WorldWideScience

Sample records for alkanes

  1. Alkane dimers interaction

    DEFF Research Database (Denmark)

    Ferrighi, Lara; Madsen, Georg Kent Hellerup; Hammer, Bjørk

    The interaction energies of a series of n-alkane dimers, from methane to decane, have been investigated with Density Functional Theory (DFT), using the MGGA-M06-L density functional. The results are compared both to the available wavefunction-based values as well as to dispersion corrected DFT...

  2. Evaporating Drops of Alkane Mixtures

    CERN Document Server

    Gu'ena, G; Poulard, C; Cazabat, Anne-Marie; Gu\\'{e}na, Geoffroy; Poulard, Christophe

    2005-01-01

    Alkane mixtures are model systems where the influence of surface tension gradients during the spreading and the evaporation of wetting drops can be easily studied. The surface tension gradients are mainly induced by concentration gradients, mass diffusion being a stabilising process. Depending on the relative concentration of the mixture, a rich pattern of behaviours is obtained.

  3. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    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).

  4. Catalytic isomerization of light alkanes

    OpenAIRE

    Løften, Thomas

    2004-01-01

    In recent years the levels of sulfur and benzene in the gasoline pool have been reduced, and in the future there may also be new regulations on vapor pressure and the level of aromatics and olefins as well. The limitations on vapor pressure and aromatics will lead to reduced use of C4 and reformate respectively. The branched isomers of C5 and C6 alkanes have high octane numbers compared to the straight chain isomers, and are consequently valuable additives to the gasoline pool. To maintain th...

  5. Scorpionate complexes as catalysts for alkane functionalization

    OpenAIRE

    Martins, Luísa M. D. R. S.

    2009-01-01

    A survey of the scorpionate tris(pyrazolyl)methane complexes synthesized by our group is presented, as well as their structural features and catalytic applications toward the funtionalization of linear and cyclic light alkanes.

  6. Supported organoiridium catalysts for alkane dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Solar photothermochemical alkane reverse combustion.

    Science.gov (United States)

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

    2016-03-01

    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

  8. Metathesis of alkanes and related reactions

    KAUST Repository

    Basset, Jean-Marie

    2010-02-16

    (Figure Presented) 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, (=SiO)2TaH, 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 aluminasupported tungsten hydride, W(H)3/Al 2O3, 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 of

  9. The organization of n-alkanes in lipid bilayers.

    Science.gov (United States)

    McIntosh, T J; Simon, S A; MacDonald, R C

    1980-04-24

    The interaction of n-alkanes (C6--C16) with phosphatidylcholine has been studied by the combined use of differential scanning calorimetry, X-ray diffraction and monolayer techniques. It has been found that the thermal properties and ultrastructure of lipid-alkane vesicles are strongly dependent on the length of the n-alkanes. Long alkanes, such as tetradecane and hexadecane, increase the transition temperature of dimyristoyl phosphatidylcholine and dipalmitoyl phosphatidylcholine, while the X-ray data indicate that these long alkanes align parallel to the lipid acyl chains. In contrast, shorter alkanes, such as hexane and octane, decrease and broaden the thermal transition and electron density profiles show that these alkanes increase bilayer width by partitioning between the apposing monolayers of the bilayer. For lipids in the gel and liquid crystalline states, the short alkanes form an alkane region in the geometric center of the bilayer. PMID:6892885

  10. Oxidative dehydrogenation of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Meiswinkel, A.; Thaller, C.; Bock, M.; Alvarado, L. [Linde AG, Pullach (Germany); Hartmann, D.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen (Germany)

    2012-07-01

    The demand of light olefins increases steadily and the current steam cracking production is highly energy demanding. This motivates the development of alternative production processes like the oxidative dehydrogenation (ODH) of light alkanes operating at comparably low temperatures. Multi-component oxides are reported to show excellent catalytic performance in the ODH. Especially, MoVTeNbO oxides present high activity and selectivity in ODH of ethane. Synthesis of MoVTeNb oxides was done by a hydrothermal method. Qualitative and quantitative phase analysis were performed by X-ray diffraction and Rietveld refinement. Surface compositions were determined by Low energy ion scattering (LEIS). Catalytic tests were carried out in a fixed bed plug flow reactor using ethane and oxygen diluted in helium, as gaseous feed. Based on laboratory investigations a first upscale to a bench-top-pilot unit was performed in order to evaluate the large scale and long term feasibility of the process under technically relevant conditions. MoVTeNb oxides show high activity combined with excellent selectivity in the ODH of ethane to ethylene (S > 95% at X < 40%). Phase analysis reveals the presence of M1, M2 and amorphous phases. Literature reports the crystalline M1 phase as essential for the performance. Indeed, the crystalline M1 phase impacts on the activity via exposing V on the surface being apparently vital to achieve an active material. A correlation of the apparent activation energy with the surface vanadium composition of the catalysts is noticed, however, surprisingly with no major impact on the ethene selectivity. As this material was identified as most promising for a technical application a scale up from less than 1g to 50g of catalyst was performed in a bench-top-pilot unit. The reaction has a significant adiabatic temperature rise and the handling of the reaction heat is a major challenge for process engineering. Furthermore different diluent media such as Helium, Nitrogen

  11. Enzymes and Genes Involved in Aerobic Alkane Degradation

    Directory of Open Access Journals (Sweden)

    ZongzeShao

    2013-05-01

    Full Text Available Alkanes are major constituents of crude oil. They are also present at low concentrations in diverse non-contaminated because many living organisms produce them as chemo-attractants or as protecting agents against water loss. Alkane degradation is a widespread phenomenon in nature. The numerous microorganisms, both prokaryotic and eukaryotic, capable of utilizing alkanes as a carbon and energy source, have been isolated and characterized. This review summarizes the current knowledge of how bacteria metabolize alkanes aerobically, with a particular emphasis on the oxidation of long-chain alkanes, including factors that are responsible for chemotaxis to alkanes , transport across cell membrane of alkanes , the regulation of alkane degradation gene and initial oxidation.

  12. 40 CFR 721.10163 - Chloro fluoro alkane (generic).

    Science.gov (United States)

    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...

  13. 40 CFR 721.536 - Halogenated phenyl alkane.

    Science.gov (United States)

    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)...

  14. Reflectance spectroscopy of organic compounds: 1. Alkanes

    Science.gov (United States)

    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.

  15. Alkane dehydrogenation over supported chromium oxide catalysts

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Schoonheydt, R.A.

    1999-01-01

    The dehydrogenation of alkanes over supported chromium oxide catalysts in the absence of oxygen is of high interest for the industrial production of propene and isobutene. In this review, a critical overview is given of the current knowledge nowadays available about chromium-based dehydrogenation ca

  16. Hydrogen Bonding to Alkanes: Computational Evidence

    DEFF Research Database (Denmark)

    Hammerum, Steen; Olesen, Solveig Gaarn

    2009-01-01

    The structural, vibrational, and energetic properties of adducts of alkanes and strong cationic proton donors were studied with composite ab initio calculations. Hydrogen bonding in [D-H+ H-alkyl] adducts contributes to a significant degree to the interactions between the two components, which is...... substantiated by NBO and AIM results. The hydrogen bonds manifest themselves in the same manner as conventional hydrogen bonds, D-H bond elongation, D-H vibrational stretching frequency red shift and intensity increase, and adduct stabilization. The alkane adducts also exhibit elongation of the C-H bonds...... involved and a concurrent red shift, which is rationalized in terms of charge-transfer interactions that cause simultaneous weakening of both the O-H and C-H bonds. Like other dihydrogen-bonded adducts, the adducts possess a bent structure and asymmetric bifurcated hydrogen bonds. The hydrogen bonds are...

  17. Discrimination of abiogenic and biogenic alkane gases

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    We have combined the analytical data of the carbon isotope distribution pattern, R/Ra and CH4/3He values of abiogenic and biogenic (referring to the thermogenic and bacterial or microbial) alkane gases in China with those of alkane gases from USA, Russia, Germany, Australia and other countries. Four discrimination criteria are derived from this comparative study: 1) Carbon isotopic composition is generally greater than -30‰ for abiogenic methane and less than -30‰ for biogenic methane; 2) Abiogenic alkane gases have a carbon isotopic reversal trend (δ 13C1> δ 13C2> δ 13C3> δ 13C4) with δ 13C1>-30‰ in general; 3) Gases with R/Ra >0.5 and δ 13C11 δ 13C2>0 are of abiogenic origin; 4) Gases (meth- ane) with CH4/3He≤106 are of abiogenic origin, whereas gases with CH4/3He≥1011 are of biogenic origin.

  18. Positronium in solid phases of n-alkane binary mixtures

    International Nuclear Information System (INIS)

    Highlights: • Rotator phase in even alkanes CnH2n+2 with n ⩽ 20 appears in mixed samples only. • Interlamellar gap width is the same for shorter chain alkane concentration x and 1 − x. • Excess electron trapping diminishes with broadening of alkane chain distribution Δn. - Abstract: Binary mixtures of even-numbered normal alkanes CnH2n+2 and Cn+2H2n+6 with n ⩽ 18 were investigated by positron annihilation spectroscopy. Formation of the rotator phase was observed in mixed structures, while no such a phase in neat alkanes in this range of n was found. Phase diagrams for n = 18 and n = 16 are very similar to the diagrams for binary mixtures of odd-numbered alkanes. The effect of positronium formation with trapped excess electrons weakens with decreasing n, at low n values the time constant of Ps rise contains the component much shorter than 1 h

  19. Polychlorinated Alkanes in Fish from Norwegian Freshwater

    OpenAIRE

    Borgen, Anders R.; Martin Schlabach; Roland Kallenborn; Eirik Fjeld

    2002-01-01

    Short-chain polychlorinated alkanes (sPCAs) have been measured in freshwater fish samples from different lakes all over Norway and from the Norwegian Arctic. The analyses were performed with high-resolution GC coupled to high-resolution MS in electron capture negative ion mode. The species investigated were trout, Arctic char, and burbot (Lota lota). Muscle tissue in the lake trout and Arctic char, and liver in burbot, were selected for analyses because of their high lipid content. ∑sPCA conc...

  20. Saturated-liquid heat capacity calculation of alkanes

    OpenAIRE

    JOVAN D. JOVANOVIC; DUSAN K. GROZDANIC

    2005-01-01

    An empirical model for the calculation of the heat capacity of alkanes is recommended. This model was tested and compared to known models (LuriaâBenson and RizickaâDomalski) using 68 sets with 1155 literature experimental heat capacity data of 39 alkanes. The obtained results indicate that the newmodel is slightly better tha the existing models, especially near the critical point.

  1. 40 CFR 721.3435 - Butoxy-substituted ether alkane.

    Science.gov (United States)

    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...

  2. Products of Chemistry: Alkanes: Abundant, Pervasive, Important, and Essential.

    Science.gov (United States)

    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)

  3. Shale gas opportunities. Dehydrogenation of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Patcas, F.C.; Dieterle, M.; Rezai, A.; Asprion, N. [BASF SE, Ludwigshafen (Germany)

    2013-11-01

    The discovery and use of shale gas in North America has become a game changer for the chemical industry by access to a cheaper feedstock compared to conventional oil. Increased number of ethane crackers spurred increasing interest in light alkanes dehydrogenation. Several companies have announced their interest in new propane dehydrogenation units in North America. BASF is developing light alkanes dehydrogenation technologies for two decades now. BASF developed jointly with Linde the isothermal C3 dehydrogenation process. The latest dehydrogenation catalyst development at BASF focused on a supported and steam resistant Pt-Sn catalyst which yielded excellent selectivity and activity. Intense research work both internally as well as in cooperation with universities contributed to the understanding of the relationship between the surface structure and catalyst performances like activity, selectivity and coking resistance. Using such type of catalysts BASF developed an autothermal propane dehydrogenation as well as a butane dehydrogenation process. The most recent catalyst development was a dehydrogenation catalyst coated on a honeycomb monolith to improve catalyst usage and pressure drop. This will probably be the first industrial usage of catalytic monoliths in a chemical synthesis process. (orig.) (Published in summary form only)

  4. Hydrocarbon metabolism by Brevibacterium erythrogenes: normal and branched alkanes.

    Science.gov (United States)

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

    1974-09-01

    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 (14)CO(2) from [1-(14)C]pristane is delayed, or entirely inhibited, in the presence of n-hexadecane, whereas CO(2) release from n-hexadecane remains unaffected. These results suggest an inducible dicarboxylic acid pathway for degradation of branched-chain alkanes. PMID:4852318

  5. Resonant diffusion of normal alkanes in zeolites: Effect of the zeolite structure and alkane molecule vibrations

    CERN Document Server

    Tsekov, R

    2015-01-01

    Diffusion of normal alkanes in one-dimensional zeolites is theoretically studied on the basis of the stochastic equation formalism. The calculated diffusion coefficient accounts for the vibrations of the diffusing molecule and zeolite framework, molecule-zeolite interaction, and specific structure of the zeolite. It is shown that when the interaction potential is predominantly determined by the zeolite pore structure, the diffusion coefficient varies periodically with the number of carbon atoms of the alkane molecule, a phenomenon called resonant diffusion. A criterion for observable resonance is obtained from the balance between the interaction potentials of the molecule due to the atomic and pore structures of the zeolite. It shows that the diffusion is not resonant in zeolites without pore structure, such as ZSM-12. Moreover, even in zeolites with developed pore structure no resonant dependence of the diffusion constant can be detected if the pore structure energy barriers are not at least three times high...

  6. Long-chain alkane production by the yeast Saccharomyces cerevisiae.

    Science.gov (United States)

    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. PMID:25545362

  7. Oxidation of long-chain alkanes by Acetobacter rancens

    International Nuclear Information System (INIS)

    The degradation of hexadecane and tetradecane by Acetobacter rancens CCM 1774 was investigated. It was found that this strain is able to grow to a limited extent on hexadecane as a carbon source. The occurrence of n-alkanoic acids and alcohols among the reaction products of growing as well as resting cells indicates a monoterminal degradation of long-chain alkanes. Both alkane-grown and glucose-grown resting cells exhibited alkane oxidizing activities which were not influenced by chloramphenicol. This suggested a constitutive nature of the appropriate enzymes. (orig.)

  8. Alkanes-filled photonic crystal fibers as sensor transducers

    Science.gov (United States)

    Marć, P.; Przybysz, N.; Stasiewicz, K.; Jaroszewicz, L. R.

    2015-09-01

    In this paper we propose alkanes-filled PCFs as the new class of transducers for optical fiber sensors. We investigated experimentally thermo-optic properties of a commercially available LMA8 partially filled with different alkanes with a higher number of carbon atoms. A partially filled PCF spliced with standard SMFs constitutes one of the newest type transducer. We have selected a group of eight alkanes which have melting points in different temperatures. An analysis of temperature spectral characteristics of these samples will allow to design an optical fiber sensor with different temperature thresholds at specific wavelengths.

  9. UNIQUAC interaction parameters for alkane/amine systems determined by Molecular Mechanics

    DEFF Research Database (Denmark)

    Jonsdottir, Svava Osk; Klein, R. A.; Rasmussen, Kjeld

    UNIQUAC interaction parameters have been successfully determined for three alkane/primary amine systems using a Molecular Mechanics method called the Consistent Force Field. Interaction parameters for alkane/alkane and alkane/ketone systems had been determined previously using this method and in...

  10. Abnormal carbon and hydrogen isotopes of alkane gases from the Qingshen gas field, Songliao Basin, China, suggesting abiogenic alkanes?

    Science.gov (United States)

    Liu, Quanyou; Dai, Jinxing; Jin, Zhijun; Li, Jian; Wu, Xiaoqi; Meng, Qingqiang; Yang, Chun; Zhou, Qinghua; Feng, Zihui; Zhu, Dongya

    2016-01-01

    It is great debate that the alkane gases of abiogenic origin would constitute a major portion of the commercial accumulation of the Qingshen gas field, Songliao Basin, China. In this study, abiogenic gases characterized by heavy δ13C1 values, reversal of the usual carbon isotopic trend of C1-C5 alkanes, very narrow variation in δ2HC1 values, and low CH4/3He ratios associated with high R/Ra values (>1) were identified. The hydrocarbon gas in the Qingshen gas field is a mixture of thermogenic alkanes derived from Cretaceous mudstone (type I kerogen) or Jurassic coal (type III kerogen) and abiogenic alkanes (mainly CH4) from mantle degassing. A quantitative estimation of abiogenic alkanes contribution to the Qingshen gas field is made based on a δ13C1 vs. δ13C2 plot: about 30-40% of alkane gases in the Qingshen gas field, along with its helium, are estimated to be derived from the mantle via magmatic activity. Particularly, the abiogenic formation of CH4 generated from the reduction of CO2 by hydrothermal activity may contribute. Our study suggests that abiogenic alkane gases in certain geological settings could be more widespread than previously thought, and may accumulate into economic reservoirs.

  11. At what chain length do unbranched alkanes prefer folded conformations?

    CERN Document Server

    Byrd, Jason N; Montgomery, John A

    2013-01-01

    Short unbranched alkanes are known to prefer linear conformations, while long unbranched alkanes are folded. It is not known with certainty at what chain length the linear conformation is no longer the global minimum. To clarify this point, we use {\\it ab initio} and density functional methods to compute the relative energies of the linear and hairpin alkane conformers for increasing chain lengths. Extensive electronic structure calculations are performed to obtain optimized geometries, harmonic frequencies and accurate single point energies for the selected alkane conformers from octane through octadecane. Benchmark CCSD(T)/cc-pVTZ single point calculations are performed for chains through tetradecane, while approximate methods are required for the longer chains up to octadecane. Using frozen natural orbitals to unambiguously truncate the virtual orbital space we are able to compute composite CCSD FNO(T) single point energies for all the chain lengths. This approximate composite method has significant comput...

  12. Molecular dynamics study of the water/n-alkane interface

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Molecular dynamics simulations on the interface between liquid water and liquid n-alkane (including octane, nonane, decane, undecane and dodecane) have been performed with the purpose to study the interfacial properties: (Ⅰ) density profile; (Ⅱ) molecular orientation; (Ⅲ) interfacial tension and the temperature effect on the interfacial tension. Simulation results show that at the interface the structures of both water and n-alkane are different from those in the bulk. Water has an orientational preference due to the number of hydrogen bonds per molecule maximized. N-alkane has a more lateral orientation with respect to the interface in order to be in close contact with water. The calculated individual phase bulk density and interfacial tension of water/n-alkane systems are in good agreement with the corresponding experimental ones.

  13. Alkane oxidation by Pseudomonas oleovorans : genes and proteins

    NARCIS (Netherlands)

    van Beilen, Jan Berthold

    1994-01-01

    This thesis deals with the molecular genetics and biochemistry of oxidation of medium chainlength alkanes by P. oleovorans, as part of a program to develop biotechnological processes, based on oxygenases.

  14. A graph theoretical method for partial ordering of alkanes

    OpenAIRE

    Vukičević, Damir; Sedlar, Jelena; Rajtmajer, Sarah Michelle

    2007-01-01

    The topological Zagreb index M-1 introduces an ordering on the set of alkanes. Recently, modified Zagreb indices M-lambda(1) have been proposed, and it is noted that they differently order alkanes. In this paper, the level of consistency between these orders is analyzed. A new partial order > as the intersection of all partial orders M-lambda(1) (where m is at least 2) is introduced and its properties are analyzed.

  15. Structure and solvation forces in confined films of alkanes

    OpenAIRE

    Dijkstra, Marjolein

    1998-01-01

    We compute by computer simulations the solvation force of a system of linear and branched alkanes confined in a slab geometry. The solvation force for linear decane oscillates with distance with a periodicity close to the width of the molecules. The branched alkanes, 2- methylundecane and 2-methylheptane, show a similar oscillatory behaviour, however the oscillations are decreased with a factor of about three and show a long-range attractive force. In addition, we show that the critical tempe...

  16. Alkane Biosynthesis Genes in Cyanobacteria and Their Transcriptional Organization

    OpenAIRE

    Stephan eKlähn; Desiree eBaumgartner; Ulrike ePfreundt; Karsten eVoigt; Verena eSchoen; Claudia eSteglich; Hess, Wolfgang R

    2014-01-01

    In cyanobacteria, alkanes are synthesized from a fatty acyl-ACP by two enzymes, acyl-acyl carrier protein reductase (AAR) and aldehyde deformylating oxygenase (ADO). Despite the great interest in the exploitation for biofuel production, nothing is known about the transcriptional organization of their genes or the physiological function of alkane synthesis. The comparison of 115 microarray datasets indicates the relatively constitutive expression of aar and ado genes. The analysis of 181 avail...

  17. New perspectives for the isomerization of light n-alkanes

    OpenAIRE

    Hubaut, Robert; Rives, Alain; Kuang, Wenxing; Fournier, Michel

    2005-01-01

    Isomerization of light n-alkanes into the high-octane number branched alkanes is an important challenge for petroleum refining industry. According to the literature, such a transformation needs two different active centres: one having a hydrogenating/dehydrogenating ability and another, a protonic acid function. From this point of view, heteropolyacids (HPAs) in mixing with one or more transition metal appear promising. Mechanical mixtures of alumina-supported platinum or of mixed palladium (...

  18. Positronium in solid phases of n-alkane binary mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Zgardzińska, B.; Goworek, T.

    2015-09-08

    Highlights: • Rotator phase in even alkanes C{sub n}H{sub 2n+2} with n ⩽ 20 appears in mixed samples only. • Interlamellar gap width is the same for shorter chain alkane concentration x and 1 − x. • Excess electron trapping diminishes with broadening of alkane chain distribution Δn. - Abstract: Binary mixtures of even-numbered normal alkanes C{sub n}H{sub 2n+2} and C{sub n+2}H{sub 2n+6} with n ⩽ 18 were investigated by positron annihilation spectroscopy. Formation of the rotator phase was observed in mixed structures, while no such a phase in neat alkanes in this range of n was found. Phase diagrams for n = 18 and n = 16 are very similar to the diagrams for binary mixtures of odd-numbered alkanes. The effect of positronium formation with trapped excess electrons weakens with decreasing n, at low n values the time constant of Ps rise contains the component much shorter than 1 h.

  19. Probing the Structure of Liquids with 129Xe NMR Spectroscopy: n-Alkanes, Cycloalkanes, and Branched Alkanes

    OpenAIRE

    Morgado, Pedro; Bonifácio, Rui; Martins, Luís F. G.; Filipe, Eduardo J. M.

    2013-01-01

    The liquid organization of linear, branched, and cyclic alkanes was studied using atomic 129Xe as a NMR probe. 129Xe chemical shifts have been experimentally determined for xenon dissolved in a total of 21 alkanes. In order to allow the comparison of the different solvents at similar thermodynamic conditions, the measurements were performed over a wide range of temperatures, from the melting point of the solvent up to 350 K. The results were rationalized in terms of the dens...

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

    OpenAIRE

    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 substi...

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

    Science.gov (United States)

    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

  2. Packing properties 1-alkanols and alkanes in a phospholipid membrane

    DEFF Research Database (Denmark)

    Westh, Peter

    2006-01-01

    We have used vibrating tube densitometry to investigate the packing properties of four alkanes and a homologous series of ten alcohols in fluid-phase membranes of dimyristoyl phosphatidylcholine (DMPC). It was found that the volume change of transferring these compounds from their pure states into...... the membrane, Vm(puremem), was positive for small (C4-C6) 1-alkanols while it was negative for larger alcohols and all alkanes. The magnitude of Vm(puremem) ranged from about +4 cm3/mol for alcohols with an alkyl chain about half the length of the fatty acids of DMPC, to -10 to -15 cm3/mol for the...... alkanes and long chain alcohols. On the basis of these observations, previously published information on the structure of the membrane-solute complexes and the free volume properties of (pure) phospholipid membranes, we suggest that two effects dominate the packing properties of hydrophobic solutes in...

  3. High Temperature Chemical Kinetic Combustion Modeling of Lightly Methylated Alkanes

    Energy Technology Data Exchange (ETDEWEB)

    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.

  4. A Quick Estimate of the Correlation Energy for Alkanes

    Institute of Scientific and Technical Information of China (English)

    黎书华; 李伟; 马晶

    2003-01-01

    Within the localized molecular orbital description, the intraand interorbital pair correlation energies calculated with the coupled cluster doubles (CCD) theory have been obtained for methane, ethane, propane, butane, isobutane, pentane,isopentane and neopentane using the 6-31G* basis set. The results showed the quantitative transferability of pair correlation energies and gross orbital correlation energies within this series of molecules. Based on the gross orbital correlation energies of five sample alkanes (butane, isobutane, pentane,isopentane and neopentane), we have derived a simple linear relationship to estimate the CCD correlation energy for an arbitrary large alkane. The correlation energy predicted by this simple relationship remarkably recovers more than 98.9% of the exact CCD correlation energy for a number of alkanes containing six to eight carbon atoms. The relative stability of less branched isomers can be correctly predicted.

  5. BIODEGRADATION AND GAS-EXCHANGE OF GASEOUS ALKANES IN MODEL ESTUARINE ECOSYSTEMS

    Science.gov (United States)

    Gas exchange-biodegradation experiments conducted in model estuarine ecosystems indicate that the ease of degradation of gaseious normal alkanes increases with chain length. The behavior of gaseous perhalogenated alkanes can be explained by gas exchange alone with no degradation....

  6. On the relation between Zenkevich and Wiener indices of alkanes

    Directory of Open Access Journals (Sweden)

    ZARKO BOSKOVIC

    2004-04-01

    Full Text Available A relatively complicated relation was found to exist between the quantity U, recently introduced by Zenkevich (providing a measure of internal molecular energy, and the Wiener index W (measuring molecular surface area and intermolecular forces. We now report a detailed analysis of this relation and show that, in the case of alkanes, its main features are reproduced by the formula U = –aW + b + gn1; where n1 is the number of methyl groups, and a, b and g are constants, depending only on the number of carbon atoms. Thus, for isomeric alkanes with the same number of methyl groups, U and W are linearly correlated.

  7. Squeezing molecularly thin alkane lubrication films: Layering transistions and wear

    DEFF Research Database (Denmark)

    Sivebæk, Ion Marius; Samoilov, V. N.; Persson, B. N. J.

    2004-01-01

    The properties of alkane lubricants confined between two approaching solids are investigated by a model that accounts for the curvature and the elastic properties of the solid surfaces. We consider linear alkane molecules of different chain lengths, C(3)H(8); C(4)H(10); C(8)H(18); C(9)H(20); C(10)H......(22); C(12)H(26), and C(14)H(30) confined between smooth gold surfaces. We observe well-defined molecular layers develop in the lubricant film when the width of the film is of the order of a few atomic diameters. An external squeezing-pressure induces discontinuous changes in the number n of lubricant...

  8. Squeezing molecular thin alkane lubrication films: layering transition and wear

    OpenAIRE

    Sivebæk, Ion Marius; Samoilov, V. N.; Persson, B. N. J.

    2003-01-01

    The properties of alkane lubricants confined between two approaching solids are investigated by a model that accounts for the curvature and the elastic properties of the solid surfaces. We consider linear alkane molecules of different chain lengths, C3H8, C4H10, C8H18, C9H20, C10H22, C12H26, and C14H30 confined between smooth gold surfaces. In most cases we observe well defined molecular layers develop in the lubricant film when the width of the film is of the order of a few atomic diameters....

  9. Regioselective alkane hydroxylation with a mutant AlkB enzyme

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Science.gov (United States)

    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...

  11. 40 CFR 721.9300 - Reaction products of substituted hydroxy-alkanes and polyalkylpolyisocyanatocarbomono- cycle.

    Science.gov (United States)

    2010-07-01

    ... hydroxy-alkanes and polyalkylpolyisocyanatocarbomono- cycle. 721.9300 Section 721.9300 Protection of... substituted hydroxy-alkanes and polyalkylpolyisocyanatocarbomono- cycle. (a) Chemical substance and... products of substituted hydroxy-alkanes and polyal- kylpoly-isocyanato-carbo-mono-cycle (PMN P-91-75)...

  12. Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts

    KAUST Repository

    Szeto, Kaï Chung

    2012-01-01

    We report a selective direct conversion of n-butane into higher molecular weight alkanes (C 5+) by alkane metathesis reaction catalysed by silica-alumina supported tungsten or tantalum hydrides at moderate temperature and pressure. The product is unprecedented, asymmetrically distributed towards heavier alkanes. This journal is © 2012 The Royal Society of Chemistry.

  13. Oxygenation of alkanes with hydrogen peroxide catalysed by osmium complexes

    OpenAIRE

    Shulpin, Georgiy B.; Süss-Fink, Georg; Shulpina, Lidia S.

    2006-01-01

    Efficient oxidation of alkanes, including methane and ethane, with H2O2 in the presence of catalytic amount of an Os complex in MeCN (addition of nitrogen-containing heterocycles significantly enhances the yield of the products) or in MeCO2H gives the corresponding ketones and alcohols.

  14. MODELING OF ALKANE EMISSIONS FROM A WOOD STAIN

    Science.gov (United States)

    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 fu...

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

    Energy Technology Data Exchange (ETDEWEB)

    Benderly, Abraham (Elkins Park, PA); Chadda, Nitin (Radnor, PA); Sevon, Douglass (Fairless Hills, PA)

    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.

  16. Theoretical study of n-alkane adsorption on metal surfaces

    DEFF Research Database (Denmark)

    Morikawa, Yoshitada; Ishii, Hisao; Seki, Kazuhiko

    2004-01-01

    The interaction between n-alkane and metal surfaces has been studied by means of density-functional theoretical calculations within a generalized gradient approximation (GGA). We demonstrate that although the GGA cannot reproduce the physisorption energy well, our calculations can reproduce the...

  17. A superoleophobic textile repellent towards impacting drops of alkanes

    Science.gov (United States)

    Artus, Georg R. J.; Zimmermann, Jan; Reifler, Felix A.; Brewer, Stuart A.; Seeger, Stefan

    2012-02-01

    A commercially available polyester fabric has been rendered superoleophobic by coating with silicone nanofilaments and subsequent plasma fluorination. The treated samples show outstanding oil-repellency. They achieve the highest possible oil-repellency grade of 8, repel impacting drops of alkanes and show a plastron layer in hexadecane. The oil repellency is shown to depend on the topography of the silicone nanofilament coating.

  18. Secondary organic aerosol composition from C12 alkanes.

    Science.gov (United States)

    Schilling Fahnestock, Katherine A; Yee, Lindsay D; Loza, Christine L; Coggon, Matthew M; Schwantes, Rebecca; Zhang, Xuan; Dalleska, Nathan F; Seinfeld, John H

    2015-05-14

    The effects of structure, NOx conditions, relative humidity, and aerosol acidity on the chemical composition of secondary organic aerosol (SOA) are reported for the photooxidation of three C12 alkanes: n-dodecane, cyclododecane, and hexylcyclohexane. Acidity was modified through seed particle composition: NaCl, (NH4)2SO4, and (NH4)2SO4 + H2SO4. Off-line analysis of SOA was carried out by solvent extraction and gas chromatography-mass spectrometry (GC/MS) and direct analysis in real-time mass spectrometry. We report here 750 individual masses of SOA products identified from these three alkane systems and 324 isomers resolved by GC/MS analysis. The chemical compositions for each alkane system provide compelling evidence of particle-phase chemistry, including reactions leading to oligomer formation. Major oligomeric species for alkane SOA are peroxyhemiacetals, hemiacetals, esters, and aldol condensation products. Furans, dihydrofurans, hydroxycarbonyls, and their corresponding imine analogues are important participants in these oligomer-producing reactions. Imines are formed in the particle phase from the reaction of the ammonium sulfate seed aerosol with carbonyl-bearing compounds present in all the SOA systems. Under high-NO conditions, organonitrate products can lead to an increase of aerosol volume concentration by up to a factor of 5 over that in low-NO conditions. Structure was found to play a key role in determining the degree of functionalization and fragmentation of the parent alkane, influencing the mean molecular weight of the SOA produced and the mean atomic O:C ratio. PMID:24814371

  19. Distribution and sources of n-alkanes in surface sediments of Taihu Lake, China

    Directory of Open Access Journals (Sweden)

    Yu Yunlong

    2016-03-01

    Full Text Available The last study on n-alkanes in surface sediments of Taihu Lake was in 2000, only 13 surface sediment samples were analysed, in order to have a comprehensive and up-to-date understanding of n-alkanes in the surface sediments of Taihu Lake, 41 surface sediment samples were analyzed by GC-MS. C10 to C37 were detected, the total concentrations of n-alkanes ranged from 2109 ng g−1 to 9096 ng g−1 (dry weight. There was strong odd carbon predominance in long chain n-alkanes and even carbon predominance in short chain n-alkanes. When this finding was combined with the analysis results of wax n-alkanes (WaxCn, carbon preference index (CPI, unresolved complex mixture (UCM, hopanes and steranes, it was considered that the long chain n-alkanes were mainly from terrigenous higher plants, and that the short chain n-alkanes mainly originated from bacteria and algae in the lake, compared with previous studies, there were no obvious anthropogenic petrogenic inputs. Terrestrial and aquatic hydrocarbons ratio (TAR and C21−/C25+ indicated that terrigenous input was higher than aquatic sources and the nearshore n-alkanes were mainly from land-derived sources. Moreover, the distribution of short chain n-alkanes presented a relatively uniform pattern, while the long chain n-alkanes presented a trend that concentrations dropped from nearshore places to the middle of lake.

  20. Image Charge Effects in the Wetting Behavior of Alkanes on Water with Accounting for Water Solubility

    Directory of Open Access Journals (Sweden)

    Kirill A. Emelyanenko

    2016-03-01

    Full Text Available Different types of surface forces, acting in the films of pentane, hexane, and heptane on water are discussed. It is shown that an important contribution to the surface forces originates from the solubility of water in alkanes. The equations for the distribution of electric potential inside the film are derived within the Debye-Hückel approximation, taking into account the polarization of the film boundaries by discrete charges at water-alkane interface and by the dipoles of water molecules dissolved in the film. On the basis of above equations we estimate the image charge contribution to the surface forces, excess free energy, isotherms of water adsorption in alkane film, and the total isotherms of disjoining pressure in alkane film. The results indicate the essential influence of water/alkane interface charging on the disjoining pressure in alkane films, and the wettability of water surface by different alkanes is discussed.

  1. Flash Points of Secondary Alcohol and n-Alkane Mixtures.

    Science.gov (United States)

    Esina, Zoya N; Miroshnikov, Alexander M; Korchuganova, Margarita R

    2015-11-19

    The flash point is one of the most important characteristics used to assess the ignition hazard of mixtures of flammable liquids. To determine the flash points of mixtures of secondary alcohols with n-alkanes, it is necessary to calculate the activity coefficients. In this paper, we use a model that allows us to obtain enthalpy of fusion and enthalpy of vaporization data of the pure components to calculate the liquid-solid equilibrium (LSE) and vapor-liquid equilibrium (VLE). Enthalpy of fusion and enthalpy of vaporization data of secondary alcohols in the literature are limited; thus, the prediction of these characteristics was performed using the method of thermodynamic similarity. Additionally, the empirical models provided the critical temperatures and boiling temperatures of the secondary alcohols. The modeled melting enthalpy and enthalpy of vaporization as well as the calculated LSE and VLE flash points were determined for the secondary alcohol and n-alkane mixtures. PMID:26491811

  2. Short-time Evolution of Alkane-in-Water Nanoemulsions

    OpenAIRE

    Urbina-Villalba, German; Rahn-Chique, Kareem

    2013-01-01

    The stability of alkane-in-water nanoemulsions during the sub-stationary regime is studied by means of Emulsion Stability Simulations (ESS). The effects of Ostwald ripening, flocculation, coalescence, gravity, and hydration forc- es are considered. According to these calculations flocculation and coalescence are predominant during the first few seconds after the preparation of the emulsion. This favors the generation of a right-skewed Drop Size Distribu- tion (DSD). As the system evolves, the...

  3. Rate effects on layering of a confined linear alkane

    OpenAIRE

    Bureau, Lionel

    2007-01-01

    We perform drainage experiments of a linear alkane fluid (n-hexadecane) down to molecular thicknesses, and focus on the role played by the confinement rate. We show that molecular layering is strongly influenced by the velocity at which the confining walls are approached: under high enough shear rates, the confined medium behaves as a structureless liquid of enhanced viscosity for film thickness below $\\sim$10 nm. Our results also lead us to conclude that a rapidly confined film can be quench...

  4. Active coke: Carbonaceous materials as catalysts for alkane dehydrogenation

    OpenAIRE

    McGregor, J.; Huang, Z; Parrott, E.; Zeitler, J.; Nguyen, K.; Rawson, J.; Carley, A; Hansen, T.; Tessonnier, J.; Su, D.; Teschner, D; Vass, E.; Knop-Gericke, A.; Schlögl, R.; Gladden, L.

    2010-01-01

    The catalytic dehydrogenation (DH) and oxidative dehydrogenation (ODH) of light alkanes are of significant industrial importance. In this work both carbonaceous materials deposited on VOx/Al2O3 catalysts during reaction and unsupported carbon nanofibres (CNFs) are shown to be active for the dehydrogenation of butane in the absence of gas-phase oxygen. Their activity in these reactions is shown to be dependent upon their structure, with different reaction temperatures yielding structurally dif...

  5. Chromium oxide catalysts in the dehydrogenation of alkanes

    OpenAIRE

    Airaksinen, Sanna

    2005-01-01

    Light alkenes, such as propene and butenes, are important intermediates in the manufacture of fuel components and chemicals. The direct catalytic dehydrogenation of the corresponding alkanes is a selective way to produce these alkenes and is frequently carried out using chromia/alumina catalysts. The aim of this work was to obtain structure–activity information, which could be utilised in the optimisation of this catalytic system. The properties of chromia/alumina catalysts were investigated ...

  6. Alkane biosynthesis genes in cyanobacteria and their transcriptional organization

    Directory of Open Access Journals (Sweden)

    Stephan eKlähn

    2014-07-01

    Full Text Available In cyanobacteria, alkanes are synthesized from a fatty acyl-ACP by two enzymes, acyl-acyl carrier protein reductase (AAR and aldehyde deformylating oxygenase (ADO. Despite the great interest in the exploitation for biofuel production, nothing is known about the transcriptional organization of their genes or the physiological function of alkane synthesis. The comparison of 115 microarray datasets indicates the relatively constitutive expression of aar and ado genes. The analysis of 181 available genomes showed that in 90% of the genomes both genes are present, likely indicating their physiological relevance. In 61% of them they cluster together with genes encoding acetyl-CoA carboxyl transferase and a short chain dehydrogenase, strengthening the link to fatty acid metabolism and in 76% of the genomes they are located in tandem, suggesting constraints on the gene arrangement. However, contrary to the expectations for an operon, we found in Synechocystis sp. PCC 6803 specific promoters for the two genes, sll0208 (ado and sll0209 (aar, that give rise to monocistronic transcripts. Moreover, the upstream located ado gene is driven by a proximal as well as a second, distal, promoter, from which a third transcript, the ~160 nt sRNA SyR9 is transcribed. Thus, the transcriptional organization of the alkane biosynthesis genes in Synechocystis sp. PCC 6803 is of substantial complexity. We verified all three promoters to function independently from each other and show a similar promoter arrangement also in the more distant Nodularia spumigena, Trichodesmium erythraeum, Anabaena sp. PCC 7120, Prochlorococcus MIT9313 and MED4. The presence of separate regulatory elements and the dominance of monocistronic mRNAs suggest the possible autonomous regulation of ado and aar. The complex transcriptional organization of the alkane synthesis gene cluster has possible metabolic implications and should be considered when manipulating the expression of these genes in

  7. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes

    OpenAIRE

    Qineng Xia, Zongjia Chen, Yi Shao, Xueqing Gong, Haifeng Wang, Xiaohui Liu, Stewart F. Parker, Xue Han, Sihai Yang & Yanqin Wang

    2016-01-01

    Being the only sustainable source of organic carbon, biomass is playing an ever-increasingly important role in our energy landscape. The conversion of renewable lignocellulosic biomass into liquid fuels is particularly attractive but extremely challenging due to the inertness and complexity of lignocellulose. Here we describe the direct hydrodeoxygenation of raw woods into liquid alkanes with mass yields up to 28.1 wt% over a multifunctional Pt/NbOPO4 catalyst in cyclohexane. T...

  8. Solvation of alkane and alcohol molecules. Energy contributions

    OpenAIRE

    Pais, A. A. C. C.; Sousa, A.; Eusébio, M. E.; Redinha, J. S.

    2001-01-01

    In this work we conduct a systematic ab initio study of the solvation of small alkane, monoalcohol and diol molecules, in polar solvents with different properties. A choice of basis set suitable for the type of compounds under study is presented. The various components of the solvent–solute interaction and the cavitation energy are treated individually and their variation with chain length and introduction of hydroxy groups assessed. The use of solute molecules in which controlled changes are...

  9. Pairwise-additive hydrophobic effect for alkanes in water

    OpenAIRE

    Wu, Jianzhong; Prausnitz, John M.

    2008-01-01

    Pairwise additivity of the hydrophobic effect is indicated by reliable experimental Henry's constants for a large number of linear and branched low-molecular-weight alkanes in water. Pairwise additivity suggests that the hydrophobic effect is primarily a local phenomenon and that the hydrophobic interaction may be represented by a semiempirical force field. By representing the hydrophobic potential between two methane molecules as a linear function of the overlap volume of the hydration layer...

  10. Cold-tolerant alkane-degrading Rhodococcus species from Antarctica

    Energy Technology Data Exchange (ETDEWEB)

    Bej, A.K.; Saul, D.; Aislabie, J.

    2000-07-01

    Bioremediation is a possible mechanism for clean-up of hydrocarbon-contaminated soils in the Antarctic. Microbes indigenous to the Antarctic are required that degrade the hydrocarbon contaminants found in the soil, and that are able to survive and maintain activity under in situ conditions. Alkane-degrading bacteria previously isolated from oil-contaminated soil from around Scott Base, Antarctica, grew on a number of n-alkanes from hexane (C6) through to eicosane (C20) and the branched alkane pristane. Mineralization of {sup 14}C-dodecane was demonstrated with four strains. Representative isolates were identified as Rhodococcus species using 16S rDNA sequence analysis. Rhodococcus spp. strains 5/14 and 7/1 grew at -2 C but numbers of viable cells declined when incubated t 37 C. Both strains appear to have the major cold-shock gene cspA. Partial nucleotide sequence analyses of the PCR-amplified cspA open reading frame from Rhodococcus spp. strains 5/14 and 7/1 were approximately 60% identical to cspA from Escherichia coli.

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

    Science.gov (United States)

    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.

  12. Comparative study of the effects of several n-alkanes on phospholipid hexagonal phases.

    OpenAIRE

    Chen, Z; Rand, R P

    1998-01-01

    The effects of a series of normal alkanes (decane, dodecane, tetradecane, hexadecane, and octadecane) on the hexagonal H(II) structures containing dioleoylphosphatidylethanolamine (DOPE) and dioleoylphosphatidylcholine (DOPC) were studied using x-ray diffraction and osmotic stress. The alkanes affect structural dimensions and the monolayer intrinsic curvature and bending modulus. The alkane effects are chain-length dependent and are attributed to their different distribution within the H(II) ...

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

    OpenAIRE

    Florin Musat

    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 hydr...

  14. Distribution and sources of n-alkanes in surface sediments of Taihu Lake, China

    OpenAIRE

    Yu Yunlong; Li Yuanyuan; Guo Zhigang; Zou Hua

    2016-01-01

    The last study on n-alkanes in surface sediments of Taihu Lake was in 2000, only 13 surface sediment samples were analysed, in order to have a comprehensive and up-to-date understanding of n-alkanes in the surface sediments of Taihu Lake, 41 surface sediment samples were analyzed by GC-MS. C10 to C37 were detected, the total concentrations of n-alkanes ranged from 2109 ng g−1 to 9096 ng g−1 (dry weight). There was strong odd carbon predominance in long chain n-alkanes and even carbon predomin...

  15. Measuring long chain alkanes in diesel engine exhaust by thermal desorption PTR-MS

    OpenAIRE

    Erickson, M. H.; Gueneron, M.; B. T. Jobson

    2014-01-01

    A method using thermal desorption sampling and analysis by proton transfer reaction mass spectrometry (PTR-MS) to measure long chain alkanes (C12–C18) and other larger organics associated with diesel engine exhaust emissions is described. Long chain alkanes undergo dissociative proton transfer reactions forming a series of fragment ions with formula CnH2n+1. The PTR-MS is insensitive to n-alkanes less than C8 but displays an increasing sensitivity for larger alkanes. Fragment ...

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

    OpenAIRE

    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° alc...

  17. Effect of alkane chain length and counterion on the freezing transition of cationic surfactant adsorbed film at alkane mixture - water interfaces.

    Science.gov (United States)

    Tokiwa, Yuhei; Sakamoto, Hiroyasu; Takiue, Takanori; Aratono, Makoto; Matsubara, Hiroki

    2015-05-21

    Penetration of alkane molecules into the adsorbed film gives rise to a surface freezing transition of cationic surfactant at the alkane-water interface. To examine the effect of the alkane chain length and counterion on the surface freezing, we employed interfacial tensiometry and ellipsometry to study the interface of cetyltrimethylammonium bromide and cetyltrimethylammonium chloride aqueous solutions against dodecane, tetradecane, hexadecane, and their mixtures. Applying theoretical equations to the experimental results obtained, we found that the alkane molecules that have the same chain length as the surfactant adsorb preferentially into the surface freezing film. Furthermore, we demonstrated that the freezing transition temperature of cationic surfactant adsorbed film was independent of the kind of counterion. PMID:25932500

  18. Solid-Liquid equilibrium of n-alkanes using the Chain Delta Lattice Parameter model

    DEFF Research Database (Denmark)

    Coutinho, João A.P.; Andersen, Simon Ivar; Stenby, Erling Halfdan

    1996-01-01

    -liquid equilibrium of n-alkanes ranging from n-C_20 to n-C_40.The model is further modified to achieve a more correct temperature dependence because it severely underestimates the excess enthalpy. It is shown that the ratio of excess enthalpy and entropy for n-alkane solid solutions, as happens for other solid...

  19. Multiple sources of alkanes in Quaternary oceanic sediment of Antarctica

    Science.gov (United States)

    Kvenvolden, K.A.; Rapp, J.B.; Golan-Bac, M.; Hostettler, F.D.

    1987-01-01

    Normal alkanes (n-C13n-C36), isoprenoid hydrocarbons (i-C15, i-C16, i-C18, i-C19, and i-C20) triterpanes (C27C32), and (C27C29) are present in low concentrations offshore Antarctica in near-surface, Quaternary sediment of the Wilkes Land continental margin and of the western Ross Sea. The distributions of these hydrocarbons are interpreted relative to possible sources and processes. The hydrocarbons appear to be mixtures of primary and recycled material from marine and terrigenous sources. The n-alkanes are most abundant and are characterized by two distinct populations, one of probable marine origin and the other likely from terrigenous, vascular plant sources. Because the continent of Antarctica today is devoid of higher plants, the plant-derived hydrocarbons in these offshore sediments probably came from wind-blown material and recycled Antarctic sediment that contains land-plant remains from an earlier period of time. Isoprenoid hydrocarbons are partially recycled and mainly of marine origin; the dominance of pristane over phytane suggests oxic paleoenvironmental conditions. Both modern and ancient triterpanes and steranes are present, and the distribution of these indicates a mixture of primary and recycled bacterial, algal, and possible higher-plant materials. Although the sampled sediments were deposited during the Quaternary, they apparently contain a significant component of hydrocarbons of pre-Quaternary age. ?? 1987.

  20. Ordering of alkane isomers by means of connectivity indices

    Directory of Open Access Journals (Sweden)

    ANKA NEDIC

    2002-02-01

    Full Text Available The connectivity index of an organic molecule whose molecular graph is G is defined as C(l = S(dudu1, where du is the degree of the vertex u in G, where the summation goes over all pairs of adjacent vertices of G and where l is a pertinently chosen exponent. The usual value of l is –1/2, in which case c = C(–1/2 is referred to as the Randic index. The ordering of isomeric alkanes according to c follows the extent of branching of the carbon-atom skeleton. We now study the ordering of the constitutional isomers of alkanes with 6 through 10 carbon atoms with respect to C( l for various values of the parameter l. This ordering significantly depends on l. The difference between the orderings with respect to c and with respect to C( l is measured by a function D and the l-dependence of D was established.

  1. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes

    Science.gov (United States)

    Xia, Qineng; Chen, Zongjia; Shao, Yi; Gong, Xueqing; Wang, Haifeng; Liu, Xiaohui; Parker, Stewart F.; Han, Xue; Yang, Sihai; Wang, Yanqin

    2016-01-01

    Being the only sustainable source of organic carbon, biomass is playing an ever-increasingly important role in our energy landscape. The conversion of renewable lignocellulosic biomass into liquid fuels is particularly attractive but extremely challenging due to the inertness and complexity of lignocellulose. Here we describe the direct hydrodeoxygenation of raw woods into liquid alkanes with mass yields up to 28.1 wt% over a multifunctional Pt/NbOPO4 catalyst in cyclohexane. The superior performance of this catalyst allows simultaneous conversion of cellulose, hemicellulose and, more significantly, lignin fractions in the wood sawdust into hexane, pentane and alkylcyclohexanes, respectively. Investigation on the molecular mechanism reveals that a synergistic effect between Pt, NbOx species and acidic sites promotes this highly efficient hydrodeoxygenation of bulk lignocellulose. No chemical pretreatment of the raw woody biomass or separation is required for this one-pot process, which opens a general and energy-efficient route for converting raw lignocellulose into valuable alkanes. PMID:27025898

  2. Measurement of n-alkanals and hydroxyalkenals in biological samples.

    Science.gov (United States)

    Holley, A E; Walker, M K; Cheeseman, K H; Slater, T F

    1993-09-01

    A modified method was developed to measure nM levels of a range of n-alkanals and hydroxyalkenals in biological samples such as blood plasma and tissue homogenates and also in Folch lipid extracts of these samples. Butylated hydroxytoluene (BHT) and desferrioxamine (Desferal) were added to samples to prevent artifactual peroxidation. Aldehydes were reacted with 1,3-cyclohexanedione (CHD), cleaned up by solid-phase extraction on a Sep-Pak C18 cartridge and the fluorescent decahydroacridine derivatives resolved by reverse-phase high-performance liquid chromatography (HPLC) with gradient elution. A wider range of aldehydes was detected in lipid extracts of plasma and liver homogenate compared to whole (unextracted) samples. Human plasma contained nM levels of acetaldehyde, propanal, butanal, pentanal, hexanal, and heptanal. 4-Hydroxynonenal (0.93 nmol/g) and alkanals with two to six carbons (up to 7.36 nmol/g) were detected in rat liver. Recovery of aldehydes added to whole plasma or to lipid extracts of plasma was dependent on carbon chain length, varying from 95% for acetaldehyde to 8% for decanal. Recovery from biological samples was significantly less than that of standards taken through the Sep-Pak clean-up procedure, suggesting that aldehydes can bind to plasma protein and lipid components. PMID:8406128

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

    International Nuclear Information System (INIS)

    Radiation induced oxidation of liquid n-hexadecane (n-C16H34) and squalane (C30H62) as a polymer model has been investigated by the measurements of the gas evolution and O2 uptake, and analyses of the oxidation products. Low O2 uptake, [G(-O2) ∼ 6.0] in liquid alkanes, indicates that the oxidation reaction does not exhibit chain kinetics, which is a big contrast to the process observed in solid, G(-O2) >> 10. H2 is the main gas product. More than 90% of the consumed O2 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 O2 and thermal oxidation of hexadecane 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 O2 reduce the H2 evolution and the acid formation in parallel. Although hydroaromatic compounds act as an energy and charge scavenger, they are selectively oxidized through the donation of hydrogen in cyclic alkyl part attached to the phenyl ring, leading to large O2 uptake and corresponding ketone formation. From the comparison of the G-values of the O2 uptake, it was found that the oxidation reactions of liquid alkanes reflect well the oxidation of amorphous part in polymers. (author)

  4. Radiation-induced synthesis of branched liquid alkanes

    International Nuclear Information System (INIS)

    The irradiation of gaseous alkane mixtures under circulation conditions was used for the synthesis of liquid branched hydrocarbons. Aurora-9B accelerator was used for irradiation with 500 keV electrons at 80 mA electron beam current, current power up to 40 kW. It was found that the synthesized liquid product was a mixture of alkanes with the average molecular weight higher than the molecular weight of the parent gas by a factor of 3-4. The resulting liquids were characterized by boiling range from 35 to 200 deg C in atmospheric distillation. The average degree of molecular branching in the synthesized liquids was evaluated on the basis of their knock resistance. The octane ratings of liquid mixtures were above 95 (motor octane number) or 103 (research octane number). The fractional composition and detonation properties of the synthesized liquids suggested the prevalence of C5-C11 isomers with highly branched structures in these liquids. Depending on irradiation conditions, 2,3-dimethylbutane, 2-methylpentane, or 3-methylpentane was predominant among hexanes. As a rule, 2,2,3-trimethylbutane and 2,3-dimethylpentane prevailed among heptanes

  5. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes.

    Science.gov (United States)

    Xia, Qineng; Chen, Zongjia; Shao, Yi; Gong, Xueqing; Wang, Haifeng; Liu, Xiaohui; Parker, Stewart F; Han, Xue; Yang, Sihai; Wang, Yanqin

    2016-01-01

    Being the only sustainable source of organic carbon, biomass is playing an ever-increasingly important role in our energy landscape. The conversion of renewable lignocellulosic biomass into liquid fuels is particularly attractive but extremely challenging due to the inertness and complexity of lignocellulose. Here we describe the direct hydrodeoxygenation of raw woods into liquid alkanes with mass yields up to 28.1 wt% over a multifunctional Pt/NbOPO4 catalyst in cyclohexane. The superior performance of this catalyst allows simultaneous conversion of cellulose, hemicellulose and, more significantly, lignin fractions in the wood sawdust into hexane, pentane and alkylcyclohexanes, respectively. Investigation on the molecular mechanism reveals that a synergistic effect between Pt, NbOx species and acidic sites promotes this highly efficient hydrodeoxygenation of bulk lignocellulose. No chemical pretreatment of the raw woody biomass or separation is required for this one-pot process, which opens a general and energy-efficient route for converting raw lignocellulose into valuable alkanes. PMID:27025898

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

    Directory of Open Access Journals (Sweden)

    Arpita eBose

    2013-12-01

    Full Text Available 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 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 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

  7. Chain length dependent alkane/β-cyclodextrin nonamphiphilic supramolecular building blocks.

    Science.gov (United States)

    Zhou, Chengcheng; Huang, Jianbin; Yan, Yun

    2016-02-01

    In this work we report the chain length dependent behavior of the nonamphiphilic supramolecular building blocks based on the host-guest inclusion complexes of alkanes and β-cyclodextrins (β-CD). (1)H NMR, ESI-MS, and SAXS measurements verified that upon increasing the chain length of alkanes, the building blocks for vesicle formation changed from channel type 2alkane@2β-CD via channel type alkane@2β-CD to non-channel type 2alkane@2β-CD. FT-IR and TGA experiments indicated that hydrogen bonding is the extensive driving force for vesicle formation. It revealed that water molecules are involved in vesicle formation in the form of structural water. Upon changing the chain length, the average number of water molecules associated with per building block is about 16-21, depending on the chain length. PMID:26660592

  8. Reactivation of coked H-ZSM-5 by treatment with hydrogen and alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, F.; Ernst, H. [Univ. of Leipzig (Germany); Geidel, E. [Univ. of Hamburg (Germany); Schoedel, R. [Leuna-Werke GmbH (Germany)

    1996-11-01

    The conversion of methanol to hydrocarbons on zeolite H-ZSM-5, in particular the long-term stability of the catalyst, was studied under different reaction conditions. Whereas no significant change in the product distribution was observed, hydrogen and alkane-containing recycle gases show lower deactivation rates than nitrogen. In addition, spent catalysts were partially reactivated by alkane treatment, increasing the time on stream before an oxidative regeneration procedure is required. Lower alkanes such as propane and isobutane yield the best results. The influence of hydrogen-containing gases on the deactivation rate and on the nature of coke on zeolite H-ZSM-5 indicates dissociative adsorption of hydrogen and alkanes on a few sites with enhanced activity. Surface hydrogen species formed by adsorption of alkanes are assumed to make possible the hydrocracking of carbonaceous deposits. 20 refs., 6 figs., 2 tabs.

  9. Reveal of small alkanes and isomers using calculated core and valence binding energy spectra and total momentum cross sections

    OpenAIRE

    Yang, Zejin; Wang, Feng

    2013-01-01

    The present study revealed quantum mechanically that the C1s binding energy spectra of the small alkanes (upto six carbons) provide a clear picture of isomeric chemical shift in linear alkanes and branched isomers, whereas the valence binding energy spectra contain more sensitive information regarding the length of the carbon chains. Total momentum cross sections of the alkanes exhibit the information of the chain length as well as constitutional isomers of the small alkanes. The C1s binding ...

  10. Genes involved in alkane degradation in the Alcanivorax hongdengensis strain A-11-3

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Wanpeng [State Oceanic Administration, Xiamen (China). Key Lab. of Marine Biogenetic Resources; Xiamen Univ. (China). School of Life Sciences; Shao, Zongze [State Oceanic Administration, Xiamen (China). Key Lab. of Marine Biogenetic Resources

    2012-04-15

    Alcanivorax hongdengensis A-11-3 is a newly identified type strain isolated from the surface water of the Malacca and Singapore Straits that can degrade a wide range of alkanes. To understand the degradation mechanism of this strain, the genes encoding alkane hydroxylases were obtained by PCR screening and shotgun sequencing of a genomic fosmid library. Six genes involved in alkane degradation were found, including alkB1, alkB2, p450-1, p450-2, p450-3 and almA. Heterogeneous expression analysis confirmed their functions as alkane oxidases in Pseudomonas putida GPo12 (pGEc47{delta}B) or Pseudomonas fluorescens KOB2{delta}1. Q-PCR revealed that the transcription of alkB1 and alkB2 was enhanced in the presence of n-alkanes C{sub 12} to C{sub 24}; three p450 genes were up-regulated by C{sub 8}-C{sub 16} n-alkanes at different levels, whereas enhanced expression of almA was observed when strain A-11-3 grew with long-chain alkanes (C{sub 24} to C{sub 36}). In the case of branched alkanes, pristane significantly enhanced the expression of alkB1, p450-3 and almA. The six genes enable strain A-11-3 to degrade short (C{sub 8}) to long (C{sub 36}) alkanes that are straight or branched. The ability of A. hongdengensis A-11-3 to thrive in oil-polluted marine environments may be due to this strain's multiple systems for alkane degradation and its range of substrates. (orig.)

  11. 40 CFR 721.10178 - Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction.

    Science.gov (United States)

    2010-07-01

    ...), hydroisomerized middle, C10-13-branched alkane fraction. 721.10178 Section 721.10178 Protection of Environment...), hydroisomerized middle, C10-13-branched alkane fraction. (a) Chemical substance and significant new uses subject... middle, C10-13-branched alkane fraction (PMN P-04-319; CAS No. 642928-30-1) is subject to reporting...

  12. Modeling of Alkane Oxidation Using Constituents and Species

    Science.gov (United States)

    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

  13. Involvement of an Alkane Hydroxylase System of Gordonia sp. Strain SoCg in Degradation of Solid n-Alkanes▿

    OpenAIRE

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

    2010-01-01

    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 (C12) to hexatriacontane (C36) 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)...

  14. Enrichment and Characterization of a Psychrotolerant Consortium Degrading Crude Oil Alkanes Under Methanogenic Conditions.

    Science.gov (United States)

    Ding, Chen; Ma, Tingting; Hu, Anyi; Dai, Lirong; He, Qiao; Cheng, Lei; Zhang, Hui

    2015-08-01

    Anaerobic alkane degradation via methanogenesis has been intensively studied under mesophilic and thermophilic conditions. While there is a paucity of information on the ability and composition of anaerobic alkane-degrading microbial communities under low temperature conditions. In this study, we investigated the ability of consortium Y15, enriched from Shengli oilfield, to degrade hydrocarbons under different temperature conditions (5-35 °C). The consortium could use hexadecane over a low temperature range (15-30 °C). No growth was detected below 10 °C and above 35 °C, indicating the presence of cold-tolerant species capable of alkane degradation. The preferential degradation of short chain n-alkanes from crude oil was observed by this consortium. The structure and dynamics of the microbial communities were examined using terminal restriction fragment length polymorphism (T-RFLP) fingerprinting and Sanger sequencing of 16S rRNA genes. The core archaeal communities were mainly composed of aceticlastic Methanosaeta spp. Syntrophaceae-related microorganisms were always detected during consecutive transfers and dominated the bacterial communities, sharing 94-96 % sequence similarity with Smithella propionica strain LYP(T). Phylogenetic analysis of Syntrophaceae-related clones in diverse methanogenic alkane-degrading cultures revealed that most of them were clustered into three sublineages. Syntrophaceae clones retrieved from this study were mainly clustered into sublineage I, which may represent psychrotolerant, syntrophic alkane degraders. These results indicate the wide geographic distribution and ecological function of syntrophic alkane degraders. PMID:25783218

  15. Isolation and characterization of a novel n-alkane-degrading strain, Acinetobacter haemolyticus AR-46

    Energy Technology Data Exchange (ETDEWEB)

    Bihari, Z.; Balazs, M.; Bartos, P.; Kesserue, P.; Kiss, I.; Mecs, I. [Bay Zoltan Foundation for Applied Research, Szeged (Hungary). Inst. for Biotechnology; Pettko-Szandtner, A. [Hungarian Academy of Sciences, Szeged (Hungary). Inst. of Plant Biology; Csanadi, G. [Szeged Univ. (Hungary). Dept. of Biotechnology

    2007-03-15

    Strain AR-46, isolated and identified as Acinetobacter haemolyticus, evolutionally distant from the known hydrocarbon-degrading Acinetobacter spp., proved to have excellent long-chain n-alkane-degrading ability. This is the first detailed report on an n-alkane-utilizing strain belonging to this species. The preferred substrate is n-hexadecane, with an optimal temperature of 37 C under aerobic conditions. Five complete and two partial open reading frames were sequenced and correlated with the early steps of monoterminal oxidation-initiated n-alkane mineralization. The encoded protein sequences and the arrangement of these genes displayed high similarity to those found in Acinetobacter sp. M-1, but AR-46 seemed to have only one alkane hydroxylase gene, with a completely different induction profile. Unique behaviour was also observed in n-alkane bioavailability. Substrate uptake occurred through the hydrophobic surface of n-alkane droplet-adhered cells possessing long, thick fimbriae, which were presumed to play a major role in n-alkane solubilization. A majority of the cells was in detached form, with thick, but short fimbriae. These free cells were permanently hydrophilic, unlike the cells of other Acinetobacter strains. (orig.)

  16. Compound-specific hydrogen isotope composition of n-alkanes in combustion residuals of fossil fuels

    Science.gov (United States)

    Bai, Huiling; Peng, Lin; Li, Zhongping; Liu, Xiaofeng; Song, Chongfang; Mu, Ling

    2014-11-01

    The hydrogen isotope compositions (δD) of n-alkanes present in the combustion residuals of fossil fuels (coal, gasoline, and diesel) were measured using GC-IRMS to distinguish between coal soot and vehicle exhaust. The n-alkane δD values of industrial and domestic coal soot ranged from -95.3‰ to -219.6‰ and -128.1‰ to -188.6‰, respectively, exhibiting similar tendencies. The δD values of the C15-C18n-alkanes in both types of coal soot were nearly consistent, and the δD values of the C19-C24n-alkanes exhibited a zigzag profile. The δD values of C16-C22n-alkanes in gasoline exhaust exhibited a saw-tooth distribution, decreased with the carbon number, and were more positive than the δD values of C16-C22n-alkanes in diesel exhaust, which increased with the carbon number. However, the δD values of the C23-C29n-alkanes in gasoline and diesel vehicle exhaust were mostly consistent. The weighted average δD values of the C16-C19n-alkanes in industrial and domestic coal soot were similar to the average δD values in gasoline and diesel vehicle exhausts; however, the average δD values of the C21-C29n-alkanes in vehicle exhausts were richer in D than those in coal soot.

  17. Modeling the solubilities of high molecular weight n-alkanes in supercritical carbon dioxide

    OpenAIRE

    Jha, Sujit Kumar; Madras, Giridhar

    2004-01-01

    The Peng-Robinson equation of state with quadratic mixing rules and a single adjustable parameter was used to model the solubilities of various high molecular weight solid n-alkanes in supercritical carbon dioxide. The key conclusion of the study is that the adjustable parameter, $k_{ij}$, varies linearly with the number of carbon atoms in the main chain of the n-alkane. Thus, the model can be used to predict the solubilities of various high molecular weight solid n-alkanes in supercritical c...

  18. Investigation on degradation of long chain n-alkanes through single cell green algae

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, E.

    1980-01-01

    30 green algae stems of the chlorococcales order and one of the volvocales were investigated for their ability to oxidize alkanes and their degradation. It could be concluded from the results that chlorella vulgaris can oxidize alkanes by subterminal ways during photosynthesis or if glucose is available, i.e. that it only attackes in cooxidation and c. vulgaris alkanes apparently do not terminally (mono or diterminally) oxidize as oxidation products as no oxidation products of this type of degradation nor any indications in the fatty acid pattern of lipids was found.

  19. Characterization and Two-Dimensional Crystallization of Membrane Component AlkB of the Medium-Chain Alkane Hydroxylase System from Pseudomonas putida GPo1

    OpenAIRE

    Alonso, Hernan; Roujeinikova, Anna

    2012-01-01

    The alkane hydroxylase system of Pseudomonas putida GPo1 allows it to use alkanes as the sole source of carbon and energy. Bacterial alkane hydroxylases have tremendous potential as biocatalysts for the stereo- and regioselective transformation of a wide range of chemically inert unreactive alkanes into valuable reactive chemical precursors. We have produced and characterized the first 2-dimensional crystals of the integral membrane component of the P. putida alkane hydroxylase system, the no...

  20. MODELLING AND PARAMETER ESTIMATION IN REACTIVE CONTINUOUS MIXTURES: THE CATALYTIC CRACKING OF ALKANES. PART I

    OpenAIRE

    F. C. PEIXOTO; J. L. de Medeiros

    1999-01-01

    Fragmentation kinetics is employed to model a continuous reactive mixture. An explicit solution is found and experimental data on the catalytic cracking of a mixture of alkanes are used for deactivation and kinetic parameter estimation.

  1. Synthesis of δ-Oxo-1,1-bis(triflyl)alkanes and Their Acidities

    OpenAIRE

    Hikaru Yanai; Masaya Fujita; Arata Takahashi; Min Zhang; Masaaki Mishima; Akira Kotani; Takashi Matsumoto; Takeo Taguchi

    2013-01-01

    The reaction of 1,1-bis(triflyl)ethylene generated in situ with enolizable carbonyls yielded δ-oxo-1,1-bis(triflyl)alkane derivatives. Their acidities in both the gas and solution phases were determined.

  2. Modeling the Role of Alkanes, Polycyclic Aromatic Hydrocarbons, and Their Oligomers in Secondary Organic Aerosol Formation

    Science.gov (United States)

    A computationally efficient method to treat secondary organic aerosol (SOA) from various length and structure alkanes as well as SOA from polycyclic aromatic hydrocarbons (PAHs) is implemented in the Community Multiscale Air Quality (CMAQ) model to predict aerosol concentrations ...

  3. Experimental proof for resonant diffusion of normal alkanes in LTL and ZSM-12 zeolites

    CERN Document Server

    Yoo, K; Smirniotis, P G

    2015-01-01

    The intra-crystalline diffusion of normal alkanes in LTL and ZSM-12 zeolite was experimentally studied via gravimetric measurements performed at different temperatures. A periodic dependence of the diffusion coefficient on the number of carbon atoms in alkane was detected, which is an experimental proof for resonant diffusion. The present observations were described on the base of the existing theory of the resonant diffusion and several important parameters of the alkane-zeolite interaction and zeolite vibrations were obtained. In the considered temperature region the diffusion coefficient follows the Arrhenius law with periodic dependences of the pre-exponential factor and activation energy on the number of carbon atoms in alkanes. A compensation effect of simultaneous increases of the pre-exponential factor and the activation energy was also established.

  4. Application of metal-modified silica gels as sorbents for alkane-thiols

    International Nuclear Information System (INIS)

    In order to elaborate high effective method of purification of industry wastes from alkane-thiols the sorption properties of silica gels modified by ions of heavy metals are studied. The optimal conditions of sorption are defined.

  5. Localized diffusive motion on two different time scales in solid alkane nanoparticles

    DEFF Research Database (Denmark)

    Wang, S. K.; Mamontov, E.; Bai, M.; Hansen, Flemming Yssing; Taub, H.; Copley, J.R.D.; Sakai, V.G.; Gasparovic, G.; Jenkins, T.; Tyagi, M.; Herwig, K.W.; Neumann, D.A.; Montfrooij, W.; Volkmann, U.G.

    2010-01-01

    High-energy-resolution quasielastic neutron scattering on three complementary spectrometers has been used to investigate molecular diffusive motion in solid nano- to bulk-sized particles of the alkane n-C32H66. The crystalline-to-plastic and plastic-to-fluid phase transition temperatures are...... the molecule. Contrary to the conventional interpretation in bulk alkanes, the fast uniaxial rotation begins in the low-temperature crystalline phase....

  6. The effect of branching on the structure of confined thin films of alkanes

    OpenAIRE

    Dijkstra, Marjolein

    1997-01-01

    We report computer simulations in the grand canonical ensemble of a system of several linear and branched alkanes between two solid surfaces. We computed the solvation force exerted by the °uid on the plates. The solvation force for linear decane oscillates with distance with a periodicity close to the width of the molecules. The branched alkanes (2-methylundecane and 2-methylheptane) show a similar oscillatory behaviour; however, the oscillations are decreased and are shifted to the attracti...

  7. The influence of extraframework aluminum on H-FAU catalyzed cracking of light alkanes

    OpenAIRE

    Narbeshuber, T.F.; Brait, A.; Seshan, K.; Lercher, J.A.

    1996-01-01

    The conversion of light linear and branched alkanes on two faujasite samples containing different concentrations of free Brønsted acid sites and extraframework alumina (EFAL) was studied between 733 K and 813 K. Protolytic cracking and bimolecular hydride transfer proceeded solely on Brønsted acid sites. For cracking of n-alkanes, the variation of the concentration of extraframework aluminum did not affect the catalytic activity per accessible Brønsted acid site. The activity to dehydrogenati...

  8. The fatty acids and alkanes of Satureja adamovicii Silic and Satureja fukarekii Silic (NOTE

    Directory of Open Access Journals (Sweden)

    DUSANKA KITIC

    1999-05-01

    Full Text Available The content and composition of fatty acids and alkanes of Satureja adamovicii Silic and Satureja fukarekii Silic were analized by GC. It was found that unsaturated acids prevailed and that the major components were palmitic, oleic, linoleic and linolenic acids. The hydrocarbon fractions of pentane extracts were shown to consist of the alkane homologues (C17 to C34 with nonacosane and hentriacontane being prevailing compounds.

  9. Bidirectional gene sequences with similar homology to functional proteins of alkane degrading bacterium pseudomonas fredriksbergensis DNA

    International Nuclear Information System (INIS)

    The potential for two overlapping fragments of DNA from a clone of newly isolated alkanes degrading bacterium Pseudomonas frederiksbergensis encoding sequences with similar homology to two parts of functional proteins is described. One strand contains a sequence with high homology to alkanes monooxygenase (alkB), a member of the alkanes hydroxylase family, and the other strand contains a sequence with some homology to alcohol dehydrogenase gene (alkJ). Overlapping of the genes on opposite strands has been reported in eukaryotic species, and is now reported in a bacterial species. The sequence comparisons and ORFS results revealed that the regulation and the genes organization involved in alkane oxidation represented in Pseudomonas frederiksberghensis varies among the different known alkane degrading bacteria. The alk gene cluster containing homologues to the known alkane monooxygenase (alkB), and rubredoxin (alkG) are oriented in the same direction, whereas alcohol dehydrogenase (alkJ) is oriented in the opposite direction. Such genomes encode messages on both strands of the DNA, or in an overlapping but different reading frames, of the same strand of DNA. The possibility of creating novel genes from pre-existing sequences, known as overprinting, which is a widespread phenomenon in small viruses. Here, the origin and evolution of the gene overlap to bacteriophages belonging to the family Microviridae have been investigated. Such a phenomenon is most widely described in extremely small genomes such as those of viruses or small plasmids, yet here is a unique phenomenon. (author)

  10. Conversion of alkanes to linear alkylsilanes using an iridium-iron-catalysed tandem dehydrogenation-isomerization-hydrosilylation

    Science.gov (United States)

    Jia, Xiangqing; Huang, Zheng

    2016-02-01

    The conversion of inexpensive, saturated hydrocarbon feedstocks into value-added speciality chemicals using regiospecific, catalytic functionalization of alkanes is a major goal of organometallic chemistry. Linear alkylsilanes represent one such speciality chemical—they have a wide range of applications, including release coatings, silicone rubbers and moulding products. Direct, selective, functionalization of alkanes at primary C-H bonds is difficult and, to date, methods for catalytically converting alkanes into linear alkylsilanes are unknown. Here, we report a well-defined, dual-catalyst system for one-pot, two-step alkane silylations. The system comprises a pincer-ligated Ir catalyst for alkane dehydrogenation and an Fe catalyst that effects a subsequent tandem olefin isomerization-hydrosilylation. This method exhibits exclusive regioselectivity for the production of terminally functionalized alkylsilanes. This dual-catalyst strategy has also been applied to regioselective alkane borylations to form linear alkylboronate esters.

  11. [Sources, Migration and Conversion of Dissolved Alkanes, Dissolved Fatty Acids in a Karst Underground River Water, in Chongqing Area].

    Science.gov (United States)

    Liang, Zuo-bing; Sun, Yu-chuan; Wang, Zun-bo; Shi, Yang; Jiang, Ze-li; Zhang, Mei; Xie, Zheng-Lan; Liao, Yu

    2015-09-01

    Dissolved alkanes and dissolved fatty acids were collected from Qingmuguan underground river in July, October 2013. By gas chromatography-mass spectrometer (GC-MS), alkanes and fatty acids were quantitatively analyzed. The results showed that average contents of alkanes and fatty acids were 1 354 ng.L-1, 24203 ng.L-1 in July, and 667 ng.L-1, 2526 ng.L-1 in October respectively. With the increasing migration distance of dissolved alkanes and dissolved fatty acids in underground river, their contents decreased. Based on the molecular characteristic indices of alkanes, like CPI, OEP, Paq and R, dissolved alkanes were mainly originated from microorganisms in July, and aquatic plants in October. Saturated straight-chain fatty acid had the highest contents in all samples with the dominant peak in C16:0, combined with the characteristics of carbon peak, algae or bacteria might be the dominant source of dissolved fatty acids. PMID:26717680

  12. Modulating the import of medium-chain alkanes in E. coli through tuned expression of FadL

    OpenAIRE

    Call, Toby P.; Akhtar, M Kalim; Baganz, Frank; Grant, Chris

    2016-01-01

    Background In recent years, there have been intensive efforts to develop synthetic microbial platforms for the production, biosensing and bio-remediation of fossil fuel constituents such as alkanes. Building predictable engineered systems for these applications will require the ability to tightly control and modulate the rate of import of alkanes into the host cell. The native components responsible for the import of alkanes within these systems have yet to be elucidated. To shed further insi...

  13. Thermal analysis as an aid to forensics: Alkane melting and oxidative stability of wool

    International Nuclear Information System (INIS)

    Interdisciplinary methods and thermal analytical techniques in particular are effective tools in aiding the identification and characterization of materials in question involved in civil or criminal law. Forensic material science uses systematic knowledge of the physical or material world gained through analysis, observation and experimentation. Thermal analytical data can be used to aid the legal system in interpreting technical variations in quite often a complex system.Calorimetry and thermal microscopic methods helped define a commercial product composed of alkanes that was involved in a major law suit. The solid-state structures of a number of normal alkanes have unique crystal structures. These alkanes melt and freeze below room temperature to more than 60C below zero. Mixtures of specific alkanes have attributes of pure chemicals. The X-ray diffraction structure of a mixture of alkanes is the same as a pure alkane, but the melting and freezing temperature are significantly lower than predicted. The jury ruled that the product containing n-alkanes had the appropriate melting characteristics. The thermal-physical properties made a commercial fluid truly unique and there was no advertising infringement according to the law and the jury trialA combination of thermogravimetry, differential thermal analysis, infrared spectroscopy and macrophotography were used to conduct an extensive modeling and analysis of physical evidence obtained in a mobile home fire and explosion. A person's death was allegedly linked to the misuse of a kerosene space heater. The thermal analytical techniques showed that external heating was the cause of the space heater's deformation, not a firing of the heater with gasoline and kerosene. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  14. Alkane Hydroxylase Gene (alkB Phylotype Composition and Diversity in Northern Gulf of Mexico Bacterioplankton

    Directory of Open Access Journals (Sweden)

    Conor Blake Smith

    2013-12-01

    Full Text Available 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.

  15. Anaerobic n-Alkane Metabolism by a Sulfate-Reducing Bacterium, Desulfatibacillum aliphaticivorans Strain CV2803T

    OpenAIRE

    Cravo-Laureau, Cristiana; Grossi, Vincent; Raphel, Danielle; Matheron, Robert; Hirschler-Réa, Agnès

    2005-01-01

    The alkane-degrading, sulfate-reducing bacterium Desulfatibacillum aliphaticivorans strain CV2803T, recently isolated from marine sediments, was investigated for n-alkane metabolism. The total cellular fatty acids of this strain had predominantly odd numbers of carbon atoms (C odd) when the strain was grown on a C-odd alkane (pentadecane) and even numbers of carbon atoms (C even) when it was grown on a C-even alkane (hexadecane). Detailed analyses of those fatty acids by gas chromatography/ma...

  16. Cyclooctane metathesis catalyzed by silica-supported tungsten pentamethyl [(ΞSiO)W(Me)5]: Distribution of macrocyclic alkanes

    KAUST Repository

    Riache, Nassima

    2014-10-03

    Metathesis of cyclic alkanes catalyzed by the new surface complex [(ΞSiO)W(Me)5] affords a wide distribution of cyclic and macrocyclic alkanes. The major products with the formula CnH2n are the result of either a ring contraction or ring expansion of cyclooctane leading to lower unsubstituted cyclic alkanes (5≤n≤7) and to an unprecedented distribution of unsubstituted macrocyclic alkanes (12≤n≤40), respectively, identified by GC/MS and by NMR spectroscopies.

  17. [Distribution Characteristics and Source Apportionment of n-Alkanes in Water from Yellow River in Henan Section].

    Science.gov (United States)

    Feng, Jing-lan; Xi, Nan-nan; Zhang, Fei; Liu, Shu-hui; Sun, Jian-hui

    2016-03-15

    To investigate the distributions and possible sources of n-alkanes in water and suspended particulate matter from Yellow River in Henan section, 26 water and suspended particulate matter samples were collected in August 2010 and 22 n-alkanes (C₁₄-C₃₆) were quantitatively determined by gas chromatography-mass spectrometer (GC-MS). Potential sources of n-alkanes were analyzed using different characteristic parameters. The results indicated that total concentrations of 22 n-alkanes were 521-5,843 ng · L⁻¹ with a mean concentration of 1,409 ng · L⁻¹, while the total amounts of n-alkanes in the suspended particulate matter were 463-11,142 ng · L⁻¹ with a mean value of 1,951 ng · L⁻¹. The composition profiles of n-alkanes in water showed unimodal distribution with a peak at C₂₅ in water. However, the composition characteristics of n-alkanes in SPM were of bimodal type, but still with the advantage of high carbon hydrocarbons peak at C₂₅. Results of characteristic parameters including CPI, TAR, OEP and % WaxCn showed that n-alkanes in the studied area were derived mainly from combustion of fossil fuel, while terrestrial higher plant played a role in the existence of n-alkanes in water and suspended particulate matter from Yellow River in Henan section. PMID:27337879

  18. Thermodynamics of mixtures containing alkoxyethanols. XXVIII: Liquid-liquid equilibria for 2-phenoxyethanol + selected alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Alonso, Victor; Garcia, Mario [G.E.T.E.F., Grupo Especializado en Termodinamica de Equilibrio entre Fases, Departamento de Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, E-47071 Valladolid (Spain); Gonzalez, Juan Antonio, E-mail: jagl@termo.uva.es [G.E.T.E.F., Grupo Especializado en Termodinamica de Equilibrio entre Fases, Departamento de Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, E-47071 Valladolid (Spain); Garcia De La Fuente, Isaias; Cobos, Jose Carlos [G.E.T.E.F., Grupo Especializado en Termodinamica de Equilibrio entre Fases, Departamento de Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, E-47071 Valladolid (Spain)

    2011-07-10

    Highlights: {yields} LLE coexistence curves were determined for mixtures of 2PhEE with alkanes. {yields} UCST values are higher for n-alkane systems than for solutions with cyclic alkanes. {yields} For the latter mixtures, UCST increases with the size of the alkyl group attached. {yields} Alkoxyethanol-alkoxyethanol interactions are enhanced by aromatic group in cellosolve. - Abstract: The coexistence curves of the liquid-liquid equilibria (LLE) for systems of 2-phenoxyethanol (2PhEE) with heptane, octane, cyclohexane, methylcyclohexane or ethylcyclohexane have been determined by the method of the critical opalescence using a laser scattering technique. All the curves show an upper critical solution temperature (UCST), have a rather horizontal top and their symmetry depends on the relative size of the mixture compounds. UCST values are higher for systems with linear alkanes than for solutions including cyclic alkanes. For these mixtures, the UCST increases with the size of the alkyl group attached to the cyclic part of the molecule. It is shown that interactions between alkoxyethanol molecules are stronger when the hydroxyether contains an aromatic group. Data are used to determine the critical exponent for the order parameter mole fraction. Values obtained are consistent with those provided by the Ising model or by the renormalization group theory.

  19. Extension of Tao-Mason Equation of State to Heavy n-Alkanes

    Institute of Scientific and Technical Information of China (English)

    Fakhri Yousefi; Hajir Karimi; Mohammad Mehdi Papari

    2013-01-01

    In our previous paper we extended the Tao and Mason equation of state (TM EOS) to refrigerant fluids, using the speed of sound data. This is a continuation for evaluating TM EOS in predicting PVT properties of heavy n-alkanes. Liquid density of long-chain n-alkane systems from C9 to C20 have been calculated using an analytical equation of state based on the statistical-mechanical perturbation theory. The second virial coefficients of these n-alkanes are scarce and there is no accurate potential energy function for their theoretical calculation. In this work the second virial coefficients are calculated using a corresponding state correlation based on surface tension and liquid density at the freezing point. The deviation of calculated densities of these alkanes is within 0.5%from ex-perimental data. The densities of n-alkanes obtained from the TM EOS are compared with those calculated from Ihm-Song-Mason equation of state and the corresponding-states liquid densities (COSTALD). Our results are in favor of the preference of the TM EOS over other two equations of state.

  20. Thermodynamics of mixtures containing alkoxyethanols. XXVIII: Liquid-liquid equilibria for 2-phenoxyethanol + selected alkanes

    International Nuclear Information System (INIS)

    Highlights: → LLE coexistence curves were determined for mixtures of 2PhEE with alkanes. → UCST values are higher for n-alkane systems than for solutions with cyclic alkanes. → For the latter mixtures, UCST increases with the size of the alkyl group attached. → Alkoxyethanol-alkoxyethanol interactions are enhanced by aromatic group in cellosolve. - Abstract: The coexistence curves of the liquid-liquid equilibria (LLE) for systems of 2-phenoxyethanol (2PhEE) with heptane, octane, cyclohexane, methylcyclohexane or ethylcyclohexane have been determined by the method of the critical opalescence using a laser scattering technique. All the curves show an upper critical solution temperature (UCST), have a rather horizontal top and their symmetry depends on the relative size of the mixture compounds. UCST values are higher for systems with linear alkanes than for solutions including cyclic alkanes. For these mixtures, the UCST increases with the size of the alkyl group attached to the cyclic part of the molecule. It is shown that interactions between alkoxyethanol molecules are stronger when the hydroxyether contains an aromatic group. Data are used to determine the critical exponent for the order parameter mole fraction. Values obtained are consistent with those provided by the Ising model or by the renormalization group theory.

  1. Effects of surfactants on bacteria and the bacterial degradation of alkanes in crude oil

    Energy Technology Data Exchange (ETDEWEB)

    Bruheim, Per

    1998-12-31

    This thesis investigates the effects of surfactants on the bacterial degradation of alkanes in crude oil. Several alkane oxidising Gram positive and Gram negative were tested for their abilities to oxidise alkanes in crude oil emulsified with surfactants. The surfactants used to make the oil in water emulsions were either of microbial or chemical origin. Oxidation rates of resting bacteria oxidising various crude oil in water emulsions were measured by Warburg respirometry. The emulsions were compared with non-emulsified oil to see which was the preferred substrate. The bacteria were pregrown to both the exponential and stationary phase of growth before harvesting and preparation for the Warburg experiments. 123 refs., 4 figs., 14 tabs.

  2. The synergetic effect of starch and alpha amylase on the biodegradation of n-alkanes.

    Science.gov (United States)

    Karimi, M; Biria, D

    2016-06-01

    The impact of adding soluble starch on biodegradation of n-alkanes (C10-C14) by Bacillus subtilis TB1 was investigated. Gas chromatography was employed to measure the residual hydrocarbons in the system. It was observed that the efficiency of biodegradation improved with the presence of starch and the obtained residual hydrocarbons in the system were 53% less than the samples without starch. The produced bacterial enzymes were studied through electrophoresis and reverse zymography for explaining the observations. The results indicated that the produced amylase by the bacteria can degrade hydrocarbons and the same was obtained by the application of a commercial alpha amylase sample. In addition, in silico docking of alpha-amylase with n-alkanes with different molecular weights was studied by Molegro virtual docker which showed high negative binding energies and further substantiated the experimental observations. Overall, the findings confirmed the catalytic effect of alpha amylase on n-alkanes degradation. PMID:26971168

  3. Prototheca zopfii Krüger Strain UMK-13 Growth on Acetate or n-Alkanes

    OpenAIRE

    Koenig, David W.; Ward, H B

    1983-01-01

    A new strain of Prototheca zopfii Krüger was grown on acetate or on pure n-alkanes. A maximum acetate-supported exponential growth of 12 divisions day−1 occurred at pH 5 and 30°C. At 25°C, growth on n-alkanes was almost as fast, but no growth occurred at 30°C. After 4 days at 25°C, 34 to 45% of the n-alkanes had been removed, whereas at 21°C and slower growth, utilization was twofold greater after 15 days. Rates of growth and utilization increased markedly after a point of sudden emulsificati...

  4. -Alkanes in surficial sediments of Visakhapatnam harbour, east coast of India

    Indian Academy of Sciences (India)

    V R Punyu; R R Harji; N B Bhosle; S S Sawant; K Venkat

    2013-04-01

    Surface sediments collected from 19 stations along Visakhapatnam harbour were analysed for organic carbon (OC), 13CoC, total lipids (TL), total hydrocarbon (THC), -alkane concentration and composition. OC, 13CoC, TL and THC ranged from 0.6% to 7.6%, -29.3 to -23.8‰, 300 to 14,948 g g−1 dw, and 0.2 to 2,277 g g−1 dw, respectively. Predominance of even carbon numbers -alkanes C12–C21 with carbon preference index (CPI) of < 1 suggests major microbial influence. Fair abundance of odd carbon number -alkanes in the range of C15–C22 and C23–C33 indicates some input from phytoplankton and terrestrial sources, respectively. Petrogenic input was evident from the presence of hopanes and steranes. The data suggest that organic matter (OM) sources varied spatially and were mostly derived from mixed source.

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

    Science.gov (United States)

    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

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

    International Nuclear Information System (INIS)

    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

  7. Reveal of small alkanes and isomers using calculated core and valence binding energy spectra and total momentum cross sections

    CERN Document Server

    Yang, Zejin

    2013-01-01

    The present study revealed quantum mechanically that the C1s binding energy spectra of the small alkanes (upto six carbons) provide a clear picture of isomeric chemical shift in linear alkanes and branched isomers, whereas the valence binding energy spectra contain more sensitive information regarding the length of the carbon chains. Total momentum cross sections of the alkanes exhibit the information of the chain length as well as constitutional isomers of the small alkanes. The C1s binding energies of small alkanes (including isomers) are position specific and the terminal carbons have the lowest energies. The length of an alkane chain does not apparently affect the C1s energies so that the terminal carbons (289.11 eV) of pentane are almost the same as those of hexane. The valence binding energy spectra of the alkanes are characterized by inner valence and outer valence regions which are separated by an energy gap at approximately 17 eV. The intensities of the total momentum cross sections of the alkanes ar...

  8. Genome Sequence of Pseudomonas aeruginosa DQ8, an Efficient Degrader of n-Alkanes and Polycyclic Aromatic Hydrocarbons

    OpenAIRE

    Gai, Zhonghui; Zhang, Zhengzhi; Wang, Xiaoyu; Tao, Fei; Tang, Hongzhi; Xu, Ping

    2012-01-01

    Pseudomonas aeruginosa DQ8, which was isolated from the crude oil polluted soil in the Daqing oilfield of China, can efficiently degrade diesel, crude oil, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs). Here, we present a 6.8-Mb assembly of its genome sequence. We have annotated 23 coding sequences (CDSs) responsible for catabolism of n-alkanes and PAHs.

  9. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Science.gov (United States)

    2010-07-01

    ...-alkane, branched and linear. 721.10103 Section 721.10103 Protection of Environment ENVIRONMENTAL..., branched and linear. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  10. Draft Genome Sequences of Three Smithella spp. Obtained from a Methanogenic Alkane-Degrading Culture and Oil Field Produced Water

    OpenAIRE

    Tan, BoonFei; de Araújo e Silva, Renata; Rozycki, Trent; Nesbø, Camilla; Foght, Julia

    2014-01-01

    Two draft genomes affiliated with Smithella spp. were obtained from a methanogenic alkane-degrading enrichment culture by single-cell sorting and metagenome contig binning, and a third was obtained by single-cell sorting of oil field produced water. Two genomes contained putative assABC genes encoding alkylsuccinate synthase, indicating genetic potential for fumarate activation of alkanes.

  11. Diversity of alkane hydroxylase systems in the environment; Diversite des systemes alcane hydroxylase dans l'environnement

    Energy Technology Data Exchange (ETDEWEB)

    Van Beilen, J.B.; Li, Z.; Duetz, W.A.; Smits, T.H.M.; Witholt, B. [Institute of Biotechnology, ETH-Honggerberg, Zurich (Switzerland); Smits, T.H.M. [Environnement Naturel, Architectural et Construt - ENAC/ISTE/LBE, EPFL, Lausanne (Switzerland)

    2003-08-01

    The first step in the aerobic degradation of alkanes by bacteria, yeasts, and fungi is catalyzed by oxygenases. These enzymes, which introduce oxygen atoms derived from molecular oxygen into the alkane substrate, play an important role in oil bio-remediation and in the co-metabolic degradation of compounds such as trichloroethylene and fuel oxygenates. In addition, they are useful bio-catalysts and important models for a difficult chemical reaction: the regio- and stereo-specific activation of C-H bonds. Several unrelated enzyme classes catalyze the oxidation of alkanes. Alkane-degrading yeast strains contain multiple alkane hydroxylases belonging to the P450 super-family, while many bacteria contain enzymes related to the Pseudomonas putida GPo1 membrane-bound alkane hydroxylase system. Short-chain alkanes are probably oxidized by alkane hydroxylases related to the soluble and particulate methane mono-oxygenases. Only the membrane-bound enzymes have been studied with respect to their prevalence in environments such as soils or aquifers. (authors)

  12. 40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino...

    Science.gov (United States)

    2010-07-01

    ... alcohol, halogenated alkane, substituted epoxide, and amino compound (generic). 721.10145 Section 721... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... epoxide, and amino compound (PMN P-06-816) is subject to reporting under this section for the...

  13. n-Alkanes in surficial sediments of Visakhapatnam harbour, east coast of India

    Digital Repository Service at National Institute of Oceanography (India)

    Punyu, V.R.; Harji, R.R.; Bhosle, N.B.; Sawant, S.S.; Venkat, K.

    et al. 2011). This is because the assemblage of n-alkanes found in marine biota is different from that found in terrestrial biota. For example, marine planktons such as algae and cyanobacteria exhibit predominance of short chain, odd carbon n.... The sediment samples were then lyophilized, powdered using agate mortar and pestle and stored at −20◦C until analysed. The sediments were then used for the estimation of OC, δ13C, TL and n-alkane concentration and composition. 2.4 Estimation of bulk geochemical...

  14. Direct dissociative chemisorption of alkanes on Pt(111): Influence of molecular complexity

    International Nuclear Information System (INIS)

    The direct dissociative chemisorption of ethane, propane, n-butane, isobutane, and neopentane on Pt(111) was investigated as a function of the initial translational energy, ET, polar angle of incidence, θi, initial vibrational temperature, and surface temperature using supersonic molecular beam techniques. For each alkane, the initial probability for direct dissociative chemisorption scales with the initial normal energy of the alkanes, En=ET cos2 θi, and is independent of both the surface temperature and initial vibrational energy of the alkanes under the experimental conditions employed. Above initial normal energies of approximately 125 kJ/mol, at constant En, the dissociation probability decreases with increasing chain length of the C2-C4 linear alkanes; however, the dissociation probability of neopentane is greater than that of isobutane, and both isobutane and neopentane are more reactive than n-butane. By assuming that cleavage of primary C-H bonds is the dominant reaction pathway for all of the alkanes investigated here, the trends in reactivity are best explained by considering the differences in the steric factors for primary C-H bond cleavage for these alkanes. Secondary C-H bond cleavage does appear to contribute to the reactivity of propane and n-butane but only at the highest energies examined. Additionally, the reaction probabilities of each of these alkanes were estimated using a statistical model recently proposed by Ukrainstev and Harrison [J. Chem. Phys. 101, 1564 (1994)]. Assuming cleavage of only primary C-H bonds, the trends in reactivity for ethane, propane, n-butane, and isobutane were qualitatively reproduced by the statistical model; however, except for ethane, which was used to obtain the necessary parameters for the theory, there was poor quantitative agreement, and the predictions for neopentane were significantly lower than the measured values. The model also predicts that the dissociation probability is enhanced by increasing the

  15. Raman study of local ordering processes of solid n-alkanes

    Science.gov (United States)

    Hacura, A.; Zimnicka, B.; Wrzalik, R.

    2016-02-01

    The microphase separation of n-alkanes with different chain length was investigated by Raman spectroscopy for binary mixture rapidly quenched from the melt. The process was observed as a function of time. The first several minutes after solidification were crucial for the demixing process. For a few weeks old sample the orientational order parameters and were calculated based on the analysis of polarized spectra recorded in the area of the formed domains. The measured values are significantly greater than zero (from 0.17 to 0.32), which indicates the mutual parallel arrangement of the molecules in the domains composed of n-alkanes of the same chain length.

  16. Effect of molecular packing on radiolytic processes of n-alkanes

    International Nuclear Information System (INIS)

    Complete text of publication follows. Effects of packing arrangements on both ionic (viz., the proton transfer from alkane radical cations to alkane molecules) and radical (viz., intermolecular radical site transfer) are being discussed. Structurally determined acceptor site selectivity in the proton transfer from alkane radical cations to alkane molecules, i.e. acceptor site selectivity resulting from donor site selectivity in combination with accessibility differences due to structural factors has been studied in γ-irradiated heptane/octane/1-chlorohexane and heptane/decane/1-chloroheptane mixed crystals. In such crystals, heptane radical cations are in the extended all-trans conformation and proton donation (from ground-state cations) takes place selectively from planar chain-end C-H bonds in these (matrix) cations to secondary C-H bonds in the alkane solute molecules. In heptane/octane/1-chlorohexane crystals, penultimate C-H bonds in octane, which as deduced from studies on γ-irradiated CCl3F/alkanes have the greatest propensity to act as proton acceptor, are also structurally very much favored over interior C-H bonds as proton acceptor resulting in very high selectivity with respect to this site. In heptane/decane/1-chloroheptane crystals accessibility factors of secondary C-H bonds in decane to planar chain-end C-H bonds in heptane radical cations are in the order C2 3 > C4 > C5 and protonation occurs in the order C2 > C3 > C4 > C5, providing evidence for both intrinsic (preference for penultimate position) and structurally-determined acceptor site selectivity. With respect to radical transformation by intermolecular radical site transfer, the accessibility of secondary C-H bonds to primary radical sites in γ-irradiated neat n-alkanes depends critically on their crystalline structure. On the basis of this information, EPR studies on the nature of undecyl radicals in γ-irradiated CCl3F/undecane as a function of undecane concentration have allowed us to

  17. Liszt och Alkan: Den virtuosa pianoetyden : Övningsstycke eller muterat monster?

    OpenAIRE

    Rådén, Anders

    1999-01-01

    Anders Rådén: Liszt & Alkan: the virtuoso piano study – practice study or monstrous mutation? Uppsala: Musikvetenskap, 1998. C-uppsats (60 p). The purpose of this essay is to analyse a selection of studies by Franz Liszt (1811-1886) and Charles- Valentin Alkan (1813-1888). Can they be definedas practice studies, or are they reshaped in such a manner, as to establish a larger form reminiscent of the concert study? First of all, typical study characteristics of this time period are determin...

  18. Regioselective alkane hydroxylation with a mutant CYP153A6 enzyme

    Science.gov (United States)

    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.

  19. Chemical similarity among domesticated and wild genotypes of peanut based on n-alkanes profiles

    Directory of Open Access Journals (Sweden)

    Renata Janaína Carvalho de Souza

    2010-11-01

    Full Text Available The objective of this work was to analyze the epicuticular n-alkane profile of domesticated and wild peanut genotypes. Foliar epicuticular n-alkanes of four Arachis hypogaea genotypes and two wild species - A. monticola and A. stenosperma - were analyzed by gas chromatography. Chemical relationships between them were evaluated using the Dice coefficient and UPGMA method. Two clusters were formed: one with four A. hypogaea genotypes and the other with the two wild species. There is more similarity between the BR1 and LIGO-PE06 genotypes and between the BRS 151 L-7 and BRS Havana genotypes.

  20. Enhanced translocation and growth of Rhodococcus erythropolis PR4 in the alkane phase of aqueous-alkane two phase cultures were mediated by GroEL2 overexpression.

    Science.gov (United States)

    Takihara, Hayato; Ogihara, Jun; Yoshida, Takao; Okuda, Shujiro; Nakajima, Mutsuyasu; Iwabuchi, Noriyuki; Sunairi, Michio

    2014-01-01

    We previously reported that R. erythropolis PR4 translocated from the aqueous to the alkane phase, and then grew in two phase cultures to which long-chain alkanes had been added. This was considered to be beneficial for bioremediation. In the present study, we investigated the proteins involved in the translocation of R. erythropolis PR4. The results of our proteogenomic analysis suggested that GroEL2 was upregulated more in cells that translocated inside of the pristane (C19) phase than in those located at the aqueous-alkane interface attached to the n-dodecane (C12) surface. PR4 (pK4-EL2-1) and PR4 (pK4-ΔEL2-1) strains were constructed to confirm the effects of the upregulation of GroEL2 in translocated cells. The expression of GroEL2 in PR4 (pK4-EL2-1) was 15.5-fold higher than that in PR4 (pK4-ΔEL2-1) in two phase cultures containing C12. The growth and cell surface lipophilicity of PR4 were enhanced by the introduction of pK4-EL2-1. These results suggested that the plasmid overexpression of groEL2 in PR4 (pK4-EL2-1) led to changes in cell localization, enhanced growth, and increased cell surface lipophilicity. Thus, we concluded that the overexpression of GroEL2 may play an important role in increasing the organic solvent tolerance of R. erythropolis PR4 in aqueous-alkane two phase cultures. PMID:25311591

  1. Catalytic activation of alkanes on noble metal-loaded zeolites : experimental studies and simulation of the dehydroalkylation of toluene with ethane

    OpenAIRE

    Rezai, Alireza

    2012-01-01

    With the recent progress in chemical reaction engineering and highly active, multi-functional catalysts, the activation of relatively inert alkanes may be achieved. The direct use of short-chain alkanes, especially methane and ethane, as basic chemical feedstocks represents an attractive alternative to alkenes. Significant reserves of alkanes are found in nature in the form of wet natural gas, whereas alkenes have to be synthesized via other chemical reactions. The activation of alkanes can b...

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

    DEFF Research Database (Denmark)

    Grant, Chris; Deszcz, Dawid; Wei, Yu-Chia;

    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...... 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...

  3. Determination of Alkane Content in Fresh Fecal Samples to Estimate Intake on Pasture

    Science.gov (United States)

    External markers of wax alkanes C32 and C36 are effective tools for determining intake of grazing animals. The technique requires daily dosing of markers which is impractical under extensive grazing conditions, so controlled release capsules (CRC) have been used. However, consistency of payout from ...

  4. Improved GC/MS method for quantitation of n-Alkanes in plant and fecal material

    Science.gov (United States)

    A gas chromatography-mass spectrometry (GC/MS) method for the quantitation of n-alkanes (carbon backbones ranging from 21 to 36 carbon atoms) in forage and fecal samples has been developed. Automated solid-liquid extraction using elevated temperature and pressure minimized extraction time to 30 min...

  5. Morphological factor in the melting point depression of polypropylene by alkanes

    Czech Academy of Sciences Publication Activity Database

    Šimek, L.; Dostál, J.; Bohdanecký, Miloslav

    2001-01-01

    Roč. 42, č. 21 (2001), s. 8897-8900. ISSN 0032-3861 R&D Projects: GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : isotactic polypropylene * n- alkanes * melting point depression Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.681, year: 2001

  6. Growth of n-alkane films on a single-crystal substrate

    DEFF Research Database (Denmark)

    Wu, Z. U.; Ehrlich, S. N.; Matthies, B.; Herwig, K. W.; Dai, P.; Volkmann, U. G.; Hansen, Flemming Yssing; Taub, H.

    The structure and growth mode of alkane films (n-C/sub n/H/sub 2n+2/; n=4, 6, 7) adsorbed on a Ag(111) surface have been investigated by synchrotron X-ray scattering. New models are proposed for the butane (n=4) and hexane (n=6) monolayer and butane bilayer structures. Specular reflectivity scans...

  7. Aromatization of alkanes over Pt promoted conventional and mesoporous gallosilicates of MEL zeolite

    Czech Academy of Sciences Publication Activity Database

    Akhtar, M. N.; Al-Yassir, N.; Al-Khattaf, S.; Čejka, Jiří

    2012-01-01

    Roč. 179, č. 1 (2012), s. 61-72. ISSN 0920-5861 Institutional research plan: CEZ:AV0Z40400503 Keywords : alkane aromatization * ZSM-11 * GaHZSM-11 Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.980, year: 2012

  8. Feasibility limits and performance of an absorption cooling machine using light alkane mixtures

    International Nuclear Information System (INIS)

    The performance of a heat-driven vapor absorption chiller with various alkane mixtures as working pairs was studied. A Thermodynamic analysis showed that under specified operating conditions and with a generator temperature below 130 °C, temperature achievable with a simple flat plate collector when solar energy is expected as the driving heat source, the application of some of the proposed alkane mixtures is not feasible. Simulations using ASPEN Plus flow sheeting program are then done with the selected working pairs. All simulations were done specifying the Peng-Robinson equation of state as the property method. A parametric study was carried out allowing the investigation of the generator temperature effect on the system performance and the comparison between performances released with each working pair. Results revealed that a water-cooled absorption machine using the C3H8/n-C9H20 pair as working fluid releases the best performances from a heat driving temperature level of about 100 °C. - Highlights: • Performance of an absorption chiller with various alkane mixtures was studied. • Some of the proposed alkane mixtures is not feasible. • Only the n-C4/n-C6 mixture may be considered for air-cooled machine. • In case of water cooling, C3/n-C9 and n-C4/n-C9 give the best COP

  9. ALKANES, METHYLALKANES, ALKENES AND ALKADIENES OF ADULT FLEA BEETLES, APHTHONA SPECIES

    Science.gov (United States)

    The adult beetles, Aphthona lacertosa and Aphthona nigriscutis, used as biocontrol agents for leafy spurge, had a complex mixture of hydrocarbons on their cuticular surface consisting of alkanes, methylalkanes, alkenes and alkadienes as determined by gas chromatography-mass spectrometry. A trace ...

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

    Science.gov (United States)

    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. PMID:24600999

  11. The influence of extraframework aluminum on H-FAU catalyzed cracking of light alkanes

    NARCIS (Netherlands)

    Narbeshuber, T.F.; Brait, A.; Seshan, K.; Lercher, J.A.

    1996-01-01

    The conversion of light linear and branched alkanes on two faujasite samples containing different concentrations of free Brønsted acid sites and extraframework alumina (EFAL) was studied between 733 K and 813 K. Protolytic cracking and bimolecular hydride transfer proceeded solely on Brønsted acid s

  12. Growth of n-alkane films on a single-crystal substrate

    DEFF Research Database (Denmark)

    Wu, Z. U.; Ehrlich, S. N.; Matthies, B.;

    2001-01-01

    The structure and growth mode of alkane films (n-C/sub n/H/sub 2n+2/; n=4, 6, 7) adsorbed on a Ag(111) surface have been investigated by synchrotron X-ray scattering. New models are proposed for the butane (n=4) and hexane (n=6) monolayer and butane bilayer structures. Specular reflectivity scans...

  13. Surface tension of cavities and Tolman’s length in n-alkanes. A positron study

    International Nuclear Information System (INIS)

    Highlights: ► Surface tension in cavities produced by Ps in alkanes is larger than in flat surface. ► Absolute value of Tolman’s length rises with temperature. ► Ortho-Ps lifetime near the melting point is identical for all liquid alkanes. ► No change of ortho-Ps lifetime at the transition liquid–rotator phase for n > 24. - Abstract: Positron annihilation lifetime spectra were measured in n-alkanes. From the lifetime of ortho-positronium (o-Ps) one can determine the surface tension and Tolman’s length for the cavity produced by positronium in the liquid. This tension is found increased by factor of 1.4 ÷ 1.7 comparing to that of flat surface. The Tolman’s length is temperature dependent; in n-nonadecane it rises from about 0.06 nm at melting point to 0.08 nm at the temperature 100 K higher. Near the melting point the value of surface tension of Ps cavities is practically identical for all alkanes under study, i.e. from heptane C7H16 to pentacontane C50H102

  14. Ordered Self-assembled Alkane Monolayer on Graphite and Graphene Surface

    Science.gov (United States)

    Su, Yudan; Han, Huiling; Wang, Feng; Cai, Qun; Tian, Chuanshan; Shen, Y. R.

    2015-03-01

    The 2D self-assembly of long chain alkane molecule on graphite and graphene had been studied with phase-sensitive sum-frequency vibrational spectroscopy (PS-SFVS) and scanning tunneling microscopy (STM). The spectrum of Imχs(2) (ωIR) which directly characterizes the surface resonances, shows 10-cm-1 red-shift of the symmetric-stretch frequency of the CH2 groups pointing towards graphite (or graphene) surface indicating Van der Waals interaction in between. The Gibbs adsorption energy of polyethylene (PE, n ~ 140) on graphite from chloroform solution was determined to be -42kJ/mol per molecule or -0.6 kJ/mol per CH2 unit. This large adsorption energy drives the long alkane chain to form an ordered self-assembled monolayer on graphite (or graphene). The sum frequency spectra suggest the orientation of carbon skeleton plane of alkane is predominately perpendicular to the graphite/graphene surface. Our STM result also provides clear evidence for the proposed molecular adsorption model. These results explain the large amount residual of long chain alkane on polystyrene (PS) or poly(methyl methacrylate) (PMMA) transferred graphene, and facilitate a better way to fabricate cleaner large-size graphene.

  15. Measurement and modelling of hydrogen bonding in 1-alkanol plus n-alkane binary mixtures

    DEFF Research Database (Denmark)

    von Solms, Nicolas; Jensen, Lars; Kofod, Jonas L.; Michelsen, Michael Locht; Kontogeorgis, Georgios

    Two equations of state (simplified PC-SAFT and CPA) are used to predict the monomer fraction of 1-alkanols in binary mixtures with n-alkanes. It is found that the choice of parameters and association schemes significantly affects the ability of a model to predict hydrogen bonding in mixtures, eve...

  16. Isotopic exchange between alkanes and deuterium on rhodium/silica gel catalysts

    International Nuclear Information System (INIS)

    Isotropic exchange between deuterium and cyclopentane and between pentane and ethane on the Rh/SiO2 catalysts of the preceding paper has been investigated after several different pretreatments. Although a more restricted number of catalysts was examined, as with 2,2-dimethylbutane, increased percentage exposed (Dh) appears to lead to increased turnover frequency (Nt). After the standard pretreatment, H2, 300 C; He, 450 C, the rates in alkane(g) rightleftharpoons alkane(ads) increase only slowly as Dh increases, but the rates in monoadsorbed alkane rightleftharpoons diadsorbed alkane decline relatively rapidly. As with 2,2-dimethylbutane, the pretreatment H2, 450 C leads to the largest values of Nt. He, 450 C following H2, 450 C removes surface hydrogen atoms and leads to reconstruction to a surface of much lower activity for exchange. Cyclopentane exchanges much faster than pentane on these catalysts. It appears that adsorption and desorption of cyclopentane involve single-step processes to and from diadsorbed cyclopentane + 2H*. Adsorption is faster than that with pentane because cyclopentane is essentially in the eclipsed conformation needed for this process. The rate of monoadsorbed rightleftharpoons diadsorbed cyclopentane is similarly augmented. Adsorbate-surface strain reduces the rate constant for adsorption of 2,2-dimethylbutane and increases rate of exchange of the hindered hydrocarbon vs that of the unhindered hydrocarbon will be larger than one would conclude merely from the relative rate constants of adsorption

  17. Calculations of gamma-ray spectral profiles of linear alkanes in the positron annihilation process

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Xiaoguang [Molecular Model Discovery Laboratory, Department of Chemistry and Biotechnology, School of Science, Faculty of Science, Engineering and Technology, Swinburne University of Technology, PO Box 218, Hawthorn, Victoria, 3122 (Australia); School of Physics and Optoelectronic Engineering, Ludong University, Shandong, Yantai, 264025 (China); Wang, Feng, E-mail: fwang@swin.edu.au [Molecular Model Discovery Laboratory, Department of Chemistry and Biotechnology, School of Science, Faculty of Science, Engineering and Technology, Swinburne University of Technology, PO Box 218, Hawthorn, Victoria, 3122 (Australia)

    2014-10-15

    Highlights: • The study calculates gamma-ray profiles for linear alkanes (n up to 12) quantum mechanically;. • “Profile quality” has been defined as the root-mean square deviation (RMSD) between the theoretical and the experimental results in the entire region of the profile. • Excellent agreement with measurements suggests that the theory model is applicable to predict other alkanes such as heptane (C{sub 7}H{sub 16}) etc. • The study suggested that gamma-ray spectra may be more sensitive to study smaller alkanes (and their isomers), rather than larger alkanes (i.e., n > 12). - Abstract: The positron–electron annihilation gamma-ray spectra of linear alkanes C{sub n}H{sub 2n+2} (n = 1–12) have been studied systematically. A profile quality (PQ) parameter, χ, is introduced to assess the agreement between the obtained theoretical profiles and the experimental measurements in the entire region of energy shift of the spectra. Together with the Doppler shift (Δε) of the gamma-ray spectra, the two parameters, χ and Δε, are able to provide a more comprehensive assessment of the calculated gamma-ray spectra with respect to available experiment. Applying the recently developed docking model, the present study determines the positrophilic electrons for individual alkanes from which the gamma-ray spectral profiles are calculated. The results achieve an excellent agreement with experiment, not only with respect to the Doppler shift, but also with respect to the gamma-ray profiles in the photon energy region up to 5 keV. The study further calculates the gamma-ray spectra of other linear alkanes in the series without available experimental measurements, such as heptane (C{sub 7}H{sub 16}), octane (C{sub 8}H{sub 18}), decane (C{sub 10}H{sub 22}) and undecane (C{sub 11}H{sub 24}). The results obtained show a dominance of the positrophilic electrons in the lowest occupied valence orbital (LOVO) in the positron–electron annihilation process, in agreement with

  18. Investigating C4 Grass Contributions to N-alkane Based Paleoclimate Reconstructions

    Science.gov (United States)

    Doman, C. E.; Enders, S. K.; Chadwick, O.; Freeman, K. H.

    2014-12-01

    Plant wax n-alkanes are long-chain, saturated hydrocarbons contained within the protective waxy cuticle on leaves. These lipids are pervasive and persistent in soils and sediments and thus are ideal biomarkers of ancient terrestrial organic matter. In ecosystems dominated by C3 plants, the relationship between the carbon isotopic value of whole leaves and lipids is fairly well documented, but this relationship has not been fully investigated for plants that use C4 photosynthesis. In both cases, it is unclear if the isotopic relationships are sensitive to environmental conditions, or reflect inherited characteristics. This study used a natural climate gradient on the Kohala peninsula of Hawaii to investigate relationships between climate and the δ13C and δ2H values of n-alkanes in C3 and C4 plants. δ13C of C3 leaves and lipids decreased 5 ‰ from the driest to the wettest sites, consistent with published data. Carbon isotope values of C4 plants showed no relationship to moisture up to 1000 mm mean annual precipitation (MAP). Above this threshold, δ 13C values were around 10‰ more depleted, likely due to a combination of canopy effects and C4 grasses growing in an uncharacteristically wet and cold environment. In C3 plants, the fractionation between leaf and lipid carbon isotopes did not vary with MAP, which allows estimations of δ13C leaf to be made from alkanes preserved in ancient sediments. Along this transect, C3 plants produce around twice the quantity of n-alkanes as C4 grasses. C4 grasses produce longer carbon chains. As a result, n-alkanes in the geologic record will be biased towards C3 plants, but the presence of alkanes C33 and C35 indicate the contributions of C4 grasses. In both C3 and C4 plants, average chain length increased with mean annual precipitation, but the taxonomic differences in chain length were greater than environmental differences. Hydrogen isotopes of n-alkanes show no trends with MAP, but do show clear differences between plant

  19. Technical Note: n-Alkane lipid biomarkers in loess: post-sedimentary or syn-sedimentary?

    Directory of Open Access Journals (Sweden)

    D. Faust

    2012-07-01

    Full Text Available There is an ongoing discussion whether n-alkane biomarkers – and organic matter (OM from loess in general – reflect a syn-sedimentary paleoenvironmental and paleoclimate signal or whether they are significantly a post-sedimentary feature contaminated by root-derived OM. We present first radiocarbon data for the n-alkane fraction of lipid extracts and for the first time luminescence ages for the Middle to Late Weichselian loess-paleosol sequence of Gleina in Saxony, Germany. Comparison of these biomarker ages with sedimentation ages as assessed by optically stimulated luminescence (OSL dating shows that one n-alkane sample features a syn-sedimentary age (14C: 29.2 ± 1.4 kyr cal BP versus OSL: 27.3 ± 3.0 kyr. By contrast, the 14C ages derived from the other n-alkane samples are clearly younger (20.3 ± 0.7 kyr cal BP, 22.1 ± 0.7 kyr cal BP and 29.8 ± 1.4 kyr cal BP than the corresponding OSL ages (26.6 ± 3.1 kyr, 32.0 ± 3.5 kyr and 45.6 ± 5.3 kyr. This finding suggests that a post-sedimentary n-alkane contamination presumably by roots has occurred. In order to estimate the post-sedimentary n-alkane contamination more quantitatively, we applied a 14C mass balance calculation based on the measured pMC (percent modern carbon values, the calculated syn-sedimentary pMC values and pMC values suspected to reflect likely time points of post-sedimentary contamination (current, modern, 3 kyr, 6 kyr and 9 kyr. Accordingly, current and modern root-contamination would account for up to 7%, a 3 kyr old root-contamination for up to 10%, and an Early and Middle Holocene root-contamination for up to 20% of the total sedimentary n-alkane pool. We acknowledge and encourage that these first radiocarbon results need further confirmation both from other loess-paleosol sequences and for different biomarkers, e.g. carboxylic acids or alcohols as further lipid biomarkers.

  20. Microbial communities in methane- and short chain alkane-rich hydrothermal sediments of Guaymas Basin

    Directory of Open Access Journals (Sweden)

    Frederick eDowell

    2016-01-01

    Full Text Available 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, 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.

  1. Polycyclic Aromatic Hydrocarbons and n-alkanes in Suspended Particulate Matter and Sediments from the Langat River, Peninsular Malaysia

    Directory of Open Access Journals (Sweden)

    Alireza Riyahi Bakhtiari

    2009-07-01

    Full Text Available The Langat River basin has seen rapid developments in industrialization, urbanization and dramatic population increases during the past two decades. The composition and sources of polycyclic aromatic hydrocarbons (PAHs and aliphatic hydrocarbon (n-alkanes concentrations were determined in surface sediments (SS and suspended particulate matter (SPM collected from six locations in the Langat River. The total n-alkanes concentrations (∑HC ranged from 5900 to 23000 µg/g in SPM and 1700 to 8600 µg/g in SS samples. Total PAHs concentrations varied from 306 to 7968 ng/g in SPM and 558 to 980 ng/g in SS. PAHs and n-alkanes were dominated by higher molecular weight compounds in SS and low-medium molecular weight compounds in SPM. Carbon preference index (CPI values for n-alkanes in ranges C 25-33, C 15-35 and C 25-35 varied from 0.95 to 2.49 in SS and close to unity in SPM. The CPIs values indicated multiple n-alkanes sources (petrogenic and natural. PAHs isomer pairs ratios indicated multiple (petrogenic and pyrogenic with predominance of pyrogenic PAH sources. Analysis of the possible source of PAHs and n-alkanes indicated a complicated, combined PAHs and n-alkanes source in the Langat River.

  2. Preferential methanogenic biodegradation of short-chain n-alkanes by microbial communities from two different oil sands tailings ponds.

    Science.gov (United States)

    Mohamad Shahimin, Mohd Faidz; Foght, Julia M; Siddique, Tariq

    2016-05-15

    Oil sands tailings ponds harbor diverse anaerobic microbial communities capable of methanogenic biodegradation of solvent hydrocarbons entrained in the tailings. Mature fine tailings (MFT) from two operators (Albian and CNRL) that use different extraction solvents were incubated with mixtures of either two (n-pentane and n-hexane) or four (n-pentane, n-hexane, n-octane and n-decane) n-alkanes under methanogenic conditions for ~600d. Microbes in Albian MFT began methane production by ~80d, achieving complete depletion of n-pentane and n-hexane in the two-alkane mixture and their preferential biodegradation in the four-alkane mixture. Microbes in CNRL MFT preferentially metabolized n-octane and n-decane in the four-alkane mixture after a ~80d lag but exhibited a lag of ~360d before commencing biodegradation of n-pentane and n-hexane in the two-alkane mixture. 16S rRNA gene pyrosequencing revealed Peptococcaceae members as key bacterial n-alkane degraders in all treatments except CNRL MFT amended with the four-alkane mixture, in which Anaerolineaceae, Desulfobacteraceae (Desulfobacterium) and Syntrophaceae (Smithella) dominated during n-octane and n-decane biodegradation. Anaerolineaceae sequences increased only in cultures amended with the four-alkane mixture and only during n-octane and n-decane biodegradation. The dominant methanogens were acetoclastic Methanosaetaceae. These results highlight preferential n-alkane biodegradation by microbes in oil sands tailings from different producers, with implications for tailings management and reclamation. PMID:26925736

  3. Study of Liquid Alkanes Production from Biomass-Derived Carbohydrates by Aldol-Condensation and Hydrogenation Processes

    OpenAIRE

    Navadol Laosiripojana; Verawat Champreda; Wassana Dedsuksophon

    2010-01-01

    This research aims to synthesis liquid alkanes from biomass-derived hydroxyl methyl furfural (HMF) and furfural by aldol-condensation and hydrogenation processes over several catalysts i.e. TiO2, TiO2-ZrO2, Pd/Al2O3 and Pd/CeO2. It was found that the catalysts make significant impact on the selectivity and yield of alkanes product. It is noted that Pd/Al2O3 provided the highest alkane yield and selectivity. The aldol-condensation and hydrogenation of HMF over Pd/Al2O3 provide high C12 selecti...

  4. High-resolution ellipsometric study of an n-alkane film, dotriacontane, adsorbed on a SiO2 surface

    DEFF Research Database (Denmark)

    Volkmann, U.G.; Pino, M.; Altamirano, L.A.;

    2002-01-01

    alkane/SiO2 interfacial region differs qualitatively from that which occurs in the surface freezing effect at the bulk alkane fluid/vapor interface. In that case, there is again a perpendicular film phase adjacent to the air interface but no parallel film phase intervenes between it and the bulk alkane...... present at higher coverages. In addition, we have performed high-resolution ellipsometry and stray-light measurements on dotriacontane films deposited from solution onto highly oriented pyrolytic graphite substrates. After film deposition, these substrates proved to be less stable in air than SiO2....

  5. Cloning and heterologous expression of a gene encoding an alkane-induced extracellular protein involved in alkane assimilation from Pseudomonas aeruginosa.

    OpenAIRE

    Hardegger, M; Koch, A K; Ochsner, U A; Fiechter, A; Reiser, J.

    1994-01-01

    Pseudomonas aeruginosa PG201 produces a 16-kDa extracellular protein in media containing n-hexadecane as a carbon source but not in media containing glycerol or glucose. This protein was purified, and the N-terminal amino acid sequence was determined. The amino acid composition of the protein was found to be very similar to that of the so-called protein-like activator for n-alkane oxidation (PA) from P. aeruginosa S7B1. This extracellular protein was previously characterized (K. Hisatsuka, T....

  6. Characterization of the Medium- and Long-Chain n-Alkanes Degrading Pseudomonas aeruginosa Strain SJTD-1 and Its Alkane Hydroxylase Genes

    OpenAIRE

    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 o...

  7. Structural and Kinetic Studies of Novel Cytochrome P450 Small-Alkane Hydroxylases

    Energy Technology Data Exchange (ETDEWEB)

    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

  8. Squeezing molecular thin alkane lubrication films between curved solid surfaces with long-range elasticity: Layering transitions and wear

    DEFF Research Database (Denmark)

    Sivebæk, Ion Marius; Samoilov, V. N.; Persson, B. N. J.

    2003-01-01

    The properties of alkane lubricants confined between two approaching solids are investigated by a model that accounts for the curvature and the elastic properties of the solid surfaces. We consider linear alkane molecules of different chain lengths, C3H8, C4H10, C8H18, C9H20, C10H22, C12H26 and C14......H30 confined between smooth gold surfaces. In most cases we observe well defined molecular layers develop in the lubricant film when the width of the film is of the order of a few atomic diameters. An external squeezing-pressure induces discontinuous, thermally activated changes in the number n of...... lubricant layers. We find that with increasing alkane chain length, the transition from n to n-1 layers occurs at higher pressure, as expected based on the increasing wettability ~or spreading pressure with increasing chain length. Thus, the longer alkanes are better boundary lubricants than the shorter...

  9. n-Alkane biosynthetic hydrogen isotope fractionation is not constant throughout the growing season in the riparian tree Salix viminalis

    Science.gov (United States)

    Newberry, Sarah L.; Kahmen, Ansgar; Dennis, Paul; Grant, Alastair

    2015-09-01

    Compound-specific δ2H values of leaf wax n-alkanes have emerged as a potentially powerful paleohydrological proxy. Research suggests terrestrial plant n-alkane δ2H values are strongly correlated with meteoric water δ2H values, and may provide information on temperature, relative humidity, evaporation, and precipitation. This is based upon several assumptions, including that biosynthetic fractionation of n-alkanes during synthesis is constant within a single species. Here we present a multi-isotope study of the n-alkanes of riparian Salix viminalis growing in Norwich, UK. We measured n-alkane δ2H, leaf water δ2H, xylem water δ2H, and bulk foliar δ13C and evaluated the variability of n-alkane δ2H values and net biosynthetic fractionation (εlw-wax) over a whole growing season. S. viminalis n-alkane δ2H values decreased by 40‰ between the start of the growing season in April and the time when they stabilized in July. Variation in leaf and xylem water δ2H did not explain this variability. εlw-wax varied from -116‰ during leaf expansion in April to -156‰ during the stable phase. This suggests that differential biosynthetic fractionation was responsible for the strong seasonal trends in S. viminalis n-alkane δ2H values. We suggest that variability in εlw-wax is driven by seasonal differences in the carbohydrate source and thus the NADPH used in n-alkane biosynthesis, with stored carbohydrates utilized during spring and recent occurring growing season assimilates used later in the season. This is further supported by bulk foliar δ13C values, which are 13C-enriched during the period of leaf flush, relative to the end of the growing season. Our results challenge the assumption that biosynthetic fractionation is constant for a given species, and suggest that 2H-enriched stored assimilates are an important source for n-alkane biosynthesis early in the growing season. These findings have implications for the interpretation of sedimentary n-alkanes and call

  10. Identification of Novel Genes Involved in Long-Chain n-Alkane Degradation by Acinetobacter sp. Strain DSM 17874▿

    Science.gov (United States)

    Throne-Holst, Mimmi; Wentzel, Alexander; Ellingsen, Trond E.; Kotlar, Hans-Kristian; Zotchev, Sergey B.

    2007-01-01

    Acinetobacter sp. strain DSM 17874 is capable of utilizing n-alkanes with chain lengths ranging from that of decane (C10H22) to that of tetracontane (C40H82) as a sole carbon source. Two genes encoding AlkB-type alkane hydroxylase homologues, designated alkMa and alkMb, have been shown to be involved in the degradation of n-alkanes with chain lengths of from 10 to 20 C atoms in this strain. Here, we describe a novel high-throughput screening method and the screening of a transposon mutant library to identify genes involved in the degradation of n-alkanes with C chain lengths longer than 20, which are solid at 30°C, the optimal growth temperature for Acinetobacter sp. strain DSM 17874. A library consisting of approximately 6,800 Acinetobacter sp. strain DSM 17874 transposon mutants was constructed and screened for mutants unable to grow on dotriacontane (C32H66) while simultaneously showing wild-type growth characteristics on shorter-chain n-alkanes. For 23 such mutants isolated, the genes inactivated by transposon insertion were identified. Targeted inactivation and complementation studies of one of these genes, designated almA and encoding a putative flavin-binding monooxygenase, confirmed its involvement in the strain's metabolism of long-chain n-alkanes. To our knowledge, almA represents the first cloned gene shown to be involved in the bacterial degradation of long-chain n-alkanes of 32 C's and longer. Genes encoding AlmA homologues were also identified in other long-chain n-alkane-degrading Acinetobacter strains. PMID:17400787

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

    OpenAIRE

    Warner, D.; Ferreira, L.M.M.; Breuer, M.J.H.; Dijkstra, J; Pellikaan, W.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 kinet...

  12. Insights into the Anaerobic Biodegradation Pathway of n-Alkanes in Oil Reservoirs by Detection of Signature Metabolites

    OpenAIRE

    Xin-Yu Bian; Serge Maurice Mbadinga; Yi-Fan Liu; Shi-Zhong Yang; Jin-Feng Liu; Ru-Qiang Ye; Ji-Dong Gu; Bo-Zhong Mu

    2015-01-01

    Anaerobic degradation of alkanes in hydrocarbon-rich environments has been documented and different degradation strategies proposed, of which the most encountered one is fumarate addition mechanism, generating alkylsuccinates as specific biomarkers. However, little is known about the mechanisms of anaerobic degradation of alkanes in oil reservoirs, due to low concentrations of signature metabolites and lack of mass spectral characteristics to allow identification. In this work, we used a mult...

  13. Novel Mesoporous Silica Materials with Hierarchically Ordered Nanochannel: Synthesis with the Assistance of Straight-Chain Alkanes and Application

    OpenAIRE

    Haidong Zhang; Xiaohong Li

    2016-01-01

    The straight-chain alkane-assisted synthesis of hierarchical mesoporous silica materials (MSM) results in variable mesostructures and morphologies due to remarkably different self-assembly routes of template agent from those without the assistance of straight-chain alkanes. The textural properties, particularly pore size, channel structure, morphology, and hierarchical structure of those MSM make them demonstrate peculiar effects in the immobilization of homogeneous catalysts.

  14. Are alkane hydroxylase genes (alkB) relevant to assess petroleum bioremediation processes in chronically polluted coastal sediments?

    OpenAIRE

    Païssé, Sandrine; Duran, Robert; Coulon, Frederic; Goni-Urriza, Marisol

    2011-01-01

    The diversity of alkB-related alkane hydroxylase sequences and the relationship between alkB gene expres- sion and the hydrocarbon contamination level have been investigated in the chronically polluted Etang-de-Berre sediments. For this purpose, these sediments were main- tained in microcosms and submitted to a controlled oil input miming an oil spill. New degenerated PCR primers targeting alkB-related alkane hydroxylase sequences were designed to explore the diversity and t...

  15. Biodegradation of crude oil and n-alkanes by fungi isolated from Oman

    International Nuclear Information System (INIS)

    Ten fungal species isolated from tar balls collected from the beaches of Oman were tested for their abilities to grow and degrade n-alkanes and crude oil. The abilities of Aspergillus niger, A. ochraceus and Penicillium chrysogenum to degrade n-alkanes (C13-C18), crude oil were compared and their mycelial biomass was measured. Significant differences were found in the utilization of C15, C16, C17 and C18 by the three fungi. Similarly, significant differences we found in the amount of biomass produced by the three fungi growing on C13, C17, C18 and crude oil. The correlation coefficient of biomass and oil utilization was not statistically significant for Aspergillus niger, significant for Aspergillus terreus and highly significant for P. chrysogenum

  16. Crossed-beam DC slice imaging of fluorine atom reactions with linear alkanes

    International Nuclear Information System (INIS)

    We report the reaction dynamics of F atom with selected alkanes studied by crossed beam scattering with DC slice ion imaging. The target alkanes are propane, n-butane, and n-pentane. The product alkyl radicals are probed by 157 nm single photon ionization following reaction at a collision energy of ∼10 kcal mol−1. The analyzed data are compared with the corresponding theoretical studies. Reduced translational energy distributions for each system show similar trends with little of the reaction exoergicity appearing in translation. However, the pentane reaction shows a somewhat smaller fraction of available energy in translation than the other two, suggesting greater energy channeled into pentyl internal degrees of freedom. The center-of-mass angular distributions all show backscattering as well as sharp forward scattering that decreases in relative intensity with the size of the molecule. Possible reasons for these trends are discussed

  17. Crossed-beam DC slice imaging of fluorine atom reactions with linear alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Yuanyuan; Kamasah, Alexander; Joalland, Baptiste; Suits, Arthur G., E-mail: asuits@chem.wayne.edu [Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, Michigan 48202 (United States)

    2015-05-14

    We report the reaction dynamics of F atom with selected alkanes studied by crossed beam scattering with DC slice ion imaging. The target alkanes are propane, n-butane, and n-pentane. The product alkyl radicals are probed by 157 nm single photon ionization following reaction at a collision energy of ∼10 kcal mol{sup −1}. The analyzed data are compared with the corresponding theoretical studies. Reduced translational energy distributions for each system show similar trends with little of the reaction exoergicity appearing in translation. However, the pentane reaction shows a somewhat smaller fraction of available energy in translation than the other two, suggesting greater energy channeled into pentyl internal degrees of freedom. The center-of-mass angular distributions all show backscattering as well as sharp forward scattering that decreases in relative intensity with the size of the molecule. Possible reasons for these trends are discussed.

  18. Electron Trapping by Polar Molecules in Alkane Liquids: Cluster Chemistry in Dilute Solution

    CERN Document Server

    Shkrob, I A; Shkrob, Ilya A.; Sauer, Myran C.

    2005-01-01

    Monomers and small clusters of such molecules can reversibly trap conduction band electrons in dilute alkane solutions. The dynamics and energetics of this trapping have been studied using pulse radiolysis - transient absorption spectroscopy and time-resolved photoconductivity. Binding energies, thermal detrapping rates, and absorption spectra of excess electrons attached to monomer and multimer solute traps are obtained and possible structures for these species are discussed. "Dipole coagulation" (stepwise growth of the solute cluster around the cavity electron) predicted by Mozumder in 1972 is observed. Acetonitrile monomer is shown to solvate the electron by its methyl group, just like the alkane solvent does. The electron is dipole-bound to the CN group; the latter points away from the cavity. The resulting negatively charged species has a binding energy of 0.4 eV and absorbs in the infrared. Molecules of straight-chain aliphatic alcohols solvate the excess electron by their OH groups; at equilibrium, the...

  19. A Novel Topological Index for the Studies on Structure-Properties of Alkanes

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A novel topological index derived from eccentric connectivity index has been proposed. The new topological index and eccentric connectivity index were correlated with eight physical properties such as the boiling point, critical temperature, critical pressure, critical volume, evaporation heat, density, heat capaci- ty, surface tension, and three thermodynamic properties such as standard enthalpy, standard entropy and standard formation free energy of alkanes. A series of empiric equations for calculating the properties were obtained. Correlation coefficients of nine properties were more than 0. 99 . Regression analysis and calcula- tion results indicated that the topological indices were well correlated with the physico-chemical properties of alkanes, and the novel topological index was far superior to eccentric connectivity index in the correlation.

  20. Fossil Leaves and Fossil Leaf n-Alkanes: Reconstructing the First Closed Canopied Rainforests

    Science.gov (United States)

    Graham, H. V.; Freeman, K. H.

    2013-12-01

    Although the age and location is disputed, the rise of the first closed-canopy forest is likely linked with the expansion of angiosperms in the late Cretacous or early Cenozoic. The carbon isotope 'canopy effect' reflects the extent of canopy closure, and is well documented in δ13C values of the leaves and leaf lipids in modern forests. To test the extent of canopy closure among the oldest documented angiosperm tropical forests, we analyzed isotopic characteristics of leaf fossils and leaf waxes from the Guaduas and Cerrejón Formations. The Guaduas Fm. (Maastrichtian) contains some of the earliest angiosperm fossils in the Neotropics, and both leaf morphology and pollen records at this site suggest an open-canopy structure. The Cerrejón Fm. (Paleocene) contains what are believed to be the first recorded fossil leaves from a closed-canopy forest. We analyzed the bulk carbon isotope content (δ13Cleaf) of 199 fossil leaves, as well as the n-alkane concentration and chain-length distribution, and δ13C of alkanes (δ13Clipid) of 73 fossil leaves and adjacent sediment samples. Fossil leaves are dominated by eudicots and include ten modern plant families (Apocynaceae, Bombaceae, Euphorbaceae, Fabaceae, Lauraceae, Malvaceae, Meliaceae, Menispermaceae, Moraceae, Sapotaceae). We interpreted extent of canopy coverage based on the range of δ13Cleaf values. The narrow range of δ13C values in leaves from the Guaduas Fm (2.7‰) is consistent with an open canopy. A significantly wider range in values (6.3‰) suggests a closed-canopy signature for site 0315 of the Cerrejón Fm,. In contrast, at Site 0318, a lacustrine deposit, leaves had a narrow range (3.3‰) in δ13C values, and this is not consistent with a closed-canopy, but is consistent with leaf assemblages from a forest edge. Leaves that accumulate in lake sediments tend to be biased toward plants living at the lake edge, which do not experience closed-canopy conditions, and do not express the isotopic

  1. Catalytic oxidation of light alkanes (C1-C4) by heteropoly compounds

    KAUST Repository

    Sun, Miao

    2014-01-22

    Heteropoly compounds (HPC) have revealed their potential to generate catalyst for selectively converting light alkanes to oxygenated products. There are various structures in which they are active the primary structure being that of the heteropolyanion itself, the secondary structure is the three-dimensional arrangements of polyanions, and the tertiary structure representing the manner in which the secondary structure assembles into solid particles. There are also a huge variety of elements inside the HPA. The heteropoly acids can have acidity, which varies dramatically depending on composition. This complexity of situation makes it very difficult to really have a predictive vision of their ability to activate and functionalize alkanes. However, a large amount of data reported suggests that the initial formula of the precatalyst is pivotal to direct the selectivity of the reaction toward different oxygenates. Inclusion of alternative transition metal atoms as addenda is highly influential with iron, vanadium, and antimony being particularly outstanding.

  2. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. I. Structure

    DEFF Research Database (Denmark)

    Enevoldsen, Ann Dorrit; Hansen, Flemming Yssing; Diama, A.;

    2007-01-01

    ) tetracosane film is roughly the same as the bulk melting point, the surface strongly stabilizes the 2D squalane film such that its melting point is 91 K above its value in bulk. Therefore, squalane, like tetracosane, will be a poor lubricant in those nanoscale devices that require a fluid lubricant at room......The structure of a monolayer film of the branched alkane squalane (C30H62) adsorbed on graphite has been studied by neutron diffraction and molecular dynamics (MD) simulations and compared with a similar study of the n-alkane tetracosane (n-C24H52). Both molecules have 24 carbon atoms along their...... backbone and squalane has, in addition, six methyl side groups. Upon adsorption, there are significant differences as well as similarities in the behavior of these molecular films. Both molecules form ordered structures at low temperatures; however, while the melting point of the two-dimensional (2D...

  3. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. II. Dynamics

    DEFF Research Database (Denmark)

    Enevoldsen, Ann Dorrit; Hansen, Flemming Yssing; Diama, A.;

    2007-01-01

    The dynamics of monolayer films of the n-alkane tetracosane (n-C24H52) and the branched alkane squalane (C30H62) adsorbed on graphite have been studied by quasielastic and inelastic neutron scattering and molecular dynamics (MD) simulations. Both molecules have 24 carbon atoms along their carbon...... backbone, and squalane has an additional six methyl side groups symmetrically placed along its length. The authors' principal objective has been to determine the influence of the side groups on the dynamics of the squalane monolayer and thereby assess its potential as a nanoscale lubricant. To investigate...... analysis of the quasielastic scattering. They conclude that there are no major differences in the monolayer dynamics caused by intramolecular branching. It remains to be seen whether this similarity in monolayer dynamics also holds for the lubricating properties of these molecules in confined geometries...

  4. Measurement of thermodiffusion coefficient in n-alkane binary mixtures: composition dependence.

    Science.gov (United States)

    Madariaga, J A; Santamaría, C; Bou-Ali, M Mounir; Urteaga, P; Alonso De Mezquia, D

    2010-05-27

    In this work, we have measured the thermodiffusion coefficient of different n-alkane binary mixtures at several concentrations using the thermogravitational technique. In particular, we have studied the n-dodecane/n-heptane system as a function of composition and other systems covering a large range of mass differences and concentration at 25 degrees C and 1 atm. The results show that for any concentration the thermodiffusion coefficient of n-alkane mixtures is proportional to the mass difference between the components and to the ratio of the thermal expansion coefficient and viscosity of the mixture. The obtained equation allows us to determine the infinite dilution values of the thermodiffusion coefficient. We compare these values with recent experimental results in dilute polymer solutions and analyze the Brenner theory of thermodiffusion. Finally, it is shown that the thermodiffusion coefficient depends linearly with the mass fraction, and it can be calculated from the viscosity and thermal expansion of the pure components. PMID:20429569

  5. Application of statistical experimental methodology to optimize bioremediation of n-alkanes in aquatic environment

    International Nuclear Information System (INIS)

    Response surface methodology (RSM) was employed to optimize nitrogen and phosphorus concentrations for removal of n-alkanes from crude oil contaminated seawater samples in batch reactors. Erlenmeyer flasks were used as bioreactors; each containing 250 mL dispersed crude oil contaminated seawater, indigenous acclimatized microorganism and different amounts of nitrogen and phosphorus based on central composite design (CCD). Samples were extracted and analyzed according to US-EPA protocols using a gas chromatograph. During 28 days of bioremediation, a maximum of 95% total aliphatic hydrocarbons removal was observed. The obtained Model F-value of 267.73 and probability F < 0.0001 implied the model was significant. Numerical condition optimization via a quadratic model, predicted 98% n-alkanes removal for a 20-day laboratory bioremediation trial using nitrogen and phosphorus concentrations of 13.62 and 1.39 mg/L, respectively. In actual experiments, 95% removal was observed under these conditions.

  6. Application of statistical experimental methodology to optimize bioremediation of n-alkanes in aquatic environment

    Energy Technology Data Exchange (ETDEWEB)

    Zahed, Mohammad Ali; Aziz, Hamidi Abdul; Mohajeri, Leila; Mohajeri, Soraya [School of Civil Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia); Kutty, Shamsul Rahman Mohamed [Civil Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Isa, Mohamed Hasnain, E-mail: hasnain_isa@petronas.com.my [Civil Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia)

    2010-12-15

    Response surface methodology (RSM) was employed to optimize nitrogen and phosphorus concentrations for removal of n-alkanes from crude oil contaminated seawater samples in batch reactors. Erlenmeyer flasks were used as bioreactors; each containing 250 mL dispersed crude oil contaminated seawater, indigenous acclimatized microorganism and different amounts of nitrogen and phosphorus based on central composite design (CCD). Samples were extracted and analyzed according to US-EPA protocols using a gas chromatograph. During 28 days of bioremediation, a maximum of 95% total aliphatic hydrocarbons removal was observed. The obtained Model F-value of 267.73 and probability F < 0.0001 implied the model was significant. Numerical condition optimization via a quadratic model, predicted 98% n-alkanes removal for a 20-day laboratory bioremediation trial using nitrogen and phosphorus concentrations of 13.62 and 1.39 mg/L, respectively. In actual experiments, 95% removal was observed under these conditions.

  7. Thermodynamic properties of (an ester + an alkane). XVIII. Experimental HmEandVmE values for (an alkyl butanoate + an alkane) at T = 318.15 K

    International Nuclear Information System (INIS)

    This work presents the experimental values of HmEandVmE obtained at a temperature of 318.15 K and atmospheric pressure for a group of 24 binary mixtures comprised of the first four alkyl butanoates (methyl to butyl) with six odd alkanes, from heptane to heptadecane. All the mixtures are endothermic, and present a regular increase in HmE with the molecular weight of the saturated hydrocarbon, while, for a same alkane, the enthalpic effects diminish with increasing alcoholic chain of the butanoate. The variation in VmE occurs in the same direction. In this paper the structural behaviour of these systems and the influence of temperature on excess properties are analysed. Experimental data are correlated with a suitable polynomial equation which is given as a function of concentration and temperature, that permits a simultaneous correlation to be established with other properties of the mixture, such as (vapour + liquid) equilibria; and acceptable results are obtained. Finally, an estimation of HmE is made with two known versions of the UNIFAC model. In the version by Dang and Tassios [J. Dang, D.P. Tassios, Ind. Eng. Chem. Process Des. Dev. 25 (1986) 22-31.], a method is proposed that considers the interaction parameters as a function of the butanoate alkanolic chain. The estimations obtained for HmE are good

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  9. A novel growth mode of alkane films on a SiO2 surface

    DEFF Research Database (Denmark)

    Mo, H.; Taub, H.; Volkmann, U.G.; Pino, M.; Ehrlich, S.N.; Hansen, Flemming Yssing; Lu, E.; Miceli, P.

    Synchrotron X-ray specular scattering measurements confirm microscopically a structural model recently inferred by very-high-resolution ellipsometry of a solid dotriacontane (n-C32H66 or C32) film formed by adsorption from solution onto a SiO2 surface. Sequentially, one or two layers adsorb on th...... previously for shorter alkanes deposited from the vapor phase onto solid surfaces....

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

    Science.gov (United States)

    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.

  11. Effect of Rhamnolipid (Biosurfactant) Structure on Solubilization and Biodegradation of n-Alkanes

    OpenAIRE

    Zhang, Y.; Miller, R M

    1995-01-01

    A study to quantify the effect of rhamnolipid biosurfactant structure on the degradation of alkanes by a variety of Pseudomonas isolates was conducted. Two dirhamnolipids were studied, a methyl ester form (dR-Me) and an acid form (dR-A). These rhamnolipids have different properties with respect to interfacial tension, solubility, and charge. For example, the interfacial tension between hexadecane and water was decreased to

  12. A QSPR STUDY OF NORMAL BOILING POINT OF ORGANIC COMPOUNDS (ALIPHATIC ALKANES) USING MOLECULAR DESCRIPTORS

    OpenAIRE

    B. Souyei; M. Korichi

    2013-01-01

    A quantitative structure–property relationship (QSPR) study is carried out to develop correlations that relate the molecular structures of organic compounds (Aliphatic Alkanes) to their normal boiling point (NBP) and two correlations were proposed for constitutionals and connectivity indices Models. The correlations are simple in application with good accuracy, which provide an easy, direct and relatively accurate way to calculate NBP. Such calculation gives us a model that gives results in r...

  13. Genome Sequence of Rhodococcus sp. Strain BCP1, a Biodegrader of Alkanes and Chlorinated Compounds

    Science.gov (United States)

    Cappelletti, M.; Di Gennaro, P.; D’Ursi, P.; Orro, A.; Mezzelani, A.; Landini, M.; Fedi, S.; Frascari, D.; Presentato, A.; Milanesi, L.

    2013-01-01

    Rhodococcus sp. strain BCP1 cometabolizes chlorinated compounds and mineralizes a broad range of alkanes, as it is highly tolerant to them. The high-quality draft genome sequence of Rhodococcus sp. strain BCP1, consisting of 6,231,823 bp, with a G+C content of 70.4%, 5,902 protein-coding genes, and 58 RNA genes, is presented here. PMID:24158549

  14. A comparative study of n-alkane biomarker and pollen records: an example from southern China

    Institute of Scientific and Technical Information of China (English)

    ZHENG YanHong; ZHOU WeiJian; XIE ShuCheng; YU XueFeng

    2009-01-01

    We report the results of a comparative study of n-alkane biomarkers and pollens in lacustrine and peat deposits at Dingnan, Jiangxi Province in southern China, and discuss the likely causes for the discrepancy in the interpretations of the n-alkane biomarker and pollen records in terms of climate and vegetation change. The results show that past changes in climate and vegetation revealed by the n-alkane record are not always consistent with the pollen assemblage record in the whole section.Biomarkers do not permit direct identification of the plant family and/or genus and mainly record compositions of local plant remains, while pollens mainly reflect the regional vegetation change. Biomarkers and pollen records complement each other, providing a better picture of local and regional environments. Furthermore, biomarkers are more sensitive than pollen to climatic and vegetational change. Several climatic events are clearly identified by the n-alkane biomarker proxies, such as C31/(C27+C29+C31) ratio and can be correlated to the North Atlantic Heinrich event, B/A, YD and two dry-cool events during the early Holocene such as the periods of 9850 to 9585 cal a B.P. and 8590 to 7920 cal a B.P. These events are consistent with those found in the surrounding regions, suggesting that the regional climate was coupled with global-scale abrupt climatic events. Our results suggest that biomarker and pollen data can record the more detailed climate and vegetation information, thus improving the resolution and precision of vegetation and climate reconstruction.

  15. The Electronic Structure of Vanadium Oxides as Catalysts in the Selective Oxidation of Small Alkanes

    OpenAIRE

    Heine, C.

    2014-01-01

    Die vorliegende Arbeit befasst sich mit Vanadiumoxiden in der Selektivoxidation kleiner Alkane. Änderungen der elektronischen (Oberflächen-) Struktur, induziert durch das chemische Potential des umgebenden Reaktionsgases, wurden hinsichtlich der Ladungsträgerdynamik, der Valenz/ Leitungsbandstruktur und Austrittsarbeitsänderungen untersucht. Die Ladungsträgerdynamik wurde kontaktfrei mit Hilfe der Mikrowellen-Resonator-Störungs- Methode unter Verwendung einer Festbettreaktorgeometrie untersuch...

  16. Modelling and parameter estimation in reactive continuous mixtures: the catalytic cracking of alkanes - part II

    Directory of Open Access Journals (Sweden)

    F. C. PEIXOTO

    1999-09-01

    Full Text Available Fragmentation kinetics is employed to model a continuous reactive mixture of alkanes under catalytic cracking conditions. Standard moment analysis techniques are employed, and a dynamic system for the time evolution of moments of the mixture's dimensionless concentration distribution function (DCDF is found. The time behavior of the DCDF is recovered with successive estimations of scaled gamma distributions using the moments time data.

  17. Characterization of the OCT plasmid encoding alkane oxidation and mercury resistance in Pseudomonas putida.

    OpenAIRE

    Harder, P A; Kunz, D A

    1986-01-01

    Transformation of Pseudomonas putida and analysis for plasmid DNA revealed that both n-alkane oxidation and mercury resistance are encoded on a single 220-megadalton OCT plasmid molecule. Derivatives of OCT having lost the mercury resistance function could be readily isolated and contained a smaller plasmid estimated to be 170 megadaltons. The results show that segregation of the mercury resistance property occurs not by loss of a separate MER plasmid as previously thought but by a deletion i...

  18. Water solubility of selected C9-C18 alkanes using a slow-stir technique: Comparison to structure - property models.

    Science.gov (United States)

    Letinski, Daniel J; Parkerton, Thomas F; Redman, Aaron D; Connelly, Martin J; Peterson, Brian

    2016-05-01

    Aqueous solubility is a fundamental physical-chemical substance property that strongly influences the distribution, fate and effects of chemicals upon release into the environment. Experimental water solubility was determined for 18 selected C9-C18 normal, branched and cyclic alkanes. A slow-stir technique was applied to obviate emulsion formation, which historically has resulted in significant overestimation of the aqueous solubility of such hydrophobic liquid compounds. Sensitive GC-MS based methods coupled with contemporary sample extraction techniques were employed to enable reproducible analysis of low parts-per billion aqueous concentrations. Water solubility measurements for most of the compounds investigated, are reported for the first time expanding available data for branched and cyclic alkanes. Measured water solubilities spanned four orders of magnitude ranging from 0.3 μg/L to 250 μg/L. Good agreement was observed for selected alkanes tested in this work and reported in earlier literature demonstrating the robustness of the slow-stir water solubility technique. Comparisons of measured alkane water solubilities were also made with those predicted by commonly used quantitative structure-property relationship models (e.g. SPARC, EPIWIN, ACD/Labs). Correlations are also presented between alkane measured water solubilities and molecular size parameters (e.g. molar volume, solvent accessible molar volume) affirming a mechanistic description of empirical aqueous solubility results and prediction previously reported for a more limited set of alkanes. PMID:26924078

  19. Transcriptional response of Desulfatibacillum alkenivorans AK-01 to growth on alkanes: insights from RT-qPCR and microarray analyses.

    Science.gov (United States)

    Herath, Anjumala; Wawrik, Boris; Qin, Yujia; Zhou, Jizhong; Callaghan, Amy V

    2016-05-01

    Microbial transformation ofn-alkanes in anaerobic ecosystems plays a pivotal role in biogeochemical carbon cycling and bioremediation, but the requisite genetic machinery is not well elucidated.Desulfatibacillum alkenivoransAK-01 utilizesn-alkanes (C13to C18) and contains two genomic loci encoding alkylsuccinate synthase (ASS) gene clusters. ASS catalyzes alkane addition to fumarate to form methylalkylsuccinic acids. We hypothesized that the genes in the two clusters would be differentially expressed depending on the alkane substrate utilized for growth. RT-qPCR was used to investigateass-gene expression across AK-01's known substrate range, and microarray-based transcriptomic analysis served to investigate whole-cell responses to growth onn-hexadecane versus hexadecanoate. RT-qPCR revealed induction ofassgene cluster 1 during growth on all tested alkane substrates, and the transcriptional start sites in cluster 1 were determined via 5'RACE. Induction ofassgene cluster 2 was not observed under the tested conditions. Transcriptomic analysis indicated that the upregulation of genes potentially involved in methylalkylsuccinate metabolism, including methylmalonyl-CoA mutase and a putative carboxyl transferase. These findings provide new directions for studying the transcriptional regulation of genes involved in alkane addition to fumarate, fumarate recycling and the processing of methylalkylsuccinates with regard to isolates, enrichment cultures and ecological datasets. PMID:27009900

  20. Long chain n-alkanes and their carbon isotopes in lichen species from western Hubei Province: implication for geological records

    Institute of Scientific and Technical Information of China (English)

    Xianyu HUANG; Jiantao XUE; Shouyu GUO

    2012-01-01

    Five coticolous lichen samples were collected from western Hubei Province of China to analyze the long chain n-alkanes and their carbon isotope compositions.The n-alkanes range in carbon number from C17 to C33 with strong odd-over-even predominance between C21and C33.Lichens are dominated by n-C29 in the samples of Dajiuhu,Shennongjia Mountain,but by both n-C23 and n-C29 at Qizimei Mountain.This difference may result from the different environmental conditions in these two sites.The δ13C values of long chain n-alkanes in lichen samples show the signature of C3 plants.Based on compoundspecific carbon isotopic values and previous results,we state that alkane homologs > C23 mainly originate from the symbiotic fungi,while symbiotic algae only contribute trace amount of long chain alkanes.Of great interesting is the occurrence of long chain 3-methylalkanes in the Qizimei samples.These anteiso compounds range from C24 to C32,displaying obvious even-over-odd predominance.This study reveals that the association of long chain 3-methylalkanes with n-C23 alkane might be used as proxies to reconstruct the paleoecological implications of lichens in Earth history.

  1. Effects of n-alkanes on the morphology of lipid bilayers. A freeze-fracture and negative stain analysis.

    Science.gov (United States)

    McIntosh, T J; Costello, M J

    1981-07-20

    The effect of n-alkanes on the ultrastructure of lipid bilayers has been investigated using freeze-fracture and negative stain electron microscopy. It has been found that the morphology of bilayers containing the long alkane tetradecane is quite different from bilayers containing the short alkane hexane. The smooth fracture faces of gel and liquid crystalline state bilayers are unmodified by tetradecane. However, hexane dramatically alters the hydrophobic bilayer interior, producing large (20 to 50 nm) mounds and depressions in the fracture faces. The fracture steps in these multilayer preparations containing hexane are variable in thickness and often considerably wider than the corresponding fracture steps in multilayers which contain tetradecane or are solvent-free. Alkanes also modify the structure of the P beta' or 'banded' phase of phosphatidylcholine bilayers. The incorporation of tetradecane removes the banded structure from both the bilayer's hydrophilic surface, as viewed by negative staining, and the bilayer's hydrophobic interior, as viewed by the freeze-fracture technique. These results are consistent with X-ray diffraction data which imply that long alkanes are primarily located between adjacent lipid hydrocarbon chains in each monolayer of the bilayer, while short alkanes can partition into the geometric center of the bilayer between apposing monolayers. PMID:6168283

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

    Energy Technology Data Exchange (ETDEWEB)

    Mbadinga, Serge Maurice; Li, Kai-Ping; Zhou, Lei; Wang, Li-Ying; Yang, Shi-Zhong; Liu, Jin-Feng; Mu, Bo-Zhong [East China Univ. of Science and Technology, Shanghai (China). State Key Lab. of Bioreactor Engineering and Inst. of Applied Chemistry; Gu, Ji-Dong [Hong Kong Univ. (China). School of Biological Sciences

    2012-10-15

    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{sub 15}-C{sub 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{sub 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. (orig.)

  3. Hydrocarbon degradation, plant colonization and gene expression of alkane degradation genes by endophytic Enterobacter ludwigii strains

    International Nuclear Information System (INIS)

    The genus Enterobacter comprises a range of beneficial plant-associated bacteria showing plant growth promotion. Enterobacter ludwigii belongs to the Enterobacter cloacae complex and has been reported to include human pathogens but also plant-associated strains with plant beneficial capacities. To assess the role of Enterobacter endophytes in hydrocarbon degradation, plant colonization, abundance and expression of CYP153 genes in different plant compartments, three plant species (Italian ryegrass, birdsfoot trefoil and alfalfa) were grown in sterile soil spiked with 1% diesel and inoculated with three endophytic E. ludwigii strains. Results showed that all strains were capable of hydrocarbon degradation and efficiently colonized the rhizosphere and plant interior. Two strains, ISI10-3 and BRI10-9, showed highest degradation rates of diesel fuel up to 68% and performed best in combination with Italian ryegrass and alfalfa. All strains expressed the CYP153 gene in all plant compartments, indicating an active role in degradation of diesel in association with plants. - Highlights: → E. ludwigii strains efficiently colonized plants in a non-sterile soil environment. → E. ludwigii strains efficiently expressed alkane degradation genes in plants. → E. ludwigii efficiently degraded alkane contaminations and promoted plant growth. → E. ludwigii interacted more effectively with Italian ryegrass than with other plants. → Degradation activity varied with plant and microbial genotype as well as with time. - Enterobacter ludwigii strains belonging to the E. cloacae complex are able to efficiently degrade alkanes when associated with plants and to promote plant growth.

  4. Adsorption Behaviors of Mixed Monolayers of n-Alkanes at the Liquid-Solid Interface.

    Science.gov (United States)

    Hibino, Masahiro

    2016-05-17

    To understand the self-assembly of monolayers at the liquid-solid interface, a thermodynamic model, which describes the contributions of the molecular interactions, is essential. We present an adapted Zimm-Bragg model of the cooperativity transitions for determining the Gibbs free energy for self-assembly at the liquid-solid interface. Scanning tunneling microscopy was used to observe the monolayers formed on graphite from phenyloctane solutions of binary mixtures of n-hexacosane (C26H54) and n-tetratriacontane (C34H70). This revealed that the sharp transition in the monolayers from the full surface coverage of the long-chain alkane, which is adsorbed preferentially, to the full coverage of the short-chain alkane is a function of the mixture composition. The model allows for the estimation of the free-energy changes associated with the difference in the alkyl chain length and the interface between the two different alkane regions in the monolayers. It is also suitable for understanding more complex systems that exhibit intermolecular interactions. PMID:27124544

  5. Calculations of gamma-ray spectral profiles of linear alkanes in the positron annihilation process

    CERN Document Server

    Ma, X G

    2014-01-01

    The positron-electron annihilation gamma-ray spectra of linear alkanes CnH2n+2 (n=1-12) have been studied systematically. A profile quality (PQ) parameter, is introduced to assess the agreement between the obtained theoretical profiles and the experimental measurements in the entire region of energy shift of the spectra. Together with the Doppler shift of the gamma-ray spectra, the two parameters,PQ and Doppler shift, are able to provide a more comprehensive assessment of the calculated gamma-ray spectra with respect to available experiment. Applying the recently developed docking model, the present study determines the positrophilic electrons for individual alkanes from which the gamma-ray spectral profiles are calculated. The results achieve an excellent agreement with experiment, not only with respect to the Doppler shift, but also with respect to the gamma-ray profiles in the photon energy region up to 5 keV. The study further calculates the gamma-ray spectra of other linear alkanes in the series without ...

  6. Critical constants and acentric factors for long-chain alkanes suitable for corresponding states applications

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Dimitrios, Tassios

    1997-01-01

    Several methods for the estimation of the critical temperature T-c, the critical pressure P-c, and the acentric factor omega for long-chain n-alkanes are reviewed and evaluated for the prediction of vapor pressures using Corresponding States (CS) methods, like the Lee-Kesler equation and the cubic...... equations of state. Most reliable and recent literature methods proposed for the estimation of the acentric factor of heavy alkanes yield similar values and the emphasis is, thus, given to the determination of the best sets of T-c and P-c. Various extrapolation schemes proposed for this purpose and several...... general group-contribution methods were investigated in this work. The correlations proposed by K. Magoulas and D. Tassios, Thermophysical properties of n-alkanes from C-1 to C-20 and their prediction for higher ones, Fluid Phase Equilibria, 56 ( 1990) 119-140; A.S. Teja, R.J. Lee, D.J. Rosenthal, M...

  7. Raman analysis of bond conformations in the rotator state and premelting of normal alkanes.

    Science.gov (United States)

    Kotula, Anthony P; Walker, Angela R Hight; Migler, Kalman B

    2016-06-14

    We perform Raman spectroscopic measurements on normal alkanes (CnH2n+2) to quantify the n dependence of the conformational disorder that occurs below the melt temperature. We employ a three-state spectral analysis method originally developed for semi-crystalline polyethylene that posits crystalline, amorphous, and non-crystalline consecutive trans (NCCT) conformations to extract their respective mass fractions. For the alkanes studied that melt via a rotator phase (21 ≤n≤ 37), we find that conformational disorder can be quantified by the loss of NCCT mass fraction, which systematically decreases with increasing chain length. For those that melt directly via the crystal phase (n≥ 40), we observe NCCT conformational mass fractions that are independent of chain length but whose disordered mass fraction increases with length. These complement prior IR measurements which measure disorder via gauche conformations, but have not been able to measure the mass fraction of this disorder as a function of n. An interesting feature of the three-state analysis when applied to alkanes is that the measured fraction of disordered chain conformations in the rotator phase of (10 to 30)% greatly exceeds the mass fraction of gauche bonds (1 to 7)% as measured from IR; we reconcile this difference through DFT calculations. PMID:27174157

  8. Catalytic conversion of light alkanes. Quarterly progress report, April 1--June 30, 1992

    Energy Technology Data Exchange (ETDEWEB)

    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).

  9. Breath alkanes as a marker of oxidative stress in different clinical conditions.

    Science.gov (United States)

    Aghdassi, E; Allard, J P

    2000-03-15

    We assessed oxidative stress in three different clinical conditions: smoking, human immunodeficiency virus (HIV) infection, and inflammatory bowel disease, using breath alkane output and other lipid peroxidation parameters such as plasma lipid peroxides (LPO) and malondialdehyde (MDA). Antioxidant micronutrients such as selenium, vitamin E, C, beta-carotene and carotenoids were also measured. Lipid peroxidation was significantly higher and antioxidant vitamins significantly lower in smokers compared to nonsmokers. Beta-carotene or vitamin E supplementation significantly reduced lipid peroxidation in that population. However, vitamin C supplementation had no effect. In HIV-infected subjects, lipid peroxidation parameters were also elevated and antioxidant vitamins reduced compared to seronegative controls. Vitamin E and C supplementation resulted in a significant decrease in lipid peroxidation with a trend toward a reduction in viral load. In patients with inflammatory bowel disease, breath alkane output was also significantly elevated when compared to healthy controls. A trial with vitamin E and C is underway. In conclusion, breath alkane output, plasma LPO and MDA are elevated in certain clinical conditions such as smoking, HIV infection, and inflammatory bowel disease. This is associated with lower levels of antioxidant micronutrients. Supplementation with antioxidant vitamins significantly reduced these lipid peroxidation parameters. The results suggest that these measures are good markers for lipid peroxidation. PMID:10802218

  10. Conversion of raw lignocellulosic biomass into branched long-chain alkanes through three tandem steps.

    Science.gov (United States)

    Li, Chunrui; Ding, Daqian; Xia, Qineng; Liu, Xiaohui; Wang, Yanqin

    2016-07-01

    Synthesis of branched long-chain alkanes from renewable biomass has attracted intensive interest in recent years, but the feedstock for this synthesis is restricted to platform chemicals. Here, we develop an effective and energy-efficient process to convert raw lignocellulosic biomass (e.g., corncob) into branched diesel-range alkanes through three tandem steps for the first time. Furfural and isopropyl levulinate (LA ester) were prepared from hemicellulose and cellulose fractions of corncob in toluene/water biphasic system with added isopropanol, which was followed by double aldol condensation of furfural with LA ester into C15 oxygenates and the final hydrodeoxygenation of C15 oxygenates into branched long-chain alkanes. The core point of this tandem process is the addition of isopropanol in the first step, which enables the spontaneous transfer of levulinic acid (LA) into the toluene phase in the form of LA ester through esterification, resulting in LA ester co-existing with furfural in the same phase, which is the basis for double aldol condensation in the toluene phase. Moreover, the acidic aqueous phase and toluene can be reused and the residues, including lignin and humins in aqueous phase, can be separated and carbonized to porous carbon materials. PMID:27241180

  11. Hydrocarbon degradation, plant colonization and gene expression of alkane degradation genes by endophytic Enterobacter ludwigii strains

    Energy Technology Data Exchange (ETDEWEB)

    Yousaf, Sohail [AIT Austrian Institute of Technology GmbH, Bioresources Unit, A-2444 Seibersdorf (Austria); Afzal, Muhammad [AIT Austrian Institute of Technology GmbH, Bioresources Unit, A-2444 Seibersdorf (Austria); National Institute for Biotechnology and Genetic Engineering (NIBGE), Faisalabad (Pakistan); Reichenauer, Thomas G. [AIT Austrian Institute of Technology GmbH, Environmental Resources and Technologies Unit, A-2444 Seibersdorf (Austria); Brady, Carrie L. [Forestry and Agricultural Biotechnology Institute, Department of Microbiology and Plant Pathology, University of Pretoria, Pretoria (South Africa); Sessitsch, Angela, E-mail: angela.sessitsch@ait.ac.at [AIT Austrian Institute of Technology GmbH, Bioresources Unit, A-2444 Seibersdorf (Austria)

    2011-10-15

    The genus Enterobacter comprises a range of beneficial plant-associated bacteria showing plant growth promotion. Enterobacter ludwigii belongs to the Enterobacter cloacae complex and has been reported to include human pathogens but also plant-associated strains with plant beneficial capacities. To assess the role of Enterobacter endophytes in hydrocarbon degradation, plant colonization, abundance and expression of CYP153 genes in different plant compartments, three plant species (Italian ryegrass, birdsfoot trefoil and alfalfa) were grown in sterile soil spiked with 1% diesel and inoculated with three endophytic E. ludwigii strains. Results showed that all strains were capable of hydrocarbon degradation and efficiently colonized the rhizosphere and plant interior. Two strains, ISI10-3 and BRI10-9, showed highest degradation rates of diesel fuel up to 68% and performed best in combination with Italian ryegrass and alfalfa. All strains expressed the CYP153 gene in all plant compartments, indicating an active role in degradation of diesel in association with plants. - Highlights: > E. ludwigii strains efficiently colonized plants in a non-sterile soil environment. > E. ludwigii strains efficiently expressed alkane degradation genes in plants. > E. ludwigii efficiently degraded alkane contaminations and promoted plant growth. > E. ludwigii interacted more effectively with Italian ryegrass than with other plants. > Degradation activity varied with plant and microbial genotype as well as with time. - Enterobacter ludwigii strains belonging to the E. cloacae complex are able to efficiently degrade alkanes when associated with plants and to promote plant growth.

  12. Catalytic conversion of light alkanes phase II. Topical report, January 1990--January 1993

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    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).

  13. Diffusion of methane and other alkanes in metal-organic frameworks for natural gas storage

    Energy Technology Data Exchange (ETDEWEB)

    Borah, B; Zhang, HD; Snurr, RQ

    2015-03-03

    Diffusion of methane, ethane, propane and n-butane was studied within the micropores of several metal organic frameworks (MOFs) of varying topologies, including the MOFs PCN-14, NU-125, NU-1100 and DUT-49. Diffusion coefficients of the pure components, as well as methane/ethane, methane/ propane and methane/butane binary mixtures, were calculated using molecular dynamics simulations to understand the effect of the longer alkanes on uptake of natural gas in MOB. The calculated self diffusion coefficients of all four components are on the order of 10(-8) m(2)/s. The diffusion coefficients of the pure components decrease as a function of chain length in all of the MOFs studied and show different behaviour as a function of loading in different MOB. The self-diffusivities follow the trend DPCN-14 < DNU-125 approximate to DNU-1100 < DDUT-49, which is exactly the reverse order of the densities of the MOFs: PCN-14 > NU-125 approximate to NU-1100 > DUT-49. By comparing the diffusion of pure methane and methane mixtures vvith the higher alkancs, it is observed that the diffusivity of methane is unaffected by the presence of the higher alkanes in the MOFs considered, indicating that the diffusion path of methane is not blocked by the higher alkanes present in natural gas. (C) 2014 Elsevier Ltd. All rights reserved.

  14. Induction and development of the oil emulsifying system in an alkane oxidizing Rhodococcus species

    International Nuclear Information System (INIS)

    There is a potential use of oil emulsifying bacteria for the clean-up of oil-contaminated natural environments, and oil transport and storage systems. The control mechanisms of the emulsifying abilities in these bacteria are important in relation to the optimization of such processes. A study was conducted to investigate the physiological criteria for the formation of the emulsifying activity in Rhodococcus sp. strain 094, which forms a hydrophobic cell surface when cultivated on alkanes, permitting oil-associated exponential growth. The ability of this bacteria to produce oil emulsifying agents is clearly inducible by crude oil or a number of single hydrophobic compounds. Before the cells are able to emulsify the oil, they must pass through a relatively short induction period followed by a longer period of synthesis of hydrophobic surface parts, coinciding with cell proliferation. The latter is due to the required coordination with new cell wall synthesis. If the cells are allowed to produce sufficient amounts of hydrophobic cell surface parts, they commence to emulsify the oil efficiently when the hydrophobic factor is released from the cell surface as part of their change to a more hydrophillic state. All the positive inducers were hydrophobic alkyl derivatives, and with one exception, also substrate for growth. Many of the better inducers were alkanes, and would require an alkane oxidizing system to be used by the cells. 14 ref., 2 tabs., 3 figs

  15. Catalytic conversion of light alkanes: Quarterly report, January 1-March 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    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. Nanoencapsulation of n-alkanes with poly(styrene-co-ethylacrylate) shells for thermal energy storage

    International Nuclear Information System (INIS)

    Highlights: • Four series of nanocapsules containing n-alkanes were synthesized in poly(styrene-co-ethylacrylate). • The emulsion co-polymerization technique was used. • Influence of core:shell ratio on encapsulation and thermal properties reported. - Abstract: In this work, we synthesized a series of four nanocapsules containing n-alkanes (CnH2n+2), namely tetradecane, pentadecane, hexadecane, and heptadecane, in poly(styrene-co-ethylacrylate) using an emulsion copolymerization method. The nanocapsules were characterized according to their geometric profiles, phase transition temperatures, phase transition heats, mean particle sizes, and chemical stabilities by means of scanning electron microscopy, differential scanning calorimetry, thermal gravimetric analysis and Fourier transform infrared spectroscopy. Furthermore, we also focused on the effect of the core/shell mass ratio on the phase change properties of the nanocapsules. We found that microcapsules were synthesized successfully and that the best core/shell mass ratio was 3:1 for this study. These results indicate that encapsulated n-alkanes with poly(styrene-co-ethylacrylate) have an excellent potential for energy storage

  17. Transport mechanisms and wetting dynamics in molecularly thin films of long-chain alkanes at solid/vapour interface : relation to the solid-liquid phase transition

    OpenAIRE

    Lazar, Paul

    2005-01-01

    Wetting and phase transitions play a very important role our daily life. Molecularly thin films of long-chain alkanes at solid/vapour interfaces (e.g. C30H62 on silicon wafers) are very good model systems for studying the relation between wetting behaviour and (bulk) phase transitions. Immediately above the bulk melting temperature the alkanes wet partially the surface (drops). In this temperature range the substrate surface is covered with a molecularly thin ordered, solid-like alkane film (...

  18. Distribution and significance of C40+ alkanes in the extracts of Cretaceous source rocks from the Songliao Basin

    Institute of Scientific and Technical Information of China (English)

    FENG; ZiHui; FANG; Wei; ZHANG; JuHe; LI; ZhenGuang; HUANG; ChunYan; WANG; Xue; ZHAO; QinLing; HUO; QiuLi

    2007-01-01

    Source rock extracts and crude oils from the Songliao Basin were analyzed by high-temperature gas chromatography (HTGC), gas chromatography-mass spectrometry (HTGC-MS) and gas chromatography-isotope ratio-mass spectrometry (GC-IRMS), for high molecular-weight alkanes. The distributions of n-alkanes in the Nenjiang Formation extracts are in the C14―C63 range; a bimodal distribution occurs in the and C21―40 regions. The C30―C37 n-alkanes are accompanied by C29―C35 hopanes, whereas the high molecular-weight C45―C47 n-alkanes co-occur with abundant isoalkanes, alkylcyclohexanes and alkylcyclopentanes. The high δ13C values of the n-alkanes and the microscopic maceral compositions indicate a highly diversified organic source input for the Nenjiang Formation source rocks, ranging from aquatic plants, blue alge-bacteria, to land plant material. In contrast, n-alkanes in the rock extracts of the Qingshankou Formation are characterized by a single modal distribution, with relatively low abundances of C29―C35 hopanes, but high molecular-weight isoalkanes, alkylcyclohexanes and alkylcyclopentanes. The relatively low δ13C values of C22―C44 n-alkanes and organic material compositions indicate that the source rocks in the Qingshankou Formation contain dominantly type I algal organic matter. The relative abundance of compounds in source rocks changes little at low maturity stage, but decreases drastically at higher maturity levels, with a concurrent reduction in the odd/even carbon predominance. In crude oils, in contrast, the relative abundance of compounds appears to relate closely with the oil source and oil viscosity.

  19. Vapour–liquid equilibria of the OPLS (Optimized Potentials for Liquid Simulations model for binary systems of alkanes and alkanes + alcohols

    Directory of Open Access Journals (Sweden)

    SLOBODAN P. SERBANOVIC

    2005-03-01

    Full Text Available The NpT - Gibbs ensemble Monte Carlo computer simulationmethod was applied to predict the vapour–liquid equlibrium (VLE behavior of the binary systems ethane + pentane at 277.55 K and 310.95 K, ethane + hexane at 298.15 K, propane + methanol at 313.15 K and propane + ethanol at 325.15 K and 425.15 K. The optimised potentials for the liquid simulating (OPLS model were used to describe the interactions of alkanes and alcohols. The simulated VLE predictions are compared with experimental data available for the pressure and phase composition of the analyzed binary systems. The agreement between the experimental data and the simulation results is found to be generally good, although slightly better for system in which both components were nonpolar.

  20. Anaerolineaceae and Methanosaeta turned to be the dominant microorganisms in alkanes-dependent methanogenic culture after long-term of incubation

    OpenAIRE

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

    2015-01-01

    The methanogenic alkanes-degrading enrichment culture which had been incubated for over 1,300 days amended with n-alkanes (C15–C20) was investigated through clone libraries of bacteria, archaea and assA, mcrA functional genes. These enrichment cultures were obtained from oily sludge after an initial incubation of the oily sludge without any carbon source and then an enrichment transfer with n-alkanes (C15–C20) for acclimation. Activation of alkanes, methane precursor generation and methanogen...

  1. Anaerolineaceae and Methanosaeta turned to be the dominant microorganisms in alkanes-dependent methanogenic culture after long-term of incubation.

    Science.gov (United States)

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

    2015-12-01

    The methanogenic alkanes-degrading enrichment culture which had been incubated for over 1,300 days amended with n-alkanes (C15-C20) was investigated through clone libraries of bacteria, archaea and assA, mcrA functional genes. These enrichment cultures were obtained from oily sludge after an initial incubation of the oily sludge without any carbon source and then an enrichment transfer with n-alkanes (C15-C20) for acclimation. Activation of alkanes, methane precursor generation and methanogenic pathways are considered as three pivotal stages for the continuous methanogenesis from degradation of alkanes. The presence of functional genes encoding the alkylsuccinate synthase α-subunit indicated that fumarate addition is most likely the one of initial activation step for degradation of n-alkanes. Degradation intermediates of n-alkanes were octadecanoate, hexadecanoate, butyrate, isobutyrate, acetate and propionate, which could provide the appropriate substrates for acetate formation. Both methyl coenzyme M reductase gene and 16S rRNA gene analysis showed that microorganisms of Methanoseata were the most dominant methanogens, capable of using acetate as the electron donor to produce methane. Bacterial clone libraries showed organisms of Anaerolineaceae (within the phylum of Chloroflexi) were predominant (45.5%), indicating syntrophically cooperation with Methanosaeta archaea was likely involved in the process of methanogenic degradation of alkanes. Alkanes may initially be activated via fumarate addition and degraded to fatty acids, then converted to acetate, which was further converted to methane and carbon dioxide by methanogens. PMID:26080793

  2. Late Quaternary environmental changes inferred from n-alkane evidence in coastal area of southern Hainan Island, China

    Science.gov (United States)

    Wang, Mengyuan; Zheng, Zhuo

    2016-04-01

    The studied core was a coastal core in Hainan Island, China. It is in length of 49.01m and divided into four Units (MIS 1~MIS 6) according to lithology description. The Optically Stimulated Luminescence (OSL) attributes the sediments from Unit 3 to the Oxygen Isotope Stage of MIS 5e (Unit 3b and 3c) and 5d (Unit 3a). To interpret the origination of organic carbons and to reconstruct paleovegetation changes, n-alkane, δ13C and TOC have been used in the present research. The result of n-alkanes distribution indicates a series of changes of sedimentary environment and terrestrial input. The shallow water facies at Unit 2, 3a and 4 is mainly characterized by short carbon chain n-alkanes and relatively low concentration. Contrasting with that of deep-water marine facies of MIS 5e (Unit 3b), the n-alkane pattern is typical bimodal and the main peaks are both in short and long carbon chains. During Unit 3b-1 (MIS 5e), more terrestrial original n-alkanes contribute to the concentration of TOC than oceanic. Organic matter source is mainly terrestrial origination. Total organic matter input mechanism of TLG-01 correlates with sediment grain size (average grain size). Total organic carbon input is enhanced with the increasing of fine grain size component. The variation of CPI (25-33) value in this study correlates with hydrological energy. The highest CPI (25-33) value is shown in the high sea level period of MIS 5e, comparing with that in MIS 5d and MIS 1. High CPI value corresponds to high TOC and average grain size (Φ) value. In the weak hydrological energy sedimentary environment, more terrestrial organic matter, together with TOC, deposit in the study area. ACL (25-33) index display higher values in the interglacial period (MIS 5 and MIS 1) than MIS 3 (sediments weathered during MIS 2) and MIS 6. Paq proxy, together with δ13C, estimates the mangrove growing depth in MIS 5e. The correlation between δ13C and each carbon chain alkane state stabilize and turbulence of

  3. Methyl ketones in high altitude Ecuadorian Andosols confirm excellent conservation of plant-specific n-alkane patterns

    Science.gov (United States)

    Jansen, B.; Nierop, K. G. J.

    2009-04-01

    Montane forest composition and specifically the position of the upper forest line (UFL) is very sensitive to climate change and human interference. As a consequence, reconstructions of past altitudinal UFL dynamics and forest species composition are crucial instruments to infer relationships between climate change and vegetation dynamics, and assess the impact of (pre)historic human settlement. One of the most detailed methods available to date to reconstruct past vegetation dynamics is the analysis of fossil pollen. Unfortunately, fossil pollen analysis does not distinguish beyond family or generic level in most cases, while its spatial resolution is limited amongst others by windblown dispersal of pollen, affecting the accuracy of pollen based reconstructions of UFL positions. To overcome these limitations, we developed a new method based on the analysis of plant-specific groups of biomarkers preserved in suitable archives, such as peat deposits, that are unravelled into the plant species of origin by the newly developed VERHIB model. In a study of UFL positions in the Northern Ecuadorian Andes we found longer chain-length n-alkanes, (C19-C35) to occur in plant-specific patterns in the dominant vegetation in the area as well as preliminary soil and peat samples. A crucial factor in determining the applicability of these n-alkanes as biomarkers for past vegetation is their preservation in soils and peat deposits. Therefore, we investigated the preservation of C19-C35 n-alkanes in a peat core and in five excavations along an altitudinal transect (3500-3860 m.a.s.l) in the study area. We were able to establish that n-methyl ketones are the main degradation product of the n-alkanes in question, while the degradation of the n-alkanes was the main source of the n-methyl ketones. This allowed us to use the relationship between the concentrations and carbon chain length patterns of n-alkanes and n-methyl ketones to assess possible (selective) degradation of the n-alkanes

  4. Effects of surfactant mixtures, including Corexit 9527, on bacterial oxidation of acetate and alkanes in crude oil

    Energy Technology Data Exchange (ETDEWEB)

    Bruheim, P.; Bredholt, H.; Eimhjellen, K. [Norwegian Univ. of Science and Technology, Trondheim (Norway). Dept. of Biotechnology

    1999-04-01

    Mixtures of nonionic and anionic surfactants, including Corexit 9527, were tested to determine their effects on bacterial oxidation of acetate and alkanes in crude oil by cells pregrown on these substrates. Corexit 9527 inhibited oxidation of the alkanes in crude oil by Acinetobacter calcoaceticus ATCC 31012, while Span 80, a Corexit 9527 constituent, markedly increased the oil oxidation rate. Another Corexit 9257 constituent, the negatively charged dioctyl sulfosuccinate (AOT), strongly reduced the oxidation rate. The combination of Span 80 and AOT increased the rate, but not as much as Span 80 alone increased it, which tentatively explained the negative effect of Corexit 9527. The results of acetate uptake and oxidation experiments indicated that the nonionic surfactants interacted with the acetate uptake system while the anionic surfactant interacted with the oxidation system of the bacteria. The overall effect of Corexit 9527 on alkane oxidation by A. calcoaceticus ATCC 31012 thus seems to be the sum of the independent effects of the individual surfactants in the surfactant mixture. When Rhodococcus sp. strain 094 was used, the alkane oxidation rate decreased to almost zero in the presence of a mixture of Tergitol 15-S-7 and AOT even though the Tergitol 15-S-7 surfactant increased the alkane oxidation rate and AOT did not affect it. This indicated that there was synergism between the two surfactants rather than an additive effect like that observed for A. calcoaceticus ATCC 31012.

  5. Added Alkane Allows Thermal Thinning of Supramolecular Columns by Forming Superlattice-An X-ray and Neutron Study.

    Science.gov (United States)

    Yen, Ming-Huei; Chaiprapa, Jitrin; Zeng, Xiangbing; Liu, Yongsong; Cseh, Liliana; Mehl, Georg H; Ungar, Goran

    2016-05-11

    We report a columnar superlattice formed by blends of dendron-like Li 3,4,5-tris(n-alkoxy)benzoates with n-alkanes. Without the alkane, the wedge-shaped molecules form liquid crystal columns with 3 dendrons in a supramolecular disk. The same structure exists in the blend, but on heating one dendron is expelled from the disks in every third column and is replaced by the alkane. This superlattice of unequal columns is confirmed by complementary X-ray and neutron diffraction studies. Lateral thermal expansion of dendrons normally leads to the expulsion of excess molecules from the column, reducing the column diameter. However, in the already narrow columns of pure Li salt, expulsion of one of only three dendrons in a disk is not viable. The added alkane facilitates the expulsion, as it replaces the missing dendron. Replacing the alkane with a functional compound can potentially lead to active nanoarrays with relatively large periodicity by using only small molecules. PMID:27101731

  6. Arbuscular mycorrhizal wheat inoculation promotes alkane and polycyclic aromatic hydrocarbon biodegradation: Microcosm experiment on aged-contaminated soil.

    Science.gov (United States)

    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. PMID:26995451

  7. The Uptake and Assembly of Alkanes within a Porous Nanocapsule in Water: New Information about Hydrophobic Confinement.

    Science.gov (United States)

    Kopilevich, Sivil; Gottlieb, Hugo; Keinan-Adamsky, Keren; Müller, Achim; Weinstock, Ira A

    2016-03-24

    In Nature, enzymes provide hydrophobic cavities and channels for sequestering small alkanes or long-chain alkyl groups from water. Similarly, the porous metal oxide capsule [{Mo(VI) 6 O21 (H2 O)6 }12 {(Mo(V) 2 O4 )30 (L)29 (H2 O)2 }](41-) (L=propionate ligand) features distinct domains for sequestering differently sized alkanes (as in Nature) as well as internal dimensions suitable for multi-alkane clustering. The ethyl tails of the 29 endohedrally coordinated ligands, L, form a spherical, hydrophobic "shell", while their methyl end groups generate a hydrophobic cavity with a diameter of 11 Å at the center of the capsule. As such, C7 to C3 straight-chain alkanes are tightly intercalated between the ethyl tails, giving assemblies containing 90 to 110 methyl and methylene units, whereas two or three ethane molecules reside in the central cavity of the capsule, where they are free to rotate rapidly, a phenomenon never before observed for the uptake of alkanes from water by molecular cages or containers. PMID:26880403

  8. Long-Term Incubation Reveals Methanogenic Biodegradation of C5 and C6 iso-Alkanes in Oil Sands Tailings.

    Science.gov (United States)

    Siddique, Tariq; Mohamad Shahimin, Mohd Faidz; Zamir, Saima; Semple, Kathleen; Li, Carmen; Foght, Julia M

    2015-12-15

    iso-Alkanes are major components of petroleum and have been considered recalcitrant to biodegradation under methanogenic conditions. However, indigenous microbes in oil sands tailings ponds exposed to solvents rich in 2-methylbutane, 2-methylpentane, 3-methylpentane, n-pentane, and n-hexane produce methane in situ. We incubated defined mixtures of iso- or n-alkanes with mature fine tailings from two tailings ponds of different ages historically exposed to different solvents: one, ~10 years old, receiving C5-C6 paraffins and the other, ~35 years old, receiving naphtha. A lengthy incubation (>6 years) revealed iso-alkane biodegradation after lag phases of 900-1800 and ~280 days, respectively, before the onset of methanogenesis, although lag phases were shorter with n-alkanes (~650-1675 and ~170 days, respectively). 2-Methylpentane and both n-alkanes were completely depleted during ~2400 days of incubation, whereas 2-methylbutane and 3-methylpentane were partially depleted only during active degradation of 2-methylpentane, suggesting co-metabolism. In both cases, pyrotag sequencing of 16S rRNA genes showed codominance of Peptococcaceae with acetoclastic (Methanosaeta) and hydrogenotrophic (Methanoregula and Methanolinea) methanogens. These observations are important for predicting long-term greenhouse-gas emissions from oil sands tailings ponds and extend the known range of hydrocarbons susceptible to methanogenic biodegradation in petroleum-impacted anaerobic environments. PMID:26571341

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Mass dependence of the activation enthalpy and entropy of unentangled linear alkane chains

    International Nuclear Information System (INIS)

    The mass scaling of the self-diffusion coefficient D of polymers in the liquid state, D ∼ Mβ, is one of the most basic characteristics of these complex fluids. Although traditional theories such as the Rouse and reptation models of unentangled and entangled polymer melts, respectively, predict that β is constant, this exponent for alkanes has been estimated experimentally to vary from −1.8 to −2.7 upon cooling. Significantly, β changes with temperature T under conditions where the chains are not entangled and at temperatures far above the glass transition temperature Tg where dynamic heterogeneity does not complicate the description of the liquid dynamics. Based on atomistic molecular dynamics simulations on unentangled linear alkanes in the melt, we find that the variation of β with T can be directly attributed to the dependence of the enthalpy ΔHa and entropy ΔSa of activation on the number of alkane backbone carbon atoms, n. In addition, we find a sharp change in the melt dynamics near a “critical” chain length, n ≈ 17. A close examination of this phenomenon indicates that a “buckling transition” from rod-like to coiled chain configurations occurs at this characteristic chain length and distinct entropy-enthalpy compensation relations, ΔSa ∝ ΔHa, hold on either side of this polymer conformational transition. We conclude that the activation free energy parameters exert a significant influence on the dynamics of polymer melts that is not anticipated by either the Rouse and reptation models. In addition to changes of ΔHa and ΔSa with M, we expect changes in these free energy parameters to be crucial for understanding the dynamics of polymer blends, nanocomposites, and confined polymers because of changes of the fluid free energy by interfacial interactions and geometrical confinement

  11. Ozone-driven photochemical formation of carboxylic acid groups from alkane groups

    Directory of Open Access Journals (Sweden)

    S. Liu

    2011-03-01

    Full Text Available Carboxylic acids are ubiquitous in atmospheric particles, and they play an important role in the physical and chemical properties of aerosol particles. During measurements in coastal California in the summer of 2009, carboxylic acid functional groups were highly associated with trajectories from an industrial region with high organic mass (OM, likely from fossil fuel combustion emissions. The concentration of carboxylic acid groups peaked during daytime, suggesting a photochemical secondary formation mechanism. This daytime increase in concentration was tightly correlated with O3 mixing ratio, indicating O3 was the likely driver in acid formation. Based on the diurnal cycles of carboxylic acid and alkane groups, the covariation of carboxylic acid groups with O3, and the composition of the Combustion factor resulted from the factor analyses, gas-phase alkane oxidation by OH radicals to form dihyfrofuran followed by further oxidation of dihydrofuran by O3 is the likely acid formation mechanism. Using the multi-day average of the daytime increase of carboxylic acid group concentrations and m/z 44-based Aged Combustion factor, we estimated the lower-bound contributions of secondary organic aerosol (SOA formed in 12-h daytime of processing in a single day to be 30% of the carboxylic acid groups and 25–45% of the Combustion factor concentration. These unique ambient observations of photochemically-driven acid formation suggest that gas-phase alkanes might be important sources of SOA formation in this coastal region.

  12. Critical wetting of n-alkanes on water; Mouillage critique des alcanes sur l`eau

    Energy Technology Data Exchange (ETDEWEB)

    Ragil, K.

    1996-10-18

    This study concerns the wetting properties of n-alkanes on water under thermodynamic equilibrium conditions, a problem that is interesting for the petroleum industry as well as for the fundamental understanding of wetting phenomena. An experimental study using ellipsometry reveals that pentane on water undergoes a continuous or critical wetting transition at a temperature equal to 53.1 deg. C. This is the first experimental observation of such a transition, confirming theoretical predictions made on this subject over ten years. This transition is characterized by a continuous and reversible evolution of the thickness of the film of pentane with temperature from a thick (but finite film) to a macroscopic film. The critical wetting transition occurs when the Hamaker constant of the system, which gives the net interaction between the two interfaces bounding the wetting layer of pentane in terms of the van der Waals forces, changes sign. A theoretical approach based on the Cahn-Landau theory, which takes into account long range forces (van der Waals forces), enables us to explain the mechanism of the critical wetting transition and to show that a first-order wetting transition should precede it. Because of their similar dispersive properties, linear alkanes could all be able to show such a succession of transitions. An ellipsometry study performed on a brine/hexane/vapor system confirms that a discontinuous transition from a thin microscopic film to a thick but finite adsorbed film takes place. THis study demonstrates that the wetting of alkanes on water is determined by subtle interplay between short range and long range forces, which can lead to an intermediary state between partial and complete wetting. (author)

  13. Mass dependence of the activation enthalpy and entropy of unentangled linear alkane chains

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Cheol; Douglas, Jack F. [Materials Science and Engineering Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States)

    2015-10-14

    The mass scaling of the self-diffusion coefficient D of polymers in the liquid state, D ∼ M{sup β}, is one of the most basic characteristics of these complex fluids. Although traditional theories such as the Rouse and reptation models of unentangled and entangled polymer melts, respectively, predict that β is constant, this exponent for alkanes has been estimated experimentally to vary from −1.8 to −2.7 upon cooling. Significantly, β changes with temperature T under conditions where the chains are not entangled and at temperatures far above the glass transition temperature T{sub g} where dynamic heterogeneity does not complicate the description of the liquid dynamics. Based on atomistic molecular dynamics simulations on unentangled linear alkanes in the melt, we find that the variation of β with T can be directly attributed to the dependence of the enthalpy ΔH{sub a} and entropy ΔS{sub a} of activation on the number of alkane backbone carbon atoms, n. In addition, we find a sharp change in the melt dynamics near a “critical” chain length, n ≈ 17. A close examination of this phenomenon indicates that a “buckling transition” from rod-like to coiled chain configurations occurs at this characteristic chain length and distinct entropy-enthalpy compensation relations, ΔS{sub a} ∝ ΔH{sub a}, hold on either side of this polymer conformational transition. We conclude that the activation free energy parameters exert a significant influence on the dynamics of polymer melts that is not anticipated by either the Rouse and reptation models. In addition to changes of ΔH{sub a} and ΔS{sub a} with M, we expect changes in these free energy parameters to be crucial for understanding the dynamics of polymer blends, nanocomposites, and confined polymers because of changes of the fluid free energy by interfacial interactions and geometrical confinement.

  14. Influence of compost amendments on the diversity of alkane degrading bacteria in hydrocarbon contaminated soils

    Directory of Open Access Journals (Sweden)

    MichaelSchloter

    2014-03-01

    Full Text Available Alkane degrading microorganisms play an important role for bioremediation of petrogenic contaminated environments. In this study, we investigated the effects of compost addition on the diversity of alkane monooxygenase gene (alkB harboring bacteria in oil-contaminated soil originated from an industrial zone in Celje, Slovenia, to improve our understanding about the bacterial community involved in alkane degradation and the effects of amendments. Soil without any amendments (control soil and soil amended with compost of different maturation stages, i 1 year and ii 2 weeks, were incubated under controlled conditions in a microcosm experiment and sampled after 0, 6, 12 and 36 weeks of incubation. By using quantitative real-time PCR higher number of alkB genes could be detected in soil samples with compost compared to the control soil after 6, 12 and 36 weeks mainly if the less maturated compost was added. To get an insight into the composition of the alkB harboring microbial communities, we performed next generation sequencing of alkB gene fragment amplicons. Richness and diversity of alkB gene harboring prokaryotes was higher in soil mixed with compost compared to control soil after 6, 12 and 36 weeks again with stronger effects of the less maturated compost. Comparison of communities detected in different samples and time points based on principle component analysis revealed that the addition of compost in general stimulated the abundance of alkB harboring Actinobacteria during the experiment independent from the maturation stage of the compost compared to the control soils. In addition alkB harboring proteobacteria like Shewanella or Hydrocarboniphaga as well as proteobacteria of the genus Agrobacterium responded positively to the addition of compost to soil The amendment of the less maturated compost resulted in addition in a large increase of alkB harboring bacteria of the Cytophaga group (Microscilla mainly at the early sampling

  15. Fractal analysis methods for solid alkane monolayer domains at SiO2/air interfaces.

    Science.gov (United States)

    Knüfing, Lydia; Schollmeyer, Hauke; Riegler, Hans; Mecke, Klaus

    2005-02-01

    A systematic evaluation of various fractal analysis methods is essential for studying morphologies of finite and noisy experimental patterns such as domains of long chain alkanes at SiO(2)/air interfaces. The derivation of trustworthy fractal dimensions crucially relies on the definition of confidence intervals for the assumed scaling range. We demonstrate that the determination of the intervals can be improved largely by comparing the scaling behavior of different morphological measures (area, boundary, curvature). We show that the combination of area and boundary data from coarse-grained structures obtained with the box-counting method reveals clear confidence limits and thus credible morphological data. This also holds for the Minkowski density method. It also reveals the confidence range. Its main drawback, the larger swing-in period at the lower cutoff compared to the box-counting method, is compensated by more details on the scaling behavior of area, boundary, and curvature. The sandbox method is less recommendable. It essentially delivers the same data as box-counting, but it is more susceptible to finite size effects at the lower cutoff. It is found that the domain morphology depends on the surface coverage of alkanes. The individual domains at low surface coverage have a fractal dimension of approximately 1.7, whereas at coverages well above 50% the scaling dimension is 2 with a large margin of uncertainty at approximately 50% coverage. This change in morphology is attributed to a crossover from a growth regime dominated by diffusion-limited aggregation of individual domains to a regime where the growth is increasingly affected by annealing and the interaction of solid growth fronts which approach each other and thus compete for the alkane supply. PMID:15667180

  16. Alkane reactions with photoactivated decatungstate in neutral and acid solution. Molecular orbital theory

    International Nuclear Information System (INIS)

    Using ASEO-MO calculations, charge-transfer photoexcitation of W10O324- abstracts H from alkanes to form H2W10O324- and increases O- hole center production, strengthening the OH bond at the anion surface to lower the activation energy. In neutral solution, resulting alkyl radicals bind weakly to the polyanions, but W10O324- yields carbocations. In acid solution, H2W10O322- will likely oxidize primary carbon and methyl radicals. 18 refs., 5 figs., 1 tab

  17. Magnetic field effect study of solvent hole deprotonation in x-irradiated liquid n-alkanes

    International Nuclear Information System (INIS)

    Complete text of publication follows. Solvent radical cations, or holes, are the key intermediates in many radiation chemical processes. Because of their short life span (ns to tens of ns), normal molecular ion mobility and the lack of specific optical spectra the holes of n-alkanes are difficult to study using conventional spectroscopic techniques. A suitable alternative is spin chemistry methods taking advantage of the hole being a partner of a spin--correlated radical ion pair. In this work stationary magnetic field effect including MARY spectroscopy was applied to study proton transfer from holes to alcohols in n-alkanes. Reactions with additives were registered as line broadening in experimental MARY spectra reflecting short time scale evolution of the pair. An extensive scan for n-alkanes from C6 to C16 and alcohols from MeOH to t-BuOH with careful provisions for solvent purity yielded diffusion-controlled rates of the pair decay for all alkane/alcohol combinations. Surprisingly, no correlation was found between the rate and the AE(PA) of the expected proton transfer reaction, extrapolated from gas phase data. One possible explanation is that the differences in sizes and charge distributions of the two cations can make a substantial (and hardly accountable) solvation contribution to the driving force of the reaction even in these non-polar solvents. Another option is that other reaction channels like interaction with the radical anion partner of the pair are possible. To clarify the matter normal magnetic effect reflecting the effective hyperfine coupling of the radical ions was employed. Providing radical anions with effective couplings significantly lower and higher than those of the solvent hole helped ascribe the observed magnetic field effects and MARY spectra. Substitution of the hole with a stable radical cation not prone to proton loss under these conditions showed that it is solvent hole that is attacked by the alcohol. The counter ion does not

  18. Synthesis, conformational and theoretical studies of 1,n-di(2-formyl-4-phenylazophenoxy)alkanes

    Science.gov (United States)

    Balachander, R.; Manimekalai, A.

    2016-01-01

    1,n-di(2-Formyl-4-phenylazophenoxy)alkanes 1 and 2 and 1,3-di(2-formyl-4-phenylazophenoxymethyl)benzene 3 were synthesis and characterized by FT-IR, UV-Vis, 1H, 13C NMR and mass spectral studies. The stable conformations of 1-3 were predicted theoretically and selected geometrical parameters were derived from optimized structures. The molecular parameters of HOMO-LUMO energies, polarizability, hyperpolarizability, natural bond orbital (NBO), atom in molecule (AIM) analysis and molecular electrostatic potential (MEP) surfaces were determined by the density functional theory (DFT) method and analysed.

  19. Selective C–H bond activation of alkanes by gas-phase metal ions

    Czech Academy of Sciences Publication Activity Database

    Roithová, J.; Schröder, Detlef

    2010-01-01

    Roč. 110, č. 2 (2010), s. 1170-1211. ISSN 0009-2665 R&D Projects: GA AV ČR KJB400550704; GA ČR GA203/08/1487 Grant ostatní: European Research Council(XE) AdG HORIZOMS Institutional research plan: CEZ:AV0Z40550506 Keywords : alkanes * C-H bond activation * density functional theory * mass spectrometry * matrix isolation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 33.033, year: 2010

  20. Isolation and Characterization of a Sulfate-Reducing Bacterium That Anaerobically Degrades Alkanes

    OpenAIRE

    So, Chi Ming; Young, L. Y.

    1999-01-01

    An alkane-degrading, sulfate-reducing bacterial strain, AK-01, was isolated from an estuarine sediment with a history of chronic petroleum contamination. The bacterium is a short, nonmotile, non-spore-forming, gram-negative rod. It is mesophilic and grows optimally at pH 6.9 to 7.0 and at an NaCl concentration of 1%. Formate, fatty acids (C4 to C16) and hydrogen were readily utilized as electron donors. Sulfate, sulfite, and thiosulfate were used as electron acceptors, but sulfur, nitrite, an...

  1. A QSPR STUDY OF NORMAL BOILING POINT OF ORGANIC COMPOUNDS (ALIPHATIC ALKANES USING MOLECULAR DESCRIPTORS

    Directory of Open Access Journals (Sweden)

    B. Souyei

    2013-12-01

    Full Text Available A quantitative structure–property relationship (QSPR study is carried out to develop correlations that relate the molecular structures of organic compounds (Aliphatic Alkanes to their normal boiling point (NBP and two correlations were proposed for constitutionals and connectivity indices Models. The correlations are simple in application with good accuracy, which provide an easy, direct and relatively accurate way to calculate NBP. Such calculation gives us a model that gives results in remarkable correlations with the descriptors of blokes constitutionals (CON, and connectivity indices (CI (R2 = 0.950, δ = 0.766 (R2 = 0.969, δ = 0.782 respectively.

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

    Science.gov (United States)

    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

  3. Isochoric thermal conductivity of solid n-alkanes: hexane C6H14

    International Nuclear Information System (INIS)

    The isochoric thermal conductivity of solid n-hexane C6H14 has been investigated on three samples of different density in the temperature interval from 100 K to the onset of melting. In all the cases the isochoric thermal conductivity varied following a dependence which is weaker than A is proportional to 1/T. The results obtained are compared with the thermal conductivities of other representatives of n-alkanes. The contributions of low-frequency phonons and 'diffuse modes' to the thermal conductivity are calculated.

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

    OpenAIRE

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

    2009-01-01

    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) al...

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

    OpenAIRE

    Mehboob, F.; Junca, H.; Schraa, G.; Stams, A.J.M.

    2009-01-01

    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) al...

  6. Study of Some Alkanes Thermodynamic Parameters Using New Liquid Crystals Containing Sulfur as Stationary Phases

    Directory of Open Access Journals (Sweden)

    Mebrouk Djedid

    2015-06-01

    Full Text Available Most of the synthesized compounds which have liquid crystalline character in their composition comprise aromatic molecules. Furthermore there are few jobs that replace this type of molecules by inhomogeneous molecules that have LC character. We will replace the aromatic rings by units of 1,3,4-oxadiazole and study the effects of these new components of the transition temperatures and the Thermodynamic characteristics of n- alkanes in these two LC's phases. have been investigated by inverse gas chromatography. The transition temperatures obtained by GC are in good agreement with those found by DSC. The results are interpreted in terms of parameters “b” and related thermodynamic quantities

  7. Structural identification of sedimentary C21 and C22 highly branched isoprenoid alkanes

    OpenAIRE

    Sinninghe Damsté, J.S.; Baas, M.; Geenevasen, J.A.J.; Kenig, F.

    2005-01-01

    C21 and C22 highly branched isoprenoid (HBI) alkanes occurring in high relative abundance in lagoonal sediments of Abu Dhabi have been unambiguously identified as 2,6,10-trimethyl-7-(3-methylpentyl)dodecane and 3,7,11-trimethyl-6- (3-methylpentyl)tridecane, respectively, using NMR spectroscopy. A second C21 HBI isomer is tentatively identified as 3,7,11-trimethyl-6-(3-methylbutyl)tridecane, on the basis of comparison of its mass spectral fragmentation with those of fully identified HBIs. The ...

  8. Effect of chain length on aggregation of n-alkanes in CCl3F matrices at 77 K. Further ESR evidence for the occurrence of hydrogen and/or proton transfer between higher alkanes and their cations

    International Nuclear Information System (INIS)

    After γ-irradiation of hexane and decane at low concentration in CCl3F at 77 K only the ESR spectrum of the corresponding radical cations is observed. At higher concentrations (from about 3 mol% hexane and 0.5 mol% decane), the spectra of alkyl radicals also appear. The signal intensity and relative contribution of these alkyl radicals to the observed ESR spectra increases with increasing alkane solute concentration. In contrast, alkane radical cations but no alkyl radicals are observed after irradiation of hexane and decane in CCl3CF3 and other matrices at concentrations where alkyl radicals are already quite prominent in CCl3F. This contrast is especially pronounced in the case of decane, the signal intensity and relative contribution of alkyl radicals in the ESR spectrum of irradiated CCl3F-decane systems being much higher than in irradiated CCl3F-hexane systems. Most of the alkane radical cations observed possess the extended structure, resulting in a triplet with substructure for hexane and a broad singlet for decane, but different conformers are also observed, viz. for hexane in CCl3CF3 and for decane in CCl3F. The results provide conclusive evidence for the occurrence of hydrogen and/or proton transfer between C6 (only weakly) and C10 (very pronounced) n-alkanes and their cations. They show further that in CCl3F at 77 K alkanes are present as small aggregates to which hole transfer still occurs efficiently and, in conjunction with other data, indicate that the extent of such aggregation increases with increasing chain length of the alkane solute. (Author)

  9. Alkane Activation Initiated by Hydride Transfer: Co-conversion of Propane and Methanol over H-ZSM-5 Zeolite.

    Science.gov (United States)

    Yu, Si-Min; Wu, Jian-Feng; Liu, Chong; Liu, Wei; Bai, Shi; Huang, Jun; Wang, Wei

    2015-06-15

    Co-conversion of alkane with another reactant over zeolite catalysts has emerged as a new approach to the long-standing challenge of alkane transformation. With the aid of solid-state NMR spectroscopy and GC-MS analysis, it was found that the co-conversion of propane and methanol can be readily initiated by hydride transfer at temperatures of ≥449 K over the acidic zeolite H-ZSM-5. The formation of (13)C-labeled methane and singly (13)C-labeled n-butanes in selective labeling experiments provided the first evidence for the initial hydride transfer from propane to surface methoxy intermediates. The results not only provide new insight into carbocation chemistry of solid acids, but also shed light on the low-temperature transformation of alkanes for industrial applications. PMID:25959356

  10. 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

    Science.gov (United States)

    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...

  11. Growth factor controls on the distribution and carbon isotope composition of n-alkanes in leaf wax

    Science.gov (United States)

    Jia, C.; Xie, S.; Huang, X.

    2012-12-01

    Cuticular wax plays pivotal physiological and ecological roles in the interactions between plants and the environments in which they grow. Plant-derived long-chain alkanes are more resistant to decay than other biochemical polymers. n-Alkane distributions (Carbon Preference Index (CPI) values and Average Chain Length (ACL) values) and carbon isotopic values are used widely in palaeoenvironmental reconstruction. However, there is little information available on how growth stages of the plant might influence the abundance of n-alkanes in the natural environment. In this study, we analyzed n-alkane distributions and carbon isotope data from two tree species (Cinnamomum camphora (L.) Presl. and Liquidambar formosana Hance) collected monthly from 2009 to 2011 in Nanwang Shan, Wuhan, Hubei Province. CPI values for n-alkanes from C. camphora remained stable in autumn and winter but fluctuated dramatically during spring and autumn each year. Positive correlations between CPI values and the relative content of (C27+C29) were observed in both sun and shade leaves of C. camphora from April to July. In L. formosana, CPI values decreased gradually from April to December. A similar trend was observed in all three years suggesting that growth stages rather than temperature or relative humidity affected the CPI values on a seasonal timescale. In the samples of L. formosana ACL values were negatively correlated with CPI values in the growing season (from April to July) and positively correlated with CPI values in the other seasons. The δ13C values of C29 and C31 n-alkanes displayed more negative carbon isotopic values in autumn and winter compared with leaves sampled at the start of the growing season from both trees. The δ13C values of C29 and C31 n-alkanes of L. formosana decreased from April to December. These results demonstrate the importance of elucidating the growing factors that influence the distribution and δ13C values of alkanes in modern leaves prior to using CPI

  12. Assessment of soil n-alkane δD and branched tetraether membrane lipid distributions as tools for paleoelevation reconstruction

    Directory of Open Access Journals (Sweden)

    J. S. Sinninghe Damsté

    2009-12-01

    Full Text Available δ18O values of pedogenic minerals forming from soil water are commonly used to reconstruct paleoelevation. To circumvent some of the disadvantages of this method, soil n-alkane δD values were recently proposed as a new tool to reconstruct elevation changes, after showing that soil n-alkane δD values track the altitude effect on precipitation δD variations (r2=0.73 along Mt. Gongga, China. To verify the suitability of soil n-alkane δD values as a paleoelevation proxy we measured the δD of soil n-alkanes along Mt. Kilimanjaro (Tanzania. At midslope, soil n-alkane δD values are possibly influenced by the present precipitation belt, causing D-depletion in precipitation, and hence in the soil n-alkanes. Consequently, soil n-alkane δD values do not linearly relate with altitude (r2=0.03, suggesting that, in this case, they can not serve as an unambiguous proxy to infer past elevation changes. In contrast, it was recently shown that the MBT/CBT temperature proxy, which is based on the distribution of branched glycerol dialkyl glycerol tetraether (GDGT membrane lipids, is linearly related with MAT, and thus altitude (r2=0.77, at Mt. Kilimanjaro. This suggests that this proxy may be more suitable for paleoelevation reconstruction for this region. However, application of the MBT/CBT proxy on the altitude gradient along Mt. Gongga showed that, although the MBT/CBT-derived temperature lapse rate (−5.9°C/1000 m resembles the measured temperature lapse rate (−6.0°C/1000 m, there is a relatively large degree of scatter (r2=0.55. Our results thus show that both proxies can be subject to relatively large uncertainties in their assessment of past elevation changes, but that a combination of the soil n-alkane δD and MBT/CBT proxies can likely result in a more reliable assessment of paleoelevation.

  13. Regioselective alkane oxygenation with H2O2 catalyzed by titanosilicalite TS-1

    OpenAIRE

    Shul’pin, Georgiy B.; Sooknoi, Tawan; Romakh, Vladimir B.; Süss-Fink, Georg; Shul’pina, Lidia S.

    2009-01-01

    Titanosilicalite TS-1 catalyses oxidation of light (methane, ethane, propane and n-butane) and normal higher (hexane, heptane, octane and nonane) alkanes to give the corresponding isomeric alcohols and ketones. The oxidation of higher alkanes proceeds in many cases with a unique regioselectivity. Thus, in the reaction with n-heptane the CH2 groups in position 3 exhibited a reactivity 2.5 times higher than those of the other methylene groups. This selectivity can be enhanced if hexan-3-ol is a...

  14. Predictive Local Composition Models for Solid/Liquid Equilibrium in n-Alkane Systems: Wilson Equation for Multicomponent Systems

    DEFF Research Database (Denmark)

    Coutinho, João A.P.; Stenby, Erling Halfdan

    1996-01-01

    The predictive local composition model is applied to multicomponent hydrocarbon systems with long-chain n-alkanes as solutes. The results show that it can successfully be extended to highorder systems and accurately predict the solid appearance temperature, also known as cloud point, in solutions...... of known composition using only binary information. The model can describe the experimentally well-known capacity of heavy alkanes to act as cloud-point depressants and explains it in terms of the nonideality of the solid solutions formed. There are good indications that no significant error is...

  15. Insertion of singlet chlorocarbenes across C-H bonds in alkanes: Evidence for two phase mechanism

    Indian Academy of Sciences (India)

    M Ramalingam; K Ramasami; P Venuvanalingam

    2007-09-01

    Transition states for the insertion reactions of singlet mono and dichlorocarbenes (1CHCl and 1CCl2) into C-H bonds of alkanes (methane, ethane, propane and -butane) have been investigated at MP2 and DFT levels with 6-31g ( , ) basis set. The of 1CHCl and 1CCl2 may interact with alkane’s filled fragment orbital of either or symmetry. So chlorocarbenes insertion reactions have been investigated for both (/) approaches. The approach has been adjudicated to be the minimum energy path over the approach both at the MP2 and DFT levels. Mulliken, NPA and ESP derived charge analyses have been carried out along the minimal energy reaction path using the IRC method for 1CHCl and 1CCl2 insertions into the primary and secondary C-H bonds of propane. The occurrence of TSs either in the electrophilic or nucleophilic phase has been identified through NBO charge analyses in addition to the net charge flow from alkane to the carbene moiety.

  16. (Liquid + liquid) extraction of methanol from alkanes using dialkylphosphate-based ionic liquids as solvents

    International Nuclear Information System (INIS)

    Highlights: • Several ILs were studied as solvents to extract methanol from alkanes. • LLE data for ternary systems were measured at T = 298.2 K and atmospheric pressure. • LLE data for ternary systems were successfully correlated by using the NRTL model. • Results of solute distribution ratio and selectivity were compared with literature. • The [MMIM][DMP] showed the best extraction effectiveness in the studied ILs. - Abstract: In this work, the feasibility of ionic liquids (ILs), 1,3-dimethylimidazolium dimethylphosphate ([MMIM][DMP]), 1-ethyl-3-methylimidazolium diethylphosphate ([EMIM][DEP]), and 1-butyl-3-methylimidazolium dibutylphosphate ([BMIM][DBP]), as solvents for the extraction of methanol from its mixtures with hexane and heptane was analyzed. The knowledge of (liquid + liquid) equilibria (LLE) of these mixtures is necessary for the design of the extraction separation process. Hence, the LLE data for the ternary systems, {methanol + hexane + ([MMIM][DMP], or [EMIM][DEP], or [BMIM][DBP])}, and {methanol + heptane + ([MMIM][DMP], or [EMIM][DEP], or [BMIM][DBP])}, were measured at T = 298.2 K and atmospheric pressure. The experimental results were correlated with the thermodynamic nonrandom two-liquid (NRTL) model. The solute distribution ratios of methanol and methanol/alkane selectivities, derived from the experimental LLE data, were calculated and analyzed to evaluate the capability of the studied ILs to accomplish the separation target. Meanwhile, these capabilities were also compared with that of other ILs obtained from the literature

  17. Ignition of alkane-rich FACE gasoline fuels and their surrogate mixtures

    KAUST Repository

    Sarathy, Mani

    2015-01-01

    Petroleum derived gasoline is the most used transportation fuel for light-duty vehicles. In order to better understand gasoline combustion, this study investigated the ignition propensity of two alkane-rich FACE (Fuels for Advanced Combustion Engines) gasoline test fuels and their corresponding PRF (primary reference fuel) blend in fundamental combustion experiments. Shock tube ignition delay times were measured in two separate facilities at pressures of 10, 20, and 40 bar, temperatures from 715 to 1500 K, and two equivalence ratios. Rapid compression machine ignition delay times were measured for fuel/air mixtures at pressures of 20 and 40 bar, temperatures from 632 to 745 K, and two equivalence ratios. Detailed hydrocarbon analysis was also performed on the FACE gasoline fuels, and the results were used to formulate multi-component gasoline surrogate mixtures. Detailed chemical kinetic modeling results are presented herein to provide insights into the relevance of utilizing PRF and multi-component surrogate mixtures to reproduce the ignition behavior of the alkane-rich FACE gasoline fuels. The two FACE gasoline fuels and their corresponding PRF mixture displayed similar ignition behavior at intermediate and high temperatures, but differences were observed at low temperatures. These trends were mimicked by corresponding surrogate mixture models, except for the amount of heat release in the first stage of a two-stage ignition events, when observed. © 2014 The Combustion Institute.

  18. Production of 14C-labeled rhamnolipid of n-alkane mixture

    International Nuclear Information System (INIS)

    This research was carried out to explore the possibility of the use of 14C-glucose by pseudomonas aeruginosa to produce 14C-rhamnolipid and its role in the bioremediation of n-alkanes mixture (n-C10, n-C14). In addition to show whether the bacterial cells can utilize the bio surfactant as a carbon source. The specific activity of 14C-rhamnolipid produced was 0.082 μCi/mmol indicating 1.12% yield of 14C-rhamnolipid from 14C-glucose on the basis of the recovery of radioactivity. Bacterial growth was increased in the growth medium containing 5.6 mmol rhamnolipid of a final specific activity 0,013 μCi/mmol (a mixture of 4.7 mmol non labeled + 0.9 mmol 14C-labeled rhamnolipid), such increase was due to the degradation of n-alkane (nC10, nC12 and n-C14). There was no detection for 14C-rhamnolipid inside the bacterial cells

  19. Translational and rotational motions of n-alkane molecules within the channels of urea inclusion compounds

    International Nuclear Information System (INIS)

    Incoherent quasielastic neutron scattering experiments were performed on a series of urea inclusion compounds n-CnH2n+2/urea with n=9.15. Using semi oriented samples, we were able to record the spectra in two geometries, i.e. with the Q momentum transfer vector parallel (Qparallel) and perpendicular (Qperpendicular) to the urea host tunnel axis. Reorientational and translational motions could therefore be investigated separately in both the low temperature (LT) and high temperature (HT) phases of the samples. The low frequency excitations observed in the LT phase and only in the Qparallel geometry could be assigned to the sliding mode of one sublattice (the n alkane guests) with respect to the other (the urea host). We have quantitatively analyzed the spectra by means of a model of damped oscillator and interpreted the results on the basis of the structural properties of these composite incommensurate systems. On the characteristic timescale of the experiments, reorientations of the n alkane chains are effective only in the HT phases of the compounds. (authors). 15 refs., 4 figs., 3 tabs

  20. Influence of alkane chain length on adsorption on an α-alumina surface by MD simulations

    International Nuclear Information System (INIS)

    Plasma surface techniques provide both an efficient and ecological tool for the functionalization of surfaces. Hence, a proper understanding of the plasma–surface interactions of precursors and radicals during the deposition process is of great importance. Especially during the initial deposition process, the deposition of molecules and fragments is difficult to investigate by experimental techniques and import insights can be obtained by molecular dynamics simulations. In this work, the reactive force field developed by the group of Kieffer at the University of Michigan was used to study the adsorption of single linear alkane chains on an α-alumina surface. The chain length was changed from 6 backbone carbon atoms to 16 carbon atoms, the deposition energy from 0.01 to 10 eV and the incidence angle from 0° to 60° with respect to the surface normal. Results show that the adsorption depends a lot on the ratio of deposition energy to alkane chain length and the incidence angle. More grazing incidence reduces the adsorption probability and a low ratio of energy to chain length increases it

  1. Alkane fluids confined and compressed by two smooth crystalline gold surfaces: Pure liquids and mixtures

    Science.gov (United States)

    Alvarez, Lina P. Merchan

    With the use of grand canonical molecular dynamics, we studied the slow compression(0.01m/s) of very thin liquid films made of equimolar mixtures of short and long alkane chains (hexane and hexadecane), and branched and unbranched alkanes (phytane and hexadecane). Besides comparing how these mixtures behave under constant speed compression, we will compare their properties with the behavior and structure of the pure systems undergoing the same type of slow compression. To understand the arrangement of the molecules inside the confinement, we present segmental and molecular density profiles, average length and orientation of the molecules inside well formed gaps. To observe the effects of the compression on the fluids, we present the number of confined molecules, the inlayer orientation, the solvation force and the inlayer diffusion coefficient, versus the thickness of the gap. We observe that pure hexadecane, although liquid at this temperature, starts presenting strong solid-like behavior when it is compressed to thicknesses under 30A, while pure hexane and pure phytane continue to behave liquid-like except at 13A when they show some weak solid-like features. When hexadecane is mixed with the short straight hexane, it remains liquid down to 28A at which point this mixture behaves solid-like with an enhanced alignment of the long molecules not seen in its pure form; but when hexade-cane is mixed with the branched phytane the system does not present the solid-like features seen when hexadecane is compressed pure.

  2. Molecular dynamics insight to phase transition in n-alkanes with carbon nanofillers

    International Nuclear Information System (INIS)

    The present work aims to investigate the phase transition, dispersion and diffusion behavior of nanocomposites of carbon nanotube (CNT) and straight chain alkanes. These materials are potential candidates for organic phase change materials(PCMs) and have attracted flurry of research recently. Accurate experimental evaluation of the mass, thermal and transport properties of such composites is both difficult as well as economically taxing. Additionally it is crucial to understand the factors that results in modification or enhancement of their characteristic at atomic or molecular level. Classical molecular dynamics approach has been extended to elucidate the same. Bulk atomistic models have been generated and subjected to rigorous multistage equilibration. To reaffirm the approach, both canonical and constant-temperature, constant- pressure ensembles were employed to simulate the models under consideration. Explicit determination of kinetic, potential, non-bond and total energy assisted in understanding the enhanced thermal and transport property of the nanocomposites from molecular point of view. Crucial parameters including mean square displacement and simulated self diffusion coefficient precisely define the balance of the thermodynamic and hydrodynamic interactions. Radial distribution function also reflected the density variation, strength and mobility of the nanocomposites. It is expected that CNT functionalization could improve the dispersion within n-alkane matrix. This would further ameliorate the mass and thermal properties of the composite. Additionally, the determined density was in good agreement with experimental data. Thus, molecular dynamics can be utilized as a high throughput technique for theoretical investigation of nanocomposites PCMs

  3. Influence of alkane chain length on adsorption on an α-alumina surface by MD simulations

    Energy Technology Data Exchange (ETDEWEB)

    Turgut, C. [Department of Science and Analysis of Materials (SAM), CRP-Gabriel Lippmann, L-4422 Belvaux (Luxembourg); Institut Jean Lamour (IJL) CNRS UMR 7198, Université de Lorraine, Faculté des Sciences et Technologies, BP 70239, F-54506 Vandoeuvre-les-Nancy Cedex (France); Pandiyan, S. [Department of Science and Analysis of Materials (SAM), CRP-Gabriel Lippmann, L-4422 Belvaux (Luxembourg); Mether, L. [Department of Physics, University of Helsinki, P.O. Box 43, FI-00014 (Finland); Belmahi, M. [Institut Jean Lamour (IJL) CNRS UMR 7198, Université de Lorraine, Faculté des Sciences et Technologies, BP 70239, F-54506 Vandoeuvre-les-Nancy Cedex (France); Nordlund, K. [Department of Physics, University of Helsinki, P.O. Box 43, FI-00014 (Finland); Philipp, P., E-mail: philipp@lippmann.lu [Department of Science and Analysis of Materials (SAM), CRP-Gabriel Lippmann, L-4422 Belvaux (Luxembourg)

    2015-06-01

    Plasma surface techniques provide both an efficient and ecological tool for the functionalization of surfaces. Hence, a proper understanding of the plasma–surface interactions of precursors and radicals during the deposition process is of great importance. Especially during the initial deposition process, the deposition of molecules and fragments is difficult to investigate by experimental techniques and import insights can be obtained by molecular dynamics simulations. In this work, the reactive force field developed by the group of Kieffer at the University of Michigan was used to study the adsorption of single linear alkane chains on an α-alumina surface. The chain length was changed from 6 backbone carbon atoms to 16 carbon atoms, the deposition energy from 0.01 to 10 eV and the incidence angle from 0° to 60° with respect to the surface normal. Results show that the adsorption depends a lot on the ratio of deposition energy to alkane chain length and the incidence angle. More grazing incidence reduces the adsorption probability and a low ratio of energy to chain length increases it.

  4. Possible room temperature superconductivity in conductors obtained by bringing alkanes into contact with a graphite surface

    Directory of Open Access Journals (Sweden)

    Yasushi Kawashima

    2013-05-01

    Full Text Available Electrical resistances of conductors obtained by bringing alkanes into contact with a graphite surface have been investigated at room temperatures. Ring current in a ring-shaped container into which n-octane-soaked thin graphite flakes were compressed did not decay for 50 days at room temperature. After two HOPG plates were immersed into n-heptane and n-octane at room temperature, changes in resistances of the two samples were measured by four terminal technique. The measurement showed that the resistances of these samples decrease to less than the smallest resistance that can be measured with a high resolution digital voltmeter (0.1μV. The observation of persistent currents in the ring-shaped container suggests that the HOPG plates immersed in n-heptane and n-octane really entered zero-resistance state at room temperature. These results suggest that room temperature superconductor may be obtained by bringing alkanes into contact with a graphite surface.

  5. Cyanobacterial Alkanes Modulate Photosynthetic Cyclic Electron Flow to Assist Growth under Cold Stress.

    Science.gov (United States)

    Berla, Bertram M; Saha, Rajib; Maranas, Costas D; Pakrasi, Himadri B

    2015-01-01

    All cyanobacterial membranes contain diesel-range C15-C19 hydrocarbons at concentrations similar to chlorophyll. Recently, two universal but mutually exclusive hydrocarbon production pathways in cyanobacteria were discovered. We engineered a mutant of Synechocystis sp. PCC 6803 that produces no alkanes, which grew poorly at low temperatures. We analyzed this defect by assessing the redox kinetics of PSI. The mutant exhibited enhanced cyclic electron flow (CEF), especially at low temperature. CEF raises the ATP:NADPH ratio from photosynthesis and balances reductant requirements of biosynthesis with maintaining the redox poise of the electron transport chain. We conducted in silico flux balance analysis and showed that growth rate reaches a distinct maximum for an intermediate value of CEF equivalent to recycling 1 electron in 4 from PSI to the plastoquinone pool. Based on this analysis, we conclude that the lack of membrane alkanes causes higher CEF, perhaps for maintenance of redox poise. In turn, increased CEF reduces growth by forcing the cell to use less energy-efficient pathways, lowering the quantum efficiency of photosynthesis. This study highlights the unique and universal role of medium-chain hydrocarbons in cyanobacterial thylakoid membranes: they regulate redox balance and reductant partitioning in these oxygenic photosynthetic cells under stress. PMID:26459862

  6. Molecular dynamics insight to phase transition in n-alkanes with carbon nanofillers

    Energy Technology Data Exchange (ETDEWEB)

    Rastogi, Monisha [School of Engineering, Indian Institute of Technology Mandi, Himachal Pradesh 175 001 (India); Vaish, Rahul, E-mail: rahul@iitmandi.ac.in [School of Engineering, Indian Institute of Technology Mandi, Himachal Pradesh 175 001 (India); Materials Research Centre, Indian Institute of Science, Bangalore 560 012 (India)

    2015-05-15

    The present work aims to investigate the phase transition, dispersion and diffusion behavior of nanocomposites of carbon nanotube (CNT) and straight chain alkanes. These materials are potential candidates for organic phase change materials(PCMs) and have attracted flurry of research recently. Accurate experimental evaluation of the mass, thermal and transport properties of such composites is both difficult as well as economically taxing. Additionally it is crucial to understand the factors that results in modification or enhancement of their characteristic at atomic or molecular level. Classical molecular dynamics approach has been extended to elucidate the same. Bulk atomistic models have been generated and subjected to rigorous multistage equilibration. To reaffirm the approach, both canonical and constant-temperature, constant- pressure ensembles were employed to simulate the models under consideration. Explicit determination of kinetic, potential, non-bond and total energy assisted in understanding the enhanced thermal and transport property of the nanocomposites from molecular point of view. Crucial parameters including mean square displacement and simulated self diffusion coefficient precisely define the balance of the thermodynamic and hydrodynamic interactions. Radial distribution function also reflected the density variation, strength and mobility of the nanocomposites. It is expected that CNT functionalization could improve the dispersion within n-alkane matrix. This would further ameliorate the mass and thermal properties of the composite. Additionally, the determined density was in good agreement with experimental data. Thus, molecular dynamics can be utilized as a high throughput technique for theoretical investigation of nanocomposites PCMs.

  7. Determination of molecular diffusion coefficient in n-alkane binary mixtures: empirical correlations.

    Science.gov (United States)

    De Mezquia, D Alonso; Bou-Ali, M Mounir; Larrañaga, M; Madariaga, J A; Santamaría, C

    2012-03-01

    In this work we have measured the molecular diffusion coefficient of the n-alkane binary series nC(i)-nC(6), nC(i)-nC(10), and nC(i)-nC(12) at 298 K and 1 atm and a mass fraction of 0.5 by using the so-called sliding symmetric tubes technique. The results show that the diffusion coefficient at this concentration is proportional to the inverse viscosity of the mixture. In addition, we have also measured the diffusion coefficient of the systems nC(12)-nC(6), nC(12)-nC(7), and nC(12)-nC(8) as a function of concentration. From the data obtained, it is shown that the diffusion coefficient of the n-alkane binary mixtures at any concentration can be calculated from the molecular weight of the components and the dynamic viscosity of the corresponding mixture at 50% mass fraction. PMID:22263833

  8. Branched aliphatic alkanes of shell bar section in Qarhan Lake, Qaidam Basin and their paleoclimate significance

    Institute of Scientific and Technical Information of China (English)

    ZHANG HuCai; CHANG FengQin; LI Bin; LEI GuoLiang; CHEN Yue; ZHANG WenXiang; NIU Jie; FAN HongFang; YANG MingSheng

    2007-01-01

    Biomarkers of paleolake deposits from Qarhan Salt Lake in Qaidam Basin, northwest China were systematically analyzed and the A-C series compounds of branched aliphatic alkanes with quaternary substituted carbon atom (BAQCs) were identified. The homologous distinguished three series, A-C,were identified as 5,5-diethylalkanes, 6,6-diethylalkanes and 5-butyl, 5-ethylalkanes series, and their relative abundance was A > B > C. Series A and C were characterized by odd carbon numbers, whereas series B was characterized by even carbon numbers. The high values of series A corresponded with the high values of series B and C. Therefore, it can be concluded that series A, B and C possess a similar biological origin. The abundance of series A was relatively Iow in the lower part of the section compared with that in the upper part, implying that these series originated from bacteria and/or algae more prevalent in fresh-mesohaline water, and such kinds of bacteria and/or algae are most likely to be thermophilous species. The A25/nC25 ratio differences in the section show that such branched aliphatic alkanes can be treated as one kind of environmental change proxy for paleolake evolution and may provide important information for the climate reconstruction of the Late Pleistocene.

  9. An Alkane-Soluble Dendrimer as Electron-Transport Layer in Polymer Light-Emitting Diodes.

    Science.gov (United States)

    Zhong, Zhiming; Zhao, Sen; Pei, Jian; Wang, Jian; Ying, Lei; Peng, Junbiao; Cao, Yong

    2016-08-10

    Polymer light-emitting diodes (PLEDs) have attracted broad interest due to their solution-processable properties. It is well-known that to achieve better performance, organic light-emitting diodes require multilayer device structures. However, it is difficult to realize multilayer device structures by solution processing for PLEDs. Because most semiconducting polymers have similar solubility in common organic solvents, such as toluene, xylene, chloroform, and chlorobenzene, the deposition of multilayers can cause layers to mix together and damage each layer. Herein, a novel semiorthogonal solubility relationship was developed and demonstrated. For the first time, an alkane-soluble dendrimer is utilized as the electron-transport layer (ETL) in PLEDs via a solution-based process. With the dendrimer ETL, the external quantum efficiency increases more than threefold. This improvement in the device performance is attributed to better exciton confinement, improved exciton energy transfer, and better charge carrier balance. The semiorthogonal solubility provided by alkane offers another process dimension in PLEDs. By combining them with water/alcohol-soluble polyelectrolytes, more exquisite multilayer devices can be fabricated to achieve high device performance, and new device structures can be designed and realized. PMID:27435357

  10. Nucleation, growth and habit modification of n-alkanes and homologous mixtures in the absence and presence of flow improving additives

    CERN Document Server

    Taggart, A M

    1996-01-01

    A detailed study has been performed on the nucleation, growth and habit modification of n-alkanes and homologous mixtures in the absence and presence of flow improving additives in an attempt to gain a clearer appreciation of the interaction mechanisms behind wax / additive crystallisation. Kinetic and structural assessment of melt phase n-alkanes illustrate the different crystallographic forms present within the homologous series. Studies demonstrate the alternating behaviour of the even and odd numbered homologues which converges as a function of increasing molecular weight. Greater crystal lattice stabilities were found for those n-alkanes which have an even carbon number and which crystallise into the triclinic crystal structure. Solid state phase behaviour of the n-alkanes was found to vary depending on the number and parity of n. Nucleation kinetic studies of n-alkanes and homologous mixtures from model diesel fuel solvents (dodecane, m-xylene, decalin, pristane and a dewaxed fuel) are assessed using tu...

  11. Graphic model for calculating the entropy of С11Н24 alkanes with allowance for multiple non-valence interactions through three atoms along the chain of a molecule

    Science.gov (United States)

    Nilov, D. Yu.; Smolyakov, V. M.

    2016-08-01

    A fourteen-constant graphic scheme is proposed for evaluating the thermodynamic properties of branched paraffin hydrocarbons. Absolute entropy S f, 298 gas of 159 alkanes, of which 157 alkanes have yet to be studied experimentally, are calculated using 105 experimental data S f, 298 K, gas for alkanes CН4-С32Н66.

  12. Shock tube measurements of the rate constants for seven large alkanes+OH

    KAUST Repository

    Badra, Jihad

    2015-01-01

    Reaction rate constants for seven large alkanes + hydroxyl (OH) radicals were measured behind reflected shock waves using OH laser absorption. The alkanes, n-hexane, 2-methyl-pentane, 3-methyl-pentane, 2,2-dimethyl-butane, 2,3-dimethyl-butane, 2-methyl-heptane, and 4-methyl-heptane, were selected to investigate the rates of site-specific H-abstraction by OH at secondary and tertiary carbons. Hydroxyl radicals were monitored using narrow-line-width ring-dye laser absorption of the R1(5) transition of the OH spectrum near 306.7 nm. The high sensitivity of the diagnostic enabled the use of low reactant concentrations and pseudo-first-order kinetics. Rate constants were measured at temperatures ranging from 880 K to 1440 K and pressures near 1.5 atm. High-temperature measurements of the rate constants for OH + n-hexane and OH + 2,2-dimethyl-butane are in agreement with earlier studies, and the rate constants of the five other alkanes with OH, we believe, are the first direct measurements at combustion temperatures. Using these measurements and the site-specific H-abstraction measurements of Sivaramakrishnan and Michael (2009) [1,2], general expressions for three secondary and two tertiary abstraction rates were determined as follows (the subscripts indicate the number of carbon atoms bonded to the next-nearest-neighbor carbon): S20=1.58×10-11exp(-1550K/T)cm3molecule-1s-1(887-1327K)S30=2.37×10-11exp(-1850K/T)cm3molecule-1s-1(887-1327K)S21=4.5×10-12exp(-793.7K/T)cm3molecule-1s-1(833-1440K)T100=2.85×10-11exp(-1138.3K/T)cm3molecule-1s-1(878-1375K)T101=7.16×10-12exp(-993K/T)cm3molecule-1s-1(883-1362K) © 2014 The Combustion Institute.

  13. Thermodynamic study of alkane-α,ω-diamines - evidence of odd-even pattern of sublimation properties

    Czech Academy of Sciences Publication Activity Database

    Fulem, Michal; Růžička, K.; Červinka, C.; Bazyleva, A.; Della Gatta, G.

    2014-01-01

    Roč. 371, Jun (2014), s. 93-105. ISSN 0378-3812 Institutional support: RVO:68378271 Keywords : alkane-diamines * odd–even effect * vapor pressure * sublimation and vaporization thermodynamic properties * statistical thermodynamic s Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.200, year: 2014

  14. Cooperative catalysis for the direct hydrodeoxygenation of vegetable oils into diesel-range alkanes over Pd/NbOPO4.

    Science.gov (United States)

    Xia, Qineng; Zhuang, Xiaojing; Li, Molly Meng-Jung; Peng, Yung-Kang; Liu, Guoliang; Wu, Tai-Sing; Soo, Yun-Liang; Gong, Xue-Qing; Wang, Yanqin; Tsang, Shik Chi Edman

    2016-04-14

    Near quantitative carbon yields of diesel-range alkanes were achieved from the hydrodeoxygenation of triglycerides over Pd/NbOPO4 under mild conditions with no catalyst deactivation: catalyst characterization and theoretical calculations suggest that the high hydrodeoxygenation activity originated from the synergistic effect of Pd and strong Lewis acidity on the unique structure of NbOPO4. PMID:26998532

  15. Cation effect of ammonium imide based ionic liquids in alcohols extraction from alcohol-alkane azeotropic mixtures

    International Nuclear Information System (INIS)

    Highlights: • Six ternary liquid+liquid equilibriums alkane + alcohol + IL were studied. • The influence of IL cation structure was evaluated. • The ethanol extraction ability from alkanes was determined for each IL. • Determination of solute distribution ratio and selectivity was required. • Experimental data correlation was realized by NRTL model. -- Abstract: During recent last years, outstanding properties of ionic liquids such as low melting point, large liquid range and negligible volatility have turned them into possible volatile organic solvents replacers to break alcohol-alkane azeotropic mixtures. On this basis, two ionic liquids, butyltrimethylammoniumbis(trifluoromethylsulfonyl)imide, [BTMA][NTf2], and tributylmethylammoniumbis(trifluoromethylsulfonyl)imide, [TBMA][NTf2], were studied through ternary liquid+liquid equilibrium (LLE) of {alkane(1) + alcohol (2) + IL(3)} at T = 298.15 K and atmospheric pressure in order to consider the effect of ionic liquid cation alkyl chain length on the extraction process. The ILs capability as azeotrope breakers was determined by the calculation of parameters such as solute distribution ratio, β, and selectivity, S and this capability was compared with other bis (trifluoromethylsulfonyl)imide based ionic liquids from literature. The consistency of tie-line data was ascertained by applying the Othmer–Tobias and Hand equations. Finally, the experimental LLE were correlated by the Non Random Two Liquid (NRTL) thermodynamic model

  16. The study on the primary processes of radiation chemistry in liquid alkanes by means of picosecond pulse radiolysis

    International Nuclear Information System (INIS)

    The primary processes of radiation chemistry in liquid alkanes were studied by using picosecond pulse radiolysis. Especially, the geminate ion recombination, the formation process of excited states and ion-molecular reaction of radical cations were directly observed and the primary processes were discussed. Also, future picosecond and femtosecond pulse radiolysis to elucidate the unsolved problem in the primary processes was discussed. (author)

  17. Use of cuticular wax alkanes to estimate digestibility and intake of cows as pasture with a view to estimating efficiency.

    Science.gov (United States)

    Determination of feed efficiency requires estimates of intake and digestibility of the diet, but they are difficult to measure on pasture. The objective of this research was to determine if plants cuticular alkanes were suitable as markers to estimate intake and diet digestibility of grazing cows wi...

  18. On-road emission rates of PAH and n-alkane compounds from heavy-duty diesel vehicles.

    Science.gov (United States)

    Shah, Sandip D; Ogunyoku, Temitope A; Miller, J Wayne; Cocker, David R

    2005-07-15

    This paper presents the quantification of the emission rates of PAH and n-alkane compounds from on-road emissions testing of nine heavy-duty diesel (HDD) vehicles tested using CE-CERT's Mobile Emissions Laboratory (MEL) over the California Air Resources Board (ARB) Four Phase Cycle. Per mile and per CO2 emission rates of PAHs and n-alkanes were highest for operation simulating congested traffic (Creep) and lowest for cruising conditions (Cruise). Significant differences were seen in emission rates over the different phases of the cycle. Creep phase fleet average emission rates (mg mi(-1)) of PAHs and n-alkanes were approximately an order of magnitude higher than Cruise phase. This finding indicates that models must account for mode of operation when performing emissions inventory estimates. Failure to account for mode of operation can potentially lead to significant over- and underpredictions of emissions inventories (up to 20 times), especially in small geographic regions with significant amounts of HDD congestion. Howeverthe PAH and n-alkane source profiles remained relatively constant for the different modes of operation. Variability of source profiles within the vehicle fleet exceeded the variability due to different operating modes. Analysis of the relative risk associated with the compounds indicated the importance of naphthalene as a significant contributor to the risk associated with diesel exhaust. This high relative risk is driven by the magnitude of the emission rate of naphthalene in comparison to other compounds. PMID:16082957

  19. Quantitative vapor-phase IR intensities and DFT computations to predict absolute IR spectra based on molecular structure: I. Alkanes

    Science.gov (United States)

    Williams, Stephen D.; Johnson, Timothy J.; Sharpe, Steven W.; Yavelak, Veronica; Oates, R. P.; Brauer, Carolyn S.

    2013-11-01

    Recently recorded quantitative IR spectra of a variety of gas-phase alkanes are shown to have integrated intensities in both the C3H stretching and C3H bending regions that depend linearly on the molecular size, i.e. the number of C3H bonds. This result is well predicted from CH4 to C15H32 by density functional theory (DFT) computations of IR spectra using Becke's three parameter functional (B3LYP/6-31+G(d,p)). Using the experimental data, a simple model predicting the absolute IR band intensities of alkanes based only on structural formula is proposed: For the C3H stretching band envelope centered near 2930 cm-1 this is given by (km/mol) CH_str=(34±1)×CH-(41±23) where CH is number of C3H bonds in the alkane. The linearity is explained in terms of coordinated motion of methylene groups rather than the summed intensities of autonomous -CH2-units. The effect of alkyl chain length on the intensity of a C3H bending mode is explored and interpreted in terms of conformer distribution. The relative intensity contribution of a methyl mode compared to the total C3H stretch intensity is shown to be linear in the number of methyl groups in the alkane, and can be used to predict quantitative spectra a priori based on structure alone.

  20. Effect of temperature on the adsorption of short alkanes in the zeolite ssz-13-adapting adsorption isotherms to microporous materials

    NARCIS (Netherlands)

    Jiang, Tao; Göltl, Florian; Bulo, Rosa E.; Sautet, Philippe

    2014-01-01

    Understanding the diffusion and adsorption of hydrocarbons in zeolites is a highly important topic in the field of catalysis in micro-and mesoporous materials. Especially, the properties of alkanes in zeolites have been studied extensively. A theoretical description of these processes is challenging

  1. Isolation of the alkane inducible cytochrome P450 (P450alk) gene from the yeast Candida tropicalis

    Science.gov (United States)

    The gene for the alkane-inducible cytochrome P450, P450alk, has been isolated from the yeast Candida tropicalis by immunoscreening a λgt11 library. Isolation of the gene has been identified on the basis of its inducibility and partial DNA sequence. Transcripts of this gene were i...

  2. Assessment of soil n-alkane δD and branched tetraether membrane lipid distributions as tools for paleoelevation reconstruction

    Directory of Open Access Journals (Sweden)

    J. S. Sinninghe Damsté

    2009-09-01

    Full Text Available δ18O values of pedogenic minerals forming from soil water are commonly used to reconstruct paleoelevation. To circumvent some of the disadvantages of this method, soil n-alkane δD values were recently proposed as a new tool to reconstruct elevation changes, after showing that soil n-alkane δD values track the altitude effect on precipitation δD variations (r2=0.73 along Mt. Gongga, China. To verify the suitability of soil n-alkane δD values as a paleoelevation proxy we measured the δD of soil n-alkanes along Mt. Kilimanjaro (Tanzania. At midslope, soil n-alkane δD values are highly influenced by the present precipitation belt, causing D-depletion. Consequently, soil n-alkane δD values do not linearly relate with altitude (r2=0.03, suggesting that they can not serve as an unambiguous proxy to infer past elevation changes. In contrast, it was recently shown that the MBT/CBT temperature proxy, which is based on the distribution of branched glycerol dialkyl glycerol tetraether (GDGT membrane lipids, is linearly related with MAT, and thus altitude (r2=0.77, at Mt. Kilimanjaro. This suggests that this proxy may be more suitable for paleoelevation reconstruction. However, application of the MBT/CBT proxy on the altitude gradient along Mt. Gongga showed that, although the MBT/CBT-derived temperature lapse rate (−5.9°C/1000 m resembles the measured temperature lapse rate (−6.0°C/1000 m, there is a relatively large degree of scatter (r2=0.55. Our results thus show that both proxies can be subject to relatively large uncertainties in their assessment of past elevation changes, but that a combination of the soil n-alkane δD and MBT/CBT proxies can likely result in a more reliable assessment of paleoelevation.

  3. Production of liquid alkanes by controlling reactivity of sorbitol hydrogenation with a Ni/HZSM-5 catalyst in water

    International Nuclear Information System (INIS)

    Graphical abstract: MCM-41-modified Ni/HZSM-5 catalyst was developed by impregnation method with high catalytic performance for sorbitol hydrogenation in water. Appropriate amount of MCM-41 addition can distinctly promote the improvement in the surface structure and modulation of acidic sites of the catalyst. The scission of C–O bond in the sorbitol molecule into liquid alkanes was easily carried out on the catalyst containing more Lewis acidic sites. - Highlights: • Ni/HZSM-5 promoted with MCM-41 is active for sorbitol hydrogenation to liquid alkanes. • Lewis acidic sites of Ni/HZSM-5 can be modulated by pure silica MCM-41. • MCM-41 added can distinctly decrease carbon deposition on the catalyst surface. - Abstract: Liquid fuels derived from renewable biomass are of great importance on the potential substitution for diminishing fossil fuels. The conversion of sorbitol (a product of biomass-derived glucose hydrogenation) into liquid alkanes such as pentane and hexane over the Ni/HZSM-5 catalysts with or without MCM-41 addition was investigated in the presence of hydrogen in water medium. The production distribution of sorbitol hydrogenation can be controlled by adjusting the acidity of the catalyst. The scission of C–C bond in the sorbitol molecule into light C1–C4 alkanes was mainly carried out over Ni/HZSM-5 containing strong Brønsted acid sites, while C–O bond scission into heavier alkanes was dominated over the catalysts added by MCM-41 containing weak Lewis acid sites. The sorbitol conversion and total liquid alkanes selectivity were found to be 67.1% and 98.7% over 2%Ni/HZSM-5 modified by 40 wt% of MCM-41, whereas the corresponding value was 40% and 35.6% over 2%Ni/HZSM-5 in the absence of MCM-41. The effect of MCM-41 on the structure, acidity, and reducibility of Ni/HZSM-5 was investigated by using XRD, Py-IR, IR, and H2-TPR. Meanwhile, the resistance of carbon deposition over the catalyst modified by MCM-41 was studied by using TG

  4. Degradability of n-alkanes during ex situ natural bioremediation of soil contaminated by heavy residual fuel oil (mazut

    Directory of Open Access Journals (Sweden)

    Ali Ramadan Mohamed Muftah

    2013-01-01

    Full Text Available It is well known that during biodegradation of oil in natural geological conditions, or oil pollutants in the environment, a degradation of hydrocarbons occurs according to the well defined sequence. For example, the major changes during the degradation process of n-alkanes occur in the second, slight and third, moderate level (on the biodegradation scale from 1 to 10. According to previous research, in the fourth, heavy level, when intensive changes of phenanthrene and its methyl isomers begin, n-alkanes have already been completely removed. In this paper, the ex situ natural bioremediation (unstimulated bioremediation, without addition of biomass, nutrient substances and biosurfactant of soil contaminated with heavy residual fuel oil (mazut was conducted during the period of 6 months. Low abundance of n-alkanes in the fraction of total saturated hydrocarbons in the initial sample (identification was possible only after concentration by urea adduction technique showed that the investigated oil pollutant was at the boundary between the third and the fourth biodegradation level. During the experiment, an intense degradation of phenanthrene and its methyl-, dimethyl-and trimethyl-isomers was not followed by the removal of the remaining n-alkanes. The abundance of n-alkanes remained at the initial low level, even at end of the experiment when the pollutant reached one of the highest biodegradation levels. These results showed that the unstimulated biodegradation of some hydrocarbons, despite of their high biodegradability, do not proceed completely to the end, even at final degradation stages. In the condition of the reduced availability of some hydrocarbons, microorganisms tend to opt for less biodegradable but more accessible hydrocarbons.

  5. Progressive degradation of crude oil n-alkanes coupled to methane production under mesophilic and thermophilic conditions.

    Directory of Open Access Journals (Sweden)

    Lei Cheng

    Full Text Available 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.

  6. Viscosity and Liquid Density of Asymmetric n-Alkane Mixtures: Measurement and Modelling

    DEFF Research Database (Denmark)

    Queimada, António J.; Marrucho, Isabel M.; Coutinho, João A.P.;

    2005-01-01

    Viscosity and liquid density Measurements were performed, at atmospheric pressure. in pure and mixed n-decane. n-eicosane, n-docosane, and n-tetracosane from 293.15 K (or above the melting point) up to 343.15 K. The viscosity was determined with a rolling ball viscometer and liquid densities with a...... vibrating U-tube densimeter. Pure component results agreed, oil average, with literature values within 0.2% for liquid density and 3% for viscosity. The measured data were used to evaluate the performance of two models for their predictions: the friction theory coupled with the Peng-Robinson equation of...... state and a corresponding states model recently proposed for surface tension, viscosity, vapor pressure, and liquid densities of the series of n-alkanes. Advantages and shortcoming of these models are discussed....

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

    Science.gov (United States)

    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.

  8. Analyzing solubility of acid gas and light alkanes in triethylene glycol

    Institute of Scientific and Technical Information of China (English)

    Alireza Bahadori; Had B.Vuthaluru; Saeid Mokhatab

    2008-01-01

    Physical solvents such as ethylene glycol (EG), diethylene glycol (DEG), and triethylene glycol (TEG) are commonly used in wet gas dehydration processes with TEG being the most popular due to ease of regeneration and low solvent losses. Unfortunately, TEG absorbs significantly more hydrocarbons and acid gases than EG or DEG. Quantifying this amount of absorption is therefore critical in order to minimize hydrocarbon losses or to optimize hydrocarbon recovery depending on the objective of the process. In this article, a new correlation that fully covers the operating ranges of TEG dehydration units is developed in order to determine the solubility of light alkanes and acid gases in TEG solvent. The influence of several parameters on hydrocarbon and acid gas solubility including temperature, pressure, and solvent content is also examined.

  9. Kinetics and mechanism of alkane hydroperoxidation with tert-butyl hydroperoxide catalysed by a vanadate anion.

    Science.gov (United States)

    Shul'pin, Georgiy B; Kozlov, Yuriy N

    2003-07-01

    tert-Butyl hydroperoxide oxidizes alkanes in acetonitrile at 60 degrees C if the soluble vanadium(v) salt, n-Bu4NVO3, is used as a catalyst. Alkyl hydroperoxides are formed as main products which decompose during the course of the reaction to produce the more stable corresponding alcohols and ketones. Turnover numbers (ie. numbers of moles of products per one mole of a catalyst) attained 250. The kinetics and selectivity of the reaction have been studied. The mechanism proposed involves the formation of a complex between the V(V) species and t-BuOOH (K5 was estimated to be 5 dm3 mol(-1)) followed by decomposition of this complex (k6 = 0.2 s(-1)). The generated V(IV) species reacts with another t-BuOOH molecule to produce an active t-BuO* radical which attacks the hydrocarbon. PMID:12945701

  10. A Quantitative Structure Property Relationship for Prediction of Flash Point of Alkanes Using Molecular Connectivity Indices

    Institute of Scientific and Technical Information of China (English)

    Morteza Atabati; Reza Emamalizadeh

    2013-01-01

    Many structure-property/activity studies use graph theoretical indices,which are based on the topological properties of a molecule viewed as a graph.Since topological indices can be derived directly from the molecular structure without any experimental effort,they provide a simple and straightforward method for property prediction.In this work the flash point of alkanes was modeled by a set of molecular connectivity indices (x),modified molecular connectivity indices (mx(1)h) and valance molecular connectivity indices (mxv),with mxv calculated using the hydrogen perturbation.A stepwise Multiple Linear Regression (MLR) method was used to select the best indices.The predicted flash points are in good agreement with the experimental data,with the average absolute deviation 4.3 K.

  11. Quantum chemical and conventional TST calculations of rate constants for the OH + alkane reaction

    International Nuclear Information System (INIS)

    Reactions of OH with methane, ethane, propane, i-butane, and n-butane have been modeled using ab initio (MP2) and hybrid DFT (BHandHLYP) methods, and the 6-311G(d,p) basis set. Furthermore, single-point calculations at the CCSD(T) level were carried out at the optimized geometries. The rate constants have been calculated using the conventional transition-state theory (CTST). Arrhenius equations are proposed in the temperature range of 250-650 K. Hindered Internal Rotation partition functions calculations were explicitly carried out and included in the total partition functions. These corrections showed to be relevant in the determination of the pre-exponential parameters, although not so important as in the NO3 + alkane reactions [G. Bravo-Perez, J.R. Alvarez-Idaboy, A. Cruz-Torres, M.E. Ruiz, J. Phys. Chem. A 106 (2002) 4645]. The explicit participation of the tunnel effect has been taken into account. The calculated rate coefficients provide a very good agreement with the experimental data. The best agreement for the overall alkane + OH reactions seemed to occur when the BHandHLYP geometries and partition functions are used. For propane and i-butane, in addition to the respective secondary and tertiary H-abstraction channels, the primary one has been considered. These pathways are confirmed to be significant in spite of the large differences in activation energies between primary and secondary or primary and tertiary channels, respectively of propane and i-butane reactions and should not be disregarded

  12. Insect attachment on crystalline bioinspired wax surfaces formed by alkanes of varying chain lengths

    Directory of Open Access Journals (Sweden)

    Elena Gorb

    2014-07-01

    Full Text Available The impeding effect of plant surfaces covered with three-dimensional wax on attachment and locomotion of insects has been shown previously in numerous experimental studies. The aim of this study was to examine the effect of different parameters of crystalline wax coverage on insect attachment. We performed traction experiments with the beetle Coccinella septempunctata and pull-off force measurements with artificial adhesive systems (tacky polydimethylsiloxane semi-spheres on bioinspired wax surfaces formed by four alkanes of varying chain lengths (C36H74, C40H82, C44H90, and C50H102. All these highly hydrophobic coatings were composed of crystals having similar morphologies but differing in size and distribution/density, and exhibited different surface roughness. The crystal size (length and thickness decreased with an increase of the chain length of the alkanes that formed these surfaces, whereas the density of the wax coverage, as well as the surface roughness, showed an opposite relationship. Traction tests demonstrated a significant, up to 30 fold, reduction of insect attachment forces on the wax surfaces when compared with the reference glass sample. Attachment of the beetles to the wax substrates probably relied solely on the performance of adhesive pads. We found no influence of the wax coatings on the subsequent attachment ability of beetles. The obtained data are explained by the reduction of the real contact between the setal tips of the insect adhesive pads and the wax surfaces due to the micro- and nanoscopic roughness introduced by wax crystals. Experiments with polydimethylsiloxane semi-spheres showed much higher forces on wax samples when compared to insect attachment forces measured on these surfaces. We explain these results by the differences in material properties between polydimethylsiloxane probes and tenent setae of C. septempunctata beetles. Among wax surfaces, force experiments showed stronger insect attachment and higher

  13. Hydrogen isotopic characteristics and their genetic relationships for individual n-alkanes in plants and sediments from Zoigê marsh sedimentary environment

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    To understand internal relations of their hydrogen isotopic compositions in typical marsh environment, we, using GC-IRMS analytical technique, measured the hydrogen isotopes of individual n-alkanes in the herbaceous plant, woody plant leaf, and sediments from Zoigê marsh in China. The results show significant differences in the hydrogen isotopic compositions of n-alkanes among the different kinds of plants and the different species in the same kind. δD values of n-alkanes in the herbaceous plants (from -254‰ to -184‰) are lighter than those in woody plant leaf ( from -195‰ to -142‰ ), and the hydrogen isotopic compositions of n-alkanes in K. tibetica P. are lighter than P. pratensis L. The mean δD values of n-alkanes in the sediments from Zoigê marsh reflect that they were derived from herbaceous plants, which is consistent with the peat samples being composed mainly of herbaceous plant remnants. The significant differences in hydrogen isotopic compositions of n-alkanes among the sedimentary samples are caused possibly by environment factors and the difference in input quantity of different herbaceous plants. A certain negative correlation exists between the δ13C and δD values of n-alkanes in the samples, and plant types can be distinguished using the cross plot of δD vs. δ13C values of n-alkanes in the plants. These data and recognitions provide scientific basis for hydrogen isotopic applied research of individual n-alkanes.

  14. n-alkane distribution coupled with organic carbon isotope composition in the shell bar section, Qarhan paleolake, Qaidam basin, NE Tibetan Plateau

    Institute of Scientific and Technical Information of China (English)

    Yang PU; Hucai ZHANG; Guoliang LEI; Fengqin CHANG; Mingsheng YANG; Xianyu HUANG

    2009-01-01

    Lipids extracted from lacustrine deposits in the paleolake Qarhan of the Qaidam basin in the northeastern Tibetan Plateau were determined by conventional gas chromatography-mass spectrometry. Several series of biomarkers were identified, mainly including n-alkanes, n-alkan-2-ones, n-alkanoic acids, branched alkanes, triter-penoids and steroids, indicative of various biogenic contributions. On the basis of cluster analysis, the n-C15, n-C17, n-C19 alkanes were proposed to be derived from algae and/or photosynthetic bacteria, the n-C21 n-C23, n-C25 homologues from aquatic plants, and the n-C29, n-C31 homologues from vascular plants. In contrast, the n-C27 alkane is not categorized in the n-C29 and n-C31 group of alkanes, probably due to more complex origins including both aquatic and vascular plants, and/or differential biodegradation. Stratigraphically, layers-2, 4 and 5 were found to show a close relationship in n-alkane distribution, associated with a positive shift in carbon isotope composition of bulk organic matter (δ13Corg), inferring a cold/dry period. Layers-1 and 6 were clustered together in association with a negative δ13Corg excursion, probably indicating a relatively warm/humid climate. The potential coupling between the n-alkane distributions and δ13Corg, suggests a consequence of vegetation change in response to climate change, with the late MIS3 being shown to be unstable, thought to be the climatic optimum in the Tibetan Plateau. Our results suggest that the cluster analysis used in this study probably provides an effective and authentic method to investigate the n-alkane distribution in paleolake sediments.

  15. Possible algal origin of long chain odd n-alkanes in immature sediments as revealed by distributions and carbon isotope ratios

    OpenAIRE

    Lichtfouse, Eric; Derenne., Sylvie; Mariotti, André; Largeau, Claude

    1994-01-01

    A Pliocene oil shale (Pula, Hungary), a C3 plant Triticum aestivum and a C4 plant Zea mays were compared using isotopic composition of bulk organic matter, along with distributions and individual carbon isotope ratios of n-alkanes from organic extracts. The microalga Botryococcus braunii (A race) was thus shown to be the main source of the predominant 27, 29 and 31 n-alkanes of Pula sediment Therefore, the dominance of odd carbon-numbered n-alkanes in the range C25–35 in extracts from immatur...

  16. Molecular, 13C, and 14C evidence for the allochthonous and ancient origin of C16-C18 n-alkanes in modern soils

    OpenAIRE

    Lichtfouse, Eric; Bardoux, Gérard; Mariotti, André; Balesdent, Jérôme; C. Ballentine, Donna; A. Macko, Stephen

    1997-01-01

    International audience The heterogeneous isotopic composition of C3 and C4 plants can be used to to follow the fate of plant carbon into soil organic molecules. Thus, after 23 years of cropping of maize (C4) on a soil which was previously under C3 vegetation, C25 C33 soil n-alkanes are 13C-enriched up to 9‰ relatively to the initial C3 soil, reflecting the input of 13C-enriched n-alkanes from maize waxes. In sharp contrast, C16-C18 soil n alkanes do not show any significant 13C/12C variati...

  17. Development of bioreporter assays for the detection of bioavailability of long chain alkanes based on the marine bacterium Alcanivorax borkumensis strain SK2

    OpenAIRE

    Kumari, Rekha; Tecon, Robin; Beggah, Siham; Rutler, Rebecca; Arey, J. Samuel; van der Meer, Jan Roelof

    2011-01-01

    Long-chain alkanes are a major component of crude oil and therefore potentially good indicators of hydrocarbon spills. Here we present a set of new bacterial bioreporters and assays that allow to detect long-chain alkanes. These reporters are based on the regulatory protein AlkS and the alkB1 promoter from Alcanivorax borkumensis SK2, a widespread alkane degrader in marine habitats. Escherichia coli cells with the reporter construct reacted strongly to octane in short-term (6 h) aqueous suspe...

  18. A Detailed Chemical Kinetic Reaction Mechanism for n-Alkane Hydrocarbons from n-Octane to n-Hexadecane

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Herbinet, O; Silke, E J; Curran, H J

    2007-09-25

    Detailed chemical kinetic reaction mechanisms have been developed to describe the pyrolysis and oxidation of the n-alkanes, including n-octane (n-C{sub 8}H{sub 18}), n-nonane (n-C{sub 9}H{sub 20}), n-decane (n-C{sub 10}H{sub 22}), n-undecane (n-C{sub 11}H{sub 24}), n-dodecane (n-C{sub 12}H{sub 26}), n-tridecane (n-C{sub 13}H{sub 28}), n-tetradecane (n-C{sub 14}H{sub 30}), n-pentadecane (n-C{sub 15}H{sub 32}), and n-hexadecane (n-C{sub 16}H{sub 34}). These mechanisms include both high temperature and low temperature reaction pathways. The mechanisms are based on previous mechanisms for n-heptane, using the same reaction class mechanism construction developed initially for n-heptane. Individual reaction class rules are as simple as possible in order to focus on the parallelism between all of the n-alkane fuels included in the mechanisms, and there is an intent to develop these mechanisms further in the future to incorporate greater levels of accuracy and predictive capability. Several of these areas for improvement are identified and explained in detail. These mechanisms are validated through comparisons between computed and experimental data from as many different sources as possible. In addition, numerical experiments are carried out to examine features of n-alkane combustion in which the detailed mechanisms can be used to compare processes in all of the n-alkane fuels. The mechanisms for all of these n-alkanes are presented as a single detailed mechanism, which can be edited to produce efficient mechanisms for any of the n-alkanes included, and the entire mechanism, with supporting thermochemical and transport data, together with an explanatory glossary explaining notations and structural details, will be available on our web page when the paper is accepted for publication.

  19. n-alkanes as indicators of natural and anthropogenic organic matter sources in the Siak River and its estuary, E Sumatra, Indonesia.

    Science.gov (United States)

    Liebezeit, Gerd; Wöstmann, Ralf

    2009-09-01

    Along the Siak River and its estuary a total of 100 sediment and 57 plant samples were taken for the analysis of n-alkanes from 2003 to 2005. Sediment n-alkanes exhibit in the majority of samples a pronounced odd over even predominance with maxima at C29 and C31 indicative of a plant origin. Plant n-alkanes analysed have chain lengths up to C39. These compounds are also present in the river sediments. In some plants the Carbon Preference Index (CPI) has extremely low values normally only found in petroleum-contaminated samples. A distinction between vegetation- and petroleum-derived n-alkanes is therefore only possible by a combination of CPI and and the absence/presence of a prominent unresolved complex mixture. Based on these criteria only a limited number of the 100 sediments analysed exhibit clear indications of a petroleum contamination. PMID:19448964

  20. Molecular sieve isolation technique for use in stable carbon isotope analysis of individual long-chain n-alkanes in crude oil

    International Nuclear Information System (INIS)

    An isolation procedure of microgram amounts of long-chain n-alkanes from crude oil using molecular sieve was examined for its applicability to stable carbon isotope analysis by gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The procedure examined is as follows: molecular sieve (type 5A, 200 mg) in 1 ml of isooctane solvent are mixed with a saturated hydrocarbon fraction extracted from an appropriate amount (approx. 20 mg) of crude oil and stayed at room temperatures for more than 3 hours. Long-chain n-alkanes are isolated by extraction with n-hexane after dissolution of the resulting molecular sieve with 47% hydrofluoric acid solution. The recoveries were 90±6% for C15-C34 n-alkanes when their total amounts applied do not exceed 1.4 mg. No effect of the isolation procedure on carbon isotope ratios of n-alkanes was observed. (author)

  1. Evidence from carbon isotope measurements for biological origins of individual longchain n-alkanes in sediments from the Nansha Sea, China

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Carbon isotopes are measured for individual long-chain n-alkanes in sediments from the Nansha Sea. The features of carbon isotopic compositions of individual n-alkanes and their origins are studied. The results show that the long-chain n-aikanes have a light carbon isotopic composition and a genetic feature of mixing sources, and low-latitude higher plants and microbes are considered to be their main end member sources. Based on the abundances and carbon isotopic compositions of individual n-alkanes, the fractional contributions of the two end member sources to individual n-aikanes are quantitatively calculated by using a mixing model. The obtained data indicate that the fractional contributions of the two biological sources are different in the three samples. A trend is that the contribution of microbes increases with the depth. These results provide the theory basis and quantitatively studied method for carbon isotopic applied research of individual n-alkanes.

  2. Re-assessing the role of plant community change and climate in the PETM n-alkane record

    Science.gov (United States)

    Bush, R. T.; Baczynski, A. A.; McInerney, F. A.; Chen, D.

    2012-12-01

    The terrestrial leaf wax n-alkane record of the Paleocene-Eocene Thermal Maximum (PETM) in the Bighorn Basin, Wyoming, shows large excursions in both carbon isotope (δ13C) values and n-alkane average chain length (ACL). At the onset of the PETM, ACL values increase from ~28.5 to ~30.1 while the negative carbon isotope excursion (CIE) is 4-6‰ in magnitude and larger than δ13C records from other materials. It has been hypothesized previously that both the ACL excursion and the large magnitude of the CIE were caused by a concurrent turnover in the local flora from a mixed conifer/angiosperm community before the PETM to a different suite of angiosperm species during the PETM. Here, we present the results of a meta-analysis of data (>2000 data from 89 sources, both published and unpublished) on n-alkane amounts and chain length distributions in modern plants from around the world. We applied the data in two sets of comparisons: 1) within and among plant groups such as herbs and graminoids, and 2) between plants and climate, using reported collection locations for outdoor plants and climate values generated via GIS extraction of WorldClim modeled data. We show that angiosperms, as group, produce more n-alkanes than do gymnosperms by 1-2 orders of magnitude, and this means that the gymnosperm contribution to a mixed soil n-alkane pool would be negligible, even in an ecosystem where gymnosperms dominated (i.e. the pre/post-PETM ecosystems). The modern plant data also demonstrate that turnover of the plant community during the PETM, even among only the angiosperm species, is likely not the source of the observed ACL excursion. First, we constructed "representative" groups of PETM and pre/post-PETM communities using living relative species at the Chicago Botanic Garden and find no significant difference in chain length distributions between the two groups. Second and moreover, the modern plant data reveal that n-alkane chain length distributions are tremendously variable

  3. How large are post-CCSD(T) contributions to the total atomization energies of medium-sized alkanes?

    Science.gov (United States)

    Karton, Amir

    2016-02-01

    The CCSD(T) method is often considered as the gold standard in quantum chemistry for single-reference systems. Using W4 and W4lite theories, we calculate post-CCSD(T) contributions to the total atomization energies (TAEs) of n-alkanes and show that they reach up to 0.65 kcal/mol for n-hexane. Furthermore, we find that post-CCSD(T) contributions increase linearly with the size of the n-alkane, indicating that they will reach ∼1 kcal/mol for n-decane (C10H22) and ∼2 kcal/mol for n-icosane (C20H42). These results are significant since today CCSD(T)/CBS-type methods are being applied to hydrocarbons of increasing size and are assumed to give TAEs with chemical accuracy for these systems.

  4. Occurrence of diverse alkane hydroxylase alkB genes in indigenous oil-degrading bacteria of Baltic Sea surface water.

    Science.gov (United States)

    Viggor, Signe; Jõesaar, Merike; Vedler, Eve; Kiiker, Riinu; Pärnpuu, Liis; Heinaru, Ain

    2015-12-30

    Formation of specific oil degrading bacterial communities in diesel fuel, crude oil, heptane and hexadecane supplemented microcosms of the Baltic Sea surface water samples was revealed. The 475 sequences from constructed alkane hydroxylase alkB gene clone libraries were grouped into 30 OPFs. The two largest groups were most similar to Pedobacter sp. (245 from 475) and Limnobacter sp. (112 from 475) alkB gene sequences. From 56 alkane-degrading bacterial strains 41 belonged to the Pseudomonas spp. and 8 to the Rhodococcus spp. having redundant alkB genes. Together 68 alkB gene sequences were identified. These genes grouped into 20 OPFs, half of them being specific only to the isolated strains. Altogether 543 diverse alkB genes were characterized in the brackish Baltic Sea water; some of them representing novel lineages having very low sequence identities with corresponding genes of the reference strains. PMID:26541986

  5. Thermodynamics of mixtures containing amines: XIII. Application of the ERAS model to cyclic amine + alkane mixtures

    Energy Technology Data Exchange (ETDEWEB)

    González, Juan Antonio, E-mail: jagl@termo.uva.es; Sanz, Luis Felipe; García De La Fuente, Isaías; Cobos, José Carlos

    2013-12-10

    Graphical abstract: - Highlights: • Primary or secondary cyclic amine + alkane mixtures are investigated using ERAS. • ERAS parameters are given. Relatively high X{sub AB} values remark the importance of physical interactions. • ERAS parameters are consistent with those of primary or secondary (linear or aromatic) amines. • H{sub m}{sup E}, V{sub m}{sup E}, and C{sub pm}{sup E} data reveal the existence of physical interactions and structural effects. • ERAS correctly describes H{sub m}{sup E}, V{sub m}{sup E}, C{sub pm}{sup E}, G{sub m}{sup E} and the enthalpy of vaporization of pure amines. - Abstract: Primary or secondary cyclic amine + alkane mixtures have been investigated in the framework of the ERAS (Extended Real Associated Solution) model. The corresponding ERAS parameters are reported. All the amines considered have the same equilibrium constant (K{sub A} = 0.75). Cyclopropylamine, cyclopentylamine, cyclohexylamine and pyrrolidine are characterized by the same enthalpy of self-association (Δh{sub A}{sup *}=−15 kJ mol{sup −1}). Piperidine and hexamethyleneimine show a less negative Δh{sub A}{sup *} value (−13 kJ mol{sup −1}). Experimental data on excess enthalpies, H{sub m}{sup E}, volumes, V{sub m}{sup E}, and isobaric heat capacities, C{sub pm}{sup E}, reveal the existence of physical interactions and structural effects in the studied solutions. The latter lead to values of self-association of pure amines, Δv{sub A}{sup *}, which may depend on the solvent in systems with a given amine. Although the model overestimates the Δh{sub A}{sup *} values, the relatively high values of the physical parameters X{sub AB} remark the importance of physical interactions. ERAS describes correctly the excess functions H{sub m}{sup E}, V{sub m}{sup E}, C{sub pm}{sup E} and G{sub m}{sup E} (molar Gibbs energy), and the enthalpy of vaporization of pure amines. Nevertheless, discrepancies with experimental data are found for the concentration

  6. Charge transport through dicarboxylic-acid-terminated alkanes bound to graphene-gold nanogap electrodes

    Science.gov (United States)

    Liu, Longlong; Zhang, Qian; Tao, Shuhui; Zhao, Cezhou; Almutib, Eman; Al-Galiby, Qusiy; Bailey, Steven W. D.; Grace, Iain; Lambert, Colin J.; Du, Jun; Yang, Li

    2016-07-01

    Graphene-based electrodes are attractive for single-molecule electronics due to their high stability and conductivity and reduced screening compared with metals. In this paper, we use the STM-based matrix isolation I(s) method to measure the performance of graphene in single-molecule junctions with one graphene electrode and one gold electrode. By measuring the length dependence of the electrical conductance of dicarboxylic-acid-terminated alkanes, we find that the transport is consistent with phase-coherent tunneling, but with an attenuation factor of βN = 0.69 per methyl unit, which is lower than the value measured for Au-molecule-Au junctions. Comparison with density-functional-theory calculations of electron transport through graphene-molecule-Au junctions and Au-molecule-Au junctions reveals that this difference is due to the difference in Fermi energies of the two types of junction, relative to the frontier orbitals of the molecules. For most molecules, their electrical conductance in graphene-molecule-Au junctions is higher than that in Au-molecule-Au junctions, which suggests that graphene offers superior electrode performance, when utilizing carboxylic acid anchor groups.Graphene-based electrodes are attractive for single-molecule electronics due to their high stability and conductivity and reduced screening compared with metals. In this paper, we use the STM-based matrix isolation I(s) method to measure the performance of graphene in single-molecule junctions with one graphene electrode and one gold electrode. By measuring the length dependence of the electrical conductance of dicarboxylic-acid-terminated alkanes, we find that the transport is consistent with phase-coherent tunneling, but with an attenuation factor of βN = 0.69 per methyl unit, which is lower than the value measured for Au-molecule-Au junctions. Comparison with density-functional-theory calculations of electron transport through graphene-molecule-Au junctions and Au

  7. Particulate PAHs and n-alkanes in the air over Southern and Eastern Mediterranean Sea.

    Science.gov (United States)

    Romagnoli, Paola; Balducci, Catia; Perilli, Mattia; Perreca, Erica; Cecinato, Angelo

    2016-09-01

    Particulate polycyclic aromatic hydrocarbons, n-alkanes and polar organic compounds were investigated in the marine atmosphere of Southern and Eastern Mediterranean Sea, in the frame of the scientific cruise of Urania ship between 27 July and 11 August 2013. The PM10 fraction of aerosol to which most organic substances are associated, were collected daily; contemporarily, gaseous regulated toxicants (ozone, nitrogen oxides and carbon oxide) and carbonyls were recorded. Samplings were carried out in front of Palermo and Messina, respectively the start and end harbors, and along the cruise, both in movement (transects, N = 14) and at stops (N = 11). Total PAHs ranged from 0.06 ng/m(3) up to 1.8 ng/m(3), with the maximums observed close to harbors. Unlike total concentrations that were in general comparable, the percent composition of PAHs was distinct for harbors, transects and stops, which allowed to draw insights about the pollution sources impact. Concentrations of n-alkanes (C18-C35) ranging from 6.7 to 43 ng/m(3) were quantified. The carbonyls evaluation revealed relatively high concentrations of formaldehyde (∼4-24 μg/m(3)) and acetone (∼5-35 μg/m(3)) near harbors, and of acrolein (up to 12 μg/m(3)) offshore, while benzaldehyde was quite independent of the site type (≈0.5 μg/m(3)). Nicotine and caffeine were detected, at different extents (0.0-2.2 ng/m(3) and 0.01-0.17 ng/m(3), respectively), in ca. 70% and 100% of samples. Alkyl phthalates ranged from 2.7 to 67 ng/m(3) and showed variable percentages in the samples. Finally, traces of N,N-diethyl-meta-toluene amide (up to 0.4 ng/m(3)) were found at all sites. PMID:27341155

  8. Direct hydrodeoxygenation of cellulose and xylan to lower alkanes on ruthenium catalysts in subcritical water

    International Nuclear Information System (INIS)

    Nano particles of Ru, Rh, Pd, Ir, Pt, and Au, protected by polyvinyl pyrrolidone (PVP), were applied to the hydrodeoxygenation of cellulose and xylan in water and 5 MPa H2 at 543 K. The distributions of products generated from cellulose and xylan were roughly similar to each other under the present reaction conditions, and therefore, the former was intensively studied. The Ru-PVP catalyst afforded mainly methane and lower alkanes, rather than producing water soluble organic compounds, such as diols and alcohols, that were formed with the use of the other catalysts. The changes in the product distributions with reaction temperature and time indicated that the reaction consisted of two consecutive reactions: cellulose or xylan → water soluble compounds → hydrogenolysis. The first transformation was promoted in subcritical water, and the second step was catalyzed by the Ru catalyst. The Ru catalyst that was supported on CeO2, γ-Al2O3, or activated carbon yielded a similar product distribution to that on Ru-PVP; however, the loading of Ru on TiO2, ZrO2, SiO2–Al2O3, or SiO2 resulted in the increment of diols. After the reaction a small portion of the CeO2 and most of the SiO2–Al2O3 and SiO2 were dissolved in water, and a portion of the Al2O3 was transformed to boehmite AlO(OH) from the γ-alumina. Little change in the catalytic activity however was observed upon the reuse of Ru/Al2O3 in the second run. Highlights: •One-path hydrodeoxygenation of cellulose and xylan to methane and lower alkanes was studied. •Ru-PVP catalysts gave the best yields among Ru-, Rh-, Pd-, Ir-, Pt-, and Au-PVP. •The reaction pathways were cellulose → water soluble compounds → hydrogenolysis. •The catalytic activity of Ru was greatly dependent on the supports

  9. Metabolic phenotyping of the cyanobacterium Synechocystis 6803 engineered for production of alkanes and free fatty acids

    International Nuclear Information System (INIS)

    Highlights: ► Synechocystis 6803 was engineered for enhanced photosynthetic conversion of CO2 to alkanes. ► Synechocystis 6803 was engineered for accumulation of free fatty acids. ► Single-cell metabolic phenotyping was performed using SR-FTIR spectromicroscopy. ► Multivariate analysis of SR-FTIR data revealed biochemical shifts in engineered cells. ► SR-FTIR spectromicroscopy provides a high-throughput tool for screening engineered cells. -- Abstract: We demonstrate a simple high-throughput single-cell approach that exploits the ultrahigh brightness and non-invasive nature of synchrotron infrared beam to characterize strains of the cyanobacterium Synechocystis 6803 (S. 6803) constructed with altered metabolic traits affecting the acyl-CoA pool. Their metabolic responses to the modified traits were phenotyped by single-cell synchrotron radiation Fourier transform infrared (SR-FTIR) spectromicroscopy and multivariate analysis. SR-FTIR difference spectra and cluster vector plots segregated the strains as phenotypic populations based on signals in the hydrocarbon and biomolecular fingerprint regions, although each population incorporated a stochastic distribution of cells with different metabolic properties. All engineered strains exhibited an increase in FTIR features attributed to functional groups in hydrocarbon, fatty acid (FA), and/or FA ester chains, and a decrease in polysaccharide features. The metabolic signatures obtained by SR-FTIR were consistent with detailed qualitative and quantitative metabolic information provided in GC/MS/NMR data. A strain with extra copies of the FAR and FAD genes, encoding, respectively, the fatty acyl-ACP reductase and fatty aldehyde decarbonylase enzymes in the alkane biosynthesis pathway, showed up to a fivefold increase in the intracellular levels of heptadecane, a threefold increase in 9-heptadecene, and a significant increase in secreted 16:0 and 18:0 free FAs (FFAs). Inactivation of the AAS gene, encoding acyl

  10. Quantifying sources of methane and light alkanes in the Los Angeles Basin, California

    Science.gov (United States)

    Peischl, Jeff; Ryerson, Thomas; Atlas, Elliot; Blake, Donald; Brioude, Jerome; Daube, Bruce; de Gouw, Joost; Frost, Gregory; Gentner, Drew; Gilman, Jessica; Goldstein, Allen; Harley, Robert; Holloway, John; Kuster, William; Santoni, Gregory; Trainer, Michael; Wofsy, Steven; Parrish, David

    2013-04-01

    We use ambient measurements to apportion the relative contributions of different source sectors to the methane (CH4) emissions budget of a U.S. megacity. This approach uses ambient measurements of methane and C2-C5 alkanes (ethane through pentanes) and includes source composition information to distinguish between methane emitted from landfills and feedlots, wastewater treatment plants, tailpipe emissions, leaks of dry natural gas in pipelines and/or local seeps, and leaks of locally produced (unprocessed) natural gas. Source composition information can be taken from existing tabulations or developed by direct sampling of emissions using a mobile platform. By including C2-C5 alkane information, a linear combination of these source signatures can be found to match the observed atmospheric enhancement ratios to determine relative emissions strengths. We apply this technique to apportion CH4 emissions in Los Angeles, CA (L.A.) using data from the CalNex field project in 2010. Our analysis of L.A. atmospheric data shows the two largest CH4 sources in the city are emissions of gas from pipelines and/or from geologic seeps (47%), and emissions from landfills (40%). Local oil and gas production is a relatively minor source of CH4, contributing 8% of total CH4 emissions in L.A. Absolute CH4 emissions rates are derived by multiplying the observed CH4/CO enhancement ratio by State of California inventory values for carbon monoxide (CO) emissions in Los Angeles. Apportioning this total suggests that emissions from the combined natural and anthropogenic gas sources account for the differences between top-down and bottom-up CH4 estimates previously published for Los Angeles. Further, total CH4 emission attributed in our analysis to local gas extraction represents 17% of local production. While a derived leak rate of 17% of local production may seem unrealistically high, it is qualitatively consistent with the 12% reported in a recent state inventory survey of the L.A. oil and

  11. Comparison of Mechanisms of Alkane Metabolism under Sulfate-Reducing Conditions among Two Bacterial Isolates and a Bacterial Consortium

    OpenAIRE

    Callaghan, Amy V.; Gieg, Lisa M.; Kropp, Kevin G.; Suflita, Joseph M.; Young, Lily Y.

    2006-01-01

    Recent studies have demonstrated that fumarate addition and carboxylation are two possible mechanisms of anaerobic alkane degradation. In the present study, we surveyed metabolites formed during growth on hexadecane by the sulfate-reducing isolates AK-01 and Hxd3 and by a mixed sulfate-reducing consortium. The cultures were incubated with either protonated or fully deuterated hexadecane; the sulfate-reducing consortium was also incubated with [1,2-13C2]hexadecane. All cultures were extracted,...

  12. Determination of n-alkanes contamination in soil samples by micro gas chromatography functionalized by multi-walled carbon nanotubes.

    Science.gov (United States)

    Li, Yubo; Zhang, Runzhou; Wang, Tao; Wang, Yonghuan; Xu, Tianbai; Li, Lingfeng; Zhao, Weijun; Dong, Shurong; Wang, Xiaozhi; Luo, Jikui

    2016-09-01

    A new method for separation of 11 n-alkanes: octane, o-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentdecne, n-hexadecath, heptadecane, n-octadecane in soil samples was developed. Kuderna-Danish (K.D.) concentrator enrichment prior to ultrasonic extraction and the silicone chromatography column purification and with gas chromatography flame ionization detection (GC-FID) could be used for n-alkanes determination. The micro channels of open tubular column were fabricated onto a silicon wafer to replace the quartz capillary chromatographic column. The column structure and analysis parameters that affected the column separation were investigated and optimized. Under optimal conditions, the extract reagent was centrifuged and collected. A silicone chromatography column and a K.D. concentrator were used for further clean-up and enrichment. Using this method, the limits of detection (LOD) and limits of quantification (LOQ) were obtained in the range of 0.03-0.15 and 0.1-0.5 mg kg(-1) in soil samples, respectively. The relative standard deviation (RSD) was under 12%. The optimized procedure that presented good analytical performance (with recoveries ranging from 56.5% to 89.2%), was successfully applied to determine n-alkane content in farmland soil samples adjacent to a highway. The results showed that the MWCNTs-functionalized column is capable of separating the alkane contaminations with high resolution in about 3 min, which is much shorter than that of GC-MS and other conventional analytical methods, demonstrating its great potential for rapid analysis. PMID:27262105

  13. Enzymes involved in the anaerobic oxidation of n-alkanes: from methane to long-chain paraffins

    OpenAIRE

    Amy V. Callaghan

    2013-01-01

    Anaerobic microorganisms play key roles in the biogeochemical cycling of methane and non-methane alkanes. To date, there appear to be at least three proposed mechanisms of anaerobic methane oxidation (AOM). The first pathway is mediated by consortia of archaeal anaerobic methane oxidizers and sulfate-reducing bacteria via ‘reverse methanogenesis’ and is catalyzed by a homologue of methyl-coenzyme M reductase. The second pathway is also mediated by anaerobic methane oxidizers and sulfate-red...

  14. Hydrocarbon activation by gas-phase lanthanide cations: interaction of Pr+, Eu+, and Gd+ with small alkanes, cycloalkanes, and alkenes

    International Nuclear Information System (INIS)

    The authors describe ion beam studies of the interaction of gas-phase lanthanide ions, praseodymium (Pr+), europium (Eu+), and gadolinium (Gd+), with small alkanes, cycloalkanes, alkenes, and several oxygen-containing compounds. Only Gd+ is seen to activate C-H and C-C bonds of alkanes. The ground state electronic configuration of Gd+ (4f75d16s1) is different from those of Pr+ (4f36s1) and Eu+ (4f76s1), leading to the conclusion that the f electrons play little part in the metal ion reactivity. Gd+ can be thought of as having two valence electrons, and indeed it reacts similarly to Sc+ and the other group 3 metal ions Y+ and La+, yielding products corresponding to elimination of hydrogen, alkanes, and alkenes. The elimination of neutral alkenes in the reaction of Gd+ with alkanes results in the formation of metal dialkyl or hydrido-alkyl complexes. This finding leads to estimates for the sum of two Gd+ σ bond dissociation energies of between 110 and 130 kcal/mol. Gd+ and Pr+ react readily with alkenes, yielding mostly dehydrogenation products along with smaller amounts of C-C bond cleavage products. Reactions of Gd+ and Pr+ with oxygen-containing species such as nitric oxide, formaldehyde, acetaldehyde, and acetone yield primarily the metal oxide ions and provide a lower limit for D(M+-O) of 179 kcal/mol, in good agreement with literature values of D(Pr+-O) = 188.4 +/- 5.2 kcal/mol and D(Gd+-0) = 181.0 +/- 4.4 kcal/mol. In keeping with the strong metal σ bonds, Gd+ is also seen to readily react with formaldehyde to eliminate CO and form GdH2+

  15. Study of Liquid Alkanes Production from Biomass-Derived Carbohydrates by Aldol-Condensation and Hydrogenation Processes

    Directory of Open Access Journals (Sweden)

    Navadol Laosiripojana

    2010-10-01

    Full Text Available This research aims to synthesis liquid alkanes from biomass-derived hydroxyl methyl furfural (HMF and furfural by aldol-condensation and hydrogenation processes over several catalysts i.e. TiO2, TiO2-ZrO2, Pd/Al2O3 and Pd/CeO2. It was found that the catalysts make significant impact on the selectivity and yield of alkanes product. It is noted that Pd/Al2O3 provided the highest alkane yield and selectivity. The aldol-condensation and hydrogenation of HMF over Pd/Al2O3 provide high C12 selectivity whereas the aldol-condensation and hydrogenation of furfural over Pd/Al2O3 provide high C8 selectivity. The effects of reaction temperature, reaction pressure and reaction time were then studied. The effect of inlet furfural to acetone molar ratio was also determined. It was also found that the optimized conditions to maximize the yield of alkane production from the aldol-condensation/hydrogenation of HMF and furfural are (i at 53oC and 24 hr for aldol-condenstation of HMF, (ii 80oC and 24 hr for aldol-condenstation of furfural, and (iii 120oC for 6 hr with HMF to acetone molar ratio of 3:1 and furfural to acetone molar ratio of 4:1 in the presence of Pd/Al2O3 (calcined at 500oC for hydrogenation reaction.

  16. Role of Sn in the Regeneration of Pt/γ-Al2O3 Light Alkane Dehydrogenation Catalysts

    OpenAIRE

    Pham, Hien N.; Sattler, Jesper J. H. B.; Weckhuysen, Bert M.; Datye, Abhaya K.

    2016-01-01

    Alumina-supported Pt is one of the major industrial catalysts for light alkane dehydrogenation. This catalyst loses activity during reaction, with coke formation often considered as the reason for deactivation. As we show in this study, the amount and nature of carbon deposits do not directly correlate with the loss of activity. Rather, it is the transformation of subnanometer Pt species into larger Pt nanoparticles that appears to be responsible for the loss of catalytic activity. Surprising...

  17. Thermodynamic modeling of saturated liquid compositions and densities for asymmetric binary systems composed of carbon dioxide, alkanes and alkanols

    International Nuclear Information System (INIS)

    Highlights: • Phase behavior of the binary systems containing largely different components. • Equation of state modeling of binary polar and non-polar systems by utilizing different mixing rules. • Three different mixing rules (one-parameter, two-parameters and Wong–Sandler) coupled with Peng–Robinson equation of state. • Two-parameter mixing rule shows promoting results compared to one-parameter mixing rule. • Wong–Sandler mixing rule is unable to predict saturated liquid densities with sufficient accuracy. - Abstract: The present study mainly focuses on the phase behavior modeling of asymmetric binary mixtures. Capability of different mixing rules and volume shift in the prediction of solubility and saturated liquid density has been investigated. Different binary systems of (alkane + alkanol), (alkane + alkane), (carbon dioxide + alkanol), and (carbon dioxide + alkane) are considered. The composition and the density of saturated liquid phase at equilibrium condition are the properties of interest. Considering composition and saturated liquid density of different binary systems, three main objectives are investigated. First, three different mixing rules (one-parameter, two parameters and Wong–Sandler) coupled with Peng–Robinson equation of state were used to predict the equilibrium properties. The Wong–Sandler mixing rule was utilized with the non-random two-liquid (NRTL) model. Binary interaction coefficients and NRTL model parameters were optimized using the Levenberg–Marquardt algorithm. Second, to improve the density prediction, the volume translation technique was applied. Finally, Two different approaches were considered to tune the equation of state; regression of experimental equilibrium compositions and densities separately and spontaneously. The modeling results show that there is no superior mixing rule which can predict the equilibrium properties for different systems. Two-parameter and Wong–Sandler mixing rule show promoting

  18. Molecular simulation of adsorption and separation of mixtures of short linear alkanes in pillared layered materials at ambient temperature.

    Science.gov (United States)

    Li, Wen-Zhuo; Liu, Zi-Yang; Che, Yu-Liang; Zhang, Dan

    2007-08-15

    Grand canonical Monte Carlo and configurational-bias Monte Carlo techniques are carried out to simulate the adsorption of ternary and quaternary mixtures of short linear alkanes, involving methane, ethane, propane, and n-butane, in pillared layered materials at ambient temperature, T=300 K. In the simulation, a pillared layered pore is modeled by a uniform distribution of pillars between two layered walls built by making two separate talc lamellas parallel each other with a given size of interlayer distance. The interaction between fluid molecules and two layered walls is measured by storing potentials calculated in advance at a series of grid points. The interaction between fluid molecules and pillars is also calculated by a site-to-site method. The potential model proposed in this work is proved to be effective because of the simulation result being good agreement with the experimental data for the adsorption of nitrogen at 77 K. Then, the adsorption isotherms of mixtures of short linear alkanes in pillared layered pores with three different porosities psi=0.98, 0.93 and 0.85, and three pore widths H=1.02, 1.70 and 2.38 nm at 300 K are obtained by taking advantage of the model. The simulation results tell us that the longer chain component is preferentially adsorbed at low pressures, and its adsorption increases and then decreases as the pressure increases while the shorter chain component is still adsorbed at high pressures. Moreover, the sorption selectivity of pillared layered materials for the longest chain component in alkane mixtures increases as the mole fraction of methane in the gas phase increases. The selectivity of pillared layered materials for the longest chain component in alkane mixtures also increases as the pore width decreases and the porosity increases. PMID:17482203

  19. Significance of medium chainn-alkanes as accompanying compounds in hemipteran defensive secretions: An investigation based on the defensive secretion ofCoridius janus.

    Science.gov (United States)

    Gunawardena, N E; Herath, H M

    1991-12-01

    A mixture oftrans-2-hexenal;n-tridecane (60:40, w/w), the natural combination present in the defensive secretion ofCoridius janus (Hemiptera; Pentatomidae) was shown by comparison with similar aldehyde mixtures having longer and shorter chainn-alkanes, to be the optimal combination as a fumigant and a repellent against three test insect species,Anoplolepis longipes, Sitotroga cerealella, andCulex quinquefasciatus. Toxic values obtained for the three insects, respectively: 1/LC50, 1.72, 4.54, and 6.66 ppm while repellencies were 63%, 50%, and 69%. This study revealed that amongt-2-hexenal:n-alkane combinations those with medium carbon chains,viz C-11 and C-12, also possessed high toxicities and repellencies comparable to that of the natural combination while those with shorter and longern-alkanes possessed lower activity. Toxicities and repellencies ofn-alkane series were only moderate to low showing highest toxic values forn-tridecane at 1/LC50, 0.39, 2.32, and 2.32 ppm and repellencies at 31%, 30%, and 32% for the three test insects, respectively. This series, nevertheless, showed similar variation, medium length chains, C-11, C-12, and C-13 showing comparatively higher activity than other alkanes of shorter and longer chains. This study also revealed that the fumigant property of both alkane and aldehyde are of equal importance while repellency is heavily dependent on the aldehyde. PMID:24258638

  20. Saccharomyces cerevisiae SHSY detoxifies petroleum n-alkanes by an induced CYP52A58 and an enhanced order in cell surface hydrophobicity.

    Science.gov (United States)

    Hanano, Abdulsamie; Shaban, Mouhnad; Almousally, Ibrahem; Al-Ktaifani, Mahmoud

    2015-09-01

    Environmental hydrocarbon contamination has a serious hazard to human health. Alkanes, the major component of hydrocarbons, can be consumed by various species of yeast. We previously identified a new strain SHSY of Saccharomyces cerevisiae with a remarkable ability to utilize the petroleum crude-oil (PCO) in aqueous solution. The current study demonstrated that the n-alkanes-assimilation activity of S. cerevisiae SHSY was related to an induced microsomal protein of 59 kDa approximately. The identified ORF encoded a protein of 517 amino acids and shared 93% sequence identity with an alkane-inducible hydroxylase CYP52A53 isolated from Scheffersomyces stipitis CBS. It was therefore referred as CYP52A58. The catalytic activity of the recombinant CYP52A58 was confirmed by the hydroxylation of n-alkanes, it showed an optimal mono-terminal hydroxylation activity toward n-hexadecane. Moreover, the ability of the yeast to use n-alkanes was accompanied with an increasing level in cell wall mannoproteins. Two differential protein bands were detected in the mannoproteins extracted from PCO-grown yeast. In parallel, a significant increase in the fatty acids content with a high degree of unsaturation was subsequently detected in the PCO-grown yeast. This study characterizes a safe and potential microorganism to remove n-alkanes from the aquatic environment. PMID:25434275

  1. Distributions of C22-C30 even-carbon-number n-alkanes in Ocean Anoxic Event 1 samples from the Basque-Cantabrian Basin.

    Science.gov (United States)

    Chaler, R; Dorronsoro, C; Grimalt, J O; Agirrezabala, L M; Fernández-Mendiola, P A; García-Mondejar, J; Gómez-Pérez, I; López-Horgue, M

    2005-05-01

    The Ocean Anoxic Event 1 (OAE-1) in central sites of the Basque-Cantabrian Basin exhibits very reducing depositional conditions of sedimentation. These sedimentation events have left a distinct mixture of hydrocarbons that are represented by C22-C30 n-alkanes with a predominance of the even-carbon-number homologues, high relative proportions of squalane and C16-C24 n-alkylcyclopentanes predominated by n-undecyl-, n-tridecyl- and n-pentadecylcyclopentane. Other minor compounds encompass a series of C18-C21 n-alkylcyclohexanes and C18-C24 dimethyl n-alkylcyclohexanes maximized by the even-carbon-number homologues as well as iso- and anteiso-alkanes. This unusual distribution of n-alkanes in this environment provides a new case for comparison with previously reported hypersaline and phosphorite sedimentary deposits where the occurrence of similar n-alkane distributions was reported. In the present case, these major n-alkanes and squalane are indicative of transformation under strong reducing conditions. In contrast, the occurrence of the alkylcyclopentanes, irrespective of the presence of even-carbon-number n-alkanes or squalane, suggests that reductive cyclization of fatty acids is less dependent on strong reducing conditions. PMID:15776255

  2. Involvement of acyl-CoA synthetase genes in n-alkane assimilation and fatty acid utilization in yeast Yarrowia lipolytica.

    Science.gov (United States)

    Tenagy; Park, Jun Seok; Iwama, Ryo; Kobayashi, Satoshi; Ohta, Akinori; Horiuchi, Hiroyuki; Fukuda, Ryouichi

    2015-06-01

    Here, we investigated the roles of YAL1 (FAA1) and FAT1 encoding acyl-CoA synthetases (ACSs) and three additional orthologs of ACS genes FAT2-FAT4 of the yeast Yarrowia lipolytica in the assimilation or utilization of n-alkanes and fatty acids. ACS deletion mutants were generated to characterize their function. The FAT1 deletion mutant exhibited decreased growth on n-alkanes of 10-18 carbons, whereas the FAA1 mutant showed growth reduction on n-alkane of 16 carbons. However, FAT2-FAT4 deletion mutants did not show any growth defects, suggesting that FAT1 and FAA1 are involved in the activation of fatty acids produced during the metabolism of n-alkanes. In contrast, deletions of FAA1 and FAT1-FAT4 conferred no defect in growth on fatty acids. The wild-type strain grew in the presence of cerulenin, an inhibitor of fatty acid synthesis, by utilizing exogenously added fatty acid or fatty acid derived from n-alkane when oleic acid or n-alkane of 18 carbons was supplemented. However, the FAA1 deletion mutant did not grow, indicating a critical role for FAA1 in the utilization of fatty acids. Fluorescent microscopic observation and biochemical analyses suggested that Fat1p is present in the peroxisome and Faa1p is localized in the cytosol and to membranes. PMID:26019148

  3. Quaternary (liquid + liquid) equilibrium data for the extraction of toluene from alkanes using the ionic liquid [EMim][MSO4

    International Nuclear Information System (INIS)

    Highlights: • EMim[MSO4] was proposed as solvent for the extraction of toluene from alkanes. • The quaternary system {heptane + cyclohexane + toluene + [EMim][MSO4]} was evaluated. • The extraction of toluene would be facilitated in the presence of one alkane. • Experimental LLE data were successfully correlated with the NRTL model. - Abstract: (Liquid + liquid) equilibrium (LLE) studies for the extraction of aromatics from alkanes present in the petroleum fractions are important to develop theoretical/semiempirical (liquid + liquid) equilibrium models, which are used in the design of extraction processes. In this work, the ionic liquid 1-ethyl-3-methylimidazolium methylsulfate, [EMim][MSO4], was evaluated as potential solvent for the separation of toluene from heptane and cyclohexane. The LLE data for the quaternary system {heptane (1) + cyclohexane (2) + toluene (3) + [EMim][MSO4] (4)} were experimentally determined at T = 298.15 K and atmospheric pressure. Moreover, the LLE data for the ternary systems {heptane or cyclohexane (1) + toluene (2) + [EMim][MSO4] (3)} were also determined. Solute distribution ratios and selectivities were calculated and analysed in order to evaluate the capability of the ionic liquid to accomplish the separation target. A comparison between the solute distribution ratios and selectivities for the quaternary and the ternary systems was also made. Finally, the experimental tie-line data were correlated with the NRTL model

  4. Acidic ionic liquids for n-alkane isomerization in a liquid-liquid or slurry-phase reaction mode

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, C.; Hager, V.; Geburtig, D.; Kohr, C.; Wasserscheid, P. [Erlangen-Nuernberg Univ. (Germany). Lehrstuhl fuer Chemische Reaktionstechnik; Haumann, M. [Chemical Reaction Engineering, FAU Busan Campus, Korea (Korea, Republic of)

    2011-07-01

    Highly acidic ionic liquid (IL) catalysts offer the opportunity to convert n-alkanes at very low reaction temperatures. The results of IL catalyzed isomerization and cracking reactions of pure n-octane are presented. Influence of IL composition, [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / H{sub 2}SO{sub 4} and [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / 1-chlorooctane, on catalyst activity and selectivities to branched alkanes was investigated. Acidic chloroaluminate IL catalysts form liquid-liquid biphasic systems with unpolar organic product mixtures. Thus, recycling of the acidic IL is enabled by simple phase separation in the liquid-liquid biphasic reaction mode or the IL can be immobilized on an inorganic support with a large specific surface area. These supported ionic liquid phase (SILP) catalysts offer the advantage to get a macroscopically heterogeneous system while still preserving all benefits of the homogeneous catalyst which can be used for the slurry-phase n-alkane isomerization. The interaction of the solid support and acidic IL influences strongly the catalytic activity. (orig.)

  5. Enzymes involved in the anaerobic oxidation of n-alkanes: from methane to long-chain paraffins

    Directory of Open Access Journals (Sweden)

    Amy V. Callaghan

    2013-05-01

    Full Text Available Anaerobic microorganisms play key roles in the biogeochemical cycling of methane and non-methane alkanes. To date, there appear to be at least three proposed mechanisms of anaerobic methane oxidation (AOM. The first pathway is mediated by consortia of archaeal anaerobic methane oxidizers and sulfate-reducing bacteria via ‘reverse methanogenesis’ and is catalyzed by a homologue of methyl-coenzyme M reductase. The second pathway is also mediated by anaerobic methane oxidizers and sulfate-reducing bacteria, wherein the archaeal members catalyze both methane oxidation and sulfate reduction and zero-valent sulfur is a key intermediate. The third AOM mechanism is a nitrite-dependent, intra-aerobic pathway described for the denitrifying bacterium, ‘Candidatus Methylomirabilis oxyfera.’ It is hypothesized that AOM proceeds via reduction of nitrite to nitric oxide, followed by the conversion of two nitric oxide molecules to dinitrogen and molecular oxygen. The latter can be used to functionalize the methane via a particulate methane monooxygenase. With respect to non-methane alkanes, there also appears to be novel mechanisms of activation. The most well-described pathway is the addition of non-methane alkanes across the double bond of fumarate to form alkyl-substituted succinates via the putative glycyl radical enzyme, alkylsuccinate synthase (also known as methylalkylsuccinate synthase. Other proposed mechanisms include anaerobic hydroxylation via ethylbenzene dehydrogenase-like enzymes and an ‘intra-aerobic’ denitrification pathway similar to that described for ‘M. oxyfera.’

  6. Characterization and distribution of polycyclic aromatic hydrocarbons and n-alkanes in groundwater from a tank farm

    Energy Technology Data Exchange (ETDEWEB)

    Riccardi, C.; Filippo, P.D.; Di Basilio, M.; Spicaglia, S.; Incoronato, F [Ispesl-dipia, Rome (Italy); Pomata, D. [CNR Inst. for Atmospheric Pollution, Rome (Italy)

    2005-07-01

    Soil and water contamination at an aboveground hydrocarbon tank farm in Italy was investigated. Groundwater samples were obtained from an existing site monitoring well network using an accelerated solvent extractor. Extracts were analyzed using a gas chromatograph (GC) and mass selective detector. The analysis demonstrated that polycyclic aromatic hydrocarbons (PAHs) and n-alkanes were present in all sampled wells, and were mainly concentrated in down-gradient samples. GC profiles showed a high predominance of n-alkanes. Distributions of n-alkanes suggested both anthropogenic and biological sources. A carbon preference index (CPI) was then used to distinguish between possible natural and anthropogenic sources. The CPI showed that pristane and phytane concentrations from biogenic sources were higher than values obtained for petrogenic hydrocarbons. However, the presence of low molecular PAH in the groundwater samples confirmed that leaks from the tanks had contributed to contamination levels. It was concluded that further research is needed to analyze other classes of compounds in the well network.

  7. Thermodynamics of adsorption of light alkanes and alkenes in single-walled carbon nanotube bundles

    CERN Document Server

    Cruz, Fernando J A L

    2016-01-01

    The thermodynamics of adsorption of light alkanes and alkenes (CH4, C2H6, C2H4, C3H8, and C3H6) in single-walled carbon nanotube bundles is studied by configurational-bias grand canonical Monte Carlo simulation. The bundles consist of uniform nanotubes with diameters in the range 11.0 < D (A) < 18.1, arranged in the usual close-packed hexagonal lattice. The phase space is systematically analyzed with calculations for adsorption at room temperature and reduced pressure range of 8.7 x 10-9 < (p/p0) < 0.9. The simulation results are interpreted in terms of the molecular nature of the adsorbate and the corresponding solid-fluid interactions. It is shown that confinement in the internal volume of the bundle (interstitial and intratubular) is energetically more favorable than physisorption on the external surface (grooves and exposed surfaces of peripheral tubes), as indicated by the curves of isosteric heat as a function of reduced pressure. However, the zero-loading properties suggest a crossover poin...

  8. Evidence from liposome encapsulation for transport-limited microbial metabolism of solid alkanes

    International Nuclear Information System (INIS)

    The recalcitrance of xenobiotics may be caused by an absence of transforming enzymes or by their inability to enter microbial cells. A nondestructive method for differentiating between these two possibilities is described. The solid n-alkanes octadecane (C18) and hexatriacontane (C36) were encapsulated into phosphatidylcholine bilayers (liposomes). The uptake and metabolism rates of encapsulated and unencapsulated substrates were then compared. During 1 h at 25 degree C, a Pseudomonas isolate took up 1.3% of radiolabeled and unencapsulated C18 (solid state) versus 23.5% of labeled and encapsulated C18. Growth at 25 degree C occurred with an apparent ks of 2453 ± 148 mg/liter. Liposome encapsulation decreased this Ks to 60 ± 12 mg/liter. At 34 degree C, growth on C18 (liquid state) occurred with an apparent Ks of 819 ± 83 mg/liter and on the readily available carbon source succinate, Ks values were 80 ± 10 and 13 ± 7 mg/liter at 25 to 34 degree C, respectively. At 25 degree C, the isolate grew on C36 with an apparent Ks of 2,698 ± 831 mg/liter. Liposome encapsulation decreased the Ks more than 60-fold to 41 ± 7 mg/liter, resulting in the complete utilization of 400 mg of C36 per liter in 16 h. Since controls excluded the metabolic utilization of phosphatidylcholine, the results clearly identify transport limitation as the cause for C36 recalcitrance

  9. Surface and liquid-crystalline properties of FmHnFm triblock semifluorinated n-alkanes.

    Science.gov (United States)

    Chachaj-Brekiesz, Anna; Górska, Natalia; Osiecka, Natalia; Makyła-Juzak, Katarzyna; Dynarowicz-Łątka, Patrycja

    2016-05-01

    A series of triblock semifluorinated n-alkanes of the general formula: F(CF2)m(CH2)n(CF2)mF, (in short FmHnFm), where m=10, 12, and n=6, 8, and 12 have been synthesized and employed for liquid crystalline studies and Langmuir monolayer characterization. Differential scanning calorimetry (DSC) measurements together with texture observation with polarizing microscope (POM) revealed the presence of liquid crystalline smectic phases for all the investigated homologs. The behavior of the studied molecules spread at the free water surface has also been investigated. Our results show for the first time that these unusual film-forming materials, which are completely hydrophobic in nature and do not possess any polar group in their structure, are surface active and form insoluble (Langmuir) monolayers at the air/water interface. Due to the fact that these molecules are chemically inert and, similar to the semifluorinated diblocks, are not toxic, they may be destined for biomedical uses as gas carriers and contrast agents, as well as in drug delivery systems. PMID:26952494

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

    Directory of Open Access Journals (Sweden)

    J. Lee-Taylor

    2012-08-01

    Full Text Available 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.

  11. Charge transport through dicarboxylic-acid-terminated alkanes bound to graphene-gold nanogap electrodes.

    Science.gov (United States)

    Liu, Longlong; Zhang, Qian; Tao, Shuhui; Zhao, Cezhou; Almutib, Eman; Al-Galiby, Qusiy; Bailey, Steven W D; Grace, Iain; Lambert, Colin J; Du, Jun; Yang, Li

    2016-08-14

    Graphene-based electrodes are attractive for single-molecule electronics due to their high stability and conductivity and reduced screening compared with metals. In this paper, we use the STM-based matrix isolation I(s) method to measure the performance of graphene in single-molecule junctions with one graphene electrode and one gold electrode. By measuring the length dependence of the electrical conductance of dicarboxylic-acid-terminated alkanes, we find that the transport is consistent with phase-coherent tunneling, but with an attenuation factor of βN = 0.69 per methyl unit, which is lower than the value measured for Au-molecule-Au junctions. Comparison with density-functional-theory calculations of electron transport through graphene-molecule-Au junctions and Au-molecule-Au junctions reveals that this difference is due to the difference in Fermi energies of the two types of junction, relative to the frontier orbitals of the molecules. For most molecules, their electrical conductance in graphene-molecule-Au junctions is higher than that in Au-molecule-Au junctions, which suggests that graphene offers superior electrode performance, when utilizing carboxylic acid anchor groups. PMID:27412865

  12. Determination and occurrence of secondary alkane sulfonates (SAS) in aquatic environments.

    Science.gov (United States)

    Baena-Nogueras, Rosa María; González-Mazo, Eduardo; Lara-Martín, Pablo A

    2013-05-01

    A new methodology has been developed for the determination of secondary alkane sulfonates (SAS), an anionic surfactant, in environmental matrices. Sediment and sludge samples were extracted using pressurized liquid extraction and sonication, whereas wastewater and surface water samples were processed using solid-phase extraction. Extraction recoveries were acceptable for both aqueous (78-120%) and solid samples (83-100%). Determination of SAS was carried out by high or ultra performance liquid chromatography - mass spectrometry using ion trap and time-of-flight detectors. The methodology was applied to samples from Guadalete River (SW Spain), where SAS concentrations below 1 μg L(-1) were measured in surface water, and from 72 to 9737 μg kg(-1) in sediments. Differential partitioning was observed for SAS homologues as those having a longer hydrocarbon chain which preferentially sorbed onto particulate matter. A preliminary environmental risk assessment also showed that SAS measured levels were not harmful to the aquatic community in the sampling area. PMID:23421983

  13. Catalytic conversion of light alkanes, Phase 3. Topical report, January 1990--December 1992

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1992-12-31

    The mission of this work is to devise a new catalyst which can be used in the first simple, economic process to convert the light alkanes in natural gas to an alcohol-rich oxygenated product which can either be used as an environmentally friendly, high-performance liquid fuel, or a precursor to a liquid hydrocarbon transportation fuel. The authors have entered the proof-of-concept stage for converting isobutane to tert butyl alcohol in a practical process and are preparing to enter proof-of-concept of a propane to isopropyl alcohol process in the near future. Methane and ethane are more refractory and thus more difficult to oxidize than the C{sub 3} and C{sub 4} hydrocarbons. Nonetheless, advances made in this area indicate that further research progress could achieve the goal of their direct conversion to alcohols. Progress in Phase 3 catalytic vapor phase methane and ethane oxidation over metals in regular oxidic lattices are the subject of this topical report.

  14. Alkane and crude oil degrading bacteria from the petroliferous soil of India

    International Nuclear Information System (INIS)

    It has been estimated that approximately 0.5 percent of transported crude oil finds its way into seawater, largely through accidental spills and discharge of ballast and wash water from oil tankers. Some microorganisms are well known for their ability to degrade a variety of hydrocarbons present in crude oil. Oil spills at sea or on land have demonstrated the hydrocarbon-degrading potential of these organisms. Under laboratory conditions, nitrogen may be supplied in soluble form (inorganic salts of ammonia or nitrate of urea). Since most natural aquatic environments are deficient in utilizable forms of nitrogen, it is necessary to add the same exogeneously, but because of rapid dilution the added source of nitrogen does not remain effective. The need for nitrogen supplements may be overcome by appropriate choice of microbes with the genetic capacity to fix molecular nitrogen. In this paper the authors are reporting the isolation of a strain of Pseudomonas stutzeri from the petroliferous soil of India. This strain has the capacity to degrade alkane and crude oil and to fix nitrogen

  15. Reactivity and fate of secondary alkane sulfonates (SAS) in marine sediments

    International Nuclear Information System (INIS)

    This research is focused on secondary alkane sulfonates (SAS), anionic surfactants widely used in household applications that access aquatic environments mainly via sewage discharges. We studied their sorption capacity and anaerobic degradation in marine sediments, providing the first data available on this topic. SAS partition coefficients increased towards those homologues having longer alkyl chains (from up to 141 L kg−1 for C14 to up to 1753 L kg−1 for C17), which were those less susceptible to undergo biodegradation. Overall, SAS removal percentages reached up to 98% after 166 days of incubation using anoxic sediments. The degradation pathway consisted on the formation of sulfocarboxylic acids after an initial fumarate attack of the alkyl chain and successive β-oxidations. This is the first study showing that SAS can be degraded in absence of oxygen, so this new information should be taken into account for future environmental risk assessments on these chemicals. - Highlights: • Anionic surfactant SAS can be anaerobically degraded in marine sediments. • Degradation is strongly influenced by the sorption capacity of SAS homologues. • Oxidation of SAS alkyl chain takes place by means of fumarate addition. • Carboxylic acids are formed during the anaerobic degradation of SAS. - Anaerobic degradation of SAS in marine sediments and the metabolites involved in this process are reported for the first time

  16. Alkane adsorption in Na-exchanged chabazite: The influence of dispersion forces

    Science.gov (United States)

    Göltl, Florian; Hafner, Jürgen

    2011-02-01

    The importance of dispersion forces for the correct description of the adsorption of short alkanes in Na-exchanged and purely siliceous chabazite has been investigated at different levels of theory: (i) standard density-functional (DFT) calculations using the Perdew, Burke, and Ernzerhof (PBE) exchange-correlation functional in the generalized gradient approximation, (ii) dispersion corrections based on empirical force fields according to Grimme [J. Computat. Chem. 134, 1463 (2004)- PBE-d], (iii) calculations based on the van der Waals density functional (vdW-DF) proposed by Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)], and (iv) using the random phase approximation (RPA) in combination with the adiabatic-connection fluctuation-dissipation theorem (RPA-ACFDT), using wave-functions calculated at the DFT and Hartree-Fock (HF) levels. A full relaxation of the adsorbate-zeolite complex was performed at the PBE, PBE-d, and vdW-DF levels. RPA and RPA-HF energies were calculated for the optimized configurations. A critical analysis of the results shows that the most accurate description is achieved at the RPA level with HF exchange energies, while both PBE-d and vdW-DF overestimate the strength of the interaction with the acid site.

  17. Catalytic conversion of light alkanes. Final report, January 1, 1990--October 31, 1994

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

    During the course of the first three years of the Cooperative Agreement (Phase I-III), we uncovered a family of metal perhaloporphyrin complexes which had unprecedented activity for the selective air-oxidation of fight alkanes to alcohols. The reactivity of fight hydrocarbon substrates with air or oxygen was in the order: isobutane>propane>ethane>methane, in accord with their homolytic bond dissociation energies. Isobutane was so reactive that the proof-of concept stage of a process for producing tert-butyl alcohol from isobutane was begun (Phase V). It was proposed that as more active catalytic systems were developed (Phases IV, VI), propane, then ethane and finally methane oxidations will move into this stage (Phases VII through IX). As of this writing, however, the program has been terminated during the later stages of Phases V and VI so that further work is not anticipated. We made excellent progress during 1994 in generating a class of less costly new materials which have the potential for high catalytic activity. New routes were developed for replacing costly perfluorophenyl groups in the meso-position of metalloporphyrin catalysts with far less expensive and lower molecular weight perfluoromethyl groups.

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

    Directory of Open Access Journals (Sweden)

    J. Lee-Taylor

    2012-06-01

    Full Text Available 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.

  19. First application of simultaneous SANS and differential scanning calorimetry: Microphase separated alkane blends

    International Nuclear Information System (INIS)

    For almost 30 years, it has been possible at synchrotron facilities to perform small-angle x-ray scattering experiments whilst simultaneously measuring phase transitions using differential scanning calorimetry (DSC). However, a range of challenges exist to enable the collection of simultaneous small-angle neutron scattering (SANS) and DSC data associated not only with intrinsic flux limitations but also scattering geometry and thermal control. The development of a DSC (temperature range ca. −150 C to 500 C) suitable for SANS is detailed here which, to our knowledge, is the first and only one of its kind. An example study is presented from the 40 m SANS instrument, QUOKKA, at the OPAL reactor at ANSTO (Figure 1), concerned with phase transitions in a binary blend of normal alkanes in which one component has been deuterium labelled[1]. The ability to conduct simultaneous DSC and neutron scattering studies allows investigators to use these two complementary techniques to provide insight into structural and thermal changes and opens up the opportunity for SANS to make significant new contributions to a range of systems in which either scattering contrast is insufficient for SAXS studies or where neutron scattering is essential or inherently desirable (e.g. isotope effects).

  20. Calculation of B/A for n-alkane liquids using the Tait equation

    Science.gov (United States)

    Hartmann; Lee; Balizer

    2000-07-01

    The B/A parameter of acoustic nonlinearity was calculated for a series of n-alkane liquids using the Tait PVT equation of state supplemented with specific heat data. The calculations of sound speed, sound speed derivatives, the two components of B/A, and the value of B/A itself were compared with experimental data taken from the literature and with earlier calculations using a different equation of state. In addition, a comparison of the results with Ballou's rule (linear relation of B/A and reciprocal sound speed) was made. It is concluded that B/A can be calculated from the Tait equation of state with about the same accuracy as direct measurements of sound speed versus pressure and temperature, though the the temperature derivatives of the sound speed are calculated with much lower accuracy than pressure derivatives. The calculations made using the Tait equation are about the same accuracy as calculations made using our equation of state. Also, Ballou's rule does not hold for these liquids. PMID:10923871

  1. Leaf physiological processes strongly affect δH2 values of leaf wax n-alkanes in C3 and C4 grasses.

    Science.gov (United States)

    Gamarra, Bruno; Sachse, Dirk; Kahmen, Ansgar

    2013-04-01

    Leaf wax n-alkanes are naturally synthesized saturated hydrocarbons. They are synthesized as part of plant leaf cuticle as a mechanism to prevent water losses. Two of the most important features of n-alkanes are their enormous environmental persistence and terrestrial ubiquity making them a solid and reliable long-term and large-scale biomarker. Their hydrogen isotopic composition (δH2) of leaf wax n-alkanes has been traditionally related to precipitation. Leaf wax n-alkanes and their δH2 values have thus been celebrated as biomarkers to reconstruct hydrological changes. δH2 values of leaf wax n-alkanes are yet to be fully comprehended. They are basically determined by three mechanisms: (1) The δH2 value of the plant source water (2) leaf water evaporative enrichment in H2 and (3) biosynthetic fractionation and depletion in H2during their biosynthesis from leaf water. Out of these three, the exact degree by which the evaporative H2-enrichment of leaf water influences the δH2 values of leaf wax n-alkanes is still unknown. We conducted an experiment where we tested and quantified the effects of leaf water evaporative H2-enrichment on the leaf wax n-alkane δH2 values of different grass species. We grew 12 C3 and C4 grass species under controlled environmental conditions in growth chambers. The plants were exposed to 3 different levels of air relative humidity (45, 65 and 85%). These treatments were to generate different degrees of leaf water H2-enrichment in the plants. The goal of our experiment was to determine by what degree the different levels of leaf water H2-enrichment influence the δH2 values of the different C3 and C4 grass species. Additional measurements of gas exchange, evapotranspiration and leaf length and area accompanied the isotopic analysis in order to explain species variability. Our experiments showed that leaf water evaporative H2-enrichment has a critical impact on leaf wax n-alkane δH2 values of all studied plants. The magnitude was

  2. Striking difference between alkane and olefin metathesis using the well-defined precursor [≡Si-O-WMe5]: Indirect evidence in favour of a bifunctional catalyst W alkylidene-hydride

    KAUST Repository

    Riache, Nassima

    2015-01-01

    Metathesis of linear alkanes catalyzed by the well-defined precursor (≡Si-O-WMe5) affords a wide distribution of linear alkanes from methane up to triacontane. Olefin metathesis using the same catalyst and under the same reaction conditions gives a very striking different distribution of linear α-olefins and internal olefins. This shows that olefin and alkane metathesis processes occur via very different pathways.

  3. Hydrogen isotopic compositions of individual alkanes as a new approach to petroleum correlation: case studies from the Western Canada Sedimentary Basin

    Energy Technology Data Exchange (ETDEWEB)

    Maowen Li; Obermajer, M.; Chunqing Jiang; Snowdon, L.R.; Fowler, M.G. [Geological Survey of Canada, Calgary (Canada); Yongsong Huang [Brown University, Providence, RI (United States). Department of Geological Science

    2001-07-01

    Isotopic compositions of carbon-bound hydrogen in individual n-alkanes and acyclic isoprenoid alkanes, from a number of crude oil samples, were measured using gas chromatography-thermal conversion-isotope ratio mass spectrometry. The precision of this technique is better than 3 per cent for most alkanes, compared to the large range of {delta}D variation among the samples (up to 160 per cent). The oils were selected from major genetic oil families in the Western Canada Sedimentary Basin, with source rocks ranging in age from Ordovician (and possibly Cambrian) to Cretaceous. The hydrogen isotopic composition of alkanes in crude oils is controlled by three factors: isotopic compositions of biosynthetic precursors, source water {delta}D values, and postdepositional processes. The inherited difference in the lipid's biosynthetic origins and/or pathways is reflected by a small hydrogen isotopic variability within n-alkanes, but much larger differences in the {delta}D values between n-alkanes and pristane/phytane. The shift toward lighter hydrogen isotopic compositions from Paleozoic to Upper Cretaceous oils in the WCSB reflects a special depositional setting and/or a minor contribution of terrestrial organic matter. The strong influence of source water {delta}D values is demonstrated by the distinctively lower {delta}D values of lacustrine oils than marine oils, and also by the high values for oils with source rocks deposited in evaporative environments. Thermal maturation may alter the {delta}D values of the alkanes in the oil to some extent, but secondary oil migration does not appear to have had any significant impact. The fact that oils derived from source rocks that could be of Cambrian age still retain a strong signature of the hydrogen isotopic compositions of source organic matter, and source water, indicates that {delta}D values are very useful for oil-source correlation and for paleoenvironmental reconstructions. (author)

  4. Presence of two transcribed malate synthase genes in an n-alkane-utilizing yeast, Candida tropicalis.

    Science.gov (United States)

    Hikida, M; Atomi, H; Fukuda, Y; Aoki, A; Hishida, T; Teranishi, Y; Ueda, M; Tanaka, A

    1991-12-01

    The presence of two genomic DNA regions encoding malate synthase (MS) was shown by Southern blot analysis of the genomic DNA from an n-alkane-assimilating yeast, Candida tropicalis, using a partial MS cDNA probe, in accordance with the fact that two types of partial MS cDNAs have previously been isolated. This was also confirmed by the restriction mapping of the two genes screened from the yeast lambda EMBL library. Nucleotide sequence analysis of the respective genomic DNAs, named MS-1 gene and MS-2 gene, revealed that both regions encoding MS had the same length of 1,653 base pairs, corresponding to 551 amino acids (molecular mass of MS-1, 62,448 Da; MS-2, 62,421 Da). Although 29 nucleotide pairs differed in the sequences of the coding regions, the number of amino acid replacements was only one: 159Asn (MS-1)----159Ser (MS-2). In the 5'-flanking regions, there were replacements of four nucleotide pairs, deletion of one pair, and insertion of four pairs. In spite of the fact that two genomic genes were present and transcribed, RNA blot analysis demonstrated that only one band (about 2 kb) was observable even when the carbon sources in the cultivation medium were changed. A comparison of the amino acid sequences was made with MSs of rape (Brassica napus L.), cucumber seed, pumpkin seed, Escherichia coli, and Hansenula polymorpha. A high homology was observed among these enzymes, the results indicating that the protein structure was relatively well conserved through the evolution of the molecule.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:1794980

  5. Contamination profiles of short-chain polychlorinated n-alkanes in foodstuff samples from Japan

    Energy Technology Data Exchange (ETDEWEB)

    Matsukami, Hidenori; Kurunthachalam, S.; Ohi, Etsumasa; Takasuga, Takumi [Shimadzu Techno Research, Inc., Kyoto (Japan); Iino, Fukuya; Nakanishi, Junko [National Inst. of Advanced Industrial Science and Technology, Tsukuba (Japan)

    2004-09-15

    Polychlorinated n-alkanes (PCAs) are group of chemicals manufactured by chlorination of liquid n-paraffin or paraffin wax that contain 30 to 70% chlorine by weight. Large amounts of PCAs are widely used as plasticizers for vinyl chloride, lubricants, paints, and flame retardants and number of other industrial applications. Annual global production of PCAs is approximately 300 kilo tones, with a majority having medium-carbon-chain (C14-C19) length. According to the investigation made by Kagaku Kogyo Nippon-Sha, the annual consumption of PCAs in Japan was about 83,000 tons in between 1986-2001. Short-carbon-chain (C10-C13) has been placed on the Priority Substance List under Canadian Environmental Protection Act and on the Environmental Protection Agency Toxic Release Inventory in the USA due to its potential to act as tumor promoters in mammals. Data on environment levels of PCAs is meager, nevertheless, PCAs have been measured at relatively high concentrations in biota from Sweden, biota, sediment from Canada and marine biota and human milk from the Canadian Arctic. In our earlier study, we reported concentrations of short-chain PCAs from sewage treatment plant (STP) collected from Tama River, Tokyo and river water and sediment from Tokyo and Osaka. STP influent water contained greater shortchain PCAs concentrations than STP effluent. In addition, some river water and sediment samples contained detectable concentrations of short-chain PCAs, which was similar to other industrial countries. However, there is no study conducted to explore the contamination profiles of short-chain PCAs in human foodstuff samples. In the present study, we analyzed eleven foodstuff samples that were purchased from various supermarkets in order to know the short-chain PCAs concentrations in the foodstuff and possible human total daily intake (TDI) amounts.

  6. Semifluorinated Alkane Eye Drops for Treatment of Dry Eye Disease—A Prospective, Multicenter Noninterventional Study

    Science.gov (United States)

    Scherer, Dieter; Krösser, Sonja; Beckert, Michael; Cursiefen, Claus; Kaercher, Thomas

    2015-01-01

    Abstract Purpose: Evaporation of the tear film is heavily discussed as one core reason for dry eye disease (DED). Subsequently, new artificial tear products are developed that specifically target this pathomechanism. Perfluorohexyloctane (F6H8, NovaTears®) from the family of semifluorinated alkanes is a novel substance that has been approved as a medical device, as a nonblurring wetting agent for the ocular surface. Methods: Thirty patients with hyperevaporative dry eye received F6H8 during a prospective, multicenter, observational 6-week study. Patients were advised to apply 1 drop 4 times daily in both eyes. Parameters assessed included best corrected visual acuity, intraocular pressure, Schirmer I test, tear fluid, tear film breakup time (TFBUT), corneal staining, meibum secretion, and Ocular Surface Disease Index (OSDI©). Results: From the 30 patients recruited, 25 completed the trial per protocol. Four patients discontinued F6H8 and 1 patient did not present for follow-up. F6H8 treatment led to significant reduction of corneal staining and significant increase of Schirmer I and TFBUT. In addition, OSDI score dropped significantly from a mean of 55 (±23.0) to 34 (±22.4). Visual acuity and ocular pressure did not change. Conclusions: This prospective observational study shows significant beneficial effects in patients suffering from evaporative DED, using F6H8 in all the relevant parameters tested. The decrease of the OSDI by a mean of 21 points was particularly remarkable and clearly exceeds minimal, clinical important differences for mild or moderate and severe disease. Overall, F6H8 (NovaTears) seems to be safe and effective in treating mild to moderate hyperevaporative DED. PMID:26296040

  7. Hopane, sterane and n-alkane distributions in shallow sediments hosting high arsenic groundwaters in Cambodia

    International Nuclear Information System (INIS)

    The presence of elevated As in ground waters exploited for drinking water and irrigation in South-East Asia is causing serious impacts on human health. A key mechanism that causes the mobilization of As in these waters is microbially mediated reductive transformation of As-bearing Fe(III) hydrated oxides and the role of degradable organic matter (OM) in this process is widely recognized. A number of different types of OM that drive As release in these aquifers have been suggested, including petroleum derived hydrocarbons naturally seeping into shallow sediments from deeper thermally mature source rocks. However, the amount of information on the characteristics of the OM in South-East Asian aquifers is limited. Here the organic geochemical analyses of the saturated hydrocarbon fractions and radiocarbon analysis, of two additional sites in SE Asia are reported. The results show that the OM in a given sedimentary horizon likely derives from multiple sources including naturally occurring petroleum. The importance of naturally occurring petroleum as one of the sources was clearly indicated by the n-alkane CPI of approximately 1, the presence of an unresolved complex mixture, and hopane (dominated by 17α(H),21β(H) hopanes) and sterane distribution patterns. The results also indicate that the OM in these aquifers varies tremendously in content, character and potential bioavailability. Furthermore, the presence of petroleum derived OM in sediments at both sites doubles the number of locations where their presence has been observed in association with As-rich, shallow aquifers, suggesting that the role of petroleum derived OM in microbially mediated As release might occur over a wider range of geographical locations than previously thought

  8. Hydrogen isotopic compositions, distributions and source signals of individual n-alkanes for some typical crude oils in Lunnan Oilfield, Tarim Basin, NW China

    Institute of Scientific and Technical Information of China (English)

    LU; Hong; LI; Chao; SUN; Yongge; PENG; Ping'an

    2005-01-01

    Isotopic compositions of carbon-bound hydrogen in individual n-alkanes from several typical crude oil samples from Lunnan Oilfield, Tarim Basin, NW China, were firstly measured using newly developed gas chromatography-thermal conversion-isotope ratio mass spectrometry. The similar range of δD of individual n-alkanes of crude oils among reservoirs of different geological times reflects that hydrocarbons are all derived from the same marine depositional environment. Compared to the theoretic value (-150‰) and the reported δD values (nC13―nC27, -160‰―-90‰) of individual n-alkanes for Ordovician-sourced crude oils in the Canadian Williston Basin, the hydrogen isotopic composition of individual n-alkanes in crude oils from Lunnan Oilfield is characterized by heavy hydrogen isotopic values (nC12―nC27, -120‰―-60‰). In terms of the factors that control the fractionation of hydrogen isotopes, relatively saline depositional environment and higher thermal maturation were attributed to the heavy δD values of individual n-alkanes in crude oils from Lunnan Oilfield.

  9. Mononuclear Nonheme High-Spin Iron(III)-Acylperoxo Complexes in Olefin Epoxidation and Alkane Hydroxylation Reactions.

    Science.gov (United States)

    Wang, Bin; Lee, Yong-Min; Clémancey, Martin; Seo, Mi Sook; Sarangi, Ritimukta; Latour, Jean-Marc; Nam, Wonwoo

    2016-02-24

    Mononuclear nonheme high-spin iron(III)-acylperoxo complexes bearing an N-methylated cyclam ligand were synthesized, spectroscopically characterized, and investigated in olefin epoxidation and alkane hydroxylation reactions. In the epoxidation of olefins, epoxides were yielded as the major products with high stereo-, chemo-, and enantioselectivities; cis- and trans-stilbenes were oxidized to cis- and trans-stilbene oxides, respectively. In the epoxidation of cyclohexene, cyclohexene oxide was formed as the major product with a kinetic isotope effect (KIE) value of 1.0, indicating that nonheme iron(III)-acylperoxo complexes prefer C═C epoxidation to allylic C-H bond activation. Olefin epoxidation by chiral iron(III)-acylperoxo complexes afforded epoxides with high enantioselectivity, suggesting that iron(III)-acylperoxo species, not high-valent iron-oxo species, are the epoxidizing agent. In alkane hydroxylation reactions, iron(III)-acylperoxo complexes hydroxylated C-H bonds as strong as those in cyclohexane at -40 °C, wherein (a) alcohols were yielded as the major products with high regio- and stereoselectivities, (b) activation of C-H bonds by the iron(III)-acylperoxo species was the rate-determining step with a large KIE value and good correlation between reaction rates and bond dissociation energies of alkanes, and (c) the oxygen atom in the alcohol product was from the iron(III)-acylperoxo species, not from molecular oxygen. In isotopically labeled water (H2(18)O) experiments, incorporation of (18)O from H2(18)O into oxygenated products was not observed in the epoxidation and hydroxylation reactions. On the basis of mechanistic studies, we conclude that mononuclear nonheme high-spin iron(III)-acylperoxo complexes are strong oxidants capable of oxygenating hydrocarbons prior to their conversion into iron-oxo species via O-O bond cleavage. PMID:26816269

  10. Two-Dimensional Stable Isotope Fractionation During Aerobic and Anaerobic Alkane Biodegradation and Implications for the Field

    Science.gov (United States)

    El Morris, Brandon; Suflita, Joseph M.; Richnow, Hans-Hermann

    2010-05-01

    Quantitatively, n-alkanes comprise a major portion of most crude oils. In petroliferous formations, it may be possible to relate the loss of these compounds to the levels of biodegradation occurring in situ [1]. Moreover, it is important to develop indicators of alkane degradation that may be used to monitor bioremediation of hydrocarbon-impacted environments. Desulfoglaeba alkanexedens and Pseudomonas putida GPo1 were used to determine if carbon and hydrogen stable isotope fractionation could differentiate between n-alkane degradation under anaerobic and aerobic conditions, respectively in the context of the Rayleigh equation model [2]. Bacterial cultures were sacrificed by acidification and headspace samples were analyzed for stable isotope composition using gas chromatography-isotope ratio mass spectrometry. Carbon enrichment factors (bulk) for anaerobic and aerobic biodegradation of hexane were -5.52 ± 0.2‰ and -4.34 ± 0.3‰, respectively. Hydrogen enrichment during hexane degradation was -43.14 ± 6.32‰ under sulfate-reducing conditions, and was too low for quantification during aerobiosis. Collectively, this indicates that the correlation between carbon and hydrogen stable isotope fractionation (may be used to help elucidate in situ microbial processes in oil reservoirs, and during intrinsic as well as engineered remediation efforts. References 1. Asif, M.; Grice, K.; Fazeelat, T., Assessment of petroleum biodegradation using stable hydrogen isotopes of individual saturated hydrocarbon and polycyclic aromatic hydrocarbon distributions in oils from the Upper Indus Basin, Pakistan. Organic Geochemistry 2009, 40, (3), 301-311. 2. Fischer, A.; Herklotz, I.; Herrmann, S.; Thullner, M.; Weelink, S. A. B.; Stams, A., J. M.; Schloemann, M.; Richnow, H.-H.; Vogt, C., Combined carbon and hydrogen isotope fractionation investigations for elucidating benzene biodegradation pathways. Environ. Sci. Technol. 2008, 42, 4356-4363.

  11. Isolation and characterization of different bacterial strains for bioremediation of n-alkanes and polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Guermouche M'rassi, A; Bensalah, F; Gury, J; Duran, R

    2015-10-01

    Crude oil is a common environmental pollutant composed of a large number of both aromatic and aliphatic hydrocarbons. Biodegradation is carried out by microbial communities that are important in determining the fate of pollutants in the environment. The intrinsic biodegradability of the hydrocarbons and the distribution in the environment of competent degrading microorganisms are crucial information for the implementation of bioremediation processes. In the present study, the biodegradation capacities of various bacteria toward aliphatic and aromatic hydrocarbons were determined. The purpose of the study was to isolate and characterize hydrocarbon-degrading bacteria from contaminated soil of a refinery in Arzew, Algeria. A collection of 150 bacterial strains was obtained; the bacterial isolates were identified by 16S rRNA gene sequencing and their ability to degrade hydrocarbon compounds characterized. The isolated strains were mainly affiliated to the Gamma-Proteobacteria class. Among them, Pseudomonas spp. had the ability to metabolize high molecular weight hydrocarbon compounds such as pristane (C19) at 35.11 % by strain LGM22 and benzo[a] pyrene (C20) at 33.93 % by strain LGM11. Some strains were able to grow on all the hydrocarbons tested including octadecane, squalene, phenanthrene, and pyrene. Some strains were specialized degrading only few substrates. In contrast, the strain LGM2 designated as Pseudomonas sp. was found able to degrade both linear and branched alkanes as well as low and high poly-aromatic hydrocarbons (PAHs). The alkB gene involved in alkane degradation was detected in LGM2 and other Pseudomonas-related isolates. The capabilities of the isolated bacterial strains to degrade alkanes and PAHs should be of great practical significance in bioremediation of oil-contaminated environments. PMID:25813636

  12. Feasibility of reconstructing paleoatmospheric records of selected alkanes, methyl halides, and sulfur gases from Greenland ice cores

    Science.gov (United States)

    Aydin, M.; Williams, M. B.; Saltzman, E. S.

    2007-04-01

    Seven short-lived atmospheric trace gases were measured in 25 ice core samples from Summit, Greenland. Samples were selected from contemporaneous sections of fluid- and dry-drilled ice cores to examine what effects using n-butyl acetate as the drill fluid would have on the measurements. The gases include three light alkanes, C2H6, C3H6, and n-C4H10; two methyl halides, CH3Cl and CH3Br; and two sulfur compounds, OCS and CS2, with gas ages from 125 to 325 years before present. Alkane levels are comparable to measurements in modern Arctic air, although C2H6 exhibits greater variability than expected compared with C3H6 and n-C4H10. These results are not consistent with the idea that the alkanes are primarily of anthropogenic origin, suggesting that the ice cores may not truly record a paleoatmospheric signal with respect to these gases. The CH3Br results are consistent with previous observations of "excess" CH3Br in Greenland firn air. In situ production processes appear to overwhelm the paleoatmospheric signal of this gas. CH3Cl exhibits the same effect to a lesser extent. OCS levels are similar to those in Antarctic ice cores and appear to reflect paleoatmospheric levels. CS2 results are similar to the limited database of modern atmospheric measurements. Only C3H8 and n-C4H10 exhibit clear evidence of contamination because of the presence of the drill fluid. The results indicate that it is possible to analyze many trace gases in fluid- and dry-drilled ice samples. However, it appears that in situ production may significantly alter the levels of some trace gases in Greenland ice cores.

  13. Characterization of n-alkanes and their carbon isotopic composition in sediments from a small catchment of the Dianchi watershed.

    Science.gov (United States)

    Wang, Yanhua; Yang, Hao; Zhang, Jixiang; Gao, Wenjing; Huang, Changchun; Xie, Biao

    2015-01-01

    The biomarker composition and stable carbon isotope values of organic matter (OM) in sediment cores from Shuanglong catchment of the Dianchi watershed show an unimodal n-alkane distribution ranging from C15-C33 with a strong predominance of odd-numbered n-alkanes, maximizing at n-C27, n-C29 and n-C31. Organic carbon to nitrogen (OC/N) ratio indicates a strong terrestrial influence on the OM. The values of δ(13)C27, δ(13)C29 and δ(13)C31 of n-alkanes range from -36.1‰ to -26.1‰, -34.1‰ to -30.1‰ and -33.8‰ to -28.7‰, respectively, suggesting a mainly C3 land plants origin. The carbon preference index (CPI25-31), odd-even preference (OEP27-31), average chain length (ACL25-33), pristine/phytane (pr/ph), Paq, (C27+C29)/2C31, nC16-23/nC24-33 and 3C17/(C21+C23+C25) values are also consistent with the predominance of C3 land plant-derived OM. Different sources of OM are reflected by the peak of n-C15, ascribed to a contribution by aquatic algae and photosynthetic bacteria. Eutrophication seems to be enhanced by both autochthonous (weak) and allochthonous (strong) contributions of OM. A major factor affecting the OM accumulation in the catchment and OM transportation to the Dianchi Lake may be increased by human activities from 1871 to 2011. PMID:24630457

  14. Tracing natural gas transport into shallow groundwater using dissolved nitrogen and alkane chemistry in Parker County, Texas

    Science.gov (United States)

    Larson, T.; Nicot, J. P.; Mickler, P. J.; Darvari, R.

    2015-12-01

    Dissolved methane in shallow groundwater drives public concern about the safety of hydraulic fracturing. We report dissolved alkane and nitrogen gas concentrations and their stable isotope values (δ13C and δ15N, respectively) from 208 water wells in Parker county, Texas. These data are used to differentiate 'stray' natural gas and low temperature microbial methane, and (2) estimate the ratio of stray gas to groundwater. The ratio of (gas-phase) stray natural gas to groundwater is estimated by correlating dissolved methane and nitrogen concentrations and dissolved nitrogen δ15N values. Our hypothesis is groundwater exposed to high volumes of stray natural gas have high dissolved methane concentrations and low dissolved nitrogen concentrations and δ15N values. Alternatively, groundwater exposed to low volumes of stray gas-phase natural gas have elevated dissolved methane, but the concentration of dissolved nitrogen and its d15N value is atmospheric. A cluster of samples in Parker county have high concentrations of dissolved methane (>10mg/L) with d13Cmethane and alkane ratios (C1/C2+C3) typical of natural gas from the Barnett Shale and the Strawn Formation. Coupling dissolved nitrogen concentrations and δ15N values with these results, we suggest that few of the wells in this cluster preserve large gas to water ratios. Many samples with high dissolved methane concentrations have atmospheric dissolved nitrogen concentrations and δ15N values, providing evidence against high flux natural gas transport into shallow groundwater. These results demonstrate that dissolved nitrogen chemistry, in addition to dissolved alkane and noble gas measurements, may be useful to discern sources of dissolved methane and estimate ratios of stray natural gas-water ratios.

  15. Are alkane hydroxylase genes (alkB) relevant to assess petroleum bioremediation processes in chronically polluted coastal sediments?

    Energy Technology Data Exchange (ETDEWEB)

    Paisse, Sandrine; Duran, Robert; Goni-Urriza, Marisol [Pau Univ. (France). Equipe Environnement et Microbiologie-UMR IPREM5254; Coulon, Frederic [Cranfield Univ. (United Kingdom). Centre for Resource Management and Efficiency

    2011-11-15

    The diversity of alkB-related alkane hydroxylase sequences and the relationship between alkB gene expression and the hydrocarbon contamination level have been investigated in the chronically polluted Etang-de-Berre sediments. For this purpose, these sediments were maintained in microcosms and submitted to a controlled oil input miming an oil spill. New degenerated PCR primers targeting alkB-related alkane hydroxylase sequences were designed to explore the diversity and the expression of these genes using terminal restriction fragment length polymorphism fingerprinting and gene library analyses. Induction of alkB genes was detected immediately after oil addition and their expression detected only during 2 days, although the n-alkane degradation was observed throughout the 14 days of incubation. The alkB gene expression within triplicate microcosms was heterogeneous probably due to the low level of alkB transcripts. Moreover, the alkB gene expression of dominant OTUs has been observed in unoiled microcosms indicating that the expression of this gene cannot be directly related to the oil contamination. Although the dominant alkB genes and transcripts detected were closely related to the alkB of Marinobacter aquaeolei isolated from an oil-producing well, and to alkB genes related to the obligate alkanotroph Alcanivorax borkumensis, no clear relationship between the oil contamination and the expression of the alkB genes could be established. This finding suggests that in such coastal environments, alkB gene expression is not a function relevant enough to monitor bacterial response to oil contamination. (orig.)

  16. Oxidation of alkanes with m-chloroperbenzoic acid catalyzed by iron(III) chloride and a polydentate amine

    OpenAIRE

    Shul’pin, Georgiy B.; Stoeckli-Evans, Helen; Mandelli, Dalmo; Kozlov, Yuriy N.; Tesouro Vallina, Ana; Woitiski, Camile B.; Jimenez, Ricardo S.; Carvalho, Wagner A.

    2009-01-01

    Tetradentate amine N,N′-bis(2-pyridylmethylene)-1,4-diaminodiphenyl ether (compound 1) dramatically accelerates the oxidation of alkanes with MCPBA in acetonitrile catalyzed by FeCl3, whereas N,N′-bis(2-pyrrolidinmethylene)-1,4-diaminodiphenyl ether (2) does not affect the reaction. The selectivity of the reaction in the presence of 1 is noticeably higher than that in its absence. On the basis of the kinetic study and selectivity parameters a mechanism has been proposed which includes the for...

  17. Study of the ionization of alkane-electron scavenger reactant mixtures irradiated by 60Co gamma rays

    International Nuclear Information System (INIS)

    This study deals with ionization of alkane-electron scavenger reactant mixtures, irradiated by 60Co γ-rays. It is shown that the extrapolated free-ion yields (extrapolated yield method) decrease with the reactant concentration. On the basis of ONSAGER model and theoretical treatment of MOZUMDER, the cross sections of epithermal electron attachment in hexane, cyclohexane, 2,2-dimethylbutane, cyclopentane, 2,2,4-trimethylpentane for CCl4, C7F14, C6H5Br, C6H5Cl, C6F14, (C6H5)2 are determined. A comparison between gas-phase and liquid-phase cross sections is established

  18. Highly organized crystalline monolayer of a semi-fluorinated alkane on a solid substrate obtained by spin-coating

    International Nuclear Information System (INIS)

    We have obtained a 40 nm parameter crystalline monolayer of a semifluorinated alkane on a silicon wafer using the spin-coating technique. Its structure, analyzed by atomic force microscopy (AFM), is identical to that recently observed at the air-water interface, showing the existence of hexagonal nanodomains, organized on a long range order hexagonal lattice of a few tens of nanometers lateral parameter. Considering AFM images published on films transferred by the usual Langmuir-Blodgett method, one can note that the monolayers form locally ordered rounded domains. With our procedure, the original highly organized large crystalline structure is recovered.

  19. A cross-linked manganese porphyrin as highly efficient heterogeneous catalyst for selective oxidation of cycloalkenes/alkanes

    Indian Academy of Sciences (India)

    Manoj Kumar Singh; Debkumar Bandyopadhyay

    2014-11-01

    The monomeric tetrakis (5,10,15,20--bromophenyl) manganese porphyrin has been converted to a micro- and mesoporous material of surface area 1301m2/g by carefully manipulating the reaction conditions of Suzuki coupling. This material has been tested for its oxidizing ability of cycloalkenes/alkane by -BuOOH, H2O2, CumOOH and m-CPBA. The catalyst is found to oxidize the alkenes selectively and it is not destroyed even 5% in 10 cycles of successive oxidation processes in one pot. The parent monomer gets destroyed appreciably under similar oxidizing conditions.

  20. Microbial Oxidation of Gaseous Hydrocarbons: Production of Methylketones from Corresponding n-Alkanes by Methane-Utilizing Bacteria

    OpenAIRE

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

    1980-01-01

    Cell suspensions of methane-utilizing bacteria grown on methane oxidized n-alkanes (propane, butane, pentane, hexane) to their corresponding methylketones (acetone, 2-butanone, 2-pentanone, 2-hexanone). The product methylketones accumulated extracellularly. The rate of production of methylketones varied with the organism used for oxidation; however, the average rate of acetone, 2-butanone, 2-pentanone, and 2-hexanone production was 1.2, 1.0, 0.15, and 0.025 μmol/h per 5.0 mg of protein in cel...

  1. Thermodynamic properties of (an ester+an alkane). XVII. Experimental HmE and VmE values for (an alkyl propanoate+an alkane) at 318.15K

    International Nuclear Information System (INIS)

    In this article, we record the experimental values of HmE and VmE, obtained at a temperature of T=318.15K and atmospheric pressure for a set of 30 binary mixtures comprised of five alkyl propanoates (methyl to pentyl) with six odd alkanes (heptane to heptadecane). The net values obtained for these properties are the result of different effects of the selected compounds on the mixing process. These effects and the variation with temperature are studied. The HmE are positive in all cases and increase with the saturated hydrocarbon chain and diminish with the alkanolic portion of the ester. The variation in VmE is similar to that occurring in the HmE. For the data correlation, a new form of polynomial equation is used in which the variable is the so-called active fraction which, in turn, is a function of the concentration of the mixture, giving acceptable estimations for simultaneous correlations between the values of Gibbs function obtained in the isobaric (liquid+vapour) equilibria and the enthalpies of the mixture, for some of the mixtures studied. The results are explained with the molecular model proposed for (ester+alkane) mixtures. Finally, the application of two versions of the UNIFAC groups contribution method to estimate enthalpies of the mixtures does not give satisfactory results, although the modified UNIFAC gives somewhat better results

  2. Thermodynamic properties of (an ester + an alkane). XVIII. Experimental H{sub m}{sup E}andV{sub m}{sup E} values for (an alkyl butanoate + an alkane) at T = 318.15 K

    Energy Technology Data Exchange (ETDEWEB)

    Ortega, J. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071 Las Palmas de Gran Canaria (Spain)], E-mail: jortega@dip.ulpgc.es; Navas, A.; Sabater, G.; Ascanio, M.; Placido, J. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071 Las Palmas de Gran Canaria (Spain)

    2007-11-15

    This work presents the experimental values of H{sub m}{sup E}andV{sub m}{sup E} obtained at a temperature of 318.15 K and atmospheric pressure for a group of 24 binary mixtures comprised of the first four alkyl butanoates (methyl to butyl) with six odd alkanes, from heptane to heptadecane. All the mixtures are endothermic, and present a regular increase in H{sub m}{sup E} with the molecular weight of the saturated hydrocarbon, while, for a same alkane, the enthalpic effects diminish with increasing alcoholic chain of the butanoate. The variation in V{sub m}{sup E} occurs in the same direction. In this paper the structural behaviour of these systems and the influence of temperature on excess properties are analysed. Experimental data are correlated with a suitable polynomial equation which is given as a function of concentration and temperature, that permits a simultaneous correlation to be established with other properties of the mixture, such as (vapour + liquid) equilibria; and acceptable results are obtained. Finally, an estimation of H{sub m}{sup E} is made with two known versions of the UNIFAC model. In the version by Dang and Tassios [J. Dang, D.P. Tassios, Ind. Eng. Chem. Process Des. Dev. 25 (1986) 22-31.], a method is proposed that considers the interaction parameters as a function of the butanoate alkanolic chain. The estimations obtained for H{sub m}{sup E} are good.

  3. Thermodynamic properties of (an ester+an alkane). XVII. Experimental H{sub m}{sup E} and V{sub m}{sup E} values for (an alkyl propanoate+an alkane) at 318.15K

    Energy Technology Data Exchange (ETDEWEB)

    Ortega, J. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071-Las Palmas de Gran Canaria (Spain)]. E-mail: jortega@dip.ulpgc.es; Espiau, F. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071-Las Palmas de Gran Canaria (Spain); Toledo, F.J. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071-Las Palmas de Gran Canaria (Spain); Dieppa, R. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071-Las Palmas de Gran Canaria (Spain)

    2005-09-15

    In this article, we record the experimental values of H{sub m}{sup E} and V{sub m}{sup E}, obtained at a temperature of T=318.15K and atmospheric pressure for a set of 30 binary mixtures comprised of five alkyl propanoates (methyl to pentyl) with six odd alkanes (heptane to heptadecane). The net values obtained for these properties are the result of different effects of the selected compounds on the mixing process. These effects and the variation with temperature are studied. The H{sub m}{sup E} are positive in all cases and increase with the saturated hydrocarbon chain and diminish with the alkanolic portion of the ester. The variation in V{sub m}{sup E} is similar to that occurring in the H{sub m}{sup E}. For the data correlation, a new form of polynomial equation is used in which the variable is the so-called active fraction which, in turn, is a function of the concentration of the mixture, giving acceptable estimations for simultaneous correlations between the values of Gibbs function obtained in the isobaric (liquid+vapour) equilibria and the enthalpies of the mixture, for some of the mixtures studied. The results are explained with the molecular model proposed for (ester+alkane) mixtures. Finally, the application of two versions of the UNIFAC groups contribution method to estimate enthalpies of the mixtures does not give satisfactory results, although the modified UNIFAC gives somewhat better results.

  4. Modeling phase equilibria for acid gas mixtures using the CPA equation of state. Part IV. Applications to mixtures of CO2 with alkanes

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Ali, Shahid; Kontogeorgis, Georgios

    2015-01-01

    The thermodynamic properties of pure gaseous, liquid or supercritical CO2 and CO2 mixtures with hydrocarbons and other compounds such as water, alcohols, and glycols are very important in many processes in the oil and gas industry. Design of such processes requires use of accurate thermodynamic...... behavior of several mixtures of interest in oil and gas industry.The purpose of this work is to evaluate the performance of CPA for CO2-alkane mixtures. CPA calculations were performed using different association schemes for CO2. Firstly, CO2 was treated as non-associating fluid and, at a second level, CO2...... was treated as self associating fluid, using the 2B, 3B and 4C association schemes. A systematic investigation of the CPA performance in correlating the phase behavior of CO2-alkane mixtures has been performed. Mixtures with alkanes up to n-hexatriacontane (n-C36) were investigated and the...

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

    Science.gov (United States)

    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.

  6. Whole-cell bio-oxidation of n-dodecane using the alkane hydroxylase system of P. putida GPo1 expressed in E. coli

    DEFF Research Database (Denmark)

    Grant, Chris; Woodley, John; Baganz, Frank

    2011-01-01

    The alkane-1-monoxygenase (alkB) complex of Pseudomonas putida GPo1 has been extensively studied in the past and shown to be capable of oxidising aliphatic C5–C12 alkanes to primary alcohols both in the wild-type organism by growth on C5–C12 alkanes as sole carbon source and in vitro. Despite this......, successful n-dodecane oxidation for the production of 1-dodecanol or dodecanoic acid has proven elusive in the past when using alkB-expressing recombinants. This article demonstrates, for the first time in vivo, by using the Escherichia coli GEC137 pGEc47ΔJ strain, that n-dodecane oxidation using this enzyme...

  7. Equation of state modeling of the phase equilibria of asymmetric CO2+n-alkane binary systems using mixing rules cubic with respect to mole fraction

    DEFF Research Database (Denmark)

    Cismondi, Martin; Mollerup, Jørgen M.; Zabaloy, Marcelo S.

    2010-01-01

    available interaction parameters) in modern equations of state.In particular, the phase equilibria of binary mixtures containing CO2 and heavy n-alkanes have been studied by an important number of authors and using different types of models, achieving only partially accurate results and realizing the...... for the first time a quite successful complete description of asymmetric CO2+n-alkane binary systems, with n-alkane carbon number from 14 to 22....... a great diversity of mixtures. Nevertheless, the models for representing phase equilibria and physico-chemical properties of asymmetric systems may require more flexible mixing rules than the classical quadratic van der Waals (vdW) mixing rules or their equivalent (with regard to the number of...

  8. Terrestrial environmental changes around the Gulf of Aden over the last 210 kyr deduced from the sediment n-alkane record: Implications for the dispersal of Homo sapiens

    Science.gov (United States)

    Isaji, Yuta; Kawahata, Hodaka; Ohkouchi, Naohiko; Murayama, Masafumi; Tamaki, Kensaku

    2015-03-01

    We analyzed long-chain (C25-C36) n-alkanes and pollen grains in sediments from the Gulf of Aden covering the last 212 kyr to reconstruct the surrounding terrestrial environment, a critical region for the dispersal of Homo sapiens. Substantial increases in the flux of n-alkanes during 200-185, 120-95, and 70-50 ka were interpreted to indicate enhanced vegetation biomass in the Arabian Peninsula and the northern part of the Horn of Africa or increase in lithogenic material inputs. Periods of enhanced n-alkane flux occurred during or immediately after pluvial episodes, indicating that the increased precipitation may have induced substantially enhanced vegetation biomass, creating favorable conditions for Homo sapiens. Additionally, vegetation may have increased due to moderate precipitation unrecorded by speleothems or in accordance with the lowering of sea level, indicating that the dispersal might have been possible even after the shift to an arid environment indicated by the speleothems.

  9. Ozone-driven daytime formation of secondary organic aerosol containing carboxylic acid groups and alkane groups

    Directory of Open Access Journals (Sweden)

    S. Liu

    2011-08-01

    -resolved spectrometric and spectroscopic characterization of the particle OM indicate that the majority of the OM formed by condensation of gas-phase oxidation products. This unique set of measurements and methods to quantify and characterize photochemically and ozone-linked carboxylic acid group formation provide independent and consistent assessments of the secondary fraction of OM, which could result from second generation products of the oxidation of gas-phase alkane (molecules.

  10. Source characterization of sedimentary organic matter using molecular and stable carbon isotopic composition of n-alkanes and fatty acids in sediment core from Lake Dianchi, China

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Jidun [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Shandong Key Laboratory of Eco-Environmental Science for Yellow River Delta, Binzhou University, Binzhou, Shandong Province 256600 (China); Wu, Fengchang, E-mail: wufengchang@163.com [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Xiong, Yongqiang [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Li, Fasheng; Du, Xiaoming; An, Da [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Wang, Lifang [State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002 (China)

    2014-03-01

    The distribution and compound-specific carbon isotope ratios of n-alkanes and fatty acids in a sediment core (63 cm) collected from Lake Dianchi were examined to investigate organic matter sources in the eutrophic lake. Fatty acids included free and bound fatty acids. The carbon isotope compositions of individual n-alkanes and fatty acids from Lake Dianchi sediments were determined using gas chromatography/isotope ratio mass spectrometry (GC–IRMS). The δ{sup 13}C values of individual n-alkanes (C{sub 16}–C{sub 31}) varied between − 24.1‰ and − 35.6‰, suggesting a dominance of {sup 13}C-depleted n-alkanes that originated from C{sub 3} plants and lacustrine algae. Fatty acids from the sediment extracts were analyzed for their abundances and carbon isotopic compositions. Molecular and isotopic evidence indicates that most of the short-chain fatty acids from Lake Dianchi sediment extracts are sourced from intense microbial recycling and resynthesis of organic matter. Long-chain free fatty acids are mainly derived from terrestrial sources. However, long-chain bound fatty acids are sourced from a combination of terrestrial organic matter, bacteria and algae, with the contribution from algal sources higher in the hypereutrophic stage. - Highlights: • Long-chain n-alkanes and FFAs are mainly derived from terrestrial sources. • Short-chain n-alkanes and fatty acids are mainly derived from bacterial and/or algal sources. • Long-chain BFAs are mainly derived from algal sources in hypereutrophic lakes.

  11. Source characterization of sedimentary organic matter using molecular and stable carbon isotopic composition of n-alkanes and fatty acids in sediment core from Lake Dianchi, China

    International Nuclear Information System (INIS)

    The distribution and compound-specific carbon isotope ratios of n-alkanes and fatty acids in a sediment core (63 cm) collected from Lake Dianchi were examined to investigate organic matter sources in the eutrophic lake. Fatty acids included free and bound fatty acids. The carbon isotope compositions of individual n-alkanes and fatty acids from Lake Dianchi sediments were determined using gas chromatography/isotope ratio mass spectrometry (GC–IRMS). The δ13C values of individual n-alkanes (C16–C31) varied between − 24.1‰ and − 35.6‰, suggesting a dominance of 13C-depleted n-alkanes that originated from C3 plants and lacustrine algae. Fatty acids from the sediment extracts were analyzed for their abundances and carbon isotopic compositions. Molecular and isotopic evidence indicates that most of the short-chain fatty acids from Lake Dianchi sediment extracts are sourced from intense microbial recycling and resynthesis of organic matter. Long-chain free fatty acids are mainly derived from terrestrial sources. However, long-chain bound fatty acids are sourced from a combination of terrestrial organic matter, bacteria and algae, with the contribution from algal sources higher in the hypereutrophic stage. - Highlights: • Long-chain n-alkanes and FFAs are mainly derived from terrestrial sources. • Short-chain n-alkanes and fatty acids are mainly derived from bacterial and/or algal sources. • Long-chain BFAs are mainly derived from algal sources in hypereutrophic lakes

  12. Simple addition of silica to an alkane solution of Wilkinson WMe6 or Schrock W alkylidyne complex give active complex for saturated and unsaturated hydrocarbons metathesis

    KAUST Repository

    Callens, Emmanuel

    2015-08-24

    Addition of PDA silica to a solution of the Wilkinson WMe6 as well as the Schrock W neopentilidyne tris neopentyl complex catalyzes linear or cyclic alkanes to produce respectively a distribution of linear alkanes from methane up to triacontane or a mixture of cyclic and macrocyclic hydrocarbons. This single catalytic system transforms also linear α-olefins into higher and lower homologues via isomerization/metathesis mechanism (ISOMET). This complex is also efficient towards functionalized olefins. Unsaturated fatty acid esters (FAEs) are converted into diesters corresponding to self-metathesis products.

  13. Relationship of the solvation enthalpies of n-alkanes in a methanol-hexamethylphosphortriamide mixture to its thermal and bulk properties

    Science.gov (United States)

    Batov, D. V.; Kustov, A. V.; Antonova, O. A.; Smirnova, N. L.

    2016-03-01

    Enthalpies of dissolution are determined thermochemically under standard conditions, and the solvation enthalpies of n-hexane, n-decane, and n-hexadecane in a mixed methanol-hexamethylphosphor-triamide (HMPT) solvent are calculated. Experimental data are compared to values obtained from model calculations. It is shown that positive deviations of the enthalpies of dissolution of alkanes in a MeOH-HMPT mixture from additivity in the range enriched with methanol are due to changes in the bulk properties of the mixed solvent, while negative deviations of enthalpies of dissolution from additivity in the range enriched with HMPT are due to the selective solvation of alkanes by HMPT.

  14. Inhibition of Growth of a Graphium sp. on Gaseous n-Alkanes by Gaseous n-Alkynes and n-Alkenes

    OpenAIRE

    Curry, S.; Ciuffetti, L.; Hyman, M.

    1996-01-01

    The growth of a filamentous fungus, a Graphium sp., on n-alkanes (C(inf2) to C(inf4)) was inhibited by low concentrations of acetylene, propyne, 1-butyne, ethylene, and propylene. Acetylene and other unsaturated hydrocarbons had no effect on the growth of the Graphium sp. on potato dextrose broth, ethanol, or acetate. Our results suggest that n-alkynes and n-alkenes are selective inhibitors of a nonspecific monooxygenase enzyme responsible for the initial oxidation of n-alkanes.

  15. Changes in the n-alkane composition of avocado pulp oil ( Persea americana, Mill.) during fruit ripening

    OpenAIRE

    Giuffrè, A. M.

    2005-01-01

    The n-alkane composition of Avocado pulp oil (cv. Hass) was investigated during fruit ripening. Three samples of fruit were harvested on March 3, 2003, March 18, 2003 and April 2, 2003. Glass gravity column chromatography was employed to separate n-alkanes from other minor components contained in the unsaponifiable fraction. Gas chromatography was used to analyze the eluate. Fourteen compounds were detected ranging from n -C21 to n -C34; mainly n -C24, followed by n -C25 and then by n -C23. Q...

  16. QSPR models based on molecular mechanics and quantum chemical calculations. 1. Construction of Boltzmann averaged descriptors for alkanes, alcohols, diols, ethers and cyclic compounds

    DEFF Research Database (Denmark)

    Dyekjær, Jane Dannow; Rasmussen, Kjeld; Jonsdottir, Svava Osk

    2002-01-01

    Values for nine descriptors for QSPR (quantitative structure-property relationships) modeling of physical properties of 96 alkanes, alcohols, ethers, diols, triols and cyclic alkanes and alcohols in conjunction with the program Codessa are presented. The descriptors are Boltzmann-averaged by...... selection of the most relevant conformers out of a set of possible molecular conformers generated by a systematic scheme presented in this paper. Six of these descriptors are calculated with molecular mechanics and three with quantum chemical methods. Especially interesting descriptors are the relative van...

  17. Nucleation, growth and habit modification of n-alkanes and homologous mixtures in the absence and presence of flow improving additives

    International Nuclear Information System (INIS)

    A detailed study has been performed on the nucleation, growth and habit modification of n-alkanes and homologous mixtures in the absence and presence of flow improving additives in an attempt to gain a clearer appreciation of the interaction mechanisms behind wax / additive crystallisation. Kinetic and structural assessment of melt phase n-alkanes illustrate the different crystallographic forms present within the homologous series. Studies demonstrate the alternating behaviour of the even and odd numbered homologues which converges as a function of increasing molecular weight. Greater crystal lattice stabilities were found for those n-alkanes which have an even carbon number and which crystallise into the triclinic crystal structure. Solid state phase behaviour of the n-alkanes was found to vary depending on the number and parity of n. Nucleation kinetic studies of n-alkanes and homologous mixtures from model diesel fuel solvents (dodecane, m-xylene, decalin, pristane and a dewaxed fuel) are assessed using turbidity as the method of crystallite detection. Saturation temperatures are found to be related to both alkane structure and molecular chain length for all solvent systems. N-alkane solubilities are lower for n-alkane like solvents. The width of the meta stable zone varies as a function of solvent in order of dodecane ≅ pristane 19H40 and solvent m-xylene. Wax precipitation from distillate fuels in the presence of flow improving additives (di-alkyl di-amino xylene, phthalic acid and sulphobenzene acid derivatives and high molecular weight polymers) reveal responsive wax crystal nucleator and growth inhibitor additives. The crystal morphology of heptacosane, C27H56 to simulate a model wax crystal is assessed in addition to its response to blocker 'tailor made' additives: methyl substituted C27H56 and di-alkyl substituted phenyl additives [additive (A) and (B)]. Pure C27H56 reveals a thin lozenge shaped platelet. All additives studied induce growth inhibition

  18. Mg2+-Dependent Control of the Spatial Arrangement of Rhodococcus erythropolis PR4 Cells in Aqueous-Alkane Two Phase Culture Containing n-Dodecane

    Science.gov (United States)

    Takihara, Hayato; Akase, Yumiko; Sunairi, Michio; Iwabuchi, Noriyuki

    2016-01-01

    We recently reported that a close relationship exists between alkane carbon-chain length, cell growth, and translocation frequency in Rhodococcus. In the present study, we examined the regulation of the spatial arrangement of cells in aqueous-alkane two phase cultures. An analysis of the effects of minerals on cell localization revealed that changes in the concentration of MgSO4 in two phase cultures containing n-dodecane (C12) altered cell localization from translocation to adhesion and vice versa. Our results indicate that the spatial arrangement of cells in two phase culture systems is controlled through the regulation of MgSO4 concentrations. PMID:27180641

  19. Reactions of C$_2$({\\it a}$^3Pi_u$) with selected saturated alkanes: A temperature dependence study

    CERN Document Server

    Hu, Renzhi; Chen, Yang

    2010-01-01

    We present a temperature dependence study on the gas phase reactions of the C$_2$({\\it a}$^3Pi_u$) radical with a selected series of saturated alkanes (C$_2$H$_6$, C$_3$H$_8$, n-C$_4$H$_10$, i-C$_4$H$_10$, and n-C$_6$H$_14$) by means of pulsed laser photolysis/laser-induced fluorescence technique. The bimolecular rate constants for these reactions were obtained between 298 and 673 K. A pronounced negative temperature effect was observed for n-C$_4$H$_10$, i-C$_4$H$_10$, and n-C$_6$H$_14$ and interpreted in terms of steric hindrance of the more reactive secondary or tertiary C-H bonds by less reactive CH$_3$ groups. Detailed analysis of our experimental results reveals quantitatively the temperature dependence of reactivities for the primary, secondary, and tertiary C-H bonds in these saturated alkanes and further lends support to a mechanism of hydrogen abstraction.

  20. Modeling of asphaltene precipitation due to steam and n-alkane co-injection in the ES-SAGD process

    Energy Technology Data Exchange (ETDEWEB)

    Badamchizadeh, A.; Kohse, Bruce F.; Kumar, A. [Computer Modelling Group Ltd (Canada)

    2011-07-01

    This paper provides an insight into the SAGD process in general, and the formation of asphaltene participates in the hybrid ES-SAGD process in particular. The objective of this work was to build an EoS model able to calculate the physical and chemical properties of the bitumen and n-alkane mixture, develop a model to quantify asphaltene participates in bitumen due to n-alkane injection, and investigate their effect on the ES-SAGD process. Athabasca bitumen properties identified under various test conditions and from the results of previous efforts, mainly the SimDist experimental data, were illustrated. These data were used to develop the EoS model, which in turn was used to generate the STARS thermal simulator. Overall, the EoS model was successfully developed and hence was able to predict bitumen and n-heptane properties. Moreover, asphaltene deposition in the ES-SAGD process was modeled in the thermal simulator its effect in causing oil blockage and restrictions in the steam chamber over a long run of the process was demonstrated.

  1. Liquid-Phase Exfoliation of Graphite into Single- and Few-Layer Graphene with α-Functionalized Alkanes.

    Science.gov (United States)

    Haar, Sébastien; Bruna, Matteo; Lian, Jian Xiang; Tomarchio, Flavia; Olivier, Yoann; Mazzaro, Raffaello; Morandi, Vittorio; Moran, Joseph; Ferrari, Andrea C; Beljonne, David; Ciesielski, Artur; Samorì, Paolo

    2016-07-21

    Graphene has unique physical and chemical properties, making it appealing for a number of applications in optoelectronics, sensing, photonics, composites, and smart coatings, just to cite a few. These require the development of production processes that are inexpensive and up-scalable. These criteria are met in liquid-phase exfoliation (LPE), a technique that can be enhanced when specific organic molecules are used. Here we report the exfoliation of graphite in N-methyl-2-pyrrolidinone, in the presence of heneicosane linear alkanes terminated with different head groups. These molecules act as stabilizing agents during exfoliation. The efficiency of the exfoliation in terms of the concentration of exfoliated single- and few-layer graphene flakes depends on the functional head group determining the strength of the molecular dimerization through dipole-dipole interactions. A thermodynamic analysis is carried out to interpret the impact of the termination group of the alkyl chain on the exfoliation yield. This combines molecular dynamics and molecular mechanics to rationalize the role of functionalized alkanes in the dispersion and stabilization process, which is ultimately attributed to a synergistic effect of the interactions between the molecules, graphene, and the solvent. PMID:27349897

  2. Optimizing carbon efficiency of jet fuel range alkanes from cellulose co-fed with polyethylene via catalytically combined processes.

    Science.gov (United States)

    Zhang, Xuesong; Lei, Hanwu; Zhu, Lei; Zhu, Xiaolu; Qian, Moriko; Yadavalli, Gayatri; Yan, Di; Wu, Joan; Chen, Shulin

    2016-08-01

    Enhanced carbon yields of renewable alkanes for jet fuels were obtained through the catalytic microwave-induced co-pyrolysis and hydrogenation process. The well-promoted ZSM-5 catalyst had high selectivity toward C8-C16 aromatic hydrocarbons. The raw organics with improved carbon yield (∼44%) were more principally lumped in the jet fuel range at the catalytic temperature of 375°C with the LDPE to cellulose (representing waste plastics to lignocellulose) mass ratio of 0.75. It was also observed that the four species of raw organics from the catalytic microwave co-pyrolysis were almost completely converted into saturated hydrocarbons; the hydrogenation process was conducted in the n-heptane medium by using home-made Raney Ni catalyst under a low-severity condition. The overall carbon yield (with regards to co-reactants of cellulose and LDPE) of hydrogenated organics that mostly match jet fuels was sustainably enhanced to above 39%. Meanwhile, ∼90% selectivity toward jet fuel range alkanes was attained. PMID:27126079

  3. An overview of dehydration, aldol-condensation and hydrogenation processes for production of liquid alkanes from biomass-derived carbohydrates

    Energy Technology Data Exchange (ETDEWEB)

    Chheda, Juben N.; Dumesic, James A. [University of Wisconsin-Madison, Department of Chemical and Biological Engineering, Madison, WI 53706 (United States)

    2007-05-30

    We present results for the conversion of carbohydrate feedstocks to liquid alkanes by the combination of dehydration, aldol-condensation/hydrogenation, and dehydration/hydrogenation processing. With respect to the first dehydration step, we demonstrate that HMF can be produced in good selectivity from abundantly available polysaccharides (such as inulin, sucrose) containing fructose monomer units using a biphasic batch reactor system. The reaction system can be optimized to achieve good yields to 5-hydroxymethylfurfural (HMF) from fructose by varying the contents of aqueous-phase modifiers such as dimethylsulfoxide (DMSO) and 1-methyl-2-pyrrolidinone (NMP). Regarding the aldol-condensation/hydrogenation step, we present the development of stable, solid base catalysts in aqueous environments. We address the effects of various reaction parameters such as the molar ratio of reactants and temperature on overall product yield for sequential aldol-condensation and hydrogenation steps. Overall, our results show that it is technically possible to convert carbohydrate feedstocks to produce liquid alkanes by the combination of dehydration, aldol-condensation/hydrogenation, and dehydration/hydrogenation processing; however, further optimization of these processes is required to decrease the overall number of separate steps (and reactors) required in this conversion. (author)

  4. Hydrocarbons, the advanced biofuels produced by different organisms, the evidence that alkanes in petroleum can be renewable.

    Science.gov (United States)

    Fu, Wen-Juan; Chi, Zhe; Ma, Zai-Chao; Zhou, Hai-Xiang; Liu, Guang-Lei; Lee, Ching-Fu; Chi, Zhen-Ming

    2015-09-01

    It is generally regarded that the petroleum cannot be renewable. However, in recent years, it has been found that many marine cyanobacteria, some eubacteria, engineered Escherichia coli, some endophytic fungi, engineered yeasts, some marine yeasts, plants, and insects can synthesize hydrocarbons with different carbon lengths. If the organisms, especially some native microorganisms and engineered bacteria and yeasts, can synthesize and secret a large amount of hydrocarbons within a short period, alkanes in the petroleum can be renewable. It has been documented that there are eight pathways for hydrocarbon biosynthesis in different organisms. Unfortunately, most of native microorganisms, engineered E. coli and engineered yeasts, only synthesize a small amount of intracellular and extracellular hydrocarbons. Recently, Aureobasidium pullulans var. melanogenum isolated from a mangrove ecosystem has been found to be able to synthesize and secret over 21.5 g/l long-chain hydrocarbons with a yield of 0.275 g/g glucose and a productivity of 0.193 g/l/h within 5 days. The yeast may have highly potential applications in alkane production. PMID:26231137

  5. Biomarkers and compound-specific stable carbon isotope of n-alkanes in crude oils from Eastern Llanos Basin, Colombia

    Science.gov (United States)

    Cortes, Jorge E.; Rincon, Jose M.; Jaramillo, Jose M.; Philp, R. Paul; Allen, Jon

    2010-03-01

    Representative samples of crude oils from Cusiana, Cupiagua, Apiay, Castilla and Chichimene fields in the Eastern Llanos Basin of Colombia were analyzed to determine its compound-specific stable carbon isotope composition (CSIA) using gas chromatography-isotopic ratio-mass spectrometry (GC-IRMS). GC-IRMS analyses of n-alkanes allowed differentiating between Cretaceous and Cretaceous/Tertiary oil samples. Cretaceous sourced samples have δ13C-enriched values than Cretaceous/Tertiary sourced samples; the heavier isotope composition of these samples is due to their major terrigenous organic matter input. Their isotope distribution patterns suggest significant algal and/or bacterial contribution (marine origin). The analysis of the n-alkane fractions by GC-IRMS confirms that the organic matter has marine origin in those samples from Cusiana, Cupiagua and Apiay while Castilla and Chichimene have marine origin with terrestrial inputs. The results were confirmed by gas chromatography/FID and gas chromatography/mass spectrometry (GC/MS). Basic geochemical composition show that samples from Cupiagua/Cusiana fields and Apiay/Castilla/Chichimene fields in the Llanos basin, Colombia present different characteristics reflecting a specific for each depositional environment.

  6. Changes in the n-alkane composition of avocado pulp oil ( Persea americana, Mill. during fruit ripening

    Directory of Open Access Journals (Sweden)

    Giuffrè, A. M.

    2005-03-01

    Full Text Available The n-alkane composition of Avocado pulp oil (cv. Hass was investigated during fruit ripening. Three samples of fruit were harvested on March 3, 2003, March 18, 2003 and April 2, 2003. Glass gravity column chromatography was employed to separate n-alkanes from other minor components contained in the unsaponifiable fraction. Gas chromatography was used to analyze the eluate. Fourteen compounds were detected ranging from n -C21 to n -C34; mainly n -C24, followed by n -C25 and then by n -C23. Quantities of n -C21, n -C22, n -C23, n -C27 and n -C28 progressively increased during ripening, whereas n -C24, n -C25, n -C26, n -C29, n -C30 and n -C34 decreased from the first harvest date to the third harvest date. While odd-numbered carbon n-alkanes increased (52.38 %, 52.85 % and 53.06 % for the three samples respectively, even-numbered carbon n-alkanes decreased as the fruit ripened (47.62 %, 47.15 % and 46.94 %. The total n-alkane content decreased during ripening, from 25.20 mg/Kg (first harvest date to 16.77 mg/Kg (third harvest date. In order to minimize.Se ha analizado la composición en hidrocarburos lineales saturados del aceite de la pulpa de aguacate (variedad Hass. Tres muestras fueron recolectadas: el 3 de marzo 2003, el 18 de marzo 2003 y el 2 de abril 2003. La separación de los hidrocarburos lineales saturados se realizó mediante fraccionamiento del insaponificable por cromatografía gravimétrica de adsorción en columna y la determinación de los mismos hidrocarburos por cromatografía gaseosa. 14 compuestos fueron detectados del n- C21 al n- C34. El n- C24 fue el mayoritario, seguido del n- C25 y el n- C23. El porcentaje de n- C21, n- C22, n- C23, n- C27 y n- C28, aumentó durante la maduración, mientras que el porcentaje de n- C24, n- C25, n- C26, n- C29, n- C30 y C34 disminuyó desde el 3 de marzo 2003 hasta el 2 de abril 2003. Los hidrocarburos lineales saturados con número impar de átomos de carbono aumentaron (52.38 %, 52

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

    Science.gov (United States)

    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

  8. Thermochemical sulphate reduction (TSR) versus maturation and their effects on hydrogen stable isotopes of very dry alkane gases

    Science.gov (United States)

    Liu, Q. Y.; Worden, R. H.; Jin, Z. J.; Liu, W. H.; Li, J.; Gao, B.; Zhang, D. W.; Hu, A. P.; Yang, C.

    2014-07-01

    Here we report the first study of the effect of thermochemical sulphate reduction (TSR) on the hydrogen isotopes of natural gas. Variably sour (H2S-bearing) and very dry (>97% methane) gas samples from Lower Triassic, Permian and Carboniferous marine carbonate reservoirs in the Sichuan Basin, China, have been analysed. All gases seem to have been sourced from mature marine kerogen and contain H2S that resulted from TSR. The Carboniferous samples are largely unaffected by TSR and were used to assess the effects of normal thermal maturation processes on the carbon and hydrogen isotopes of methane and ethane as a function of gas dryness (a proxy for thermal maturity). Maturation led to heavier carbon isotopes of methane and ethane and hydrogen isotopes of ethane; in contrast methane hydrogen isotopes seem to have little systematic variation with increasing maturity. TSR did not have a systematic effect on the hydrogen isotopes of methane, although the spread of values diminished (ending up at a constant -120‰) as TSR proceeded. This was possibly due to the partial thermochemical sulphate reduction of ethane adding isotopically light methane and thus offsetting the Rayleigh fractionation effects of TSR of methane. In contrast, hydrogen isotopes of ethane became much heavier as TSR proceeded, to values greater than those for samples only influenced by maturation. Under some circumstances, the effects of TSR can be identified and discerned from the effects of normal thermal maturation by plotting the difference between the carbon isotope compositions of methane and ethane and the difference between the hydrogen isotope compositions of methane and ethane. Do the hydrogen isotope ratios of alkane gases systematically vary as a function of dryness or sourness? Do the hydrogen isotope ratios of alkane gases from the Carboniferous, Permian and Lower Triassic dry gas reservoirs help reveal the maturity and/or extent of TSR in the Sichuan Basin? Is it possible to separate and

  9. Enthalpies of reaction, formation, and hydrogenation among long chain alkanes, monoalkenes, acids, alcohols, and amines: G4 computed and experimental results

    International Nuclear Information System (INIS)

    Highlights: • We present a comparison of 59 G4 calculations with experimental results. • Enthalpies of formation, isomerization, and hydrogenation are covered. • Linear functions for experiment and calculation lead to a linear conversion function. • Results are given for alkanes, alkenes, acids, alcohols, and amines. - Abstract: We have carried out a comparison of experimental results and 59 G4 calculations of the enthalpies of formation ΔfH298Ko and hydrogenation ΔhydH298Ko of alkenes from 4 to 12 carbon atoms. We present a systematic calculation of the cis–trans isomerization enthalpy and a systematic comparison of experimental enthalpies of hydrogenation determined in this laboratory with the computed results of the same hydrogenations. The linear function of experimental results for alkanes and the linear function of the computed values lead to a linear function for converting one to the other. This result is an alternative to the commonly-used “atomization method” for finding the enthalpy of formation of an alkane relative to the thermodynamic reference state of the elements in their standard states. We calculate results in vector and matrix representation for compactness and consistency in treating large sets of computed G4 results. We show that the methods given here are sufficiently accurate so that reliable extrapolations to larger molecules can be made and that they are applicable to acids of biological interest, to alcohols, amines, and, in principle, to many other compounds such as polyenes, alkynes, and substituted alkanes

  10. Alkane-induced expression, substrate binding profile, and immunolocalization of a cytochrome P450 encoded on the nifD excision element of Anabaena 7120

    Directory of Open Access Journals (Sweden)

    Fjetland Conrad R

    2005-03-01

    Full Text Available Abstract Background Alkanes have been hypothesized to act as universal inducers of bacterial cytochrome P450 gene expression. We tested this hypothesis on an unusual P450 gene (cyp110 found on a conserved 11 kilobase episomal DNA element of unknown function found in filamentous cyanobacteria. We also monitored the binding of potential substrates to the P450 protein and explored the distribution of P450 protein in vegetative cells and nitrogen-fixing heterocysts using immuno-electron microscopy. Results Hexadecane treatments resulted in a two-fold increase in mRNA, and a four-fold increase in P450 protein levels relative to control cultures. Hexane, octane and dodecane were toxic and induced substantial changes in membrane morphology. Long-chain saturated and unsaturated fatty acids were shown to bind the CYP110 protein using a spectroscopic spin-shift assay, but alkanes did not bind. CYP110 protein was detected in vegetative cells but not in differentiated heterocysts where nitrogen fixation occurs. Conclusion Hexadecane treatment was an effective inducer of CYP110 expression in cyanobacteria. Based on substrate binding profiles and amino acid sequence similarities it is hypothesized that CYP110 is a fatty acid ω-hydroxylase in photosynthetic cells. CYP110 was found associated with membrane fractions unlike other soluble microbial P450 proteins, and in this regard CYP110 more closely resembles eukarytotic P450s. Substrate stablization is an unlikely mechanism for alkane induction because alkanes did not bind to purified CYP110 protein.

  11. Phase Equilibria of Mixtures Containing Glycol and n-Alkane: Experimental Study of Infinite Dilution Activity Coefficients and Modeling Using the Cubic-Plus-Association Equation of State

    DEFF Research Database (Denmark)

    Afzal, Waheed; Breil, Martin Peter; Théveneau, Pascal;

    2009-01-01

    In this work, we report the infinite dilution activity coefficients for four n-alkanes (n-pentane, n-hexane, n-heptane, and n-octane) in monoethylene glycol in the temperature range from 298 to 334 K and at atmospheric pressure. Experimental data were measured using a previously described inert gas...

  12. Draft Genome Sequence of Alkane-Degrading Acinetobacter venetianus JKSF02, Isolated from Contaminated Sediment of the San Jacinto River in Houston, Texas

    Science.gov (United States)

    Damania, Ashish

    2016-01-01

    Acinetobacter venetianus JKSF02 was isolated from contaminated sediment in eastern Houston, Texas along the San Jacinto River. This microorganism specializes in n-alkane degradation and is well suited for bioremediation of the petroleum hydrocarbon deposited throughout the region by shipping and industrial activity from the Houston Ship Channel. PMID:27081144

  13. Diversity and abundance of n-alkane degrading bacteria in the near surface soils of a Chinese onshore oil and gas field

    Directory of Open Access Journals (Sweden)

    K. Zhao

    2012-10-01

    Full Text Available Alkane degrading bacteria have long been used as an important biological indicator for oil and gas prospecting, but their ecological characteristics in hydrocarbon microseep habitats are still poorly understood. In this study, the diversity and abundance of n-alkane degrading bacterial community in the near surface soils of a Chinese onshore oil and gas field were investigated using molecular techniques. Terminal restriction fragment length polymorphism (T-RFLP analyses in combination with cloning and sequencing of alkB genes revealed that trace amount of volatile hydrocarbons migrated from oil and gas reservoirs caused a shift of the n-alkane degrading bacterial community from Gram-positive bacteria (Mycobacterium and Rhodococcus to Gram-negative genotypes (Alcanivorax and Acinetobacter. Real-time PCR results furthermore showed that the abundance of alkB genes increased substantially in the surface soils underlying oil and gas reservoirs even though only low or undetectable concentrations of hydrocarbons were measured in these soils due to efficient microbial degradation. Our findings broadened the knowledge on the ecological characteristics of alkane degrading community in hydrocarbon microseeps and may provide a new approach for microbial prospecting for oil and gas (MPOG.

  14. Diversity and abundance of n-alkane degrading bacteria in the near surface soils of a Chinese onshore oil and gas field

    Science.gov (United States)

    Xu, K.; Tang, Y.; Ren, C.; Zhao, K.; Sun, Y.

    2012-10-01

    Alkane degrading bacteria have long been used as an important biological indicator for oil and gas prospecting, but their ecological characteristics in hydrocarbon microseep habitats are still poorly understood. In this study, the diversity and abundance of n-alkane degrading bacterial community in the near surface soils of a Chinese onshore oil and gas field were investigated using molecular techniques. Terminal restriction fragment length polymorphism (T-RFLP) analyses in combination with cloning and sequencing of alkB genes revealed that trace amount of volatile hydrocarbons migrated from oil and gas reservoirs caused a shift of the n-alkane degrading bacterial community from Gram-positive bacteria (Mycobacterium and Rhodococcus) to Gram-negative genotypes (Alcanivorax and Acinetobacter). Real-time PCR results furthermore showed that the abundance of alkB genes increased substantially in the surface soils underlying oil and gas reservoirs even though only low or undetectable concentrations of hydrocarbons were measured in these soils due to efficient microbial degradation. Our findings broadened the knowledge on the ecological characteristics of alkane degrading community in hydrocarbon microseeps and may provide a new approach for microbial prospecting for oil and gas (MPOG).

  15. Essential-Oil Constituents and Alkanes of Cephalaria ambrosioides Roem. & Schult. (Family Caprifoliaceae, Subfamily Dipsacaceae) and (Chemo)taxonomic Discernment of the Subfamilies Dipsacaceae and Morinaceae.

    Science.gov (United States)

    Vukićević, Dušan R; Stevanović, Dragana D; Genčić, Marija S; Blagojević, Polina D; Radulović, Niko S

    2016-02-01

    Herein, the results of the first study of the volatile and alkane profiles of Cephalaria ambrosioides Roem. & Schult. (Caprifoliaceae, subfamily Dipsacaceae) were reported. The GC-FID and GC/MS analyses of the essential oils hydrodistilled from leaves and stems (CA1) and flowers (CA2) of C. ambrosioides allowed the identification of 284 different components. The main compounds of the studied oil samples were palmitic acid (24.3 and 32.5% for CA1 and CA2, resp.), hexahydrofarnesyl acetone (1.4 and 10.8% for CA1 and CA2, resp.), (Z)-hex-3-en-1-ol (7.0 and genus Cephalaria and its infrageneric relations, especially concerning the subfamily Morinaceae (formerly a genus within Dipsacaceae). The results of multivariate statistical analyses (25 different essential-oil samples) supported the exclusion of Morina species from the Dipsacaceae subfamily. The relative abundances of alkanes from n-, iso-, and anteiso-series followed a (distorted) Gaussian-like distribution and suggested that the biosyntheses of n- and branched alkanes in C. ambrosioides are possibly not controlled by the same elongase. Also, the obtained results suggested that there was a difference in the biosynthesis/accumulation of alkanes in the vegetative and reproductive parts of C. ambrosioides. PMID:26880432

  16. Both water source and atmospheric water impact leaf wax n-alkane 2H/1H values of hydroponically grown angiosperm trees

    Science.gov (United States)

    Tipple, B. J.; Berke, M. A.; Hambach, B.; Roden, J. S.; Ehleringer, J. R.

    2013-12-01

    The extent to which both water source and leaf water 2H-enrichment affect the δ2H values of terrestrial plant leaf waxes is an area of active research as ecologists seek a mechanistic understanding of the environmental determinants of leaf wax isotope values before applying δ2H values of leaf waxes to reconstruct past hydrologic conditions. To elucidate the effects of both water source and atmospheric water vapor on δ2H values of leaf waxes for broad-leaved angiosperms, we analyzed hydrogen isotope ratios of high-molecular weight n-alkanes from two tree species that were grown throughout the spring and summer (five months) in a hydroponic system under controlled atmospheric conditions. Here, 12 subpopulations each of Populus fremontii and Betula occidentalis saplings were grown under one of six source different waters ranging in hydrogen isotope ratio values from -120 to +180 ‰ and under either 40 % or 75 % relative humidity conditions. We found n-alkane δ2H values of both species were linearly related to source water δ2H values with differences in slope associated with differing atmospheric humidity. A Craig-Gordon model was used to predict the δ2H values of leaf water and, by extension, n-alkane δ2H values under the range of growth conditions. The modeled leaf water values were found to be linearly related to observed n-alkane δ2H values with a statistically indistinguishable slope between the high and low humidity treatments. These leaf wax observations support a constant biosynthetic fractionation factor between evaporatively-enriched leaf water and n-alkanes for each species. However, we found the calculated biosynthetic fractionation between modeled leaf-water and n-alkane to be different between the two species. We submit that these dissimilarities were due to model inputs and not differences in the specific-species biochemistry. Nonetheless, these results are significant as they indicated that the δ2H value of atmospheric water vapor and

  17. A molecular dynamics study of the effect of thermal boundary conductance on thermal transport of ideal crystal of n-alkanes with different number of carbon atoms

    Science.gov (United States)

    Rastgarkafshgarkolaei, Rouzbeh; Zeng, Yi; Khodadadi, J. M.

    2016-05-01

    Phase change materials such as n-alkanes that exhibit desirable characteristics such as high latent heat, chemical stability, and negligible supercooling are widely used in thermal energy storage applications. However, n-alkanes have the drawback of low thermal conductivity values. The low thermal conductivity of n-alkanes is linked to formation of randomly oriented nano-domains of molecules in their solid structure that is responsible for excessive phonon scattering at the grain boundaries. Thus, understanding the thermal boundary conductance at the grain boundaries can be crucial for improving the effectiveness of thermal storage systems. The concept of the ideal crystal is proposed in this paper, which describes a simplified model such that all the nano-domains of long-chain n-alkanes are artificially aligned perfectly in one direction. In order to study thermal transport of the ideal crystal of long-chain n-alkanes, four (4) systems (C20H42, C24H50, C26H54, and C30H62) are investigated by the molecular dynamics simulations. Thermal boundary conductance between the layers of ideal crystals is determined using both non-equilibrium molecular dynamics (NEMD) and equilibrium molecular dynamics (EMD) simulations. Both NEMD and EMD simulations exhibit no significant change in thermal conductance with the molecular length. However, the values obtained from the EMD simulations are less than the values from NEMD simulations with the ratio being nearly three (3) in most cases. This difference is due to the nature of EMD simulations where all the phonons are assumed to be in equilibrium at the interface. Thermal conductivity of the n-alkanes in three structures including liquid, solid, and ideal crystal is investigated utilizing NEMD simulations. Our results exhibit a very slight rise in thermal conductivity values as the number of carbon atoms of the chain increases. The key understanding is that thermal transport can be significantly altered by how the molecules and the

  18. Alkane, terpene and polycyclic aromatic hydrocarbon geochemistry of the Mackenzie River and Mackenzie shelf: Riverine contributions to Beaufort Sea coastal sediment

    Science.gov (United States)

    Yunker, Mark B.; Macdonald, Robie W.; Cretney, Walter J.; Fowler, Brian R.; McLaughlin, Fiona A.

    1993-07-01

    To study the largest source of river sediment to the Arctic Ocean, we have collected suspended particulates from the Mackenzie River in all seasons and sediments from the Mackenzie shelf between the river mouth and the shelf edge. These samples have been analyzed for alkanes, triterpenes and polycyclic aromatic hydrocarbons (PAHs). We found that naturally occurring hydrocarbons predominate in the river and on the shelf. These hydrocarbons include biogenic alkanes and triterpenes with a higher plant/peat origin, diagenetic PAHs from peat and plant detritus, petrogenic alkanes, triterpenes and PAHs from oil seeps and/or bitumens and combustion PAHs that are likely relict in peat deposits. Because these components vary independently, the season is found to strongly influence the concentration and composition of hydrocarbons in the Mackenzie River. While essentially the same pattern of alkanes, diagenetic hopanes and alkyl PAHs is observed in all river and most shelf sediment samples, alkane and triterpene concentration variations are strongly linked to the relative amount of higher plant/peat material. Polycyclic aromatic hydrocarbon molecular-mass profiles also appear to be tied primarily to varying proportions of peat, with an additional petrogenic component which is most likely associated with lithic material mobilized by the Mackenzie River at freshet. Consistent with the general lack of alkyl PAHs in peat, the higher PAHs found in the river are probably derived from forest and tundra fires. A few anthropogenic/pyrogenic compounds are manifest only at the shelf edge, probably due to a weakening of the river influence. We take this observation of pyrogenic PAHs and the pronounced source differences between two sediment samples collected at the shelf edge as evidence of a transition from dominance by the Mackenzie River to the geochemistry prevalent in Arctic regions far removed from major rivers.

  19. Comparison of bulk and compound-specific δ 13C analyses and determination of carbon sources to salt marsh sediments using n-alkane distributions (Maine, USA)

    Science.gov (United States)

    Tanner, Benjamin R.; Uhle, Maria E.; Mora, Claudia I.; Kelley, Joseph T.; Schuneman, Patrick J.; Lane, Chad S.; Allen, Evan S.

    2010-01-01

    Sources of sedimentary organic matter to a Morse River, Maine (USA) salt marsh over the last 3390 ± 60 RCYBP (Radiocarbon Years Before Present) are determined using distribution patterns of n-alkanes, bulk carbon isotopic analysis, and compound-specific carbon isotopic analysis. Marsh foraminiferal counts suggest a ubiquitous presence of high marsh and higher-high marsh deposits (dominated by Trochammina macrescens forma macrescens, Trochammina comprimata, and Trochammina inflata), implying deposition from ˜0.2 m to 0.5 m above mean high water. Distributions of n-alkanes show a primary contribution from higher plants, confirmed by an average chain length value of 27.5 for the core sediments, and carbon preference index values all >3. Many sample depths are dominated by the C 25 alkane. Salicornia depressa and Ruppia maritima have similar n-alkane distributions to many of the salt marsh sediments, and we suggest that one or both of these plants is either an important source to the biomass of the marsh through time, or that another unidentified higher plant source is contributing heavily to the sediment pool. Bacterial degradation or algal inputs to the marsh sediments appear to be minor. Compound-specific carbon isotopic analyses of the C 27 alkane are on average 7.2‰ depleted relative to bulk values, but the two records are strongly correlated ( R2 = 0.89), suggesting that marsh plants dominate the bulk carbon isotopic signal. Our study underscores the importance of using caution when applying mixing models of plant species to salt marsh sediments, especially when relatively few plants are included in the model.

  20. Comparison of Bulk and Compound-Specific Carbon Isotope Analyses and Determination of Carbon Sources to Salt Marsh Sediments Using n-Alkane Distributions (Maine, USA)

    Science.gov (United States)

    Tanner, B. R.; Uhle, M. E.; Kelley, J. T.; Mora, C. I.

    2005-12-01

    Sources of sedimentary organic matter to a Morse River, Maine (USA) salt marsh over the last 3390+/-60 RCYBP are determined using distribution patterns of n-alkanes as well as bulk and compound-specific carbon isotopic analysis. Marsh foraminiferal counts indicate the ubiquitous presence of zone 1B deposits, suggesting that the deposits were laid down ~0.2 to 0.5m above mean high water. Distributions of n-alkanes show a primary contribution from higher plants, confirmed by an average ACL value of 27.5 for the core sediments and CPI values above 3. Many sample depths have a maximum abundance at the C25 alkane. Ten low marsh, high marsh, and higher-high marsh plant species common to Maine salt marshes were sampled, including Spartina alterniflora, Spartina patens, Juncus gerardi and Solidago sempervirens. The ACL value for the average of the 10 marsh species is 29.1. Salicornia europa, usually not considered to be a dominant species in Maine marshes, has a similar n-alkane distribution to many of the salt marsh sediments, suggesting that it is an important source to the biomass of the marsh through time. Bacterial degradation or algal inputs to the marsh sediments appear to be minor. Compound specific carbon isotopic analyses of the C27 alkanes are, on average, 7.2ppt. depleted relative to bulk values, but the two records are strongly correlated (R2 = 0.87), suggesting that marsh plants are "swamping" the bulk carbon isotopic signal. The apparent abundance of a subordinate (though common) salt marsh plant species (Salicornia europa) within our core underscores the importance of using caution when applying mixing models of relatively few plant species to marsh sediments.

  1. Soil n-alkane δD and Branched GDGTs Distributions Track Elevation-induced Precipitation and Temperature Changes along the South Central Andes (Argentina)

    Science.gov (United States)

    Nieto-Moreno, V.; Rohrmann, A.; van der Meer, M.; S Sinninghe Damsté, J.; Sachse, D.; Tofelde, S.; Niedermeyer, E. M.; Strecker, M. R.; Mulch, A.

    2015-12-01

    Orogenic surface uplift and topographic evolution of tectonically active mountain belts exert a strong impact on climatic teleconnections and Earth surface processes, including changes in global atmospheric circulation patterns, erosion rates, distribution of biomes, and precipitation patterns. Hence, quantifying the driving processes shaping the evolution of topography in ancient and active orogens is required in order to disentangle the dynamic interactions and feedbacks among surface uplift, climate, erosion and sedimentation. The south central Andes of Argentina provide a particularly suitable setting to study the interplay between the tectonic and climatic evolution of an actively subduction orogen over short and long time-scales. We present δD values of soil-derived n-alkane and brGDGTs distributions to assess their suitability for paleoelevation reconstructions in the southern central Andes. We collected soil samples from two different environmental and hydrological gradients, across the hillslope (26-28°S) and along a river-valley (22-24°S) of two individual mountain ranges. δD n-alkane and brGDGTs distributions are both linearly related with elevation and may be used for paleoaltimetry studies along the windward flanks of the south central Andes. δD n-alkane and brGDGT-derived temperature lapse rates broadly follow regional lapse rates along steep orographic fronts. The observed lapse rates are lower than the annual mean values of satellite-derived temperatures but approach those of temperature loggers along each transect. Instead, δD n-alkane lapse rates are in line with regional stream-water data. These linear relationships along the windward slopes break down when entering the internally drained part of the Puna plateau. Our data document that δD n-alkane and brGDGTs distributions can be used over time scales relevant for paleoclimate/-altimetry reconstructions but also stress that such reconstructions require knowledge of the depositional

  2. Prediction of retention times of polycyclic aromatic hydrocarbons and n-alkanes in temperature-programmed gas chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Aldaeus, Fredrik; Thewalim, Yasar; Colmsjoe, Anders [Stockholm University, Department of Analytical Chemistry, Stockholm (Sweden)

    2007-10-15

    We have developed an iterative procedure for predicting the retention times of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes during separations by temperature-programmed gas chromatography. The procedure is based on estimates of two thermodynamic properties for each analyte (the differences in enthalpy and entropy associated with movements between the stationary and mobile phases) derived from data acquired experimentally in separations under isothermal conditions at temperatures spanning the range covered by the temperature programs in ten-degree increments. The columns used for this purpose were capillary columns containing polydimethylsiloxane-based stationary phases with three degrees of phenyl substitution (0%, 5%, and 50%). Predicted values were mostly within 1% of experimentally determined values, implying that the method is stable and precise. (orig.)

  3. Efficient Hydrogenolysis of Alkanes at Low Temperature and Pressure Using Tantalum Hydride on MCM-41, and a Quantum Chemical Study

    KAUST Repository

    Polshettiwar, Vivek

    2012-02-10

    Hydrogenolysis of hydrocarbons is of considerable technological importance for applications such as the hydroprocessing of petrochemical feedstocks to generate high-value and useful chemicals and fuels. We studied the catalytic activity of tantalum hydride supported on MCM-41 for the hydrogenolysis of alkanes at low temperature and low atmospheric pressure in a dynamic reactor. The reactions proceed with good turnover numbers, and the catalyst could be reused for several times, which makes the overall catalytic process sustainable. We derived the plausible mechanism by using DFT calculations and identified the preferred pathways by the analysis of potential energy surface. Our results and the proposed reaction mechanism demonstrate the viability of the "catalyst-by-design" approach. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Predominance and sources of alkane and fatty acid biomarkers in the surface sediments of Chitrapuzha River (South India).

    Science.gov (United States)

    Sanil Kumar, K S; Nair, S M

    2015-04-01

    Surface sediment samples were collected from Chitrapuzha (Cochin) estuarine system to identify the natural and anthropogenic origin of organic matter. The distribution and sources of organic matter were assessed with the help of fatty acid and alkane biomarkers. Fatty acids ranging from C12 to C28 were identified and C16:0 was the most abundant fatty acid, which contributed between 23.5 % and 52.4 % to total fatty acids. The low levels of polyunsaturated fatty acids indicate the effective bacterial recycling of algal fatty acids during the whole settling and depositing process. Aliphatic hydrocarbons ranging from C12 to C33 were identified and the total concentration ranged from 7876 to 43,357 ng g(-1). The presence of unresolved complex mixtures and lower pristane to phytane ratios indicates the petroleum contamination in the study area. PMID:25694163

  5. Excess molar volumes and isentropic compressibilities of binary liquid mixtures containing n-alkanes at 298.15 K

    Indian Academy of Sciences (India)

    V Vyas; T Nautiyal

    2002-10-01

    Excess molar volumes (E) and deviation in isentropic compressibilities (s) have been investigated from the density and speed of sound measurements of six binary liquid mixtures containing -alkanes over the entire range of composition at 298.15 K. Excess molar volume exhibits inversion in sign in one binary mixture, i.e., n-heptane + n-hexane. Remaining five binary mixtures, n-heptane + toluene, cyclohexane + n-heptane, cyclohexane + n-hexane, toluene + nhexane and n-decane + n-hexane show negative excess molar volumes over the whole composition range. However, the large negative values of excess molar volume becomes dominant in toluene + n-hexane mixture. Deviation in isentropic compressibility is negative over the whole range of composition in the case of all the six binary mixtures. Existence of specific intermolecular interactions in the mixtures has been analyzed in terms of excess molar volume and deviation in isentropic compressibility.

  6. Phase separation in the organic solid state: simultaneous Synchrotron SAXS / DSC studies of unstable n-alkane blends

    International Nuclear Information System (INIS)

    Full text: Blends of normal alkanes form lamellar structures, when quenched from the melt, in which the separation of the individual chains may be controlled by the chain-length difference, molar composition, isotopic substitution and confinement. We have performed simultaneous synchrotron small-angle X-ray scattering and differential scanning calorimetry studies on 2:1 C28H58:C36D74 mixtures as a function of cooling protocol. Their simultaneous collection enables the temperature-dependent nanostructural changes to be correlated with phase transitions. The data are further complemented by small-angle neutron scattering highlighting the separation of the individual chains via isotopic contrast and optical microscopy indicating changes occurring on the macroscopic scale. Copyright (2005) Australian Institute of Physics

  7. Catalytic conversion of light alkanes-proof-of-concept stage -- Phase 6. Final report, February 1--October 31, 1994

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1994-12-31

    During the course of the first three years of the Cooperative Agreement, the authors uncovered a family of metal perhaloporphyrin complexes which had unprecedented activity for the selective air-oxidation of light alkanes to alcohols. The reactivity of light hydrocarbon substrates with air or oxygen was in the order: isobutane > propane > ethane > methane, in accord with their homolytic bond dissociation energies. Isobutane was so reactive that the proof-of-concept stage of a process for producing tert-butyl alcohol from isobutane was begun (Phase 5). It was proposed that as more active catalytic systems were developed (Phases 4, 6), propane, then ethane and finally methane oxidations will move into this stage (Phases 7 through 9). As of this writing, however, the program has been terminated during the later stages of Phase 5 and 6 so that further work is not anticipated. 72 refs.

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

    Science.gov (United States)

    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.

  9. Carbon Isotopes of Alkanes in Hydrothermal Abiotic Organic Synthesis Processes at High Temperatures and Pressures: An Experimental Study

    Science.gov (United States)

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

    2010-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques [1-4]. With more evidence showing extensive water-rock interaction in Martian history [5-7], abiotic formation by Fischer-Tropsch Type (FTT) synthesis during serpentization reactions may be one possible process responsible for methane generation on Mars [8, 9]. While the experimental studies performed to date leave little doubt that chemical reactions exist for the abiotic synthesis of organic compounds by mineral surface-catalyzed reactions [10-12], little is known about the reaction pathways by which CO2 and/or CO are reduced under hydrothermal conditions. Carbon and hydrogen isotope measurements of alkanes have been used as an effective tool to constrain the origin and reaction pathways of hydrocarbon formation. Alkanes generated by thermal breakdown of high molecular weight organic compounds have carbon and hydrogen isotopic signatures completely distinct from those formed abiotically [13-15]. Recent experimental studies, however, showed that different abiogenic hydrocarbon formation processes (e.g., polymerization vs. depolymerization) may have different carbon and hydrogen isotopic patterns [16]. Results from previous experiments studying decomposition of higher molecular weight organic compounds (lignite) also suggested that pressure could be a crucial factor affecting fractionation of carbon isotopes [17]. Under high pressure conditions, no experimental data are available describing fractionation of carbon isotope during mineral catalyzed FTT synthesis. Thus, hydrothermal experiments present an excellent opportunity to provide the requisite carbon isotope data. Such data can also be used to identify reaction pathways of abiotic organic synthesis under experimental conditions.

  10. Gas-Phase Reactions of (n, γ) and Isomeric Transition-Activated Br80 with Alkanes and Haloalkanes

    International Nuclear Information System (INIS)

    Experimental data are presented on the gas-phase reactions of alkanes and haloalkanes with bromine atoms and ions activated by nuclear transformations. The target molecules include CH4 CD4, C2H6, C2D6, CH3Cl, CH2Cl2, CHCI3, CCl4, CH2F2, CHF3, CF4, C2F6, CF3Br, and CH3Br. The nuclear reactions and transformations used in producing the energetic recoil atoms and ions were Br80m (isomeric transition), Br80, and Br79 (n, γ) Br80. The percentage of the radioactivity found in organic combination (the organic yield, O. Y.) was determined as a function of the concentration of the target molecule in the mole-fraction range of about 0.95 to 1.00. Elemental Br2 served both as a source of hot atoms and as a scavenger. Usually 20-50 separate samples of each reaction system were examined and the data of O.Y. as a function of the concentration of scavenger were plotted and extrapolated to unit mole fraction of target molecule. In all cases, die O.Y. decreased with increasing halogen concentration. Data on the (n, γ) activated reactions of Br80 with isotopic alkanes suggest a comparable extrapolated O.Y. for C2H6 and C2D6, but an O.Y. for CD4 about half of the O.Y. with CH4. Gas chromatographic analysis of the organic products indicates that about 90% of the O.Y. in CH4 is caused by CH3Br and 10% by CH2Br2 For CD4 as the target the distribution of organic activity is approx. 75% CD3Br and 25% CD2Br2. These various data are discussed in terms of possible mechanisms involving hot halogen atoms and ions

  11. Radical formation in the [MeReO3]-catalyzed aqueous peroxidative oxidation of alkanes: a theoretical mechanistic study.

    Science.gov (United States)

    Kuznetsov, Maxim L; Pombeiro, Armando J L

    2009-01-01

    Plausible mechanisms of radical formation in the catalytic system [MeReO(3)]/H(2)O(2)/H(2)O-CH(3)CN for the oxidation of alkanes to alcohols and ketones, via radical pathways, are investigated extensively at the density functional theory level. The most favorable route is based on the monoperoxo complex [MeReO(2)(O(2))(H(2)O)] and includes the formation of an H(2)O(2) adduct, water-assisted H-transfer from H(2)O(2) to the peroxo ligand, and generation of HOO(*). The thus formed reduced Re(VI) complex [MeReO(2)(OOH)(H(2)O)] reacts with H(2)O(2), resulting, upon water-assisted H-transfer and O-OH bond homolysis, in the regeneration of the oxo-Re(VII) catalyst and formation of the HO(*) radical that reacts further with the alkane. Water plays a crucial role by (i) stabilizing transition states for the proton migrations and providing easy intramolecular H-transfers in the absence of any N,O-ligands and (ii) saturating the Re coordination sphere what leads to a decrease of the activation barrier for the formation of HOO(*). The activation energy of the radical formation calculated for [MeReO(3)] (17.7 kcal/mol) is compatible with that determined experimentally [Shul'pin et al. J. Chem. Soc., Perkin Trans. 2 2001, 1351 .] for oxo-V-based catalytic systems (17 +/- 2 kcal/mol), and the overall type of mechanism proposed for such V catalysts is also effective for [MeReO(3)]. PMID:19049432

  12. Distribution and stable isotope composition of leaf wax n-alkanes as tracers for organic matter transport along hydrological transects in the NW Argentine Andes

    Science.gov (United States)

    Tofelde, Stefanie; Sachse, Dirk; Schildgen, Taylor; Strecker, Manfred R.

    2015-04-01

    The burial of organic matter in marine sediments represents the main long-term sink for reduced carbon in the global carbon cycle, with the fluvial system being the predominant transport mechanism. Organic matter deposited in marine and continental sediments contains valuable information on ecological and climatic conditions, and organic proxy data is thus often used in paleoclimate research. To use sedimentary records to investigate past environmental conditions in the terrestrial realm, processes dictating the transport of organic matter, including spatial and temporal resolution as well as the influence of climatic and tectonic processes, have to be understood. In this study, we test if a lipid biomarker based approach can be used to trace present-day organic matter sources in a fluvial watershed draining two intermontane basins in the southern-central Andes of NW Argentina, a tectonically active region with pronounced topographic, rainfall, and vegetation gradients. We investigated the distribution of long-chain leaf-wax n-alkanes, a terrestrial plant biomarker (and as such representative of terrestrially sourced carbon), in river sediments and coarse particulate organic matter (CPOM) along two altitudinal and hydrological gradients. We used n-alkane abundances and their stable carbon and hydrogen isotopic values as three independent parameters for source discrimination. Additionally, we analyzed the control of environmental parameters on the isotopic signatures in leaf-wax n-alkanes. The general pattern of n-alkane distribution in river sediments and CPOM samples in our study area suggest that vascular plants are the major source of riverine organic matter. The stable carbon isotopic composition of nC29 alkanes suggests a nearly exclusive input of C3 vegetation. Although C4 plants are present in the lower catchment areas, the total percentage is too low to have a detectable influence on the carbon isotopic composition in river sediment and CPOM samples

  13. Predominance of even carbon-numbered n-alkanes from lacustrine sediments in Linxia Basin, NE Tibetan Plateau: Implications for climate change

    International Nuclear Information System (INIS)

    Research highlights: → This study reports the first observation of predominant even carbon-numbered n-alkanes of sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. → Certain types of special autochthonous bacteria are a possible source for the special distribution of even carbon-numbered n-alkanes in lacustrine sediments. → These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change. → A close correspondence among the low ratio of n-C27/n-C31, the heavy δ13C values of TOC and a strong even carbon-number predominance (low OEP16-20 values) from approximately 6.5 to 4.4 Ma and at approximately 8 Ma in the studied section suggests that n-alkanes with a high predominance of even carbon-numbers may be treated as geochemical proxies for arid climate. - Abstract: This study reports the first observation of predominant even C-numbered n-alkanes from sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. The n-alkanes showed a bimodal distribution that is characterised by a centre at n-C16-n-C20 with maximum values at n-C18 and n-C27-n-C31 as well as at n-C29. The first mode shows a strong even C-number predominance (OEP16-20 0.34-0.66). In contrast, the second mode has a strong odd C-number predominance (OEP27-31 1.20-2.45). Certain types of special autochthonous bacteria are a possible source for this distribution of even C-numbered n-alkanes in lacustrine sediments. These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change.

  14. A compound-specific n-alkane δ 13C and δD approach for assessing source and delivery processes of terrestrial organic matter within a forested watershed in northern Japan

    Science.gov (United States)

    Seki, Osamu; Nakatsuka, Takeshi; Shibata, Hideaki; Kawamura, Kimitaka

    2010-01-01

    We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ 13C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ 13C values of odd carbon numbered C 23-C 33n-alkanes ranged from -37.2‰ to -31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from -244‰ to -180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ 13C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C 25-C 31n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment.

  15. Partial resolution of sources of n-alkanes in the saline portion of the Parachute Creek Member, Green River Formation (Piceance Creek Basin, Colorado)

    Science.gov (United States)

    Collister, J. W.; Lichtfouse, E.; Hieshima, G.; Hayes, J. M.

    1994-01-01

    Systematic variations in the 13C contents of individual extractable n-alkanes (C16-C29) can be modelled quantitatively and interpreted as indicating contributions from at least five distinct sources. These appear to be cyanobacterial (C16-C18, delta 13C = -37% vs PDB), phytoplanktonic (C16-C23, delta = -32%), chemoautotrophic bacterial (C20-C29, delta = -38%), phytoplanktonic or heterotrophic bacterial (C20-C29, delta = -30%), and vascular plants (C23-C29, delta = -29%). Hydrous pyrolysis of related kerogens yields large quantities of additional n-alkanes with different and much more uniform delta values. The latter materials are apparently derived from the thermolysis of aliphatic biopolymers whose presence in the Green River Oil Shale has been recognized visually.

  16. Equilibrium 2H/ 1H fractionations in organic molecules. II: Linear alkanes, alkenes, ketones, carboxylic acids, esters, alcohols and ethers

    Science.gov (United States)

    Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A., III

    2009-12-01

    Equilibrium 2H/ 1H fractionation factors (α eq) for various H positions in alkanes, alkenes, ketones, carboxylic acids, esters, alcohols, and ethers were calculated between 0 and 100 °C using vibrational frequencies from ab initio QM calculations (B3LYP/6-311G**). Results were then corrected using a temperature-dependent linear calibration curve based on experimental data for H α in ketones ( Wang et al., 2009). The total uncertainty in reported α eq values is estimated at 10-20‰. The effects of functional groups were found to increase the value of α eq for H next to electron-donating groups, e.g. sbnd OR, sbnd OH or sbnd O(C dbnd O)R, and to decrease the value of α eq for H next to electron-withdrawing groups, e.g. sbnd (C dbnd O)R or sbnd (C dbnd O)OR. Smaller but significant functional group effects are also observed for H β and sometimes H γ. By summing over individual H positions, we estimate the equilibrium fractionation relative to water to be -90‰ to -70‰ for n-alkanes and around -100‰ for pristane and phytane. The temperature dependence of these fractionations is very weak between 0 and 100 °C. Our estimates of α eq agree well with field data for thermally mature hydrocarbons (δ 2H values between -80‰ and -110‰ relative to water). Therefore the observed δ 2H increase of individual hydrocarbons and the disappearance of the biosynthetic δ 2H offset between n-alkyl and linear isoprenoid lipids during maturation of organic matter can be confidently attributed to H exchange towards an equilibrium state. Our results also indicate that many n-alkyl lipids are biosynthesized with δ 2H values that are close to equilibrium with water. In these cases, constant down-core δ 2H values for n-alkyl lipids cannot be reliably used to infer a lack of isotopic exchange.

  17. Compound-specific carbon isotope compositions of individual long-chain n-alkanes in severe Asian dust episodes in the North China coast in 2002

    Institute of Scientific and Technical Information of China (English)

    GUO Zhigang; LI Juyuan; FENG Jialiang; FANG Ming; YANG Zuosheng

    2006-01-01

    The molecular compositions and compound-specific carbon isotope compositions of individual long-chain n-alkanes of atmospheric aerosols collected during two severe Asian dust episodes in Qingdao in spring of 2002 were analyzed using gas chromatography/mass spectrometry (GC/MS) and gas chromatography/isotope ratio mass spectrometry (GC/IRMS). Typical plant wax n-alkanes (C29 and C31) had lowerδ13C values than those from anthropogenic (engine exhaust) sources (C21―C23). The average δ13C value of plant wax n-alkane C29 in non-dust episode periods was -30.5‰ (-30.3‰― -31.9‰), while -31.3‰ (-31.1‰―-31.5‰) in dust episode periods; for C31, it was -31.4‰ (-31.1‰―-33.0‰) in non-dust episode periods, and -31.7‰ (-31.3‰―-32.6‰) in dust episode periods. Plant wax in the dust episode samples was mainly from herbaceous plants via long-range transport, while local plant wax was mainly from deciduous plants and woody plants. In North China coast, 83.3% of the plant wax in the severe dust episode samples was from C3 plants while 80.0% for the non-dust samples, indicating that plant wax transported to the northwestern Pacific Ocean by airborne dust from East Asia was mainly from C3 plants. The results suggest that the molecular and molecular-isotopic compositions of individual long-chain n-alkanes can, as an effective indicator, identify the terrestrial organic components in the dust from East Asia and sediments in the northwest Pacific Ocean.

  18. Preferential activation of primary C–H bonds in the reactions of small alkanes with the diatomic MgO+. cation

    Czech Academy of Sciences Publication Activity Database

    Schröder, Detlef; Roithová, J.; Alikhani, E.; Kwapien, K.; Sauer, J.

    2010-01-01

    Roč. 16, č. 13 (2010), s. 4110-4119. ISSN 0947-6539 R&D Projects: GA AV ČR KJB400550704; GA ČR GA203/08/1487 Grant ostatní: ERC(XE) HORIZOMS AdG226373 Institutional research plan: CEZ:AV0Z40550506 Keywords : alkanes * C-H activation * density functional calculations * magnesium oxide Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.476, year: 2010

  19. Anomalous tunneling in carbon/alkane/TiO(2)/gold molecular electronic junctions: energy level alignment at the metal/semiconductor interface.

    Science.gov (United States)

    Yan, Haijun; McCreery, Richard L

    2009-02-01

    Carbon/TiO(2)/gold electronic junctions show slightly asymmetric electronic behavior, with higher current observed in current density (J)/voltage (V) curves when carbon is biased negative with respect to the gold top contact. When a approximately 1-nm-thick alkane film is deposited between the carbon and TiO(2), resulting in a carbon/alkane/TiO(2)/gold junction, the current increases significantly for negative bias and decreases for positive bias, thus creating a much less symmetric J/V response. Similar results were obtained when SiO(2) was substituted for the alkane layer, but Al(2)O(3) did not produce the effect. The observation that, by the addition of an insulating material between carbon and TiO(2), the junction becomes more conductive is unexpected and counterintuitive. Kelvin probe measurements revealed that while the apparent work function of the pyrolyzed photoresist film electrode is modulated by surface dipoles of different surface-bound molecular layers, the anomalous effect is independent of the direction of the surface dipole. We propose that by using a nanometer-thick film with a low dielectric constant as an insertion layer, most of the applied potential is dropped across this thin film, thus permitting alignment between the carbon Fermi level and the TiO(2) conduction band. Provided that the alkane layer is sufficiently thin, electrons can directly tunnel from carbon to the TiO(2) conduction band. Therefore, the electron injection barrier at the carbon/TiO(2) interface is effectively reduced by this energy-level alignment, resulting in an increased current when carbon is biased negative. The modulation of injection barriers by a low-kappa molecular layer should be generally applicable to a variety of materials used in micro- and nanoelectronic fabrication. PMID:20353235

  20. Fidelity of leaf-wax n-alkane and n-alkanoic acid D/H ratios in space and time

    Science.gov (United States)

    Polissar, P. J.; Preefer, M. B.; Liu, C.

    2014-12-01

    There is great potential for reconstructing past changes in the hydrologic cycle using the hydrogen isotopic composition of plant-wax biomarkers. However, empirical relationships relating plant-wax hydrogen isotope compositions (δDwax) to source water are almost exclusively based upon modern plants, soils and sediments and a single compound class such as n-alkanes or n-alkanoic acids. Relatively little is known about the relationship between these compound classes and differences in how they record the hydrogen isotopic composition of source water. Here we present new hydrogen isotopic measurements from a suite of modern and late Quaternary lake sediment samples to test the fidelity of δDwaxto source water δD in space and time. We find that within compound class the shared variance between C29 and C31 n-alkane and C28 and C30 n-alkanoic acid δD values is 87% and 86%. Between compound classes there is 53% shared variance between C29 n-alkane and C28 n-acid δD values. The apparent isotopic fractionation between source water and n-alkane δD values is consistent with prior studies from these regions that show the influence of vegetation type and climate. However, the n-alkanoic acid apparent fractionation values cannot be explained by these factors alone. Rather, the data require that for a large proportion of the samples there is a substantial contribution of long-chain n-acids from vegetation that uses lake water as the hydrogen source for lipid synthesis. This is consistent with overlapping n-acid compound distributions in lake sediment, soils, and aquatic and terrestrial plants from many of these regions. Our results emphasize the utility of plant-wax δD for reconstructing water δD values and highlight the potential importance of non-terrestrial sources of long-chain n-acids in lake systems.

  1. Organometallic Model Complexes Elucidate the Active Gallium Species in Alkane Dehydrogenation Catalysts Based on Ligand Effects in Ga K-Edge XANES

    Energy Technology Data Exchange (ETDEWEB)

    Getsoian, Andrew ' Bean' ; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-08-21

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  2. Development of bioreporter assays for the detection of bioavailability of long-chain alkanes based on the marine bacterium Alcanivorax borkumensis strain SK2.

    Science.gov (United States)

    Kumari, Rekha; Tecon, Robin; Beggah, Siham; Rutler, Rebecca; Arey, J Samuel; van der Meer, Jan Roelof

    2011-10-01

    Long-chain alkanes are a major component of crude oil and therefore potentially good indicators of hydrocarbon spills. Here we present a set of new bacterial bioreporters and assays that allow to detect long-chain alkanes. These reporters are based on the regulatory protein AlkS and the alkB1 promoter from Alcanivorax borkumensis SK2, a widespread alkane degrader in marine habitats. Escherichia coli cells with the reporter construct reacted strongly to octane in short-term (6 h) aqueous suspension assays but very slightly only to tetradecane, in line with what is expected from its low water solubility. In contrast, long-term assays (up to 5 days) with A. borkumensis bioreporters showed strong induction with tetradecane and crude oil. Gel-immobilized A. borkumensis reporter cells were used to demonstrate tetradecane and crude oil bioavailability at a distance from a source. Alcanivorax borkumensis bioreporters induced fivefold more rapid and more strongly when allowed physical contact with the oil phase in standing flask assays, suggesting a major contribution of adhered cells to the overall reporter signal. Using the flask assays we further demonstrated the effect of oleophilic nutrients and biosurfactants on oil availability and degradation by A. borkumensis. The fluorescence signal from flask assays could easily be captured with a normal digital camera, making such tests feasible to be carried out on, e.g. marine oil responder vessels in case of oil accidents. PMID:21895911

  3. Correlation and prediction of mixing thermodynamic properties of ester-containing systems: Ester + alkane and ester + ester binary systems and the ternary dodecane + ethyl pentanoate + ethyl ethanoate

    International Nuclear Information System (INIS)

    Highlights: ► Excess enthalpies and volumes were measured for ester–ester–alkane. ► Mixing behaviour for ester–ester, ester–alkane and ester–ester–alkane are analyzed. ► Correlations with a new polynomial model reproduce well the mixing properties. ► UNIFAC predictions for hE result acceptable excluding the ester–ester mixtures. - Abstract: Excess thermodynamic properties VmE and HmE, have been measured for the ternary mixture dodecane + ethyl pentanoate + ethyl ethanoate and for the corresponding binaries dodecane + ethyl pentanoate, dodecane + ethyl ethanoate, ethyl pentanoate + ethyl ethanoate at 298.15 K. All mixtures show endothermic and expansive effects. Experimental results are correlated with a suitable equation whose final form for the excess ternary quantity ME contains the particular contributions of the three binaries (i–j) and a last term corresponding to the ternary, all of them obtained considering fourth-order interactions. The fit goodness for all mixtures is good and comparable to others equations taken from the literature. In this work the dissolution model for the binaries and ternary is analyzed with a special attention to ester–ester binaries whose behaviour is discussed. The application of the UNIFAC group contribution model to estimate the HmE yields acceptable results for the binaries (with the exception of ester–ester) and for the ternary mixture.

  4. Diversity and abundance of n-alkane-degrading bacteria in the near-surface soils of a Chinese onshore oil and gas field

    Directory of Open Access Journals (Sweden)

    K. Xu

    2013-03-01

    Full Text Available Alkane-degrading bacteria have long been used as an important biological indicator for oil and gas prospecting, but their ecological characteristics in hydrocarbon microseep habitats are still poorly understood. In this study, the diversity and abundance of n-alkane-degrading bacterial community in the near-surface soils of a Chinese onshore oil and gas field were investigated using molecular techniques. Terminal restriction fragment length polymorphism (T-RFLP analyses in combination with cloning and sequencing of alkB genes revealed that Gram-negative genotypes (Alcanivorax and Acinetobacter dominated n-alkane-degrading bacterial communities in the near-surface soils of oil and gas reservoirs, while the dominant microbial communities were Gram-positive bacteria (Mycobacterium and Rhodococcus in background soil. Real-time quantitative polymerase chain reaction (PCR results furthermore showed that the abundance of alkB genes increased substantially in the surface soils above oil and gas reservoirs even though only low or undetectable concentrations of hydrocarbons were measured in these soils. The results of this study implicate that trace amounts of volatile hydrocarbons migrate from oil and gas reservoirs, and likely result in the changes of microbial communities in the near-surface soil.

  5. Diversity and abundance of n-alkane-degrading bacteria in the near-surface soils of a Chinese onshore oil and gas field

    Science.gov (United States)

    Xu, K.; Tang, Y.; Ren, C.; Zhao, K.; Sun, Y.

    2013-03-01

    Alkane-degrading bacteria have long been used as an important biological indicator for oil and gas prospecting, but their ecological characteristics in hydrocarbon microseep habitats are still poorly understood. In this study, the diversity and abundance of n-alkane-degrading bacterial community in the near-surface soils of a Chinese onshore oil and gas field were investigated using molecular techniques. Terminal restriction fragment length polymorphism (T-RFLP) analyses in combination with cloning and sequencing of alkB genes revealed that Gram-negative genotypes (Alcanivorax and Acinetobacter) dominated n-alkane-degrading bacterial communities in the near-surface soils of oil and gas reservoirs, while the dominant microbial communities were Gram-positive bacteria (Mycobacterium and Rhodococcus) in background soil. Real-time quantitative polymerase chain reaction (PCR) results furthermore showed that the abundance of alkB genes increased substantially in the surface soils above oil and gas reservoirs even though only low or undetectable concentrations of hydrocarbons were measured in these soils. The results of this study implicate that trace amounts of volatile hydrocarbons migrate from oil and gas reservoirs, and likely result in the changes of microbial communities in the near-surface soil.

  6. Normal alkanes and the unresolved complex mixture as diagnostic indicators of hydrocarbon source contributions to marine sediments of the Northern Gulf of Alaska

    International Nuclear Information System (INIS)

    Coal beds, hydrocarbon source rocks, and natural oil seeps represent potentially significant sources of hydrocarbons contamination of marine sediments in the northern Gulf of Alaska. Intensive studies of several supposedly diagnostic polycyclic aromatic (PAH) and aliphatic hydrocarbon compounds have been conducted to solve the controversy of whether the hydrocarbons come from natural or anthropogenic sources. These hydrocarbons could be associated with a refractory matrix not biologically available, as strongly suggested by the n-alkane profile characteristic of the marine sediments. There are similarities between the unresolved complex mixture (UCM) profile of the marine sediments and those of eroding coals and source rocks. However, there were differences with the UCM of seep oils entering the Gulf of Alaska. The seep-oils possess low concentrations of n-alkanes due to biodegradation before entering the Gulf of Alaska, and have large UCM and PAH concentrations. Additional strong constraints are placed on hydrocarbon contributions from natural sources to the marine sediments of the northern portion of the Gulf of Alaska as a result of inclusion of n-alkane and UCM results into hydrocarbon source allocation models. The authors indicated that seep-oils are unlikely to be significant contributors. 19 refs., 1 tab., 6 figs

  7. MPN- and Real-Time-Based PCR Methods for the Quantification of Alkane Monooxygenase Homologous Genes (alkB) in Environmental Samples

    Science.gov (United States)

    Pérez-de-Mora, Alfredo; Schulz, Stephan; Schloter, Michael

    Hydrocarbons are major contaminants of soil ecosystems as a result of uncontrolled oil spills and wastes disposal into the environment. Ecological risk assessment and remediation of affected sites is often constrained due to lack of suitable prognostic and diagnostic tools that provide information of abiotic-biotic interactions occurring between contaminants and biological targets. Therefore, the identification and quantification of genes involved in the degradation of hydrocarbons may play a crucial role for evaluating the natural attenuation potential of contaminated sites and the development of successful bioremediation strategies. Besides other gene clusters, the alk operon has been identified as a major player for alkane degradation in different soils. An oxygenase gene (alkB) codes for the initial step of the degradation of aliphatic alkanes under aerobic conditions. In this work, we present an MPN- and a real-time PCR method for the quantification of the bacterial gene alkB (coding for rubredoxin-dependent alkane monooxygenase) in environmental samples. Both approaches enable a rapid culture-independent screening of the alkB gene in the environment, which can be used to assess the intrinsic natural attenuation potential of a site or to follow up the on-going progress of bioremediation assays.

  8. Wax ester-like compounds as biosurfactants produced by Dietzia maris from n-alkane as a sole carbon source.

    Science.gov (United States)

    Nakano, Miyo; Kihara, Masaki; Iehata, Shunpei; Tanaka, Reiji; Maeda, Hiroto; Yoshikawa, Takeshi

    2011-10-01

    The hydrocarbon-degrading bacterium Dietzia maris WR-3 was isolated from a consortium comprising ammonia-oxidizing and denitrifying bacteria derived from marine sediments. Here, we examined biosurfactant production by strain WR-3 when cultured using several different carbon (D-glucose, n -decane, n -hexadecane, motor oil, olive oil, and rapeseed oil) and nitrogen (NH(4) )(2) SO(4) , NaNO(3) , yeast extract, and polypeptone) sources as growth substrates. Strain WR-3 was able to grow and reduce the surface tension of culture broth to 31±1.0 mN m(-1) when cultured using n -hexadecane and nitrate ions. The surface-active compounds produced by strain WR-3 were extracted and analyzed by thin layer chromatography. Moreover, the main components in the extract were further purified and subjected to gas chromatography/mass spectrometry (GC/MS). From the analysis, the surface-active compounds were tentatively identified as wax ester-like compounds, which were synthesized from the degradation process of n -alkane. The production of surface-active compounds by strain WR-3 promoted attachment of cells to hydrocarbon droplets via increased cell hydrophobicity, thus allowing enhanced degradation of water immiscible substrates. As Dietzia spp. can grow and produce wax esters from the degradation process of hydrocarbons, these marine bacteria are potentially useful for the bioremediation of hydrocarbon-contaminated environments. PMID:21656811

  9. Superposition-additive approach: thermodynamic parameters of clusterization of monosubstituted alkanes at the air/water interface.

    Science.gov (United States)

    Vysotsky, Yu B; Belyaeva, E A; Fomina, E S; Fainerman, V B; Aksenenko, E V; Vollhardt, D; Miller, R

    2011-12-21

    The applicability of the superposition-additive approach for the calculation of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole electric polarisabilities, molecular diamagnetic susceptibilities, π-electron circular currents, as well as for the estimation of the thermodynamic parameters of substituted alkanes, was demonstrated earlier. Now the applicability of the superposition-additive approach for the description of clusterization of fatty alcohols, thioalcohols, amines, carboxylic acids at the air/water interface is studied. Two superposition-additive schemes are used that ensure the maximum superimposition of the graphs of the considered molecular structures including the intermolecular CH-HC interactions within the clusters. The thermodynamic parameters of clusterization are calculated for dimers, trimers and tetramers. The calculations are based on the values of enthalpy, entropy and Gibbs' energy of clusterization calculated earlier using the semiempirical quantum chemical PM3 method. It is shown that the proposed approach is capable of the reproduction with sufficiently enough accuracy of the values calculated previously. PMID:22042000

  10. Viscosity and surface tension of binary systems of N,N-dimethylformamide with alkan-1-ols at different temperatures

    International Nuclear Information System (INIS)

    Highlights: ► Physical properties of binary mixtures of DMF+1-pentanol, 1-hexanol, or 1-heptanol. ► Viscosity and surface tension were measured. ►Δη, Δσσ and G∗E were calculated using the experimental data. ► Hσ and Sσ were determined using the surface tension data. ► Semi-empirical relations were used to estimate the viscosity of liquid mixtures. - Abstract: Viscosity η and surface tension σ were measured for binary mixtures of N,N-dimethylformamide DMF with pentan-1-ol, hexan-1-ol, and heptan-1-ol at T = (298.15, 303.15, 308.15, and 313.15) K and atmospheric pressure over the entire mole fraction range. Deviations in viscosity Δη and surface tension Δσ were calculated using experimental results. Moreover, the values of the excess Gibbs free energy of activation G∗E, surface enthalpy Hσ and surface entropy Sσ of these mixtures were determined. Viscosity measurements of the binary systems were correlated with Grunberg and Nissan, the three-body and four-body McAllister expressions. Viscosity deviation, surface tension deviation and excess Gibbs energy of activation functions were fitted to the method of Redlich–Kister (R–K) polynomial to estimate the coefficients and standard deviations. The effects of chain length of alkan-1-ols and temperature on the thermodynamic properties of binary systems were studied.

  11. Transport behavior of n-alkane penetrants into castor oil based polyurethane-polyester nonwoven fabric composites

    International Nuclear Information System (INIS)

    Castor oil based polyurethane (PU)-polyester nonwoven fabric composites were fabricated by impregnating the polyester nonwoven fabric in a composition containing castor oil and diisocyanate. Composites were fabricated with two different isocyanates such as toluene-2,4-diisocyanate (TDI) and hexamethylene diisocyanate (HMDI). Transport behavior of n-alkane penetrants (pentane, hexane and heptane) into both PUs and PU-polyester nonwoven fabric composites were studied. Sorption studies were carried out at different temperatures. From the sorption results, the diffusion (D) and permeation (P) coefficients of penetrants have been calculated. Significant increase in the diffusion and permeation coefficients was observed with increase in the temperature of sorption experiments. Drastical reduction in diffusion and permeation coefficients was noticed in the composites compared to neat PUs. Attempts were made to estimate the empirical parameters like n, which suggests the mode of transport and K is a constant depends on the structural characteristics of the composite in addition to its interaction with penetrants. The temperature dependence of the transport coefficients has been used to estimate the activation energy parameter for diffusion (ED) and permeation (EP) processes from Arrhenius plots. Furthermore, the sorption results have been interpreted in terms of the thermodynamic parameters such as enthalpy (ΔH) and entropy (ΔS)

  12. Catalytic conversion of light alkanes-proof-of-concept stage - Phase IV. Topical report, February 1, 1994--January 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

    This report details the research performed on Phase IV of the extended Cooperative Agreement. This Phase, entitled C{sub 1}-C{sub 4} Research, provides the research support which accompanies the C{sub 4} Proof-of-Concept Phase (Phase V) as the two major activities of the Cooperative Agreement during calendar 1993. It is the objective of this phase to understand the nature of the catalysts and catalytic activity of perhaloporphyrin complexes uncovered during Phases I-III in order that superior catalytic materials can be made and tested which meet commercial criteria for the oxidation of the C{sub 1}-C{sub 4} light alkane gases found in natural gas and other available hydrocarbon streams. During Phase IV, we have examined the physical and electronic structures of the very active perhaloporphyrin catalysts which we have developed, and have gained an understanding of the properties which make them active. This has led us to design and synthesize materials which are cheaper, more active, more robust and, in general superior for carrying out practical catalysis. Our early generation perhaloporphyrin catalysts, while exhibiting unprecedented catalytic activity, were far too expensive for use in converting natural gas or its C{sub 1}-C{sub 4} components.

  13. Explanation and correction of false step heights in amplitude modulation atomic force microscopy measurements on alkane films

    International Nuclear Information System (INIS)

    We use a prototypical alkane film (n-C32H66 or C32) adsorbed on a SiO2 surface to compare step heights measured by amplitude modulation atomic force microscopy (AM-AFM) with those measured in the contact mode. The C32 film exhibits layers in which the molecules are oriented with their long axis parallel to the SiO2 surface followed by partial layers of perpendicular molecules. We show that step heights measured in the AM and contact modes agree in all cases except where the step is between a surface formed by a layer of parallel molecules and one of perpendicular molecules. In this case, the AM mode gives a false step height that is as much as 20% lower than that measured in the contact mode and inferred from synchrotron X-ray specular reflectivity measurements. We propose that the weaker van der Waals forces between the AFM tip and a perpendicular layer compared to a parallel layer causes this discrepancy. We show how to correct the false step height by using the approximately linear relationship observed between phase angle (cantilever oscillation relative to the drive signal) and cantilever height measured in an approach curve

  14. Size-distributions of n-alkanes, PAHs and hopanes and their sources in the urban, mountain and marine atmospheres over East Asia

    Directory of Open Access Journals (Sweden)

    Z. Wang

    2009-11-01

    Full Text Available Size-segregated (9 stages n-alkanes, polycyclic aromatic hydrocarbons (PAHs and hopanes in the urban (Baoji city in inland China, mountain (Mt. Tai in east coastal China and marine (Okinawa Island, Japan atmospheres over East Asia were studied using a GC/MS technique. Ambient concentrations of n-alkanes (1698±568 ng m−3 in winter and 487±145 ng m−3 in spring, PAHs (536±80 and 161±39 ng m−3, and hopanes (65±24 and 20±2.4 ng m−3 in the urban air are 1–2 orders of magnitude higher than those in the mountain aerosols and 2–3 orders of magnitude higher than those in the marine samples. Mass ratios of n-alkanes, PAHs and hopanes clearly demonstrate coal-burning emissions as their major source. Size distributions of fossil fuel derived n-alkane, PAHs and hopanes were found to be unimodal in most cases, peaking at 0.7–1.1 μm size. In contrast, plant wax derived n-alkanes presented a bimodal distribution with two peaks at the sizes of 0.7–1.1 μm and >4.7 μm in the summer mountain and spring marine samples. Among the three types of samples, geometric mean diameter (GMD of the organics in fine mode (<2.1 μm was found to be smallest (av. 0.63 μm in spring for the urban samples and largest (1.01 μm for the marine samples, whereas the GMD in coarse mode (≥2.1 μm was found to be smallest (3.48 μm for the marine aerosols and largest (4.04 μm for the urban aerosols. The fine mode GMDs of the urban and mountain samples were larger in winter than in spring and summer. Moreover, GMDs of 3- and 4-ring PAHs were larger than those of 5- and 6-ring PAHs in the three types of atmospheres. Such differences in GMDs can be interpreted by the repartitioning of organic compounds and the coagulation and hygroscopic growth of particles during a long-range transport from the inland continent to the marine area, as well as the difference in their sources among the three regions.

  15. The ORF slr0091 of Synechocystis sp. PCC6803 encodes a high-light induced aldehyde dehydrogenase converting apocarotenals and alkanals

    KAUST Repository

    Trautmann, Danika

    2013-07-05

    Oxidative cleavage of carotenoids and peroxidation of lipids lead to apocarotenals and aliphatic aldehydes called alkanals, which react with vitally important compounds, promoting cytotoxicity. Although many enzymes have been reported to deactivate alkanals by converting them into fatty acids, little is known about the mechanisms used to detoxify apocarotenals or the enzymes acting on them. Cyanobacteria and other photosynthetic organisms must cope with both classes of aldehydes. Here we report that the Synechocystis enzyme SynAlh1, encoded by the ORF slr0091, is an aldehyde dehydrogenase that mediates oxidation of both apocarotenals and alkanals into the corresponding acids. Using a crude lysate of SynAlh1-expressing Escherichia coli cells, we show that SynAlh1 converts a wide range of apocarotenals and alkanals, with a preference for apocarotenals with defined chain lengths. As suggested by in vitro incubations and using engineered retinal-forming E. coli cells, we found that retinal is not a substrate for SynAlh1, making involvement in Synechocystis retinoid metabolism unlikely. The transcript level of SynAlh1 is induced by high light and cold treatment, indicating a role in the stress response, and the corresponding gene is a constituent of a stress-related operon. The assumptions regarding the function of SynAlh are further supported by the surprisingly high homology to human and plant aldehyde dehydrogenase that have been assigned to aldehyde detoxification. SynAlh1 is the first aldehyde dehydrogenase that has been shown to form both apocarotenoic and fatty acids. This dual function suggests that its eukaryotic homologs may also be involved in apocarotenal metabolism, a function that has not been considered so far. Aldehyde dehydrogenases play an important role in detoxification of reactive aldehydes. Here, we report on a cyanbacterial enzyme capable in converting two classes of lipid-derived aldehydes, apocaotenals and alkanals. The corresponding gene is a

  16. Hydrogen isotope composition of leaf wax n-alkanes in glaucous and non-glaucous varieties of wheat (Triticum spp.)

    Science.gov (United States)

    Pedentchouk, Nikolai; Eley, Yvette; Frizell-Armitage, Amelia; Uauy, Cristobal

    2015-04-01

    The use of the 2H/1H composition of terrestrial plants in climate and ecology studies depends on fundamental understanding of the processes within the plant that control fractionation of these two isotopes. Little is currently known about the extent of 2H/1H fractionation at different steps of biosynthesis, after the initial H uptake following leaf water photolysis. Knowing this effect is particularly important when seeking to interpret the 2H/1H composition of leaf wax biomarkers from plants that differ in the amount and type of individual compound classes in their leaf waxes. The purpose of this study was to investigate the link between the quantity and distribution of n-alkyl lipids in leaf waxes and their isotopic composition. We used a genetic approach to suppress glaucousness in 2 varieties of wheat (Alchemy and Malacca), which resulted in glaucous and non-glaucous phenotypes of both varieties. Both phenotypes were then grown outdoors under identical environmental conditions in central Norfolk, UK. At the end of the growing season, the plants were sampled for soil water, leaf water, and leaf wax isotopic measurements. Comparison of the leaf wax composition of the non-glaucous and glaucous phenotypes revealed that the non-glaucous varieties were characterised by the absence of diketones and a greater concentration of n-alkanes and primary alcohols.. Our results showed very small differences between glaucous and non-glaucous varieties with regard to soil (mean values, lipids from these plants will provide further details regarding the role of biosynthesis in controlling 2H/1H fractionation within leaf waxes.

  17. Preparation and surface active properties of oxypropylated α-hydroxyacids, α-hydroxyesters and α-, β-alkane diols

    Directory of Open Access Journals (Sweden)

    Shaker, N. O.

    1994-10-01

    Full Text Available A series of a-hydroxyacids RCH(OHCO2H, α-hydroxyesters RCH(OHCO2CH3 and α, β-alkane diols was synthetized and condensed with 5-20 moles propylene oxide to obtain nonionic surfactants. Some of the physicochemical properties and the biodegradability of these products were examined. The results showed that the best wetting properties were obtained by the addition of 15 oxypropylene groups to methyl α-hydroxymyristate. The α-hydroxymyristic acid with 20 moles of propylene oxide gave the highest foam. Biodegradation studies indicated that increasing both the chain length of the hydrophobic alkyl chain or the number of oxypropylene groups in the adduct decreased biodegradation.

    Una serie de α-hidroxiácidos RCH(OHCO2H, α-hidroxiésteres RCH(OHCO2CH3 y α, β-alcanodioles se sintetizaron y condensaron con 5-20 moles de óxido de propileno para obtener tensioactivos no iónicos. Se examinaron algunas propiedades fisicoquímicas y de biodegradabilidad de estos productos. Los resultados mostraron que las mejores propiedades humectantes se obtuvieron por adición de 15 grupos oxipropilenos a α-hidroximiristato de metilo.
    El ácido α-hidroximirístico con 20 moles de óxido de propileno dio la espuma más poderosa. Estudios de biodegradación indicaron que tanto el aumento de la longitud de cadena de los grupos alquilo hidrofóbicos como el número de grupos oxipropilenos en el aducto disminuyeron la biodegradación.

  18. Modeling SOA formation from alkanes and alkenes in chamber experiments: effect of gas/wall partitioning of organic vapors.

    Science.gov (United States)

    Stéphanie La, Yuyi; Camredon, Marie; Ziemann, Paul; Ouzebidour, Farida; Valorso, Richard; Madronich, Sasha; Lee-Taylor, Julia; Hodzic, Alma; Aumont, Bernard

    2014-05-01

    Oxidation products of Intermediate Volatility Organic Compounds (IVOC) are expected to be the major precursors of secondary organic aerosols (SOA). Laboratory experiments were conducted this last decade in the Riverside APRC chamber to study IVOC oxidative mechanisms and SOA formation processes for a large set of linear, branched and cyclic aliphatic hydrocarbons (Ziemann, 2011). This dataset are used here to assess the explicit oxidation model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) (Aumont et al., 2005). The simulated SOA yields agree with the general trends observed in the chamber experiments. They are (i) increasing with the increasing carbon number; (ii) decreasing with increasing methyl branch number; and (iii) increasing for cyclic compounds compared to their corresponding linear analogues. However, simulated SOA yields are systematically overestimated regardless of the precursors, suggesting missing processes in the model. In this study, we assess whether gas-to-wall partitioning of organic vapors can explain these model/observation mismatches (Matsunaga and Ziemann, 2010). First results show that GECKO-A outputs better match the observations when wall uptake of organic vapors is taken into account. Effects of gas/wall partitioning on SOA yields and composition will be presented. Preliminary results suggest that wall uptake is a major process influencing SOA production in the Teflon chambers. References Aumont, B., Szopa, S., Madronich, S.: Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach. Atmos.Chem.Phys., 5, 2497-2517 (2005). P. J. Ziemann: Effects of molecular structure on the chemistry of aerosol formation from the OH-radical-initiated oxidation of alkanes and alkenes, Int. Rev.Phys.Chem., 30:2, 161-195 (2011). Matsunaga, A., Ziemann, P. J.: Gas-wall partitioning of organic compounds in a Teflon film

  19. Polyoxometalate systems for the catalytic selective production of nonthermodynamic alkenes from alkanes. Nature of excited-state deactivation processes and control of subsequent thermal processes in polyoxometalate photoredox chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Renneke, R.F.; Pasquali, M.; Hill, C.L. (Emory Univ., Atlanta, GA (USA))

    1990-08-29

    The photooxidations of exemplary branched acyclic alkanes and cycloalkanes by a range of polyoxotungstates varying in charge density, ground-state redox potential, acidity, and other properties were examined in detail. The organic products generated in these reactions depend on the polyoxometalate used, and in particular on the ground-state redox potential of the complex. Under anaerobic conditions acyclic branched alkanes yield principally alkenes, while cycloalkanes yield principally alkenes and dimers. Alkyl methyl ketones, derived in part from reaction with acetonitrile solvent, and isomerized alkanes are produced with some alkane substrates. Under aerobic conditions, autoxidation, initiated by radicals generated in the photoinduced redox chemistry, is observed. Under aerobic conditions the polyoxotungstates with formal redox potentials more negative than {minus}1.0 V vs Ag/AgNO{sub 3}(CH{sub 3}CN), such as W{sub 10}O{sub 32}{sup 4{minus}} and W{sub 6}O{sub 19}{sup 2{minus}}, photochemically dehydrogenate branched acyclic alkanes in high selectivity to {alpha}-olefins and the least substituted alkenes, products heretofore undocumented in photooxidation reactions catalyzed by polyoxometalates.

  20. Functional roles and substrate specificities of twelve cytochromes P450 belonging to CYP52 family in n-alkane assimilating yeast Yarrowia lipolytica.

    Science.gov (United States)

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

    2016-06-01

    Yarrowia lipolytica possesses twelve ALK genes, which encode cytochromes P450 in the CYP52 family. In this study, using a Y. lipolytica strain from which all twelve ALK genes had been deleted, strains individually expressing each of the ALK genes were constructed and their roles and substrate specificities were determined by observing their growth on n-alkanes and analyzing fatty acid metabolism. The results suggested that the twelve Alk proteins can be categorized into four groups based on their substrate specificity: Alk1p, Alk2p, Alk9p, and Alk10p, which have significant activities to hydroxylate n-alkanes; Alk4p, Alk5p, and Alk7p, which have significant activities to hydroxylate the ω-terminal end of dodecanoic acid; Alk3p and Alk6p, which have significant activities to hydroxylate both n-alkanes and dodecanoic acid; and Alk8p, Alk11p, and Alk12p, which showed faint or no activities to oxidize these substrates. The involvement of Alk proteins in the oxidation of fatty alcohols and fatty aldehydes was also analyzed by measuring viability of the mutant deleted for twelve ALK genes in medium containing dodecanol and by observing growth on dodecanal of a mutant strain, in which twelve ALK genes were deleted along with four fatty aldehyde dehydrogenase genes. It was suggested that ALK gene(s) is/are involved in the detoxification of dodecanol and the assimilation of dodecanal. These results imply that genes encoding CYP52-family P450s have undergone multiplication and diversification in Y. lipolytica for assimilation of various hydrophobic compounds. PMID:27039152

  1. Two-Step Freezing in Alkane Monolayers on Colloidal Silica Nanoparticles: From a Stretched-Liquid to an Interface-Frozen State.

    Science.gov (United States)

    Gao, Xia; Huber, Patrick; Su, Yunlan; Zhao, Weiwei; Wang, Dujin

    2016-08-01

    The crystallization behavior of an archetypical soft/hard hybrid nanocomposite, that is, an n-octadecane C18/SiO2-nanoparticle composite, was investigated by a combination of differential scanning calorimetry (DSC) and variable-temperature solid-state (13)C nuclear magnetic resonance (VT solid-state (13)C NMR) as a function of silica nanoparticles loading. Two latent heat peaks prior to bulk freezing, observed for composites with high silica loading, indicate that a sizable fraction of C18 molecules involve two phase transitions unknown from the bulk C18. Combined with the NMR measurements as well as experiments on alkanes and alkanols at planar amorphous silica surfaces reported in the literature, this phase behavior can be attributed to a transition toward a 2D liquid-like monolayer and subsequently a disorder-to-order transition upon cooling. The second transition results in the formation of a interface-frozen monolayer of alkane molecules with their molecular long axis parallel to the nanoparticles' surface normal. Upon heating, the inverse phase sequence was observed, however, with a sizable thermal hysteresis in accord with the characteristics of the first-order phase transition. A thermodynamic model considering a balance of interfacial bonding, chain stretching elasticity, and entropic effects quantitatively accounts for the observed behavior. Complementary synchrotron-based wide-angle X-ray diffraction (WAXD) experiments allow us to document the strong influence of this peculiar interfacial freezing behavior on the surrounding alkane melts and in particular the nucleation of a rotator phase absent in the bulk C18. PMID:27386888

  2. Role of α-Methylacyl Coenzyme A Racemase in the Degradation of Methyl-Branched Alkanes by Mycobacterium sp. Strain P101

    OpenAIRE

    Sakai, Yasuyoshi; Takahashi, Hironori; Wakasa, Yuori; Kotani, Tetsuya; Yurimoto, Hiroya; Miyachi, Nobuya; Van Veldhoven, Paul P.; Kato, Nobuo

    2004-01-01

    A new isolate, Mycobacterium sp. strain P101, is capable of growth on methyl-branched alkanes (pristane, phytane, and squalane). Among ca. 10,000 Tn5-derived mutants, we characterized 2 mutants defective in growth on pristane or n-hexadecane. A single copy of Tn5 was found to be inserted into the coding region of mcr (α-methylacyl coenzyme A [α-methylacyl-CoA] racemase gene) in mutant P1 and into the coding region of mls (malate synthase gene) in mutant H1. Mutant P1 could not grow on methyl-...

  3. A new Organopalladium compound containing four Iron (III) Porphyrins for the selective oxidation of alkanes/alkenes by t-BuOOH

    Indian Academy of Sciences (India)

    Manoj Kumar Singh; Debkumar Bandyopadhyay

    2016-03-01

    Two iron(III) tetraphenyl porphyrin catalytic units are connected by an azo-link to form the dimeric compound A. The compound A was then reacted with Pd2+ to make a tetrameric iron(III) porphyrin complex B with all four iron(III) catalytic sites open to the substrates and reactants. Both the compounds were characterized spectroscopically and the results of homogeneous oxidation of some alkanes and alkenes with t-BuOOH in presence of catalytic quantities of A and B have indicated remarkable improvement in selectivity and efficiency of A over the monomeric catalyst and B over A.

  4. Application of headspace solid-phase microextraction followed by gas chromatography–mass spectrometry to determine short-chain alkane monocarboxylic acids in aqueous samples

    OpenAIRE

    Banel, Anna; Wasielewska, Marta; Zygmunt, Bogdan

    2010-01-01

    In this study, a procedure was developed to determine short-chain alkane monocarboxylic acids (SCMAs) in aqueous samples using headspace solid-phase microextraction (HS-SPME) followed by gas chromatography (GC) coupled with mass spectrometry (MS). A Stabilwax-DA capillary column (30 m × 0.32-mm inner diameter, 0.50-μm film thickness) was used for GC separation and a 60-μm poly(ethylene glycol) fiber was used to isolate SCMAs from water and introduce them into the gas chromatograph. Parameters...

  5. n-alkanes as a substratum for riboflavin production. I. Investigations of the dynamics of the flavinogenesis in chosen yeasts of the genus candida.

    Science.gov (United States)

    Olczyk, C

    1978-01-01

    For the first time the flavinogenic abilities of Candida flareri on a simple, fully defined medium with hydrocarbons were demonstrated. C flareri and C. guilliermondi on a synthetic medium with biotin and n-alkanes (n-decane and hexadecane) overproduce riboflavin with a considerable but varying efficiency. Among the two hydrocarbons examined n-hexadecane proved to be a more favourable source of carbon for the biosynthesis of this vitamin than n-decane. The quantities of riboflavin accumulated by C. flareri in an aerated culture are twice higher than those for C. guilliermondii (50.5 microgram/ml on hexadecane) in analogous conditions. PMID:643742

  6. 光引发长链正构烷烃多氯代反应机理与动力学%Mechanism and Kinetics of Polychlorination of Long Chain n-Alkanes by Photo-Initiation

    Institute of Scientific and Technical Information of China (English)

    易玲敏; 詹晓力; 陈丰秋

    2004-01-01

    Based on the mechanism analysis of the polychlorination of long chain n-alkanes by photo-initiation,a kinetic model was developed. The model parameters were obtained by the method of non-linear fitting. The influences of luminous intensity and concentration of molecular chlorine on the rate of polychlorination are demonstrated by the model. If the luminous intensity is adequate, the polychlorination rate of n-alkane is only controlled by the flow rate of molecular chlorine in a wide range of temperature, and the changes of temperature and luminous intensity have less effect on the reaction rate. In addition, the predictions of chlorine content of polychlorinated n-alkane calculated with the model agree very well with experimental results.

  7. Reconstructing Quaternary vegetation history in the Carpathian Basin, SE-Europe, using n-alkane biomarkers as molecular fossils

    Directory of Open Access Journals (Sweden)

    Michael Zech

    2010-07-01

    Full Text Available Seit einigen Jahren gibt es zunehmend Studien, die, basierend auf der Untersuchung von fossilen Holzkohlen und Schneckenschalen aus Löss-Paläoboden Sequenzen, die traditionelle Vorstellung von weitestgehend baumlosen Steppen im Karpaten-Becken während der letzten Kaltzeit in Frage stellen. Mit unseren Arbeiten versuchen wir anhand von Biomarkern einen Beitrag zu dieser Diskussion zu leisten und herauszufinden, welches Potenzial in der Untersuchung von Alkan Biomarkern für die Rekonstruktion der Vegetationsgeschichte während der letzten glazialen Zyklen steckt. Kürzlich veröffentlichte erste Ergebnisse weisen darauf hin, dass der Degradationsgrad der pflanzenbürtigen organischen Substanz einen starken Einfluss auf das Alkanmuster in Böden hat und dass der in der Literatur häufig verwendete Alkanquotient nC31/nC27 kein reiner Vegetations-Proxy ist, sondern auch maßgeblich die unterschiedliche Degradation widerspiegelt. In der vorliegenden Arbeit führen wir daher erstmals einen End Member Modellierungsansatz ein, bei dem der Degradationsgrad der organischen Bodensubstanz mit berücksichtig wird. Das Modell wird auf die Loess-Paläoboden Sequenz Crvenka auf dem Bačka Loess Plateau (Serbien zwischen Donau und Theiss angewendet. Die so für den letzten Interglazial-Glazial-Zyklus rekonstruierte Vegetationsgeschichte bestätigt die Holzkohle- und Mollusken-Befunde und deutet auf Gras-Steppen während des letzten Interglazials und -stadials hin (Marine Isotopenstadien (MIS 5 bzw. 3. Die Ergebnisse machen deutlich, dass Steppen während des gesamten letzten glazialen Zyklus vorgeherrscht haben. Für das letzte Interglazial und das Interstadial der Marinen Isotopen Stufe (MIS 3 deuten die Biomarker Befunde auf reine Grassteppen hin. Dagegen prägten in den Glazialen vermutlich auch vereinzelte Bäume das Landschaftsbild einer ‚Taiga-Steppe’. Die so rekonstruierte Vegetationsgeschichte steht im Einklang mit den Holzkohle- und

  8. Exhaust emissions of polycyclic aromatic hydrocarbons, n-alkanes and phenols from vehicles coming within different European classes

    Science.gov (United States)

    Perrone, Maria Grazia; Carbone, Claudio; Faedo, Davide; Ferrero, Luca; Maggioni, Angela; Sangiorgi, Giorgia; Bolzacchini, Ezio

    2014-01-01

    EU emission standards for vehicles do not include many particulate (PM) and gaseous species, despite their considerable impact on air pollution and health. Emission factors (EFs) were measured for unregulated species, i.e. polycyclic aromatic hydrocarbons (PAHs) and n-alkanes (ALKs) in the particle phase, and, for the first time, EFs for phenols in both particle and gas phases. Exhaust samples were collected under controlled operating conditions (chassis dynamometer tests) for in-service vehicles (private cars, PCs and light duty vehicles, LDVs) from different EURO classes. EFs of trace organics were highest for the old EURO 1 vehicles (the tested EURO 1 vehicles were without emission-control devices), and lowest for the more recent EURO 3 and 4 vehicles. ALKs (C20-C32) were the most abundant trace organic compounds found in PM vehicle exhaust, and their EF ranged between 2034 and 101 μg km-1 (Euro 1-4 LDVs). PM-phased phenols EFs were in the range 0.42-2.50 μg km-1, and 4-nitrophenol was the most abundant one. The highest EFs were measured for phenols in the gas phase (dominated by the presence of phenol) for gasoline EURO 1 (43.16 ± 9.99 μg km-1). Emissions of PAHs changed depending on the fuel used. The PAH EFs of diesel-driven PCs were 4-5 times higher than those of gasoline vehicles, with PAHs diesel exhaust being mainly enriched in low 4-ring PAHs (85%), while 5-6 ring PAHs were prevalent (55%) in gasoline vehicles. Results of source profiles from chassis dynamometer tests were compared with ambient data, and the traffic PAH source profile derived from a tunnel study (Milan) agreed with the estimated emissions from a mix of diesel and gasoline vehicles circulating in the same area. Moreover, the impact of EURO regulatory changes on exhaust emissions was calculated, and this made it possible to estimate the downward trend of PAH emissions in the Province of Milan in the period 2005-2020.

  9. Premarital Sexual Practice among Unmarried First Year Undergraduate Students in Alkan University College in Addis Ababa, Ethiopia

    Directory of Open Access Journals (Sweden)

    Endalew Gemechu Sendo

    2014-03-01

    Full Text Available BACKGROUND: Premarital sexual practice among unmarried College students has markedly increased recently in Ethiopia. College students are recognized as one of the age groups most affected by sexually transmitted infections including HIV. However, little has been explored about the magnitude of premarital sexual activity and predisposing factors in the circumstance of private higher education institutions in Ethiopia. OBJECTIVE: To investigate the magnitude of premarital sexual practice and predisposing factors among unmarried undergraduate first year students in Alkan University College in Addis Ababa, Ethiopia. METHODS: A cross-sectional survey of college students was conducted in April-May 2013. Study participants were selected by stratified random sampling. A self-administered questionnaire was completed by 207 unmarried first year undergraduate students, and was analyzed using SPSS V.16.0. Multi-variate logistic regression was used to see association between variables. Results were summarized in frequencies and percentages and presented in tables. RESULTS: A total of 207 students took part in the survey. The mean age of respondents was 21.8 ±2.0 years. More than half of survey respondents (60.9% reported that they have had premarital sex. Multi-variate logistic regression analysis showed that male respondents were more than seven times to ever have sexual intercourse as compared to female respondents (AOR= 7.6; 95%CI: 4.51, 34.87. However, age less than 18 years was found to be protective against premarital sexual practice (AOR=0.42.; 95%CI: 0.27-0.73. Compared to respondents who do not use alcohol, those who are alcohol users after joining college were 3.8 times (AOR 3.05, 95% CI: 1.51-4.32 as likely to begin premarital sex. Similarly, ever chewing khat after joining college was found to be positively associated with premarital sex in this study. (AOR=2.60.; 95%CI: 0.62-1.43. CONCLUSION: A significant number of students had started

  10. Kinetics and mechanism of reductive elimination of dimethyl Pt(4) complex in aqueous solutions. Decomposition of Cs2Pt(CH3)2Cl4 as the independent route of generation of intermediates of alkane activation by Pt(2)

    International Nuclear Information System (INIS)

    Unconventional method for formation of ethane during decomposition of Pt(4)(CH3)2 in aqueous solutions is revealed: the breaking of C-H bond is prefixed to the reducing elimination of C2H6. The intermediates of dimethylplatinum(4) decomposition was demonstrated to be identical to the intermediates formed during activation of alkanes (ethane) of Pt(2). The activation mechanism involving oxidizing addition of the alkanes to Pt(2) with Pt(4) alkylhydride complexes formation was suggested. 24 refs., 3 figs., 2 tabs

  11. Novel long-chain anteiso-alkanes and anteiso-alkanoic acids in Antarctic rocks colonized by living and fossil cryptoendolithic microorganisms

    Science.gov (United States)

    Matsumoto, G. I.; Friedmann, E. I.; Watanuki, K.; Ocampo-Friedmann, R.

    1992-01-01

    Saponified extracts of rock samples colonized by cryptoendolithic microbial communities from the McMurdo Dry Valleys of Southern Victoria Land, Antarctica, were separated into hydrocarbon and fatty acid fractions by silica gel column chromatography. Hydrocarbons and methyl esters of fatty acids were analyzed by capillary gas chromatography-mass spectrometry. Unusually, a suite of long-chain anteiso-alkanes (a-C20 to a-C30) and anteiso-alkanoic acids (a-C20 to a-C30) were detected in many samples, together with straight-chain, branched and/or cyclic and acyclic isoprenoid compounds. These novel compounds are probably derived from unidentified heterotrophic bacteria or symbiotic processes in a unique microbial community in the Antarctic cold desert and suggest the occurrence of a special biosynthetic pathway. Long-chain anteiso-alkanes are probably formed through microbial decarboxylation of corresponding anteiso-alkanoic acids. They may serve as new biomarkers in environmental and geochemical studies.

  12. Comparing the accuracy of high-dimensional neural network potentials and the systematic molecular fragmentation method: A benchmark study for all-trans alkanes.

    Science.gov (United States)

    Gastegger, Michael; Kauffmann, Clemens; Behler, Jörg; Marquetand, Philipp

    2016-05-21

    Many approaches, which have been developed to express the potential energy of large systems, exploit the locality of the atomic interactions. A prominent example is the fragmentation methods in which the quantum chemical calculations are carried out for overlapping small fragments of a given molecule that are then combined in a second step to yield the system's total energy. Here we compare the accuracy of the systematic molecular fragmentation approach with the performance of high-dimensional neural network (HDNN) potentials introduced by Behler and Parrinello. HDNN potentials are similar in spirit to the fragmentation approach in that the total energy is constructed as a sum of environment-dependent atomic energies, which are derived indirectly from electronic structure calculations. As a benchmark set, we use all-trans alkanes containing up to eleven carbon atoms at the coupled cluster level of theory. These molecules have been chosen because they allow to extrapolate reliable reference energies for very long chains, enabling an assessment of the energies obtained by both methods for alkanes including up to 10 000 carbon atoms. We find that both methods predict high-quality energies with the HDNN potentials yielding smaller errors with respect to the coupled cluster reference. PMID:27208939

  13. Excess molar enthalpies of binary mixtures containing 2-decanone or dipentyl ether with long-chain n-alkanes at T = 298.15 K

    International Nuclear Information System (INIS)

    Research highlights: → An isothermal titration calorimeter was used for enthalpy data measurment. → The investigated systems are 2-decanone or dipentyl ether with long-chain n-alkanes. → The excess enthalpies are all positive over entire composition range. → The Patel-Teja equation of state with two parameters gives the best representation. - Abstract: Excess molar enthalpies (HE) of binary mixtures of 2-decanone or dipentyl ether with n-alkanes, including n-dodecane, n-tetradecane, and n-hexadecane, were measured with an isothermal titration calorimeter (ITC) at T = 298.15 K under atmospheric pressure. All the measured HE values are positive over the entire range of composition, indicating that all these mixing processes are endothermic. The HE values varying with composition are found to be nearly symmetric for each binary system. It was also shown that the HE values follow the order of n-hexadecane > n-tetradecane > n-dodecane at a given composition in either the 2-decanone or dipentyl ether binary systems. An empirical Redlich-Kister equation correlated quantitatively these new HE data. The Peng-Robinson and the Patel-Teja equations of state, and the NRTL model were also applied to fit the HE results. Among these tested correlative models, the Patel-Teja equation of state with two adjustable binary interaction parameters generally yielded the best representation.

  14. Comparing the accuracy of high-dimensional neural network potentials and the systematic molecular fragmentation method: A benchmark study for all-trans alkanes

    Science.gov (United States)

    Gastegger, Michael; Kauffmann, Clemens; Behler, Jörg; Marquetand, Philipp

    2016-05-01

    Many approaches, which have been developed to express the potential energy of large systems, exploit the locality of the atomic interactions. A prominent example is the fragmentation methods in which the quantum chemical calculations are carried out for overlapping small fragments of a given molecule that are then combined in a second step to yield the system's total energy. Here we compare the accuracy of the systematic molecular fragmentation approach with the performance of high-dimensional neural network (HDNN) potentials introduced by Behler and Parrinello. HDNN potentials are similar in spirit to the fragmentation approach in that the total energy is constructed as a sum of environment-dependent atomic energies, which are derived indirectly from electronic structure calculations. As a benchmark set, we use all-trans alkanes containing up to eleven carbon atoms at the coupled cluster level of theory. These molecules have been chosen because they allow to extrapolate reliable reference energies for very long chains, enabling an assessment of the energies obtained by both methods for alkanes including up to 10 000 carbon atoms. We find that both methods predict high-quality energies with the HDNN potentials yielding smaller errors with respect to the coupled cluster reference.

  15. Modeling Study of Hydrogen/Oxygen and n-alkane/Oxygen Counterflow Diffusion Flames%氢、碳氢燃料对向扩散火焰

    Institute of Scientific and Technical Information of China (English)

    汪小卫; 蔡国飙; Vigor Yang

    2011-01-01

    A comprehensive analysis of hydrogen/oxygen and hydrocarbon/oxygen counterflow diffusion flames has been conducted using corresponding detailed reaction mechanisms. The hydrocarbon fuels contain n-alkanes from CH4 to C16H34. The basic diffusion flame structures are demonstrated, analyzed, and compared. The effects of pressure, and strain rate on the flame behavior and energy-release rate for each fuel are examined systematically. The detailed chemical kinetic reaction mechanisms from Lawrence Livermore National Laboratory (LLNL) are employed, and the largest one of them contains 2115 species and 8157 reversible reactions. The results indicate for all of the fuels the flame thickness and heat release rate correlate well with the square root of the pressure multiplied by the strain rate. Under the condition of any strain rate and pressure, H2 has thicker flame than hydrocarbons, while the hydrocarbons have the similar temperature and main products distributions and almost have the same flame thickness and heat release rate. The result indicates that the fuels composed with these hydrocarbons will still have the same flame properties as any pure n-alkane fuel.

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

    Science.gov (United States)

    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. PMID:25941716

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

    Science.gov (United States)

    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.

  18. Crystal structures of eight mono-methyl alkanes (C26–C32 via single-crystal and powder diffraction and DFT-D optimization

    Directory of Open Access Journals (Sweden)

    Lee Brooks

    2015-09-01

    Full Text Available The crystal structures of eight mono-methyl alkanes have been determined from single-crystal or high-resolution powder X-ray diffraction using synchrotron radiation. Mono-methyl alkanes can be found on the cuticles of insects and are believed to act as recognition pheromones in some social species, e.g. ants, wasps etc. The molecules were synthesized as pure S enantiomers and are (S-9-methylpentacosane, C26H54; (S-9-methylheptacosane and (S-11-methylheptacosane, C28H58; (S-7-methylnonacosane, (S-9-methylnonacosane, (S-11-methylnonacosane and (S-13-methylnonacosane, C30H62; and (S-9-methylhentriacontane, C32H66. All crystallize in space group P21. Depending on the position of the methyl group on the carbon chain, two packing schemes are observed, in which the molecules pack together hexagonally as linear rods with terminal and side methyl groups clustering to form distinct motifs. Carbon-chain torsion angles deviate by less than 10° from the fully extended conformation, but with one packing form showing greater curvature than the other near the position of the methyl side group. The crystal structures are optimized by dispersion-corrected DFT calculations, because of the difficulties in refining accurate structural parameters from powder diffraction data from relatively poorly crystalline materials.

  19. Process for functionalizing alkanes

    Science.gov (United States)

    Bergman, R.G.; Janowicz, A.H.; Periana-Pillai, R.A.

    1984-06-12

    Process for functionalizing saturated hydrocarbons selectively in the terminal position comprises: (a) reacting said saturated hydrocarbons with a metal complex CpRhPMe/sub 3/H/sub 2/ in the presence of ultraviolet radiation at -60/sup 0/ to -17/sup 0/C to form a hydridoalkyl complex CpRhPMe/sub 3/RH; (b) reacting said hydridoalkyl complex with a haloform CHX/sub 3/ at -60/sup 0/ to -17/sup 0/C to form the corresponding haloalkyl complex of step (a) CpRhPMe/sub 3/RX; and (c) reacting said haloalkyl complex with halogen -60 to 25/sup 0/C to form a functional haloalkyl compound.

  20. Millisecond Oxidation of Alkanes

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    Mathys; Schmid; Witholt

    1999-08-20

    Pseudomonas oleovorans and recombinant strains containing the 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. We 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, we 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, we describe overall designs of fed-batch and continuous-fermentation processes for the oxidation of octane to 1-octanol by Pseudomonas oleovorans, and we discuss the economics of these processes. In both systems the two-liquid phase system consists of an apolar phase with hexadecene as the apolar carrier solvent into which n-octane is dissolved, while the cells are present in the aqueous phase. In one system, multiple-batch fermentations are followed by continuous processing of the product from the separated apolar phase. The second system is based on alkane oxidation by continuously growing cultures, again followed by continuous processing of the product. Fewer fermentors were required and a higher space-time-yield was possible for production of 1-octanol in a continuous process. The overall performance of each of these two systems has been modeled with Aspen software. Investment and operating costs were estimated with input from equipment manufacturers and bulk-material suppliers. Based on this study, the production cost of 1-octanol is about 7 US$kg-1 when produced in the fed-batch process, and 8 US$kg-1 when produced continuously. The comparison of upstream and downstream capital costs and production

  2. Expression of alkane monooxygenase (alkB) genes by plant-associated bacteria in the rhizosphere and endosphere of Italian ryegrass (Lolium multiflorum L.) grown in diesel contaminated soil

    International Nuclear Information System (INIS)

    For phytoremediation of organic contaminants, plants have to host an efficiently degrading microflora. To assess the role of endophytes in alkane degradation, Italian ryegrass was grown in sterile soil with 0, 1 or 2% diesel and inoculated either with an alkane degrading bacterial strain originally derived from the rhizosphere of Italian ryegrass or with an endophyte. We studied plant colonization of these strains as well as the abundance and expression of alkane monooxygenase (alkB) genes in the rhizosphere, shoot and root interior. Results showed that the endophyte strain better colonized the plant, particularly the plant interior, and also showed higher expression of alkB genes suggesting a more efficient degradation of the pollutant. Furthermore, plants inoculated with the endophyte were better able to grow in the presence of diesel. The rhizosphere strain colonized primarily the rhizosphere and showed low alkB gene expression in the plant interior. - Bacterial alkane degradation genes are expressed in the rhizosphere and in the plant interior.

  3. Expression of alkane monooxygenase (alkB) genes by plant-associated bacteria in the rhizosphere and endosphere of Italian ryegrass (Lolium multiflorum L.) grown in diesel contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    Andria, Verania [AIT Austrian Institute of Technology GmbH, Bioresources Unit, A-2444 Seibersdorf (Austria); Reichenauer, Thomas G. [AIT Austrian Institute of Technology GmbH, Unit of Environmental Resources and Technologies, A-2444 Seibersdorf (Austria); Sessitsch, Angela, E-mail: angela.sessitsch@ait.ac.a [AIT Austrian Institute of Technology GmbH, Bioresources Unit, A-2444 Seibersdorf (Austria)

    2009-12-15

    For phytoremediation of organic contaminants, plants have to host an efficiently degrading microflora. To assess the role of endophytes in alkane degradation, Italian ryegrass was grown in sterile soil with 0, 1 or 2% diesel and inoculated either with an alkane degrading bacterial strain originally derived from the rhizosphere of Italian ryegrass or with an endophyte. We studied plant colonization of these strains as well as the abundance and expression of alkane monooxygenase (alkB) genes in the rhizosphere, shoot and root interior. Results showed that the endophyte strain better colonized the plant, particularly the plant interior, and also showed higher expression of alkB genes suggesting a more efficient degradation of the pollutant. Furthermore, plants inoculated with the endophyte were better able to grow in the presence of diesel. The rhizosphere strain colonized primarily the rhizosphere and showed low alkB gene expression in the plant interior. - Bacterial alkane degradation genes are expressed in the rhizosphere and in the plant interior.

  4. Determination of n-alkanes in C. annuum (bell pepper) fruit and seed using GC-MS: comparison of extraction methods and application to samples of different geographical origin.

    Science.gov (United States)

    de Rijke, E; Fellner, C; Westerveld, J; Lopatka, M; Cerli, C; Kalbitz, K; de Koster, C G

    2015-07-01

    An efficient extraction and analysis method was developed for the isolation and quantification of n-alkanes from bell peppers of different geographical locations. Five extraction techniques, i.e., accelerated solvent extraction (ASE), ball mill extraction, ultrasonication, rinsing, and shaking, were quantitatively compared using gas chromatography coupled to mass spectrometry (GC-MS). Rinsing of the surface wax layer of freeze-dried bell peppers with chloroform proved to be a relatively quick and easy method to efficiently extract the main n-alkanes C27, C29, C31, and C33. A combined cleanup and fractionation approach on Teflon-coated silica SPE columns resulted in clean chromatograms and gave reproducible results (recoveries 90-95 %). The GC-MS method was reproducible (R(2) = 0.994-0.997, peak area standard deviation = 2-5%) and sensitive (LODs, S/N = 3, 0.05-0.15 ng/μL). The total main n-alkane concentrations were in the range of 5-50 μg/g dry weight. Seed extractions resulted in much lower total amounts of extracted n-alkanes compared to flesh and surface extractions, demonstrating the need for further improvement of pre-concentration and cleanup. The method was applied to 131 pepper samples from four different countries, and by using the relative n-alkane concentration ratios, Dutch peppers could be discriminated from those of the other countries, with the exception of peppers from the same cultivar. Graphical Abstract Procedure for pepper origin determination. PMID:26018628

  5. A comprehensive detailed chemical kinetic reaction mechanism for combustion of n-alkane hydrocarbons from n-octane to n-hexadecane

    OpenAIRE

    Westbrook, Charles K.; William J. Pitz; Herbinet, Olivier; Curran, Henry J.; Silke, Emma J.

    2008-01-01

    Detailed chemical kinetic reaction mechanisms have been developed to describe the pyrolysis and oxidation of nine n-alkanes larger than n-heptane, including n-octane (n-C8H18), n-nonane (n C9H20), n-decane (n-C10H22), n-undecane (n-C11H24), n-dodecane (n-C12H26), n-tridecane (n C13H28), n tetradecane (n-C14H30), n-pentadecane (n-C15H32), and n-hexadecane (n-C16H34). These mechanisms include both high temperature and low temperature reaction pathways. The mechanisms are based on previous mecha...

  6. Prediction of Boiling Point of Alkanes by Artificial Neural Network%利用人工神经网络法预测烷烃的沸点

    Institute of Scientific and Technical Information of China (English)

    李谦; 王黎; 李伟; 房晓敏

    2001-01-01

    有机物沸点是有机物的一种非常重要的性质. 采用人工神经网络模型,选用结构描述码作为输入特征参数对烷烃的沸点进行预测,得到了很高的预测精度. 该方法还可作为对有机化合物的其他性质进行预测的一种有效手段.%The boiling point is a very important property of organics. The paper uses the structural discribing code as input data to predict precisely the boiling point of alkanes by artificial neural network. This method proves effective on predicting other important properties of organics.

  7. Simultaneous correlation of the excess enthalpy and W-shaped excess heat capacity of 1,4-dioxane+n-alkane systems by PRSV-HVOS CEOS

    Directory of Open Access Journals (Sweden)

    SLOBODAN P. SERBANOVIC

    2003-01-01

    Full Text Available In this work the Peng-Robinson-Stryjek-Vera (PRSV equation of state coupled with the Huron-Vidal-Orbey-Sandler (HVOS rule was tested for the correlation of the excess enthalpy (HE and the excess heat capacity (cpE alone and simultaneously. The HVOS mixing rule incorporates the NRTL equation as the GE model. All calculations were performed using the linear and reciprocal forms of the temperature dependent parameters of the models. For all the evaluations the 1,4-dioxane+n-alkane systems were chosen having in mind the unusually W-shaped concentration dependence of cpE for these systems. The correlation of the HE and cpE data alone for all the investigated systems using four coefficients and for the simultaneous correlation of HE+cpE data using six coefficients of the temperature dependent parameters of the PRSV-HVOS models could be considered as being very satisfactory.

  8. The mechanism of hydrogen peroxide-induced aerobic oxidation of alkanes in catalysis by a vanadium complex and pyrazine-2-carboxylic acid

    International Nuclear Information System (INIS)

    It was established that effective oxy generation of alkanes by oxygen of the air in acetonitrile was catalyzed by vanadate anion in the presence of pyrazine-2-carboxylic acid (PCA) and hydrogen peroxide. Alkyl hydroxy peroxide smoothly decomposing during the process with formation of conforming ketone (aldehyde) and alcohol is a primary product of the reaction. It is shown that hydroxyl radicals come into being by reaction of complex between vanadium oxo compound derivative and hydrogen peroxide in the system; decomposition of vanadium monoperoxocomplex with PCA is a limiting stage of the process, and V(4) derivative and hydro peroxyl radicals are defined as products of its decomposition. Adequate agreement of suggested kinetic model of the process with all totality of the experimental data was obtained. The constants of suggested equilibria and the constant of the rate of decomposition of vanadium monoperoxocomplex with PCA are estimated

  9. Modeling the adsorption of short alkanes in the zeolite SSZ-13 using "van der Waals" DFT exchange correlation functionals: Understanding the advantages and limitations of such functionals

    Science.gov (United States)

    Göltl, Florian; Sautet, Philippe

    2014-04-01

    The inclusion of non-local interactions is one of the large challenges in density functional theory. Very promising methods are the vdW-DF2 and BEEF-vdW functionals, which combine a semi-local approximation for exchange interactions and a non-local correlation expression. In this work we apply those functionals to model the adsorption of short alkanes in the zeolite SSZ-13. Even though results for energetics are improved with respect to other vdW-DF based methods, we still find a comparatively large error compared to high-level calculations. These errors result from approximations in the determination of the dielectric function and of the van der Waals kernel. The insights presented in this work will help to understand the performance not only of vdW-DF2 and BEEF-vdW, but all vdW-DF based functionals in various chemically or physically important systems.

  10. Superposition-additive approach in the description of thermodynamic parameters of formation and clusterization of substituted alkanes at the air/water interface.

    Science.gov (United States)

    Vysotsky, Yu B; Belyaeva, E A; Fomina, E S; Vasylyev, A O; Vollhardt, D; Fainerman, V B; Aksenenko, E V; Miller, R

    2012-12-01

    The superposition-additive approach developed previously was shown to be applicable for the calculations of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole polarizability, molecular diamagnetic susceptibility, π-electronic ring currents, etc. In the present work, the applicability of this approach for the calculation of the thermodynamic parameters of formation and clusterization at the water/air interface of alkanes, fatty alcohols, thioalcohols, amines, nitriles, fatty acids (C(n)H(2n+1)X, X is the functional group) and cis-unsaturated carboxylic acids (C(n)H(2n-1)COOH) is studied. Using the proposed approach the thermodynamic quantities determined agree well with the available data, either calculated using the semiempirical (PM3) quantum chemical method, or obtained in experiments. In particular, for enthalpy and Gibbs' energy of the formation of substituted alkane monomers from the elementary substances, and their absolute entropy, the standard deviations of the values calculated according to the superposition-additive scheme with the mutual superimposition domain C(n-2)H(2n-4) (n is the number of carbon atoms in the alkyl chain) from the results of PM3 calculations for alkanes, alcohols, thioalcohols, amines, fatty acids, nitriles and cis-unsaturated carboxylic acids are respectively: 0.05, 0.004, 2.87, 0.02, 0.01, 0.77, and 0.01 kJ/mol for enthalpy; 2.32, 5.26, 4.49, 0.53, 1.22, 1.02, 5.30 J/(molK) for absolute entropy; 0.69, 1.56, 3.82, 0.15, 0.37, 0.69, 1.58 kJ/mol for Gibbs' energy, whereas the deviations from the experimental data are: 0.52, 5.75, 1.40, 1.00, 4.86 kJ/mol; 0.52, 0.63, 1.40, 6.11, 2.21 J/(molK); 2.52, 5.76, 1.58, 1.78, 4.86 kJ/mol, respectively (for nitriles and cis-unsaturated carboxylic acids experimental data are not available). The proposed approach provides also quite accurate estimates of enthalpy, entropy and Gibbs' energy of boiling and melting, critical temperatures and standard heat

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

    KAUST Repository

    Bugler, John

    2015-07-16

    © 2015 American Chemical Society. 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.

  12. Pressurized liquid extraction technique for the analysis of pesticides, PCBs, PBDEs, OPEs, PAHs, alkanes, hopanes, and steranes in atmospheric particulate matter.

    Science.gov (United States)

    Clark, Adelaide E; Yoon, Subin; Sheesley, Rebecca J; Usenko, Sascha

    2015-10-01

    An analytical method has been developed for the pressurized liquid extraction (PLE) of a wide range of semi-volatile organic compounds (SVOCs) from atmospheric particulate matter. Approximately 130 SVOCs from eight compound classes were selected as molecular markers of (1) agricultural activity (30 current and historic-use pesticides), (2) industrial activity (18 PCBs), (3) consumer products and building materials (16 PBDEs, 11 OPEs), and (4) motor vehicle exhaust (22 PAHs, 16 alkanes, 9 hopanes, 8 steranes). Currently, there is no analytical method validated for the extraction of all eight compound classes in a single automated technique. The extraction efficiencies of varying solvents and solvent combinations at high temperatures and pressures were examined. Extracts were concentrated and analyzed by gas chromatography coupled with mass spectrometry. The optimized PLE method utilized methylene chloride:acetone (2:1 v/v) at 100 °C with three (5 min) static cycles, flush volume of 80%, and a 100 s N2 purge. Spike and recovery experiments (n=7) provided average percent recoveries for pesticides, PCBs, PBDEs, OPEs, PAHs, alkanes, hopanes, and steranes of 88.8±4.0%, 86.9±2.6%, 83.8±2.9%, 101±6%, 90.3±6.1%, 74.4±8.8%, 104±8%, and 86.5±8.6%, respectively. The developed method was applied to atmospheric particulate matter samples collected in the greater Houston, TX metropolitan area. Ambient concentrations of eight classes of compounds (92 SVOCs) were reported in pg m(-3). PMID:25985427

  13. Pd/Nb2O5/SiO2 catalyst for the direct hydrodeoxygenation of biomass-related compounds to liquid alkanes under mild conditions.

    Science.gov (United States)

    Shao, Yi; Xia, Qineng; Liu, Xiaohui; Lu, Guanzhong; Wang, Yanqin

    2015-05-22

    A simple Pd-loaded Nb2 O5 /SiO2 catalyst was prepared for the hydrodeoxygenation of biomass-related compounds to alkanes under mild conditions. Niobium oxide dispersed in silica (Nb2 O5 /SiO2 ) as the support was prepared by the sol-gel method and characterized by various techniques, including N2 adsorption, XRD, NH3 temperature-programmed desorption (TPD), TEM, and energy-dispersive X-ray spectroscopy (EDAX) atomic mapping. The characterization results showed that the niobium oxide species were amorphous and well dispersed in silica. Compared to commercial Nb2 O5 , Nb2 O5 /SiO2 has significantly more active niobium oxide species exposed on the surface. Under mild conditions (170 °C, 2.5 MPa), Pd/10 %Nb2 O5 /SiO2 was effective for the hydrodeoxygenation reactions of 4-(2-furyl)-3-buten-2-one (aldol adduct of furfural with acetone), palmitic acid, tristearin, and diphenyl ether (model compounds of microalgae oils, vegetable oils, and lignin), which gave high yields (>94 %) of alkanes with little CC bond cleavage. More importantly, owing to the significant promotion effect of NbOx species on CO bond cleavage and the mild reaction conditions, the CC cleavage was considerably restrained, and the catalyst showed an excellent activity and stability for the hydrodeoxygenation of palmitic acid with almost no decrease in hexadecane yield (94-95 %) in a 150 h time-on-stream test. PMID:25876904

  14. Correlation of bulk sedimentary and compound-specific δ13C values indicates minimal pre-aging of n-alkanes in a small tropical watershed

    Science.gov (United States)

    Lane, Chad S.; Horn, Sally P.; Taylor, Zachary P.; Kerr, Matthew T.

    2016-08-01

    Inherent to sedimentary compound-specific isotopic proxies of paleoecological and paleoclimate change is the assumption that biomarkers are coeval with the surrounding sedimentary matrix. Compound-specific radiocarbon analyses of lake and nearshore marine sediments have indicated a potential offset between the ages of terrestrial biomarkers and their surrounding sediments that could confound efforts to establish strong chronological control for compound-specific isotopic data. We conducted high-resolution compound-specific δ13C analyses of n-alkanes (δ13Calkane) in a well-studied sediment core from Laguna Castilla, Dominican Republic, and compared the results to bulk sedimentary δ13C (δ13Cbulk), fossil pollen, and sediment geochemistry to assess potential 'pre-aging' of alkanes in the terrestrial environment prior to deposition. We found significant positive correlations between δ13Cbulk values and δ13Calkane values, indicating little or no temporal lag in the response of δ13Calkane values to vegetation change and thus little or no offset in the age of terrestrially-derived compounds and the organic fraction of the sedimentary matrix. While this study highlights the need for further research into the variables affecting age offsets between proxy data, we propose the comparison of δ13Cbulk and δ13Calkane values as a method to assess potential age offsets between compound-specific and other proxy datasets, particularly in small watersheds with sediment records containing a high proportion of allochthonous organic matter. This method is more available to researchers than obtaining numerous compound-specific radiocarbon analyses, which are costly and not a routine service offered by radiocarbon facilities.

  15. Different altitude effect of leaf wax n-alkane δD values in surface soils along two vapor transport pathways, southeastern Tibetan Plateau

    Science.gov (United States)

    Bai, Yan; Fang, Xiaomin; Jia, Guodong; Sun, Jimin; Wen, Rong; Ye, Yuqing

    2015-12-01

    Here we present 76 hydrogen isotope values for leaf wax-derived n-alkanes (δDwax, being the abundance-weighted average δD values of C29 and C31n-alkanes) in surface soils along two vapor transport pathway transects running across the southeastern Tibetan Plateau (TP). The first is the South Himalayan (SH) Transect (with an altitude range of 1660-5050 m∗ above sea level, and representing the Southern Himalayan air mass), and the second a combination of the Zayu-Bomi (ZB; altitude 1468-4800 m) and Bayi-Lhasa (BL; altitude 3050-4970 m) transects, together representing the Brahmaputra-Yarlung Zangbo river valley air mass. δDwax values and their relation to altitude did exhibit some variability. Nonetheless, altitude was the predominant factor in determining soil δDwax values, with a lapse rate of -2.2‰/100 m (R2 = 0.78; n = 76) based on overall soil δDwax values, despite changes in precipitation amount, relative humidity (RH) and vegetation type. Furthermore, our εwax/rw values (the isotopic fractionation between the δDwax and δD values of river water (δDrw)) remained approximately constant at -104.5‰ (ranging between -99‰ and -110‰), confirming that the relation between altitude and isotopic hydrology (river water and precipitation) controls the n-alkane δDwax altitudinal gradients for all of the sample localities in the Southern Himalaya (SH) and the southern TP. This endorses the efficacy of using δDwax to reconstruct paleoelevation. Along the SH Transect, soil δDwax values varied from -151‰ to -264‰, with an altitudinal lapse rate of -2.4‰/100 m (R2 = 0.84, n = 32). This was due to the significant change in altitude over short distances. Along the ZB Transect, soil δDwax values varied from -174‰ to -263‰, with a lower lapse rate of -1.9‰/100 m (R2 = 0.68, n = 29). The altitudinal lapse rate was -3.3‰/100 m above 3000 m (R2 = 0.63, n = 19), and -1.35‰/100 m below 3000 m (R2 = 0.64, n = 10); in the lower sub-transect, the

  16. Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

    KAUST Repository

    Chen, Yin

    2015-01-21

    By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

  17. Can leaf wax n-alkane δ²H and GDGTs be used conjointly to reconstruct past environmental changes along altitudinal transects in East Africa?

    Science.gov (United States)

    Coffinet, Sarah; Huguet, Arnaud; Pedentchouk, Nikolai; Omuombo, Christine; Williamson, David; Bergonzini, Laurent; Wagner, Thomas; Derenne, Sylvie

    2016-04-01

    Leaf wax n-alkanes (C27-C31) and branched glycerol dialkyl glycerol tetraethers (br GDGTs) are increasingly being used as molecular proxies to investigate past environmental conditions. Indices were previously developed to relate the br GDGT distribution to temperature and pH in soils. Furthermore, the δ²Hwax of leaf wax n-alkanes in soils was shown to track the 'altitude effect', suggesting it could be used to reconstruct paleoelevation. Combination of these two proxies could bring information on both past uplift elevation and past temperature changes, as illustrated by the pioneer paleostudy of Hren et al. (2010) in the Sierra Nevada. In the present study, δ²Hwax and br GDGTs were analysed in ca. 60 surface soils collected along Mt. Rungwe (Southwest Tanzania) and Mt. Kenya (Central Kenya). A weak link was identified between δ²Hwax and altitude (R² = 0.33) along Mt. Kenya, whereas no trend was observed along Mt. Rungwe, as also previously shown by Peterse et al. (2009) for Mt. Kilimanjaro. This shows that the strength of the relationship between soil δ²Hwax and elevation depends on which mountain is considered in East Africa and can be overprinted by numerous poorly understood environmental and/or physiological parameters. In contrast, br GDGT-derived mean annual air temperature (MAAT) and temperature lapse rate (5 °C/1000 m) were in agreement with values recorded along both Mt. Rungwe and Mt. Kenya, highlighting the robustness of this proxy for paleotemperature reconstruction in East Africa. Moreover, the combination of these br GDGT data with previous results obtained from East African surface soils (along Mts. Kilimanjaro (Tanzania), Sinninghe Damsté et al., 2008; Rwenzori (Uganda), Loomis et al., 2011; Rungwe (Tanzania), Coffinet et al., 2014), allowed the establishment of a regional soil calibration between br GDGT distribution and MAAT. This new East African calibration, based on 105 samples, leads to a substantial improvement of both the R2 (0

  18. Digestibilidade determinada pelo método indireto usando o n-alcano C35 Digestibility determinate by indirect method using C35 n-alkane

    Directory of Open Access Journals (Sweden)

    Dimas Estrásulas de Oliveira

    2000-06-01

    Full Text Available Foi feito um trabalho de extração e análise de n-alcanos com o objetivo de investigar o uso do n-alcano (C35 presente nas forragens como um indicador interno para determinação de digestibilidade. Foram utilizadas amostras de experimentos de digestibilidade convencional realizados previamente entre os anos de 1978 e 1982. O C35 subestimou as digestibilidades da matéria seca e orgânica, apresentando diferença média, em relação ao método in vivo, de 4,68 (± 0,69 e 4,43 (± 0,85 unidades percentuais, respectivamente. O coeficiente de regressão não diferiu da unidade, indicando que os métodos foram equivalentes, havendo, porém, a necessidade de um fator de correção. Os coeficientes de correlação para a matéria seca e orgânica, observados entre os dois métodos, foram 0,87 e 0,85, respectivamente. O C35 apresentou recuperação fecal média de 91,76% (± 7,94, que contribuiu para o vício da técnica.An experiment was conducted, on extraction and analysis of n-alkanes, to investigate the use of n-alkane (C35 present in forages as an internal marker for the digestibility determination. Samples of forages and feces were taken from conventional digestibility trials, which were previous conducted from 1978 to 1982. The C35 underestimated the dry matter and organic matter digestibilities, presenting an average difference in relation to in vivo of 4.68 (± 0.69 and 4,43 (± 0.85 perceptual units, respectively. The coefficient of regression did not differ from the unit, indicating that both methods were equivalent, having, however, the necessity of a correction factor. The coefficients of correlation observed for the dry and organic matter between the two methods were 0.87 and 0.85, respectively. The average fecal recovery of C35 was 91.76% (± 7.94, and this contributed to the bias of the method.

  19. Sources of organic matter (PAHs and n-alkanes) in PM2.5 of Beijing in haze weather analyzed by combining the C-N isotopic and PCA-MLR analyses.

    Science.gov (United States)

    Guo, Xinyue; Li, Cai; Gao, Yang; Tang, Lei; Briki, Meryem; Ding, Huaijian; Ji, Hongbing

    2016-03-16

    Organic molecular composition and carbon and nitrogen isotope ratios of PM2.5 samples collected in November 2013 were analyzed using gas chromatography/mass spectrometry and isotope ratio mass spectrometry. The samples represented six potential sources and seven sampling sites situated in concentric zones around Beijing under both haze and non-haze conditions. Our results showed that the average concentrations of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes were 258.2 ± 208.8 ng m(-3) and 499.5 ± 347.8 ng m(-3), while the δ(13)C and δ(15)N values for PM2.5 varied from -26.29 to -25.26‰ and from 8.68 to 14.50‰ with an average of -25.70 ± 0.3‰ and 11.97 ± 1.79‰, respectively. The highest concentrations of PAHs and n-alkanes were recorded in the sixth ring road, with the lowest ones in the third ring road. Concentrations of PAHs during haze were higher than during non-haze conditions, while concentrations of n-alkanes were not markedly different. Principal component analysis/multiple linear regression analyses indicated that the main sources of PAHs were vehicle and coal combustion emissions, while n-alkanes had high contributions from petroleum emissions. These sources were supported by isotopic analyses. Thus, the main sources of organic matter contributing to haze in Beijing were coal combustion and vehicle emissions. Such results provide guidance towards managing haze in Beijing. PMID:26938832

  20. (Liquid + liquid) equilibrium at T = 298.15 K for ternary mixtures of alkane + aromatic compounds + imidazolium-based ionic liquids

    International Nuclear Information System (INIS)

    Highlights: • The LLE ternary phase diagrams with 2 imidazolium-based ionic liquids were measured. • The LLE data were experimental determined at T = 298.15 K and p = 1 atm. • Mixtures of (octane or nonane) and (benzene or toluene or ethylbenzene) were studied. • LLE experimental data were correlated with NRTL and UNIQUAC thermodynamic models. - Abstract: Ionic liquids, with their unique and tunable properties, can be an advantageous alternative as extractive solvents in separation processes involving systems containing aliphatic and aromatic hydrocarbons. In this work, (liquid + liquid) equilibrium (LLE) data for the ternary systems {nonane (1) + benzene (2) + 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [BMim][NTf2] (3)}, {octane (1) + benzene (2) + 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide, [PMim][NTf2] (3)}, and {nonane (1) + aromatic compound (benzene or toluene or ethylbenzene) (2) + [PMim][NTf2] (3)} were determined at T = 298.15 K and atmospheric pressure. Selectivity and solute distribution ratio, derived from the equilibrium data, were used to determine if this ionic liquid can be considered as a potential solvent for the separation of aromatic compounds (benzene, toluene, and ethylbenzene) from alkanes (octane and nonane). The experimental data were satisfactorily correlated with NRTL and UNIQUAC models

  1. (Liquid + liquid) equilibria for the ternary mixtures (alkane + toluene + ionic liquid) at T = 298.15 K: Influence of the anion on the phase equilibria

    International Nuclear Information System (INIS)

    Highlights: ► [BMpyr][NTF2] and [BMpyr][TFO] were studied as solvents to extract aromatics from alkanes. ► (Liquid + liquid) equilibrium data were measured at 298.15 K for six ternary systems. ► Selectivity and solute distribution ratio were calculated and compared. ► The influence of the structure of anion of the ionic liquid was analyzed. ► Experimental data were satisfactorily correlated using NRTL model. - Abstract: (Liquid + liquid) equilibrium data for the ionic liquids 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [BMpyr][NTf2], and 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, [BMpyr][TFO], with toluene, and heptane or cyclohexane were determined at T = 298.15 K and atmospheric pressure. In order to check if these ILs can be used as potential solvents for the extraction of toluene from aliphatic compounds, the ability of the ILs as solvents was evaluated in terms of selectivity and solute distribution ratio. The experimental data were correlated accurately with the Non Random Two-Liquid model.

  2. Performance of ab initio and density functional methods for conformational equilibria of CnH2n+2 alkane isomers (n=2-8)

    CERN Document Server

    Gruzman, David; Martin, Jan M L

    2009-01-01

    Conformational energies of n-butane, n-pentane, and n-hexane have been calculated at the CCSD(T) level and at or near the basis set limit. Post-CCSD(T) contribution were considered and found to be unimportant. The data thus obtained were used to assess the performance of a variety of density functional methods. Double-hybrid functionals like B2GP-PLYP and B2K-PLYP, especially with a small Grimme-type empirical dispersion correction, are capable of rendering conformational energies of CCSD(T) quality. These were then used as a `secondary standard' for a larger sample of alkanes, including isopentane and the branched hexanes as well as key isomers of heptane and octane. Popular DFT functionals like B3LYP, B3PW91, BLYP, PBE, and PBE0 tend to overestimate conformer energies without dispersion correction, while the M06 family severely underestimates GG interaction energies. Grimme-type dispersion corrections for these overcorrect and lead to qualitatively wrong conformer orderings. All of these functionals also ex...

  3. Elucidating Structure-Bioactivity Relationships of Methyl-Branched Alkanes in the Contact Sex Pheromone of the Parasitic Wasp Lariophagus distinguendus

    Directory of Open Access Journals (Sweden)

    Stephan Kühbandner

    2013-12-01

    Full Text Available The exoskeletons of insects are covered by complex mixtures of cuticular hydrocarbons (CHCs which are involved in social and sexual communication. However, little is known about the relationship between the structures of CHCs and their behavioral activity. The key component of the contact sex pheromone of the parasitoid Lariophagus distinguendus is 3-methylheptacosane (3-MeC27, which is present in CHC profiles of both females and newly emerged males. The CHCs of females and young males elicit wing-fanning behavior in older males. However, as young males age, 3-MeC27 disappears from their CHC profiles and they no longer elicit wing-fanning responses from other males. We applied enantiopure 3-MeC27 and structurally related CHCs (with respect to chain length or methyl-branch position to the cuticle of aged male dummies and recorded the wing-fanning behavior of responding males. Only the two enantiomers of 3-MeC27 restored the dummies’ attractiveness. The addition of structurally related CHCs or various n-alkanes to bioactive dummies of young males and females significantly decreased wing-fanning by test males. Hence, L. distinguendus males respond specifically but not enantioselectively to 3-MeC27, and perceive the CHC profiles as a whole. Both removal (as is the case with 3-MeC27 in aging males and addition of individual compounds may disrupt the behavioral response.

  4. Estimativa da ingestão e digestibilidade de erva e bolota em porcos alentejanos pela técnica dos n-alcanos Estimation of intake and digestibility of pasture and acorns by alentejano pigs using n-alkanes

    Directory of Open Access Journals (Sweden)

    C. Mendes

    2007-01-01

    Full Text Available Com o objectivo de estimar, em porcos Alentejanos, a ingestão e a digestibilidade de erva e bolota, foi realizado um ensaio utilizando n-alcanos de cadeia longa como marcadores fecais. Oito animais, alojados em caixas metabólicas, distribuídos aleatoriamente em 2 grupos de 4 animais cada, foram sujeitos a dois tratamentos. Cada animal do grupo 1 recebeu um bolinho por dia, contendo 100 mg de C32 e 150 mg de C36 e do grupo 2, dois bolinhos por dia contendo 50 mg de C32 e 75 mg de C36. Os animais foram alimentados com erva e bolota ao longo de todo o ensaio. A ingestão e a digestibilidade da dieta foram determinadas individualmente, através da medição das quantidades de alimento ingeridas e de fezes produzidas durante 5 dias e estimadas através da utilização da técnica dos n-alcanos. As estimativas da digestibilidade feitas através da utilização dos n-alcanos naturais C25 e C27 permitiram a obtenção de resultados muito próximos das medições in vivo. Os C29 e C31, em combinação com os nalcanos artificiais (C32 e C36, forneceram as estimativas da digestibilidade mais próximas da determinada, sendo os pares C29:C32 e C29:C36 os que forneceram as melhores estimativas para a ingestão. A administração dos C32 e C36 uma ou duas vezes por dia não demonstrou ter qualquer influência nas estimativas realizadas. A composição da dieta (bolota e erva, estimada pelos n-alcanos, apresentou valores próximos dos medidos in vivo, sendo as melhores estimativas dadas pelas combinações dos n-alcanos C29 e C31.The aim of this experiment was to estimate intake and digestibility of grass and acorns in Alentejano pigs, using long chain n-alkanes as fecal markers. Eight male Alentejano pigs, housed in metabolic cages were randomly allocated into two groups. Group 1 received one small cake per animal per day containing 100 mg of C32 and 150 mg of C36 and group 2 received two small cakes per animal per day containing 50 mg of C32 and 75 mg of C

  5. Hydrogen isotope systematics in C3 and C4 saltmarsh plants: the importance of biochemical processes in controlling interspecies variation in n-alkane 2H/1H composition

    Science.gov (United States)

    Eley, Y.; Pedentchouk, N.

    2013-12-01

    Palaeohydrological studies have increasingly utilised the 2H/1H composition of leaf wax n-alkyl lipids to extract information from the geological record. Interpretation of the sedimentary biomarker δ2H signal, however, requires detailed understanding of the mechanisms controlling hydrogen isotope fractionation between source water and n-alkyl lipids (ɛl/w). The existence of large ranges in published n-alkyl δ2H and ɛl/w among modern plant species growing at a single location suggests that the lipid signal incorporated into the sedimentary record could be sensitive to relatively small-scale changes in vegetation assemblages. The mechanisms responsible for these interspecies differences are currently poorly constrained. Previous research has had limited success explaining n-alkyl δ2H by reference to physical processes controlling the movement of water inside/outside and within the leaf, while the relative importance of biochemical processes remains largely unexplored. This project aims to identify the mechanisms controlling interspecies variation in n-alkane 2H/1H among a range of C3 and C4 plants from a Norfolk saltmarsh in the UK. To distinguish between environmental, physical and biochemical controls, we conducted 2H/1H analysis of soil, xylem, and leaf waters and n-alkanes (i) across multiple sampling sites within the marsh, (ii) throughout the 2012 growth season, and (iii) at different times of the day. We also measured the 2H/1H of chloroplast phytol in 7 samples collected at the end of 2012. Leaf wax n-alkane δ2H varied among the sampled species by over 100‰ throughout the 2012 growth season. Environmental processes that could influence control source water 2H/1H did not fully account for this interspecies variation - soil water 2H/1H varied by only 35‰ with marsh sub-environment and exhibited site-specific seasonal shifts by no more than 31‰. Maximum interspecies variation in xylem water was 38‰, while leaf waters differed by only 29‰. We

  6. Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements: Caffeines, n-Alkanes, Fatty Acid Methyl Esters, Glycines, l-Valines, Polyethylenes, and Oils.

    Science.gov (United States)

    Schimmelmann, Arndt; Qi, Haiping; Coplen, Tyler B; Brand, Willi A; Fong, Jon; Meier-Augenstein, Wolfram; Kemp, Helen F; Toman, Blaza; Ackermann, Annika; Assonov, Sergey; Aerts-Bijma, Anita T; Brejcha, Ramona; Chikaraishi, Yoshito; Darwish, Tamim; Elsner, Martin; Gehre, Matthias; Geilmann, Heike; Gröning, Manfred; Hélie, Jean-François; Herrero-Martín, Sara; Meijer, Harro A J; Sauer, Peter E; Sessions, Alex L; Werner, Roland A

    2016-04-19

    An international project developed, quality-tested, and determined isotope-δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope-δ scales. The RMs span a range of δ(2)HVSMOW-SLAP values from -210.8 to +397.0 mUr or ‰, for δ(13)CVPDB-LSVEC from -40.81 to +0.49 mUr and for δ(15)NAir from -5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C16 n-alkanes, n-C20-fatty acid methyl esters (FAMEs), glycines, and l-valines, together with polyethylene powder and string, one n-C17-FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a (2)H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ(2)H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain (13)C and carbon-bound organic (2)H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies. PMID:26974360

  7. GC×GC measurements of C7-C11 aromatic and n-alkane hydrocarbons on Crete, in air from Eastern Europe during the MINOS campaign

    Directory of Open Access Journals (Sweden)

    X. Xu

    2003-01-01

    Full Text Available During the Mediterranean Intensive Oxidant Study (MINOS campaign in August 2001 gas-phase organic compounds were measured using comprehensive two-dimensional gas chromatography (GCxGC at the Finokalia ground station, Crete. In this paper, C7-C11 aromatic and n-alkane measurements are presented and interpreted. The mean mixing ratios of the hydrocarbons varied from 1±1 pptv (i-propylbenzene to 43±36 pptv (toluene. The observed mixing ratios showed strong day-to-day variations and generally higher levels during the first half of the campaign. Mean diel profiles showed maxima at local midnight and late morning, and minima in the early morning and evening. Results from analysis using a simplified box model suggest that both the chemical sink (i.e. reaction with OH and the variability of source strengths were the causes of the observed variations in hydrocarbon mixing ratios. The logarithms of hydrocarbon concentrations were negatively correlated with the OH concentrations integral over a day prior to the hydrocarbon measurements. Slopes of the regression lines derived from these correlations for different compounds are compared with literature rate constants for their reactions with OH. The slopes for most compounds agree reasonably well with the literature rate constants. A sequential reaction model has been applied to the interpretation of the relationship between ethylbenzene and two of its potential products, i.e. acetophenone and benzeneacetaldehyde. The model can explain the good correlation observed between [acetophenone]/[ethylbenzene] and [benzeneacetaldehyde]/[ethylbenzene]. The model results and field measurements suggest that the reactivity of benzeneacetaldehyde may lie between those of acetophenone and ethylbenzene and that the ratio between yields of acetophenone and benzeneacetaldehyde may be up to 28:1. Photochemical ages of trace gases sampled at Finokalia during the campaign are estimated using the sequential reaction model and

  8. Influence of Late Pleistocene and Holocene climate on vegetation distributions in southwest Africa elucidated from sedimentary n-alkanes - Differences between 12°S and 20°S

    Science.gov (United States)

    Badewien, Tanja; Vogts, Angela; Dupont, Lydie; Rullkötter, Jürgen

    2015-10-01

    Global and local climatic forcing, e.g. concentration of atmospheric CO2 or insolation, influence the distribution of C3 and C4 plants in southwest Africa. C4 plants dominate in more arid and warmer areas and are favoured by lower pCO2 levels. Several studies have assessed past and present continental vegetation by the analysis of terrestrial n-alkanes in near-coastal deep sea sediments using single samples or a small number of samples from a given climatic stage. The objectives of this study were to evaluate vegetation changes in southwest Africa with regard to climatic changes during the Late Pleistocene and the Holocene and to elucidate the potential of single sample simplifications. We analysed two sediment cores at high resolution, altogether ca. 240 samples, from the Southeast Atlantic Ocean (20°S and 12°S) covering the time spans of 18 to 1 ka and 56 to 2 ka, respectively. Our results for 20°S showed marginally decreasing C4 plant domination (of ca. 5%) during deglaciation based on average chain length (ACL27-33 values) and carbon isotopic composition of the C31 and C33n-alkanes. Values for single samples from 18 ka and the Holocene overlap and, thus, are not significantly representative of the climatic stages they derive from. In contrast, at 12°S the n-alkane parameters show a clear difference of plant type for the Late Pleistocene (C4 plant domination, 66% C4 on average) and the Holocene (C3 plant domination, 40% C4 on average). During deglaciation vegetation change highly correlates with the increase in pCO2 (r² = 0.91). Short-term climatic events such as Heinrich Stadials or Antarctic warming periods are not reflected by vegetation changes in the catchment area. Instead, smaller vegetation fluctuations during the Late Pleistocene occur in accordance with local variations of insolation.

  9. 烷基芳基磺酸钠对烷烃的乳化性能%Emulsifing Properties of Sodium Alkyl Aryl Sulfonate to Alkanes

    Institute of Scientific and Technical Information of China (English)

    于涛; 刘华沙; 王超群; 丁伟; 曲广淼

    2011-01-01

    采用分水时间法考察了结构明确的高纯度烷基芳基磺酸钠在烷烃中的乳化现象.以液态石蜡为油相,讨论了乳化剂浓度对乳状液稳定性的影响,确定了最适宜的乳化剂浓度,并研究了烷基链长度、芳基结构和芳基在烷基链位置对形成的乳状液稳定性的影响关系,考察了不同油相对乳状液稳定性的影响.结果表明,最适宜的乳化剂质量分数为0.1%;当固定芳基结构时,随着烷基链上碳数的增加,乳状液稳定性线性增强;当固定烷基链碳数时,随着芳基仁碳原子的增加,乳状液稳定性增强;随着芳基位置向烷基链中间位置移动,乳状液稳定性增强;随着油相分子量的增加,能形成稳定乳状液所需的乳化剂的分子量随之递增.%The abilities of sodium alkyl aryl sulfonate, which had high-purity and defined structure, to emulsify alkanes, were investigated by a water diversion method. Using liquid paraffin wax as the oil phase, the effects of the concentration of emulsion, length of alkyl chain, structures and locations of aryl groups in alkyl chain on emulsion stability were studied, and the best concentration of emulsion were determined. Meanwhile, the effects of different oil phases to emulsion stability were discussed. The experimental data showed that the best mass fraction of emulsion was 0. 1 %. With definite structures of aryl group, emulsion stability increased linearly with the increasing of the length of carbonic chain. When the length of alkyl chain on alkyl group was set, the emulsion stability was enhanced with the increasing of the length of alkyl chain on aryl group. With the aromatic ring shifts from the terminal to the center of the long alkyl chain, the emulsion stability increased. With the increase of molecular mass of oil phases, the molecular mass of emulsifier to achieve stable emulsifying liquid increased.

  10. High molecular weight n-alkanes of high-waxy condensate and its source kitchen orientation in the Qianmiqiao burial-hill zone, Bohai Gulf Basin

    Institute of Scientific and Technical Information of China (English)

    WANG; Tieguan(WANG; T.-G.)

    2004-01-01

    [1]Philp, R. P., Bishop, A. N., Del Rio, J., Characterization of high molecular weight hydrocarbons (>C40) in the oils and reservoir rocks, in The Geochemistry of Reservoirs (eds. Cubitt, J. M., England, W. A.), London: The Geological Society, 1995, 71-85.[2]Hsieh, M., Philp, R. P., Ubiquitous occurrence of high molecular weight hydrocarbons in crude oils, Organic Geochemistry, 2001, 32: 955-966.[3]Lipsky, S. R., Duffy, M. L., High temperature gas chromatography: The development of new aluminum clad flexible fused silica glass capillary columns coated with thermostable nonpolar phases (Part 1), J. of High Resolution Chromatography, 1986, 9: 376-382.[4]Philp, R. P., High temperature gas chromatography for the analysis of fossil fuels: A review, J. of High Resolution Chromatography, 1994, 17: 398-406.[5]Wang Tieguan, Zhu Dan, Lu Hong et al., High molecular weight (C35+) n-alkanes of Neogene heavily biodegraded oil in the Qianmiqiao region, North China, Chinese Science Bulletin, 2002, 47: 1402-1407.[6]The Editorial Board of Petroleam Geology of Dogang Oilfield, Petroleum Geology of China, Vol. 4: Dagang Oilfield, Beijing: Petroleum Industry Press, 1991, 149-153.[7]Yu Zhihai, Yang Chiyin, Liao Qianjun et al., Natural Gas Geology in Huanghua Depression, Beijing: Petroleum Industry Press, 1997, 122-145.[8]Lu Hong, Wang, T. -G., Wang Chunjiang et al., Hydrocarbon sources of high waxy oil and gas pools in Qianmiqiao buried-hill zone, Huanghua depression, Petroleum Exploration and Development (in Chinese), 2001, 28(4): 17-21.[9]Zhang Yousheng, Wang Tieguan, Wang Feiyu, Oil source and entrapment epoch of the Mesozoic oil reservoir in the Kongxi Burial-hill zone, Huanghua Depression, North China, Scientia Geologica Sinica, 1001(4): 257-274.[10]Wang Tieguan, Wang Feiyu, Lu Hong et al., Oil source and entrapment epoch of the Ordovician oil reservoir in the Kongxi Burial-hill zone, Huanghua Depression, North China, Acta Geologica Sinica

  11. Potencial discriminatório dos N-alcanos em plantas forrageiras tropicais por análises multivariadas Discriminatory potential of the N-alkanes in tropical forages by multivariate analysis

    Directory of Open Access Journals (Sweden)

    Cristiano Côrtes

    2005-08-01

    Full Text Available O potencial dos n-alcanos em discriminar frações ou espécies de gramíneas (Brachiaria brizantha Stapf. cv. Marandu, Cynodon dactylon Pers. cv. Coast-cross 1 e Panicum maximum Jacq. cv. Tanzânia 1 e leguminosas tropicais (Arachis pintoi Koprov & Gregory. cv. Amarillo e Glycine wightii Verdc. Soja Perene foi avaliado neste estudo. As forrageiras foram amostradas na primavera, no verão e inverno, com quatro repetições por espécie. Utilizaram-se nas análises os n-alcanos C24 a C35, sendo o C32 e C34 padrões internos. As concentrações dos n-alcanos nas diferentes espécies e respectivas frações (lâminas foliares, haste porções superior e inferior e matéria morta, para gramíneas; folhas, caule porções superior e inferior e matéria morta para leguminosas foram avaliadas mediante análises multivariadas. O potencial discriminatório dos n-alcanos foi determinado pela análise de variáveis canônicas. As espécies e frações foram divididas em grupos por meio da análise de agrupamento. Os alcanos com menor potencial discriminatório foram: C26, C29, C25, C27 e C28 (primavera, C26, C28, C27, C30 e C29 (verão e C28, C26, C25, C29 e C27 (inverno. Nos períodos de primavera e inverno, a técnica de n-alcanos permitiu distinguir a lâmina foliar do coastcross das hastes superior e inferior, bem como das gramíneas e leguminosas. Em pastagens exclusivas de Brachiaria brizantha, no período de verão, seria possível discriminar as frações de importância nutricional, lâmina foliar e haste superior, pela determinação dos n-alcanos. As análises multivariadas, as variáveis canônicas e a análise de agrupamento representam boas alternativas de cálculo para melhorar a aplicabilidade da técnica dos n-alcanos na discriminação das dietas de herbívoros.The discriminatory potential of n-alkanes in tropical grasses (Brachiaria brizantha Stapf. cv. Marandu, Cynodon dactylon Pers. cv. Coast-cross 1 and Panicum maximum Jacq. cv. Tanz

  12. Long n-alkanes isomerization by medium pore zeolites with pore mouth and key lock mechanisms; Isomerisation des paraffines longues par des zeolithes a pores moyens selon les mecanismes ouverture de pore et cle serrure

    Energy Technology Data Exchange (ETDEWEB)

    Claude, M.

    1999-10-01

    Skeletal isomerization of long n-alkanes is practiced to improve cold flow properties of diesel and lubricant fractions. In this work, model long n-alkanes (n-C{sub 10} - n-C{sub 24}) were hydro-isomerized in a fixed bed down flow vapour phase reactor loaded with bifunctional Pt/H-ZSM-22 zeolite catalyst. The skeletal isomers were analysed and identified with GC/MS. High isomer yields were obtained. The distribution of positional mono-methyl-branched isomers obtained from n-C{sub 12} to n-C{sub 24} are typically bimodal. This is explained by adsorption and reaction of the alkanes in pore mouths and locks on the external surface of the zeolite crystals. The pore mouth mode favours branching at C{sub 2} and C{sub 3}. The 'key lock' type proceeds by penetration of the two ends of the hydrocarbon chain into a different pore opening and favours more central mono-branching of the chain. The contribution of the key lock mode increases with increasing chain length and with the reaction temperature. The preferentially formed dimethyl-branched isomers have a separation between branchings of three up to fourteen carbon atoms. The formation of the second methyl-branching occurs preferentially from a centrally branched mono-methyl-branched isomer, so that the second branching is generated always more toward the end of the chain. Owing to the differences in adsorption entropy among the locks, at higher temperatures the largest lock is preferred and the distance between the two branching along the carbon chain in the preferred isomers is biggest. Thus the work resulted in the formulation of structure-selectivity relationships. n-C{sub 18} was hydro-isomerized on other zeolites. The nature and distribution of the isomers obtained suggest that the tubular 10-ring zeolites ZSM-23, ZSM-35 and SAPO-11 also operate according to pore mouth and key lock concepts. Zeolites with 12-rings show typical product patterns for catalysis in absence of steric hindrance. (author)

  13. Chemical characterization of fatty acids, alkanes, n-diols and alkyl esters produced by a mixed culture of Trichoderma koningii and Penicillium janthinellum grown aerobically on undecanoic acid, potatoe dextrose and their mixture.

    Science.gov (United States)

    Monreal, Carlos M; Chahal, Amarpreet; Schnitzer, Morris; Rowland, Owen

    2016-05-01

    Little is known about the mixed fungal synthesis of high-value aliphatics derived from the metabolism of simple and complex carbon substrates. Trichoderma koningii and Penicillium janthinellum were fed with undecanoic acid (UDA), potatoe dextrose broth (PDB), and their mixture. Pyrolysis Field Ionization Mass Spectrometry (Py-FIMS) together with (1)H and (13)C Nuclear Magnetic Resonance (NMR) characterized CHCl3 soluble aliphatics in the fungal cell culture. Data from NMR and Py-FIMS analysis were complementary to each other. On average, the mixed fungal species produced mostly fatty acids (28% of total ion intensity, TII) > alkanes (2% of TII) > n-diols (2% of TII) > and alkyl esters (0.8% of TII) when fed with UDA, PDB or UDA+PDB. The cell culture accumulated aliphatics extracellularly, although most of the identified compounds accumulated intracellularly. The mixed fungal culture produced high-value chemicals from the metabolic conversion of simple and complex carbon substrates. PMID:26852878

  14. Low temperature hydrogenolysis of waxes to diesel range gasoline and light alkanes: Comparison of catalytic properties of group 4, 5 and 6 metal hydrides supported on silica-alumina

    KAUST Repository

    Norsic, Sébastien

    2012-01-01

    A series of metal hydrides (M = Zr, Hf, Ta, W) supported on silica-alumina were studied for the first time in hydrogenolysis of light alkanes in a continuous flow reactor. It was found that there is a difference in the reaction mechanism between d 0 metal hydrides of group 4 and d 0 ↔ d 2 metal hydrides of group 5 and group 6. Furthermore, the potential application of these catalysts has been demonstrated by the transformation of Fischer-Tropsch wax in a reactive distillation set-up into typical gasoline and diesel molecules in high selectivity (up to 86 wt%). Current results show that the group 4 metal hydrides have a promising yield toward liquid fuels.

  15. Prediction of the vapor–liquid equilibria and speed of sound in binary systems of 1-alkanols and n-alkanes with the simplified PC-SAFT equation of state

    DEFF Research Database (Denmark)

    Liang, Xiaodong; Thomsen, Kaj; Yan, Wei;

    2013-01-01

    Prediction of speed of sound is a challenging task for any equation of state because it needs the first- and second-order derivatives of the Helmholtz free energy with respect to both temperature and volume. Equally challenging is the simultaneous predictions of phase behavior and speed of sound...... (or other derivative properties) with satisfactory accuracy over wide temperature, pressure and composition conditions. This work presents the prediction of the vapor–liquid equilibria and speed of sound in binary mixtures of 1-alkanols and n-alkanes using the simplified PC-SAFT equation of state...... for 1533 experimental data points in the temperature range from 273 to 493K, and 1.7% for the speed of sound for 2490 experimental data points at temperature between 293 and 318K and pressure up to 120MPa. The results reveal that it is possible to simultaneously model the vapor–liquid equilibria and speed...

  16. Perfil de n-alcanos em cinco espécies de plantas forrageiras tropicais - DOI: 10.4025/actascianimsci.v27i3.1207 Profile of n-alkanes in five species of plants tropical forages - DOI: 10.4025/actascianimsci.v27i3.1207

    Directory of Open Access Journals (Sweden)

    Antônio Ferriani Branco

    2005-03-01

    Full Text Available O objetivo do experimento foi estudar o perfil de n-alcanos em espécies de gramíneas (Brachiaria brizantha, Cynodon dactylon e Panicum maximum e leguminosas (Arachis pintoi e Glycine wightii. Foram identificados e quantificados por meio de cromatografia gasosa, os n-alcanos C24 a C35, sendo C32 e C34 padrões internos. As concentrações dos n-alcanos nas diferentes espécies e respectivas frações (lâminas foliares, colmos porções superior e inferior e matéria morta para gramíneas; folhas, caule porção superior e inferior e matéria morta para leguminosas foram submetidas à análise de variância e teste de média (Tukey. Nos períodos de primavera e inverno, para a maioria das espécies e frações, há predomínio dos n-alcanos de cadeia ímpar. Houve maior concentração de C29, C31 e C33 na primavera, C27, C28, C29, C30 e C31, no verão e C27, C29, C31 e C33 no invernoThis experiment aimed to study the profile of n-alkanes in tropical grasses species (Brachiaria brizantha, Cynodon dactylon and Panicum maximum and legumes (Arachis pintoi and Glycine wightii. They were identified and quantified, through gas cromatography, the n-alkanes C24 to C35, being the alkanes C32 and C34 internal indices. The n-alkanes concentrations in the different species and respective fractions (leaf blade, stem higher and lower portion and dead matter for grasses; leaves, stem higher portion, stem lower portion and dead matter for legumes were submitted to variance analysis and mean test (Tukey. For most of the species and fractions, there is prevalence of odd chain n-alkanes during springtime and winter. There was larger concentration of the alkanes C29, C31 and C33 in springtime, C27, C28, C29, C30 and C31 in summer and C27, C29, C31 and C33 in winter

  17. 咸水湖泊沉积物中正构烷烃及其氢同位素组成与成因%Composition and Genesis of n-Alkanes and Their Hydrogen Isotope in Sediments from Saline Lake, China

    Institute of Scientific and Technical Information of China (English)

    段毅; 何金先; 吴保祥; 徐丽; 张晓丽; 孙涛

    2011-01-01

    The Qinghai ILake is the largest saline lake in China. We study the compositions of n-alkanes and their hydrogen isotope in sediments from the lake, and discuss the genesis of their compositions by the comparison with previous study results of plants from the lake and its surrounding areas. Our results show that the n-alkanes in the surface and core sediments have a similar distribution which reflects the source from terrestrial herbaceous plants in the surrounding regions of the lake. The hydrogen isotopic compositions of n-alkanes in the surface and core sediments are also similar, which indicates that n-alkanes in the sediments were derived from terrestrial herbaceous plants in surrounding regions of the lake. This study further demonstrates that the hydrogen isotopic compositions of n-alkanes in lake sediment reflect the biological source hydrogen isotopic signals that are related to paleoclimate. Therefore, δD values of n-alkanes in lake sediment can be used to indicate paleoclimate.%青海湖是我国最大的内陆咸水湖泊,对这种湖泊沉积物中正构烷烃及其氢同位素进行了分析,研究了沉积物中正构烷烃及其同位素组成,并且与青海湖水生植物及其周围陆生植物的研究结果进行了对比,研究了它们的成因.结果显示了青海湖表层和柱状沉积物中正构烷烃分布都是类似的,其特征反映了它们起源于湖泊周围陆生草本植物.青海湖表层沉积物中正构烷烃氢同位素组成特征也与柱状沉积物中的类似,沉积物样品中正构烷烃氧同位素的组成和分布特征反映了它们主要来自陆生草本植物.从而进一步证实了水体中沉积物的正构烷烃氢同位素组成,反映了生物源的氢同位素组成,后者与古气候相关,因此沉积物的正构烷烃氢同位素组成可以指示古气候.

  18. Uso de N-alcanos na estimativa da composição botânica em amostras com diferentes proporções de Brachiaria brizantha e Arachis pintoi Use of N-alkanes for estimations of botanical composition in samples with different proportions of Brachiaria brizantha and Arachis pintoi

    Directory of Open Access Journals (Sweden)

    Cristiano Côrtes

    2005-10-01

    Full Text Available Este trabalho foi conduzido para se determinar a composição de n-alcanos (C24 a C36 em diferentes proporções de dietas hipotéticas de Brachiaria brizantha Stapf. cv. Marandu e Arachis pintoi Koprov & Gregory. cv. Amarillo (0; 15; 30; 45; 60 e 100% de Arachis pintoi e identificar a combinação de alcanos que permite calcular a composição botânica de dietas com o menor valor residual (real menos o estimado. As forragens foram amostradas no verão e os n-alcanos extraídos pelo método de saponificação direta, sendo identificados e quantificados por meio de análise de cromatografia gasosa. O alcano C34 foi utilizado como padrão interno. As proporções de A. pintoi nas dietas foram estimadas pela minimização do z (soma dos quadrados dos desvios entre a proporção real dos alcanos analisados e as proporções pré-estabelecidas (tratamentos, utilizando-se a equação de Duncan et al. (1999. Observou-se que houve predomínio das cadeias carbônicas ímpares e que a concentração total de n-alcanos decresceu à medida que se aumentou a proporção de A. pintoi nos tratamentos. Estimativas acuradas da composição botânica de misturas de A. pintoi com B. brizantha foram obtidas utilizando-se os alcanos C29, C31, C33 e C35. O alcano C35 foi fundamental para a qualidade das estimativas. Os resultados indicaram o grande potencial da técnica para estudos com animais em pastejo.This trial was carried out to determine the composition of n-alkanes (C24 to C36 in hypothetical diets comprising of pure Brachiaria brizantha Stapf. cv. Marandu and Arachis pintoi Koprov & Gregory. cv. Amarillo and mixtures of these two spececies with 15%, 30%, 45%, or 60% of Arachis pintoi; it also intended to identify the combination of alkanes that allows to calculate the botanical composition of diets with the smallest residual value (real less estimated values. The forages were sampled in the summer. The n-alkanes were extracted for the direct saponification

  19. Research on determination method of alkane mixtures in cooking oil fumes%烹调油烟中十一烷、十二烷等烷烃混合物的测定方法研究

    Institute of Scientific and Technical Information of China (English)

    柯华; 郑申西; 陈柯星; 林捷

    2013-01-01

    目的:研究日常烧菜油烟中十一烷、十二烷、十八烷、二十烷4种烷烃混合物一次性吸附、一次分离的定量分析方法.方法:采用溶剂解吸型活性炭采样管吸附油烟后,进行溶剂(CS2)解析,样品在气相色谱上用毛细管柱进行分离,外标法峰面积定量,分析这4种烷烃化合物的含量.结果:上述4种物质的回归曲线相关系数均大于0.998,样品平均解析率为85% ~ 98%,相对标准偏差为0.76% ~ 1.6%,检出限在0.10 μg/mL~0.20 μg/mL之间.结论:该方法可以一次进样快速检测上述烷烃在油烟中的含量,简便、准确,重现性好.%Objective:To study the deter mination method for four kinds of alkane mixtures including undecane,dodecane,octadecane,eicosane in day-to-day cooking oil fumes by once disposable adsorption and once disposable separation.Methods:Cooking oil fumes was collected by the solvent-desorption activated carbon sampling tube,then four kinds of alkenes mixtures were desorbed by solvent(CS2) and separated on capillary column,quantified by the external standard method.Results:With this method,the correlation coefficients of the regression curve of above-mentioned four kinds of alkenes mixtures are greater than 0.998,the average desorption rate of sample was from 85% to 98%,the relative standard deviation was from 0.76% to 1.6%,the detection limit was between 0.10 μg/mL ~ 0.20 μ/mL.Conclusion:This method is rapid for deter mination of above-mentioned four kinds of alkanes in cooking oil fumes with a single injection,with accuracy and good reproducibility.

  20. Pt-Sn/SBA-15催化剂的制备、表征和长链烷烃脱氢催化性能%Preparation and Characterization of Pt-Sn/SBA-15 Catalysts and Their Catalytic Performances for Long Chain Alkane Dehydrogenation

    Institute of Scientific and Technical Information of China (English)

    卢泽湘; 季生福; 刘辉; 李成岳

    2008-01-01

    A series of the Pt-Sn/SBA-15 catalysts were prepared and their properties characterized by using X-ray powder diffraction(XRD),N2 adsorption-desorption,high resolution transmission electron m~croscope,X-ray pho- toelectron spectroscopy(XPS)and H2-temperature programmed reduction.Their performances in long chain alkane dehydrogen-atiOn were evaluated in a fixed-bed microreactor with dodecane as a model alkane.The results indicated that SBA-15 maintained the well-order mesoporous structure during the reaction.The performance of the catalyst was found not dominated by its textural properties.but by the molar ratio of Sn to Pt which governed the degree of Sn reduction.Owing to the highest degree of Sn reduction,1%(by mass)Pt-1.8%(by mass)Sn/sBA-15 showed the best catalytic activity.At 0.1 Mpa and 470℃,the molar ratio of hydrogen to alkane at 4,and liquid hourly space velocity(LHSV)20 h-1,the dodecane conversion iS 10%,and the dodecene selectivity iS about 70%.