We report highly active iridium precatalysts, [Cp*Ir(N,N)Cl]Cl (1-4), for water oxidation that are supported by recently designed dihydroxybipyridine (dhbp) ligands. These ligands can readily be deprotonated in situ to alter the electronic properties at the metal; thus, these catalyst precursors have switchable properties that are pH-dependent. The pKa values in water of the iridium complexes are 4.6(1) and 4.4(2) with (N,N) = 6,6'-dhbp and 4,4'-dhbp, respectively, as measured by UV-vis spectroscopy. For homogeneous water oxidation catalysis, the sacrificial oxidant NaIO4 was found to be superior (relative to CAN) and allowed for catalysis to occur at higher pH values. With NaIO4 as the oxidant at pH 5.6, water oxidation occurred most rapidly with (N,N) = 4,4'-dhbp, and activity decreased in the order 4,4'-dhbp (3) > 6,6'-dhbp (2) ≫ 4,4'-dimethoxybipyridine (4) > bipy (1). Furthermore, initial rate studies at pH 3-6 showed that the rate enhancement with dhbp complexes at high pH is due to ligand deprotonation rather than the pH alone accelerating water oxidation. Thus, the protic groups in dhbp improve the catalytic activity by tuning the complexes' electronic properties upon deprotonation. Mechanistic studies show that the rate law is first-order in an iridium precatalyst, and dynamic light scattering studies indicate that catalysis appears to be homogeneous. It appears that a higher pH facilitates oxidation of precatalysts 2 and 3 and their [B(Ar(F))4](-) salt analogues 5 and 6. Both 2 and 5 were crystallographically characterized.

  7. 40 CFR 721.3435 - Butoxy-substituted ether alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Butoxy-substituted ether alkane. 721... Substances § 721.3435 Butoxy-substituted ether alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as butoxy-substituted ether...

  8. Melting of linear alkanes between swollen elastomers and solid substrates.

    PubMed

    Nanjundiah, Kumar; Dhinojwala, Ali

    2013-10-01

    We have measured the melting and freezing behavior of linear alkanes confined between cross-linked poly(dimethylsiloxane) (PDMS) elastomers and solid sapphire substrates. Small molecules are often used as lubricants to reduce friction or as plasticizers, but very little is directly known about the migration or changes in physical properties of these small molecules at interfaces, particularly the changes in transition temperatures upon confinement. Our previous studies highlighted striking differences between the crystal structure of confined and unconfined pentadecane crystals in contact with sapphire substrates. Here, we have used surface-sensitive infrared-visible sum-frequency-generation spectroscopy (SFG) to study the melting temperatures (Tm) of alkanes in nanometer thick interfacial regions between swollen PDMS elastomers in contact with sapphire substrate. We find that confined alkanes show depression in Tm compared to the melting temperature of unconfined bulk alkanes. The depression in Tm is a function of chain length, and these differences were smallest for shorter alkanes and largest for 19 unit long alkanes. In comparison, the DSC results for swollen PDMS elastomer show a broad distribution of melting points corresponding to different sizes of crystals formed within the network. The Tm for confined alkanes has been modeled using the combination of Flory-Rehner and Gibbs-Thomson models, and the depression in Tm is related to the thickness of the confined alkanes. These findings have important implications in understanding friction and adhesion of soft elastomeric materials and also the effects of confinement between two solid materials.

  9. Products of Chemistry: Alkanes: Abundant, Pervasive, Important, and Essential.

    ERIC Educational Resources Information Center

    Seymour, Raymond B.

    1989-01-01

    Discusses the history and commercialization of alkanes. Examines the nomenclature and uses of alkanes. Studies polymerization and several types of polyethylenes: low-density, high-density, low-molecular-weight, cross-linked, linear low-density, and ultrahigh-molecular-weight. Includes a glossary of hydrocarbon terms. (MVL)

  10. Products of Chemistry: Alkanes: Abundant, Pervasive, Important, and Essential.

    ERIC Educational Resources Information Center

    Seymour, Raymond B.

    1989-01-01

    Discusses the history and commercialization of alkanes. Examines the nomenclature and uses of alkanes. Studies polymerization and several types of polyethylenes: low-density, high-density, low-molecular-weight, cross-linked, linear low-density, and ultrahigh-molecular-weight. Includes a glossary of hydrocarbon terms. (MVL)

  11. Effect of cooling rate on achieving thermodynamic equilibrium in uranium-plutonium mixed oxides

    NASA Astrophysics Data System (ADS)

    Vauchy, Romain; Belin, Renaud C.; Robisson, Anne-Charlotte; Hodaj, Fiqiri

    2016-02-01

    In situ X-ray diffraction was used to study the structural changes occurring in uranium-plutonium mixed oxides U1-yPuyO2-x with y = 0.15; 0.28 and 0.45 during cooling from 1773 K to room-temperature under He + 5% H2 atmosphere. We compare the fastest and slowest cooling rates allowed by our apparatus i.e. 2 K s-1 and 0.005 K s-1, respectively. The promptly cooled samples evidenced a phase separation whereas samples cooled slowly did not due to their complete oxidation in contact with the atmosphere during cooling. Besides the composition of the annealing gas mixture, the cooling rate plays a major role on the control of the Oxygen/Metal ratio (O/M) and then on the crystallographic properties of the U1-yPuyO2-x uranium-plutonium mixed oxides.

  12. Modelling of silicon oxynitridation by nitrous oxide using the reaction rate approach

    SciTech Connect

    Dominique Krzeminski, Christophe

    2013-12-14

    Large technological progress in oxynitridation processing leads to the introduction of silicon oxynitride as ultra-thin gate oxide. On the theoretical side, few studies have been dedicated to the process modelling of oxynitridation. Such an objective is a considerable challenge regarding the various atomistic mechanisms occurring during this fabrication step. In this article, some progress performed to adapt the reaction rate approach for the modelling of oxynitride growth by a nitrous ambient are reported. The Ellis and Buhrman's approach is used for the gas phase decomposition modelling. Taking into account the mass balance of the species at the interface between the oxynitride and silicon, a minimal kinetic model describing the oxide growth has been calibrated and implemented. The influence of nitrogen on the reaction rate has been introduced in an empirical way. The oxidation kinetics predicted with this minimal model compares well with several experiments.

  13. Oxidation and decomposition mechanisms of air sensitive aluminum clusters at high heating rates

    NASA Astrophysics Data System (ADS)

    DeLisio, Jeffery B.; Mayo, Dennis H.; Guerieri, Philip M.; DeCarlo, Samantha; Ives, Ross; Bowen, Kit; Eichhorn, Bryan W.; Zachariah, Michael R.

    2016-09-01

    Molecular near zero oxidation state clusters of metals are of interest as fuel additives. In this work high heating rate decomposition of the Al(I) tetrameric cluster, [AlBr(NEt3)]4 (Et = C2H5), was studied at heating rates of up to 5 × 105 K/s using temperature-jump time-of-flight mass spectrometry (T-jump TOFMS). Gas phase Al and AlHx species were rapidly released during decomposition of the cluster, at ∼220 °C. The activation energy for decomposition was determined to be ∼43 kJ/mol. Addition of an oxidizer, KIO4, increased Al, AlO, and HBr signal intensities, showing direct oxidation of the cluster with gas phase oxygen.

  14. Ammonia Oxidation Rate is a Fundamental Control on Thaumarchaeal Lipid Composition and the TEX86 Proxy

    NASA Astrophysics Data System (ADS)

    Hurley, S.; Elling, F. J.; Könneke, M.; Buchwald, C.; Wankel, S. D.; Santoro, A. E.; Lipp, J. S.; Hinrichs, K. U.; Pearson, A.

    2016-02-01

    Planktonic Thaumarchaeota are the ocean's major aerobic oxidizers of ammonia and produce membrane lipids known as GDGTs. These lipids are the basis of the TEX86 sea surface temperature (SST) proxy - a geochemical paleothermometer used to reconstruct SST from the Jurassic to the present. However the mechanistic underpinning of the TEX86-SST proxy remains a mystery: How do GDGT lipids predict SST, when the maximum activity of Thaumarchaeota occurs below the surface mixed layer? Here we investigated the influence of ammonia oxidation rate on the distribution of GDGT lipids using isothermal studies of the model thaumarchaeon Nitrosopumilus maritimus SCM1. The results show that TEX86 values scale inversely with the ammonia oxidation rate, indicating that this proxy depends on available reducing power. The TEX86 ratio decreases by 5.4°C of SST-calibrated temperature over a 5.5 fmol cell-1 day-1 decrease in ammonia oxidation rate. Depth profiles from the marine water column show similar patterns of minimum TEX86 values at the depth of maximum ammonia oxidation rates, consistent with the chemostat results. Our findings suggest that the integrated signal of archaeal membrane lipids reaching the sediments is a function of the dynamics of ammonia oxidation in the overlying water column. The TEX86-SST calibration is therefore likely governed by the structure of the nutricline and its relationship to ocean thermal properties. This attribute of the TEX86 ratio may make it a promising tracer for understanding the ocean's nutrient dynamics and patterns of paleoproductivity.

  15. High-rate lithium-sulfur batteries promoted by reduced graphene oxide coating.

    PubMed

    Li, Nianwu; Zheng, Mingbo; Lu, Hongling; Hu, Zibo; Shen, Chenfei; Chang, Xiaofeng; Ji, Guangbin; Cao, Jieming; Shi, Yi

    2012-04-28

    Lithium-sulfur batteries have a poor rate performance and low cycle stability due to the shuttling loss of intermediate lithium polysulfides. To address this issue, a carbon-sulfur nanocomposite coated with reduced graphene oxide was designed to confine the polysulfides.

  16. n-Alkane adsorption to polar silica surfaces.

    PubMed

    Brindza, Michael R; Ding, Feng; Fourkas, John T; Walker, Robert A

    2010-03-21

    The structures of medium-length n-alkane species (C(8)-C(11)) adsorbed to a hydrophilic silica/vapor interface were examined using vibrational sum frequency spectroscopy. Experiments sampling out-of-plane orientation show a clear pattern in vibrational band intensities that implies chains having primarily all-trans conformations lying flat along the interface. Further analysis shows that the methylene groups of the alkane chains have their local symmetry axes directed into and away from the surface. Spectra acquired under different polarization conditions interlock to reinforce this picture of interfacial structure and organization. Variation in signal intensities with chain length suggests that correlation between adsorbed monomers weakens with increasing chain length. This result stands in contrast with alkane behavior at neat liquid/vapor interfaces where longer length alkanes show considerably more surface induced ordering than short chain alkanes.

  17. Sophorolipids from Torulopsis bombicola: possible relation to alkane uptake.

    PubMed Central

    Ito, S; Inoue, S

    1982-01-01

    Torulopsis bombicola produces extracellular sophorolipids when it is grown on water-insoluble alkanes. Sophorolipids and related model compounds, which were not themselves used for growth, were found to stimulate markedly the growth of T. bombicola on alkanes. This stimulatory effect was restricted to growth on C10 to C20 alkanes, whereas no significantly influence was observed for growth on fatty alcohols, fatty acids, glucose, or glycerol. The nonionic methyl ester of the glycolipid supported the greatest cell yield. However, a number of synthetic nonionic surfactants were unable to replace the glycolipid. When organisms were grown on hexadecane, stimulation of growth by sophorolipids was observed almost exclusively with strains of Torulopsis yeasts. In contrast, the growth of other typical alkane-utilizing yeasts, such as candida and Pichia strains, was inhibited or not affected. It appears that sophorolipids are involved in alkane dissimilation by T. bombicola through an undetermined mechanism. PMID:7201782

  18. Alkanes in benthic organisms from the Buccaneer oil field

    SciTech Connect

    Middleditch, B.S.; Basile, B.

    1980-06-01

    About 200 g per day of alkanes are present in brine discharged from each of two production platforms in the Buccaneer oil field in the NW Gulf of Mexico. These alkanes disperse rapidly in the water column, so that seawater concentrations of petroleum alkanes in this region are generally very low. They can be taken up to some extent by plankton, fish, and barnacles, but the petroleum alkane concentrations in these organisms are also relatively low. The largest pool of petroleum alkanes is in the surficial sediments, where concentrations of up to 25 ppM are observed, with concentration gradients extending more than 20 m from the production platforms. Organisms are examined which are exposed to these sediments and, for comparison, other specimens from control sites around structures from which there are no discharges.

  19. Utilization of n-Alkanes by Cladosporium resinae

    PubMed Central

    Teh, J. S.; Lee, K. H.

    1973-01-01

    Four different isolates of Cladosporium resinae from Australian soils were tested for their ability to utilize liquid n-alkanes ranging from n-hexane to n-octadecane under standard conditions. The isolates were unable to make use of n-hexane, n-heptane, and n-octane for growth. In fact, these hydrocarbons, particularly n-hexane, exerted an inhibitory effect on spore germination and mycelial growth. All higher n-alkanes from n-nonane to n-octadecane were assimilated by the fungus, although only limited growth occurred on n-nonane and n-decane. The long chain n-alkanes (C14 to C18) supported good growth of all isolates, but there was no obvious correlation between cell yields and chain lengths of these n-alkanes. Variation in growth responses to individual n-alkane among the different isolates was also observed. The cause of this variation is unknown. PMID:4735447

  20. Numerical and experimental studies of ethanol flames and autoignition theory for higher alkanes

    NASA Astrophysics Data System (ADS)

    Saxena, Priyank

    oxides of nitrogen and other potential pollutants in similar partially premixed flames of ethanol and other fuels for comparison purposes. The computational results with the present mechanism are in reasonable agreement with experiment and perform as well as or better than predictions of other, generally much larger, mechanisms available in the literature. Further research is, however, warranted for providing additional and more stringent tests of the mechanism and its predictions, especially for condition at higher pressures. The second part of the dissertation consists of analytical study of autoignition of higher alkane fuels. It is shown that, above about 1000 K, ignition delay times for propane and all higher alkanes, as well as for a number of other fuels, can be calculated well by employing rate parameters of only three types of elementary steps, namely CmHn+HO2→C mHn-1+H2O2, H2O2+M→2OH+M and 2HO2→H2O2+O2, only the first of which is fuel-specific, the other two clearly being common to all fuels. The prediction of this remarkably simple result relies on a steady-state approximation for HO2, as well as steady states for more active radicals during induction. The resulting approximation to the chemistry exhibits a slow, finite-rate buildup of H2O2 and removal of fuel during the induction period. The criterion employed for termination of the induction period is the complete depletion of the original fuel subject to the approximations introduced. Numerical comparisons of the ignition-time formula with the experiments show that the predictions work well not only for higher alkanes but also for propene and JP-10. The analytical approximation thus produces reasonable results for a wide range of fuels. These results provide a new perspective on high-temperature autoignition chemistry and a general means of easily estimating ignition times of the large number of fuels of practical importance.

  1. Heterogeneous OH oxidation of motor oil particles causes selective depletion of branched and less cyclic hydrocarbons.

    PubMed

    Isaacman, Gabriel; Chan, Arthur W H; Nah, Theodora; Worton, David R; Ruehl, Chris R; Wilson, Kevin R; Goldstein, Allen H

    2012-10-02

    Motor oil serves as a useful model system for atmospheric oxidation of hydrocarbon mixtures typical of anthropogenic atmospheric particulate matter, but its complexity often prevents comprehensive chemical speciation. In this work we fully characterize this formerly "unresolved complex mixture" at the molecular level using recently developed soft ionization gas chromatography techniques. Nucleated motor oil particles are oxidized in a flow tube reactor to investigate the relative reaction rates of observed hydrocarbon classes: alkanes, cycloalkanes, bicycloalkanes, tricycloalkanes, and steranes. Oxidation of hydrocarbons in a complex aerosol is found to be efficient, with approximately three-quarters (0.72 ± 0.06) of OH collisions yielding a reaction. Reaction rates of individual hydrocarbons are structurally dependent: compared to normal alkanes, reaction rates increased by 20-50% with branching, while rates decreased ∼20% per nonaromatic ring present. These differences in rates are expected to alter particle composition as a function of oxidation, with depletion of branched and enrichment of cyclic hydrocarbons. Due to this expected shift toward ring-opening reactions heterogeneous oxidation of the unreacted hydrocarbon mixture is less likely to proceed through fragmentation pathways in more oxidized particles. Based on the observed oxidation-induced changes in composition, isomer-resolved analysis has potential utility for determining the photochemical age of atmospheric particulate matter with respect to heterogeneous oxidation.

  2. Rates of hydrous ferric oxide crystallization and the influence on coprecipitated arsenate.

    PubMed

    Ford, Robert G

    2002-06-01

    Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 degrees C. Comparison of extraction data and X-ray diffraction results confirmed that hematite and goethite were the primary transformation products. HFO transformation was significantly retarded at or above an arsenate solid loading of 29 455 mg As/kg HFO. However, HFO transformation proceeded at a significant rate for arsenate solid loadings of 4208 and 8416 mg As/kg HFO. At a solid loading of 8416 mg As/kg HFO, XRD results suggested arsenate primarily partitioned to hematite. Comparison of HFO transformation rates observed in this research to rates obtained from the literature at pH 6 and temperatures ranging from 24 to 70 degrees C suggests that arsenate stabilization could be realized in oxic environments with a significantfraction of iron (hydr)oxides. While this process has not been documented in natural systems, the predicted half-life for transformation of an arsenic-bearing HFO is approximately 300 days at 25 degrees C at solid loading < 8415 mg As/kg HFO. The projected time frame for arsenate stabilization indicates this process should be considered during development of conceptual and analytical models describing arsenic fate and transport in oxic systems containing reactive iron (hydr)oxides. The likelihood of this process would depend on the chemical dynamics of the soil or sediment system relative to iron (hydr)oxide precipitation-dissolution reactions and the potential retarding/competing influence of ions such as silicate and organic matter.

  3. Changes in heart rate variability during anaesthesia induction using sevoflurane or isoflurane with nitrous oxide.

    PubMed

    Nishiyama, Tomoki

    2016-01-01

    The purpose of this study was to compare cardiac sympathetic and parasympathetic balance using heart rate variability (HRV) during induction of anaesthesia between sevoflurane and isoflurane in combination with nitrous oxide. 40 individuals aged from 30 to 60 years, scheduled for general anaesthesia were equally divided into sevoflurane or isoflurane groups. After 100% oxygen inhalation for a few minutes, anaesthesia was induced with nitrous oxide 3 L min-1, oxygen 3 L min-1 and sevoflurane or isoflurane. Sevoflurane or isoflurane concentration was increased by 0.5% every 2 to 3 breaths until 5% was attained for sevoflurane, or 3% for isoflurane. Vecuronium was administered to facilitate tracheal intubation. After intubation, sevoflurane was set to 2% while isoflurane was set to 1% with nitrous oxide with oxygen (1:1) for 5 min. Both sevoflurane and isoflurane provoked a decrease in blood pressure, total power, the low frequency component (LF), and high frequency component (HF) of HRV. Although the heart rate increased during isoflurane anaesthesia, it decreased under sevoflurane. The power of LF and HF also decreased in both groups. LF was higher in the isoflurane group while HF was higher in the sevoflurane group. The LF/HF ratio increased transiently in the isoflurane group, but decreased in the sevoflurane group. Anaesthesia induction with isoflurane-nitrous oxide transiently increased cardiac sympathetic activity, while sevoflurane-nitrous oxide decreased both cardiac sympathetic and parasympathetic activities. The balance of cardiac parasympathetic/sympathetic activity was higher in sevoflurane anaesthesia.

  4. Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide

    DOE PAGES

    Richards-Henderson, Nicole K.; Goldstein, Allen H.; Wilson, Kevin R.

    2015-10-27

    In this paper we report an unexpectedly large acceleration in the effective heterogeneous OH reaction rate in the presence of NO. This 10–50 fold acceleration originates from free radical chain reactions, propagated by alkoxy radicals that form inside the aerosol by the reaction of NO with peroxy radicals, which do not appear to produce chain terminating products (e.g., alkyl nitrates), unlike gas phase mechanisms. Lastly, a kinetic model, constrained by experiments, suggests that in polluted regions heterogeneous oxidation plays a much more prominent role in the daily chemical evolution of organic aerosol than previously believed.

  5. Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide

    SciTech Connect

    Richards-Henderson, Nicole K.; Goldstein, Allen H.; Wilson, Kevin R.

    2015-10-27

    In this paper we report an unexpectedly large acceleration in the effective heterogeneous OH reaction rate in the presence of NO. This 10–50 fold acceleration originates from free radical chain reactions, propagated by alkoxy radicals that form inside the aerosol by the reaction of NO with peroxy radicals, which do not appear to produce chain terminating products (e.g., alkyl nitrates), unlike gas phase mechanisms. Lastly, a kinetic model, constrained by experiments, suggests that in polluted regions heterogeneous oxidation plays a much more prominent role in the daily chemical evolution of organic aerosol than previously believed.

  6. High rates of anaerobic methane oxidation in freshwater wetlands reduce potential atmospheric methane emissions.

    PubMed

    Segarra, K E A; Schubotz, F; Samarkin, V; Yoshinaga, M Y; Hinrichs, K-U; Joye, S B

    2015-06-30

    The role of anaerobic oxidation of methane (AOM) in wetlands, the largest natural source of atmospheric methane, is poorly constrained. Here we report rates of microbially mediated AOM (average rate=20 nmol cm(-3) per day) in three freshwater wetlands that span multiple biogeographical provinces. The observed AOM rates rival those in marine environments. Most AOM activity may have been coupled to sulphate reduction, but other electron acceptors remain feasible. Lipid biomarkers typically associated with anaerobic methane-oxidizing archaea were more enriched in (13)C than those characteristic of marine systems, potentially due to distinct microbial metabolic pathways or dilution with heterotrophic isotope signals. On the basis of this extensive data set, AOM in freshwater wetlands may consume 200 Tg methane per year, reducing their potential methane emissions by over 50%. These findings challenge precepts surrounding wetland carbon cycling and demonstrate the environmental relevance of an anaerobic methane sink in ecosystems traditionally considered strong methane sources.

  7. Rates of chemical cleavage of DNA and RNA oligomers containing guanine oxidation products.

    PubMed

    Fleming, Aaron M; Alshykhly, Omar; Zhu, Judy; Muller, James G; Burrows, Cynthia J

    2015-06-15

    The nucleobase guanine in DNA (dG) and RNA (rG) has the lowest standard reduction potential of the bases, rendering it a major site of oxidative damage in these polymers. Mapping the sites at which oxidation occurs in an oligomer via chemical reagents utilizes hot piperidine for cleaving oxidized DNA and aniline (pH 4.5) for cleaving oxidized RNA. In the present studies, a series of time-dependent cleavages of DNA and RNA strands containing various guanine lesions were examined to determine the strand scission rate constants. The guanine base lesions 8-oxo-7,8-dihydroguanine (OG), spiroiminodihydantoin (Sp), 5-guanidinohydantoin (Gh), 2,2,4-triamino-2H-oxazol-5-one (Z), and 5-carboxamido-5-formamido-2-iminohydantoin (2Ih) were evaluated in piperidine-treated DNA and aniline-treated RNA. These data identified wide variability in the chemical lability of the lesions studied in both DNA and RNA. Further, the rate constants for cleaving lesions in RNA were generally found to be significantly smaller than for lesions in DNA. The OG nucleotides were poorly cleaved in DNA and RNA; Sp nucleotides were slowly cleaved in DNA and did not cleave significantly in RNA; Gh and Z nucleotides cleaved in both DNA and RNA at intermediate rates; and 2Ih oligonucleotides cleaved relatively quickly in both DNA and RNA. The data are compared and contrasted with respect to future experimental design.

  8. Rates of Chemical Cleavage of DNA and RNA Oligomers Containing Guanine Oxidation Products

    PubMed Central

    2016-01-01

    The nucleobase guanine in DNA (dG) and RNA (rG) has the lowest standard reduction potential of the bases, rendering it a major site of oxidative damage in these polymers. Mapping the sites at which oxidation occurs in an oligomer via chemical reagents utilizes hot piperidine for cleaving oxidized DNA and aniline (pH 4.5) for cleaving oxidized RNA. In the present studies, a series of time-dependent cleavages of DNA and RNA strands containing various guanine lesions were examined to determine the strand scission rate constants. The guanine base lesions 8-oxo-7,8-dihydroguanine (OG), spiroiminodihydantoin (Sp), 5-guanidinohydantoin (Gh), 2,2,4-triamino-2H-oxazol-5-one (Z), and 5-carboxamido-5-formamido-2-iminohydantoin (2Ih) were evaluated in piperidine-treated DNA and aniline-treated RNA. These data identified wide variability in the chemical lability of the lesions studied in both DNA and RNA. Further, the rate constants for cleaving lesions in RNA were generally found to be significantly smaller than for lesions in DNA. The OG nucleotides were poorly cleaved in DNA and RNA; Sp nucleotides were slowly cleaved in DNA and did not cleave significantly in RNA; Gh and Z nucleotides cleaved in both DNA and RNA at intermediate rates; and 2Ih oligonucleotides cleaved relatively quickly in both DNA and RNA. The data are compared and contrasted with respect to future experimental design. PMID:25853314

  9. Nitrification rates in Arctic soils are associated with functionally distinct populations of ammonia-oxidizing archaea

    PubMed Central

    Alves, Ricardo J Eloy; Wanek, Wolfgang; Zappe, Anna; Richter, Andreas; Svenning, Mette M; Schleper, Christa; Urich, Tim

    2013-01-01

    The functioning of Arctic soil ecosystems is crucially important for global climate, and basic knowledge regarding their biogeochemical processes is lacking. Nitrogen (N) is the major limiting nutrient in these environments, and its availability is strongly dependent on nitrification. However, microbial communities driving this process remain largely uncharacterized in Arctic soils, namely those catalyzing the rate-limiting step of ammonia (NH3) oxidation. Eleven Arctic soils were analyzed through a polyphasic approach, integrating determination of gross nitrification rates, qualitative and quantitative marker gene analyses of ammonia-oxidizing archaea (AOA) and bacteria (AOB) and enrichment of AOA in laboratory cultures. AOA were the only NH3 oxidizers detected in five out of 11 soils and outnumbered AOB in four of the remaining six soils. The AOA identified showed great phylogenetic diversity and a multifactorial association with the soil properties, reflecting an overall distribution associated with tundra type and with several physico-chemical parameters combined. Remarkably, the different gross nitrification rates between soils were associated with five distinct AOA clades, representing the great majority of known AOA diversity in soils, which suggests differences in their nitrifying potential. This was supported by selective enrichment of two of these clades in cultures with different NH3 oxidation rates. In addition, the enrichments provided the first direct evidence for NH3 oxidation by an AOA from an uncharacterized Thaumarchaeota–AOA lineage. Our results indicate that AOA are functionally heterogeneous and that the selection of distinct AOA populations by the environment can be a determinant for nitrification activity and N availability in soils. PMID:23466705

  10. A new binuclear oxovanadium(V) complex as a catalyst in combination with pyrazinecarboxylic acid (PCA) for efficient alkane oxygenation by H2O2.

    PubMed

    Sutradhar, Manas; Shvydkiy, Nikita V; Guedes da Silva, M Fátima C; Kirillova, Marina V; Kozlov, Yuriy N; Pombeiro, Armando J L; Shul'pin, Georgiy B

    2013-09-07

    A new binuclear oxovanadium(V) complex [{VO(OEt)(EtOH)}2L] (1) where H4L is bis(2-hydroxybenzylidene)terephthalohydrazide has been synthesized and fully characterized. The combination of 1 with pyrazine-2-carboxylic acid (PCA; a cocatalyst) affords a catalytic system for the efficient oxidation of saturated hydrocarbons, RH, with hydrogen peroxide and air in acetonitrile solution at 50 °C to produce alkyl hydroperoxides, ROOH, as the main primary products. Very high turnover numbers (TONs) have been attained in this reaction: for example, after 2220 min, TON = 44,000 and initial TOF (turnover frequency) = 3300 h(-1) per molecule of complex 1. The estimated activation energy of the cyclohexane oxygenation in the presence of 1/PCA is E(a) = 16 ± 2 kcal mol(-1). This value is identical to that obtained for the cyclohexane oxidation with H2O2 catalyzed by the (n-Bu4N)[VO3]/PCA combination (17 ± 2 kcal mol(-1)). The dependences of initial oxidation rates W0 on the initial concentrations of all components of the reaction mixture have been determined. Based on these kinetic data and on the regio- and bond-selectivity parameters measured in the oxidation of linear and branched alkanes a mechanism of the oxidation has been proposed which includes the generation of hydroxyl radicals in the crucial stage.

  11. Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

    NASA Astrophysics Data System (ADS)

    McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

    2004-10-01

    Long-chain, odd-carbon-numbered C25 to C35n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (alkane fractions essentially free of interfering components. The δ13C values obtained by MW-irMS did not differ significantly from weighted averages of individual n-alkane δ13C values obtained by irmGC-MS. Isotopic variations in compound-class n-alkane fractions from a latitudinal transect of core-top sediments from the Southwest African margin (3°N-28°S) were congruent with those measured by compound-specific isotopic analyses of plant-wax n-alkanes. The amplitude of the variations was smaller, indicating contributions from non-plant-wax hydrocarbons, but the measurements revealed variations in carbon isotopic composition that are consistent with vegetation zones on the adjacent continent.

  12. Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

    NASA Astrophysics Data System (ADS)

    McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

    2004-10-01

    Long-chain, odd-carbon-numbered C25 to C35 n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (alkane fractions essentially free of interfering components. The δ13C values obtained by MW-irMS did not differ significantly from weighted averages of individual n-alkane δ13C values obtained by irmGC-MS. Isotopic variations in compound-class n-alkane fractions from a latitudinal transect of core-top sediments from the Southwest African margin (3°N-28°S) were congruent with those measured by compound-specific isotopic analyses of plant-wax n-alkanes. The amplitude of the variations was smaller, indicating contributions from non-plant-wax hydrocarbons, but the measurements revealed variations in carbon isotopic composition that are consistent with vegetation zones on the adjacent continent.

  13. Catalytic conversion of light alkanes. Quarterly progress report, April 1--June 30, 1992

    SciTech Connect

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  14. Catalytic conversion of light alkanes phase II. Topical report, January 1990--January 1993

    SciTech Connect

    1998-12-31

    The Topical Report on Phase II of the project entitled, Catalytic Conversion of Light Alkanes reviews work done between January 1, 1990 and September 30, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products which can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon transportation fuel. This Topical Report documents our efforts to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. Research on the Cooperative Agreement is divided into three Phases relating to three molecular environments for the active catalytic species that we are trying to generate. In this report we present our work on catalysts which have oxidation-active metals in polyoxoanions (PHASE II).

  15. Catalytic conversion of light alkanes: Quarterly report, January 1-March 31, 1992

    SciTech Connect

    Biscardi, J.; Bowden, P.T.; Durante, V.A.; Ellis, P.E. Jr.; Gray, H.B.; Gorbey, R.G.; Hayes, R.C.; Hodge, J.; Hughes, M.; Langdale, W.A.; Lyons, J.E.; Marcus, B.; Messick, D.; Merrill, R.A.; Moore, F.A.; Myers, H.K. Jr.; Seitzer, W.H.; Shaikh, S.N.; Tsao, W.H.; Wagner, R.W.; Warren, R.W.; Wijesekera, T.P.

    1997-05-01

    The first Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between January 1. 1992 and March 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products which can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon transportation fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient porphryinic macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE III).

  16. Thermal analysis of thermo-gravimetric measurements of spent nuclear fuel oxidation rates

    SciTech Connect

    Cramer, E.R.

    1997-10-09

    A detailed thermal analysis was completed of the sample temperatures in the Thermo-Gravimetric Analysis (TGA) system used to measure irradiated N Reactor fuel oxidation rates. Sample temperatures during the oxidation process did not show the increase which was postulated as a result of the exothermic reactions. The analysis shows the axial conduction of heat in the sample holder effectively removes the added heat and only a very small, i.e., <10 C, increase in temperature is calculated. A room temperature evaporation test with water showed the sample thermocouple sensitivity to be more than adequate to account for a temperature change of approximately 5 C. Therefore, measured temperatures in the TGA are within approximately 10 C of the actual sample temperatures and no adjustments to reported data to account for the heat input from the oxidation process are necessary.

  17. Effects of air flow rate on the oxidation of NBG-18 and NBG-25 nuclear graphite

    NASA Astrophysics Data System (ADS)

    Chi, Se-Hwan; Chan Kim, Gen

    2017-08-01

    The effects of air flow rate (FR) (FR range: 1-10 L/min) on the oxidation of NBG-18 and NBG-25 nuclear graphite grades at temperatures between 600 and 1100 °C were studied, in reference to the standard test procedure for measuring oxidation rates of nuclear graphite in air (ASTM D 7542-09). The results showed that the FR effects on oxidation rate (OR) increase with increasing temperature with negligible FR effects at 600 °C for both materials. At high temperatures (>800 °C) there appears to be a two-stage relationship between FR and OR, which corresponds to the transition between reaction rates dominated by chemical kinetics and those dominated by diffusion. The material-specific microstructure appeared strongly influences this transition. The overall OR-FR behaviours of NBG-18 were higher than NBG-25 at 600-800 °C while negligible differences in the OR-FR behaviours between the two grades were observed at 900-1100 °C. The mercury porosimetry data showed that the higher OR-FR behaviours observed in NBG-18 may partly be attributed to the differences in the pore size distribution (open porosity and cumulative pore area) between the grades, especially for the large size pores (diameter ≫ 5 × 103 nm).

  18. High-order harmonic generation in alkanes

    SciTech Connect

    Altucci, C.; Velotta, R.; Heesel, E.; Springate, E.; Marangos, J. P.; Vozzi, C.; Benedetti, E.; Calegari, F.; Sansone, G.; Stagira, S.; Nisoli, M.; Tosa, V.

    2006-04-15

    We have investigated the process of high-order harmonic generation in light alkanes by using femtosecond laser pulses. We show the experimental results cannot be matched by a model that assumes a single active electron only in a hydrogenic s orbital. Clear evidences are shown of the important role played by the p-like character originating from the covalent C-H bond. By constructing a suitable mixture of s-type and p-type atomic wave functions, an excellent agreement between measurements in methane and simulations is found, thus confirming the validity of the developed method as a general tool for the analysis of high-order harmonic generation in complex molecules.

  19. Expanding the product profile of a microbial alkane biosynthetic pathway.

    PubMed

    Harger, Matthew; Zheng, Lei; Moon, Austin; Ager, Casey; An, Ju Hye; Choe, Chris; Lai, Yi-Ling; Mo, Benjamin; Zong, David; Smith, Matthew D; Egbert, Robert G; Mills, Jeremy H; Baker, David; Pultz, Ingrid Swanson; Siegel, Justin B

    2013-01-18

    Microbially produced alkanes are a new class of biofuels that closely match the chemical composition of petroleum-based fuels. Alkanes can be generated from the fatty acid biosynthetic pathway by the reduction of acyl-ACPs followed by decarbonylation of the resulting aldehydes. A current limitation of this pathway is the restricted product profile, which consists of n-alkanes of 13, 15, and 17 carbons in length. To expand the product profile, we incorporated a new part, FabH2 from Bacillus subtilis , an enzyme known to have a broader specificity profile for fatty acid initiation than the native FabH of Escherichia coli . When provided with the appropriate substrate, the addition of FabH2 resulted in an altered alkane product profile in which significant levels of n-alkanes of 14 and 16 carbons in length are produced. The production of even chain length alkanes represents initial steps toward the expansion of this recently discovered microbial alkane production pathway to synthesize complex fuels. This work was conceived and performed as part of the 2011 University of Washington international Genetically Engineered Machines (iGEM) project.

  20. The vapor-particle partitioning of n-alkanes

    SciTech Connect

    Doskey, P.V.

    1994-04-01

    A mixed-phase partitioning model has been proposed to predict the distribution of n-alkanes between the vapor and particle phases in the atmosphere. n-Alkanes having terrestrial plant wax and petroleum origins are assumed to be associated with atmospheric particles as microcrystalline solids and subcooled liquids, respectively. The fraction of n-alkanes on atmospheric particles having plant wax and petroleum origins is estimated with carbon preference indices. Hypothetical terrestrial plant wax and petroleum mixtures are used to estimate the mole fractions of the n-alkanes in each phase and the molecular weights of the phases. Solid and subcooled liquid phase n-alkane vapor pressures are used in the model to predict the fraction of n-alkanes associated with particles in the atmosphere. Trends in the prediction of vapor-particle partitioning using these assumptions agree well with field observations. However, the fraction of particle phase n-alkanes predicted by the model was significantly different from the field observations.

  1. Heterologous biosynthesis and manipulation of alkanes in Escherichia coli.

    PubMed

    Cao, Ying-Xiu; Xiao, Wen-Hai; Zhang, Jin-Lai; Xie, Ze-Xiong; Ding, Ming-Zhu; Yuan, Ying-Jin

    2016-11-01

    Biosynthesis of alkanes in microbial foundries offers a sustainable and green supplement to traditional fossil fuels. The dynamic equilibrium of fatty aldehydes, key intermediates, played a critical role in microbial alkanes production, due to the poor catalytic capability of aldehyde deformylating oxygenase (ADO). In our study, exploration of competitive pathway together with multi-modular optimization was utilized to improve fatty aldehydes balance and consequently enhance alkanes formation in Escherichia coli. Endogenous fatty alcohol formation was supposed to be competitive with alkane production, since both of the two routes consumed the same intermediate-fatty aldehyde. Nevertheless, in our case, alkanes production in E. coli was enhanced from trace amount to 58.8mg/L by the facilitation of moderate fatty alcohol biosynthesis, which was validated by deletion of endogenous aldehyde reductase (AHR), overexpression of fatty alcohol oxidase (FAO) and consequent transcriptional assay of aar, ado and adhP genes. Moreover, alkanes production was further improved to 81.8mg/L, 86.6mg/L or 101.7mg/L by manipulation of fatty acid biosynthesis, lipids degradation or electron transfer system modules, which directly referenced to fatty aldehydes dynamic pools. A titer of 1.31g/L alkanes was achieved in 2.5L fed-batch fermentation, which was the highest reported titer in E. coli. Our research has offered a reference for chemical overproduction in microbial cell factories facilitated by exploring competitive pathway.

  2. Long-chain alkane production by the yeast Saccharomyces cerevisiae.

    PubMed

    Buijs, Nicolaas A; Zhou, Yongjin J; Siewers, Verena; Nielsen, Jens

    2015-06-01

    In the past decade industrial-scale production of renewable transportation biofuels has been developed as an alternative to fossil fuels, with ethanol as the most prominent biofuel and yeast as the production organism of choice. However, ethanol is a less efficient substitute fuel for heavy-duty and maritime transportation as well as aviation due to its low energy density. Therefore, new types of biofuels, such as alkanes, are being developed that can be used as drop-in fuels and can substitute gasoline, diesel, and kerosene. Here, we describe for the first time the heterologous biosynthesis of long-chain alkanes by the yeast Saccharomyces cerevisiae. We show that elimination of the hexadecenal dehydrogenase Hfd1 and expression of a redox system are essential for alkane biosynthesis in yeast. Deletion of HFD1 together with expression of an alkane biosynthesis pathway resulted in the production of the alkanes tridecane, pentadecane, and heptadecane. Our study provides a proof of principle for producing long-chain alkanes in the industrial workhorse S. cerevisiae, which was so far limited to bacteria. We anticipate that these findings will be a key factor for further yeast engineering to enable industrial production of alkane based drop-in biofuels, which can allow the biofuel industry to diversify beyond bioethanol.

  3. Reduction of Iron-Oxide-Carbon Composites: Part I. Estimation of the Rate Constants

    NASA Astrophysics Data System (ADS)

    Halder, S.; Fruehan, R. J.

    2008-12-01

    A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO2 and wüstite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wüstite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wüstite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wüstite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (>1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

  4. Long-chain acylhomoserine lactones increase the anoxic ammonium oxidation rate in an OLAND biofilm.

    PubMed

    De Clippeleir, Haydée; Defoirdt, Tom; Vanhaecke, Lynn; Vlaeminck, Siegfried E; Carballa, Marta; Verstraete, Willy; Boon, Nico

    2011-05-01

    The oxygen-limited autotrophic nitrification/denitrification (OLAND) process comprises one-stage partial nitritation and anammox, catalyzed by aerobic and anoxic ammonium-oxidizing bacteria (AerAOB and AnAOB), respectively. The goal of this study was to investigate whether quorum sensing influences anoxic ammonium oxidation in an OLAND biofilm, with AnAOB colonizing 13% of the biofilm, as determined with fluorescent in situ hybridization (FISH). At high biomass concentrations, the specific anoxic ammonium oxidation rate of the OLAND biofilm significantly increased with a factor of 1.5 ± 0.2 compared to low biomass concentrations. Supernatant obtained from the biofilm showed no ammonium-oxidizing activity on itself, but its addition to low OLAND biomass concentrations resulted in a significant activity increase of the biomass. In the biofilm supernatant, the presence of long-chain acylhomoserine lactones (AHLs) was shown using the reporter strain Chromobacterium violaceum CV026, and one specific AHL, N-dodecanoyl homoserine lactone (C(12)-HSL), was identified via LC-MS/MS. Furthermore, C(12)-HSL was detected in an AnAOB-enriched community, but not in an AerAOB-enriched community. Addition of C(12)-HSL to low OLAND biomass concentrations resulted in a significantly higher ammonium oxidation rate (p < 0.05). To our knowledge, this is the first report demonstrating that AHLs enhance the anoxic ammonium oxidation process. Future work should confirm which species are responsible for the in situ production of C(12)-HSL in AnAOB-based applications.

  5. Heterogeneity of Alkane Chain Length in Freshwater and Marine Cyanobacteria

    PubMed Central

    Shakeel, Tabinda; Fatma, Zia; Fatma, Tasneem; Yazdani, Syed Shams

    2015-01-01

    The potential utilization of cyanobacteria for the biological production of alkanes represents an exceptional system for the next generation of biofuels. Here, we analyzed a diverse group of freshwater and marine cyanobacterial isolates from Indian culture collections for their ability to produce both alkanes and alkenes. Among the 50 cyanobacterial isolates screened, 32 isolates; 14 freshwater and 18 marine isolates; produced predominantly alkanes. The GC-MS/MS profiles revealed a higher percentage of pentadecane and heptadecane production for marine and freshwater strains, respectively. Oscillatoria species were found to be the highest producers of alkanes. Among the freshwater isolates, Oscillatoria CCC305 produced the maximum alkane level with 0.43 μg/mg dry cell weight, while Oscillatoria formosa BDU30603 was the highest producer among the marine isolates with 0.13 μg/mg dry cell weight. Culturing these strains under different media compositions showed that the alkane chain length was not influenced by the growth medium but was rather an inherent property of the strains. Analysis of the cellular fatty acid content indicated the presence of predominantly C16 chain length fatty acids in marine strains, while the proportion of C18 chain length fatty acids increased in the majority of freshwater strains. These results correlated with alkane chain length specificity of marine and freshwater isolates indicating that alkane chain lengths may be primarily determined by the fatty acid synthesis pathway. Moreover, the phylogenetic analysis showed clustering of pentadecane-producing marine strains that was distinct from heptadecane-producing freshwater strains strongly suggesting a close association between alkane chain length and the cyanobacteria habitat. PMID:25853127

  6. High-rate, high-yield production of methanol by ammonia-oxidizing bacteria.

    PubMed

    Taher, Edris; Chandran, Kartik

    2013-04-02

    The overall goal of this study was to develop an appropriate biological process for achieving autotrophic conversion of methane (CH(4)) to methanol (CH3OH). In this study, we employed ammonia-oxidizing bacteria (AOB) to selectively and partially oxidize CH(4) to CH(3)OH. In fed-batch reactors using mixed nitrifying enrichment cultures from a continuous bioreactor, up to 59.89 ± 1.12 mg COD/L of CH(3)OH was produced within an incubation time of 7 h, which is approximately ten times the yield obtained previously using pure cultures of Nitrosomonas europaea. The maximum specific rate of CH(4) to CH(3)OH conversion obtained during this study was 0.82 mg CH(3)OH COD/mg AOB biomass COD-d, which is 1.5 times the highest value reported with pure cultures. Notwithstanding these positive results, CH(4) oxidation to CH(3)OH by AOB was inhibited by NH(3) (the primary substrate for the oxidative enzyme, ammonia monooxygenase, AMO) as well as the product, CH(3)OH, itself. Further, oxidation of CH(4) to CH(3)OH by AOB was also limited by reducing equivalents supply, which could be overcome by externally supplying hydroxylamine (NH(2)OH) as an electron donor. Therefore, a potential optimum design for promoting CH(4) to CH(3)OH oxidation by AOB could involve supplying NH(3) (needed to maintain AMO activity) uncoupled from the supply of NH(2)OH and CH(4). Partial oxidation of CH(4)-containing gases to CH3OH by AOB represents an attractive platform for the conversion of a gaseous mixture to an aqueous compound, which could be used as a commodity chemical. Alternately, the nitrate and CH(3) OH thus produced could be channeled to a downstream anoxic zone in a biological nitrogen removal process to effect nitrate reduction to N(2), using an internally produced organic electron donor.

  7. Potential methane production and methane oxidation rates in peatland ecosystems of the Appalachian Mountains, United States

    SciTech Connect

    Yavitt, J.B.; Lang, G.E.; Downey, D.M. )

    1988-09-01

    Potential rates of methane production and carbon dioxide production were measured on 11 dates in 1986 in peat from six plant communities typical of moss-dominated peatlands in the Appalachian Mountains. Annual methane production ranged from 2.7 to 17.5 mol/sq m, and annual carbon dioxide production ranged from 30.6 to 79.0 mol/sq m. The wide range in methane production values among the communities found within a single peatland indicates that obtaining one production value for a peatland may not be appropriate. Low temperature constrained the potential for methane production in winter, while the chemical quality of the peat substrate appears to control methane production in the summer. Methane oxidation was measured throughout the peat profile to a depth of 30 cm. Values for methane oxidation ranged from 0.08 to 18.7 microM/hr among the six plant communities. Aerobic methane-oxidizing bacteria probably mediated most of the activity. On a daily basis during the summer, between 11 and 100% of the methane produced is susceptible to oxidation within the peat column. Pools of dissolved methane and dissolved carbon dioxide in pore waters were less than 0.2 and less than 1.0 mol/sq m, respectively, indicating that methane does not accumulate in the pore waters. Peatlands have been considered as an important source of biologically produced methane. Despite the high rates of methane production, the high rates of methane oxidation dampen the potential emission of methane to the atmosphere. 41 refs., 7 figs., 4 tabs.

  8. [Effects of methane stress on oxidation rates and microbial community structures in different landfill cover soils].

    PubMed

    He, Ruo; Jiang, Chen-jing; Wang, Jing; Gao, Qing-jun; Shen, Dong-sheng

    2008-12-01

    As compared with the ordinary landfill cover material, clay soil, the effect of methane stress on oxidation rate and microbial community structure was investigated in waste soil (material from biologically treated municipal solid waste). The results showed that the moisture content of the clay soil was low, due to the low water retaining capacity. As environmental temperature and rainfall changed, the clay soil caked and inhibited methanotrophs growth. However, with a high organic matter, water-holding capacity and porosity, the waste soil provided a favor condition for methanotrophs growth and propagation. After exposure to methane flow for 120 days, methane oxidation potential in the middle and bottom layers of the waste soil column increased to 11.25-13.48 micromol/(g x h), which was 10.4-24.5 times higher than that in clay soil column. The topsoils were both found to be dried and inhibit methane oxidation. Methane oxidation (removal) efficiency by the waste soil column reached 48.3% at the end of the experiment, which was 5-6 times higher than that by the clay soil column. The amounts of the phospholipid fatty acid (PLFA) biomarks 16:1 omega 8c and 18:1 omega 8c for Type I and II methanotrophs, respectively, showed that a strong linear relationship was observed between methane oxidation potential and PLFA 18:1 omega 8c content in soil samples.

  9. Catalytic conversion of light alkanes -- research and proof-of-concept stages

    SciTech Connect

    Lyons, J.E.; Hancock, A.W. II

    1993-12-31

    Objective is to find new catalysts for direct reaction of methane, ethane, propane, butanes with O{sub 2} to form alcohols, and to develop practical processes for direct oxidative conversion of natural gas and its C{sub 1}-C{sub 4} components to produce alcohol-rich liquid oxygenates for use as alternative transportation fuels/environmentally superior reformulated gasolines. The proposed mechanism for oxidation activity of cytochrome P-450 and methane monoxygenase suggested that a catalyst able to reductively bind oxygen, not between Fe(III) center and a proton, but between two Fe(III) centers, might give the desired dioxygenase activity for alkane hydroxylation. Selective oxidation of light alkanes could be done by oxidation-active metal (Fe) centers in electron-deficient prophyrin-like macrocycles, polyoxoanions, and zeolites. In the isobutane conversion to tert-butanol proof-of-concept, it was found that nitro groups on the periphery of Fe porphyrin complexes give the greatest increase in Fe(III)/(II) reduction potential. 8 figs, 6 tabs, 40 refs.

  10. High basal metabolic rate does not elevate oxidative stress during reproduction in laboratory mice.

    PubMed

    Brzęk, Paweł; Książek, Aneta; Ołdakowski, Łukasz; Konarzewski, Marek

    2014-05-01

    Increased oxidative stress (OS) has been suggested as a physiological cost of reproduction. However, previous studies reported ambiguous results, with some even showing a reduction of oxidative damage during reproduction. We tested whether the link between reproduction and OS is mediated by basal metabolic rate (BMR), which has been hypothesized to affect both the rate of radical oxygen species production and antioxidative capacity. We studied the effect of reproduction on OS in females of laboratory mice divergently selected for high (H-BMR) and low (L-BMR) BMR, previously shown to differ with respect to parental investment. Non-reproducing L-BMR females showed higher oxidative damage to lipids (quantified as the level of malondialdehyde in internal organ tissues) and DNA (quantified as the level of 8-oxodG in blood serum) than H-BMR females. Reproduction did not affect oxidative damage to lipids in either line; however, it reduced damage to DNA in L-BMR females. Reproduction increased catalase activity in liver (significantly stronger in L-BMR females) and decreased it in kidneys. We conclude that the effect of reproduction on OS depends on the initial variation in BMR and varies between studied internal organs and markers of OS.

  11. Effects of methane on the microbial populations and oxidation rates in different landfill cover soil columns.

    PubMed

    He, Ruo; Ruan, Aidong; Shen, Dong-Sheng

    2007-05-01

    A considerable fraction of methane produced in landfills is oxidized by landfill cover soils. In this work, microbial populations and oxidation rates developed in response to the presence of methane were studied in three soil columns simulated landfill cover soil environments. The population of aerobic heterotrophic bacteria was highest in the waste soil, middle in the clay soil, and lowest in the red soil. After exposure to methane-rich environments, the populations of methanotrophic bacteria showed increases in the waste and clay soils. The population of methanotrophic bacteria increased from 30.77x10(4) to 141.77x10(4) cfu g d.w.-1 in the middle layer of the waste soil column as a function of exposure to methane for 120 days. The populations of methanotrophic bacteria were correlated with the potential methane oxidation rates in the waste and clay soils, respectively. The topsoil was observed to be dried in the three soil columns. Most of methane oxidation occurred at the depth of between 10 and 20 cm in the waste soil column, while it took place mainly at the depth of between 20 and 30 cm in the clay soil column.

  12. Gene Structures and Regulation of the Alkane Hydroxylase Complex in Acinetobacter sp. Strain M-1

    PubMed Central

    Tani, Akio; Ishige, Takeru; Sakai, Yasuyoshi; Kato, Nobuo

    2001-01-01

    In the long-chain n-alkane degrader Acinetobacter sp. strain M-1, two alkane hydroxylase complexes are switched by controlling the expression of two n-alkane hydroxylase-encoding genes in response to the chain length of n-alkanes, while rubredoxin and rubredoxin ruductase are encoded by a single gene and expressed constitutively. PMID:11160120

  13. Comparison of two lung clearance models based on the dissolution rates of oxidized depleted uranium

    SciTech Connect

    Crist, K.C.

    1984-10-01

    An in-vitro dissolution study was conducted on two respirable oxidized depleted uranium samples. The dissolution rates generated from this study were then utilized in the International Commission on Radiological Protection Task Group lung clearance model and a lung clearance model proposed by Cuddihy. Predictions from both models based on the dissolution rates of the amount of oxidized depleted uranium that would be cleared to blood from the pulmonary region following an inhalation exposure were compared. It was found that the predictions made by both models differed considerably. The difference between the predictions was attributed to the differences in the way each model perceives the clearance from the pulmonary region. 33 references, 11 figures, 9 tables.

  14. Effect of Oxidation Rate and Fe(II) State on Microbial Nitrate-Dependent Fe(III) Mineral Formation

    PubMed Central

    Senko, John M.; Dewers, Thomas A.; Krumholz, Lee R.

    2005-01-01

    A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems. PMID:16269756

  15. Effect of the oxidation rate and Fe(II) state on microbial nitrate-dependent Fe(III) mineral formation

    USGS Publications Warehouse

    Senko, John M.; Dewers , Thomas A.; Krumholz, Lee R.

    2005-01-01

    A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems.

  16. Use of radiolabeled acetate to evaluate the rate of clearance of cerebral oxidative metabolites

    SciTech Connect

    Lear, J.L.; Kasliwal, R.; Duryea, R.A.

    1994-05-01

    Radiolabel derived from glucose (GLC) has been shown to have different cerebral retention kinetics than radiolabel derived from deoxyglucose (DG). In particular, activated structures with high metabolic rates have more rapid loss of GLC-derived radiolabel than DG-derived radiolabel. Because GLC-derived radiolabel can be lost from the brain glycolytically through lactate or oxidatively through CO{sub 2}, the cause of the difference between GLC and FDG is uncertain. We investigated the isolated oxidative pathway using radiolabeled acetate, which is only metabolized through the Krebs cycle. Male albino rats were anesthetized with halothane and femoral vein and artery catheters were placed. The rats were allowed to awaken for two hours prior to the studies. 100 uCi of {sup 14}C-acetate was administered as a 30 second IV infusion to each rat. Arterial samples were obtained at regular intervals. Groups of rats were killed at 5, 10, 15, 30, and 60 minutes. Brains were rapidly removed, sectioned, and used to produce autoradiograms. The extracted and retained radiolabel was calculated as the brain concentration at time of death divided by the integral of the arterial tracer concentration. No detectable loss of radiolabel was found over the initial 10 minutes. Thereafter the rate of loss gradually increased reaching a maximum of 1.2% per minute by 60 minutes. This corresponds to a k4 rate constant of 0.012 min{sup -1}. The rate of loss of oxidative metabolites from rat brain was found to be very slow. This probably results from exchange of radiolabel with amino acid pools as the tracer is metabolized through the Krebs cycle. Therefore in conditions were glycolysis is increased out of proportion to oxidation and cerebral lactate concentration rises, radiolabel loss through lactate efflux can be a substantial fraction of overall loss.

  17. Diverse sulfate-reducing bacteria of the Desulfosarcina/Desulfococcus clade are the key alkane degraders at marine seeps

    PubMed Central

    Kleindienst, Sara; Herbst, Florian-Alexander; Stagars, Marion; von Netzer, Frederick; von Bergen, Martin; Seifert, Jana; Peplies, Jörg; Amann, Rudolf; Musat, Florin; Lueders, Tillmann; Knittel, Katrin

    2014-01-01

    Biogeochemical and microbiological data indicate that the anaerobic oxidation of non-methane hydrocarbons by sulfate-reducing bacteria (SRB) has an important role in carbon and sulfur cycling at marine seeps. Yet, little is known about the bacterial hydrocarbon degraders active in situ. Here, we provide the link between previous biogeochemical measurements and the cultivation of degraders by direct identification of SRB responsible for butane and dodecane degradation in complex on-site microbiota. Two contrasting seep sediments from Mediterranean Amon mud volcano and Guaymas Basin (Gulf of California) were incubated with 13C-labeled butane or dodecane under sulfate-reducing conditions and analyzed via complementary stable isotope probing (SIP) techniques. Using DNA- and rRNA-SIP, we identified four specialized clades of alkane oxidizers within Desulfobacteraceae to be distinctively active in oxidation of short- and long-chain alkanes. All clades belong to the Desulfosarcina/Desulfococcus (DSS) clade, substantiating the crucial role of these bacteria in anaerobic hydrocarbon degradation at marine seeps. The identification of key enzymes of anaerobic alkane degradation, subsequent β-oxidation and the reverse Wood–Ljungdahl pathway for complete substrate oxidation by protein-SIP further corroborated the importance of the DSS clade and indicated that biochemical pathways, analog to those discovered in the laboratory, are of great relevance for natural settings. The high diversity within identified subclades together with their capability to initiate alkane degradation and growth within days to weeks after substrate amendment suggest an overlooked potential of marine benthic microbiota to react to natural changes in seepage, as well as to massive hydrocarbon input, for example, as encountered during anthropogenic oil spills. PMID:24722631

  18. Diverse sulfate-reducing bacteria of the Desulfosarcina/Desulfococcus clade are the key alkane degraders at marine seeps.

    PubMed

    Kleindienst, Sara; Herbst, Florian-Alexander; Stagars, Marion; von Netzer, Frederick; von Bergen, Martin; Seifert, Jana; Peplies, Jörg; Amann, Rudolf; Musat, Florin; Lueders, Tillmann; Knittel, Katrin

    2014-10-01

    Biogeochemical and microbiological data indicate that the anaerobic oxidation of non-methane hydrocarbons by sulfate-reducing bacteria (SRB) has an important role in carbon and sulfur cycling at marine seeps. Yet, little is known about the bacterial hydrocarbon degraders active in situ. Here, we provide the link between previous biogeochemical measurements and the cultivation of degraders by direct identification of SRB responsible for butane and dodecane degradation in complex on-site microbiota. Two contrasting seep sediments from Mediterranean Amon mud volcano and Guaymas Basin (Gulf of California) were incubated with (13)C-labeled butane or dodecane under sulfate-reducing conditions and analyzed via complementary stable isotope probing (SIP) techniques. Using DNA- and rRNA-SIP, we identified four specialized clades of alkane oxidizers within Desulfobacteraceae to be distinctively active in oxidation of short- and long-chain alkanes. All clades belong to the Desulfosarcina/Desulfococcus (DSS) clade, substantiating the crucial role of these bacteria in anaerobic hydrocarbon degradation at marine seeps. The identification of key enzymes of anaerobic alkane degradation, subsequent β-oxidation and the reverse Wood-Ljungdahl pathway for complete substrate oxidation by protein-SIP further corroborated the importance of the DSS clade and indicated that biochemical pathways, analog to those discovered in the laboratory, are of great relevance for natural settings. The high diversity within identified subclades together with their capability to initiate alkane degradation and growth within days to weeks after substrate amendment suggest an overlooked potential of marine benthic microbiota to react to natural changes in seepage, as well as to massive hydrocarbon input, for example, as encountered during anthropogenic oil spills.

  19. Effect of loading time on the survival rate of anodic oxidized implants: prospective multicenter study

    PubMed Central

    Kim, Seok-Gyu; Yun, Pil-Young; Park, Hyun-Sik; Shim, June-Sung; Hwang, Jung-Won

    2012-01-01

    PURPOSE The purpose of this prospective study was to evaluate the effect of early loading on survival rate or clinical parameter of anodic oxidized implants during the 12-month postloading period. MATERIALS AND METHODS Total 69 implants were placed in 42 patients. Anodic oxidized implants (GS II, Osstem Cor., Busan, Korea) placed on the posterior mandibles were divided into two groups, according to their prosthetic loading times: test group (2 to 6 weeks), and control group (3 to 4 months). The implant survival rates were determined during one-year postloading period and analyzed by Kaplan-Meier method. The radiographic peri-implant bone loss and periodontal parameters were also evaluated and statistically analyzed by unpaired t-test. RESULTS Total 69 implants were placed in 42 patients. The cumulative postloading implant survival rates were 88.89% in test group, compared to 100% in control group (P<.05). Periimplant marginal bone loss (T: 0.27±0.54 mm, C: 0.40±0.55 mm) and periodontal parameters showed no significant difference between the groups (P>.05). CONCLUSION Within the limitation of the present study, implant survival was affected by early loading on the anodic oxidized implants placed on posterior mandibles during one-year follow-up. Early implant loading did not influence peri-implant marginal bone loss, and periodontal parameters. PMID:22439096

  20. Dual fluorescence and fast intramolecular charge transfer with 4-(diisopropylamino)benzonitrile in alkane solvents

    NASA Astrophysics Data System (ADS)

    Demeter, Attila; Druzhinin, Sergey; George, Mathew; Haselbach, Edwin; Roulin, Jean-Luc; Zachariasse, Klaas A.

    2000-06-01

    Dual fluorescence and fast intramolecular charge transfer (ICT) is observed with 4-(diisopropylamino)benzonitrile (DIABN) in alkane solvents. The rate constant ka for the reaction from the locally excited (LE) to the ICT state has a value of 3.4×10 11 s -1 in n-hexane at 25°C, with an activation energy Ea of 6 kJ mol -1. Efficient intersystem crossing with a yield of 0.94 takes place from the ICT state. With 4-(dimethylamino)benzonitrile, in contrast, dual fluorescence is not observed in alkanes. The charge transfer reaction of DIABN is mainly favoured by its small energy gap Δ E( S1, S2), in accordance with the PICT model for ICT in aminobenzonitriles.

  1. Carbon limitation of biomass production in high-rate oxidation ponds.

    PubMed

    Azov, Y; Shelef, G; Moraine, R

    1982-03-01

    Theoretical considerations confirmed by outdoor experiments indicated carbon limitation of biomass production in high-rate oxidation ponds at certain seasonal and operational conditions. Apparently, free carbon dioxide concentration in the pond is the major determinant of carbonlimiting algal photosynthesis. High concentrations of free CO(2) are provided through bacterial respiration which is the main contributor to algal photosynthesis. At high photosynthetic activities and low organic loadings, free CO(2) concentrations are low; its flux into algal cells determines photosynthesis and biomass production rate in the pond.

  2. New covalent modifications of phosphatidylethanolamine by alkanals: mass spectrometry based structural characterization and biological effects

    PubMed Central

    Annibal, Andrea; Schubert, Kristin; Wagner, Ulf; Hoffmann, Ralf; Schiller, Jürgen; Fedorova, Maria

    2014-01-01

    The pathophysiology of numerous human disorders, such as atherosclerosis, diabetes, obesity and Alzheimer's disease, is accompanied by increased production of reactive oxygen species (ROS). ROS can oxidatively damage nearly all biomolecules, including lipids, proteins and nucleic acids. In particular, (poly)unsaturated fatty acids within the phospholipid (PL) structure are easily oxidized by ROS to lipid peroxidation products (LPP) carrying reactive carbonyl groups. Carbonylated LPP are characterized by high in vivo toxicity due to their reactivity with nucleophilic substrates (Lys-, Cys-and His-residues in proteins or amino groups of phosphatidylethanolamines [PE]). Adducts of unsaturated LPP with PE amino groups have been reported before, whereas less is known about the reactivity of saturated alkanals – which are significantly increased in vivo under oxidative stress conditions – towards nucleophilic groups of PLs. Here, we present a study of new alkanal-dipalmitoyl-phosphatidylethanolamine (DPPE) adducts by MS-based approaches, using consecutive fragmentation (MSn) and multiple reaction monitoring techniques. At least eight different DPPE–hexanal adducts were identified, including Schiff base and amide adducts, six of which have not been reported before. The structures of these new compounds were determined by their fragmentation patterns using MSn experiments. The new PE-hexanal adducts contained dimeric and trimeric hexanal conjugates, including cyclic adducts. A new pyridine ring containing adduct of DPPE and hexanal was purified by HPLC, and its biological effects were investigated. Incubation of peripheral blood mononuclear cells and monocytes with modified DPPE did not result in increased production of TNF-α as one selected inflammation marker. However, incorporation of modified DPPE into 1,2-dipalmitoleoyl-sn-phosphatidylethanolamine multilamellar vesicles resulted in a negative shift of the transition temperature, indicating a possible role of

  3. Chemical sympathectomy restores baroreceptor-heart rate reflex and heart rate variability in rats with chronic nitric oxide deficiency.

    PubMed

    Chaswal, M; Das, S; Prasad, J; Katyal, A; Fahim, M

    2015-01-01

    Nitric oxide (NO) plays a crucial role not only in regulation of blood pressure but also in maintenance of cardiac autonomic tone and its deficiency induced hypertension is accompanied by cardiac autonomic dysfunction. However, underlying mechanisms are not clearly defined. We hypothesized that sympathetic activation mediates hemodynamic and cardiac autonomic changes consequent to deficient NO synthesis. We used chemical sympathectomy by 6-hydroxydopamine to examine the influence of sympathetic innervation on baroreflex sensitivity (BRS) and heart rate variability (HRV) of chronic N(G)-nitro-L-arginine methyl ester (L-NAME) treated adult Wistar rats. BRS was determined from heart rate responses to changes in systolic arterial pressure achieved by intravenous administration of phenylephrine and sodium nitroprusside. Time and frequency domain measures of HRV were calculated from 5-min electrocardiogram recordings. Chronic L-NAME administration (50 mg/kg per day for 7 days orally through gavage) in control rats produced significant elevation of blood pressure, tachycardia, attenuation of BRS for bradycardia and tachycardia reflex and fall in time as well as frequency domain parameters of HRV. Sympathectomy completely abolished the pressor as well as tachycardic effect of chronic L-NAME. In addition, BRS and HRV improved after removal of sympathetic influence in chronic L-NAME treated rats. These results support the concept that an exaggerated sympathetic activity is the principal mechanism of chronic L-NAME hypertension and associated autonomic dysfunction.

  4. Design, microstructure, and high-temperature behavior of silicon nitride sintered with rate-earth oxides

    SciTech Connect

    Ciniculk, M.K. . Dept. of Materials Science and Mineral Engineering)

    1991-08-01

    The processing-microstructure-property relations of silicon nitride ceramics sintered with rare-earth oxide additives have been investigated with the aim of improving their high-temperature behavior. The additions of the oxides of Y, Sm, Gd, Dy, Er, or Yb were compositionally controlled to tailor the intergranular phase. The resulting microstructure consisted of {beta}-Si{sub 3}N{sub 4} grains and a crystalline secondary phase of RE{sub 2}Si{sub 2}O{sub 7}, with a thin residual amorphous phase present at grain boundaries. The lanthanide oxides were found to be as effective as Y{sub 2}O{sub 3} in densifying Si{sub 3}N{sub 4}, resulting in identical microstructures. The crystallization behavior of all six disilicates was similar, characterized by a limited nucleation and rapid growth mechanism resulting in large single crystals. Complete crystallization of the intergranular phase was obtained with the exception of a residual amorphous, observed at interfaces and believed to be rich in impurities, the cause of incomplete devitrification. The low resistance to oxidation of these materials was attributed to the minimization of amorphous phases via devitrification to disilicates, compatible with SiO{sub 2}, the oxidation product of Si{sub 3}N{sub 4}. The strength retention of these materials at 1300{degrees}C was found to be between 80% and 91% of room-temperature strength, due to crystallization of the secondary phase and a residual but refractory amorphous grain-boundary phase. The creep behavior was found to be strongly dependent on residual amorphous phase viscosity as well as on the oxidation behavior, as evidenced by the nonsteady-state creep rates of all materials. 122 refs., 51 figs., 12 tabs.

  5. Nitrous oxide emissions and denitrification rates: A blueprint for smart management and remediation of agricultural landscapes.

    NASA Astrophysics Data System (ADS)

    Tomasek, A.; Hondzo, M.; Kozarek, J. L.

    2015-12-01

    resulting in the release of nitrous oxide, a greenhouse gas with 300 times the warming potential of carbon dioxide. The investigation of nitrous oxide emissions and correlation to denitrification rates will facilitate smart management and remediation efforts of agricultural landscapes.

  6. Oxidation mechanism and overall removal rates of endocrine disrupting chemicals by aquatic plants.

    PubMed

    Reis, A R; Tabei, K; Sakakibara, Y

    2014-01-30

    The purpose of this study was to evaluate experimentally and theoretically the oxidation mechanisms and overall removal rates of phenolic endocrine disrupting chemicals (EDCs) by aquatic plants. EDCs used in this study were bisphenol-A (BPA), 2,4-dichlorophenol (2,4-DCP), 4-tert-octylphenol (4-t-OP), and pentachlorophenol (PCP). Referring to reported detection levels in aquatic environments and contaminated sites, the feed concentration of each EDC was set from 1 to 100μg/L. Experimental results showed that, except for PCP, phenolic EDCs were stably and concurrently removed by different types of aquatic plants over 70 days in long-term continuous treatments. Primal enzymes responsible for oxidation of BPA, 2,4-DCP, and 4-t-OP were peroxidases (POs). Moreover, enzymatic removal rates of BPA, 2,4-DCP, and 4-t-OP by POs were more than 2 orders of magnitude larger than those by aquatic plants. Assuming that overall removal rates of EDCs are controlled by mass transfer rates onto liquid films on the surface of aquatic plants, an electrochemical method based on the limiting current theory was developed to measure the mass transfer rates of EDCs. Because of extremely large removal rates of EDCs by POs, observed removal rates by aquatic plants were in reasonably good agreement with calculated results by a mathematical model developed based on an assumption that mass transfer limitation is a rate-limiting step. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

  7. Nitrate reduction by denitrifying anaerobic methane oxidizing microorganisms can reach a practically useful rate.

    PubMed

    Cai, Chen; Hu, Shihu; Guo, Jianhua; Shi, Ying; Xie, Guo-Jun; Yuan, Zhiguo

    2015-12-15

    Methane in biogas has been proposed to be an electron donor to facilitate complete nitrogen removal using denitrifying anaerobic methane oxidizing (DAMO) microorganisms in an anaerobic ammonium oxidation (anammox) reactor, by reducing the nitrate produced. However, the slow growth and the low activity of DAMO microorganisms cast a serious doubt about the practical usefulness of such a process. In this study, a previously established lab-scale membrane biofilm reactor (MBfR), with biofilms consisting of a coculture of DAMO and anammox microorganisms, was operated to answer if the DAMO reactor can achieve a nitrate reduction rate that can potentially be applied for wastewater treatment. Through progressively increasing nitrate and ammonium loading rates to the reactor, a nitrate removal rate of 684 ± 10 mg-N L(-1) d(-1) was achieved after 453 days of operation. This rate is, to our knowledge, by far the highest reported for DAMO reactors, and far exceeds what is predicted to be required for nitrate removal in a sidestream (5.6-135 mg-N L(-1) d(-1)) or mainstream anammox reactor (3.2-124 mg-N L(-1) d(-1)). Mass balance analysis showed that the nitrite produced by nitrate reduction was jointly reduced by anammox bacteria at a rate of 354 ± 3 mg-N L(-1) d(-1), accompanied by an ammonium removal rate of 268 ± 2 mg-N L(-1) d(-1), and DAMO bacteria at a rate of 330 ± 9 mg-N L(-1) d(-1). This study shows that the nitrate reduction rate achieved by the DAMO process can be high enough for removing nitrate produced by anammox process, which would enable complete nitrogen removal from wastewater.

  8. Short-term training alters the control of mitochondrial respiration rate before maximal oxidative ATP synthesis

    PubMed Central

    Layec, Gwenael; Haseler, Luke J.; Hoff, Jan; Hart, Corey R.; Liu, Xin; Le Fur, Yann; Jeong, Eun-Kee; Richardson, Russell S.

    2013-01-01

    Aim Short-term exercise training may induce metabolic and performance adaptations before any changes in mitochondrial enzyme potential. However, there has not been a study that has directly assessed changes in mitochondrial oxidative capacity or metabolic control as a consequence of such training in vivo. Therefore, we used 31P-magnetic resonance spectroscopy (31P-MRS) to examine the effect of short-term plantar flexion exercise training on phosphocreatine (PCr) recovery kinetics and the control of respiration rate. Method To this aim, we investigated 12 healthy men, experienced with this exercise modality (TRA), and 7 time-control subjects (TC). Results After 5 days of training, maximum work rate during incremental plantar flexion exercise was significantly improved (P < 0.01). During the recovery period, the maximal rate of oxidative ATP synthesis (PRE: 28 ± 13 mM.min−1; POST: 26 ± 15 mM.min−1) and the PCr recovery time constant (PRE: 31 ± 19 s; POST: 29 ± 16) were not significantly altered. In contrast, the Hill coefficient (nH) describing the cooperativity between respiration rate and ADP was significantly increased in TRA (PRE:nH = 2.7 ± 1.4; POST: nH = 3.4 ± 1.9, P < 0.05). Meanwhile, there were no systematic variations in any of these variables in TC. Conclusion This study reveals that 5 days of training induces rapid adaptation in the allosteric control of respiration rate by ADP before any substantial improvement in muscle oxidative capacity occurs. PMID:23582030

  9. Optimization of synthesis and peptization steps to obtain iron oxide nanoparticles with high energy dissipation rates

    NASA Astrophysics Data System (ADS)

    Mérida, Fernando; Chiu-Lam, Andreina; Bohórquez, Ana C.; Maldonado-Camargo, Lorena; Pérez, María-Eglée; Pericchi, Luis; Torres-Lugo, Madeline; Rinaldi, Carlos

    2015-11-01

    Magnetic Fluid Hyperthermia (MFH) uses heat generated by magnetic nanoparticles exposed to alternating magnetic fields to cause a temperature increase in tumors to the hyperthermia range (43-47 °C), inducing apoptotic cancer cell death. As with all cancer nanomedicines, one of the most significant challenges with MFH is achieving high nanoparticle accumulation at the tumor site. This motivates development of synthesis strategies that maximize the rate of energy dissipation of iron oxide magnetic nanoparticles, preferable due to their intrinsic biocompatibility. This has led to development of synthesis strategies that, although attractive from the point of view of chemical elegance, may not be suitable for scale-up to quantities necessary for clinical use. On the other hand, to date the aqueous co-precipitation synthesis, which readily yields gram quantities of nanoparticles, has only been reported to yield sufficiently high specific absorption rates after laborious size selective fractionation. This work focuses on improvements to the aqueous co-precipitation of iron oxide nanoparticles to increase the specific absorption rate (SAR), by optimizing synthesis conditions and the subsequent peptization step. Heating efficiencies up to 1048 W/gFe (36.5 kA/m, 341 kHz; ILP=2.3 nH m2 kg-1) were obtained, which represent one of the highest values reported for iron oxide particles synthesized by co-precipitation without size-selective fractionation. Furthermore, particles reached SAR values of up to 719 W/gFe (36.5 kA/m, 341 kHz; ILP=1.6 nH m2 kg-1) when in a solid matrix, demonstrating they were capable of significant rates of energy dissipation even when restricted from physical rotation. Reduction in energy dissipation rate due to immobilization has been identified as an obstacle to clinical translation of MFH. Hence, particles obtained with the conditions reported here have great potential for application in nanoscale thermal cancer therapy.

  10. Process for converting light alkanes to higher hydrocarbons

    DOEpatents

    Noceti, Richard P.; Taylor, Charles E.

    1988-01-01

    A process is disclosed for the production of aromatic-rich, gasoline boiling range hydrocarbons from the lower alkanes, particularly from methane. The process is carried out in two stages. In the first, alkane is reacted with oxygen and hydrogen chloride over an oxyhydrochlorination catalyst such as copper chloride with minor proportions of potassium chloride and rare earth chloride. This produces an intermediate gaseous mixture containing water and chlorinated alkanes. The chlorinated alkanes are contacted with a crystalline aluminosilicate catalyst in the hydrogen or metal promoted form to produce gasoline range hydrocarbons with a high proportion of aromatics and a small percentage of light hydrocarbons (C.sub.2 -C.sub.4). The light hydrocarbons can be recycled for further processing over the oxyhydrochlorination catalyst.

  11. Influence of ammonia oxidation rate on thaumarchaeal lipid composition and the TEX86 temperature proxy.

    PubMed

    Hurley, Sarah J; Elling, Felix J; Könneke, Martin; Buchwald, Carolyn; Wankel, Scott D; Santoro, Alyson E; Lipp, Julius Sebastian; Hinrichs, Kai-Uwe; Pearson, Ann

    2016-07-12

    Archaeal membrane lipids known as glycerol dibiphytanyl glycerol tetraethers (GDGTs) are the basis of the TEX86 paleotemperature proxy. Because GDGTs preserved in marine sediments are thought to originate mainly from planktonic, ammonia-oxidizing Thaumarchaeota, the basis of the correlation between TEX86 and sea surface temperature (SST) remains unresolved: How does TEX86 predict surface temperatures, when maximum thaumarchaeal activity occurs below the surface mixed layer and TEX86 does not covary with in situ growth temperatures? Here we used isothermal studies of the model thaumarchaeon Nitrosopumilus maritimus SCM1 to investigate how GDGT composition changes in response to ammonia oxidation rate. We used continuous culture methods to avoid potential confounding variables that can be associated with experiments in batch cultures. The results show that the ring index scales inversely (R(2) = 0.82) with ammonia oxidation rate (ϕ), indicating that GDGT cyclization depends on available reducing power. Correspondingly, the TEX86 ratio decreases by an equivalent of 5.4 °C of calculated temperature over a 5.5 fmol·cell(-1)·d(-1) increase in ϕ. This finding reconciles other recent experiments that have identified growth stage and oxygen availability as variables affecting TEX86 Depth profiles from the marine water column show minimum TEX86 values at the depth of maximum nitrification rates, consistent with our chemostat results. Our findings suggest that the TEX86 signal exported from the water column is influenced by the dynamics of ammonia oxidation. Thus, the global TEX86-SST calibration potentially represents a composite of regional correlations based on nutrient dynamics and global correlations based on archaeal community composition and temperature.

  12. Influence of ammonia oxidation rate on thaumarchaeal lipid composition and the TEX86 temperature proxy

    PubMed Central

    Hurley, Sarah J.; Elling, Felix J.; Könneke, Martin; Buchwald, Carolyn; Wankel, Scott D.; Santoro, Alyson E.; Lipp, Julius Sebastian; Hinrichs, Kai-Uwe; Pearson, Ann

    2016-01-01

    Archaeal membrane lipids known as glycerol dibiphytanyl glycerol tetraethers (GDGTs) are the basis of the TEX86 paleotemperature proxy. Because GDGTs preserved in marine sediments are thought to originate mainly from planktonic, ammonia-oxidizing Thaumarchaeota, the basis of the correlation between TEX86 and sea surface temperature (SST) remains unresolved: How does TEX86 predict surface temperatures, when maximum thaumarchaeal activity occurs below the surface mixed layer and TEX86 does not covary with in situ growth temperatures? Here we used isothermal studies of the model thaumarchaeon Nitrosopumilus maritimus SCM1 to investigate how GDGT composition changes in response to ammonia oxidation rate. We used continuous culture methods to avoid potential confounding variables that can be associated with experiments in batch cultures. The results show that the ring index scales inversely (R2 = 0.82) with ammonia oxidation rate (ϕ), indicating that GDGT cyclization depends on available reducing power. Correspondingly, the TEX86 ratio decreases by an equivalent of 5.4 °C of calculated temperature over a 5.5 fmol·cell−1·d−1 increase in ϕ. This finding reconciles other recent experiments that have identified growth stage and oxygen availability as variables affecting TEX86. Depth profiles from the marine water column show minimum TEX86 values at the depth of maximum nitrification rates, consistent with our chemostat results. Our findings suggest that the TEX86 signal exported from the water column is influenced by the dynamics of ammonia oxidation. Thus, the global TEX86–SST calibration potentially represents a composite of regional correlations based on nutrient dynamics and global correlations based on archaeal community composition and temperature. PMID:27357675

  13. Evidence that crude oil alkane activation proceeds by different mechanisms under sulfate-reducing and methanogenic conditions

    NASA Astrophysics Data System (ADS)

    Aitken, C. M.; Jones, D. M.; Maguire, M. J.; Gray, N. D.; Sherry, A.; Bowler, B. F. J.; Ditchfield, A. K.; Larter, S. R.; Head, I. M.

    2013-05-01

    Fumarate addition has been widely proposed as an initial step in the anaerobic oxidation of both aromatic and aliphatic hydrocarbons. Alkyl and aryl succinates have been reported as metabolites of hydrocarbon degradation in laboratory studies with both pure and enrichment cultures of sulfate-, nitrate-, and iron-reducing bacteria. In addition these compounds have been reported in samples from environments such as hydrocarbon contaminated aquifers where, in addition to the above redox processes, hydrocarbon degradation linked to methanogenesis was observed. Here we report data from anaerobic crude oil degrading microcosms which revealed significant differences between the acid metabolite profiles of crude oil degraded under sulfate-reducing or methanogenic conditions. Under sulfate-reducing conditions fumarate addition and the formation of alkylsuccinate metabolites was the principal mechanism for the anaerobic degradation of n-alkanes and branched chain alkanes. Other than alkyl succinates that represent indigenous metabolites in the sediment inoculum, alkyl succinate metabolites were never detected in sediment microcosms where methane generation was quantitatively linked to n-alkane degradation. This indicates that alternative mechanisms of alkane activation may operate under methanogenic conditions.

  14. Site-selective Alkane Dehydrogenation of Fatty Acids

    DTIC Science & Technology

    2011-12-14

    dehydrogenation of fatty acids Contract/Grant#: FA9550-10-1-0532 Final Reporting Period: 15 September 2011 to 14 September 2011...directly incorporate fatty acids into the ligand. The preparation of the acyl phosphines (1-5) was easily accomplished starting from the corresponding...AFOSR Final Report Final Report 
 The proposed research examines the site-selective dehydrogenation of alkanes. The alkanes employed were fatty

  15. Transition-state enthalpy and entropy effects on reactivity and selectivity in hydrogenolysis of n-alkanes.

    PubMed

    Flaherty, David W; Iglesia, Enrique

    2013-12-11

    Statistical mechanics and transition state (TS) theory describe rates and selectivities of C-C bond cleavage in C2-C10 n-alkanes on metal catalysts and provide a general description for the hydrogenolysis of hydrocarbons. Mechanistic interpretation shows the dominant role of entropy, over enthalpy, in determining the location and rate of C-C bond cleavage. Ir, Rh, and Pt clusters cleave C-C bonds at rates proportional to coverages of intermediates derived by removing 3-4 H-atoms from n-alkanes. Rate constants for C-C cleavage reflect large activation enthalpies (ΔH(‡), 217-257 kJ mol(-1)) that are independent of chain length and C-C bond location in C4+ n-alkanes. C-C bonds cleave because of large, positive activation entropies (ΔS(‡), 164-259 J mol(-1) K(-1)) provided by H2 that forms with TS. Kinetic and independent spectroscopic evidence for the composition and structure of these TS give accurate estimates of ΔS(‡) for cleavage at each C-C bond. Large differences between rate constants for ethane and n-decane (~10(8)) reflect an increase in the entropy of gaseous alkanes retained at the TS. The location of C-C bond cleavage depends solely on the rotational entropies of alkyl chains attached to the cleaved C-C bond, which depend on their chain length. Such entropy considerations account for the ubiquitous, but previously unexplained, preference for cleaving nonterminal C-C bonds in n-alkanes. This mechanistic analysis and thermodynamic treatment illustrates the continued utility of such approaches even for hydrogenolysis reactions, with complexity seemingly beyond the reach of classical treatments, and applies to catalytic clusters beyond those reported here (0.6-2.7 nm; Ir, Rh, Pt).

  16. Chemical characterization of organosulfates in secondary organic aerosol derived from the photooxidation of alkanes

    NASA Astrophysics Data System (ADS)

    Riva, Matthieu; Da Silva Barbosa, Thais; Lin, Ying-Hsuan; Stone, Elizabeth A.; Gold, Avram; Surratt, Jason D.

    2016-09-01

    We report the formation of aliphatic organosulfates (OSs) in secondary organic aerosol (SOA) from the photooxidation of C10-C12 alkanes. The results complement those from our laboratories reporting the formation of OSs and sulfonates from gas-phase oxidation of polycyclic aromatic hydrocarbons (PAHs). Both studies strongly support the formation of OSs from the gas-phase oxidation of anthropogenic precursors, as hypothesized on the basis of recent field studies in which aromatic and aliphatic OSs were detected in fine aerosol collected from several major urban locations. In this study, dodecane, cyclodecane and decalin, considered to be important SOA precursors in urban areas, were photochemically oxidized in an outdoor smog chamber in the presence of either non-acidified or acidified ammonium sulfate seed aerosol. Effects of acidity and relative humidity on OS formation were examined. Aerosols collected from all experiments were characterized by ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS). Most of the OSs identified could be explained by formation of gaseous epoxide precursors with subsequent acid-catalyzed reactive uptake onto sulfate aerosol and/or heterogeneous reactions of hydroperoxides. The OSs identified here were also observed and quantified in fine urban aerosol samples collected in Lahore, Pakistan, and Pasadena, CA, USA. Several OSs identified from the photooxidation of decalin and cyclodecane are isobars of known monoterpene organosulfates, and thus care must be taken in the analysis of alkane-derived organosulfates in urban aerosol.

  17. Theoretically predicted rate constants for mercury oxidation by hydrogen chloride in coal combustion flue gases.

    PubMed

    Wilcox, Jennifer; Robles, Joe; Marsden, David C J; Blowers, Paul

    2003-09-15

    In this work, theoretical rate constants are estimated for mercury oxidation reactions by hydrogen chloride that may occur in the flue gases of coal combustion. Rate constants are calculated using transition state theory at the quadratic configuration interaction (QCI) level of theory with single and double excitations, and are compared to results obtained from density functional theory, both including high level pseudopotentials for mercury. Thermodynamic and kinetic data from the literature are used to assess the accuracy of the theoretical calculations when possible. Validation of the chosen methods and basis sets is based upon previous and current research on mercury reactions involving chlorine. The present research shows that the QCISD method with the 1992 Stevens et al. basis set leads to the most accurate kinetic and thermodynamic results for the oxidation of mercury via chlorine containing molecules. Also, a comparison of the heats of reaction data for a series of mercury oxidation reactions reveals that the density functional method, B3LYP, with the 1997 Stuttgart basis set provides reasonably accurate results for these large systems.

  18. Nitrification rates in Arctic soils are associated with functionally distinct populations of ammonia-oxidizing archaea

    NASA Astrophysics Data System (ADS)

    Alves, Ricardo J. E.; Wanek, Wolfgang; Zappe, Anna; Richter, Andreas; Svenning, Mette M.; Schleper, Christa; Urich, Tim

    2014-05-01

    The functioning of Arctic soil ecosystems is crucially important for global climate, although basic knowledge regarding their biogeochemical processes is lacking. Nitrogen (N) is the major limiting nutrient in these environments, and therefore it is particularly important to gain a better understanding of the microbial populations catalyzing transformations that influence N bioavailability. However, microbial communities driving this process remain largely uncharacterized in Arctic soils, namely those catalyzing the rate-limiting step of ammonia (NH3) oxidation. Eleven Arctic soils from Svalbard were analyzed through a polyphasic approach, including determination of gross nitrification rates through a 15N pool dilution method, qualitative and quantitative analyses of ammonia-oxidizing archaea (AOA) and bacteria (AOB) populations based on the functional marker gene amoA (encoding the ammonia monooxygenase subunit A), and enrichment of AOA in laboratory cultures. AOA were the only NH3 oxidizers detected in five out of 11 soils, and outnumbered AOB by 1 to 3 orders of magnitude in most others. AOA showed a great overall phylogenetic diversity that was differentially distributed across soil ecosystems, and exhibited an uneven population composition that reflected the dominance of a single AOA phylotype in each population. Moreover, AOA populations showed a multifactorial association with the soil properties, which reflected an overall distribution associated with tundra type and with several physico-chemical parameters combined, namely pH and soil moisture and N contents (i.e., NO3- and dissolved organic N). Remarkably, the different gross in situ and potential nitrification rates between soils were associated with distinct AOA phylogenetic clades, suggesting differences in their nitrifying potential, both under the native NH3 conditions and as a response to higher NH3 availability. This was further supported by the selective enrichment of two AOA clades that exhibited

  19. Screening of a minimal enriched P450 BM3 mutant library for hydroxylation of cyclic and acyclic alkanes.

    PubMed

    Weber, Evelyne; Seifert, Alexander; Antonovici, Mihaela; Geinitz, Christopher; Pleiss, Jürgen; Urlacher, Vlada B

    2011-01-21

    A minimal enriched P450 BM3 library was screened for the ability to oxidize inert cyclic and acyclic alkanes. The F87A/A328V mutant was found to effectively hydroxylate cyclooctane, cyclodecane and cyclododecane. F87V/A328F with high activity towards cyclooctane hydroxylated acyclic n-octane to 2-(R)-octanol (46% ee) with high regioselectivity (92%).

  20. Investigation on laboratory and pilot-scale airlift sulfide oxidation reactor under varying sulfide loading rate.

    PubMed

    Pokasoowan, Chanya; Kanitchaidecha, Wilawan; K C, Bal Krishna; Annachhatre, Ajit P

    2009-01-01

    Airlift bioreactor was established for recovering sulfur from synthetic sulfide wastewater under controlled dissolved oxygen condition. The maximum recovered sulfur was 14.49 g/day when sulfide loading rate, dissolved oxygen (DO) and pH values were 2.97 kgHS(-)/m(3)-day, 0.2-1.0 mg/L and 7.2-7.8, respectively. On the other hand, the increase in recovered sulfur reduced the contact surface of sulfide oxidizing bacteria which affects the recovery process. This effect caused to reduce the conversion of sulfide to sulfur. More recovered sulfur was produced at high sulfide loading rate due to the change of metabolic pathway of sulfide-oxidizing bacteria which prevented the toxicity of sulfide in the culture. The maximum activity in this system was recorded to be about 3.28 kgS/kgVSS-day. The recovered sulfur contained organic compounds which were confirmed by the results from XRD and CHN analyzer. Afterwards, by annealing the recovered sulfur at 120 degrees C for 24 hrs under ambient Argon, the percentage of carbon reduced from 4.44% to 0.30%. Furthermore, the percentage of nitrogen and hydrogen decreased from 0.79% and 0.48% to 0.00% and 0.14%, respectively. This result showed the success in increasing the purity of recovered sulfur by using the annealing technique. The pilot-scale biological sulfide oxidation process was carried out using real wastewater from Thai Rayon Industry in Thailand. The airlift reactor successfully removed sulfide more than 90% of the influent sulfide at DO concentration of less than 0.1 mg/L, whereas the elementary sulfur production was 2.37 kgS/m(3)-day at sulfide loading rate of 2.14 kgHS(-)/m(3)-day. The sulfur production was still increasing as the reactor had not yet reached its maximum sulfide loading rate.

  1. Influences of organic carbon supply rate on uranium bioreduction in initially oxidizing, contaminated sediment.

    PubMed

    Tokunaga, Tetsu K; Wan, Jiamin; Kim, Yongman; Daly, Rebecca A; Brodie, Eoin L; Hazen, Terry C; Herman, Don; Firestone, Mary K

    2008-12-01

    Remediation of uranium-contaminated sediments through in situ stimulation of bioreduction to insoluble UO2 is a potential treatment strategy under active investigation. Previously, we found that newly reduced U(IV) can be reoxidized under reducing conditions sustained by a continuous supply of organic carbon (OC) because of residual reactive Fe(III) and enhanced U(VI) solubilitythrough complexation with carbonate generated through OC oxidation. That finding motivated this investigation directed at identifying a range of OC supply rates that is optimal for establishing U bioreduction and immobilization in initially oxidizing sediments. The effects of OC supply rate, from 0 to 580 mmol of OC (kg of sediment)(-1) year(-1), and OC form (lactate and acetate) on U bioreduction were tested in flow-through columns containing U-contaminated sediments. An intermediate supply rate on the order of 150 mmol of OC (kg of sediment)(-1) year(-1) was determined to be most effective at immobilizing U. At lower OC supply rates, U bioreduction was not achieved, and U(VI) solubilitywas enhanced by complexation with carbonate (from OC oxidation). At the highest OC supply rate, the resulting highly carbonate-enriched solutions also supported elevated levels of U(VI), even though strongly reducing conditions were established. Lactate and acetate were found to have very similar geochemical impacts on effluent U concentrations (and other measured chemical species), when compared at equivalent OC supply rates. While the catalysts of U(VI) reduction to U(IV) are presumably bacteria, the composition of the bacterial community,the Fe-reducing community, and the sulfate-reducing community had no direct relationship with effluent U concentrations. The OC supply rate has competing effects of driving reduction of U(VI) to low-solubility U(IV) solids, as well as causing formation of highly soluble U(VI)-carbonato complexes. These offsetting influences will require careful control of OC supply rates

  2. Influences of Organic Carbon Supply Rate on Uranium Bioreduction in Initially Oxidizing, Contaminated Sediment

    SciTech Connect

    Tokunaga, Tetsu K.; Wan, Jiamin; Kim, Yongman; Daly, Rebecca A.; Brodie, Eoin L.; Hazen, Terry C.; Herman, Don; Firestone, Mary K.

    2008-06-10

    Remediation of uranium (U) contaminated sediments through in-situ stimulation of bioreduction to insoluble UO{sub 2} is a potential treatment strategy under active investigation. Previously, we found that newly reduced U(IV) can be reoxidized under reducing conditions sustained by a continuous supply of organic carbon (OC) because of residual reactive Fe(III) and enhanced U(VI) solubility through complexation with carbonate generated through OC oxidation. That finding motivated this investigation directed at identifying a range of OC supply rates that is optimal for establishing U bioreduction and immobilization in initially oxidizing sediments. The effects of OC supply rate, from 0 to 580 mmol OC (kg sediment){sup -1} year{sup -1}, and OC form (lactate and acetate) on U bioreduction were tested in flow-through columns containing U-contaminated sediments. An intermediate supply rate on the order of 150 mmol OC (kg sediment){sup -1} year{sup -1} was determined to be most effective at immobilizing U. At lower OC supply rates, U bioreduction was not achieved, and U(VI) solubility was enhanced by complexation with carbonate (from OC oxidation). At the highest OC supply rate, resulting highly carbonate-enriched solutions also supported elevated levels of U(VI), even though strongly reducing conditions were established. Lactate and acetate were found to have very similar geochemical impacts on effluent U concentrations (and other measured chemical species), when compared at equivalent OC supply rates. While the catalysts of U(VI) reduction to U(IV) are presumably bacteria, the composition of the bacterial community, the Fe reducing community, and the sulfate reducing community had no direct relationship with effluent U concentrations. The OC supply rate has competing effects of driving reduction of U(VI) to low solubility U(IV) solids, as well as causing formation of highly soluble U(VI)-carbonato complexes. These offsetting influences will require careful control of OC

  3. Hydrogen-hydrogen bonds in highly branched alkanes and in alkane complexes: A DFT, ab initio, QTAIM, and ELF study.

    PubMed

    Monteiro, Norberto K V; Firme, Caio L

    2014-03-06

    The hydrogen-hydrogen (H-H) bond or hydrogen-hydrogen bonding is formed by the interaction between a pair of identical or similar hydrogen atoms that are close to electrical neutrality and it yields a stabilizing contribution to the overall molecular energy. This work provides new, important information regarding hydrogen-hydrogen bonds. We report that stability of alkane complexes and boiling point of alkanes are directly related to H-H bond, which means that intermolecular interactions between alkane chains are directional H-H bond, not nondirectional induced dipole-induced dipole. Moreover, we show the existence of intramolecular H-H bonds in highly branched alkanes playing a secondary role in their increased stabilities in comparison with linear or less branched isomers. These results were accomplished by different approaches: density functional theory (DFT), ab initio, quantum theory of atoms in molecules (QTAIM), and electron localization function (ELF).

  4. Analysis of flow decay potential on Galileo. [oxidizer flow rate reduction by iron nitrate precipitates

    NASA Technical Reports Server (NTRS)

    Cole, T. W.; Frisbee, R. H.; Yavrouian, A. H.

    1987-01-01

    The risks posed to the NASA's Galileo spacecraft by the oxidizer flow decay during its extended mission to Jupiter is discussed. The Galileo spacecraft will use nitrogen tetroxide (NTO)/monomethyl hydrazine bipropellant system with one large engine thrust-rated at a nominal 400 N, and 12 smaller engines each thrust-rated at a nominal 10 N. These smaller thrusters, because of their small valve inlet filters and small injector ports, are especially vulnerable to clogging by iron nitrate precipitates formed by NTO-wetted stainless steel components. To quantify the corrosion rates and solubility levels which will be seen during the Galileo mission, corrosion and solubility testing experiments were performed with simulated Galileo materials, propellants, and environments. The results show the potential benefits of propellant sieving in terms of iron and water impurity reduction.

  5. Rate of the reduction of the iron oxides in red mud by hydrogen and converted gas

    NASA Astrophysics Data System (ADS)

    Teplov, O. A.; Lainer, Yu. A.

    2013-01-01

    The drying and gas reduction of the iron oxides in the red mud of bauxite processing are studied. It is shown that at most 25% of aluminum oxide are fixed by iron oxides in this red mud, and the other 75% are fixed by sodium aluminosilicates. A software package is developed to calculate the gas reduction of iron oxides, including those in mud. Small hematite samples fully transform into magnetite in hydrogen at a temperature below 300°C and a heating rate of 500 K/h, and complete reduction of magnetite to metallic iron takes place below 420°C. The densification of a thin red mud layer weakly affects the character and temperature range of magnetizing calcination, and the rate of reduction to iron decreases approximately twofold and reduction covers a high-temperature range (above 900°C). The substitution of a converted natural gas for hydrogen results in a certain delay in magnetite formation and an increase in the temperature of the end of reaction to 375°C. In the temperature range 450-550°C, the transformation of hematite into magnetite in red mud pellets 1 cm in diameter in a converted natural gas is 30-90 faster than the reduction of hematite to iron in hydrogen. The hematite-magnetite transformation rate in pellets is almost constant in the temperature range under study, and reduction occurs in a diffusion mode. At a temperature of ˜500°C, the reaction layer thickness of pellets in a shaft process is calculated to be ˜1 m at a converted-gas flow rate of 0.1 m3/(m2 s) and ˜2.5 m at a flow rate of 0.25 m3/(m2 s). The specific capacity of 1 m2 of the shaft cross section under these conditions is 240 and 600 t/day, respectively. The use of low-temperature gas reduction processes is promising for the development of an in situ optimum red mud utilization technology.

  6. Short-chain alkanes synergise responses of moth pests to their sex pheromones.

    PubMed

    Gurba, Alexandre; Guerin, Patrick M

    2016-05-01

    The use of sex pheromones for mating disruption of moth pests of crops is increasing worldwide. Efforts are under way to augment the efficiency and reliability of this control method by adding molecules derived from host plants to the sex attractants in dispensers. We show how attraction of the European grapevine moth, Lobesia botrana Den. & Schiff., and the codling moth, Cydia pomonella L., males to underdosed levels of their sex pheromones is increased by adding heptane or octane over a range of release rates. Pheromone-alkane mixtures enhance male recruitment by up to 30%, reaching levels induced by calling females, and shorten the flight time to the sex attractant by a factor of 2. The findings show the promise of using short-chain alkanes as pheromone synergists for mating disruption of insect pests of food crops. Alkane-pheromone combinations are expected to increase the competitiveness of dispensers with females, and to reduce the amount of pheromone needed for the control of these pests. © 2015 Society of Chemical Industry.

  7. Properties of Langmuir monolayers from semifluorinated alkanes

    NASA Astrophysics Data System (ADS)

    Broniatowski, M.; Macho, I. Sandez; Miñones, J.; Dynarowicz-Łątka, P.

    2005-06-01

    The aim of this study was to characterize several semifluorinated alkanes (SFA), of the general formula F(CF 2) m(CH 2) nH (in short F mH n), containing 25 carbon atoms in total (pentacosanes) differing in the m/ n ratio, as Langmuir monolayers at the free water surface. The following compounds have been studied: F6H19, F8H17, F10H15 and F12H13. Surface pressure ( π) and electric surface potential (Δ V) isotherms were recorded in addition to quantitative Brewster angle microscopy results. The negative sign of Δ V evidenced for the orientation of all the investigated semifluorinated pentacosanes, regardless the length of the hydrogenated segment, with their perfluorinated parts directed towards the air. As inferred from apparent dipole moment values and relative reflectivity results, the fluorinated pentacosanes with shorter perfluorinated fragment (F6H19 and F8H17) were found to be vertically oriented at the air/water interface, while those with longer perfluorinated moiety (F10H15 and F12H13) remain titled even in the vicinity of the film collapse.

  8. Thermodiffusion in multicomponent n-alkane mixtures.

    PubMed

    Galliero, Guillaume; Bataller, Henri; Bazile, Jean-Patrick; Diaz, Joseph; Croccolo, Fabrizio; Hoang, Hai; Vermorel, Romain; Artola, Pierre-Arnaud; Rousseau, Bernard; Vesovic, Velisa; Bou-Ali, M Mounir; Ortiz de Zárate, José M; Xu, Shenghua; Zhang, Ke; Montel, François; Verga, Antonio; Minster, Olivier

    2017-01-01

    Compositional grading within a mixture has a strong impact on the evaluation of the pre-exploitation distribution of hydrocarbons in underground layers and sediments. Thermodiffusion, which leads to a partial diffusive separation of species in a mixture due to the geothermal gradient, is thought to play an important role in determining the distribution of species in a reservoir. However, despite recent progress, thermodiffusion is still difficult to measure and model in multicomponent mixtures. In this work, we report on experimental investigations of the thermodiffusion of multicomponent n-alkane mixtures at pressure above 30 MPa. The experiments have been conducted in space onboard the Shi Jian 10 spacecraft so as to isolate the studied phenomena from convection. For the two exploitable cells, containing a ternary liquid mixture and a condensate gas, measurements have shown that the lightest and heaviest species had a tendency to migrate, relatively to the rest of the species, to the hot and cold region, respectively. These trends have been confirmed by molecular dynamics simulations. The measured condensate gas data have been used to quantify the influence of thermodiffusion on the initial fluid distribution of an idealised one dimension reservoir. The results obtained indicate that thermodiffusion tends to noticeably counteract the influence of gravitational segregation on the vertical distribution of species, which could result in an unstable fluid column. This confirms that, in oil and gas reservoirs, the availability of thermodiffusion data for multicomponent mixtures is crucial for a correct evaluation of the initial state fluid distribution.

  9. Photocatalytic oxidation mechanism of alkanes in contact with titanium dioxide

    NASA Technical Reports Server (NTRS)

    Formenti, M.; Juillet, F.; Teichner, S. J.

    1977-01-01

    Isobutane was photooxidized on titanium dioxide between -16 and +180 C in tertiary butanol and acetone. The formation of tertiary butanol preceded the formation of acetone. Above 20 C the latter compound became clearly predominant. The reaction kinetics obeyed a steady state model of oxygen chemisorption with the involvement of isobutane in the physisorbed phase.

  10. Hydrogen isotopic composition of individual n-alkanes as an intrinsic tracer for bioremediation and source identification of petroleum contamination.

    PubMed

    Pond, Kristy L; Huang, Yongsong; Wang, Yi; Kulpa, Charles F

    2002-02-15

    The isotopic signatures of crude oil hydrocarbons are potentially powerful intrinsic tracers to their origins and the processes by which the oils are modified in the environment. Stable carbon isotopic data are of limited use for studying petroleum contaminants because of the relatively small amount of isotopic fractionation that occurs during natural processes. Hydrogen isotopes, in contrast, are commonly fractionated to a much greater extent and as a result display larger variations in delta values. We studied the effect of in vitro aerobic biodegradation on the hydrogen isotopic composition of individual n-alkanes from crude oil. The isotopic analysis was conducted using gas chromatography-thermal conversion-isotope ratio mass spectrometry. In general, biodegradation rates decreased with increasing hydrocarbon chain length, consistent with previous studies. More importantly the n-alkanes that were degraded at the fastest rates (n-C15 to n-C18) also showed the largest overall isotopic fractionation (approximately 12-25 per thousand deuterium enrichment), suggesting that the lower molecular weight n-alkanes can be used to monitor in-situ bioremediation of crude oil contamination. The hydrogen isotopic compositions of the longer chain alkanes (n-C19 to n-C27) were relatively stable during biodegradation (<5%o overall deuterium enrichment), indicating that these compounds are effective tracers for oil-source identification studies.

  11. Nitrogen-doped reduced graphene oxide as electrode material for high rate supercapacitors

    NASA Astrophysics Data System (ADS)

    Śliwak, Agata; Grzyb, Bartosz; Díez, Noel; Gryglewicz, Grażyna

    2017-03-01

    Nitrogen-doped reduced graphene oxides (N-rGOs) have been synthesized at various temperatures by a facile hydrothermal route involving the doping of an aqueous graphene oxide dispersion with amitrole. The N-rGOs had a nitrogen content ranging from 10.9 to 13.4 at%, which is among the highest reported for this type of material. The predominant nitrogen species were pyridinic followed by amide/amine, pyrrolic, and quaternary nitrogen. Cyclic voltammetry and impedance spectroscopy measurements performed on the N-doped and nitrogen-free samples revealed that nitrogen fixation provided the material with pseudocapacitive behaviour and improved ion diffusion and charge propagation. A high specific capacitance of 244 F g-1 was obtained at a high scan rate of 100 mV s-1 for the N-rGO with the highest nitrogen content. An outstanding rate capability for the N-rGO, with increasing scan rates, of 98% was obtained, while only 70% was obtained for the non-doped rGO. 92% of the initial capacitance was maintained over 5000 charge/discharge cycles due to the high stability of the electrochemically active nitrogen moieties. Hydrothermal synthesis using amitrole as a nitrogen dopant represents a simple route for the synthesis of graphene with very high nitrogen content and exceptional behaviour for use as electrode material in high-power supercapacitors.

  12. Fat oxidation rate and the exercise intensity that elicits maximal fat oxidation decreases with pubertal status in young male subjects.

    PubMed

    Riddell, M C; Jamnik, V K; Iscoe, K E; Timmons, Brian W; Gledhill, N

    2008-08-01

    The range of exercise intensities that elicit high fat oxidation rates (FOR) in youth and the influence of pubertal status on peak FOR are unknown. In a longitudinal design, we compared FOR over a range of exercise intensities in a small cohort of developing prepubertal male subjects. Five boys all at Tanner stage 1 (ages 11-12 yr) and nine men (ages 20-26 yr) underwent an incremental cycle ergometry test to volitional exhaustion. FOR curves were determined from indirect calorimetry during the final 30 s of each increment. The same protocol was duplicated annually in the boys as they progressed through puberty. The peak FOR was considerably higher (P<0.05) in boys at Tanner 1 (8.6+/-1.5 mg.kg lean body mass(-1).min(-1)) (mean+/-SD) compared with men (4.2+/-1.1 mg.kg lean body mass(-1).min(-1)). FOR dropped as boys developed through puberty (Tanner 2/3 peak rate=7.6+/-0.6 mg.kg lean body mass(-1).min(-1); Tanner 4 peak rate=5.4+/-1.8 mg.kg lean body mass(-1).min(-1), main effect of Tanner stage; P<0.05) to the levels found in men (not significant). The exercise intensity that elicited peak FOR was higher in the boys at Tanner 1 [56+/-6% peak aerobic power (VO2 peak)] than in men (31+/-4% VO2 peak) (P<0.001). This value tended to decrease by Tanner stage 4 (45+/-10% VO2 peak, main effect of Tanner stage; P=0.06). We conclude that, compared with men, prepubertal boys have higher relative FOR throughout a wide range of exercise intensities and that FOR drops as boys develop through puberty.

  13. Nitric oxide modulates the discharge rate of basal forebrain neurones: a study in freely moving rats.

    PubMed

    Kostin, Andrey; Stenberg, Dag; Porkka-Heiskanen, Tarja

    2009-12-01

    In urethane-anaesthetized rats the infusion of a nitric oxide (NO)-donor [NOC-18, 1 mM (DETA/NO); 2,2'-(hydroxynitrosohydrazino)bis-ethanamine)] into the basal forebrain (BF) inhibited the discharge rate of most neurones, suggesting that NO may promote sleep via inhibition of wake-promoting neurones in the BF. However, this hypothesis still needs to be confirmed in freely moving rats. The objective of this study was to examine whether NO modulates the discharge rate of BF neurones in freely moving rats in a similar manner to anaesthetized rats. We measured the discharge rates of BF neurones in freely moving rats during microdialysis infusion of a NO-donor (1 mm; NOC-18) in different vigilance states. Neurones were characterized as wake (W)-on (51.8%), W-off (28.6%) and W/non-rapid eye movement (REM)-independent (21.4%) based on their discharge profiles during wakefulness (W) and non-REM sleep. The NO-donor affected the discharge rate of most BF neurones during quiet wakefulness (QW; 55%) and non-REM sleep (64%). The most prominent response in all neuronal groups was a decrease in the discharge rate during QW and non-REM sleep. A small subpopulation of neurones increased the discharge rate. The increase in NO in the BF during prolonged wakefulness may facilitate sleep via inhibition of wake-promoting neurones.

  14. Structure of zirconium alloy oxides formed in pure water studied with synchrotron radiation and optical microscopy: relation to corrosion rate

    NASA Astrophysics Data System (ADS)

    Yilmazbayhan, Aylin; Motta, Arthur T.; Comstock, Robert J.; Sabol, George P.; Lai, Barry; Cai, Zhonghou

    2004-01-01

    A detailed study was undertaken of oxides formed in 360 °C water on four Zr-based alloys (Zircaloy-4, ZIRLO™, Zr-2.5%Nb and Zr-2.5%Nb-0.5%Cu) in an effort to relate oxide structure to corrosion performance. Micro-beam X-ray diffraction was used along with transmitted light optical microscopy to obtain information about the structure of these oxides as a function of distance from the oxide-metal interface. Optical microscopy revealed a layered oxide structure in which the average layer thickness was inversely proportional to the post-transition corrosion rate. The detailed diffraction studies showed an oxide that contained both tetragonal and monoclinic ZrO 2, with a higher fraction of tetragonal oxide near the oxide-metal interface, in a region roughly corresponding to one oxide layer. Evidence was seen also of a cyclic variation of the tetragonal and monoclinic oxide across the oxide thickness with a period of the layer thickness. The results also indicate that the final grain size of the tetragonal phase is smaller than that of the monoclinic phase and the monoclinic grain size is smaller in Zircaloy-4 and ZIRLO than in the other two alloys. These results are discussed in terms of a model of oxide growth based on the periodic breakdown and reconstitution of a protective layer. ZIRLO is a trademark of Westinghouse Electric Co.

  15. Size-dependant heating rates of iron oxide nanoparticles for magnetic fluid hyperthermia.

    PubMed

    Gonzales-Weimuller, Marcela; Zeisberger, Matthias; Krishnan, Kannan M

    2009-07-01

    Using the thermal decomposition of organometallics method we have synthesized high-quality, iron oxide nanoparticles of tailorable size up to ~15nm and transferred them to a water phase by coating with a biocompatible polymer. The magnetic behavior of these particles was measured and fit to a log-normal distribution using the Chantrell method and their polydispersity was confirmed to be very narrow. By performing calorimetry measurements with these monodisperse particles we have unambiguously demonstrated, for the first time, that at a given frequency, heating rates of superparamagnetic particles are dependent on particle size, in agreement with earlier theoretical predictions.

  16. Quantification of chemotaxis-related alkane accumulation in Acinetobacter baylyi using Raman microspectroscopy.

    PubMed

    Li, Hanbing; L Martin, Francis Luke; Zhang, Dayi

    2017-03-03

    Alkanes are one of the most widespread contaminants in the natural environment, primarily as a consequence of biological synthesis and oil spills. Many indigenous microbes metabolize alkanes, and the chemotaxis and accumulation in some strains has been identified. For the first time, we apply Raman microspectroscopy to identify such chemotaxis-related affinity, and quantify the alkane concentrations via spectral alterations. Raman spectral alterations were only found for the alkane chemo-attractant bacteria Acinetobacter baylyi ADP1, not for Pseudomonas fluorescence, which exhibits limited chemotaxis towards alkane. The significant alterations were attributed to the strong chemotactic ability of A. baylyi enhancing the affinity and accumulation of alkane molecules on cell membranes or cellular internalization. Spectral fingerprints of A. baylyi significantly altered after 1-h exposure to pure alkanes (dodecane or tetradecane) and alkane mixtures (mineral oil or crude oil), but not monocyclic aromatic hydrocarbons (MAHs) or polycyclic aromatic hydrocarbons (PAHs). A semi-log linear regression relationship between Raman spectral alterations and alkane concentrations showed its feasibility in quantifying alkane concentration in environmental samples. Pure alkanes or alkane mixtures exhibited different limits of detection and regression slopes, indicating that the chemotaxis-related alkane accumulation in A. baylyi is dependent on the carbon chain length. This work provides a novel biospectroscopy approach to characterize the chemotaxis-related alkane bioaccumulation, and has immense potential for fast and high-throughput screening bacterial chemotaxis.

  17. Inhibition of phenol on the rates of ammonia oxidation by Nitrosomonas europaea grown under batch, continuous fed, and biofilm conditions.

    PubMed

    Lauchnor, Ellen G; Semprini, Lewis

    2013-09-01

    Ammonia oxidation by Nitrosomonas europaea, an ammonia oxidizing bacterium prevalent in wastewater treatment, is inhibited in the presence of phenol, due to interaction of the phenol with the ammonia monooxygenase enzyme. Suspended cells of N. europaea were cultured in batch reactors and continuous flow reactors at dilution rates of 0.01-0.2 d(-1). The rate of ammonia oxidation in the continuous cultures correlated to the dilution rate in the reactor. The batch and continuous cultures were exposed to 20 μM phenol and ammonia oxidation activity was measured by specific oxygen uptake rates (SOURs). Inhibition of NH3 oxidation by 20 μM phenol ranged from a 77% reduction of SOUR observed with suspended cells harvested during exponential growth, to 26% in biofilms. The extent of inhibition was correlated with ammonia oxidation rates in both suspended and biofilm cells, with greater percent inhibition observed with higher initial rates of NH3 oxidation. In biofilm grown cells, an increase in activity and phenol inhibition were both observed upon dispersing the biofilm cells into fresh, liquid medium. Under higher oxygen tension, an increase in the NO2(-) production of the biofilms was observed and biofilms were more susceptible to phenol inhibition. Dissolved oxygen microsensor measurements showed oxygen limited conditions existed in the biofilms. The ammonia oxidation rate was much lower in biofilms, which were less inhibited during phenol exposure. The results clearly indicate in both suspended and attached cells of N. europaea that a higher extent of phenol inhibition is positively correlated with a higher rate of NH3 oxidation (enzyme turnover).

  18. Progressive Degradation of Crude Oil n-Alkanes Coupled to Methane Production under Mesophilic and Thermophilic Conditions

    PubMed Central

    Cheng, Lei; Shi, Shengbao; Li, Qiang; Chen, Jianfa; Zhang, Hui; Lu, Yahai

    2014-01-01

    Although methanogenic degradation of hydrocarbons has become a well-known process, little is known about which crude oil tend to be degraded at different temperatures and how the microbial community is responded. In this study, we assessed the methanogenic crude oil degradation capacity of oily sludge microbes enriched from the Shengli oilfield under mesophilic and thermophilic conditions. The microbial communities were investigated by terminal restriction fragment length polymorphism (T-RFLP) analysis of 16S rRNA genes combined with cloning and sequencing. Enrichment incubation demonstrated the microbial oxidation of crude oil coupled to methane production at 35 and 55°C, which generated 3.7±0.3 and 2.8±0.3 mmol of methane per gram oil, respectively. Gas chromatography-mass spectrometry (GC-MS) analysis revealed that crude oil n-alkanes were obviously degraded, and high molecular weight n-alkanes were preferentially removed over relatively shorter-chain n-alkanes. Phylogenetic analysis revealed the concurrence of acetoclastic Methanosaeta and hydrogenotrophic methanogens but different methanogenic community structures under the two temperature conditions. Candidate divisions of JS1 and WWE 1, Proteobacteria (mainly consisting of Syntrophaceae, Desulfobacteraceae and Syntrophorhabdus) and Firmicutes (mainly consisting of Desulfotomaculum) were supposed to be involved with n-alkane degradation in the mesophilic conditions. By contrast, the different bacterial phylotypes affiliated with Caldisericales, “Shengli Cluster” and Synergistetes dominated the thermophilic consortium, which was most likely to be associated with thermophilic crude oil degradation. This study revealed that the oily sludge in Shengli oilfield harbors diverse uncultured microbes with great potential in methanogenic crude oil degradation over a wide temperature range, which extend our previous understanding of methanogenic degradation of crude oil alkanes. PMID:25409013

  19. Progressive degradation of crude oil n-alkanes coupled to methane production under mesophilic and thermophilic conditions.

    PubMed

    Cheng, Lei; Shi, Shengbao; Li, Qiang; Chen, Jianfa; Zhang, Hui; Lu, Yahai

    2014-01-01

    Although methanogenic degradation of hydrocarbons has become a well-known process, little is known about which crude oil tend to be degraded at different temperatures and how the microbial community is responded. In this study, we assessed the methanogenic crude oil degradation capacity of oily sludge microbes enriched from the Shengli oilfield under mesophilic and thermophilic conditions. The microbial communities were investigated by terminal restriction fragment length polymorphism (T-RFLP) analysis of 16S rRNA genes combined with cloning and sequencing. Enrichment incubation demonstrated the microbial oxidation of crude oil coupled to methane production at 35 and 55°C, which generated 3.7±0.3 and 2.8±0.3 mmol of methane per gram oil, respectively. Gas chromatography-mass spectrometry (GC-MS) analysis revealed that crude oil n-alkanes were obviously degraded, and high molecular weight n-alkanes were preferentially removed over relatively shorter-chain n-alkanes. Phylogenetic analysis revealed the concurrence of acetoclastic Methanosaeta and hydrogenotrophic methanogens but different methanogenic community structures under the two temperature conditions. Candidate divisions of JS1 and WWE 1, Proteobacteria (mainly consisting of Syntrophaceae, Desulfobacteraceae and Syntrophorhabdus) and Firmicutes (mainly consisting of Desulfotomaculum) were supposed to be involved with n-alkane degradation in the mesophilic conditions. By contrast, the different bacterial phylotypes affiliated with Caldisericales, "Shengli Cluster" and Synergistetes dominated the thermophilic consortium, which was most likely to be associated with thermophilic crude oil degradation. This study revealed that the oily sludge in Shengli oilfield harbors diverse uncultured microbes with great potential in methanogenic crude oil degradation over a wide temperature range, which extend our previous understanding of methanogenic degradation of crude oil alkanes.

  20. Effect of pH and nitrite concentration on nitrite oxidation rate.

    PubMed

    Jiménez, E; Giménez, J B; Ruano, M V; Ferrer, J; Serralta, J

    2011-10-01

    The effect of pH and nitrite concentration on the activity of the nitrite oxidizing bacteria (NOB) in an activated sludge reactor has been determined by means of laboratory batch experiments based on respirometric techniques. The bacterial activity was measured at different pH and at different total nitrite concentrations (TNO₂). The experimental results showed that the nitrite oxidation rate (NOR) depends on the TNO₂ concentration independently of the free nitrous acid (FNA) concentration, so FNA cannot be considered as the real substrate for NOB. NOB were strongly affected by low pH values (no activity was detected at pH 6.5) but no inhibition was observed at high pH values (activity was nearly the same for the pH range 7.5-9.95). A kinetic expression for nitrite oxidation process including switch functions to model the effect of TNO₂ concentration and pH inhibition is proposed. Substrate half saturation constant and pH inhibition constants have been obtained.

  1. Intrinsic activity and poisoning rate for HCOOH oxidation on platinum stepped surfaces.

    PubMed

    Grozovski, Vitali; Climent, Víctor; Herrero, Enrique; Feliu, Juan M

    2010-08-21

    Pulsed voltammetry has been used to study formic acid oxidation on platinum stepped surfaces to determine the kinetics of the reaction and the role of the surface structure in the reactivity. From the current transients at different potentials, the intrinsic activity of the electrode through the active intermediate reaction path (j(theta = 0)), as well as the rate constant for the CO formation (k(ads)) have been calculated. The kinetics for formic acid oxidation through the active intermediate reaction path is strongly dependent on the surface structure of the electrode, with the highest activity found for the Pt(100) surface. The presence of steps, both on (100) and (111) terraces, does not increase the activity of these surfaces. CO formation only takes place in a narrow potential window very close to the local potential of zero total charge. The extrapolation of the results obtained with stepped surfaces with (111) terraces to zero step density indicates that CO formation should not occur on an ideal Pt(111) electrode. Additionally, the analysis of the Tafel slopes obtained for the different electrodes suggests that the oxidation of formic acid is strongly affected by the presence of adsorbed anions, hydrogen and water.

  2. Optimization of synthesis and peptization steps to obtain iron oxide nanoparticles with high energy dissipation rates

    PubMed Central

    Mérida, Fernando; Chiu-Lam, Andreina; Bohórquez, Ana C.; Maldonado-Camargo, Lorena; Pérez, María-Eglée; Pericchi, Luis; Torres-Lugo, Madeline; Rinaldi, Carlos

    2015-01-01

    Magnetic Fluid Hyperthermia (MFH) uses heat generated by magnetic nanoparticles exposed to alternating magnetic fields to cause a temperature increase in tumors to the hyperthermia range (43–47 °C), inducing apoptotic cancer cell death. As with all cancer nanomedicines, one of the most significant challenges with MFH is achieving high nanoparticle accumulation at the tumor site. This motivates development of synthesis strategies that maximize the rate of energy dissipation of iron oxide magnetic nanoparticles, preferable due to their intrinsic biocompatibility. This has led to development of synthesis strategies that, although attractive from the point of view of chemical elegance, may not be suitable for scale-up to quantities necessary for clinical use. On the other hand, to date the aqueous co-precipitation synthesis, which readily yields gram quantities of nanoparticles, has only been reported to yield sufficiently high specific absorption rates after laborious size selective fractionation. This work focuses on improvements to the aqueous co-precipitation of iron oxide nanoparticles to increase the specific absorption rate (SAR), by optimizing synthesis conditions and the subsequent peptization step. Heating efficiencies up to 1,048 W/gFe (36.5 kA/m, 341 kHz; ILP = 2.3 nH·m2·kg−1) were obtained, which represent one of the highest values reported for iron oxide particles synthesized by co-precipitation without size-selective fractionation. Furthermore, particles reached SAR values of up to 719 W/gFe (36.5 kA/m, 341 kHz; ILP = 1.6 nH·m2·kg−1) when in a solid matrix, demonstrating they were capable of significant rates of energy dissipation even when restricted from physical rotation. Reduction in energy dissipation rate due to immobilization has been identified as an obstacle to clinical translation of MFH. Hence, particles obtained with the conditions reported here have great potential for application in nanoscale thermal cancer therapy. PMID:26273124

  3. Discrimination of the prochiral hydrogens at the C-2 position of n-alkanes by the methane/ammonia monooxygenase family proteins.

    PubMed

    Miyaji, Akimitsu; Miyoshi, Teppei; Motokura, Ken; Baba, Toshihide

    2015-08-14

    The selectivity of ammonia monooxygenase from Nitrosomonas europaea (AMO-Ne) for the oxidation of C4-C8n-alkanes to the corresponding alcohol isomers was examined to show the ability of AMO-Ne to recognize the n-alkane orientation within the catalytic site. AMO-Ne in whole cells produces 1- and 2-alcohols from C4-C8n-alkanes, and the regioselectivity is dependent on the length of the carbon chain. 2-Alcohols produced from C4-C7n-alkanes were predominantly either the R- or S-enantiomers, while 2-octanol produced from n-octane was racemic. These results indicate that AMO-Ne can discriminate between the prochiral hydrogens at the C-2 position, with the degree of discrimination varying according to the n-alkane. Compared to the particulate methane monooxygenase (pMMO) of Methylococcus capsulatus (Bath) and that of Methylosinus trichosporium OB3b, AMO-Ne showed a distinct ability to discriminate between the orientation of n-butane and n-pentane in the catalytic site.

  4. Structural and mechanistic insight into alkane hydroxylation by Pseudomonas putida AlkB.

    PubMed

    Alonso, Hernan; Kleifeld, Oded; Yeheskel, Adva; Ong, Poh C; Liu, Yu C; Stok, Jeanette E; De Voss, James J; Roujeinikova, Anna

    2014-06-01

    Pseudomonas putida GPo1 alkane hydroxylase (AlkB) is an integral membrane protein that catalyses the hydroxylation of medium-chain alkanes (C3-C12). 1-Octyne irreversibly inhibits this non-haem di-iron mono-oxygenase under turnover conditions, suggesting that it acts as a mechanism-based inactivator. Upon binding to the active site, 1-octyne is postulated to be oxidized to an oxirene that rapidly rearranges to a reactive ketene which covalently acylates nearby residues, resulting in enzyme inactivation. In analysis of inactivated AlkB by LC-MS/MS, several residues exhibited a mass increase of 126.1 Da, corresponding to the octanoyl moiety derived from oxidative activation of 1-octyne. Mutagenesis studies of conserved acylated residues showed that Lys18 plays a critical role in enzyme function, as a single-point mutation of Lys18 to alanine (K18A) completely abolished enzymatic activity. Finally, we present a computational 3D model structure of the transmembrane domain of AlkB, which revealed the overall packing arrangement of the transmembrane helices within the lipid bilayer and the location of the active site mapped by the 1-octyne modifications.

  5. An Alkane-Responsive Expression System for the Production of Fine Chemicals

    PubMed Central

    Panke, Sven; Meyer, Andreas; Huber, Caroline M.; Witholt, Bernard; Wubbolts, Marcel G.

    1999-01-01

    Membrane-located monooxygenase systems, such as the Pseudomonas putida mt-2-derived xylene oxygenase, are attractive for challenging transformations of apolar compounds, including enantiospecific epoxidations, but are difficult to synthesize at levels that are useful for application to biotechnological processes. In order to construct efficient biocatalysis strains, we utilized the alkane-responsive regulatory system of the OCT plasmid-located alk genes of Pseudomonas oleovorans GPo1, a very attractive system for recombinant biotransformation processes. Determination of the nucleotide sequence of alkS, whose activated gene product positively regulates the transcription of the structural genes alkBFGHJKL, on a 3.7-kb SalI-HpaI OCT plasmid fragment was completed, and the N-terminal amino acid sequence of an AlkS-LacZ fusion protein was found to be consistent with the predicted DNA sequence. The alkS gene and the alkBp promoter were assembled into a convenient alkane-responsive genetic expression cassette which allowed expression of the xylene oxygenase genes in a recombinant Escherichia coli strain at a specific activity of 91 U per g (dry weight) of cells when styrene was the substrate. This biocatalyst was used to produce (S)-styrene oxide in two-liquid-phase cultures. Volumetric productivities of more than 2 g of styrene oxide per h per liter of aqueous phase were obtained; these values represented a fivefold improvement compared with previous results. PMID:10347009

  6. Determination of in Situ Rates of Methane Production and Oxidation From Terrestrial Wetlands

    NASA Astrophysics Data System (ADS)

    Shoemaker, J. K.; Schrag, D. P.

    2005-12-01

    Wetlands are responsible for over 70% of non-anthropogenic methane emissions. We present a method, using the δ13C of CO2 in pore water, to obtain the in situ rates of methanogenesis occurring beneath the wetland surface. This method allows us to distinguish methanogenesis from methane oxidation during escape, both of which contribute to the net methane flux. The δ13C of CO2(aq) - the dominant form of DIC in acidic natural waters - reflects the processes occurring at that location modified by transport of gas from surrounding depths. Methane production and oxidation are imprinted in the δ13C signature of the aqueous CO2 with heaviest values at depth resulting from the fractionation associated with methane production. We measured δ13C profiles with depth along with CO2 and CH4 concentrations from Sallie's Fen in Barrington, NH. Although the δ13C profiles varied considerably between locations and seasons, the logarithmic shape of the curves showed that methane production was restricted below a certain depth in the sediment - sometimes as shallow as 30 cm. Using a one-dimensional diffusion-reaction model, we are able to estimate rates of methane oxidation and successfully reproduce features present in the data's seasonal cycle. Features of the data not reproducible by the model indicate the importance of alternate gas transport routes such as ebullition and plant-mediated transport. The model also provides evidence for low-level oxygen availability during the winter-spring transition and narrow zones of very high productivity at depths of 60-70cm during the winter. We suggest that this method provides insight directly into the processes that determine methane fluxes from natural wetlands and has great potential for improving our understanding of the biogeochemistry of these systems.

  7. Variation in n-Alkane Distributions of Modern Plants: Questioning Applications of n-Alkanes in Chemotaxonomy and Paleoecology

    NASA Astrophysics Data System (ADS)

    Bush, R. T.; McInerney, F. A.

    2010-12-01

    Long chain n-alkanes (n-C21 to n-C37) are synthesized as part of the epicuticular leaf wax of terrestrial plants and are among the most recognizable and widely used plant biomarkers. n-Alkane distributions have been utilized in previous studies on modern plant chemotaxonomy, testing whether taxa can be identified based on characteristic n-alkane profiles. Dominant n-alkanes (e.g. n-C27 or n-C31) have also been ascribed to major plant groups (e.g. trees or grasses respectively) and have been used in paleoecology studies to reconstruct fluctuations in plant functional types. However, many of these studies have been based on relatively few modern plant data; with the wealth of modern n-alkane studies, a more comprehensive analysis of n-alkanes in modern plants is now possible and can inform the usefulness of n-alkane distributions as paleoecological indicators. The work presented here is a combination of measurements made using plant leaves collected from the Chicago Botanic Garden and a compilation of published literature data from six continents. We categorized plants by type: angiosperms, gymnosperms, woody plants, forbs, grasses, ferns and pteridophytes, and mosses. We then quantified n-alkane distribution parameters such as carbon preference index (CPI), average chain length (ACL), and dispersion (a measure of the spread of the profile over multiple chain lengths) and used these to compare plant groups. Among all plants, one of the emergent correlations is a decrease in dispersion with increasing CPI. Within and among plant groups, n-alkane distributions show a very large range of variation, and the results show little or no correspondence between broad plant groups and a single dominant n-alkane or a ratio of n-alkanes. These findings are true both when data from six continents are combined and when plants from a given region are compared (North America). We also compared the n-alkane distributions of woody angiosperms, woody gymnosperms, and grasses with one

  8. Oxidative damage, skin aging, antioxidants and a novel antioxidant rating system.

    PubMed

    Palmer, Debbie M; Kitchin, Jennifer Silverman

    2010-01-01

    It is believed that oxidative stress is caused by an imbalance between the production of reactive oxygen and a biological system's ability to neutralize the reactive intermediates. Oxidative damage occurs because of both intrinsic and extrinsic mechanisms. Together, intrinsic and extrinsic damage are the primary causes of skin aging. The skin uses a series of intrinsic antioxidants to protect itself from free radical damage. Naturally occurring extrinsic antioxidants have also been widely shown to offset and alleviate these changes. Unlike sunscreens, which have an SPF rating system to guide consumers in their purchases, there is no widely accepted method to choose antioxidant anti-aging products. ORAC (Oxygen Radical Absorbance Capacity) and ABEL-RAC (Analysis By Emitted Light-Relative Antioxidant Capacity), are both accepted worldwide as a standard measure of the antioxidant capacity of foods, and are rating systems that could be applied to all antioxidant skincare products. The standardization of antioxidant creams could revolutionize the cosmeceutical market and give physicians and consumers the ability to compare and choose effectively.

  9. Determination of the thermal, oxidative and photochemical degradation rates of scintillator liquid by fluorescence EEM spectroscopy.

    PubMed

    Andrews, N L P; Fan, J Z; Forward, R L; Chen, M C; Loock, H-P

    2016-12-21

    The thermal, oxidative and photochemical stability of the scintillator liquid proposed for the SNO+ experiment has been tested experimentally using accelerated aging methods. The stability of the scintillator constituents was determined through fluorescence excitation emission matrix (EEM) spectroscopy and absorption spectroscopy, using parallel factor analysis (PARAFAC) as an multivariate analysis tool. By exposing the scintillator liquid to a well-known photon flux at 365 nm and by measuring the decay rate of the fluorescence shifters and the formation rate of their photochemical degradation products, we can place an upper limit on the acceptable photon flux as 1.38 ± 0.09 × 10(-11) photon mol L(-1). Similarly, the oxidative stability of the scintillator liquid was determined by exposure to air at several elevated temperatures. Through measurement of the corresponding activation energy it was determined that the average oxygen concentration would have to be kept below 4.3-7.1 ppbw (headspace partial pressure below 24 ppmv). On the other hand, the thermal stability of the scintillator cocktail in the absence of light and oxygen was remarkable and poses no concern to the SNO+ experiment.

  10. Effect of intermediate compounds and products on wet oxidation and biodegradation rates of pharmaceutical compounds.

    PubMed

    Collado, Sergio; Laca, Adriana; Diaz, Mario

    2013-06-01

    Kinetics of pure compounds in batch agitated reactors are useful data to clarify the characteristics of a given reaction, but they frequently do not provide the required information to design industrial mixed continuous processes because in this case the final and intermediate products interact with the reaction of interest, due to backmixing effects. Simultaneously, the presence and transformations of other compounds, frequent in industrial wastewater treatments, adds more complexity to these types of interactions, whose effect can be different, favorable or unfavorable, for chemical or biological reactions. In this work, batch laboratory reactor data were obtained for the wet oxidation and biodegradation of four phenolic compounds present in a pharmaceutical wastewater and then compared with those collected from industrial continuous stirred tank reactors. For wet oxidation, batch laboratory degradation rates were significantly lower than those found in industrial continuous stirred operation. This behavior was explained by a different distribution of intermediate compounds in lab and industrial treatments, caused by the degree of backmixing and the synergistic effects between phenolic compounds (matrix effects). On the other hand, the specific utilization rates during aerobic biodegradation in the continuous industrial operation were lower than those measured in the laboratory, due to the simultaneous presence of the four pollutants in the industrial process (matrix effects) increasing the inhibitory effects of these compounds and its intermediates.

  11. Tuning electron transfer rates through molecular bridges in quantum dot sensitized oxides.

    PubMed

    Wang, Hai; McNellis, Erik R; Kinge, Sachin; Bonn, Mischa; Cánovas, Enrique

    2013-11-13

    Photoinduced electron transfer processes from semiconductor quantum dots (QDs) molecularly bridged to a mesoporous oxide phase are quantitatively surveyed using optical pump-terahertz probe spectroscopy. We control electron transfer rates in donor-bridge-acceptor systems by tuning the electronic coupling strength through the use of n-methylene (SH-[CH2]n-COOH) and n-phenylene (SH-[C6H4](n)-COOH) molecular bridges. Our results show that electron transfer occurs as a nonresonant quantum tunneling process with characteristic decay rates of β(n) = 0.94 ± 0.08 and β(n) = 1.25 per methylene and phenylene group, respectively, in quantitative agreement with reported conductance measurements through single molecules and self-assembled monolayers. For a given QD donor-oxide acceptor separation distance, the aromatic n-phenylene based bridges allow faster electron transfer processes when compared with n-methylene based ones. Implications of these results for QD sensitized solar cell design are discussed.

  12. Detailed chemical kinetic models for large n-alkanes and iso-alkanes found in conventional and F-T diesel fuels

    SciTech Connect

    Westbrook, C K; Pitz, W J; Curran, H J; Mehl, M

    2008-12-15

    Detailed chemical kinetic models are needed to simulate the combustion of current and future transportation fuels. These models should represent the various chemical classes in these fuels. Conventional diesel fuels are composed of n-alkanes, iso-alkanes, cycloalkanes and aromatics (Farrell et al. 2007). For future fuels, there is a renewed interest in Fischer-Tropsch (F-T) processes which can be used to synthesize diesel and other transportation fuels from biomass, coal and natural gas. F-T diesel fuels are expected to be similar to F-T jet fuels which are commonly comprised of iso-alkanes with some n-alkanes (Smith and Bruno, 2008). Thus, n-alkanes and iso-alkanes are common chemical classes in these conventional and future fuels. This paper reports on the development of chemical kinetic models of large n-alkanes and iso-alkanes to represent these chemical classes in conventional and future fuels. Two large iso-alkanes are 2,2,4,4,6,8,8-heptamethylnonane, which is a primary reference fuel for diesel, and isooctane, a primary reference fuel for gasoline. Other iso-alkanes are branched alkanes with a single methyl side chain, typical of most F-T fuels. The chemical kinetic models are then used to predict the effect of these fuel components on ignition characteristics under conditions found in internal combustion engines.

  13. Surface freezing in binary alkane-alcohol mixtures

    SciTech Connect

    Ofer, E.; Sloutskin, E.; Tamam, L.; Deutsch, M.; Ocko, B. M.

    2006-08-15

    Surface freezing was detected and studied in mixtures of alcohol and alkane molecules, using surface tensiometry and surface-specific x-ray scattering methods. Considering that surface freezing in pure alkanes forms an ordered monolayer and in alcohols it forms an ordered bilayer, the length mismatch repulsion was minimized by varying the carbon number of the alkane component around 2n, where n is the carbon number of the alcohol molecule. A solutionlike behavior was found for all mixtures, where the ideal liquid mixture phase-separates upon freezing both in the bulk and the surface. The solid exhibits a herringbone crystalline phase below an alkane mole fraction {phi}{sub t}{approx_equal}0.8 and a rotator phase above it. The surface frozen film below {phi}{sub t} is an alkane monolayer exhibiting a next-nearest neighbor molecular tilt of a composition-dependent magnitude. Above {phi}{sub t}, no diffraction peaks were observed. This could be explained by the intrinsically shorter-range order of the rotator phase and a possible proliferation of defects.

  14. Cellular oxidative damage is more sensitive to biosynthetic rate than to metabolic rate: A test of the theoretical model on hornworms (Manduca sexta larvae).

    PubMed

    Amunugama, Kaushalya; Jiao, Lihong; Olbricht, Gayla R; Walker, Chance; Huang, Yue-Wern; Nam, Paul K; Hou, Chen

    2016-09-01

    We develop a theoretical model from an energetic viewpoint for unraveling the entangled effects of metabolic and biosynthetic rates on oxidative cellular damage accumulation during animal's growth, and test the model by experiments in hornworms. The theoretical consideration suggests that most of the cellular damages caused by the oxidative metabolism can be repaired by the efficient maintenance mechanisms, if the energy required by repair is unlimited. However, during growth a considerable amount of energy is allocated to the biosynthesis, which entails tradeoffs with the requirements of repair. Thus, the model predicts that cellular damage is more influenced by the biosynthetic rate than the metabolic rate. To test the prediction, we induced broad variations in metabolic and biosynthetic rates in hornworms, and assayed the lipid peroxidation and protein carbonyl. We found that the increase in the cellular damage was mainly caused by the increase in biosynthetic rate, and the variations in metabolic rate had negligible effect. The oxidative stress hypothesis of aging suggests that high metabolism leads to high cellular damage and short lifespan. However, some empirical studies showed that varying biosynthetic rate, rather than metabolic rate, changes animal's lifespan. The conflicts between the empirical evidence and the hypothesis are reconciled by this study.

  15. The effect of soil moisture on nitrous oxide production rates in large enclosed ecosystems

    NASA Astrophysics Data System (ADS)

    van Haren, J.; Colodner, D.; Lin, G.; Murthy, R.

    2001-12-01

    On land, nitrous oxide (N2O) is mainly produced in soils by bacterial processes such as nitrification and denitrification. Once in the atmosphere N2O contributes to the greenhouse effect and stratospheric ozone destruction. Nitrification and denitrification are strongly dependent on soil moisture content, amongst other soil parameters. At Biosphere 2 Center we have begun to test the utility of meso-scale closed systems for understanding the relationship between soil properties and trace gas production at larger scales. We investigated the relationship between soil moisture content and soil N2O efflux in two large experimental closed systems (Tropical Rainforest (TR) and Intensive Forestry (IF) Mesocosms) at Biosphere 2 Center. N2O was measured every hour with an automated GC system. The daily N2O production rate was calculated as the rate of increase of N2O during the daytime, when the mesocosm was materially closed. We furthermore measured N2O and nitrate concentrations in the soil, as well as nitrate and N2O production rates in local areas. In the Rainforest Mesocosm, we found a very reproducible relationship between soil moisture content and N2O efflux, including the transient spikes in production rate upon wetting. In the Forestry Mesocosm the relation between soil moisture and N2O efflux was less clearcut.

  16. Low-level 14C methane oxidation rate measurements modified for remote field settings

    NASA Astrophysics Data System (ADS)

    Pack, M. A.; Pohlman, J.; Ruppel, C. D.; Xu, X.

    2012-12-01

    Aerobic methane oxidation limits atmospheric methane emissions from degraded subsea permafrost and dissociated methane hydrates in high latitude oceans. Methane oxidation rate measurements are a crucial tool for investigating the efficacy of this process, but are logistically challenging when working on small research vessels in remote settings. We modified a low-level 14C-CH4 oxidation rate measurement for use in the Beaufort Sea above hydrate bearing sediments during August 2012. Application of the more common 3H-CH4 rate measurement that uses 106 times more radioactivity was not practical because the R/V Ukpik cannot accommodate a radiation van. The low-level 14C measurement does not require a radiation van, but careful isolation of the 14C-label is essential to avoid contaminating natural abundance 14C measurements. We used 14C-CH4 with a total activity of 1.1 μCi, which is far below the 100 μCi permitting level. In addition, we modified field procedures to simplify and shorten sample processing. The original low-level 14C-CH4 method requires 6 steps in the field: (1) collect water samples in glass serum bottles, (2) inject 14C-CH4 into bottles, (3) incubate for 24 hours, (4) filter to separate the methanotrophic bacterial cells from the aqueous sample, (5) kill the filtrate with sodium hydroxide (NaOH), and (6) purge with nitrogen to remove unused 14C-CH4. Onshore, the 14C-CH4 respired to carbon dioxide or incorporated into cell material by methanotrophic bacteria during incubation is quantified by accelerator mass spectrometry (AMS). We conducted an experiment to test the possibility of storing samples for purging and filtering back onshore (steps 4 and 6). We subjected a series of water samples to steps 1-3 & 5, and preserved with mercuric chloride (HgCl2) instead of NaOH because HgCl2 is less likely to break down cell material during storage. The 14C-content of the carbon dioxide in samples preserved with HgCl2 and stored for up to 2 weeks was stable

  17. Regioselective Carbohydrate Oxidations: A Nuclear Magnetic Resonance (NMR) Study on Selectivity, Rate, and Side-Product Formation

    PubMed Central

    2017-01-01

    Palladium/neocuproine catalyzed oxidation of glucosides shows an excellent selectivity for the C3-OH, but in mannosides and galactosides, unselective oxidation was initially observed. For further application in more-complex (oligo)saccharides, a better understanding of the reaction, in terms of selectivity and reactivity, is required. Therefore, a panel of different glycosides was synthesized, subjected to palladium/neocuproine catalyzed oxidation and subsequently analyzed by qNMR. Surprisingly, all studied glucosides, mannosides, galactosides, and xylosides show selective oxidation of the C3-OH. However, subsequent reaction of the resulting ketone moiety is the main culprit for side product formation. Measures are reported to suppress these side reactions. The observed differences in reaction rate, glucosides being the most rapidly oxidized, may be exploited for the selective oxidation of complex oligosaccharides. PMID:28367353

  18. Global observation of nitrous oxide: changes in growth rate and spatial patterns

    NASA Astrophysics Data System (ADS)

    Hall, B. D.; Dlugokencky, E. J.; Dutton, G. S.; Nance, J. D.; Crotwell, A. M.; Mondeel, D. J.; Elkins, J. W.

    2015-12-01

    Nitrous oxide (N2O) currently exerts the third largest climate forcing of the long-lived greenhouse gases, after CO2 and CH4. N2O is also involved in the destruction of stratospheric ozone. It is produced by microbial activity in soils and oceans, and also by industry. The atmospheric burden of N2O has increased more than 20% from its preindustrial level of ~270 nmol mol-1 (ppb). Much of this increase is related to the application of nitrogen-containing fertilizers, including manure. The NOAA Global Monitoring Division has measured the atmospheric mole fraction of N2O at Earth's surface in air samples collected around the globe (since the late 1970s) and at in situ sites mostly in the Western Hemisphere (since 1998). ). Measurements of the global burden and growth rate constrain global emissions, e.g. 18.2 ± 2.7 Tg N yr-1 in 2013, where most of the uncertainty is related to uncertainty in the global lifetime. The average growth rate of N2O from 1990 to 2010 was ~0.75 ppb yr-1. Since 2004, however, the growth rate has been increasing, and is now about 25% higher than the 1990-2010 average. Between 2010 and 2013 the growth rate averaged ~0.95 ppb yr-1. As the growth rate increased from 2004-2013, gradients derived from surface, zonal-mean N2O mole fraction, such the mean pole-to-pole difference, and the difference between NH temperate latitudes and the southern polar region, decreased. This suggests a change in the distribution of N2O emissions over this period. We will present our N2O data and examine trends, gradients, and other features that could shed light on recent changes in the growth rate. We will also compare N2O gradients to those of other trace gases, such as SF6.

  19. Surface crystallization in normal-alkanes and alcohols

    SciTech Connect

    Deutsch, M.; Ocko, B.M.; Wu, X.Z. |; Sirota, E.B.; Sinha, S.K.

    1995-06-01

    A new, rare surface freezing, phenomenon is observed in molten normal-alkanes and their derivatives (alcohols, thiols, etc.). X-ray and surface tension measurements show the formation of a crystalline monolayer on the surface of the liquid alkane at temperatures up to 3 C above the bulk solidification temperature, T{sub f}. For alcohols, a single bilayer is formed. In both cases, the molecules in the layer are hexagonally packed and oriented normal to the surface for short chain lengths, and tilted for long ones. In both cases the single layer persists down to T{sub f}. In terms of wetting theory, this constitutes a very limited partial wetting of the liquid surface by the crystalline layer. The new surface phase is obtained only for chain lengths 14 < n {le} 50 in alkanes, and 16 < n < 30 in alcohols. The measurements are satisfactorily accounted for within a simple theory based on surface energy considerations.

  20. High Temperature Chemical Kinetic Combustion Modeling of Lightly Methylated Alkanes

    SciTech Connect

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M

    2011-03-01

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed high temperature chemical kinetic mechanism for n-octane and three lightly branched isomers octane (i.e., 2-methylheptane, 3-methylheptane, and 2,5-dimethylhexane). The model is validated against experimental data from a variety of fundamental combustion devices. This new model is used to show how the location and number of methyl branches affects fuel reactivity including laminar flame speed and species formation.

  1. Infrared Spectroscopic Investigation on CH Bond Acidity in Cationic Alkanes

    NASA Astrophysics Data System (ADS)

    Matsuda, Yoshiyuki; Xie, Min; Fujii, Asuka

    2016-06-01

    We have demonstrated large enhancements of CH bond acidities in alcohol, ether, and amine cations through infrared predissociation spectroscopy based on the vacuum ultraviolet photoionization detection. In this study, we investigate for the cationic alkanes (pentane, hexane, and heptane) with different alkyl chain lengths. The σ electrons are ejected in the ionization of alkanes, while nonbonding electrons are ejected in ionization of alcohols, ethers, and amines. Nevertheless, the acidity enhancements of CH in these cationic alkanes have also been demonstrated by infrared spectroscopy. The correlations of their CH bond acidities with the alkyl chain lengths as well as the mechanisms of their acidity enhancements will be discussed by comparison of infrared spectra and theoretical calculations.

  2. Alkanes in shrimp from the Buccaneer Oil Field

    SciTech Connect

    Middleditch, B.S.; Basile, B.; Chang, E.S.

    1982-07-01

    A total of 36 samples of shrimp were examined from the region of the Buccaneer oil field, eighteen of which were representatives of the commercial species Penaeus aztecus and the rest were various other species: Penaeus duorarum (pink shrimp), Trachypenaeus duorarum (sugar shrimp), Squilla empusa (mantis shrimp), and Sicyonia dorsalis (chevron shrimp). The alkanes and deuteriated alkanes were completely separated by GC, so a mass spectrometer was not required for their detection and quantitation. To confirm the identities of individual compounds, however, some samples were examined by combined gas chromatography-mass spectrometry. Results show that only thirteen of the forty shrimp collected from the region of the Buccaneer oil field contained petroleum alkanes, and the majority of these were obtained from trawls immediately adjacent to the production platforms. It appears that shrimp caught in the region of the Buccaneer oil field are not appreciably tainted with hydrocarbons discharged from the production platforms. (JMT)

  3. The effects of pre-oxidation heating rate on bio-based carbon fibers and its surface repair

    NASA Astrophysics Data System (ADS)

    Wu, H.; Cheng, L. F.; Fan, S. W.; Yuan, X. W.; Bhattacharyya, D.

    2015-03-01

    Low-cost carbon fibers (CFs) are fabricated from jute fibers after pre-oxidation, carbonization and surface repair. This paper investigates the effects of pre-oxidation heating rate on jute fibers, and explores a repair method for surface defects of CFs in C/C composite. The results show the reaction mechanism of jute fibers in air is not changed at higher pre-oxidation heating rates while a low heating rate is still required as the oxidation of jute fibers cannot be fully achieved under rapid heating. The tensile strength of CFs increases after repair with a 5% phenolic resin solution. Jute-based CFs play a positive role in C/C composite performance through crack bridging and deflection.

  4. Iron oxide nanoparticle agglomeration influences dose rates and modulates oxidative stress-mediated dose–response profiles in vitro

    PubMed Central

    Sharma, Gaurav; Kodali, Vamsi; Gaffrey, Matthew; Wang, Wei; Minard, Kevin R.; Karin, Norman J.; Teeguarden, Justin G.; Thrall, Brian D.

    2014-01-01

    Spontaneous agglomeration of engineered nanoparticles (ENPs) is a common problem in cell culture media which can confound interpretation of in vitro nanotoxicity studies. The authors created stable agglomerates of iron oxide nanoparticles (IONPs) in conventional culture medium, which varied in hydrodynamic size (276 nm–1.5 μm) but were composed of identical primary particles with similar surface potentials and protein coatings. Studies using C10 lung epithelial cells show that the dose rate effects of agglomeration can be substantial, varying by over an order of magnitude difference in cellular dose in some cases. Quantification by magnetic particle detection showed that small agglomerates of carboxylated IONPs induced greater cytotoxicity and redox-regulated gene expression when compared with large agglomerates on an equivalent total cellular IONP mass dose basis, whereas agglomerates of amine-modified IONPs failed to induce cytotoxicity or redox-regulated gene expression despite delivery of similar cellular doses. Dosimetry modelling and experimental measurements reveal that on a delivered surface area basis, large and small agglomerates of carboxylated IONPs have similar inherent potency for the generation of ROS, induction of stress-related genes and eventual cytotoxicity. The results suggest that reactive moieties on the agglomerate surface are more efficient in catalysing cellular ROS production than molecules buried within the agglomerate core. Because of the dynamic, size and density-dependent nature of ENP delivery to cells in vitro, the biological consequences of agglomeration are not discernible from static measures of exposure concentration (μg/ml) alone, highlighting the central importance of integrated physical characterisation and quantitative dosimetry for in vitro studies. The combined experimental and computational approach provides a quantitative framework for evaluating relationships between the biocompatibility of nanoparticles and their

  5. Iron Oxide Nanoparticle Agglomeration Influences Dose-Rates and Modulates Oxidative Stress Mediated Dose-Response Profiles In Vitro

    SciTech Connect

    Sharma, Gaurav; Kodali, Vamsi K.; Gaffrey, Matthew J.; Wang, Wei; Minard, Kevin R.; Karin, Norman J.; Teeguarden, Justin G.; Thrall, Brian D.

    2013-07-31

    Spontaneous agglomeration of engineered nanoparticles (ENPs) is a common problem in cell culture media which can confound interpretation of in vitro nanotoxicity studies. The authors created stable agglomerates of iron oxide nanoparticles (IONPs) in conventional culture medium, which varied in hydrodynamic size (276 nm-1.5 μm) but were composed of identical primary particles with similar surface potentials and protein coatings. Studies using C10 lung epithelial cells show that the dose rate effects of agglomeration can be substantial, varying by over an order of magnitude difference in cellular dose in some cases. Quantification by magnetic particle detection showed that small agglomerates of carboxylated IONPs induced greater cytotoxicity and redox-regulated gene expression when compared with large agglomerates on an equivalent total cellular IONP mass dose basis, whereas agglomerates of amine-modified IONPs failed to induce cytotoxicity or redox-regulated gene expression despite delivery of similar cellular doses. Dosimetry modelling and experimental measurements reveal that on a delivered surface area basis, large and small agglomerates of carboxylated IONPs have similar inherent potency for the generation of ROS, induction of stress-related genes and eventual cytotoxicity. The results suggest that reactive moieties on the agglomerate surface are more efficient in catalysing cellular ROS production than molecules buried within the agglomerate core. Because of the dynamic, size and density-dependent nature of ENP delivery to cells in vitro, the biological consequences of agglomeration are not discernible from static measures of exposure concentration (μg/ml) alone, highlighting the central importance of integrated physical characterisation and quantitative dosimetry for in vitro studies. The combined experimental and computational approach provides a quantitative framework for evaluating relationships between the biocompatibility of nanoparticles and their

  6. A Process for Microbial Hydrocarbon Synthesis: Overproduction of Fatty Acids in Escherichia coli and Catalytic Conversion to Alkanes

    PubMed Central

    Lennen, Rebecca M.; Braden, Drew J.; West, Ryan M.; Dumesic, James A.; Pfleger, Brian F.

    2013-01-01

    The development of renewable alternatives to diesel and jet fuels is highly desirable for the heavy transportation sector, and would offer benefits over the production and use of short-chain alcohols for personal transportation. Here, we report the development of a metabolically engineered strain of Escherichia coli that overproduces medium-chain length fatty acids via three basic modifications: elimination of β-oxidation, overexpression of the four subunits of acetyl-CoA carboxylase, and expression of a plant acyl–acyl carrier protein (ACP) thioesterase from Umbellularia californica (BTE). The expression level of BTE was optimized by comparing fatty acid production from strains harboring BTE on plasmids with four different copy numbers. Expression of BTE from low copy number plasmids resulted in the highest fatty acid production. Up to a seven-fold increase in total fatty acid production was observed in engineered strains over a negative control strain (lacking β-oxidation), with a composition dominated by C12 and C14 saturated and unsaturated fatty acids. Next, a strategy for producing undecane via a combination of biotechnology and heterogeneous catalysis is demonstrated. Fatty acids were extracted from a culture of an overproducing strain into an alkane phase and fed to a Pd/C plug flow reactor, where the extracted fatty acids were decarboxylated into saturated alkanes. The result is an enriched alkane stream that can be recycled for continuous extractions. Complete conversion of C12 fatty acids extracted from culture to alkanes has been demonstrated yielding a concentration of 0.44 g L−1 (culture volume) undecane. PMID:20073090

  7. Nitrous oxide uptake rates in boreal coniferous forests are associated with soil characteristics

    NASA Astrophysics Data System (ADS)

    Siljanen, Henri; Biasi, Christina; Martikainen, Pertti

    2014-05-01

    Nitrous oxide (N2O) is a strong greenhouse gas and a significant contributor to the destruction of the ozone layer. The radiative forcing of N2O is considered to be 320 more efficient than carbon dioxide.The major portion of global N2O is emitted from agricultural soils. There are studies suggesting that N2O has also a sink in forest soils. However there is relatively limited knowledge on factors controlling N2O consumption in forest soils. Hence N2O consumption was studied in boreal coniferous forests having different forest cover, soil chemical and physical structure and land-use history. The N2O consumption was measured by static chamber technique in the field across spatio-seasonal sampling design. Typical and atypical denitrifiers were quantified with nosZ functional gene marker. Additionally chemical and physical environmental parameters were analyzed to link N2O flux, microbial community and composition of soils. Nitrous oxide uptake could be associated with specific ecosystem and environmental conditions. Soil physical structure and land-use history were shown to be prior factors determining the strength of the uptake rate.

  8. Amide proton exchange rates of oxidized and reduced Saccharomyces cerevisiae iso-1-cytochrome c.

    PubMed Central

    Marmorino, J. L.; Auld, D. S.; Betz, S. F.; Doyle, D. F.; Young, G. B.; Pielak, G. J.

    1993-01-01

    Proton NMR spectroscopy was used to determine the rate constant, kobs, for exchange of labile protons in both oxidized (Fe(III)) and reduced (Fe(II)) iso-1-cytochrome c. We find that slowly exchanging backbone amide protons tend to lack solvent-accessible surface area, possess backbone hydrogen bonds, and are present in regions of regular secondary structure as well as in omega-loops. Furthermore, there is no correlation between kobs and the distance from a backbone amide nitrogen to the nearest solvent-accessible atom. These observations are consistent with the local unfolding model. Comparisons of the free energy change for denaturation, delta Gd, at 298 K to the free energy change for local unfolding, delta Gop, at 298 K for the oxidized protein suggest that certain conformations possessing higher free energy than the denatured state are detected at equilibrium. Reduction of the protein results in a general increase in delta Gop. Comparisons of delta Gd to delta Gop for the reduced protein show that the most open states of the reduced protein possess more structure than its chemically denatured form. This persistent structure in high-energy conformations of the reduced form appears to involve the axially coordinated heme. PMID:8268806

  9. Characterization of the globular oxide inclusion ratings in steel using laser-induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Yong; Jia, Yun-Hai; Yang, Chun; Li, Dong-Ling; Liu, Jia; Chen, Yong-Yan; Liu, Ying; Duan, Yi-Xiang

    2016-12-01

    Grade assessment of steel is generally performed via the metallographic method, which is timeconsuming and is not able to provide the elemental distribution information. In this paper, we present a method to measure the globular oxide inclusion ratings in steel using laser-induced breakdown spectroscopy (LIBS). The measurement is performed in two basic steps: steel samples are polished using metallographic sand paper and the Al2O3 inclusion number and size distribution in a marked area are observed using scanning electron microscope/energy dispersive X-ray spectroscopy (SEM/EDS) for further LIBS scanning analysis. The threshold intensity that distinguishes soluble aluminum and insoluble aluminum inclusions is determined using LIBS combined with the SEM/EDS statistical data. Carbon steel (the sample number is S9256) and bearing steel (the sample number is GCr15) are analyzed in scanning mode, and the number of Al2O3 inclusions in different size ranges is obtained from the statistical information derived from the Al2O3 size calibration curve. According to heavy and thin series for globular oxide inclusions grade assessment, the method we propose is comparable to the traditional metallographic method in terms of accuracy; however, the process is simplified and the measurement speed is significantly improved.

  10. Mesoscale Biotransformation of Uranium: Influences of Organic Carbon Supply Rates and Sediment Oxides

    SciTech Connect

    Tetsu Tokunaga; Jiamin Wan; Yongman Kim; Rebecca Daly; Eoin Brodie; Mary Firestone; Terry Hazen; Steve Sutton; Matt Newville; Tony Lanzirotti; Bill Rao

    2007-04-19

    Remediation and long-term stewardship of uranium-contaminated sediments and groundwaters are critical problems at a number of DOE facilities and mining sites. Some remediation strategies based on in-situ bioreduction of U are potentially effective in significantly decreasing U concentrations in groundwaters. However, a number of basic processes require understanding in order to identify conditions more conducive to success of reduction-based U stabilization. Our current research targets several of these issues including: (1) effects of organic carbon (OC) forms and supply rates on stability of bioreduced U, (2) the roles of Fe(III)- and Mn(III,IV)-oxides as potential U oxidants in sediments, and (3) microbial community changes in relation to U redox changes. These issues were identified in our previous study on U bioreduction and reoxidation (Wan et al., 2005). Most of our studies are being conducted on historically U-contaminated sediments from Area 2 of the Field Research Center, Oak Ridge National Laboratory, in flow-through columns simulating in-situ field remediation.

  11. Oral pseudoephedrine decreases the rate of transmucosal nitrous oxide exchange for the middle ear.

    PubMed

    Teixeira, Miriam S; Alper, Cuneyt M; Martin, Brian S; Doyle, Brendan M Cullen; Doyle, William J

    2015-09-01

    Determine if oral treatment with a vasoconstrictor decreases the blood to middle ear exchange rate of the perfusion-limited gas, nitrous oxide (N2O). Randomized, double-blind, crossover study. Ten adult subjects with and 10 without past middle ear disease completed paired experimental sessions, identical except for oral treatment with either pseudoephedrine hydrochloride or lactose placebo. At each session, subjects were fitted with a nonrebreathing mask and breathed room air for 20 minutes (acclimation period), 50% N2O:50% O2 for 20 minutes (experimental period), and 100% O2 for 10 minutes (recovery period). Throughout, heart rate, blood pressure, and O2 saturation were monitored, and bilateral middle ear pressures were recorded by tympanometry every minute. The primary outcome was the slope of the middle ear pressure-time function for the experimental period, which estimates the volume N2O exchange rate. Using repeated measures analysis of variance, the effects of group (disease history), treatment (active vs. placebo), and period (1 vs. 2) on the recorded vital signs, and of group, treatment, and ear (left/right) on the middle ear pressure-time slope were evaluated for statistical significance. Statistically significant effects of period on O2 saturation (period 2 > period 1) and of treatment on heart rate (active > placebo) were documented. Only treatment was statistically significant for the middle ear pressure-time slope, with a shallower slope characterizing the active treatment session. The volume exchange rate across the middle ear mucosa of perfusion-limited gases can be modulated pharmacologically. Theoretically, similar drugs can be used to reduce the requisite eustachian tube opening efficiency for adequate middle ear pressure regulation. 1b. © 2015 The American Laryngological, Rhinological and Otological Society, Inc.

  12. Assimilation of chlorinated alkanes by hydrocarbon-utilizing fungi

    SciTech Connect

    Murphy, G.L.; Perry, J.J.

    1984-12-01

    The fatty acid compositions of two filamentous fungi (Cunninghamella elegans and Penicillium zonatum) and a yeast (Candida lipolytica) were determined after the organisms were grown on 1-chlorohexadecane or 1-chlorooctadecane. These organisms utilized the chlorinated alkanes as sole sources of carbon and energy. Analyses of the fatty acids present after growth on the chlorinated alkanes indicated that 60 to 70% of the total fatty acids in C. elegans were chlorinated. Approximately 50% of the fatty acids in C. lipolytica were also chlorinated. P. zonatum contained 20% 1-chlorohexadecanoic acid after growth on either substrate but did not incorporate C/sub 18/ chlorinated fatty acids.

  13. Modeling of alkane emissions from a wood stain

    SciTech Connect

    Chang, J.C.S.; Guo, Z.

    1993-01-01

    The article discusses full-scale residential house tests to evaluate the effects of organic emissions from a wood finishing product--wood stain--on indoor air quality (IAQ). The test house concentrations of three alkane species, nonane, decane, and undecane, were measured as a function of time after the application of the wood stain. It was found that the test house concentrations can be simulated by an integrated IAQ model which takes into consideration source, sink, and ventilation effects. The alkane emissions were controlled by an evaporation-like process.

  14. Effect of Oxide Film on the Reduction of Hydrogen Permeation Rate in Stainless Steel

    NASA Astrophysics Data System (ADS)

    Yamazaki, Takahisa; Ikeshoji, Toshi-Taka; Suzumura, Akio; Naito, Takafumi

    Characteristics of hydrogen permeation in the stainless steel 304 modified by either facing, ion sputtering, carbon coating or annealing were investigated in order to establish the safe hydrogen-energy-infrastructure using welding. A stationary hydrogen flux from the stainless steel surface was measured by using a system with an orifice. The pressure difference of the specimen was able to maintain constant by controlling the gas flow rate from the orifice in low pressure vessel. The hydrogen permeability was low in two cases of a thin stainless steel with fine facing and that annealed at 1370K for 2 hours. In these cases, the specimens’ surfaces were considered to play hydrogen trap role and to prevent from pairing hydrogen atoms. On the other hand, high hydrogen permeability was obtained in the case of Argon plasma cleaning a low-pressure-vessel side surface. These results suggest that oxide film on the specimens’ surface prevent hydrogen desorption.

  15. Measurement of Nitric Oxide (NO) Generation Rate by Chloroplasts Employing Electron Spin Resonance (ESR).

    PubMed

    Galatro, Andrea; Puntarulo, Susana

    2016-01-01

    Chloroplasts are among the more active organelles involved in free energy transduction in plants (photophosphorylation). Nitric oxide (NO) generation by soybean (Glycine max, var ADM 4800) chloroplasts was measured as an endogenous product assessed by electron paramagnetic resonance (ESR) spin-trapping technique. ESR spectroscopy is a methodology employed to detect species with unpaired electrons (paramagnetic). This technology has been successfully applied to different plant tissues and subcellular compartments to asses both, NO content and generation. The spin trap MGD-Fe(2+) is extensively employed to efficiently detect NO. Here, we describe a simple methodology to asses NO generation rate by isolated chloroplasts in the presence of either L-Arginine or nitrite (NO2 (-)) as substrates, since these compounds are required for enzymatic activities considered as the possible sources of NO generation in plants.

  16. Denitrification Rates, Nitrous Oxide, and Methane Fluxes Along Soil Moisture Gradients In Stormwater Control Structures.

    NASA Astrophysics Data System (ADS)

    Bettez, N. D.; Morse, J. L.; Groffman, P. M.

    2014-12-01

    Urbanization has significant impacts on the landscape resulting in increased volume and velocity of stormwater runoff following precipitation events. The primary method used to control stormwater discharge and prevent downstream erosion is the use of best management practices (BMP's) such as retention basins, detention basins and rain gardens. Although the BMP's were designed to mitigate hydrologic impacts associated with urban development they have the potential to remove nitrogen through denitrification. In this study we set up transects along moisture gradients in two BMP's in Baltimore MD, USA and measured denitrification rates using the Nitrogen Free Air Removal Method (N-FARM) method and monitored both soil conditions (oxygen, moisture and temperature measured hourly) and trace gas fluxes (methane, carbon dioxide, and nitrous oxide measured monthly) for 1 year.

  17. The conformation-independent QSPR approach for predicting the oxidation rate constant of water micropollutants.

    PubMed

    Ortiz, Erlinda V; Bennardi, Daniel O; Bacelo, Daniel E; Fioressi, Silvina E; Duchowicz, Pablo R

    2017-10-03

    In advanced water treatment processes, the degradation efficiency of contaminants depends on the reactivity of the hydroxyl radical toward a target micropollutant. The present study predicts the hydroxyl radical rate constant in water (k OH) for 118 emerging micropollutants, by means of quantitative structure-property relationships (QSPR). The conformation-independent QSPR approach is employed, together with a large number of 15,251 molecular descriptors derived with the PaDEL, Epi Suite, and Mold2 freewares. The best multivariable linear regression (MLR) models are found with the replacement method variable subset selection technique. The proposed five-descriptor model has the following statistics for the training set: [Formula: see text], RMS train = 0.21, while for the test set is [Formula: see text], RMS test = 0.11. This QSPR serves as a rational guide for predicting oxidation processes of micropollutants.

  18. Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption.

    PubMed

    Strmcnik, Dusan; Uchimura, Masanobu; Wang, Chao; Subbaraman, Ram; Danilovic, Nemanja; van der Vliet, Dennis; Paulikas, Arvydas P; Stamenkovic, Vojislav R; Markovic, Nenad M

    2013-04-01

    The development of hydrogen-based energy sources as viable alternatives to fossil-fuel technologies has revolutionized clean energy production using fuel cells. However, to date, the slow rate of the hydrogen oxidation reaction (HOR) in alkaline environments has hindered advances in alkaline fuel cell systems. Here, we address this by studying the trends in the activity of the HOR in alkaline environments. We demonstrate that it can be enhanced more than fivefold compared to state-of-the-art platinum catalysts. The maximum activity is found for materials (Ir and Pt₀.₁Ru₀.₉) with an optimal balance between the active sites that are required for the adsorption/dissociation of H₂ and for the adsorption of hydroxyl species (OHad). We propose that the more oxophilic sites on Ir (defects) and PtRu material (Ru atoms) electrodes facilitate the adsorption of OHad species. Those then react with the hydrogen intermediates (Had) that are adsorbed on more noble surface sites.

  19. Imbalance of heterologous protein folding and disulfide bond formation rates yields runaway oxidative stress

    PubMed Central

    2012-01-01

    Background The protein secretory pathway must process a wide assortment of native proteins for eukaryotic cells to function. As well, recombinant protein secretion is used extensively to produce many biologics and industrial enzymes. Therefore, secretory pathway dysfunction can be highly detrimental to the cell and can drastically inhibit product titers in biochemical production. Because the secretory pathway is a highly-integrated, multi-organelle system, dysfunction can happen at many levels and dissecting the root cause can be challenging. In this study, we apply a systems biology approach to analyze secretory pathway dysfunctions resulting from heterologous production of a small protein (insulin precursor) or a larger protein (α-amylase). Results HAC1-dependent and independent dysfunctions and cellular responses were apparent across multiple datasets. In particular, processes involving (a) degradation of protein/recycling amino acids, (b) overall transcription/translation repression, and (c) oxidative stress were broadly associated with secretory stress. Conclusions Apparent runaway oxidative stress due to radical production observed here and elsewhere can be explained by a futile cycle of disulfide formation and breaking that consumes reduced glutathione and produces reactive oxygen species. The futile cycle is dominating when protein folding rates are low relative to disulfide bond formation rates. While not strictly conclusive with the present data, this insight does provide a molecular interpretation to an, until now, largely empirical understanding of optimizing heterologous protein secretion. This molecular insight has direct implications on engineering a broad range of recombinant proteins for secretion and provides potential hypotheses for the root causes of several secretory-associated diseases. PMID:22380681

  20. Nickel-regulated heart rate variability: The roles of oxidative stress and inflammation

    SciTech Connect

    Chuang, Hsiao-Chi; Hsueh, Tzu-Wei; Chang, Chuen-Chau; Hwang, Jing-Shiang; Chuang, Kai-Jen; Yan, Yuan-Horng; Cheng, Tsun-Jen

    2013-01-15

    Heart rate variability (HRV) has been reported to be a putative marker of cardiac autonomic imbalance caused by exposure to ambient particulate matter (PM). Our objective in this study was to determine the effects on HRV from exposure to nickel, an important chemical component of ambient PM that results in oxidative stress and inflammation. HRV data were collected for 72 h before lung exposure (baseline) and 72 h after intratracheal exposure (response) to nickel sulphate (NiSO{sub 4}; 526 μg) in Wistar Kyoto (WKY) and spontaneously hypertensive (SH) rats. The antioxidant N-acetyl-L-cysteine (NAC) and the anti-inflammatory celecoxib were intraperitoneally injected to examine post-exposure oxidative and inflammatory responses. Self-controlled experiments examined the effects of NiSO{sub 4} exposure on average normal-to-normal intervals (ANN), natural logarithm-transformed standard deviation of the normal-to-normal intervals (LnSDNN) and root mean square of successive differences of adjacent normal-to-normal intervals (LnRMSSD); the resulting data were sequentially analysed using the generalised estimating equation model. HRV effects on NiSO{sub 4}-exposed SH rats were greater than those on NiSO{sub 4}-exposed WKY rats. After adjusted the HRV responses in the WKY rats as control, ANN and LnRMSSD were found to be quadratically increased over 72 h after exposure to NiSO{sub 4}. Both NAC and celecoxib mitigated the NiSO{sub 4}-induced alterations in HRV during the exposure period. The results suggest that concurrent Ni-induced oxidative stress and inflammatory responses play important roles in regulating HRV. These findings help bridge the gap between epidemiological and clinical studies on the plausible mechanisms of the cardiovascular consequences induced by chemical components in ambient PM. -- Highlights: ► To determine the effects on HRV from exposure to nickel. ► ANN and LnRMSSD were found to be quadratically increased after exposure to Ni. ► NAC and

  1. Low effective activation energies for oxygen release from metal oxides: evidence for mass-transfer limits at high heating rates.

    PubMed

    Jian, Guoqiang; Zhou, Lei; Piekiel, Nicholas W; Zachariah, Michael R

    2014-06-06

    Oxygen release from metal oxides at high temperatures is relevant to many thermally activated chemical processes, including chemical-looping combustion, solar thermochemical cycles and energetic thermite reactions. In this study, we evaluated the thermal decomposition of nanosized metal oxides under rapid heating (~10(5) K s(-1)) with time-resolved mass spectrometry. We found that the effective activation-energy values that were obtained using the Flynn-Wall-Ozawa isoconversional method are much lower than the values found at low heating rates, indicating that oxygen transport might be rate-determining at a high heating rate.

  2. In situ estimates of iron-oxidation and accretion rates for iron-oxidizing bacterial mats at Lō'ihi Seamount

    NASA Astrophysics Data System (ADS)

    Emerson, David; Scott, Jarrod J.; Leavitt, Anna; Fleming, Emily; Moyer, Craig

    2017-08-01

    It is increasingly recognized that diffuse, hydrothermal venting is an important source of iron to the deep-sea that can influence oceanic iron dynamics and abundance. Lithotrophic Fe-oxidizing bacteria (FeOB) are dominant at diffuse hydrothermal vent sites, producing microbial iron mats that are often centimeters or more thick. At present, little is known about in situ growth rates of FeOB, specific Fe-oxidation rates, or accretion rates for iron mats. An in situ productivity chamber was developed that took advantage of the unique mineral morphotypes produced by FeOB to estimate rates of Fe-oxidation and accretion. Chambers were placed at two diffuse vents (1179 and 1300 mbsl) at Lō'ihi Seamount where they were colonized by FeOB for different amounts of time. From this analysis, it was estimated that Fe-oxidation rates could range from 8.2 to 51.9 × 10-6 mol h-1, and that iron mats could accrete at around 2.2 cm. yr-1. Molecular analysis indicated that the relative abundance of Zetaproteobacteria, a group of known FeOB, accounted for 80-90% of the bacteria colonizing the chambers. There was a distinct difference between populations at the 1179 m site (Pohaku), and the 1300 m site (North Hiolo Ridge). Microscope slides placed within the productivity chambers were colonized by different morphotypes of FeOB. The cells responsible for one common morphotype that produces a Y-shaped filament were identified as Zetaproteobacteria by use of a small subunit rRNA probe. This work confirms the importance of FeOB in the formation of chemosynthetic iron mats, and provides the first estimates for in situ Fe-oxidation rates and mat accretion rates.

  3. Exogenous carbohydrate oxidation rates are elevated after combined ingestion of glucose and fructose during exercise in the heat.

    PubMed

    Jentjens, Roy L P G; Underwood, Katie; Achten, Juul; Currell, Kevin; Mann, Christopher H; Jeukendrup, Asker E

    2006-03-01

    The first purpose of this study was to investigate whether a glucose (GLU)+fructose (FRUC) beverage would result in a higher exogenous carbohydrate (CHO) oxidation rate and a higher fluid availability during exercise in the heat compared with an isoenergetic GLU beverage. A second aim of the study was to examine whether ingestion of GLU at a rate of 1.5 g/min during exercise in the heat would lead to a reduced muscle glycogen oxidation rate compared with ingestion of water (WAT). Eight trained male cyclists (maximal oxygen uptake: 64+/-1 ml.kg-1.min-1) cycled on three different occasions for 120 min at 50% maximum power output at an ambient temperature of 31.9+/-0.1 degrees C. Subjects received, in random order, a solution providing either 1.5 g/min of GLU, 1.0 g/min of GLU+0.5 g/min of FRUC, or WAT. Exogenous CHO oxidation during the last hour of exercise was approximately 36% higher (P<0.05) in GLU+FRUC compared with GLU, and peak oxidation rates were 1.14+/-0.05 and 0.77+/-0.08 g/min, respectively. Endogenous CHO oxidation was significantly lower (P<0.05) in GLU+FRUC compared with WAT. Muscle glycogen oxidation was not different after ingestion of GLU or WAT. Plasma deuterium enrichments were significantly higher (P<0.05) in WAT and GLU+FRUC compared with GLU. Furthermore, at 60 and 75 min of exercise, plasma deuterium enrichments were higher (P<0.05) in WAT compared with GLU+FRUC. Ingestion of GLU+FRUC during exercise in the heat resulted in higher exogenous CHO oxidation rates and fluid availability compared with ingestion of GLU and reduced endogenous CHO oxidation compared with ingestion of WAT.

  4. Effects of chloride and sulfate on the rate of oxidation of ferrous ion by H2O2.

    PubMed

    Truong, Giang Le; De Laat, Joseph; Legube, Bernard

    2004-05-01

    The rates of oxidation of Fe(II) by H(2)O(2) in the presence of sodium perchlorate, sodium nitrate, sodium chloride and sodium sulfate salts (0-1M) have been compared in the study. Experiments were carried out in a batch reactor, in the dark, at pH <3, 25+/-0.5 degrees C and at controlled ionic strength (< or =1M). The experimental results showed that the rates of oxidation of Fe(II) in the presence of chloride, nitrate and perchlorate were identical. In the presence of sulfate, the rate of oxidation of Fe(II) was faster and depended on the pH and the concentration of sulfate. The pseudo second-order rate constants for the reaction of H(2)O(2) with Fe(2+), FeCl(+) and FeSO(4) were determined as 55+/-1, 55+/-1 and 78+/-3 M(-1) s(-1), respectively.

  5. Evaluation of emission rates and observation of natural sources of nitrogen oxides in acid rain area of southern China

    SciTech Connect

    Miao-Qin Lu; Yu-Bao Wang

    1996-12-31

    The present paper reports the observation results of natural sources of NO, N{sub 2}O, NO{sub 2} in the area of Fujien province, southeast of China, where acidic rain occurs at relatively high frequency. The emission rates of NO, N{sub 2}O, NO{sub 2} in paddy field and dry farmland in Xiamen, Jimei district, Tongan and Guoan counties were measured in this investigation. The measurement results shows that the emission rates of nitrogen oxides from paddy field are higher than that from dry farmland. The emission rate of NO{sub 2} was the highest among the three nitrogen oxides. But no more difference between NO and N{sub 2}O. It should be noted that the emission rates of nitrogen oxides from paddy field in Jimei area are obviously higher than that in Tongan. The main reason for this difference resulted from the different types of soils between those two areas.

  6. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  7. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  8. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  9. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  10. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  11. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  12. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  13. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  14. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  15. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  16. Comparison and modeling of aqueous dissolution rates of various uranium oxides

    SciTech Connect

    Steward, S.A.

    1996-11-01

    Purpose of this work was to measure and model the intrinsic dissolution rates of U oxides under a variety of well-controlled conditions that are relevant to a geologic repository. When exposed to air at elevated temperature, spent fuel may form the stable phase U{sub 3}O{sub 8}. Dehydrated schoepite, UO{sub 3}{center_dot}H{sub 2}O, exists in drip tests on spent fuel. Equivalent sets of U{sub 3}O{sub 8} and UO{sub 3}{center_dot}H{sub 2}O dissolution experiments allowed a systematic examination of the effects of temperature (25-75 C), pH(8-10), and carbonate (2-200x10{sup -4}molar) concentrations at atmospheric oxygen conditions. Results indicate that UO{sub 3}{center_dot}H{sub 2}O has a much higher dissolution rate (at least tenfold) than U{sub 3}O{sub 8} under the same conditions. The intrinsic dissolution rate of unirradiated U{sub 3}O{sub 8} is about twice that of UO{sub 2}. Dissolution of both U{sub 3}O{sub 8} and UO{sub 3}{center_dot}H{sub 2}O shows a very high sensitivity to carbonate concentration. Present results show a 25 to 50-fold increase in room-temperature UO{sub 3}{center_dot}H{sub 2}O dissolution rates between the highest and lowest carbonate concentrations. As with the UO{sub 2} dissolution data, the classical observed chemical kinetic rate law was used to model the U{sub 3}O{sub 8} dissolution rate data. The pH did not have much effect on the models, in agreement with earlier analysis of the UO{sub 2} and spent fuel dissolution data. However, carbonate concentration, not temperature, had the strongest effect on the U{sub 3}O{sub 8} dissolution rate. The U{sub 3}O{sub 8} dissolution activation energy was about 6000 cal/mol, compared with 7300 and 8000 cal/mol for spent fuel and UO{sub 2}, respectively.

  17. Atmospheric fate of a series of carbonyl nitrates: photolysis frequencies and OH-oxidation rate constants.

    PubMed

    Suarez-Bertoa, R; Picquet-Varrault, B; Tamas, W; Pangui, E; Doussin, J-F

    2012-11-20

    Multifunctional organic nitrates are potential NO(x) reservoirs whose atmospheric chemistry is somewhat little known. They could play an important role in the spatial distribution of reactive nitrogen species and consequently in ozone formation and distribution in remote areas. In this work, the rate constants for the reaction with OH radical and the photolysis frequencies of α-nitrooxyacetone, 3-nitrooxy-2-butanone, and 3-methyl-3-nitrooxy-2-butanone have been determined at room temperature at 1000 mbar total pressure of synthetic air. The rate constants for the OH oxidation were measured using the relative rate technique, with methanol as reference compound. The following rate constants were obtained for the reaction with OH: k(OH) = (6.7 ± 2.5) × 10(-13) cm(3) molecule(-1) s(-1) for α-nitrooxyacetone, (10.6 ± 4.1) × 10(-13) cm(3) molecule(-1) s(-1) for 3-nitrooxy-2-butanone, and (2.6 ± 0.9) × 10(-13) cm(3) molecule(-1) s(-1) for 3-methyl-3-nitrooxy-2-butanone. The corresponding photolysis frequencies extrapolated to typical atmospheric conditions for July first at noon at 40° latitude North were (4.8 ± 0.3) × 10(-5) s(-1), (5.7 ± 0.3) × 10(-5) s(-1), and (7.4 ± 0.2) × 10(-5) s(-1), respectively. The data show that photolysis is a major atmospheric sink for these organic nitrates.

  18. Assessment of the GECKO-A modeling tool using chamber observations for C12 alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; La, S.; Ouzebidour, F.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J. M.; Hodzic, A.; Madronich, S.; Yee, L. D.; Loza, C. L.; Craven, J. S.; Zhang, X.; Seinfeld, J.

    2013-12-01

    Secondary Organic Aerosol (SOA) production and ageing is the result of atmospheric oxidation processes leading to the progressive formation of organic species with higher oxidation state and lower volatility. Explicit chemical mechanisms reflect our understanding of these multigenerational oxidation steps. Major uncertainties remain concerning the processes leading to SOA formation and the development, assessment and improvement of such explicit schemes is therefore a key issue. The development of explicit mechanism to describe the oxidation of long chain hydrocarbons is however a challenge. Indeed, explicit oxidation schemes involve a large number of reactions and secondary organic species, far exceeding the size of chemical schemes that can be written manually. The chemical mechanism generator GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) is a computer program designed to overcome this difficulty. GECKO-A generates gas phase oxidation schemes according to a prescribed protocol assigning reaction pathways and kinetics data on the basis of experimental data and structure-activity relationships. In this study, we examine the ability of the generated schemes to explain SOA formation observed in the Caltech Environmental Chambers from various C12 alkane isomers and under high NOx and low NOx conditions. First results show that the model overestimates both the SOA yields and the O/C ratios. Various sensitivity tests are performed to explore processes that might be responsible for these disagreements.

  19. Comparison of the oxidation rate and degree of graphitization of selected IG and NBG nuclear graphite grades

    NASA Astrophysics Data System (ADS)

    Chi, Se-Hwan; Kim, Gen-Chan

    2008-10-01

    The oxidation rate and degree of graphitization (DOG) were determined for some selected nuclear graphite grades (i.e., IG-110, IG-430, NBG-18, NBG-25) and compared in view of their filler coke type (i.e., pitch or petroleum coke) and the physical property of the grades. Oxidation rates were determined at six temperatures between 600 and 960 °C in air by using a three-zone vertical tube furnace at a 10 l/min air flow rate. The specimens were a cylinder with a 25.4 mm diameter and a 25.4 mm length. The DOG was determined based on the lattice parameter c determined from an X-ray diffraction (XRD). Results showed that, even though the four examined nuclear graphite grades showed a highly temperature-sensitive oxidation behavior through out the test temperature range of 600-950 °C, the differences between the grades were not significant. The oxidation rates determined for a 5-10% weight loss at the six temperatures were nearly the same except for 702 and 808 °C, where the pitch coke graphites showed an apparent decrease in their oxidation rate, more so than the petroleum coke graphites. These effects of the coke type reduced or nearly disappeared with an increasing temperature. The average activation energy determined for 608-808 °C was 161.5 ± 7.3 kJ/mol, showing that the dominant oxidation reaction occurred by a chemical control. A relationship between the oxidation rate and DOG was not observed.

  20. Model predictions of higher-order normal alkane ignition from dilute shock-tube experiments

    NASA Astrophysics Data System (ADS)

    Rotavera, B.; Petersen, E. L.

    2013-07-01

    Shock-induced oxidation of two higher-order linear alkanes was measured using a heated shock tube facility. Experimental overlap in stoichiometric ignition delay times obtained under dilute (99 % Ar) conditions near atmospheric pressure was observed in the temperature-dependent ignition trends of n-nonane ( n-C9H20) and n-undecane ( n-C11H24). Despite the overlap, model predictions of ignition using two different detailed chemical kinetics mechanisms show discrepancies relative to both the measured data as well as to one another. The present study therefore focuses on the differences observed in the modeled, high-temperature ignition delay times of higher-order n-alkanes, which are generally regarded to have identical ignition behavior for carbon numbers above C7. Comparisons are drawn using experimental data from the present study and from recent work by the authors relative to two existing chemical kinetics mechanisms. Time histories from the shock-tube OH* measurements are also compared to the model predictions; a double-peaked structure observed in the data shows that the time response of the detector electronics is crucial for properly capturing the first, incipient peak near time zero. Calculations using the two mechanisms were carried out at the dilution level employed in the shock-tube experiments for lean {({φ} = 0.5)}, stoichiometric, and rich {({φ} = 2.0)} equivalence ratios, 1230-1620 K, and for both 1.5 and 10 atm. In general, the models show differing trends relative to both measured data and to one another, indicating that agreement among chemical kinetics models for higher-order n-alkanes is not consistent. For example, under certain conditions, one mechanism predicts the ignition delay times to be virtually identical between the n-nonane and n-undecane fuels (in fact, also for all alkanes between at least C8 and C12), which is in agreement with the experiment, while the other mechanism predicts the larger fuels to ignite progressively more slowly.

  1. Effects of dissolved oxygen and pH on nitrous oxide production rates in autotrophic partial nitrification granules.

    PubMed

    Rathnayake, Rathnayake M L D; Oshiki, Mamoru; Ishii, Satoshi; Segawa, Takahiro; Satoh, Hisashi; Okabe, Satoshi

    2015-12-01

    The effects of dissolved oxygen (DO) and pH on nitrous oxide (N2O) production rates and pathways in autotrophic partial nitrification (PN) granules were investigated at the granular level. N2O was primarily produced by betaproteobacterial ammonia-oxidizing bacteria, mainly Nitrosomonas europaea, in the oxic surface layer (<200μm) of the autotrophic PN granules. N2O production increased with increasing bulk DO concentration owing to activation of the ammonia (i.e., hydroxylamine) oxidation in this layer. The highest N2O emissions were observed at pH 7.5, although the ammonia oxidation rate was unchanged between pH 6.5 and 8.5. Overall, the results of this study suggest that in situ analyses of PN granules are essential to gaining insight into N2O emission mechanisms in a granule. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Oxidation and haem loss kinetics of poly(ethylene glycol)-conjugated haemoglobin (MP4): dissociation between in vitro and in vivo oxidation rates.

    PubMed

    Vandegriff, Kim D; Malavalli, Ashok; Minn, Charles; Jiang, Eva; Lohman, Jeff; Young, Mark A; Samaja, Michele; Winslow, Robert M

    2006-11-01

    Haemoglobin-based oxygen carriers can undergo oxidation of ferrous haemoglobin into a non-functional ferric form with enhanced rates of haem loss. A recently developed human haemoglobin conjugated to maleimide-activated poly(ethylene glycol), termed MP4, has unique physicochemical properties (increased molecular radius, high oxygen affinity and low cooperativity) and lacks the typical hypertensive response observed with most cell-free haemoglobin solutions. The rate of in vitro MP4 autoxidation is higher compared with the rate for unmodified SFHb (stroma-free haemoglobin), both at room temperature (20-22 degrees C) and at 37 degrees C (P<0.001). This appears to be attributable to residual catalase activity in SFHb but not MP4. In contrast, MP4 and SFHb showed the same susceptibility to oxidation by reactive oxygen species generated by a xanthine-xanthine oxidase system. Once fully oxidized to methaemoglobin, the rate