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Sample records for alkane conversion chemistry

  1. Catalytic conversion of light alkanes

    SciTech Connect

    Lyons, J.E.

    1992-06-30

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

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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. PMID:26791899

  4. Alkane metathesis by tandem alkane-dehydrogenation-olefin-metathesis catalysis and related chemistry.

    PubMed

    Haibach, Michael C; Kundu, Sabuj; Brookhart, Maurice; Goldman, Alan S

    2012-06-19

    Methods for the conversion of both renewable and non-petroleum fossil carbon sources to transportation fuels that are both efficient and economically viable could greatly enhance global security and prosperity. Currently, the major route to convert natural gas and coal to liquids is Fischer-Tropsch catalysis, which is potentially applicable to any source of synthesis gas including biomass and nonconventional fossil carbon sources. The major desired products of Fischer-Tropsch catalysis are n-alkanes that contain 9-19 carbons; they comprise a clean-burning and high combustion quality diesel, jet, and marine fuel. However, Fischer-Tropsch catalysis also results in significant yields of the much less valuable C(3) to C(8)n-alkanes; these are also present in large quantities in oil and gas reserves (natural gas liquids) and can be produced from the direct reduction of carbohydrates. Therefore, methods that could disproportionate medium-weight (C(3)-C(8)) n-alkanes into heavy and light n-alkanes offer great potential value as global demand for fuel increases and petroleum reserves decrease. This Account describes systems that we have developed for alkane metathesis based on the tandem operation of catalysts for alkane dehydrogenation and olefin metathesis. As dehydrogenation catalysts, we used pincer-ligated iridium complexes, and we initially investigated Schrock-type Mo or W alkylidene complexes as olefin metathesis catalysts. The interoperability of the catalysts typically represents a major challenge in tandem catalysis. In our systems, the rate of alkane dehydrogenation generally limits the overall reaction rate, whereas the lifetime of the alkylidene complexes at the relatively high temperatures required to obtain practical dehydrogenation rates (ca. 125 -200 °C) limits the total turnover numbers. Accordingly, we have focused on the development and use of more active dehydrogenation catalysts and more stable olefin-metathesis catalysts. We have used thermally

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

    PubMed

    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

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

    ERIC Educational Resources Information Center

    Seymour, Raymond B.

    1989-01-01

    Discusses the history and commercialization of alkanes. Examines the nomenclature and uses of alkanes. Studies polymerization and several types of polyethylenes: low-density, high-density, low-molecular-weight, cross-linked, linear low-density, and ultrahigh-molecular-weight. Includes a glossary of hydrocarbon terms. (MVL)

  7. Organic Chemistry Self Instructional Package 5: Alkanes Preparations and Reactions.

    ERIC Educational Resources Information Center

    Zdravkovich, V.

    This booklet, one of a series of 17 developed at Prince George's Community College, Largo, Maryland, provides an individualized, self-paced undergraduate organic chemistry instruction module designed to augment any course in organic chemistry but particularly those taught using the text "Organic Chemistry" by Morrison and Boyd. The entire series…

  8. Organic Chemistry Self Instructional Package 4: Alkanes-Nomenclature.

    ERIC Educational Resources Information Center

    Zdravkovich, V.

    This booklet, one of a series of 17 developed at Prince George's Community College, Largo, Maryland, provides an individualized, self-paced undergraduate organic chemistry instruction module designed to augment any course in organic chemistry but particularly those taught using the text "Organic Chemistry" by Morrison and Boyd. The entire series…

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

    SciTech Connect

    Lyons, J.E.

    1992-06-30

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

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

    SciTech Connect

    1998-12-31

    The Topical Report on Phase II of the project entitled, Catalytic Conversion of Light Alkanes reviews work done between January 1, 1990 and September 30, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products which can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon transportation fuel. This Topical Report documents our efforts to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. Research on the Cooperative Agreement is divided into three Phases relating to three molecular environments for the active catalytic species that we are trying to generate. In this report we present our work on catalysts which have oxidation-active metals in polyoxoanions (PHASE II).

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

    SciTech Connect

    Biscardi, J.; Bowden, P.T.; Durante, V.A.; Ellis, P.E. Jr.; Gray, H.B.; Gorbey, R.G.; Hayes, R.C.; Hodge, J.; Hughes, M.; Langdale, W.A.; Lyons, J.E.; Marcus, B.; Messick, D.; Merrill, R.A.; Moore, F.A.; Myers, H.K. Jr.; Seitzer, W.H.; Shaikh, S.N.; Tsao, W.H.; Wagner, R.W.; Warren, R.W.; Wijesekera, T.P.

    1997-05-01

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

  12. Catalytic conversion of light alkanes, Phase 1. Topical report, January 1990--January 1993

    SciTech Connect

    1993-12-31

    The authors have found a family of new catalytic materials which, if successfully developed, will be effective in the conversion of light alkanes to alcohols or other oxygenates. Catalysts of this type have the potential to convert natural gas to clean-burning high octane liquid fuels directly without requiring the energy-intensive steam reforming step. In addition they also have the potential to upgrade light hydrocarbons found in natural gas to a variety of high value fuel and chemical products. In order for commercially useful processes to be developed, increases in catalytic life, reaction rate and selectivity are required. Recent progress in the experimental program geared to the further improvement of these catalysts is outlined.

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

    SciTech Connect

    Lyons, J.E.

    1992-07-01

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

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

    SciTech Connect

    Lyons, J.E.

    1992-01-01

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

  15. Chemistry of Energy Conversion and Storage.

    PubMed

    Su, Dang-Sheng; Schlögl, R

    2016-02-19

    Special Issue: Energy Conversion and Storage. Critical issues in current energy-based societies are its generation through methods utilizing alternatives to fossil fuels as well as its storage. Considering the scope, it is not surprising that the research becomes more and more multidisciplinary. Therefore, it is important to keep focused. The ChemEner symposia, the last one being highlighted in this Special Issue, achieve this by focusing on the state of the art and the newest development of the Chemistry of hydrogen generation, carbon dioxide reduction, and other related topics, exploring new concepts for clean future energy. PMID:26914171

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

    SciTech Connect

    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.

  17. A Process for Microbial Hydrocarbon Synthesis: Overproduction of Fatty Acids in Escherichia coli and Catalytic Conversion to Alkanes

    PubMed Central

    Lennen, Rebecca M.; Braden, Drew J.; West, Ryan M.; Dumesic, James A.; Pfleger, Brian F.

    2013-01-01

    The development of renewable alternatives to diesel and jet fuels is highly desirable for the heavy transportation sector, and would offer benefits over the production and use of short-chain alcohols for personal transportation. Here, we report the development of a metabolically engineered strain of Escherichia coli that overproduces medium-chain length fatty acids via three basic modifications: elimination of β-oxidation, overexpression of the four subunits of acetyl-CoA carboxylase, and expression of a plant acyl–acyl carrier protein (ACP) thioesterase from Umbellularia californica (BTE). The expression level of BTE was optimized by comparing fatty acid production from strains harboring BTE on plasmids with four different copy numbers. Expression of BTE from low copy number plasmids resulted in the highest fatty acid production. Up to a seven-fold increase in total fatty acid production was observed in engineered strains over a negative control strain (lacking β-oxidation), with a composition dominated by C12 and C14 saturated and unsaturated fatty acids. Next, a strategy for producing undecane via a combination of biotechnology and heterogeneous catalysis is demonstrated. Fatty acids were extracted from a culture of an overproducing strain into an alkane phase and fed to a Pd/C plug flow reactor, where the extracted fatty acids were decarboxylated into saturated alkanes. The result is an enriched alkane stream that can be recycled for continuous extractions. Complete conversion of C12 fatty acids extracted from culture to alkanes has been demonstrated yielding a concentration of 0.44 g L−1 (culture volume) undecane. PMID:20073090

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

    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.

  1. Organic Chemistry Self Instructional Package 3: Alkanes-Homologous Series and Isomerism.

    ERIC Educational Resources Information Center

    Zdravkovich, V.

    This booklet, one of a series of 17 developed at Prince George's Community College, Largo, Maryland, provides an individualized, self-paced undergraduate organic chemistry instruction module designed to augment any course in organic chemistry but particularly those taught using the text "Organic Chemistry" by Morrison and Boyd. The entire series…

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

    SciTech Connect

    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.

  3. Gas-Phase Tropospheric Chemistry of Volatile Organic Compounds: 1. Alkanes and Alkenes

    SciTech Connect

    Atkinson, R. |

    1997-03-01

    Literature data (through mid-1996) concerning the gas-phase reactions of alkanes and alkenes (including isoprene and monoterpenes) leading to their first generation products are reviewed and evaluated for tropospheric conditions. The recommendations of the most recent IUPAC evaluation [J. Phys. Chem. Ref. Data, {bold 26}, No. 3 (1997)] are used for the {le}C{sub 3} organic compounds, unless more recent data necessitates reevaluation. The most recent review and evaluation of Atkinson [J. Phys. Chem. Ref. Data, Monograph {bold 2}, 1 (1994)] concerning the kinetics of the reactions of OH radicals, NO{sub 3} radicals, and O{sub 3} is also updated for these two classes of volatile organic compounds. {copyright} {ital 1997 American Institute of Physics and American Chemical Society.} {copyright} {ital 1997} {ital American Institute of Physics and American Chemical Society}

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

    PubMed

    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

  5. Nanoparticle conversion chemistry: Kirkendall effect, galvanic exchange, and anion exchange

    NASA Astrophysics Data System (ADS)

    Anderson, Bryan D.; Tracy, Joseph B.

    2014-10-01

    Conversion chemistry is a rapidly maturing field, where chemical conversion of template nanoparticles (NPs) into new compositions is often accompanied by morphological changes, such as void formation. The principles and examples of three major classes of conversion chemical reactions are reviewed: the Kirkendall effect for metal NPs, galvanic exchange, and anion exchange, each of which can result in void formation in NPs. These reactions can be used to obtain complex structures that may not be attainable by other methods. During each kind of conversion chemical reaction, NPs undergo distinct chemical and morphological changes, and insights into the mechanisms of these reactions will allow for improved fine control and prediction of the structures of intermediates and products. Conversion of metal NPs into oxides, phosphides, sulphides, and selenides often occurs through the Kirkendall effect, where outward diffusion of metal atoms from the core is faster than inward diffusion of reactive species, resulting in void formation. In galvanic exchange reactions, metal NPs react with noble metal salts, where a redox reaction favours reduction and deposition of the noble metal (alloying) and oxidation and dissolution of the template metal (dealloying). In anion exchange reactions, addition of certain kinds of anions to solutions containing metal compound NPs drives anion exchange, which often results in significant morphological changes due to the large size of anions compared to cations. Conversion chemistry thus allows for the formation of NPs with complex compositions and structures, for which numerous applications are anticipated arising from their novel catalytic, electronic, optical, magnetic, and electrochemical properties.

  6. Oxidative conversion of C1-C3 alkanes by vanadium oxide catalysts. DFT results and their accuracy

    NASA Astrophysics Data System (ADS)

    Rozanska, Xavier; Sauer, Joachim

    Elementary steps in the oxidative conversion of methane, ethane, and propane by supported vanadium oxide species are studied by density functional theory, specifically B3LYP. Two models are adopted, namely O dbond V(OH)3 and O dbond VSi7O12H7, which yield similar energy profiles. The initial and rate-determining step is hydrogen abstraction. Within the C1-C3 series, energy barriers and reaction energies follow the same trend as the C bond H bond strength in the different alkanes. For methane, only methanol formation is possible whereas for ethane and propane, oxidative dehydrogenation yields the corresponding alkenes. Single point CCSD(T)/TZVP calculations are used to assess the B3LYP error. For the barrier of the initial hydrogen abstraction the B3LYP error is larger than usual, -40 to -60 kJ/mol. With the non-hybrid BP86 and PBE functionals even larger errors occur and the potential energy surface is qualitatively different.

  7. Catalytic conversion of light alkanes-proof-of-concept stage -- Phase 6. Final report, February 1--October 31, 1994

    SciTech Connect

    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. Oxygen-free conversion of methane to higher alkanes through an isothermal two-step reaction on ruthenium

    SciTech Connect

    Belgued, M.; Amariglio, A.; Lefort, L.; Amariglio, H.

    1996-06-01

    Ruthenium dispersed on silica is able to chemisorb CH{sub 4} at temperatures significantly lower than EUROPT-1. At the temperatures used ({ge}80{degrees}C), H{sub 2} desorption parallels CH{sub 4} chemisorption but no C{sub 2}H{sub 6} is observed. During the following temperature programmed desorption under flowing argon, CH{sub 4} is removed through a wide range of temperature (from room temperature to 300{degrees}C) with a first contribution peaking at less than 100{degrees}C. Very small amounts of CH{sub 4} are desorbed after an adsorption carried out at T{ge} 180{degrees}C, due to strong dehydrogenation of the adspecies. Subsequent temperature programmed surface reaction of the remaining adspecies with hydrogen displays upto four CH{sub 4} peaks at well defined temperatures (ranging from {approx} 60 to {approx} 340{degrees}C), accompanied by a negligible formation of ethane. No C{sub {gamma}} was formed. The total amount of adsorbed CH{sub 4} and the average H/C ratio of the corresponding adspecies can be derived from these experiments. In a separate set of experiments, CH{sub 4} is switched to H{sub 2} at the end of the exposure step, the temperature being fixed. An immediate formation of alkanes ranging from C{sub 1} to C{sub 6} is then evidenced. A sizeable fraction of the chemisorbed layer can so be homologated to higher alkanes. The influences of the various operating factors are reported. In particular a neat maximum of the C{sub 2+} production versus temperature (at 160{degrees}C) is evidenced and is clearly due to the adverse hydrogenolysis reactions, efficiently catalyzed by Ru. All the results can be interpreted in complete similarity with the Pt case. 5 refs., 16 figs., 3 tabs.

  9. Catalytic conversion of light alkanes-proof-of-concept stage - Phase IV. Topical report, February 1, 1994--January 31, 1995

    SciTech Connect

    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.

  10. Reducing the Degrees of Freedom in Chemistry Classroom Conversations

    ERIC Educational Resources Information Center

    Criswell, Brett A.

    2012-01-01

    Five high-school chemistry teachers were asked to enact a lesson in which they posed a problem for which students were likely to generate solutions based on reasoning that was not aligned with accepted principles of chemistry. Four teachers selected a problem related to the stoichiometry of a reaction; the fifth chose a problem associated with…

  11. Dehydrogenation of n-alkanes catalyzed by iridium ``pincer`` complexes: Regioselective formation of {alpha}-olefins

    SciTech Connect

    Liu, F.; Singh, B.; Goldman, A.S.; Pak, E.B.; Jensen, C.M.

    1999-04-28

    The development of methods for the functionalization of alkanes is of cardinal importance in catalytic chemistry. A specific functionalization of particularly great potential value is the conversion of n-alkanes to the corresponding 1-alkenes ({alpha}-olefins) since these serve as precursors for a wide range of commodity-scale chemicals (>2 {times} 10{sup 9} kg/yr). Such a conversion is also an intriguing challenge as viewed from a fundamental perspective. n-Alkanes are the simplest organic molecules with the potential to undergo regioselective transformations; {alpha}-olefins are the thermodynamically least stable of the corresponding double-bond isomers and any mechanism for their formation must presumably involve activation of the strongest bond (primary C-{single_bond}H) in the molecule.

  12. Mimicking enzymatic active sites on surfaces for energy conversion chemistry.

    PubMed

    Gutzler, Rico; Stepanow, Sebastian; Grumelli, Doris; Lingenfelder, Magalí; Kern, Klaus

    2015-07-21

    Metal-organic supramolecular chemistry on surfaces has matured to a point where its underlying growth mechanisms are well understood and structures of defined coordination environments of metal atoms can be synthesized in a controlled and reproducible procedure. With surface-confined molecular self-assembly, scientists have a tool box at hand which can be used to prepare structures with desired properties, as for example a defined oxidation number and spin state of the transition metal atoms within the organic matrix. From a structural point of view, these coordination sites in the supramolecular structure resemble the catalytically active sites of metallo-enzymes, both characterized by metal centers coordinated to organic ligands. Several chemical reactions take place at these embedded metal ions in enzymes and the question arises whether these reactions also take place using metal-organic networks as catalysts. Mimicking the active site of metal atoms and organic ligands of enzymes in artificial systems is the key to understanding the selectivity and efficiency of enzymatic reactions. Their catalytic activity depends on various parameters including the charge and spin configuration in the metal ion, but also on the organic environment, which can stabilize intermediate reaction products, inhibits catalytic deactivation, and serves mostly as a transport channel for the reactants and products and therefore ensures the selectivity of the enzyme. Charge and spin on the transition metal in enzymes depend on the one hand on the specific metal element, and on the other hand on its organic coordination environment. These two parameters can carefully be adjusted in surface confined metal-organic networks, which can be synthesized by virtue of combinatorial mixing of building synthons. Different organic ligands with varying functional groups can be combined with several transition metals and spontaneously assemble into ordered networks. The catalytically active metal

  13. Gas-phase chemistry of transition-metal ions with alkanes: do initial electrostatic interaction control final product distributions

    SciTech Connect

    Hankinson, D.J.; Allison, J.

    1987-09-24

    There are features of the dynamics of gas-phase ion/molecule reactions that make them unique when compared to neutral/neutral reactions and solution processes. Exceedingly rich and complex chemistry can be observed in gas-phase systems in which a reactant is charged, due, in part, to the relatively long lifetime of the ion/molecule complex that is initially formed. Here possible correlations between final reaction products and geometry-specific complexes that are initially formed are discussed. The chemistry under study is that for univalent first-row transition-metal ions with n-butane, in which cleavage of C-H and C-C bonds is observed for some metals.

  14. Symposium on the Physical Chemistry of Solar Energy Conversion, Indianapolis American Chemical Society Meetings, Fall 2013

    SciTech Connect

    Lian, Tianquan

    2013-09-20

    The Symposium on the Physical Chemistry of Solar Energy Conversion at the Fall ACS Meeting in Indianapolis, IN (Sept. 8-12) featured the following sessions (approx. 6 speakers per session): (1) Quantum Dots and Nanorods for Solar Energy Conversion (2 half-day sessions); (2) Artificial Photosynthesis: Water Oxidation; (3) Artificial Photosynthesis: Solar Fuels (2 half-day sessions); (4) Organic Solar Cells; (5) Novel Concepts for Solar Energy Conversion (2 half-day sessions); (6) Emerging Techniques for Solar Energy Conversion; (7) Interfacial Electron Transfer

  15. ATMOSPHERIC CHEMISTRY OF POTENTIAL EMISSIONS FROM FUEL CONVERSION FACILITIES. A SMOG CHAMBER STUDY

    EPA Science Inventory

    The atmospheric chemistry of chemical species that may be emitted from fuel conversion facilities were studied in smog chambers. Of 17 compounds assessed for ozone-forming potential, 6 compounds were selected along with a control species, propylene, for testing in the presence of...

  16. EDITORIAL: Non-thermal plasma-assisted fuel conversion for green chemistry Non-thermal plasma-assisted fuel conversion for green chemistry

    NASA Astrophysics Data System (ADS)

    Nozaki, Tomohiro; Gutsol, Alexander

    2011-07-01

    This special issue is based on the symposium on Non-thermal Plasma Assisted Fuel Conversion for Green Chemistry, a part of the 240th ACS National Meeting & Exposition held in Boston, MA, USA, 22-26 August 2010. Historically, the Division of Fuel Chemistry of the American Chemical Society (ACS) has featured three plasma-related symposia since 2000, and has launched special issues in Catalysis Today on three occasions: 'Catalyst Preparation using Plasma Technologies', Fall Meeting, Washington DC, USA, 2000. Special issue in Catalysis Today 72 (3-4) with 12 peer-reviewed articles. 'Plasma Technology and Catalysis', Spring Meeting, New Orleans, LA, USA, 2003. Special issue in Catalysis Today 89 (1-2) with more than 30 peer-reviewed articles. 'Utilization of Greenhouse Gases II' (partly focused on plasma-related technologies), Spring Meeting, Anaheim, CA, USA, 2004. Special issue in Catalysis Today 98 (4) with 25 peer-reviewed articles. This time, selected presentations are published in this Journal of Physics D: Applied Physics special issue. An industrial material and energy conversion technology platform is established on thermochemical processes including various catalytic reactions. Existing industry-scale technology is already well established; nevertheless, further improvement in energy efficiency and material saving has been continuously demanded. Drastic reduction of CO2 emission is also drawing keen attention with increasing recognition of energy and environmental issues. Green chemistry is a rapidly growing research field, and frequently highlights renewable bioenergy, bioprocesses, solar photocatalysis of water splitting, and regeneration of CO2 into useful chemicals. We would also like to emphasize 'plasma catalysis' of hydrocarbon resources as an important part of the innovative next-generation green technologies. The peculiarity of non-thermal plasma is that it can generate reactive species almost independently of reaction temperature. Plasma

  17. Identification and Characterization of the CYP52 Family of Candida tropicalis ATCC 20336, Important for the Conversion of Fatty Acids and Alkanes to α,ω-Dicarboxylic Acids

    PubMed Central

    Craft, David L.; Madduri, Krishna M.; Eshoo, Mark; Wilson, C. Ron

    2003-01-01

    Candida tropicalis ATCC 20336 excretes α,ω-dicarboxylic acids as a by-product when cultured on n-alkanes or fatty acids as the carbon source. Previously, a β-oxidation-blocked derivative of ATCC 20336 was constructed which showed a dramatic increase in the production of dicarboxylic acids. This paper describes the next steps in strain improvement, which were directed toward the isolation and characterization of genes encoding the ω-hydroxylase enzymes catalyzing the first step in the ω-oxidation pathway. Cytochrome P450 monooxygenase (CYP) and the accompanying NADPH cytochrome P450 reductase (NCP) constitute the hydroxylase complex responsible for the first and rate-limiting step of ω-oxidation of n-alkanes and fatty acids. 10 members of the alkane-inducible P450 gene family (CYP52) of C. tropicalis ATCC20336 as well as the accompanying NCP were cloned and sequenced. The 10 CYP genes represent four unique genes with their putative alleles and two unique genes for which no allelic variant was identified. Of the 10 genes, CYP52A13 and CYP52A14 showed the highest levels of mRNA induction, as determined by quantitative competitive reverse transcription-PCR during fermentation with pure oleic fatty acid (27-fold increase), pure octadecane (32-fold increase), and a mixed fatty acid feed, Emersol 267 (54-fold increase). The allelic pair CYP52A17 and CYP52A18 was also induced under all three conditions but to a lesser extent. Moderate induction of CYP52A12 was observed. These results identify the CYP52 and NCP genes as being involved in α,ω-dicarboxylic acid production by C. tropicalis and provide the foundation for biocatalyst improvement. PMID:14532053

  18. Superacid Catalyzed Coal Conversion Chemistry. Final Technical Report, September 1, 1983-September 1, 1986

    DOE R&D Accomplishments Database

    Olah, G. A.

    1986-01-01

    This research project involved the study of a raw comparatively mild coal conversion process. The goal of the project was to study model systems to understand the basic chemistry involved and to provide a possible effective pretreatment of coal which significantly improves liquefaction-depolymerization under mild conditions. The conversion process operates at relatively low temperatures (170 degrees C) and pressures and uses an easily recyclable, stable superacid catalysts (HF-BF{sub 3}). It consequently offers an attractive alternative to currently available processes. From the present studies it appears that the modification of coal structure by electrophilic alkylation and subsequent reaction of alkylated coal with HF-BF{sub 3}-H{sub 2} system under mild conditions considerably improves the extractability of coal in pyridine and cyclohexane. On the other hand, nitration of coal and its subsequent reaction with HF-BF{sub 3}H{sub 2} decreases the pyridine and cyclohexane extractability. Study of model compounds under conditions identical with the superacidic HF/BF{sub 3}/H{sub 2} system provided significant information about the basic chemistry of the involved cleavage-hydrogenation reactions.

  19. Superacid catalyzed coal conversion chemistry. Final technical report, September 1, 1983-September 1, 1986

    SciTech Connect

    Olah, G.A.

    1986-01-01

    This research project involved the study of a raw comparatively mild coal conversion process. The goal of the project was to study model systems to understand the basic chemistry involved and to provide a possible effective pretreatment of coal which significantly improves liquefaction-depolymerization under mild conditions. The conversion process operates at relatively low temperatues (170/sup 0/C) and pressures and uses an easily recyclable, stable superacid catalysts (HF-BF/sub 3/). It consequently offers an attractive alternative to currently available processes. From the present studies it appears that the modification of coal structure by electrophilic alkylation and subsequent reaction of alkylated coal with HF-BF/sub 3/-H/sub 2/ system under mild conditions considerably improves the extractability of coal in pyridine and cyclohexane. On the other hand, nitration of coal and its subsequent reaction with HF-BF/sub 3/H/sub 2/ decreases the pyridine and cyclohexane extractability. Study of model compounds under conditions identical with the superacidic HF/BF/sub 3//H/sub 2/ system provided significant information about the basic chemistry of the involved cleavage-hydrogenation reactions.

  20. Gas-to-Particle Conversion in Surface Discharge Nonthermal Plasmas and Its Implications for Atmospheric Chemistry

    PubMed Central

    Kim, Hyun-Ha; Ogata, Atsushi

    2011-01-01

    This paper presents some experimental data on gas-to-particle conversion of benzene using nonthermal plasma (NTP) technology and discusses the possibility of its technical application in atmospheric chemistry. Aerosol measurement using a differential mobility analyzer (DMA) revealed that the parts of benzene molecules were converted into a nanometer-sized aerosol. Aerosol formation was found to be highly related with the missing part in carbon balance. Scanning electron microscopy analysis showed that the aerosols formed in synthetic humid air are the collection of nanoparticles. The carbonyl band (C=O) was found to be an important chemical constituent in the aerosol. The potential of the NTP as an accelerated test tool in studying secondary organic aerosol (SOA) formation from VOCs will be also addressed. PMID:22163781

  1. Metathesis of alkanes and related reactions.

    PubMed

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

    2010-02-16

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

  2. The hydrodeoxygenation of bioderived furans into alkanes

    NASA Astrophysics Data System (ADS)

    Sutton, Andrew D.; Waldie, Fraser D.; Wu, Ruilian; Schlaf, Marcel; ‘Pete' Silks, Louis A.; Gordon, John C.

    2013-05-01

    The conversion of biomass into fuels and chemical feedstocks is one part of a drive to reduce the world's dependence on crude oil. For transportation fuels in particular, wholesale replacement of a fuel is logistically problematic, not least because of the infrastructure that is already in place. Here, we describe the catalytic defunctionalization of a series of biomass-derived molecules to provide linear alkanes suitable for use as transportation fuels. These biomass-derived molecules contain a variety of functional groups, including olefins, furan rings and carbonyl groups. We describe the removal of these in either a stepwise process or a one-pot process using common reagents and catalysts under mild reaction conditions to provide n-alkanes in good yields and with high selectivities. Our general synthetic approach is applicable to a range of precursors with different carbon content (chain length). This allows the selective generation of linear alkanes with carbon chain lengths between eight and sixteen carbons.

  3. The hydrodeoxygenation of bioderived furans into alkanes.

    PubMed

    Sutton, Andrew D; Waldie, Fraser D; Wu, Ruilian; Schlaf, Marcel; Silks, Louis A Pete; Gordon, John C

    2013-05-01

    The conversion of biomass into fuels and chemical feedstocks is one part of a drive to reduce the world's dependence on crude oil. For transportation fuels in particular, wholesale replacement of a fuel is logistically problematic, not least because of the infrastructure that is already in place. Here, we describe the catalytic defunctionalization of a series of biomass-derived molecules to provide linear alkanes suitable for use as transportation fuels. These biomass-derived molecules contain a variety of functional groups, including olefins, furan rings and carbonyl groups. We describe the removal of these in either a stepwise process or a one-pot process using common reagents and catalysts under mild reaction conditions to provide n-alkanes in good yields and with high selectivities. Our general synthetic approach is applicable to a range of precursors with different carbon content (chain length). This allows the selective generation of linear alkanes with carbon chain lengths between eight and sixteen carbons. PMID:23609095

  4. Exploratory study of coal-conversion chemistry. Quarterly report No. 4, February 19-May 18, 1982

    SciTech Connect

    Ross, D.S.; McMillen, D.F.; Ogier, W.C.; Fleming, R.H.; Hum, G.P.

    1982-06-01

    SRI is conducting a program on the chemistry of the conversion of coal to liquid fuels: Task A deals with mechanisms of donor solvent liquefaction; Task B is a study of the conversion of coal and model compounds in the CO/H/sub 2/O system. In Task A, determination of the products, rates, and mechanisms of central bond scission of diphenyl ether and 1,2-dinaphthylmethane in tetralin, 9,10-dihydroanthracene, and 9,10-dihydrophenanthrene allows us to determine the predominant mechanism of hydrogen transfer to these substrates. Diphenyl ether decomposes in the above three solvents by a radical addition-elimination mechanism, with defined first-order rate constants of approx. 1 x 10/sup -7/, 2 x 10/sup -6/, and 2 x 10/sup -7/ s/sup -1/, respectively. The relative reactivity of the two substrates, the relative reactivity in the three solvents, and the positional preference for hydrogen transfer provide compelling evidence for the previously unreported single-step transfer of hydrogen from a radical to a closed-shell ..pi..-system. Efforts in Task B were concentrated on the conversion of anisole in D/sub 2/O and in tetralin at 400/sup 0/C. Experiments were conducted in two different reactor systems, small glass ampoules and 1/4-in. 316 stainless steel tubes. Benzene and phenol were the major products with the rates of product formation affected by the reaction medium and the reactor walls. The rate of benzene formation was found to be more rapid in D/sub 2/O than tetralin, and somewhat greater in glass ampoules than in stainless steel reactors for 20 min. We also studied the conversion of bibenzyl in D/sub 2/O and in tetralin in stainless steel tubes at 400/sup 0/C. In tetralin, toluene was the major product. In D/sub 2/O, the products were toluene, benzene, diphenylmethane, stilbene, and phenanthrene. A novel hydration scheme is suggested for the reactions of bibenzyl in water.

  5. Defect chemistry and defect engineering of TiO2-based semiconductors for solar energy conversion.

    PubMed

    Nowotny, Janusz; Alim, Mohammad Abdul; Bak, Tadeusz; Idris, Mohammad Asri; Ionescu, Mihail; Prince, Kathryn; Sahdan, Mohd Zainizan; Sopian, Kamaruzzaman; Mat Teridi, Mohd Asri; Sigmund, Wolfgang

    2015-12-01

    This tutorial review considers defect chemistry of TiO2 and its solid solutions as well as defect-related properties associated with solar-to-chemical energy conversion, such as Fermi level, bandgap, charge transport and surface active sites. Defect disorder is discussed in terms of defect reactions and the related charge compensation. Defect equilibria are used in derivation of defect diagrams showing the effect of oxygen activity and temperature on the concentration of both ionic and electronic defects. These defect diagrams may be used for imposition of desired semiconducting properties that are needed to maximize the performance of TiO2-based photoelectrodes for the generation of solar hydrogen fuel using photo electrochemical cells (PECs) and photocatalysts for water purification. The performance of the TiO2-based semiconductors is considered in terms of the key performance-related properties (KPPs) that are defect related. It is shown that defect engineering may be applied for optimization of the KPPs in order to achieve optimum performance. PMID:26446476

  6. Developing new synthetic methods for colloidal hybrid nanoparticles: Conversion chemistry and chemoselectivity

    NASA Astrophysics Data System (ADS)

    Bradley, Matthew

    Colloidal hybrid nanoparticles contain multiple domains, and through their solidsolid interfaces, can facilitate synergistic relationships between domains, resulting in the incorporation of multiple functionalities as well as modification of the intrinsic properties of each domain. Although there is a growing number of materials and applications associated with these unique types of particles, new synthetic methods must be investigated in order to realize the full potential of this new class of particles. To address this need, we demonstrate that the concepts used in total synthesis of complex organic molecules, can be applied to the synthesis of colloidal hybrid nanoparticles. Site selective growth, conversion chemistry, condensation chemistry, and protection/deprotection reactions are examined as ways to add complexity to colloidal hybrid nanoparticles. First, we will discuss the synthesis of PtPb-Fe3O4 and Pt3Sn-Fe3O4 heterodimer particles via a solution mediated conversion chemistry process. These types of reactions are known to be useful for nanoparticle systems but had not been explored as a method for adding complexity to colloidal heterodimers. Pt-Fe3O 4 heterodimers react with Pb(acac)2 and Sn(acac)2 at 180-200°C in a mixture of benzyl ether, oleylamine, oleic acid, and tert-butylamine borane to form PtPb-Fe3O4 and Pt3Sn-Fe3O4 heterodimers, respectively. This chemical transformation reaction introduces intermetallic and alloy components into the heterodimers, proceeds with morphological retention, and preserves the solid-solid interface that characterizes these hybrid nanoparticle systems. In addition, the PtPb-Fe3O4 heterodimers spontaneously aggregate to form colloidally stable (PtPb-Fe3O4) n nanoflowers via a process that is conceptually analogous to a molecular condensation reaction. Next, we will discuss the methanol oxidation activity of PtPb-Fe 3O4 and Pt3Sn- Fe3O4 heterodimers as well as examine the role of ligand exchange in this process. Before

  7. Organic Chemistry and the Native Plants of the Sonoran Desert: Conversion of Jojoba Oil to Biodiesel

    ERIC Educational Resources Information Center

    Daconta, Lisa V.; Minger, Timothy; Nedelkova, Valentina; Zikopoulos, John N.

    2015-01-01

    A new, general approach to the organic chemistry laboratory is introduced that is based on learning about organic chemistry techniques and research methods by exploring the natural products found in local native plants. As an example of this approach for the Sonoran desert region, the extraction of jojoba oil and its transesterification to…

  8. More than a Conversation: Using Cogenerative Dialogues in the Professional Development of High School Chemistry Teachers

    ERIC Educational Resources Information Center

    Martin, Sonya N.; Scantlebury, Kathryn

    2009-01-01

    This paper focuses on content-based and pedagogical instructors' use of cogenerative dialogues to improve instructional practice and to evaluate program effectiveness in a professional development program for high school chemistry teachers. We share our research findings from using cogenerative dialogues as an evaluative tool for general…

  9. Potential and challenges of zeolite chemistry in the catalytic conversion of biomass.

    PubMed

    Ennaert, Thijs; Van Aelst, Joost; Dijkmans, Jan; De Clercq, Rik; Schutyser, Wouter; Dusselier, Michiel; Verboekend, Danny; Sels, Bert F

    2016-02-01

    Increasing demand for sustainable chemicals and fuels has pushed academia and industry to search for alternative feedstocks replacing crude oil in traditional refineries. As a result, an immense academic attention has focused on the valorisation of biomass (components) and derived intermediates to generate valuable platform chemicals and fuels. Zeolite catalysis plays a distinct role in many of these biomass conversion routes. This contribution emphasizes the progress and potential in zeolite catalysed biomass conversions and relates these to concepts established in existing petrochemical processes. The application of zeolites, equipped with a variety of active sites, in Brønsted acid, Lewis acid, or multifunctional catalysed reactions is discussed and generalised to provide a comprehensive overview. In addition, the feedstock shift from crude oil to biomass involves new challenges in developing fields, like mesoporosity and pore interconnectivity of zeolites and stability of zeolites in liquid phase. Finally, the future challenges and perspectives of zeolites in the processing of biomass conversion are discussed. PMID:26691750

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

    DOEpatents

    Bhinde, Manoj V.; Bierl, Thomas W.

    1998-01-01

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

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

    DOEpatents

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

    1998-03-03

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

  12. Exploratory study of coal conversion chemistry. Quarterly report, September 20, 1979-December 19, 1979

    SciTech Connect

    Not Available

    1980-03-05

    The objective of this task is to determine the mechanism of cleavage of key bond types in coal under nominal donor solvent coal conversion conditions. This is to be done by using selected model compounds as well as coals themselves under conditions comparable to those used in current donor solvent liquefaction processes. The specific model compounds have been chosen because i) they represent linkages and heteratom functionalities that are important in coals and ii) because their reported conversion rates are substantially greater than can be accounted for by the traditionally invoked free radical mechanism. Initially, we are focusing on a particular class of model compounds: hydroxylated diphenylmethanes. This class of compounds is important for two reasons: first, because the linkage and ring substituents are common in bituminous coals, and second, because it has been reported by Collins et al. that substitution of an -OH group on diphenylmethane makes the rate of conversion of hydroxy-diphenylmethanes to toluene and phenol (in Tetralin at 400/sup 0/C) roughly as fast as that of bibenzyl. The phenyl-CH/sub 2/ bond strength of hydroxyl diphenylmethane is at least 15 kcal/mole greater than the central bond in bibenzyl. Thus, if hydroxydiphenylmethane underwent conversion in tetralin by homolytic bond scission, its conversion at 400/sup 0/C would be slower by almost five orders of magnitude. In this report we discuss a possible mechanism that could account for this rapid conversion. Simple homolytic cleavage of the indicated bond in an intermediate would be fast, since it is at least 20 kcal/mole weaker than the central bond in bibenzyl.

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

    PubMed

    Bordeaux, Mélanie; Galarneau, Anne; Drone, Jullien

    2012-10-22

    Selective catalysts for sustainable oxidation of alkanes are highly demanded because of the abundance of these molecules in the environment, the possibility to transform them into higher-value compounds, such as chemicals or synthetic fuels, and the fact that, kinetically speaking, this is a difficult reaction. Numerous chemical and biological catalysts have been developed in the lasts decades for this purpose, rendering the overview over this field of chemistry difficult. After giving a definition of the ideal catalyst for alkane oxyfunctionalization, this review aims to present the catalysts available today that are closest to ideal. PMID:22996726

  14. Exploratory study of coal-conversion chemistry. Quarterly report No. 6, August 19, 1982-November 18, 1982

    SciTech Connect

    Ross, D.S.; McMillen, D.F.; Fleming, R.H.; Hum, G.P.; Mansani, R.; Green, T.K.

    1982-01-01

    Initial experiments combining compound-class (HPLC) separation of coal liquefaction products and field ionization mass spectrometric (FIMS) analysis of the various fractions to obtain improved correlations between donor-solvent structure and coal-conversion effectiveness have been performed. These experiments have used a very low-fluidity bituminous coal (PSOC-1116, Sunnyside, Utah) and tetralin and 1,2,3,4-tetrahydroquinoline (THQ) as donor solvents. Apart from indicating ways in which the chromatography procedure needs to be adjusted to achieve better separation on the basis of functional groups (compound-class separation), FIMS analysis of the various fractions has allowed us to conclude that the observed THQ incorporation (a 100%) is comprised less than 2% physical or hydrogen bonded incorporation, less than 30% by self-polymerization reactions of THQ, and at least 70% by covalent incorporation of the entire THQ molecule into coal structures. This incorporation apparently takes place by way of electrophilic substitution on coal structures, notwithstanding THQ's obvious nucleophilic properties. The conversion of bibenzyl in D/sub 2/O/CO systems at 400/sup 0/C was also studied. The experiments were conducted in stainless steel tubes. The products of the conversion of neat bibenzyl were in accord with previously reported chemistry, with toluene and stilbene the major products. D/sub 2/O had no effect on the product distributions. The addition of CO in the system reduced the amount of stilbene observed, and under basic conditions, stilbene was observed only as a minor product. The disappearance of stilbene paralleled the water-gas shift reaction. It is suggested that molecular hydrogen reacts with thermally produced benzyl radicals to give toluene and/or that stilbene is hydrogenated to give bibenzyl. The implications of this reaction in the conversion of coals in the CO/D/sub 2/O system are briefly discussed.

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

    SciTech Connect

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M

    2011-03-01

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed high temperature chemical kinetic mechanism for n-octane and three lightly branched isomers octane (i.e., 2-methylheptane, 3-methylheptane, and 2,5-dimethylhexane). The model is validated against experimental data from a variety of fundamental combustion devices. This new model is used to show how the location and number of methyl branches affects fuel reactivity including laminar flame speed and species formation.

  16. Internal conversion and intersystem crossing pathways in UV excited, isolated uracils and their implications in prebiotic chemistry.

    PubMed

    Yu, Hui; Sanchez-Rodriguez, Jose A; Pollum, Marvin; Crespo-Hernández, Carlos E; Mai, Sebastian; Marquetand, Philipp; González, Leticia; Ullrich, Susanne

    2016-07-27

    The photodynamic properties of molecules determine their ability to survive in harsh radiation environments. As such, the photostability of heterocyclic aromatic compounds to electromagnetic radiation is expected to have been one of the selection pressures influencing the prebiotic chemistry on early Earth. In the present study, the gas-phase photodynamics of uracil, 5-methyluracil (thymine) and 2-thiouracil-three heterocyclic compounds thought to be present during this era-are assessed in the context of their recently proposed intersystem crossing pathways that compete with internal conversion to the ground state. Specifically, time-resolved photoelectron spectroscopy measurements evidence femtosecond to picosecond timescales for relaxation of the singlet (1)ππ* and (1)nπ* states as well as for intersystem crossing to the triplet manifold. Trapping in the excited triplet state and intersystem crossing back to the ground state are investigated as potential factors contributing to the susceptibility of these molecules to ultraviolet photodamage. PMID:27189184

  17. Superacid Catalyzed Coal Conversion Chemistry. 1st and 2nd Quarterly Technical Progress Reports, September 1, 1983-March 30, 1984.

    DOE R&D Accomplishments Database

    Olah, G. A.

    1984-01-01

    In our laboratories we have previously developed a mild coal conversion process. This involves the use of a superacid system consisting of HF and BF{sub 3} in presence of hydrogen and/or a hydrogen donor solvent. In order to understand the chemistry involved in the process of depolymerization of coal by the HF:BF{sub 3}:H{sub 2} system we are carrying out a systematic study of a number of coal model compounds. The model compounds selected for present study have two benzene rings connected with various bridging units such as alkylidene, ether, sulfide etc. From studies so far carried out it appears that high pyridine extractibilities achieved by treating coal at temperature below 100 degrees C results from the cleavage of bridges such as present in bibenzyl, diphenyl methane, dibenzyl ether, dibenzyl sulfide etc. On the other hand the increased cyclohexane extractibility and distillability observed at relatively higher temperatures and hydrogen pressures reflects the hydrogenation and cleavage of the aromatic backbone in coal structure similar to what is seen in the conversion of model compounds such as biphenyl, diphenyl ether, diphenyl sulfide, anthracene, etc.

  18. Surface chemistry and corrosion behavior of aluminum-copper systems: Air-formed films to complex conversion coatings

    NASA Astrophysics Data System (ADS)

    Chidambaram, Devicharan

    Understanding the mechanism of corrosion inhibition by carcinogenic chromates is critical to the development of environmentally safe coatings containing benign chromate substitutes. An integrated approach to correlate the surface chemistry and corrosion behavior of a wide range of systems has been undertaken. Electrochemical behavior was studied by open circuit potential (OCP) measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS). Surface chemistry was studied using variable-angle X-ray photoelectron spectroscopy (VAXPS), X-ray absorption near edge spectroscopy (XANES), secondary ion mass spectroscopy (SIMS), infrared spectroscopy and synchrotron infrared micro spectroscopy (SIRMS) and Raman spectroscopy. Using SIRMS, the ASTM recommended acetone degreasing was shown to initiate pitting of AA2024-T3 via photochemical formation of acetic acid. Due to the known tendency for photoreduction of Cr6+(3d0) following soft X-ray dosage during XPS, a novel method has been developed to prevent this reduction. This method yields, for the first time, an accurate determination of the Cr6+ content of a CCC. The pretreatment of the alloy prior to conversion coating has been shown to have significant influence on the surface intermetallic distribution, composition and corrosion resistance of the initial oxide film and subsequent conversion coating. AlconoxRTM pretreatment was found to result in a highly protective surface film that inhibits the subsequent formation of CCC. The study also shows that coupling of the alloy to platinum during the bromate pretreatment increases the corrosion resistance of the subsequently formed CCC by over an order of magnitude due to reduction in surface copper content. Adsorption of chromate ion on the passive oxide film formed on the metal surface was observed to induce fixed negative charges that inhibit chloride ingress on planar surfaces. While deprotonation of the aluminum hydroxide film by chromate was

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

    SciTech Connect

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

    2008-08-01

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

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

    DOEpatents

    Benderly, Abraham; Chadda, Nitin; Sevon, Douglass

    2011-12-20

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

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

    PubMed

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

    2016-01-01

    Typical renewable liquid fuel alternatives to gasoline are not entirely compatible with current infrastructure. We have engineered Escherichia coli to selectively produce alkanes found in gasoline (propane, butane, pentane, heptane, and nonane) from renewable substrates such as glucose or glycerol. Our modular pathway framework achieves carbon-chain extension by two different mechanisms. A fatty acid synthesis route is used to generate longer chains heptane and nonane, while a more energy efficient alternative, reverse-β-oxidation, is used for synthesis of propane, butane, and pentane. We demonstrate that both upstream (thiolase) and intermediate (thioesterase) reactions can act as control points for chain-length specificity. Specific free fatty acids are subsequently converted to alkanes using a broad-specificity carboxylic acid reductase and a cyanobacterial aldehyde decarbonylase (AD). The selectivity obtained by different module pairings provides a foundation for tuning alkane product distribution for desired fuel properties. Alternate ADs that have greater activity on shorter substrates improve observed alkane titer. However, even in an engineered host strain that significantly reduces endogenous conversion of aldehyde intermediates to alcohol byproducts, AD activity is observed to be limiting for all chain lengths. Given these insights, we discuss guiding principles for pathway selection and potential opportunities for pathway improvement. PMID:26556131

  2. Secondary organic aerosol composition from C12 alkanes.

    PubMed

    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

  3. Photocatalytic acceptorless alkane dehydrogenation: scope, mechanism, and conquering deactivation with carbon dioxide.

    PubMed

    Chowdhury, Abhishek Dutta; Julis, Jennifer; Grabow, Kathleen; Hannebauer, Bernd; Bentrup, Ursula; Adam, Martin; Franke, Robert; Jackstell, Ralf; Beller, Matthias

    2015-01-01

    Alkane dehydrogenation is of special interest for basic science but also offers interesting opportunities for industry. The existing dehydrogenation methodologies make use of heterogeneous catalysts, which suffer from harsh reaction conditions and a lack of selectivity, whereas homogeneous methodologies rely mostly on unsolicited waste generation from hydrogen acceptors. Conversely, acceptorless photochemical alkane dehydrogenation in the presence of trans-Rh(PMe3 )2 (CO)Cl can be regarded as a more benign and atom efficient alternative. However, this methodology suffers from catalyst deactivation over time. Herein, we provide a detailed investigation of the trans-Rh(PMe3 )2 (CO)Cl-photocatalyzed alkane dehydrogenation using spectroscopic and theoretical investigations. These studies inspired us to utilize CO2 to prevent catalyst deactivation, which leads eventually to improved catalyst turnover numbers in the dehydrogenation of alkanes that include liquid organic hydrogen carriers. PMID:25346450

  4. Millisecond Oxidation of Alkanes

    SciTech Connect

    Scott Han

    2011-09-30

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

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

    PubMed

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

    2016-03-20

    Alkanes constitute one of the vastest reserves of raw materials for the production of fine chemicals. This paper focuses on recent advances in alkane biohydroxylation, i.e. the bioactivation of alkanes into their corresponding alcohols. Enzyme and whole-cell biocatalysts have been reviewed. Process considerations to implement such biocatalysts in bioreactors at large scale by coupling the bioconversion with cofactor regeneration and product removal are also discussed. PMID:26853477

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  8. Gas-phase reactions of the bare Th2+ and U2+ ions with small alkanes, CH4, C2H6, and C3H8: experimental and theoretical study of elementary organoactinide chemistry.

    PubMed

    Di Santo, Emanuela; Santos, Marta; Michelini, Maria C; Marçalo, Joaquim; Russo, Nino; Gibson, John K

    2011-02-16

    The gas-phase reactions of two dipositive actinide ions, Th(2+) and U(2+), with CH(4), C(2)H(6), and C(3)H(8) were studied by both experiment and theory. Fourier transform ion cyclotron resonance mass spectrometry was employed to study the bimolecular ion-molecule reactions; the potential energy profiles (PEPs) for the reactions, both observed and nonobserved, were computed by density functional theory (DFT). The experiments revealed that Th(2+) reacts with all three alkanes, including CH(4) to produce ThCH(2)(2+), whereas U(2+) reacts with C(2)H(6) and C(3)H(8), with different product distributions than for Th(2+). The comparative reactivities of Th(2+) and U(2+) toward CH(4) are well explained by the computed PEPs. The PEPs for the reactions with C(2)H(6) effectively rationalize the observed reaction products, ThC(2)H(2)(2+) and UC(2)H(4)(2+). For C(3)H(8) several reaction products were experimentally observed; these and additional potential reaction pathways were computed. The DFT results for the reactions with C(3)H(8) are consistent with the observed reactions and the different products observed for Th(2+) and U(2+); however, several exothermic products which emerge from energetically favorable PEPs were not experimentally observed. The comparison between experiment and theory reveals that DFT can effectively exclude unfavorable reaction pathways, due to energetic barriers and/or endothermic products, and can predict energetic differences in similar reaction pathways for different ions. However, and not surprisingly, a simple evaluation of the PEP features is insufficient to reliably exclude energetically favorable pathways. The computed PEPs, which all proceed by insertion, were used to evaluate the relationship between the energetics of the bare Th(2+) and U(2+) ions and the energies for C-H and C-C activation. It was found that the computed energetics for insertion are entirely consistent with the empirical model which relates insertion efficiency to the

  9. Reaction pathway for alkane dehydrocyclization

    SciTech Connect

    Shi, Buchang; Davis, B.H.

    1996-08-01

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

  10. Alkane-Based Urethane Potting Compounds

    NASA Technical Reports Server (NTRS)

    Morris, D. E.

    1986-01-01

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

  11. Exploratory study of coal-conversion chemistry. Quarterly report, December 20, 1979-March 19, 1980. [Ortho and para-hydroxydiphenylmethanes

    SciTech Connect

    McMillen, Donald F.; Ogier, Walter C.; Ross, David S.; Nguyen, Quyen Cu

    1980-06-18

    This report describes work accomplished under two tasks: Task A, Mechanism of Cleavage of Key Bond Types Present in Coals and Task B, Catalysis of Conversion in CO-H/sub 2/O Systems. Under Task A, the mechanism of the anomalously rapid donor solvent conversion of ortho- and para-hydroxydiphenylmethanes to phenol and toluene has been shown to involve an ionically established enol-keto equilibrium followed by rate limiting homolytic scission of the weakly bonded keto form. Consistent with a rate-limiting second step, the overall conversion rate is not subject to catalysis of acids, bases, or radical initiators, substances which could increase the rate at which the tautomeric pre-equilibrium is achieved. The rate of conversion, however, is markedly enhanced by the addition of iron oxides, with the mixed oxide Fe/sub 3/O/sub 4/ being roughly ten times more active than Fe/sub 2/O/sub 3/. Addition of crushed fused silica was also found to significantly enhance the conversion rates. Under Task B, the conversion of coal to 50% benzene soluble coal products in CO/H/sub 2/O systems displays a striking dependence on the pH of the starting aqueous phase (measured at room temperature). Thus below a starting pH of 12.6, the product benzene solubility is about 10% and steeply climbs to the 50% level under more basic conditions. The operation of the water-gas shift reaction parallels the conversion, with CO/sub 2/ and H/sub 2/ formed as product gases and CO consumed in the basic systems where conversion is effective. Hydrogen used in place of CO is ineffective. In a test of the intermediacy of formate in the system the use of potassium formate with nitrogen as the charge gas was similarly ineffective. Formate thus cannot be an intermediate in the conversion. The use of Mo(VI) (as molybdate) was effective, and a pH dependence on its operation was also observed.

  12. A Conversion of Methyl Ketones into Acetylenes: A Project for a Problem-Oriented or Microscale Organic Chemistry Course.

    ERIC Educational Resources Information Center

    Silveira, Augustine, Jr.; Orlando, Steven C.

    1988-01-01

    Describes a process for producing terminal or internal alkynes from ketones. Recommends using the experiment to aid in understanding acid-base strength, enolate anion chemistry, reaction at carbon versus oxygen, use of polar aprotic solvents, and elimination and nucleophilic substitution reactions. (ML)

  13. Dielectric barrier discharges used for the conversion of greenhouse gases: modeling the plasma chemistry by fluid simulations

    NASA Astrophysics Data System (ADS)

    De Bie, Christophe; Martens, Tom; van Dijk, Jan; Paulussen, Sabine; Verheyde, Bert; Corthals, Steven; Bogaerts, Annemie

    2011-04-01

    The conversion of methane to value-added chemicals and fuels is considered to be one of the challenges of the 21st century. In this paper we study, by means of fluid modeling, the conversion of methane to higher hydrocarbons or oxygenates by partial oxidation with CO2 or O2 in a dielectric barrier discharge. Sixty-nine different plasma species (electrons, ions, molecules, radicals) are included in the model, as well as a comprehensive set of chemical reactions. The calculation results presented in this paper include the conversion of the reactants and the yields of the reaction products as a function of residence time in the reactor, for different gas mixing ratios. Syngas (i.e. H2 + CO) and higher hydrocarbons (C2Hx) are typically found to be important reaction products.

  14. Exploratory study of coal-conversion chemistry. Quarterly report No. 9, March 20, 1980-June 19, 1980. [Hydroxydiphenylmethane, diphenylether, diphenymethane

    SciTech Connect

    McMillen, Donald F.; Ogier, Walter C.

    1980-11-19

    This report describes work accomplished under two tasks: Task A, Mechanism of Cleavage of Key Bond Types Present in Coals, and Task B, Catalysis of Conversion in CO-H/sub 2/O Systems. Under Task A, the very effective catalysis of carbon-carbon bond cleavage by iron oxides in hydroxydiphenylmethane structures has been further characterized. An electron-transfer mechanism offers the most likely explanation of the observations that (1) alumina and silica-alumina surfaces are less active catalysts than Fe/sub 3/O/sub 4/, (2) meta-hydroxydiphenylmethane is almost as subject to catalysis as para-hydroxydiphenylmethane, (3) diphenyl ether is less subject to Fe/sub 3/O/sub 4/ catalysis than diphenylmethane, and (4) ortho-methoxydiphenylmethane exhibits the same susceptibility to Fe/sub 3/O/sub 4/ catalysis as ortho-hydroxydiphenylmethane. Under Task B, this quarter we have completed the survey of possible metal catalysts present in the Hastelloy C autoclave. We have found that coal conversion in CO-H/sub 2/O systems is effective when metal oxides such as MoO/sub 4//sup =/, Cr/sub 2/O/sub 7//sup =/, and MnO/sub 4//sup -/ are used as catalysts, but there is less or no coal conversion with FeCl/sub 3/ or Ni(CH/sub 3/COO)/sub 2/. While studying the fate of the catalyst after the reaction, we have isolated formate in the water-soluble fraction. This important information could help us in studying the role of formate in coal conversion. During this quarter, we have also studied the influence of reaction time and fresh CO on coal conversion in the presence of a catalyst. A striking result of 67% of benzene-soluble materials was obtained with an equivalent of 6000 ppM of Cr as sodium dichromate.

  15. Chemical analog-to-digital signal conversion based on robust threshold chemistry and its evaluation in the context of microfluidics-based quantitative assays.

    PubMed

    Huynh, Toan; Sun, Bing; Li, Liang; Nichols, Kevin P; Koyner, Jay L; Ismagilov, Rustem F

    2013-10-01

    In this article, we describe a nonlinear threshold chemistry based on enzymatic inhibition and demonstrate how it can be coupled with microfluidics to convert a chemical concentration (analog input) into patterns of ON or OFF reaction outcomes (chemical digital readout). Quantification of small changes in concentration is needed in a number of assays, such as that for cystatin C, where a 1.5-fold increase in concentration may indicate the presence of acute kidney injury or progression of chronic kidney disease. We developed an analog-to-digital chemical signal conversion that gives visual readout and applied it to an assay for cystatin C as a model target. The threshold chemistry is based on enzymatic inhibition and gives sharper responses with tighter inhibition. The chemistry described here uses acetylcholinesterase (AChE) and produces an unambiguous color change when the input is above a predetermined threshold concentration. An input gives a pattern of ON/OFF responses when subjected to a monotonic sequence of threshold concentrations, revealing the input concentration at the point of transition from OFF to ON outcomes. We demonstrated that this threshold chemistry can detect a 1.30-fold increase in concentration at 22 °C and that it is robust to experimental fluctuations: it provided the same output despite changes in temperature (22-34 °C) and readout time (10-fold range). We applied this threshold chemistry to diagnostics by coupling it with a traditional sandwich immunoassay for serum cystatin C. Because one quantitative measurement comprises several assays, each with its own threshold concentration, we used a microfluidic SlipChip device to process 12 assays in parallel, detecting a 1.5-fold increase (from 0.64 (49 nM) to 0.96 mg/L (74 nM)) of cystatin C in serum. We also demonstrated applicability to analysis of patient serum samples and the ability to image results using a cell phone camera. This work indicates that combining developments in nonlinear

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

    PubMed Central

    Musat, Florin

    2015-01-01

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

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

    PubMed

    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

  18. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes

    PubMed Central

    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

  19. Catalytic dehydroaromatization of n-alkanes by pincer-ligated iridium complexes

    NASA Astrophysics Data System (ADS)

    Ahuja, Ritu; Punji, Benudhar; Findlater, Michael; Supplee, Carolyn; Schinski, William; Brookhart, Maurice; Goldman, Alan S.

    2011-02-01

    Aromatic hydrocarbons are among the most important building blocks in the chemical industry. Benzene, toluene and xylenes are obtained from the high temperature thermolysis of alkanes. Higher alkylaromatics are generally derived from arene-olefin coupling, which gives branched products—that is, secondary alkyl arenes—with olefins higher than ethylene. The dehydrogenation of acyclic alkanes to give alkylaromatics can be achieved using heterogeneous catalysts at high temperatures, but with low yields and low selectivity. We present here the first catalytic conversion of n-alkanes to alkylaromatics using homogeneous or molecular catalysts—specifically ‘pincer’-ligated iridium complexes—and olefinic hydrogen acceptors. For example, the reaction of n-octane affords up to 86% yield of aromatic product, primarily o-xylene and secondarily ethylbenzene. In the case of n-decane and n-dodecane, the resulting alkylarenes are exclusively unbranched (that is, n-alkyl-substituted), with selectivity for the corresponding o-(n-alkyl)toluene.

  20. Supported organoiridium catalysts for alkane dehydrogenation

    DOEpatents

    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.

  1. Exploratory study of coal-conversion chemistry. Quarterly report, June 20, 1980-September 19, 1980. [Diphenylmethane, diphenyl ether

    SciTech Connect

    Not Available

    1981-03-04

    This report describes work accomplished under two task: Task A, Mechanism of Cleavage of Key Bond types Present in Coals, and Task B, Catalysis of Conversion in CO-H/sub 2/O Systems. Under Task A, we have made additional measurements of catalytic carbon-carbon and carbon-oxygen bond cleavage in coal-related diphenylmethane and diphenyl ether structures. The results provide further support for, but do not definitely confirm, the tentative conclusion that the highly effective iron oxide catalysts involves oxidation to radical cation species. The homogeneous scission of carbon-oxygen bonds in diphenyl ether structure has also been studied. In the Task B studies of CO-H/sub 2/O systems, we typically obtain 50% benzene-soluble product material from 20 min. reaction of beneficiated Illinois No. 6 coal. This conversion level is obtained with aqueous solutions either at a starting pH above 12.6 or in neutral solutions with water-soluble catalysts present. We have studied a number of catalysts, including the potassium or sodium salts of molybdate, chromate, manganate, and tungstate; all are effective in the 3000 to 6000 ppM range. A striking result is that sodium nitrate at 6000 ppM is as effective as the metal salts. We found that the nitrate was converted to ammonium ion; also, formate was detected in the product aqueous phase. Finally, we find that catalytic quantities of sodium formate in CO/H/sub 2/O at pH 7 are effective in the conversion. However, in a control run in N/sub 2//H/sub 2/O, with a quantity of sodium formate equivalent to twice the molar quantity of hydrogen transferred to the coal in a successful run, the coal was converted to a product totally insoluble in benzene and with a lower hydrogen content than the starting coal.

  2. Solar photothermochemical alkane reverse combustion

    PubMed Central

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

    2016-01-01

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

  3. Solar photothermochemical alkane reverse combustion.

    PubMed

    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

  4. Gas-phase chemistry during the conversion of cyclohexane to carbon: Flow reactor studies at low and intermediate pressure

    SciTech Connect

    Osterheld, T.H.; Allendorf, M.D.; Larson, R.

    1995-07-01

    The gas-phase branching during the conversion of cyclohexane to solid carbon has been measured in a high-temperature-flow reactor. The experiments show that cyclohexane decomposes into a broad distribution of hydrocarbons that further decompose into the more kinetically stable products hydrogen, methane, acetylene, ethylene, benzene, and PAH. At 1363 K, the evolution to these species occurs quickly. We also observe the buildup of significant amounts of aromatic molecules at later stages in the decomposition, with as much as 15% of the total carbon in PAH and 25% in benzene. At later stages, the gas-phase molecules react slowly, even though the system is not at equilibrium, because of their kinetic stability and the smaller radical pool. The decomposition does not appear to depend sensitively on pressure in the regime of 25 to 250 torr. Thus, to a first approximation, these results can be extrapolated to atmospheric pressure.

  5. Exploratory study of coal conversion chemistry. Quarterly report No. 2, August 19, 1981-November 18, 1981. [Hydroxydipnenylmethanes, triphenylmethane, diphenylether

    SciTech Connect

    Not Available

    1982-01-29

    This report describes work accomplished under two tasks: Task A, mechanisms of donor-solvent coal liquefaction, and Task B, CO/H/sub 2/O conversion systems. Under Task A, we describe additional evidence relating to the question of the mechanism of the iron oxide catalyzed cleavage of hydroxydiphenylmethanes. o-Hydroxydiphenylmethane is relatively more sensitive to catalysis by Fe/sub 3/O/sub 4/, a possible one electron oxidant, and triphenylmethane is relatively more sensitive to catalyzed cleavage by SiO/sub 2//Al/sub 2/O/sub 3/, a strong Bronsted acid catalyst. This provides further evidence that in the former case the reactions of radical cations are important in the cleavage mechanism. Tests with Cr/sub 2/O/sub 3/ show it to be ineffective under our reaction conditions as a catalyst for hydroxydiphenylmethane cleavage. We have also used the decomposition of diphenylether in tetralin, which we have previously shown to occur by a radical displacement reaction, as an indicator of steady state radical concentration in tetralin. The results of these experiments indicate that radical concentrations in tetralin are not significantly increased by spiking the tetralin with 1,2-dihydronaphthalene. This in turn suggests that rapid disproportionation of 1,2-dihydronaphthalene to tetralin and naphthalene takes place by way of a concerted reaction, in addition to a slower radical disproportionation process that may provide the steady state radical concentration supported by the equilibrium concentration of 1,2-dihydronaphthalene. Under Task B1, we have found a correlation between initial pH and CO pressure on the conversion of PSOC-26 coal to toluene soluble products. A pH dependence was also observed for PSOC-233 coal, similar to results with PSOC-26. Under Task B2, we have studied anisole as a model oxygen containing structure in coal.

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

    PubMed Central

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

    2013-01-01

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

  7. Exploratory study of coal-conversion chemistry. Quarterly report No. 5, May 19, 1982-August 18, 1982

    SciTech Connect

    Ross, D.S.; McMillen, D.F.; Ogier, W.C.; Fleming, R.H.; Hum, G.P.

    1982-10-01

    Initial runs of coal liquefaction products through the automatically switched, multicolumn, solvent-extraction/high-pressure liquid chromatography systems have been performed. This separation was followed by field ionization mass spectrometric analysis of the volatile portions of each of the separated fractions. The separation scheme is described, and results of one of the initial separations are summarized. The FIMS spectrum of one of the fractions (lower molecular weight nitrogen heterocycles) is presented and the types of information available from this less-than-ideal case (i.e., broad HPLC fraction) are discussed in the context of the objective of this subtask. We studied the thermolysis of bibenzyl in D/sub 2/O at 400/sup 0/C. The major products were toluene and stilbene. Minor products were benzene, ethylbenzene, styrene, diphenylmethane, and phenanthrene. The recovered bibenzyl and products contained significant quantities of deuterium. From the degree of deuterium incorporation, a statistical determination for a simple series of consecutive exchange reactions was derived. The reaction scheme involves an initial slow homolysis of the starting bibenzyl to yield benzyl radical, which, in turn, reacts with D/sub 2/O to form OD. OD then rapidly reacts with bibenzyl to yield bibenzyl radical, and the formed bibenzyl radical abstracts deuterium from the medium to form products. The chemistry suggested here demonstrates that water can act as an H-donor because it readily transfers hydrogen to organic free radicals. We further suggest that water can generate hydrogen atoms if CO is present.

  8. Role of precursor chemistry in the direct fluorination to form titanium based conversion anodes for lithium ion batteries

    DOE PAGESBeta

    Adcock, Jamie; Dai, Sheng; Veith, Gabriel M.; Bridges, Craig A.; Powell, Jonathan M.

    2015-10-13

    In this study, a new synthetic route for the formation of titanium oxydifluoride (TiOF2) through the process of direct fluorination via a fluidized bed reactor system and the associated electrochemical properties of the powders formed from this approach are reported. The flexibility of this synthetic route was demonstrated using precursor powders of titanium dioxide (TiO2) nanoparticles, as well as a reduced TiOxNy. An advantage of this synthetic method is the ability to directly control the extent of fluorination as a function of reaction temperature and time. The reversible capacity of TiOF2 anodes was found to depend greatly upon the precursormore » employed. The TiOF2 synthesized from TiO2 and TiOxNy showed reversible capacities of 300 mAh g-1 and 440 mAh g-1, respectively, over 100 cycles. The higher reversible capacity of the TiOF2 powders derived from TiOxNy likely relate to the partial reduction of the Ti in the fluorinated electrode material, highlighting a route to optimize the properties of conversion electrode materials.« less

  9. Role of precursor chemistry in the direct fluorination to form titanium based conversion anodes for lithium ion batteries

    SciTech Connect

    Adcock, Jamie; Dai, Sheng; Veith, Gabriel M.; Bridges, Craig A.; Powell, Jonathan M.

    2015-10-13

    In this study, a new synthetic route for the formation of titanium oxydifluoride (TiOF2) through the process of direct fluorination via a fluidized bed reactor system and the associated electrochemical properties of the powders formed from this approach are reported. The flexibility of this synthetic route was demonstrated using precursor powders of titanium dioxide (TiO2) nanoparticles, as well as a reduced TiOxNy. An advantage of this synthetic method is the ability to directly control the extent of fluorination as a function of reaction temperature and time. The reversible capacity of TiOF2 anodes was found to depend greatly upon the precursor employed. The TiOF2 synthesized from TiO2 and TiOxNy showed reversible capacities of 300 mAh g-1 and 440 mAh g-1, respectively, over 100 cycles. The higher reversible capacity of the TiOF2 powders derived from TiOxNy likely relate to the partial reduction of the Ti in the fluorinated electrode material, highlighting a route to optimize the properties of conversion electrode materials.

  10. Enzymes and genes involved in aerobic alkane degradation

    PubMed Central

    Wang, Wanpeng; Shao, Zongze

    2013-01-01

    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. PMID:23755043

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

    PubMed

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

    2013-01-01

    Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapor pressure. Intermediate Volatility Organic Compounds (IVOC) emitted to the atmosphere are expected to be a substantial source of SOA. These emitted IVOC constitute a complex mixture including linear, branched and cyclic alkanes. The explicit gas-phase oxidation mechanisms are here generated for various linear and branched C10-C22 alkanes using the GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) and SOA formation is investigated for various homologous series. Simulation results show that both the size and the branching of the carbon skeleton are dominant factors driving the SOA yield. However, branching appears to be of secondary importance for the particle oxidation state and composition. The effect of alkane molecular structure on SOA yields appears to be consistent with recent laboratory observations. The simulated SOA composition shows, however, an unexpected major contribution from multifunctional organic nitrates. Most SOA contributors simulated for the oxidation of the various homologous series are far too reduced to be categorized as highly oxygenated organic aerosols (OOA). On a carbon basis, the OOA yields never exceeded 10% regardless of carbon chain length, molecular structure or ageing time. This version of the model appears clearly unable to explain a large production of OOA from alkane precursors. PMID:24600999

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

    NASA Technical Reports Server (NTRS)

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

    2014-01-01

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

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

    PubMed

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

    2015-07-01

    Cyanobacteria possess the unique capacity to produce alkane. In this study, effects of nitrogen deficiency and salt stress on biosynthesis of alkanes were investigated in three kinds of cyanobacteria. Intracellular alkane accumulation was increased in nitrogen-fixing cyanobacterium Anabaena sp. PCC7120, but decreased in non-diazotrophic cyanobacterium Synechococcus elongatus PCC7942 and constant in a halotolerant cyanobacterium Aphanothece halophytica under nitrogen-deficient condition. We also found that salt stress increased alkane accumulation in Anabaena sp. PCC7120 and A. halophytica. The expression levels of two alkane synthetic genes were not upregulated significantly under nitrogen deficiency or salt stress in Anabaena sp. PCC7120. The transformant Anabaena sp. PCC7120 cells with additional alkane synthetic gene set from A. halophytica increased intracellular alkane accumulation level compared to control cells. These results provide a prospect to improve bioproduction of alkanes in nitrogen-fixing halotolerant cyanobacteria via abiotic stresses and genetic engineering. PMID:25971893

  14. 40 CFR 721.10163 - Chloro fluoro alkane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  15. 40 CFR 721.10163 - Chloro fluoro alkane (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 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...

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

    PubMed Central

    Agrawal, Akhil; Gieg, Lisa M.

    2013-01-01

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

  17. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

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

    1994-01-01

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

  18. Reflectance spectroscopy of organic compounds: 1. Alkanes

    USGS Publications Warehouse

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

    2009-01-01

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

  19. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

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

    1992-01-01

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

  20. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

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

    1994-01-18

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

  1. Modeling of Alkane Oxidation Using Constituents and Species

    NASA Technical Reports Server (NTRS)

    Bellan, Jasette; Harstad, Kenneth G.

    2010-01-01

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

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

    SciTech Connect

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

    2011-03-16

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

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

    NASA Astrophysics Data System (ADS)

    Gordon, Benjamin Willis Franklin

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

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

    PubMed

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

    2010-12-16

    Branched alkane hydrocarbons are thermodynamically more stable than straight-chain linear alkanes. This thermodynamic stability is also manifest in alkane bond separation energies. To understand the physical differences between branched and linear alkanes, we have utilized a novel density functional theory (DFT) definition of steric energy based on the Weizäcker kinetic energy. Using the M06-2X functional, the total DFT energy was partitioned into a steric energy term (E(s)[ρ]), an electrostatic energy term (E(e)[ρ]), and a fermionic quantum energy term (E(q)[ρ]). This analysis revealed that branched alkanes have less (destabilizing) DFT steric energy than linear alkanes. The lower steric energy of branched alkanes is mitigated by an equal and opposite quantum energy term that contains the Pauli component of the kinetic energy and exchange-correlation energy. Because the steric and quantum energy terms cancel, this leaves the electrostatic energy term that favors alkane branching. Electrostatic effects, combined with correlation energy, explains why branched alkanes are more stable than linear alkanes. PMID:21086970

  5. Density Functional Steric Analysis of Linear and Branched Alkanes

    SciTech Connect

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

    2010-11-18

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

  6. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

    Kung, Harold H.; Chaar, Mohamed A.

    1988-01-01

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

  7. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

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

    1988-10-11

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

  8. Enthalpy difference between conformations of normal alkanes: effects of basis set and chain length on intramolecular basis set superposition error

    NASA Astrophysics Data System (ADS)

    Balabin, Roman M.

    2011-03-01

    The quantum chemistry of conformation equilibrium is a field where great accuracy (better than 100 cal mol-1) is needed because the energy difference between molecular conformers rarely exceeds 1000-3000 cal mol-1. The conformation equilibrium of straight-chain (normal) alkanes is of particular interest and importance for modern chemistry. In this paper, an extra error source for high-quality ab initio (first principles) and DFT calculations of the conformation equilibrium of normal alkanes, namely the intramolecular basis set superposition error (BSSE), is discussed. In contrast to out-of-plane vibrations in benzene molecules, diffuse functions on carbon and hydrogen atoms were found to greatly reduce the relative BSSE of n-alkanes. The corrections due to the intramolecular BSSE were found to be almost identical for the MP2, MP4, and CCSD(T) levels of theory. Their cancelation is expected when CCSD(T)/CBS (CBS, complete basis set) energies are evaluated by addition schemes. For larger normal alkanes (N > 12), the magnitude of the BSSE correction was found to be up to three times larger than the relative stability of the conformer; in this case, the basis set superposition error led to a two orders of magnitude difference in conformer abundance. No error cancelation due to the basis set superposition was found. A comparison with amino acid, peptide, and protein data was provided.

  9. Oxidation of Alkyl-substituted Cyclic Hydrocarbons by a Nocardia during Growth on n-Alkanes

    PubMed Central

    Davis, J. B.; Raymond, R. L.

    1961-01-01

    Nocardia 107-332, a soil isolate, oxidizes short-chain alkyl-substituted cyclic hydrocarbons to cyclic acids while growing on n-alkanes. Cyclic acids are produced also from relatively long-chain alkyl-substituted cyclics such as n-nonylbenzene or n-dodecylbenzene which alone support growth in a mineral-salts medium. ω-Oxidation of the alkyl substituents is followed by β-oxidation. It is of particular interest that cyclic acids such as cyclohexaneacetic and phenylacetic with C2 residual carboxylic acid substituents are resistant to further oxidation by the nocardia but cyclic acids with C1 or C3 substituents are readily oxidized and utilized for growth. The specificity of microbial oxidations is demonstrated by the conversion of p-isopropyltoluene (p-cymene) to p-isopropylbenzoic acid in n-alkane, growth-supported nocardia cultures. PMID:13720182

  10. Chemistry of secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Yee, Lindsay Diana

    The photooxidation of volatile organic compounds (VOCs) in the atmosphere can lead to the formation of secondary organic aerosol (SOA), a major component of fine particulate matter. Improvements to air quality require insight into the many reactive intermediates that lead to SOA formation, of which only a small fraction have been measured at the molecular level. This thesis describes the chemistry of secondary organic aerosol (SOA) formation from several atmospherically relevant hydrocarbon precursors. Photooxidation experiments of methoxyphenol and phenolic compounds and C12 alkanes were conducted in the Caltech Environmental Chamber. These experiments include the first photooxidation studies of these precursors run under sufficiently low NOx levels, such that RO2 + HO2 chemistry dominates, an important chemical regime in the atmosphere. Using online Chemical Ionization Mass Spectrometery (CIMS), key gas-phase intermediates that lead to SOA formation in these systems were identified. With complementary particle-phase analyses, chemical mechanisms elucidating the SOA formation from these compounds are proposed. Three methoxyphenol species (phenol, guaiacol, and syringol) were studied to model potential photooxidation schemes of biomass burning intermediates. SOA yields (ratio of mass of SOA formed to mass of primary organic reacted) exceeding 25% are observed. Aerosol growth is rapid and linear with the organic conversion, consistent with the formation of essentially non-volatile products. Gas and aerosol-phase oxidation products from the guaiacol system show that the chemical mechanism consists of highly oxidized aromatic species in the particle phase. Syringol SOA yields are lower than that of phenol and guaiacol, likely due to unique chemistry dependent on methoxy group position. The photooxidation of several C12 alkanes of varying structure n-dodecane, 2-methylundecane, cyclododecane, and hexylcyclohexane) were run under extended OH exposure to investigate the

  11. Stimulation of Lipase Production During Bacterial Growth on Alkanes

    PubMed Central

    Breuil, Colette; Shindler, D. B.; Sijher, J. S.; Kushner, D. J.

    1978-01-01

    Acinetobacter lwoffi strain O16, a facultative psychrophile, can grow on crude oil, hexadecane, octadecane, and most alkanes when tested at 20 but not at 30°C. Growth occurred on a few alkanes at 30°C but after a longer lag than at 20°C. Cells grown on alkanes as sole carbon sources had high levels of cell-bound lipase. In contrast, previous work has shown that those grown on complex medium produced cell-free lipase and those grown on defined medium without alkanes produced little or no lipase. Low concentrations of the detergent Triton X-100 caused the liberation of most of the lipase activity of alkane-grown cells and increased total lipase activity. When ethanol and hexadecane were both present in a mineral medium, diauxic growth occurred; until the ethanol was completely used up, hexadecane was not utilized, and the lipase activity was very low. When growth on hexadecane began, lipase activity increased, reaching a level 50- to 100-fold higher than that of cells growing on ethanol. A similar pattern of lipase formation and hexadecane utilization was observed with Pseudomonas aeruginosa. Whenever A. lwoffi and other bacteria degraded alkanes they exhibited substantial lipase activity. Not all bacteria that produced lipase, however, could attack alkanes. Bacteria that could not produce lipase did not attack alkanes. The results suggest that a correlation may exist between lipase formation and alkane utilization. PMID:627533

  12. The Conversion of Starch and Sugars into Branched C10 and C11 Hydrocarbons.

    PubMed

    Sutton, Andrew D; Kim, Jin K; Wu, Ruilian; Hoyt, Caroline B; Kimball, David B; Silks, Louis A; Gordon, John C

    2016-09-01

    Oligosaccharides, such as starch, cellulose, and hemicelluloses, are abundant and easily obtainable bio-derived materials that can potentially be used as precursors for fuels and chemical feedstocks. To access the pertinent molecular building blocks (i.e., 5- or 6-carbon containing sugar units) located within these biopolymers and transform them into useful fuel precursors, oligosaccharide depolymerization followed by chain extension is required. This chain extension can readily be performed via a Garcia-Gonzalez-like approach using β-diketones under mild conditions to provide fuel precursors containing an increased carbon atom content that meets fuel requirements. In a subsequent step, ring opening and hydrodeoxygenation chemistry of these species allows for the preparation of branched alkanes under relatively mild conditions. This approach can be applied to monomeric sugars (glucose and xylose), oligosaccharides (starch), and potentially to hydrolyzed dedicated energy crops to allow the conversion of real biomass into fuel type molecules. PMID:27428812

  13. Conformation of liquid N-alkanes.

    PubMed Central

    Goodsaid-Zalduondo, F; Engelman, D M

    1981-01-01

    The conformations of liquid n-alkanes have been studied using neutron scattering techniques to better understand the conformational forces present in membrane lipid interiors. We have studied hydrocarbon chains having lengths comparable to those found for esterified membrane lipid fatty acids, and find that the steric constraints of packing in the liquid state do not change the conformational distributions of hydrocarbon chains from those imposed by the intrachain forces present in the gas phase. It follows that the central region of membranes containing lipids in the disordered state should contain hydrocarbon chain conformations determined primarily by intrachain forces. PMID:7272453

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

    SciTech Connect

    Arnold, Frances H.

    2012-02-27

    The goals of this project are to investigate (1) the kinetics and stabilities of engineered cytochrome P450 (P450) small alkane hydroxylases and their evolutionary intermediates, (2) the structural basis for catalytic proficiency on small alkanes of these engineered P450s, and (3) the changes in redox control resulting from protein engineering. To reach these goals, we have established new methods for determining the kinetics and stabilities of multicomponent P450s such as CYP153A6. Using these, we were able to determine that CYP153A6 is proficient for hydroxylation of alkanes as small as ethane, an activity that has never been observed previously in any natural P450. To elucidate the structures of the engineered P450s, we obtained x-ray diffraction data for two variants in the P450PMO (propane monooxygenase) lineage and a preliminary structure for the most evolved variant. This structure shows changes in the substrate binding regions of the enzyme and a reduction in active site volume that are consistent with the observed changes in substrate specificity from fatty acids in the native enzyme to small alkanes in P450PMO. We also constructed semi-rational designed libraries mutating only residues in the enzyme active site that in one round of mutagenesis and screening produced variants that achieved nearly half of the activity of the most evolved enzymes of the P450PMO lineage. Finally, we found that changes in redox properties of the laboratory-evolved P450 alkane hydroxylases did not reflect the improvement in their electron transfer efficiency. The heme redox potential remained constant throughout evolution, while activity increased and coupling efficiency improved from 10% to 90%. The lack of correlation between heme redox potential and enzyme activity and coupling efficiency led us to search for other enzyme properties that could be better predictors for activity towards small alkanes, specifically methane. We investigated the oxidation potential of the radical

  15. Release of alkanes from sedimentary organic matter via sequential degradation involving catalytic hydropyrolysis

    SciTech Connect

    Love, G.D.; McAulay, A.; Snape, C.E.

    1996-12-31

    Fixed-bed pyrolysis of petroleum source rocks (type I and II kerogens) and high-volatile coals (type III ketogens) at high hydrogen pressures (> 10 MN, hydropyrolysis) in the presence of a dispersed sulphided molydenum catalyst gives rise to extremely high oil (dichloromethane-soluble) yields (>60%) with overall conversions of the organic matter being greater than 90%. The yields and conformations of the hopanes and steranes released from a selection of petroleum source rocks and coals by sequential dichloromethane and pyridine extraction, catalytic hydrogenation and hydropyrolysis will be presented, together with the influence of hydrogen pressure and heating rate on alkane yields and sterochemistry. The aim of the hydrogenation step (conducted at 300{degrees}C cf. 520{degrees}C for hydropyrolysis) in this sequential degradation scheme is to cleave only the weaker covalent bonds. The findings have demonstrated the unique ability of hydropyrolysis to mainline the yields of covalently-bound alkanes while maintaining the biologically-inherited 17{beta}(H), 21{beta}(H) stereochemistries of the hopanes, largely intact, even for coals. The total alkane yields from hydropyrolysis represented ca 30% w/w of the organic matter remaining in immature type I kerogens with yields of the C{sub 29}-C{sub 35} 17{beta}(H), 21{beta}(H) hopanes being much higher than from both normal pyrolysis and the hydrogenation step.

  16. 40 CFR 721.535 - Halogenated alkane (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.535 Halogenated alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkane (PMN P-01-433) is...

  17. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical 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)...

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

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.535 Halogenated alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkane (PMN P-01-433) is...

  19. Thomas Reiche Kuhn populations in alkanes

    NASA Astrophysics Data System (ADS)

    Lazzeretti, P.; Caputo, M. C.; Ferraro, M. B.

    1999-07-01

    Atomic populations in a molecule have been defined via the Thomas-Reiche-Kuhn sum rule for oscillator strengths written within the acceleration gauge. These atomic populations are related to nuclear electric shieldings, i.e., to geometrical derivatives of electric dipole moment, and can therefore be connected with observable infrared intensities. A number of relationships can be considered to test a priori the quality of calculated electronic charges and to assess their physical meaning. It is shown via extended numerical tests on the first members of the alkane series that the Thomas-Reiche-Kuhn populations are consistent with a (small) polarity C +-H - of carbon-hydrogen bond in methane, for which a bond dipole moment can be exactly defined. Although the idea of bond dipole cannot be extended to the C-H fragments belonging to other alkane molecules in the absence of local C3 v symmetry, the calculations prove that the same electron charge polarization should characterize the whole homologous series.

  20. Alkanes in benthic organisms from the Buccaneer oil field

    SciTech Connect

    Middleditch, B.S.; Basile, B.

    1980-06-01

    About 200 g per day of alkanes are present in brine discharged from each of two production platforms in the Buccaneer oil field in the NW Gulf of Mexico. These alkanes disperse rapidly in the water column, so that seawater concentrations of petroleum alkanes in this region are generally very low. They can be taken up to some extent by plankton, fish, and barnacles, but the petroleum alkane concentrations in these organisms are also relatively low. The largest pool of petroleum alkanes is in the surficial sediments, where concentrations of up to 25 ppM are observed, with concentration gradients extending more than 20 m from the production platforms. Organisms are examined which are exposed to these sediments and, for comparison, other specimens from control sites around structures from which there are no discharges.

  1. Utilization of n-Alkanes by Cladosporium resinae

    PubMed Central

    Teh, J. S.; Lee, K. H.

    1973-01-01

    Four different isolates of Cladosporium resinae from Australian soils were tested for their ability to utilize liquid n-alkanes ranging from n-hexane to n-octadecane under standard conditions. The isolates were unable to make use of n-hexane, n-heptane, and n-octane for growth. In fact, these hydrocarbons, particularly n-hexane, exerted an inhibitory effect on spore germination and mycelial growth. All higher n-alkanes from n-nonane to n-octadecane were assimilated by the fungus, although only limited growth occurred on n-nonane and n-decane. The long chain n-alkanes (C14 to C18) supported good growth of all isolates, but there was no obvious correlation between cell yields and chain lengths of these n-alkanes. Variation in growth responses to individual n-alkane among the different isolates was also observed. The cause of this variation is unknown. PMID:4735447

  2. Sophorolipids from Torulopsis bombicola: possible relation to alkane uptake.

    PubMed Central

    Ito, S; Inoue, S

    1982-01-01

    Torulopsis bombicola produces extracellular sophorolipids when it is grown on water-insoluble alkanes. Sophorolipids and related model compounds, which were not themselves used for growth, were found to stimulate markedly the growth of T. bombicola on alkanes. This stimulatory effect was restricted to growth on C10 to C20 alkanes, whereas no significantly influence was observed for growth on fatty alcohols, fatty acids, glucose, or glycerol. The nonionic methyl ester of the glycolipid supported the greatest cell yield. However, a number of synthetic nonionic surfactants were unable to replace the glycolipid. When organisms were grown on hexadecane, stimulation of growth by sophorolipids was observed almost exclusively with strains of Torulopsis yeasts. In contrast, the growth of other typical alkane-utilizing yeasts, such as candida and Pichia strains, was inhibited or not affected. It appears that sophorolipids are involved in alkane dissimilation by T. bombicola through an undetermined mechanism. PMID:7201782

  3. Spectroscopy of the tilde A state of NO-alkane complexes (alkane = methane, ethane, propane, and n-butane)

    NASA Astrophysics Data System (ADS)

    Tamé-Reyes, Victor M.; Gardner, Adrian M.; Harris, Joe P.; McDaniel, Jodie; Wright, Timothy G.

    2012-12-01

    We have recorded (1+1) resonance-enhanced multiphoton ionization spectra of complexes formed between NO and the alkanes: CH4, C2H6, C3H8, and n-C4H10. The spectra correspond to the tilde A ← tilde X transition, which is a NO-localized 3s ← 2pπ* transition. In line with previous work, the spectrum for NO-CH4 has well-defined structure, but this is only partially resolved for the other complexes. The spectra recorded in the NO+-alkane mass channels all show a slowly rising onset, followed by a sharp offset, which is associated with dissociation of NO-alkane, from which binding energies in the tilde X and tilde A states are deduced. Beyond this sharp offset, there is a further rise in signal, which is attributed to fragmentation of higher complexes, NO-(alkane)n. Analysis of these features allows binding energies for (NO-alkane) ... alkane to be estimated, and these suggest that in the NO-(alkane)2 complexes, the second alkane molecule is bound to the first, rather than to NO. Calculated structures for the 1:1 complexes are reported, as well as binding energies.

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

    SciTech Connect

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

    1997-09-01

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

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

    PubMed

    Buijs, Nicolaas A; Zhou, Yongjin J; Siewers, Verena; Nielsen, Jens

    2015-06-01

    In the past decade industrial-scale production of renewable transportation biofuels has been developed as an alternative to fossil fuels, with ethanol as the most prominent biofuel and yeast as the production organism of choice. However, ethanol is a less efficient substitute fuel for heavy-duty and maritime transportation as well as aviation due to its low energy density. Therefore, new types of biofuels, such as alkanes, are being developed that can be used as drop-in fuels and can substitute gasoline, diesel, and kerosene. Here, we describe for the first time the heterologous biosynthesis of long-chain alkanes by the yeast Saccharomyces cerevisiae. We show that elimination of the hexadecenal dehydrogenase Hfd1 and expression of a redox system are essential for alkane biosynthesis in yeast. Deletion of HFD1 together with expression of an alkane biosynthesis pathway resulted in the production of the alkanes tridecane, pentadecane, and heptadecane. Our study provides a proof of principle for producing long-chain alkanes in the industrial workhorse S. cerevisiae, which was so far limited to bacteria. We anticipate that these findings will be a key factor for further yeast engineering to enable industrial production of alkane based drop-in biofuels, which can allow the biofuel industry to diversify beyond bioethanol. PMID:25545362

  6. Alkanes-filled photonic crystal fibers as sensor transducers

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  9. Process for converting light alkanes to higher hydrocarbons

    DOEpatents

    Noceti, Richard P.; Taylor, Charles E.

    1988-01-01

    A process is disclosed for the production of aromatic-rich, gasoline boiling range hydrocarbons from the lower alkanes, particularly from methane. The process is carried out in two stages. In the first, alkane is reacted with oxygen and hydrogen chloride over an oxyhydrochlorination catalyst such as copper chloride with minor proportions of potassium chloride and rare earth chloride. This produces an intermediate gaseous mixture containing water and chlorinated alkanes. The chlorinated alkanes are contacted with a crystalline aluminosilicate catalyst in the hydrogen or metal promoted form to produce gasoline range hydrocarbons with a high proportion of aromatics and a small percentage of light hydrocarbons (C.sub.2 -C.sub.4). The light hydrocarbons can be recycled for further processing over the oxyhydrochlorination catalyst.

  10. Pd/NbOPO₄ multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans.

    PubMed

    Xia, Qi-Neng; Cuan, Qian; Liu, Xiao-Hui; Gong, Xue-Qing; Lu, Guan-Zhong; Wang, Yan-Qin

    2014-09-01

    Great efforts have been made to convert renewable biomass into transportation fuels. Herein, we report the novel properties of NbO(x)-based catalysts in the hydrodeoxygenation of furan-derived adducts to liquid alkanes. Excellent activity and stability were observed with almost no decrease in octane yield (>90% throughout) in a 256 h time-on-stream test. Experimental and theoretical studies showed that NbO(x) species play the key role in C-O bond cleavage. As a multifunctional catalyst, Pd/NbOPO4 plays three roles in the conversion of aldol adducts into alkanes: 1) The noble metal (in this case Pd) is the active center for hydrogenation; 2) NbO(x) species help to cleave the C-O bond, especially of the tetrahydrofuran ring; and 3) a niobium-based solid acid catalyzes the dehydration, thus enabling the quantitative conversion of furan-derived adducts into alkanes under mild conditions. PMID:25045056

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

    PubMed

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

    2015-11-01

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

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

    PubMed Central

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

    2015-01-01

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

  13. Superacid catalyzed coal conversion chemistry. 1st and 2nd quarterly technical progress reports, September 1, 1983-March 30, 1984. [Model compound consisting of 2 benzene rings connected with various bridging units such as alkylidene, ether, sulfide, etc

    SciTech Connect

    Olah, G.A.

    1984-01-01

    In our laboratories we have previously developed a mild coal conversion process. This involves the use of a superacid system consisting of HF and BF/sub 3/ in presence of hydrogen and/or a hydrogen donor solvent. In order to understand the chemistry involved in the process of depolymerization of coal by the HF:BF/sub 3/:H/sub 2/ system we are carrying out a systematic study of a number of coal model compounds. The model compounds selected for present study have two benzene rings connected with various bridging units such as alkylidene, ether, sulfide etc. From studies so far carried out it appears that high pyridine extractibilities achieved by treating coal at temperature below 100/sup 0/C results from the cleavage of bridges such as present in bibenzyl, diphenyl methane, dibenzyl ether, dibenzyl sulfide etc. On the other hand the increased cyclohexane extractibility and distillability observed at relatively higher temperatures and hydrogen pressures reflects the hydrogenation and cleavage of the aromatic backbone in coal structure similar to what is seen in the conversion of model compounds such as biphenyl, diphenyl ether, diphenyl sulfide, anthracene, etc.

  14. Hydrogen isotopic compositions of n-alkanes from terrestrial plants correlate with their ecological life forms.

    PubMed

    Liu, Weiguo; Yang, Hong; Li, Liwu

    2006-11-01

    Stable hydrogen isotopic compositions (deltaD) of compound-specific biomarkers, such as n-alkanes from plant leaf waxes, can be used as a proxy for paleoclimatic change. However, the relationship between hydrogen isotopes of plant leaf wax and plant ecological life forms is not well understood. Here, we report the deltaD of n-alkanes from 34 modern terrestrial plants, including twenty-one C(3) plants and thirteen C(4) plants from northwestern China, determined using gas chromatography/thermal conversion/isotope ratio mass spectrometry. Our data show that the stable hydrogen isotopes are poorly correlated with the plant photosynthetic pathway (C(3) vs. C(4)) and that they do not give clear regional precipitation signals. Together with a comparative analysis of published deltaD values from plant leaf waxes in other regions, we believe that the stable hydrogen isotope of plant leaf waxes is more closely related to ecological life forms of these terrestrial plants (i.e. tree, shrub, and grass). In general, the grasses have more negative deltaD values than the co-occurring trees and shrubs. Our findings suggest that the deltaD values of sedimentary leaf waxes from higher plants may record changes of a plant ecosystem under the influence of environmental alteration and imply that reconstruction of the paleoclimate using deltaD values from plant n-alkanes should be based upon specific plant taxa, and comparison should be made among plants with similar ecological life forms. PMID:16977462

  15. Exploratory study of coal-conversion chemistry. Quarterly report No. 3, November 19, 1981-February 18, 1982. [Dihydronaphthalene, 1,2'-dinaphthylmethane, methoxynaphthalene diphenyl ether

    SciTech Connect

    Ross, D.S.; McMillen, D.F.; Ogier, W.C.; Bunnell, R.; Hum, G.P.

    1982-03-01

    Work in Task A has provided additional data on the rate and mechanisms of radical-induced cleavage of strong C-C and C-0 bonds in coal structures. This work has shown that even resonance-stabilized radicals, which form relatively weak C-C bonds, can displace other resonance-stabilized radicals from methylene-bridged coal structures. Kinetic studies reveal that either the self-disproportionation of 1,2-dihydronaphthalene is much faster than previously reported or that the 1,2-dihydronaphthalene-tetralin disproportionation is much less important as a radical initiation process than thermochemical estimates had suggested. 1,2'-Dinaphthylmethane undergoes radical-induced CH/sub 2/-Ar bond scission ten times faster than diphenyl ether. This factor is shown to be consistent with the thermochemistry of displacement by tetralyl radical. In Task B we studied CO/H/sub 2/O conversion of a second, high volatile bituminous coal, PSOC-233. We found that, as with PSOC-026, the initial pH did affect the conversion rate, increasing with higher pH. We also conducted experiments with several oxygen-containing model compounds in CO/D/sub 2/O at 400/sup 0/C for 20 min. We had shown earlier in preliminary control experiments that simple aromatics, such as toluene, did not incorporate deuterium under these conditions. This quarter we found that anisole (Ph-O-CH/sub 3/) was converted to several products, with benzene as the most prominent. About 60% of the anisole was recovered in several experiments with mass balances at about 85%. There was a net incorporation of deuterium in the product benzene. The corresponding conversion in tetralin under the same conditions was two orders of magnitude slower and yielded phenol as the major product. We conclude that in the aqueous medium a chain process can occur that yields phenyl radical, which can then receive protium from a starting anisole or deuterium from the mineral medium.

  16. Selective hydroxylation of alkanes by an extracellular fungal peroxygenase.

    PubMed

    Peter, Sebastian; Kinne, Matthias; Wang, Xiaoshi; Ullrich, René; Kayser, Gernot; Groves, John T; Hofrichter, Martin

    2011-10-01

    Fungal peroxygenases are novel extracellular heme-thiolate biocatalysts that are capable of catalyzing the selective monooxygenation of diverse organic compounds, using only H(2)O(2) as a cosubstrate. Little is known about the physiological role or the catalytic mechanism of these enzymes. We have found that the peroxygenase secreted by Agrocybe aegerita catalyzes the H(2)O(2)-dependent hydroxylation of linear alkanes at the 2-position and 3-position with high efficiency, as well as the regioselective monooxygenation of branched and cyclic alkanes. Experiments with n-heptane and n-octane showed that the hydroxylation proceeded with complete stereoselectivity for the (R)-enantiomer of the corresponding 3-alcohol. Investigations with a number of model substrates provided information about the route of alkane hydroxylation: (a) the hydroxylation of cyclohexane mediated by H(2)(18)(2) resulted in complete incorporation of (18)O into the hydroxyl group of the product cyclohexanol; (b) the hydroxylation of n-hexane-1,1,1,2,2,3,3-D(7) showed a large intramolecular deuterium isotope effect [(k(H)/k(D))(obs)] of 16.0 ± 1.0 for 2-hexanol and 8.9 ± 0.9 for 3-hexanol; and (c) the hydroxylation of the radical clock norcarane led to an estimated radical lifetime of 9.4 ps and an oxygen rebound rate of 1.06 × 10(11) s(-1). These results point to a hydrogen abstraction and oxygen rebound mechanism for alkane hydroxylation. The peroxygenase appeared to lack activity on long-chain alkanes (> C(16)) and highly branched alkanes (e.g. tetramethylpentane), but otherwise exhibited a broad substrate range. It may accordingly have a role in the bioconversion of natural and anthropogenic alkane-containing structures (including alkyl chains of complex biomaterials) in soils, plant litter, and wood. PMID:21812933

  17. One Instructor's Approach to Computer Assisted Instruction in General Chemistry.

    ERIC Educational Resources Information Center

    DeLorenzo, Ronald

    1982-01-01

    Discusses advantages of using computer-assisted instruction in a college general chemistry course. Advantages include using programs which generate random equations with double arrows (equilibrium systems) or generate alkane structural formula, asking for the correct IUPAC name of the structure. (Author/JN)

  18. Variation in n-Alkane Distributions of Modern Plants: Questioning Applications of n-Alkanes in Chemotaxonomy and Paleoecology

    NASA Astrophysics Data System (ADS)

    Bush, R. T.; McInerney, F. A.

    2010-12-01

    Long chain n-alkanes (n-C21 to n-C37) are synthesized as part of the epicuticular leaf wax of terrestrial plants and are among the most recognizable and widely used plant biomarkers. n-Alkane distributions have been utilized in previous studies on modern plant chemotaxonomy, testing whether taxa can be identified based on characteristic n-alkane profiles. Dominant n-alkanes (e.g. n-C27 or n-C31) have also been ascribed to major plant groups (e.g. trees or grasses respectively) and have been used in paleoecology studies to reconstruct fluctuations in plant functional types. However, many of these studies have been based on relatively few modern plant data; with the wealth of modern n-alkane studies, a more comprehensive analysis of n-alkanes in modern plants is now possible and can inform the usefulness of n-alkane distributions as paleoecological indicators. The work presented here is a combination of measurements made using plant leaves collected from the Chicago Botanic Garden and a compilation of published literature data from six continents. We categorized plants by type: angiosperms, gymnosperms, woody plants, forbs, grasses, ferns and pteridophytes, and mosses. We then quantified n-alkane distribution parameters such as carbon preference index (CPI), average chain length (ACL), and dispersion (a measure of the spread of the profile over multiple chain lengths) and used these to compare plant groups. Among all plants, one of the emergent correlations is a decrease in dispersion with increasing CPI. Within and among plant groups, n-alkane distributions show a very large range of variation, and the results show little or no correspondence between broad plant groups and a single dominant n-alkane or a ratio of n-alkanes. These findings are true both when data from six continents are combined and when plants from a given region are compared (North America). We also compared the n-alkane distributions of woody angiosperms, woody gymnosperms, and grasses with one

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

    PubMed

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

    2016-01-01

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

  20. Detailed chemical kinetic models for large n-alkanes and iso-alkanes found in conventional and F-T diesel fuels

    SciTech Connect

    Westbrook, C K; Pitz, W J; Curran, H J; Mehl, M

    2008-12-15

    Detailed chemical kinetic models are needed to simulate the combustion of current and future transportation fuels. These models should represent the various chemical classes in these fuels. Conventional diesel fuels are composed of n-alkanes, iso-alkanes, cycloalkanes and aromatics (Farrell et al. 2007). For future fuels, there is a renewed interest in Fischer-Tropsch (F-T) processes which can be used to synthesize diesel and other transportation fuels from biomass, coal and natural gas. F-T diesel fuels are expected to be similar to F-T jet fuels which are commonly comprised of iso-alkanes with some n-alkanes (Smith and Bruno, 2008). Thus, n-alkanes and iso-alkanes are common chemical classes in these conventional and future fuels. This paper reports on the development of chemical kinetic models of large n-alkanes and iso-alkanes to represent these chemical classes in conventional and future fuels. Two large iso-alkanes are 2,2,4,4,6,8,8-heptamethylnonane, which is a primary reference fuel for diesel, and isooctane, a primary reference fuel for gasoline. Other iso-alkanes are branched alkanes with a single methyl side chain, typical of most F-T fuels. The chemical kinetic models are then used to predict the effect of these fuel components on ignition characteristics under conditions found in internal combustion engines.

  1. Tropospheric Chemistry

    NASA Technical Reports Server (NTRS)

    Mohnen, V.

    1984-01-01

    The fundamental processes that control the chemical composition and cycles of the global troposphere and how these processes and properties affect the physical behavior of the atmosphere are examined. The long-term information needs for tropospheric chemistry are: to be able to predict tropospheric responses to perturbations, both natural and anthropogenic, of these cycles, and to provide the information required for the maintenance and effective future management of the atmospheric component of our global life support system. The processes controlling global tropospheric biogeochemical cycles include: the input of trace species into the troposphere, their long-range transport and distribution as affected by the mean wind and vertical venting, their chemical transformations, including gas to particle conversion, leading to the appearance of aerosols or aqueous phase reactions inside cloud droplets, and their removal from the troposphere via wet (precipitation) and dry deposition.

  2. Alkane inducible proteins in Geobacillus thermoleovorans B23

    PubMed Central

    2009-01-01

    Background Initial step of β-oxidation is catalyzed by acyl-CoA dehydrogenase in prokaryotes and mitochondria, while acyl-CoA oxidase primarily functions in the peroxisomes of eukaryotes. Oxidase reaction accompanies emission of toxic by-product reactive oxygen molecules including superoxide anion, and superoxide dismutase and catalase activities are essential to detoxify them in the peroxisomes. Although there is an argument about whether primitive life was born and evolved under high temperature conditions, thermophilic archaea apparently share living systems with both bacteria and eukaryotes. We hypothesized that alkane degradation pathways in thermophilic microorganisms could be premature and useful to understand their evolution. Results An extremely thermophilic and alkane degrading Geobacillus thermoleovorans B23 was previously isolated from a deep subsurface oil reservoir in Japan. In the present study, we identified novel membrane proteins (P16, P21) and superoxide dismutase (P24) whose production levels were significantly increased upon alkane degradation. Unlike other bacteria acyl-CoA oxidase and catalase activities were also increased in strain B23 by addition of alkane. Conclusion We first suggested that peroxisomal β-oxidation system exists in bacteria. This eukaryotic-type alkane degradation pathway in thermophilic bacterial cells might be a vestige of primitive living cell systems that had evolved into eukaryotes. PMID:19320977

  3. Diffusion of Benzene and Alkylbenzenes in n-Alkanes.

    PubMed

    Kowert, Bruce A; Register, Paul M

    2015-10-01

    The translational diffusion constants, D, of benzene and a series of alkylbenzenes have been determined in four n-alkanes at room temperature using capillary flow techniques. The alkylbenzenes are toluene, ethylbenzene, 1-phenylpropane, 1-phenylpentane, 1-phenyloctane, 1-phenylundecane, 1-phenyltetradecane, and 1-phenylheptadecane. The n-alkanes are n-nonane, n-decane, n-dodecane, and n-pentadecane. Ratios of the solutes' D values are independent of solvent and in general agreement with the predictions of diffusion models for cylinders and lollipops. For the latter, an alkylbenzene's phenyl ring is the lollipop's candy; the alkyl chain is its handle. A model that considers the solutes to be spheres with volumes determined by the van der Waals increments of their constituent atoms is not in agreement with experiment. The diffusion constants of 1-alkene and n-alkane solutes in n-alkane solvents also are compared with the cylinder model; reasonably good agreement is found. The n-alkanes are relatively extended, and this appears to be the case for the alkyl chains of the 1-alkenes and alkylbenzenes as well. PMID:26417941

  4. One-step hydrotreatment of vegetable oil to produce high quality diesel-range alkanes.

    PubMed

    Wang, Congxin; Tian, Zhijian; Wang, Lei; Xu, Renshun; Liu, Qianhe; Qu, Wei; Ma, Huaijun; Wang, Bingchun

    2012-10-01

    A one-step hydrotreatment of vegetable oil combining deoxygenation and isomerization to directly produce low cloud point, high quality diesel is devised. The Pt/zeolite bifunctional catalysts prepared by using SAPO-11 and ZSM-22 zeolites as supports are used in this process. Catalytic reactions are conducted in a fixed-bed reactor under a hydrogen atmosphere. Over the bifunctional catalyst, 100 % conversion of soybean oil is obtained at 357 °C, 4 MPa, and 1 h(-1), and 80 % organic liquid yield is achieved, which is close to the maximum theoretical liquid yield. In the organic products, the alkanes selectivity is 100 % with an i-alkanes selectivity above 63 %. NH(3)-temperature programmed desorption (TPD), pyridine IR spectroscopy, and other characterization techniques are used to study the effect of the support acidity on the reaction pathway. Over the Pt/zeolite bifunctional catalyst with less strong Lewis acid sites, the reaction proceeds via the decarboxylation plus decarbonylation pathway. This one-step method provides a new strategy to produce low cloud point, high quality diesel from biomass feedstock in a more economic and attractive way. PMID:22764086

  5. Structure, Energetics, and Dynamics of Screw Dislocations in Even n-Alkane Crystals.

    PubMed

    Olson, Isabel A; Shtukenberg, Alexander G; Hakobyan, Gagik; Rohl, Andrew L; Raiteri, Paolo; Ward, Michael D; Kahr, Bart

    2016-08-18

    Spiral hillocks on n-alkane crystal surfaces were observed immediately after Frank recognized the importance of screw dislocations for crystal growth, yet their structures and energies in molecular crystals remain ill-defined. To illustrate the structural chemistry of screw dislocations that are responsible for plasticity in organic crystals and upon which the organic electronics and pharmaceutical industries depend, molecular dynamics was used to examine heterochiral dislocation pairs with Burgers vectors along [001] in n-hexane, n-octane, and n-decane crystals. The cores were anisotropic and elongated in the (110) slip plane, with significant local changes in molecular position, orientation, conformation, and energy. This detailed atomic level picture produced a distribution of strain consistent with linear elastic theory, giving confidence in the simulations. Dislocations with doubled Burgers vectors split into pairs with elementary displacements. These results suggest a pathway to understanding the mechanical properties and failure associated with elastic and plastic deformation in soft crystals. PMID:27478906

  6. Alkanes in shrimp from the Buccaneer Oil Field

    SciTech Connect

    Middleditch, B.S.; Basile, B.; Chang, E.S.

    1982-07-01

    A total of 36 samples of shrimp were examined from the region of the Buccaneer oil field, eighteen of which were representatives of the commercial species Penaeus aztecus and the rest were various other species: Penaeus duorarum (pink shrimp), Trachypenaeus duorarum (sugar shrimp), Squilla empusa (mantis shrimp), and Sicyonia dorsalis (chevron shrimp). The alkanes and deuteriated alkanes were completely separated by GC, so a mass spectrometer was not required for their detection and quantitation. To confirm the identities of individual compounds, however, some samples were examined by combined gas chromatography-mass spectrometry. Results show that only thirteen of the forty shrimp collected from the region of the Buccaneer oil field contained petroleum alkanes, and the majority of these were obtained from trawls immediately adjacent to the production platforms. It appears that shrimp caught in the region of the Buccaneer oil field are not appreciably tainted with hydrocarbons discharged from the production platforms. (JMT)

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

    PubMed Central

    Callaghan, Amy V.

    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 (SRB) via “reverse methanogenesis” and is catalyzed by a homolog of methyl-coenzyme M reductase. The second pathway is also mediated by anaerobic methane oxidizers and SRB, 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 appear 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 ‘Methylomirabilis oxyfera.’ PMID:23717304

  8. Oxaloacetate-to-malate conversion by mineral photoelectrochemistry: implications for the viability of the reductive tricarboxylic acid cycle in prebiotic chemistry

    NASA Astrophysics Data System (ADS)

    Guzman, Marcelo I.; Martin, Scot T.

    2008-10-01

    The carboxylic acids produced by the reductive tricarboxylic acid (rTCA) cycle are possibly a biosynthetic core of initial life, although several steps such as the reductive kinetics of oxaloacetate (OAA) to malate (MA) are problematic by conventional chemical routes. In this context, we studied the kinetics of this reaction as promoted by ZnS mineral photoelectrochemistry. The quantum efficiency φMA of MA production from the photoelectrochemical reduction of OAA followed φMA=0.13 [OAA] (2.1×10-3+[OAA])-1 and was independent of temperature (5 to 50°C). To evaluate the importance of this forward rate under a prebiotic scenario, we also studied the temperature-dependent rate of the backward thermal decarboxylation of OAA to pyruvate (PA), which followed an Arrhenius behavior as log (k-2)=11.74 4956/T, where k-2 is in units of s-1. These measured rates were employed in conjunction with the indirectly estimated carboxylation rate of PA to OAA to assess the possible importance of mineral photoelectrochemistry in the conversion of OAA to MA under several scenarios of prebiotic conditions on early Earth. As an example, our analysis shows that there is 90% efficiency with a forward velocity of 3 yr/cycle for the OAA→MA step of the rTCA cycle at 280 K. Efficiency and velocity both decrease for increasing temperature. These results suggest high viability for mineral photoelectrochemistry as an enzyme-free engine to drive the rTCA cycle through the early aeons of early Earth, at least for the investigated OAA→MA step.

  9. Nitrogen Oxide Atom-Transfer Redox Chemistry; Mechanism of NO(g) to Nitrite Conversion Utilizing μ-oxo Heme-Fe(III)-O-Cu(II)(L) Constructs.

    PubMed

    Hematian, Shabnam; Kenkel, Isabell; Shubina, Tatyana E; Dürr, Maximilian; Liu, Jeffrey J; Siegler, Maxime A; Ivanovic-Burmazovic, Ivana; Karlin, Kenneth D

    2015-05-27

    While nitric oxide (NO, nitrogen monoxide) is a critically important signaling agent, its cellular concentrations must be tightly controlled, generally through its oxidative conversion to nitrite (NO2(-)) where it is held in reserve to be reconverted as needed. In part, this reaction is mediated by the binuclear heme a3/CuB active site of cytochrome c oxidase. In this report, the oxidation of NO(g) to nitrite is shown to occur efficiently in new synthetic μ-oxo heme-Fe(III)-O-Cu(II)(L) constructs (L being a tridentate or tetradentate pyridyl/alkylamino ligand), and spectroscopic and kinetic investigations provide detailed mechanistic insights. Two new X-ray structures of μ-oxo complexes have been determined and compared to literature analogs. All μ-oxo complexes react with 2 mol equiv NO(g) to give 1:1 mixtures of discrete [(L)Cu(II)(NO2(-))](+) plus ferrous heme-nitrosyl compounds; when the first NO(g) equiv reduces the heme center and itself is oxidized to nitrite, the second equiv of NO(g) traps the ferrous heme thus formed. For one μ-oxo heme-Fe(III)-O-Cu(II)(L) compound, the reaction with NO(g) reveals an intermediate species ("intermediate"), formally a bis-NO adduct, [(NO)(porphyrinate)Fe(II)-(NO2(-))-Cu(II)(L)](+) (λmax = 433 nm), confirmed by cryo-spray ionization mass spectrometry and EPR spectroscopy, along with the observation that cooling a 1:1 mixture of [(L)Cu(II)(NO2(-))](+) and heme-Fe(II)(NO) to -125 °C leads to association and generation of the key 433 nm UV-vis feature. Kinetic-thermodynamic parameters obtained from low-temperature stopped-flow measurements are in excellent agreement with DFT calculations carried out which describe the sequential addition of NO(g) to the μ-oxo complex. PMID:25974136

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

    EPA Science Inventory

    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....

  11. Modeling of alkane emissions from a wood stain

    SciTech Connect

    Chang, J.C.S.; Guo, Z.

    1993-01-01

    The article discusses full-scale residential house tests to evaluate the effects of organic emissions from a wood finishing product--wood stain--on indoor air quality (IAQ). The test house concentrations of three alkane species, nonane, decane, and undecane, were measured as a function of time after the application of the wood stain. It was found that the test house concentrations can be simulated by an integrated IAQ model which takes into consideration source, sink, and ventilation effects. The alkane emissions were controlled by an evaporation-like process.

  12. A nonequilibrium molecular dynamics study of the rheology of alkanes

    SciTech Connect

    Gupta, S.A.; Cui, S.T.; Cummings, P.T.; Cochran, H.D. |

    1996-05-01

    We examine the rheological properties of four different alkanes: n-decane, n-hexadecane, n-tetracosane, and squalane. Simulations of Couette flow are performed for a range of shear rates with 100 molecules in each case using a replicated data version of our code. Number of interaction sites ranges from 1000 to 3000. We have performed extremely long simulations required to obtain acceptable statistics at low shear rates. The alkanes show a transition from non-Newtonian to Newtonian behavior as the shear rate decreases to low values. 1 tab, 1 fig, 17 refs.

  13. Regioselective alkane hydroxylation with a mutant AlkB enzyme

    DOEpatents

    Koch, Daniel J.; Arnold, Frances H.

    2012-11-13

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

  14. Assimilation of chlorinated alkanes by hydrocarbon-utilizing fungi

    SciTech Connect

    Murphy, G.L.; Perry, J.J.

    1984-12-01

    The fatty acid compositions of two filamentous fungi (Cunninghamella elegans and Penicillium zonatum) and a yeast (Candida lipolytica) were determined after the organisms were grown on 1-chlorohexadecane or 1-chlorooctadecane. These organisms utilized the chlorinated alkanes as sole sources of carbon and energy. Analyses of the fatty acids present after growth on the chlorinated alkanes indicated that 60 to 70% of the total fatty acids in C. elegans were chlorinated. Approximately 50% of the fatty acids in C. lipolytica were also chlorinated. P. zonatum contained 20% 1-chlorohexadecanoic acid after growth on either substrate but did not incorporate C/sub 18/ chlorinated fatty acids.

  15. Iron-phthalocyanine immobilized on activated carbon black: A selective catalyst for alkane oxidation

    SciTech Connect

    Parton, R.F.; Neys, P.E.; Jacobs, P.A.

    1996-12-01

    Carbon black is tested as a support for iron-phthalocyanine within the frame of the oxidation of hydrocarbons with t-butyl-hydroperoxide as oxygen donor. The increased hydrophobicity of the carrier surface, with respect to zeolite Y, changes the adsorption behavior of the components in the reaction mixture towards the alkane. A major improvement in the oxidation conversion and efficiency of cyclohexane has been established. Furthermore, the kinetic isotope effect and the reactivity order of secondary and tertiary carbon atoms measured with adamantane provide evidence for an {open_quotes}oxygen rebound{close_quotes} reaction mechanism, a non-free-radical oxidation pathway where the metallo-complex is responsible for the hydrogen abstraction. 40 refs., 7 figs., 2 tabs.

  16. Nitrogen Oxide Atom-Transfer Redox Chemistry; Mechanism of NO(g) to Nitrite Conversion Utilizing µ-oxo Heme-FeIII−O−CuII(L) Constructs

    PubMed Central

    Hematian, Shabnam; Kenkel, Isabell; Shubina, Tatyana E.; Dürr, Maximilian; Liu, Jeffrey J.; Siegler, Maxime A.; Ivanovic-Burmazovic, Ivana; Karlin, Kenneth D.

    2015-01-01

    While nitric oxide (NO, nitrogen monoxide) is a critically important signaling agent, its cellular concentrations must be tightly controlled, generally through its oxidative conversion to nitrite (NO2−) where it is held in reserve to be reconverted as needed. In part, this reaction is mediated by the binuclear heme a3/CuB active site of cytochrome c oxidase. In this report, the oxidation of NO(g) to nitrite is shown to occur efficiently in new synthetic µ-oxo heme-FeIII−O−CuII(L) constructs (L being a tridentate or tetradentate pyridyl/alkylamino ligand), and spectroscopic and kinetic investigations provide detailed mechanistic insights. Two new X-ray structures of µ-oxo complexes have been determined and compared to literature analogs. All µ-oxo complexes react with 2 mol equiv NO(g) to give 1:1 mixtures of discrete [(L)CuII(NO2−)]+ plus ferrous heme-nitrosyl compounds; when the first NO(g) equiv reduces the heme center and itself is oxidized to nitrite, the second equiv of NO(g) traps the ferrous heme thus formed. For one µ-oxo heme-FeIII−O−CuII(L) compound, the reaction with NO(g) reveals an intermediate species (“intermediate”), formally a bis-NO adduct, [(NO)(porphyrinate)FeII-(NO2−)−CuII(L)]+ (λmax = 433 nm), confirmed by cryo-spray ionization mass spectrometry and EPR spectroscopy, along with the observation that cooling a 1:1 mixture of [(L)CuII(NO2−)]+ and heme-FeII(NO) to −125 °C leads to association and generation of the key 433 nm UV–vis feature. Kinetic-thermodynamic parameters obtained from low-temperature stopped-flow measurements are in excellent agreement with DFT calculations carried out which describe the sequential addition of NO(g) to the µ-oxo complex. PMID:25974136

  17. Radiation-initiated conversion of paraffins to engine fuel: Direct and indirect initiation

    NASA Astrophysics Data System (ADS)

    Metreveli, A. K.; Ponomarev, A. V.

    2016-07-01

    Formation of gasoline and diesel fuel has been investigated using three various radiation-induced ways: (1) cracking of wax, (2) synthesis from methane, (3) high-temperature conversion of wax dilute solution in methane. The wax, synthesized by Fischer-Tropsch method, initially contained a mixture of C17-C120 linear paraffins. The yield of wax conversion to liquid mixture (C4-C27 alkenes and 61.5% alkanes) via mode (1) was 0.83±0.09 μmole/J, whereas yield of gas conversion to liquid mixture (C5-C13 alkanes) via mode (2) was 0.95±0.02 μmole/J. In the dilute solution wax underwent indirect action of radiation. In comparison with (1) the mode (3) produces similar amount of lighter fuel containing 80% of alkanes (C5-C15). At the same time degree of methane fixation is almost three times higher.

  18. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  19. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  20. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  1. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  2. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

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

    DOEpatents

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

    1993-05-18

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

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

    DOEpatents

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

    1993-01-01

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

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

    DOEpatents

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

    1995-01-17

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

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

    DOEpatents

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

    1995-01-01

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

  7. MODELING OF ALKANE EMISSIONS FROM A WOOD STAIN

    EPA Science Inventory

    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...

  8. Analysis of the vibrational bandwidths of alkane-urea clathrates

    NASA Astrophysics Data System (ADS)

    Wood, Kurt A.; Snyder, Robert G.; Strauss, Herbert L.

    1989-11-01

    The only large amplitude motion possible for an n-alkane molecule in urea-inclusion compounds is libration-torsion about the long axis of the chain. We present a quantitative model that incorporates the effect of this motion on the widths of the alkane vibrational bands. This model explains the difference in the widths of the different vibrations of the alkanes and their temperature dependence. Two effects are combined: (1) a modulation of the angles between the components of the polarizability in the space and the molecule-fixed frames for Raman spectra or between the components of the dipole moment for the infrared spectra, and (2) a modulation of the frequency of the alkane vibration via anharmonic coupling terms with the libration-torsion. The first effect gives rise to a distinctly non-Lorentzian band shape, which is convoluted with the approximately Lorentzian band of the second effect to produce the final result. The libration-torsional motion is modeled as that of a Brownian harmonic oscillator. Most of the parameters that enter the calculation are obtained from data other than that involving the bandwidths themselves. The libration-torsion relaxation time of about 1 ps obtained from fitting the observed bandwidths agrees with the value obtained from recent quasielastic neutron scattering experiments. Other bandwidth mechanisms that have been proposed are evaluated and it is shown that site hopping is too slow to account for the observations.

  9. Diverse alkane hydroxylase genes in microorganisms and environments

    PubMed Central

    Nie, Yong; Chi, Chang-Qiao; Fang, Hui; Liang, Jie-Liang; Lu, She-Lian; Lai, Guo-Li; Tang, Yue-Qin; Wu, Xiao-Lei

    2014-01-01

    AlkB and CYP153 are important alkane hydroxylases responsible for aerobic alkane degradation in bioremediation of oil-polluted environments and microbial enhanced oil recovery. Since their distribution in nature is not clear, we made the investigation among thus-far sequenced 3,979 microbial genomes and 137 metagenomes from terrestrial, freshwater, and marine environments. Hundreds of diverse alkB and CYP153 genes including many novel ones were found in bacterial genomes, whereas none were found in archaeal genomes. Moreover, these genes were detected with different distributional patterns in the terrestrial, freshwater, and marine metagenomes. Hints for horizontal gene transfer, gene duplication, and gene fusion were found, which together are likely responsible for diversifying the alkB and CYP153 genes adapt to the ubiquitous distribution of different alkanes in nature. In addition, different distributions of these genes between bacterial genomes and metagenomes suggested the potentially important roles of unknown or less common alkane degraders in nature. PMID:24829093

  10. Roaming radical pathways for the decomposition of alkanes.

    SciTech Connect

    Harding, L. B.; Klippenstein, S. J.

    2010-01-01

    CASPT2 calculations predict the existence of roaming radical pathways for the decomposition of propane, n-butane, isobutane and neopentane. The roaming radical paths lead to the formation of an alkane and an alkene instead of the expected radical products. The predicted barriers for the roaming radical paths lie {approx}1 kcal/mol below the corresponding radical asymptotes.

  11. Improving alkane synthesis in Escherichia coli via metabolic engineering.

    PubMed

    Song, Xuejiao; Yu, Haiying; Zhu, Kun

    2016-01-01

    Concerns about energy security and global petroleum supply have made the production of renewable biofuels an industrial imperative. The ideal biofuels are n-alkanes in that they are chemically and structurally identical to the fossil fuels and can "drop in" to the transportation infrastructure. In this work, an Escherichia coli strain that produces n-alkanes was constructed by heterologous expression of acyl-acyl carrier protein (ACP) reductase (AAR) and aldehyde deformylating oxygenase (ADO) from Synechococcus elongatus PCC7942. The accumulation of alkanes ranged from 3.1 to 24.0 mg/L using different expressing strategies. Deletion of yqhD, an inherent aldehyde reductase in E. coli, or overexpression of fadR, an activator for fatty acid biosynthesis, exhibited a nearly twofold increase in alkane titers, respectively. Combining yqhD deletion and fadR overexpression resulted in a production titer of 255.6 mg/L in E. coli, and heptadecene was the most abundant product. PMID:26476644

  12. Cyano- and polycyanometalloporphyrins as catalysts for alkane oxidation

    DOEpatents

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

    1992-01-01

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

  13. Diffusion of squalene in n-alkanes and squalane.

    PubMed

    Kowert, Bruce A; Watson, Michael B; Dang, Nhan C

    2014-02-27

    Squalene, an intermediate in the biosynthesis of cholesterol, has a 24-carbon backbone with six methyl groups and six isolated double bonds. Capillary flow techniques have been used to determine its translational diffusion constant, D, at room temperature in squalane, n-C16, and three n-C8-squalane mixtures. The D values have a weaker dependence on viscosity, η, than predicted by the Stokes-Einstein relation, D = kBT/(6πηr). A fit to the modified relation, D/T = ASE/η(p), gives p = 0.820 ± 0.028; p = 1 for the Stokes-Einstein limit. The translational motion of squalene appears to be much like that of n-alkane solutes with comparable chain lengths; their D values show similar deviations from the Stokes-Einstein model. The n-alkane with the same carbon chain length as squalene, n-C24, has a near-equal p value of 0.844 ± 0.018 in n-alkane solvents. The values of the hydrodynamic radius, r, for n-C24, squalene, and other n-alkane solutes decrease as the viscosity increases and have a common dependence on the van der Waals volumes of the solute and solvent. The possibility of studying squalene in lipid droplets and membranes is discussed. PMID:24528091

  14. MODELING OF ALKANE EMISSIONS FROM A WOOD STAIN

    EPA Science Inventory

    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). he test house concentrations of three alkane species, nonane, decane, and undecane, were measured as a fun...

  15. A superoleophobic textile repellent towards impacting drops of alkanes

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

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

    1999-08-20

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

  17. Isolating the non-polar contributions to the intermolecular potential for water-alkane interactions

    NASA Astrophysics Data System (ADS)

    Ballal, Deepti; Venkataraman, Pradeep; Fouad, Wael A.; Cox, Kenneth R.; Chapman, Walter G.

    2014-08-01

    Intermolecular potential models for water and alkanes describe pure component properties fairly well, but fail to reproduce properties of water-alkane mixtures. Understanding interactions between water and non-polar molecules like alkanes is important not only for the hydrocarbon industry but has implications to biological processes as well. Although non-polar solutes in water have been widely studied, much less work has focused on water in non-polar solvents. In this study we calculate the solubility of water in different alkanes (methane to dodecane) at ambient conditions where the water content in alkanes is very low so that the non-polar water-alkane interactions determine solubility. Only the alkane-rich phase is simulated since the fugacity of water in the water rich phase is calculated from an accurate equation of state. Using the SPC/E model for water and TraPPE model for alkanes along with Lorentz-Berthelot mixing rules for the cross parameters produces a water solubility that is an order of magnitude lower than the experimental value. It is found that an effective water Lennard-Jones energy ɛW/k = 220 K is required to match the experimental water solubility in TraPPE alkanes. This number is much higher than used in most simulation water models (SPC/E—ɛW/k = 78.2 K). It is surprising that the interaction energy obtained here is also higher than the water-alkane interaction energy predicted by studies on solubility of alkanes in water. The reason for this high water-alkane interaction energy is not completely understood. Some factors that might contribute to the large interaction energy, such as polarizability of alkanes, octupole moment of methane, and clustering of water at low concentrations in alkanes, are examined. It is found that, though important, these factors do not completely explain the anomalously strong attraction between alkanes and water observed experimentally.

  18. Impacts of Conformational Geometries in Fluorinated Alkanes.

    PubMed

    Brandenburg, Tim; Golnak, Ronny; Nagasaka, Masanari; Atak, Kaan; Sreekantan Nair Lalithambika, Sreeju; Kosugi, Nobuhiro; Aziz, Emad F

    2016-01-01

    Research of blood substitute formulations and their base materials is of high scientific interest. Especially fluorinated microemulsions based on perfluorocarbons, with their interesting chemical properties, offer opportunities for applications in biomedicine and physical chemistry. In this work, carbon K-edge absorption spectra of liquid perfluoroalkanes and their parent hydrocarbons are presented and compared. Based on soft X-ray absorption, a comprehensive picture of the electronic structure is provided with the aid of time dependent density functional theory. We have observed that conformational geometries mainly influence the chemical and electronic interactions in the presented liquid materials, leading to a direct association of conformational geometries to the dissolving capacity of the presented perfluorocarbons with other solvents like water and possibly gases like oxygen. PMID:27527753

  19. Impacts of Conformational Geometries in Fluorinated Alkanes

    PubMed Central

    Brandenburg, Tim; Golnak, Ronny; Nagasaka, Masanari; Atak, Kaan; Sreekantan Nair Lalithambika, Sreeju; Kosugi, Nobuhiro; Aziz, Emad F.

    2016-01-01

    Research of blood substitute formulations and their base materials is of high scientific interest. Especially fluorinated microemulsions based on perfluorocarbons, with their interesting chemical properties, offer opportunities for applications in biomedicine and physical chemistry. In this work, carbon K-edge absorption spectra of liquid perfluoroalkanes and their parent hydrocarbons are presented and compared. Based on soft X-ray absorption, a comprehensive picture of the electronic structure is provided with the aid of time dependent density functional theory. We have observed that conformational geometries mainly influence the chemical and electronic interactions in the presented liquid materials, leading to a direct association of conformational geometries to the dissolving capacity of the presented perfluorocarbons with other solvents like water and possibly gases like oxygen. PMID:27527753

  20. Numerical and experimental studies of ethanol flames and autoignition theory for higher alkanes

    NASA Astrophysics Data System (ADS)

    Saxena, Priyank

    In order to enhance the fuel efficiency of an engine and to control pollutant formation, an improved understanding of the combustion chemistry of the fuels at a fundamental level is paramount. This knowledge can be gained by developing detailed reaction mechanisms of the fuels for various combustion processes and by studying combustion analytically employing reduced-chemistry descriptions. There is a need for small detailed reaction mechanisms for alkane and alcohol fuels with reduced uncertainties in their combustion chemistry that are computationally cheaper in multidimensional CFD calculations. Detailed mechanisms are the starting points in identifying reduced-chemistry descriptions of combustion processes to study problems analytically. This research includes numerical, experimental and analytical studies. The first part of the dissertation consists of numerical and experimental studies of ethanol flames. Although ethanol has gained popularity as a possible low-pollution source of renewable energy, significant uncertainties remain in its combustion chemistry. To begin to address ethanol combustion, first a relatively small detailed reaction mechanism, commonly known as the San Diego Mech, is developed for the combustion of hydrogen, carbon monoxide, formaldehyde, methane, methanol, ethane, ethylene, and acetylene, in air or oxygen-inert mixtures. This mechanism is tested for autoignition, premixed-flame burning velocities, and structures and extinction of diffusion flames and of partially premixed flames of many of these fuels. The reduction in uncertainties in the combustion chemistry can best be achieved by consistently updating a reaction mechanism with reaction rate data for the elementary steps based on newer studies in literature and by testing it against as many experimental conditions as available. The results of such a testing for abovementioned fuels are reported here along with the modifications of reaction-rate parameters of the most important

  1. [Carbon isotopic compositions of n-alkanes and n-alkanoic acids in the smoke from combustion of rice straw].

    PubMed

    Liu, Gang; Sun, Li-Na; Li, Jiu-Hai; Xu, Hui

    2012-12-01

    In order to investigate the carbon isotopic fractionation in n-alkanes and n-alkanoic acids in smoke from rice straw combustion, six types of rice straw were burned in laboratory under flaming and smoldering conditions, and the compound specific isotopic compositions for the two classes of biomarkers in the smoke were determined. The results showed that the delta13C values of individual n-alkanes and n-alkanoic acids released from flaming burns of all the rice species ranged from -28.6 per thousand to -38.8 per thousand and from -29.6 per thousand to -41.9per thousand, respectively, and that the mean delta13C values for the two compound classes in the flaming smoke for the six types of rice straw were in the range of -32.6 per thousand to -36. 4per thousand and -34.0 per thousand to -36.2 per thousand, respectively. Moreover, the n-alkanes in the smoke from the most straws were more depleted in 13C in general than the identical substances with equal carbon number in corresponding unburned biomass. The magnitude of the isotopic discrimination (delta) was up to 4.1per thousand. Conversely, the n-alkanoic acids in the smoke tended to be more enriched in 13C than the corresponding biomarkers in the unburned straw for all of the species, and the delta was up to 6.3 per thousand. The delta13C values of the individual n-alkanes and n-alkanoic acids in the smoke from smoldering burns of the six species varied between -31.7 per thousand and -39.0 per thousand and between -31.3 per thousand and -38.8 per thousand, respectively. The average values for the two compound classes in the smoke for a species were in the range of -35.1 per thousand to -36.4 per thousand and -34.4 per thousand to -35.6 per thousand, respectively. The compound specific delta13C values of the n-alkanes in the smoke for most species were smaller than those of the same substances in the corresponding rice straw, and the greatest delta was 6.1 per thousand. However, the delta13C values of n-alkanoic acids

  2. Recent Advances in Catalytic Conversion of Ethanol to Chemicals

    SciTech Connect

    Sun, Junming; Wang, Yong

    2014-04-30

    With increased availability and decreased cost, ethanol is potentially a promising platform molecule for the production of a variety of value-added chemicals. In this review, we provide a detailed summary of recent advances in catalytic conversion of ethanol to a wide range of chemicals and fuels. We particularly focus on catalyst advances and fundamental understanding of reaction mechanisms involved in ethanol steam reforming (ESR) to produce hydrogen, ethanol conversion to hydrocarbons ranging from light olefins to longer chain alkenes/alkanes and aromatics, and ethanol conversion to other oxygenates including 1-butanol, acetaldehyde, acetone, diethyl ether, and ethyl acetate.

  3. Hydrogen isotope composition of leaf wax n-alkanes in glaucous and non-glaucous varieties of wheat (Triticum spp.)

    NASA Astrophysics Data System (ADS)

    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, <2 per mil) and leaf (<1 per mil) water 2H/1H. Conversely, there was 15-20 and 10-15 per mil 2H-depletion in the C29 and C31 n-alkanes, respectively, from the non-glaucous phenotype. This 2H-depletion in the non-glaucous phenotype demonstrated that the suppression of diketone production and the increase in n-alkane and primary alcohol concentrations are linked with a shift in the 2H/1H composition of n-alkanes. The initial results of this work suggest that plants using the same environmental water

  4. The vibrational spectrum of water in liquid alkanes.

    PubMed Central

    Conrad, M P; Strauss, H L

    1985-01-01

    The water wire hypothesis of hydrogen-ion transport in lipid bilayers has prompted a search for water aggregates in bulk hydrocarbons. The asymmetric stretching vibration of the water dissolved in n-decane and in a number of other alkanes and alkenes has been observed. The water band in the alkanes is very wide and fits to the results of a J-diffusion calculation for the water rotation. This implies that the water is freely rotating between collisions with the solvent and certainly not hydrogen bonded to anything. The existence of water aggregates is thus most unlikely. In contrast, water in an alkene is hydrogen bonded to the solvent molecules (although not to other water molecules) and shows an entirely different spectrum. PMID:4016205

  5. Site isolation in vanadium phosphorus oxide alkane oxidation

    SciTech Connect

    Thompson, M R; Ebner, J R

    1991-06-01

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

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

    PubMed

    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

  7. Adsorption of n-alkane vapours at the water surface.

    PubMed

    Biscay, Frédéric; Ghoufi, Aziz; Malfreyt, Patrice

    2011-06-21

    Monte Carlo simulations are reported here to predict the surface tension of the liquid-vapour interface of water upon adsorption of alkane vapours (methane to hexane). A decrease of the surface tension has been established from n-pentane. A correlation has been evidenced between the decrease of the surface tension and the absence of specific arrangement at the water surface for n-pentane and n-hexane. The thermodynamic stability of the adsorption layer and the absence of film for longer alkanes have been checked through the calculation of a potential of mean force. This complements the work recently published [Ghoufi et al., Phys. Chem. Chem. Phys., 2010, 12, 5203] concerning the adsorption of methane at the water surface. The decrease of the surface tension has been interpreted in terms of the degree of hydrogen bonding of water molecules at the liquid-vapour interface upon adsorption. PMID:21584320

  8. Alkane Biosynthesis Genes in Cyanobacteria and Their Transcriptional Organization

    PubMed Central

    Klähn, Stephan; Baumgartner, Desirée; Pfreundt, Ulrike; Voigt, Karsten; Schön, Verena; Steglich, Claudia; Hess, Wolfgang R.

    2014-01-01

    In cyanobacteria, alkanes are synthesized from a fatty acyl-ACP by two enzymes, acyl–acyl carrier protein reductase and aldehyde deformylating oxygenase. 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), which 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 cyanobacteria. PMID

  9. Hydroxylation of alkanes using sodium hypochlorite catalyzed by iron porphyrins

    SciTech Connect

    Sorokin, A.B.; Khenkin, A.M.

    1988-10-01

    This communication presents data about the oxidation of alkanes to alcohols with hypochlorite in the presence of Fe(III) phenylporphyrin derivatives in the system water-benzene. We used as catalysts the following compounds: tetraphenylporphyrin iron chloride, tetramesitylporphyrin iron chloride, tetra(2-fluorophenyl)porphyrin from chloride, and tetra (2-ntrophenyl)porphyrin iron chloride. The reaction products were analyzed by gas-liquid chromatography. The efficiency of the reaction was determined by the structure of the porphyrin used.

  10. Nanoscale Trapping and Squeeze-Out of Confined Alkane Monolayers.

    PubMed

    Gosvami, N N; O'Shea, S J

    2015-12-01

    We present combined force curve and conduction atomic force microscopy (AFM) data for the linear alkanes CnH2n+2 (n = 10, 12, 14, 16) confined between a gold-coated AFM tip and a graphite surface. Solvation layering is observed in the force curves for all liquids, and conduction AFM is used to study in detail the removal of the confined (mono)layer closest to the graphite surface. The squeeze-out behavior of the monolayer can be very different depending upon the temperature. Below the monolayer melting transition temperatures the molecules are in an ordered state on the graphite surface, and fast and complete removal of the confined molecules is observed. However, above the melting transition temperature the molecules are in a disordered state, and even at large applied pressure a few liquid molecules are trapped within the tip-sample contact zone. These findings are similar to a previous study for branched alkanes [ Gosvami Phys. Rev. Lett. 2008, 100, 076101 ], but the observation for the linear alkane homologue series demonstrates clearly the dependence of the squeeze-out and trapping on the state of the confined material. PMID:26529283

  11. Dielectric constant of liquid alkanes and hydrocarbon mixtures

    NASA Technical Reports Server (NTRS)

    Sen, A. D.; Anicich, V. G.; Arakelian, T.

    1992-01-01

    The complex dielectric constants of n-alkanes with two to seven carbon atoms have been measured. The measurements were conducted using a slotted-line technique at 1.2 GHz and at atmospheric pressure. The temperature was varied from the melting point to the boiling point of the respective alkanes. The real part of the dielectric constant was found to decrease with increasing temperature and correlate with the change in the molar volume. An upper limit to all the loss tangents was established at 0.001. The complex dielectric constants of a few mixtures of liquid alkanes were also measured at room temperature. For a pentane-octane mixture the real part of the dielectric constant could be explained by the Clausius-Mosotti theory. For the mixtures of n-hexane-ethylacetate and n-hexane-acetone the real part of the dielectric constants could be explained by the Onsager theory extended to mixtures. The dielectric constant of the n-hexane-acetone mixture displayed deviations from the Onsager theory at the highest fractions of acetone. The dipole moments of ethylacetate and acetone were determined for dilute mixtures using the Onsager theory and were found to be in agreement with their accepted gas-phase values. The loss tangents of the mixtures exhibited a linear relationship with the volume fraction for low concentrations of the polar liquids.

  12. Alkane production from biomass: chemo-, bio- and integrated catalytic approaches.

    PubMed

    Deneyer, Aron; Renders, Tom; Van Aelst, Joost; Van den Bosch, Sander; Gabriëls, Dries; Sels, Bert F

    2015-12-01

    Linear, branched and cyclic alkanes are important intermediates and end products of the chemical industry and are nowadays mainly obtained from fossil resources. In search for alternatives, biomass feedstocks are often presented as a renewable carbon source for the production of fuels, chemicals and materials. However, providing a complete market for all these applications seems unrealistic due to both financial and logistic issues. Despite the very large scale of current alkane-based fuel applications, biomass definitely has the potential to offer a partial solution to the fuel business. For the smaller market of chemicals and materials, a transition to biomass as main carbon source is more realistic and even probably unavoidable in the long term. The appropriate use and further development of integrated chemo- and biotechnological (catalytic) process strategies will be crucial to successfully accomplish this petro-to-bio feedstock transition. Furthermore, a selection of the most promising technologies from the available chemo- and biocatalytic tool box is presented. New opportunities will certainly arise when multidisciplinary approaches are further explored in the future. In an attempt to select the most appropriate biomass sources for each specific alkane-based application, a diagram inspired by van Krevelen is applied, taking into account both the C-number and the relative functionality of the product molecules. PMID:26360875

  13. Biochemical studies on the metabolic activation of halogenated alkanes.

    PubMed Central

    Cheeseman, K H; Albano, E F; Tomasi, A; Slater, T F

    1985-01-01

    This paper reviews recent investigations by Slater and colleagues into the metabolic activation of halogenated alkanes in general and carbon tetrachloride in particular. It is becoming increasingly accepted that free radical intermediates are involved in the toxicity of many such compounds through mechanisms including lipid peroxidation, covalent binding, and cofactor depletion. Here we describe the experimental approaches that are used to establish that halogenated alkanes are metabolized in animal tissues to reactive free radicals. Electron spin resonance spectroscopy is used to identify free-radical products, often using spin-trapping compounds. The generation of specific free radicals by radiolytic methods is useful in the determination of the precise reactivity of radical intermediates postulated to be injurious to the cell. The enzymic mechanism of the production of such free radicals and their subsequent reactions with biological molecules is studied with specific metabolic inhibitors and free-radical scavengers. These combined techniques provide considerable insight into the process of metabolic activation of halogenated compounds. It is readily apparent, for instance, that the local oxygen concentration at the site of activation is of crucial importance to the subsequent reactions; the formation of peroxy radical derivatives from the primary free-radical product is shown to be of great significance in relation to carbon tetrachloride and may be of general importance. However, while these studies have provided much information on the biochemical mechanisms of halogenated alkane toxicity, it is clear that many problems remain to be solved. PMID:3007102

  14. Energy conversion and storage program

    NASA Astrophysics Data System (ADS)

    1990-12-01

    The Energy Conversion and Storage Program applies chemical and chemical engineering principles to solve problems in (1) production of new synthetic fuels; (2) development of high-performance rechargeable batteries and fuel cells; (3) development of advanced thermochemical processes for energy storage; (4) characterization of complex chemical processes; and (5) the application of novel materials for energy conversion and transmission. Projects focus on transport-process principles, chemical kinetics, thermodynamics, separation processes, organic and physical chemistry, and advanced methods of analysis. The following five areas are discussed: electrochemical energy storage and conversion; microstructured materials; biotechnology; fossil fuels; and high temperature superconducting processing. Papers have been processed separately for inclusion on the data base.

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

    DOE PAGESBeta

    Wang, Zhandong; Zhang, Lidong; Moshammer, Kai; Popolan-Vaida, Denisia M.; Shankar, Vijai Shankar Bhavani; Lucassen, Arnas; Hemken, Christian; Taatjes, Craig A.; Leone, Stephen R.; Kohse-Hoinghaus, Katharina; et al

    2015-12-31

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

  16. Chemistry Notes

    ERIC Educational Resources Information Center

    School Science Review, 1972

    1972-01-01

    Thirteen ideas are presented that may be of use to chemistry teachers. Topics covered include vitamin C, industrial chemistry, electrical conductivity, electrolysis, alkali metals, vibration modes infra-red, dynamic equilibrium, and some new demonstrations in gaseous combinations. (PS)

  17. Chemistry Notes

    ERIC Educational Resources Information Center

    School Science Review, 1976

    1976-01-01

    Described are eight chemistry experiments and demonstrations applicable to introductory chemistry courses. Activities include: measure of lattice enthalpy, Le Chatelier's principle, decarboxylation of soap, use of pocket calculators in pH measurement, and making nylon. (SL)

  18. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1983

    1983-01-01

    Presents background information, laboratory procedures, classroom materials/activities, and chemistry experiments. Topics include sublimation, electronegativity, electrolysis, experimental aspects of strontianite, halide test, evaluation of present and future computer programs in chemistry, formula building, care of glass/saturated calomel…

  19. ENVIRONMENTAL CHEMISTRY

    EPA Science Inventory

    Environmental chemistry is applied to estimating the exposure of ecosystems and humans to various chemical environmental stressors. Among the stressors of concern are mercury, pesticides, and arsenic. Advanced analytical chemistry techniques are used to measure these stressors ...

  20. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1982

    1982-01-01

    Presents background information, laboratory procedures, classroom materials/activities, and experiments for chemistry. Topics include superheavy elements, polarizing power and chemistry of alkali metals, particulate carbon from combustion, tips for the chemistry laboratory, interesting/colorful experiments, behavior of bismuth (III) iodine, and…

  1. Modeling the role of alkanes, polycyclic aromatic hydrocarbons, and their oligomers in secondary organic aerosol formation.

    PubMed

    Pye, Havala O T; Pouliot, George A

    2012-06-01

    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 over the United States. Oxidation of alkanes is predicted to produce more aerosol than oxidation of PAHs driven by relatively higher alkane emissions. SOA from alkanes and PAHs, although small in magnitude, can be a substantial fraction of the SOA from anthropogenic hydrocarbons, particularly in winter, and could contribute more if emission inventories lack intermediate volatility alkanes (>C(13)) or if the vehicle fleet shifts toward diesel-powered vehicles. The SOA produced from oxidation of alkanes correlates well with ozone and odd oxygen in many locations, but the lower correlation of anthropogenic oligomers with odd oxygen indicates that models may need additional photochemically dependent pathways to low-volatility SOA. PMID:22568386

  2. Catalytic conversion of light alkanes - phase V. Topical report, February 1993--October 1994

    SciTech Connect

    1998-12-31

    We have made excellent progress toward a practical route from field butanes to MTBE, the oxygenate of choice for high-octane, clean-burning, environmentally acceptable reformulated gasoline. We have evaluated two proprietary process possibilities with a potential commercial partner and have conducted a joint catalyst evaluation program. The first of the two potential processes considered during the past quarter utilizes a two-step route from isobutane to tert-butyl alcohol, TBA. Not only is TBA an intermediate for MTBE production but is equally applicable for ETBE-an oxygenate which utilizes renewable ethanol in its` manufacture. In the two-step process, isobutane is oxidized in a non-catalytic reaction to a roughly equal mixture of TBA and tert-butyl hydroperoxide. TBHP, eq. 1. We have developed an inexpensive new catalyst system based on an electron-deficient macrocyclic metal complex that selectively converts TBHP to TBA, eq. 2, and meets or exceeds all of the process criteria that we have set.

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

    PubMed

    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

  4. Synthesis of chiral 2-alkanols from n-alkanes by a P. putida whole-cell biocatalyst.

    PubMed

    Tieves, Florian; Erenburg, Isabelle N; Mahmoud, Osama; Urlacher, Vlada B

    2016-09-01

    The cytochrome P450 monooxygenase CYP154A8 from Nocardia farcinica was previously found to catalyze hydroxylation of linear alkanes (C7 -C9 ) with a high regio- and stereoselectivity. The objective of this study was to integrate CYP154A8 along with suitable redox partners into a whole-cell system for the production of chiral 2-alkanols starting from alkanes. Both recombinant Escherichia coli and Pseudomonas putida whole-cell biocatalysts tested for this purpose showed the ability to produce chiral alkanols, but a solvent tolerant P. putida strain demonstrated several advantages in the applied biphasic reaction system. The optimized P. putida whole-cell system produced ∼16 mM (S)-2-octanol with 87% ee from octane, which is more than sevenfold higher than the previously described system with isolated enzymes. The achieved enantiopurity of the product could further be increased up to 99% ee by adding an alcohol dehydrogenase (ADH) to the alkane-oxidizing P. putida whole-cell systems. By using this setup for the individual conversions of heptane, octane or nonane, 2.6 mM (S)-2-heptanol with 91% ee, 5.4 mM (S)-2-octanol with 97% ee, or 5.5 mM (S)-2-nonanol with 97% ee were produced, respectively. The achieved concentrations of chiral 2-alkanols are the highest reported for a P450-based whole-cell system so far. Biotechnol. Bioeng. 2016;113: 1845-1852. © 2016 Wiley Periodicals, Inc. PMID:26887569

  5. Reaction chemistry of cerium

    SciTech Connect

    1997-01-01

    It is truly ironic that a synthetic organic chemist likely has far greater knowledge of the reaction chemistry of cerium(IV) than an inorganic colleague. Cerium(IV) reagents have long since been employed as oxidants in effecting a wide variety of organic transformations. Conversely, prior to the late 1980s, the number of well characterized cerium(IV) complexes did not extend past a handful of known species. Though in many other areas, interest in the molecular chemistry of the 4f-elements has undergone an explosive growth over the last twenty years, the chemistry of cerium(IV) has for the most part been overlooked. This report describes reactions of cerium complexes and structure.

  6. Fundamental Flame Velocities of Pure Hydrocarbons I : Alkanes, Alkenes, Alkynes Benzene, and Cyclohexane

    NASA Technical Reports Server (NTRS)

    Gerstein, Melvin; Levine, Oscar; Wong, Edgar L

    1950-01-01

    The flame velocities of 37 pure hydrocarbons including normal and branched alkanes, alkenes, and alkynes; as well as benzene and cyclohexane, together with the experimental technique employed are presented. The normal alkanes have about the same flame velocity from ethane through heptane with methane being about 16 percent lower. Unsaturation increases the flame velocity in the order of alkanes, alkenes, and alkynes. Branching reduces the flame velocity.

  7. Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

    DOEpatents

    Crabtree, Robert H.; Brown, Stephen H.

    1988-01-01

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

  8. Draft Genome Sequence of Gordonia sihwensis Strain 9, a Branched Alkane-Degrading Bacterium

    PubMed Central

    Brown, Lisa M.; Gunasekera, Thusitha S.; Striebich, Richard C.

    2016-01-01

    Gordonia sihwensis strain 9 is a Gram-positive bacterium capable of efficient aerobic degradation of branched and normal alkanes. The draft genome of G. sihwensis S9 is 4.16 Mb in size, with 3,686 coding sequences and 68.1% G+C content. Alkane monooxygenase and P-450 cytochrome genes required for alkane degradation are predicted in G. sihwensis S9. PMID:27340079

  9. Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

    DOEpatents

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

    1988-02-16

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

  10. CLUSTER CHEMISTRY

    SciTech Connect

    Muetterties, Earl L.

    1980-05-01

    Metal cluster chemistry is one of the most rapidly developing areas of inorganic and organometallic chemistry. Prior to 1960 only a few metal clusters were well characterized. However, shortly after the early development of boron cluster chemistry, the field of metal cluster chemistry began to grow at a very rapid rate and a structural and a qualitative theoretical understanding of clusters came quickly. Analyzed here is the chemistry and the general significance of clusters with particular emphasis on the cluster research within my group. The importance of coordinately unsaturated, very reactive metal clusters is the major subject of discussion.

  11. Forensic Chemistry

    NASA Astrophysics Data System (ADS)

    Bell, Suzanne

    2009-07-01

    Forensic chemistry is unique among chemical sciences in that its research, practice, and presentation must meet the needs of both the scientific and the legal communities. As such, forensic chemistry research is applied and derivative by nature and design, and it emphasizes metrology (the science of measurement) and validation. Forensic chemistry has moved away from its analytical roots and is incorporating a broader spectrum of chemical sciences. Existing forensic practices are being revisited as the purview of forensic chemistry extends outward from drug analysis and toxicology into such diverse areas as combustion chemistry, materials science, and pattern evidence.

  12. Hydrocarbons. Independent Learning Project for Advanced Chemistry (ILPAC). Unit O1.

    ERIC Educational Resources Information Center

    Inner London Education Authority (England).

    This unit on hydrocarbons is one of 10 first year units produced by the Independent Learning Project for Advanced Chemistry (ILPAC). The unit is divided into sections dealing with alkanes, alkenes, alkynes, arenes, and several aspects of the petroleum industry. Two experiments, exercises (with answers), and pre- and post-tests are included.…

  13. Digital biology and chemistry.

    PubMed

    Witters, Daan; Sun, Bing; Begolo, Stefano; Rodriguez-Manzano, Jesus; Robles, Whitney; Ismagilov, Rustem F

    2014-09-01

    This account examines developments in "digital" biology and chemistry within the context of microfluidics, from a personal perspective. Using microfluidics as a frame of reference, we identify two areas of research within digital biology and chemistry that are of special interest: (i) the study of systems that switch between discrete states in response to changes in chemical concentration of signals, and (ii) the study of single biological entities such as molecules or cells. In particular, microfluidics accelerates analysis of switching systems (i.e., those that exhibit a sharp change in output over a narrow range of input) by enabling monitoring of multiple reactions in parallel over a range of concentrations of signals. Conversely, such switching systems can be used to create new kinds of microfluidic detection systems that provide "analog-to-digital" signal conversion and logic. Microfluidic compartmentalization technologies for studying and isolating single entities can be used to reconstruct and understand cellular processes, study interactions between single biological entities, and examine the intrinsic heterogeneity of populations of molecules, cells, or organisms. Furthermore, compartmentalization of single cells or molecules in "digital" microfluidic experiments can induce switching in a range of reaction systems to enable sensitive detection of cells or biomolecules, such as with digital ELISA or digital PCR. This "digitizing" offers advantages in terms of robustness, assay design, and simplicity because quantitative information can be obtained with qualitative measurements. While digital formats have been shown to improve the robustness of existing chemistries, we anticipate that in the future they will enable new chemistries to be used for quantitative measurements, and that digital biology and chemistry will continue to provide further opportunities for measuring biomolecules, understanding natural systems more deeply, and advancing molecular and

  14. Molecular screening for alkane hydroxylase genes in Gram-negative and Gram-positive strains.

    PubMed

    Smits, T H; Röthlisberger, M; Witholt, B; van Beilen, J B

    1999-08-01

    We have developed highly degenerate oligonucleotides for polymerase chain reaction (PCR) amplification of genes related to the Pseudomonas oleovorans GPo1 and Acinetobacter sp. ADP1 alkane hydroxylases, based on a number of highly conserved sequence motifs. In all Gram-negative and in two out of three Gram-positive strains able to grow on medium- (C6-C11) or long-chain n-alkanes (C12-C16), PCR products of the expected size were obtained. The PCR fragments were cloned and sequenced and found to encode peptides with 43.2-93.8% sequence identity to the corresponding fragment of the P. oleovorans GPo1 alkane hydroxylase. Strains that were unable to grow on n-alkanes did not yield PCR products with homology to alkane hydroxylase genes. The alkane hydroxylase genes of Acinetobacter calcoaceticus EB104 and Pseudomonas putida P1 were cloned using the PCR products as probes. The two genes allow an alkane hydroxylase-negative mutant of Acinetobacter sp. ADP1 and an Escherichia coli recombinant containing all P. oleovorans alk genes except alkB, respectively, to grow on n-alkanes, showing that the cloned genes do indeed encode alkane hydroxylases. PMID:11207749

  15. Gas-Phase Reactions of Atomic Gold Cations with Linear Alkanes (C2-C9).

    PubMed

    Zhang, Ting; Li, Zi-Yu; Zhang, Mei-Qi; He, Sheng-Gui

    2016-06-30

    To develop proper ionization methods for alkanes, the reactivity of bare or ligated transition metal ions toward alkanes has attracted increasing interests. In this study, the reactions of the gold cations with linear alkanes from ethane up to nonane (CnH2n+2, n = 2-9) under mild conditions have been characterized by mass spectrometry and density functional theory calculations. When reacting with Au(+), small alkanes (n = 2-6) were confirmed to follow specific reaction channels of dehydrogenation for ethane and hydride transfer for others to generate product ions characteristic of the original alkanes, which indicates that Au(+) can act as a reagent ion to ionize alkanes from ethane to n-hexane. Strong dependence of the chain length of alkanes was observed for the rate constants and reaction efficiencies. Extensive fragmentation took place for larger alkanes (n > 6). Theoretical results show that the fragmentation induced by the hydride transfer occurs after the release of AuH. Moreover, the fragmentation of n-heptane was successfully avoided when the reaction took place in a high-pressure reactor. This implies that Au(+) is a potential reagent ion to ionize linear and even the branched alkanes. PMID:27266670

  16. Metric Conversion

    Atmospheric Science Data Center

    2013-03-12

    ... 1,000,000 1,000,000 micrometers nano- 1,000,000,000 1,000,000,000 nanometers ... conversions, see the National Institute of Standards and Technology (NIST) Special Publications: NIST Guide to SI Units: ...

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  18. Analysis of Pseudomonas putida alkane-degradation gene clusters and flanking insertion sequences: evolution and regulation of the alk genes.

    PubMed

    van Beilen, J B; Panke, S; Lucchini, S; Franchini, A G; Röthlisberger, M; Witholt, B

    2001-06-01

    The Pseudomonas putida GPo1 (commonly known as Pseudomonas oleovorans GPo1) alkBFGHJKL and alkST gene clusters, which encode proteins involved in the conversion of n-alkanes to fatty acids, are located end to end on the OCT plasmid, separated by 9.7 kb of DNA. This DNA segment encodes, amongst others, a methyl-accepting transducer protein (AlkN) that may be involved in chemotaxis to alkanes. In P. putida P1, the alkBFGHJKL and alkST gene clusters are flanked by almost identical copies of the insertion sequence ISPpu4, constituting a class 1 transposon. Other insertion sequences flank and interrupt the alk genes in both strains. Apart from the coding regions of the GPo1 and P1 alk genes (80-92% sequence identity), only the alkB and alkS promoter regions are conserved. Competition experiments suggest that highly conserved inverted repeats in the alkB and alkS promoter regions bind ALKS: PMID:11390693

  19. Optimization of H3O+/O2+ Dual-mode Ionization in PTR-MS for Simultaneous Detection of Alkanes, Olefins and Aromatic Compounds

    NASA Astrophysics Data System (ADS)

    Amador-Muñoz, O.; Misztal, P. K.; Weber, R.; Drozd, G.; Worton, D. R.; Goldstein, A. H.

    2014-12-01

    Measurements of VOC composition from fossil fuels are analytically challenging because of the complex mixture of hydrocarbons (saturated, unsaturated, aromatics, etc). Speciated chemical measurements typically rely on relatively slow GC separation. Proton transfer reaction mass spectrometry (PTR-MS) is advantageous due to its fast response and high sensitivity. The most common ionization mechanism applied to VOC detection by PTR-MS is proton transfer from hydronium ion (H3O+). However, alkanes cannot be detected using H3O+ ionization chemistry because their proton affinities are too low. Ionization of alkanes is possible via electron transfer and/or hydride abstraction using O2+ or NO+. We used PTR-MS to analyze aromatic, alkene and alkane (linear, branched and cyclic) compounds simultaneously not by switching the ionization agents, but by adjusting the drift tube voltage and optimizing the ratio of H3O+/O2+ produced in the instrument's ion source. The highest detection sensitivity for aromatic and alkene compounds was produced by proton transfer from H3O+, while hydride abstraction by O2+ allowed detection of alkanes. For alkanes, sensitivities ranged from 1.1±0.01 cps/ppbv for n-decane to 74.7±0.25 cps/ppbv for decalin. Sensitivities in O2+ mode were from 6 (Adamantane) to 146 (4-Methyl nonane) times higher than those obtained in H3O+ mode under the same ion source and drift tube voltage conditions. Sensitivities for butyl benzene and 1-decene were 157±0.57 and 66.8±0.21 cps/ppbv, respectively. Sensitivity differences among C10 hydrocarbons are related to their structure, which affects their ionization energies (IE) and hence ease of hydride abstraction. Sensitivities at the parent ion mass were inversely correlated with IE (142 cps/ppbv/eV). This suggests higher electronic stability for cyclic non substituted compounds, followed by cyclic substituted, branch linear and linear C10 hydrocarbons. Although selectivity is a known shortcoming of quadrupole

  20. Energy Conversion & Storage Program, 1993 annual report

    SciTech Connect

    Cairns, E.J.

    1994-06-01

    The Energy Conversion and Storage Program applies chemistry and materials science principles to solve problems in: production of new synthetic fuels; development of high-performance rechargeable batteries and fuel cells; development of high-efficiency thermochemical processes for energy conversion; characterization of complex chemical processes and chemical species; and the study and application of novel materials for energy conversion and transmission. Projects focus on transport-process principles, chemical kinetics, thermodynamics, chemical kinetics, thermodynamics, separation processes, organic and physical chemistry, novel materials, and advanced methods of analysis.

  1. Energy conversion & storage program. 1994 annual report

    SciTech Connect

    Cairns, E.J.

    1995-04-01

    The Energy Conversion and Storage Program investigates state-of-the-art electrochemistry, chemistry, and materials science technologies for: (1) development of high-performance rechargeable batteries and fuel cells; (2) development of high-efficiency thermochemical processes for energy conversion; (3) characterization of complex chemical processes and chemical species; (4) study and application of novel materials for energy conversion and transmission. Research projects focus on transport process principles, chemical kinetics, thermodynamics, separation processes, organic and physical chemistry, novel materials, and advanced methods of analysis.

  2. Developing Educational Specifications for Academic Chemistry Buildings.

    ERIC Educational Resources Information Center

    Chlad, Frank L.

    1985-01-01

    Provides information related to the design of chemistry classrooms and laboratories. Project cost estimates, space assignment by function, generation of space requirements, educational specifications, and space conversion formulas (considering net assignable square feet) are among the topics discussed. (JN)

  3. Preliminary assessment of halogenated alkanes as vapor-phase tracers

    SciTech Connect

    Adams, Michael C.; Moore, Joseph N.; Hirtz, Paul

    1991-01-01

    New tracers are needed to evaluate the efficiency of injection strategies in vapor-dominated environments. One group of compounds that seems to meet the requirements for vapor-phase tracing are the halogenated alkanes (HCFCs). HCFCs are generally nontoxic, and extrapolation of tabulated thermodynamic data indicate that they will be thermally stable and nonreactive in a geothermal environment. The solubilities and stabilities of these compounds, which form several homologous series, vary according to the substituent ratios of fluorine, chlorine, and hydrogen. Laboratory and field tests that will further define the suitability of HCFCs as vapor-phase tracers are under way.

  4. Transporter engineering for improved tolerance against alkane biofuels in Saccharomyces cerevisiae

    PubMed Central

    2013-01-01

    Background Hydrocarbon alkanes, components of major fossil fuels, are considered as next-generation biofuels because their biological production has recently been shown to be possible. However, high-yield alkane production requires robust host cells that are tolerant against alkanes, which exhibit cytotoxicity. In this study, we aimed to improve alkane tolerance in Saccharomyces cerevisiae, a key industrial microbial host, by harnessing heterologous transporters that potentially pump out alkanes. Results To this end, we attempted to exploit ABC transporters in Yarrowia lipolytica based on the observation that it utilizes alkanes as a carbon source. We confirmed the increased transcription of ABC2 and ABC3 transporters upon exposure to a range of alkanes in Y. lipolytica. We then showed that the heterologous expression of ABC2 and ABC3 transporters significantly increased tolerance against decane and undecane in S. cerevisiae through maintaining lower intracellular alkane level. In particular, ABC2 transporter increased the tolerance limit of S. cerevisiae about 80-fold against decane. Furthermore, through site-directed mutagenesis for glutamate (E988 for ABC2, and E989 for ABC3) and histidine (H1020 for ABC2, and H1021 for ABC3), we provided the evidence that glutamate was essential for the activity of ABC2 and ABC3 transporters, with ATP most likely to be hydrolyzed by a catalytic carboxylate mechanism. Conclusions Here, we demonstrated that transporter engineering through expression of heterologous efflux pumps led to significantly improved tolerance against alkane biofuels in S. cerevisiae. We believe that our results laid the groundwork for developing robust alkane-producing yeast cells through transporter engineering, which will greatly aid in next-generation alkane biofuel production and recovery. PMID:23402697

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  6. Assessment of the GECKO-A modeling tool using chamber observations for C12 alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; La, S.; Ouzebidour, F.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J. M.; Hodzic, A.; Madronich, S.; Yee, L. D.; Loza, C. L.; Craven, J. S.; Zhang, X.; Seinfeld, J.

    2013-12-01

    Secondary Organic Aerosol (SOA) production and ageing is the result of atmospheric oxidation processes leading to the progressive formation of organic species with higher oxidation state and lower volatility. Explicit chemical mechanisms reflect our understanding of these multigenerational oxidation steps. Major uncertainties remain concerning the processes leading to SOA formation and the development, assessment and improvement of such explicit schemes is therefore a key issue. The development of explicit mechanism to describe the oxidation of long chain hydrocarbons is however a challenge. Indeed, explicit oxidation schemes involve a large number of reactions and secondary organic species, far exceeding the size of chemical schemes that can be written manually. The chemical mechanism generator GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) is a computer program designed to overcome this difficulty. GECKO-A generates gas phase oxidation schemes according to a prescribed protocol assigning reaction pathways and kinetics data on the basis of experimental data and structure-activity relationships. In this study, we examine the ability of the generated schemes to explain SOA formation observed in the Caltech Environmental Chambers from various C12 alkane isomers and under high NOx and low NOx conditions. First results show that the model overestimates both the SOA yields and the O/C ratios. Various sensitivity tests are performed to explore processes that might be responsible for these disagreements.

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  8. Chemistry Notes

    ERIC Educational Resources Information Center

    School Science Review, 1972

    1972-01-01

    Twelve new chemistry expermiments are described. Broad areas covered include atomic structure, solubility, gaseous diffusion, endothermic reactions, alcohols, equilibrium, atomic volumes, and some improvised apparatus. (PS)

  9. Technetium chemistry

    SciTech Connect

    Burns, C.; Bryan, J.; Cotton, F.; Ott, K.; Kubas, G.; Haefner, S.; Barrera, J.; Hall, K.; Burrell, A.

    1996-04-01

    Technetium chemistry is a young and developing field. Despite the limited knowledge of its chemistry, technetium is the workhorse for nuclear medicine. Technetium is also a significant environmental concern because it is formed as a byproduct of nuclear weapons production and fission-power generators. Development of new technetium radio-pharmaceuticals and effective environmental control depends strongly upon knowledge of basic technetium chemistry. The authors performed research into the basic coordination and organometallic chemistry of technetium and used this knowledge to address nuclear medicine and environmental applications. This is the final report of a three-year Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL).

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

    PubMed

    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

  11. The Doctorate in Chemistry. Carnegie Essays on the Doctorate: Chemistry.

    ERIC Educational Resources Information Center

    Breslow, Ronald

    The Carnegie Foundation commissioned a collection of essays as part of the Carnegie Initiative on the Doctorate (CID). Essays and essayists represent six disciplines that are part of the CID: chemistry, education, English, history, mathematics, and neuroscience. Intended to engender conversation about the conceptual foundation of doctoral…

  12. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... hydrofluoro alkene. 721.4464 Section 721.4464 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  13. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... hydrofluoro alkene. 721.4464 Section 721.4464 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  14. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... hydrofluoro alkene. 721.4464 Section 721.4464 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  15. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... hydrofluoro alkene. 721.4464 Section 721.4464 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  16. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... hydrofluoro alkene. 721.4464 Section 721.4464 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... 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...

  17. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of alkane-diol...

  18. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkane-diol...

  19. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkane-diol...

  20. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of alkane-diol...

  1. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of alkane-diol...

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

    PubMed

    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. Multiple sources of alkanes in Quaternary oceanic sediment of Antarctica

    USGS Publications Warehouse

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

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

    PubMed Central

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

    2013-01-01

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

  6. To Form a Favorable Idea of Chemistry

    ERIC Educational Resources Information Center

    Heikkinen, Henry W.

    2010-01-01

    "To confess the truth, Mrs. B., I am not disposed to form a very favorable idea of chemistry, nor do I expect to derive much entertainment from it." That 200-year-old statement by Caroline to Mrs. Bryan, her teacher, appeared on the first page of Jane Marcet's pioneering secondary school textbook, "Conversations on Chemistry". It was published 17…

  7. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1981

    1981-01-01

    Outlines laboratory procedures, demonstrations, teaching suggestions, and content information related to chemistry. Topics include polarizing power; calorimetry and momentum; microcomputers in school chemistry; a constant-volume dispenser for liquids, floating magnets, and crystal lattices; preparation of chromium; and solvent polarity and…

  8. Conversation Classes.

    ERIC Educational Resources Information Center

    Xia, Jiang

    1998-01-01

    Describes an activity for use in the conversational English-as-a-foreign-language classroom. The activity involves having each student say one or two sentences that continues a story being made up as the activity goes along. Students were positive about the activity, because saying only one or two sentences helped them not to feel pressured or…

  9. Structure-property relationships of BaCeO perovskites for the oxidative dehydrogenation of alkanes

    SciTech Connect

    Nenoff, T.M.; Jackson, N.B.; Miller, J.E.; Sault, A.G.; Trudell, D.

    1997-12-01

    The oxidative dehydrogenation (ODH) reactions for the formation of two important organic feedstocks ethylene and propylene are of great interest because of the potential in capital and energy savings associated with these reactions. Theoretically, ODH can achieve high conversions of the starting materials (ethane and propane) at lower temperatures than conventional dehydrogenation reactions. The important focus in this study of ODH catalysts is the development of a structure-property relationship for catalyst with respect to selectivity, so as to avoid the more thermodynamically favorable combustion reaction. Catalysts for the ODH reaction generally consist of mixed metal oxides. Since for the most selective catalyst lattice oxygen is known to participate in the reaction, catalysts are sought with surface oxygen atoms that are labile enough to perform dehydrogenation, but not so plentiful or weakly bound as to promote complete combustion. Also, catalysts must be able to replenish surface oxygen by transport from the bulk. Perovskite materials are candidates to fulfill these requirements. The authors are studying BaCeO{sub 3} perovskites doped with elements such as Ca, Mg, and Sr. During the ODH of the alkanes at high temperatures, the perovskite structure is not retained and a mixture of carbonates and oxides is formed, as revealed by XRD. While the Ca doped materials showed enhanced total combustion activity below 600 C, they only showed enhanced alkene production at 700 C. Bulk structural and surface changes, as monitored by powder X-ray diffraction, and X-ray photoelectron spectroscopy are being correlated with activity in order to understand the factors affecting catalyst performance, and to modify catalyst formulations to improve conversion and selectivity.

  10. Energy Conversion and Storage Program

    NASA Astrophysics Data System (ADS)

    Cairns, E. J.

    1993-06-01

    This report is the 1992 annual progress report for the Energy Conversion and Storage Program, a part of the Energy and Environment Division of the Lawrence Berkeley Laboratory. Work described falls into three broad areas: electrochemistry; chemical applications; and materials applications. The Energy Conversion and Storage Program applies principles of chemistry and materials science to solve problems in several areas: (1) production of new synthetic fuels, (2) development of high-performance rechargeable batteries and fuel cells, (3) development of advanced thermochemical processes for energy conversion, (4) characterization of complex chemical processes and chemical species, and (5) study and application of novel materials for energy conversion and transmission. Projects focus on transport-process principles, chemical kinetics, thermodynamics, separation processes, organic and physical chemistry, novel materials, and advanced methods of analysis. Electrochemistry research aims to develop advanced power systems for electric vehicle and stationary energy storage applications. Chemical applications research includes topics such as separations, catalysis, fuels, and chemical analyses. Included in this program area are projects to develop improved, energy-efficient methods for processing product and waste streams from synfuel plants, coal gasifiers, and biomass conversion processes. Materials applications research includes evaluation of the properties of advanced materials, as well as development of novel preparation techniques. For example, techniques such as sputtering, laser ablation, and poised laser deposition are being used to produce high-temperature superconducting films.

  11. Introduction to Solar Photon Conversion

    SciTech Connect

    Nozik, Arthur J; Miller, John

    2010-11-10

    This Thematic Issue on Solar Photon Conversion will provide a review by leading researchers on the present status and prognosis of the science and technology of direct solar photoconversion to electricity and fuels. The topics covered include advanced and novel concepts for low-cost photovoltaic (PV) energy based on chemistry (dye-sensitized photoelectrodes, organic and molecular PV, multiple exciton generation in quantum dots, singlet fission), solar water splitting, redox catalysis for water oxidation and reduction, the role of nanoscience and nanocrystals in solar photoconversion, photoelectrochemical energy conversion, and photoinduced electron transfer.

  12. Copper-Catalyzed Intermolecular Amidation and Imidation of Unactivated Alkanes

    PubMed Central

    2015-01-01

    We report a set of rare copper-catalyzed reactions of alkanes with simple amides, sulfonamides, and imides (i.e., benzamides, tosylamides, carbamates, and phthalimide) to form the corresponding N-alkyl products. The reactions lead to functionalization at secondary C–H bonds over tertiary C–H bonds and even occur at primary C–H bonds. [(phen)Cu(phth)] (1-phth) and [(phen)Cu(phth)2] (1-phth2), which are potential intermediates in the reaction, have been isolated and fully characterized. The stoichiometric reactions of 1-phth and 1-phth2 with alkanes, alkyl radicals, and radical probes were investigated to elucidate the mechanism of the amidation. The catalytic and stoichiometric reactions require both copper and tBuOOtBu for the generation of N-alkyl product. Neither 1-phth nor 1-phth2 reacted with excess cyclohexane at 100 °C without tBuOOtBu. However, the reactions of 1-phth and 1-phth2 with tBuOOtBu afforded N-cyclohexylphthalimide (Cy-phth), N-methylphthalimide, and tert-butoxycyclohexane (Cy-OtBu) in approximate ratios of 70:20:30, respectively. Reactions with radical traps support the intermediacy of a tert-butoxy radical, which forms an alkyl radical intermediate. The intermediacy of an alkyl radical was evidenced by the catalytic reaction of cyclohexane with benzamide in the presence of CBr4, which formed exclusively bromocyclohexane. Furthermore, stoichiometric reactions of [(phen)Cu(phth)2] with tBuOOtBu and (Ph(Me)2CO)2 at 100 °C without cyclohexane afforded N-methylphthalimide (Me-phth) from β-Me scission of the alkoxy radicals to form a methyl radical. Separate reactions of cyclohexane and d12-cyclohexane with benzamide showed that the turnover-limiting step in the catalytic reaction is the C–H cleavage of cyclohexane by a tert-butoxy radical. These mechanistic data imply that the tert-butoxy radical reacts with the C–H bonds of alkanes, and the subsequent alkyl radical combines with 1-phth2 to form the corresponding N-alkyl imide product

  13. Circumstellar chemistry

    NASA Technical Reports Server (NTRS)

    Glassgold, Alfred E.; Huggins, Patrick J.

    1987-01-01

    The study of the outer envelopes of cool evolved stars has become an active area of research. The physical properties of CS envelopes are presented. Observations of many wavelengths bands are relevant. A summary of observations and a discussion of theoretical considerations concerning the chemistry are summarized. Recent theoretical considerations show that the thermal equilibrium model is of limited use for understanding the chemistry of the outer CS envelopes. The theoretical modeling of the chemistry of CS envelopes provides a quantitive test of chemical concepts which have a broader interest than the envelopes themselves.

  14. Multimetallic catalysed radical oxidative C(sp(3))-H/C(sp)-H cross-coupling between unactivated alkanes and terminal alkynes.

    PubMed

    Tang, Shan; Wang, Pan; Li, Haoran; Lei, Aiwen

    2016-01-01

    Radical involved transformations are now considered as extremely important processes in modern organic synthetic chemistry. According to the demand by atom-economic and sustainable chemistry, direct C(sp(3))-H functionalization through radical oxidative coupling represents an appealing strategy for C-C bond formations. However, the selectivity control of reactive radical intermediates is still a great challenge in these transformations. Here we show a selective radical oxidative C(sp(3))-H/C(sp)-H cross-coupling of unactivated alkanes with terminal alkynes by using a combined Cu/Ni/Ag catalytic system. It provides a new way to access substituted alkynes from readily available materials. Preliminary mechanistic studies suggest that this reaction proceeds through a radical process and the C(sp(3))-H bond cleavage is the rate-limiting step. This study may have significant implications for controlling selective C-C bond formation of reactive radical intermediates by using multimetallic catalytic systems. PMID:27339161

  15. Equilibrium thermophysical properties of alkanes at very high temperatures

    SciTech Connect

    Arunachalam, C.; Bozkurt, B.; Eubank, P.T.

    1996-01-01

    In order to perform calculations for thermal plasmas, sparks, and arcs, as in the thermal arc and electrical discharge machining (EDM) processes, thermophysical properties, such as the density, enthalpy, and heat capacity, of the original ambient dielectric liquid are required at very high temperatures and often pressures in the plasma state. A statistical model has been developed to provide these properties. At high temperatures, these hydrocarbons undergo a series of reactions to first dissociate and then to ionize to produce a plasma. The partition functions of each of the species generated are calculated and sued to determine the equilibrium mole fractions or particle fractions of each constituent of the resultant plasma. Only the hydrogen-to-carbon ratio matters so mixtures of alkanes can also be used. Specifically, tables of particles fractions, densities, enthalpies, and specific heat capacities are provided for methane and for hexadecane to 60,000 K and 10 kbar.

  16. Thermal analysis of n-alkane phase change material mixtures

    SciTech Connect

    Chio, Y.I.; Choi, E.; Lorsch, H.G.

    1991-03-31

    Tests were performed to characterize the thermal behavior of it number of n-alkanes to be used as phase change materials (PCMs) in district cooling applications. Hexadecane and tetradecane were mixed in different fractions, and their thermal behavior was experimentally evaluated. Test results for melting temperature and fusion energy for laboratory grade hexadecane and tetradecane showed good agreement with datain the literature. However, values for commercial grade hexadecane were found to be considerably lower. In the range of temperatures of interest for district cooling, mixtures of tetradecane and hexadecane can be treated as homogeneous substances. However, their heats of fusion are slightly lower than those of the pure substances. Their melting temperatures are also lower by an amount that can be predicted.

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

    SciTech Connect

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

    2015-12-31

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

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

    PubMed Central

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

    2003-01-01

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

  19. Conversational sensing

    NASA Astrophysics Data System (ADS)

    Preece, Alun; Gwilliams, Chris; Parizas, Christos; Pizzocaro, Diego; Bakdash, Jonathan Z.; Braines, Dave

    2014-05-01

    Recent developments in sensing technologies, mobile devices and context-aware user interfaces have made it pos- sible to represent information fusion and situational awareness for Intelligence, Surveillance and Reconnaissance (ISR) activities as a conversational process among actors at or near the tactical edges of a network. Motivated by use cases in the domain of Company Intelligence Support Team (CoIST) tasks, this paper presents an approach to information collection, fusion and sense-making based on the use of natural language (NL) and controlled nat- ural language (CNL) to support richer forms of human-machine interaction. The approach uses a conversational protocol to facilitate a ow of collaborative messages from NL to CNL and back again in support of interactions such as: turning eyewitness reports from human observers into actionable information (from both soldier and civilian sources); fusing information from humans and physical sensors (with associated quality metadata); and assisting human analysts to make the best use of available sensing assets in an area of interest (governed by man- agement and security policies). CNL is used as a common formal knowledge representation for both machine and human agents to support reasoning, semantic information fusion and generation of rationale for inferences, in ways that remain transparent to human users. Examples are provided of various alternative styles for user feedback, including NL, CNL and graphical feedback. A pilot experiment with human subjects shows that a prototype conversational agent is able to gather usable CNL information from untrained human subjects.

  20. Conversational sensemaking

    NASA Astrophysics Data System (ADS)

    Preece, Alun; Webberley, Will; Braines, Dave

    2015-05-01

    Recent advances in natural language question-answering systems and context-aware mobile apps create opportunities for improved sensemaking in a tactical setting. Users equipped with mobile devices act as both sensors (able to acquire information) and effectors (able to act in situ), operating alone or in collectives. The currently- dominant technical approaches follow either a pull model (e.g. Apple's Siri or IBM's Watson which respond to users' natural language queries) or a push model (e.g. Google's Now which sends notifications to a user based on their context). There is growing recognition that users need more flexible styles of conversational interaction, where they are able to freely ask or tell, be asked or told, seek explanations and clarifications. Ideally such conversations should involve a mix of human and machine agents, able to collaborate in collective sensemaking activities with as few barriers as possible. Desirable capabilities include adding new knowledge, collaboratively building models, invoking specific services, and drawing inferences. As a step towards this goal, we collect evidence from a number of recent pilot studies including natural experiments (e.g. situation awareness in the context of organised protests) and synthetic experiments (e.g. human and machine agents collaborating in information seeking and spot reporting). We identify some principles and areas of future research for "conversational sensemaking".

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

    PubMed

    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

  2. MIR and NIR group spectra of n-alkanes and 1-chloroalkanes

    NASA Astrophysics Data System (ADS)

    Kwaśniewicz, Michał; Czarnecki, Mirosław A.

    2015-05-01

    Numerous attempts were undertaken to resolve the absorption originating from different parts of alkanes. The separation of the contributions from the terminal and midchain methylene units was observed only in the spectra of solid alkanes at low temperatures. On the other hand, for liquid alkanes this effect was not reported as yet. In this study, ATR-IR, Raman and NIR spectra of eight n-alkanes and seven 1-chloroalkanes in the liquid phase were measured from 1000 to 12,000 cm-1. The spectra were analyzed by using two-dimensional (2D) correlation approach and chemometrics methods. It was shown that in 2D asynchronous contour plots, constructed from the spectra of n-alkanes and 1-chloroalkanes, the methylene band was resolved into two components. These two components were assigned to the terminal and midchain methylene groups. For the first time, the contributions from these two molecular fragments were resolved in the spectra of liquid n-alkanes and 1-chloroalkanes. MCR-ALS resolved these spectra into two components that were assigned to the ethyl and midchain methylene groups. These components represent the group spectra that can be used for assignment, spectral analysis and prediction of unknown spectra. The spectral prediction based on the group spectra provides very good results for n-alkanes, especially in the first and second overtone regions.

  3. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1980

    1980-01-01

    Describes equipment, activities, and experiments useful in chemistry instruction, including among others, a rapid method to determine available chlorine in bleach, simple flame testing apparatus, and a simple apparatus demonstrating the technique of flash photolysis. (SK)

  4. Chemistry Notes

    ERIC Educational Resources Information Center

    School Science Review, 1973

    1973-01-01

    Several ideas are proposed for chemistry teachers to try in their classrooms. Subjects included are polymerization of acrylate, polymerization of styrene, conductivity, pollution, preparation of chlorine, redox equations, chemiluminescence, and molecular sieves. (PS)

  5. Nuclear Chemistry.

    ERIC Educational Resources Information Center

    Chemical and Engineering News, 1979

    1979-01-01

    Provides a brief review of the latest developments in nuclear chemistry. Nuclear research today is directed toward increased activity in radiopharmaceuticals and formation of new isotopes by high-energy, heavy-ion collisions. (Author/BB)

  6. Catalytic Chemistry.

    ERIC Educational Resources Information Center

    Borer, Londa; And Others

    1996-01-01

    Describes an approach for making chemistry relevant to everyday life. Involves the study of kinetics using the decomposition of hydrogen peroxide by vegetable juices. Allows students to design and carry out experiments and then draw conclusions from their results. (JRH)

  7. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1981

    1981-01-01

    Describes 13 activities, experiments and demonstrations, including the preparation of iron (III) chloride, simple alpha-helix model, investigating camping gas, redox reactions of some organic compounds, a liquid crystal thermometer, and the oxidation number concept in organic chemistry. (JN)

  8. Precolumbian Chemistry.

    ERIC Educational Resources Information Center

    Robinson, Janet Bond

    1995-01-01

    Describes the content and development of a curriculum that provides an approach to descriptive chemistry and the history of technology through consideration of the pottery, metallurgy, pigments, dyes, agriculture, and medicine of pre-Columbian people. (DDR)

  9. Adsorption of alkanes on stoichiometric and oxygen-rich RuO2(110).

    PubMed

    Li, Tao; Kim, Minkyu; Rai, Rahul; Liang, Zhu; Asthagiri, Aravind; Weaver, Jason F

    2016-08-10

    We investigated the molecular adsorption of methane, ethane, propane and n-butane on stoichiometric and oxygen-rich RuO2(110) surfaces using temperature-programmed desorption (TPD) and dispersion-corrected density functional theory (DFT-D3) calculations. We find that each alkane adsorbs strongly on the coordinatively-unsaturated Ru (Rucus) atoms of s-RuO2(110), with desorption from this state producing a well-defined TPD peak at low alkane coverage. As the coverage increases, we find that alkanes first form a compressed layer on the Rucus atoms and subsequently adsorb on the bridging O atoms of the surface until the monolayer saturates. DFT-D3 calculations predict that methane preferentially adsorbs on top of a Rucus atom and that the C2 to C4 alkanes preferentially adopt bidentate configurations in which each molecule aligns parallel to the Rucus atom row and datively bonds to neighboring Rucus atoms. DFT-D3 predicts binding energies that agree quantitatively with our experimental estimates for alkane σ-complexes on RuO2(110). We find that oxygen atoms adsorbed on top of Rucus atoms (Oot atoms) stabilize the adsorbed alkane complexes that bind in a given configuration, while also blocking the sites needed for σ-complex formation. This site blocking causes the coverage of the most stable, bidentate alkane complexes to decrease sharply with increasing Oot coverage. Concurrently, we find that a new peak develops in the C2 to C4 alkane TPD spectra with increasing Oot coverage, and that the desorption yield in this TPD feature passes through a maximum at Oot coverages between ∼50% and 60%. We present evidence that the new TPD peak arises from C2 to C4 alkanes that adsorb in upright, monodentate configurations on stranded Rucus sites located within the Oot layer. PMID:27477390

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

    SciTech Connect

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

    1998-07-01

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

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Stratospheric chemistry

    SciTech Connect

    Brune, W.H. )

    1991-01-01

    Advances in stratospheric chemistry made by investigators in the United States from 1987 to 1990 are reviewed. Subject areas under consideration include photochemistry of the polar stratosphere, photochemistry of the global stratosphere, and assessments of inadvertent modification of the stratosphere by anthropogenic activity. Particular attention is given to early observations and theories, gas phase chemistry, Antarctic observations, Arctic observations, odd-oxygen, odd-hydrogen, odd-nitrogen, halogens, aerosols, modeling of stratospheric ozone, and reactive nitrogen effects.

  13. Characterization of cyclic and acyclic alkanes in Forties and Kuwait petroleum crudes

    SciTech Connect

    Jones, D.W. ); Pakdel, H. ); Bartle, K.D. )

    1990-01-01

    Alkane hydrocarbon fractions from Forties (North Sea) and Kuwait petroleum crudes, separated by distillation, solvent extraction and silicagel column chromatography and sub-fractionated by molecular-sieve adsorption, have been examined by gas chromatography (GC), {sup 1}H and {sup 13}C NMR spectroscopy, GC-mass spectrometry (MS) and field desorption (FD)MS. GC indicates that Forties contains rather more acyclic isoprenoids and cyclic alkanes than Kuwait; FDMS of Kuwait shows molecular-weight ranges for mono-, di-, tri-, tetra-, and pentacyclic alkanes. {sup 13}C NMR spectra provide evidence of higher aromatic carbon, C{sub A}, in Forties than Kuwait and longer T{sub 1} relaxation times.

  14. Adsorption and dissociation kinetics of alkanes on CaO(100)

    NASA Astrophysics Data System (ADS)

    Chakradhar, A.; Liu, Y.; Schmidt, J.; Kadossov, E.; Burghaus, U.

    2011-08-01

    The adsorption kinetics of ethane, butane, pentane, and hexane on CaO(100) have been studied by multi-mass thermal desorption (TDS) spectroscopy. The sample cleanliness was checked by Auger electron spectroscopy. A molecular and dissociative adsorption pathway was evident for the alkanes, except for ethane, which does not undergo bond activation. Two TDS peaks appeared when recording the parent mass, which are assigned to different adsorption sites/configurations of the molecularly adsorbed alkanes. Bond activation leads to desorption of hydrogen and several alkane fragments assigned to methane and ethylene formation. Only one TDS feature is seen in this case. Formation of carbon residuals was absent.

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

    DOEpatents

    Crabtree, Robert H.; Brown, Stephen H.

    1989-01-01

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

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

    DOEpatents

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

    1989-10-17

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

  17. Effect of n-alkanes on asphaltene structuring in petroleum oils.

    PubMed

    Stachowiak, Christian; Viguié, Jean-Romain; Grolier, Jean-Pierre E; Rogalski, Marek

    2005-05-24

    The interactions between asphaltenes and short- to medium-chain n-alkanes were studied using titration microcalorimetry and inverse chromatography. The exothermic heat effects observed upon mixing of asphaltenes and n-alkanes were interpreted in terms of assembling of the two types of compounds into mixed structures. We show that the energy of the interactions between n-alkanes and the asphaltene hydrocarbon chains is close to the energy of the interactions between the asphaltene chains. We propose that the latter interactions are responsible for the formation of the asphaltene aggregates and are the driving force of the aggregate assembly into higher structures. PMID:15896019

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

    PubMed Central

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

    2014-01-01

    A gram-negative aliphatic hydrocarbon-degrading bacterium SJTD-1 isolated from oil-contaminated soil was identified as Pseudomonas aeruginosa by comparative analyses of the 16S rRNA sequence, phenotype, and physiological features. SJTD-1 could efficiently mineralize medium- and long-chain n-alkanes (C12-C30) as its sole carbon source within seven days, showing the most optimal growth on n-hexadecane, followed by n-octadecane, and n-eicosane. In 36 h, 500 mg/L of tetradecane, hexadecane, and octadecane were transformed completely; and 2 g/L n-hexadecane was degraded to undetectable levels within 72 h. Two putative alkane-degrading genes (gene 3623 and gene 4712) were characterized and our results indicated that their gene products were rate-limiting enzymes involved in the synergetic catabolism of C12–C16 alkanes. On the basis of bioinformatics and transcriptional analysis, two P450 monooxygenases, along with a putative AlmA-like oxygenase, were examined. Genetically defective mutants lacking the characteristic alkane hydroxylase failed to degrade n-octadecane, thereby suggesting a different catalytic mechanism for the microbial transformation of alkanes with chain lengths over C18. PMID:25165808

  19. Energy Conversion and Storage Program

    SciTech Connect

    Cairns, E.J.

    1992-03-01

    The Energy Conversion and Storage Program applies chemistry and materials science principles to solve problems in (1) production of new synthetic fuels, (2) development of high-performance rechargeable batteries and fuel cells, (3) development of advanced thermochemical processes for energy conversion, (4) characterization of complex chemical processes, and (5) application of novel materials for energy conversion and transmission. Projects focus on transport-process principles, chemical kinetics, thermodynamics, separation processes, organic and physical chemistry, novel materials, and advanced methods of analysis. Electrochemistry research aims to develop advanced power systems for electric vehicle and stationary energy storage applications. Topics include identification of new electrochemical couples for advanced rechargeable batteries, improvements in battery and fuel-cell materials, and the establishment of engineering principles applicable to electrochemical energy storage and conversion. Chemical Applications research includes topics such as separations, catalysis, fuels, and chemical analyses. Included in this program area are projects to develop improved, energy-efficient methods for processing waste streams from synfuel plants and coal gasifiers. Other research projects seek to identify and characterize the constituents of liquid fuel-system streams and to devise energy-efficient means for their separation. Materials Applications research includes the evaluation of the properties of advanced materials, as well as the development of novel preparation techniques. For example, the use of advanced techniques, such as sputtering and laser ablation, are being used to produce high-temperature superconducting films.

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

    PubMed

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

    2015-08-13

    The oxidation of n-alkanes (C1-C7) has been studied with and without the effects of a nanosecond, non-equilibrium plasma discharge at 1 atm pressure from 420 to 1250 K. Experiments have been performed under nearly isothermal conditions in a flow reactor, where reactive mixtures are diluted in Ar to minimize temperature changes from chemical reactions. Sample extraction performed at the exit of the reactor captures product and intermediate species and stores them in a multi-position valve for subsequent identification and quantification using gas chromatography. By fixing the flow rate in the reactor and varying the temperature, reactivity maps for the oxidation of fuels are achieved. Considering all the fuels studied, fuel consumption under the effects of the plasma is shown to have been enhanced significantly, particularly for the low-temperature regime (T<800 K). In fact, multiple transitions in the rates of fuel consumption are observed depending on fuel with the emergence of a negative-temperature-coefficient regime. For all fuels, the temperature for the transition into the high-temperature chemistry is lowered as a consequence of the plasma being able to increase the rate of fuel consumption. Using a phenomenological interpretation of the intermediate species formed, it can be shown that the active particles produced from the plasma enhance alkyl radical formation at all temperatures and enable low-temperature chain branching for fuels C3 and greater. The significance of this result demonstrates that the plasma provides an opportunity for low-temperature chain branching to occur at reduced pressures, which is typically observed at elevated pressures in thermal induced systems. PMID:26170423

  1. Converse Piezoelectricity

    NASA Astrophysics Data System (ADS)

    Springborg, Michael; Kirtman, Bernard

    2013-03-01

    Piezoelectricity results from a coupling between responses to mechanical and electric perturbations and leads to changes in the polarization due to strain or stress or, alternatively, the occurrence of strain as a function of an applied external, electrostatic field (i.e., converse piezoelectricity). Theoretical studies of those properties for extended systems require accordingly that their dipole moment or polarization can be calculated. However, whereas the definition of the operator for the dipole moment for any finite system is trivial, it is only within the last 2 decades that the expressions for the equivalent operator in the independent-particle approximation for the infinite and periodic system have been presented. Here, we demonstrate that the so called branch dependence of the polarization for the infinite, periodic system is related to physical observables in contrast to what often is assumed. This is related to the finding that converse piezoelectric properties depend both on the surfaces of the samples of interest even for samples with size well above the thermodynamic limit. However, we shall demonstrate that these properties can be calculated without explicitly taking the surfaces into account. Both the foundations and results for real system shall be presented.

  2. A Discovery-Based Experiment Involving Rearrangement in the Conversion of Alcohols to Alkyl Halides: Permanent Magnet [to the thirteenth power]C NMR in the First-Semester Organic Chemistry Lab

    ERIC Educational Resources Information Center

    Kjonaas, Richard A.; Tucker, Ryand J. F.

    2008-01-01

    The use of permanent magnet [to the thirteenth power]C NMR in large-section first-semester organic chemistry lab courses is limited by the availability of experiments that not only hinge on first-semester lecture topics, but which also produce at least 0.5 mL of neat liquid sample. This article reports a discovery-based experiment that meets both…

  3. Radiation Chemistry

    NASA Astrophysics Data System (ADS)

    Wojnárovits, L.

    Ionizing radiation causes chemical changes in the molecules of the interacting medium. The initial molecules change to new molecules, resulting in changes of the physical, chemical, and eventually biological properties of the material. For instance, water decomposes to its elements H2 and O2. In polymers, degradation and crosslinking take place. In biopolymers, e.g., DNS strand breaks and other alterations occur. Such changes are to be avoided in some cases (radiation protection), however, in other cases they are used for technological purposes (radiation processing). This chapter introduces radiation chemistry by discussing the sources of ionizing radiation (radionuclide sources, machine sources), absorption of radiation energy, techniques used in radiation chemistry research, and methods of absorbed energy (absorbed dose) measurements. Radiation chemistry of different classes of inorganic (water and aqueous solutions, inorganic solids, ionic liquids (ILs)) and organic substances (hydrocarbons, halogenated compounds, polymers, and biomolecules) is discussed in concise form together with theoretical and experimental backgrounds. An essential part of the chapter is the introduction of radiation processing technologies in the fields of polymer chemistry, food processing, and sterilization. The application of radiation chemistry to nuclear technology and to protection of environment (flue gas treatment, wastewater treatment) is also discussed.

  4. STRUCTURE-REACTIVITY RELATIONSHIPS IN DEHYDROHALOGENATION REACTIONS OF POLYCHLORINATED AND POLYBROMINATED ALKANES

    EPA Science Inventory

    Current information is inadequate to predict the rates at which polyhalogenated alkanes undergo dehydrohalogenation rations under environmental conditions, forming olefins that are frequently more toxic and more recalcitrant than the products of substitution reactions. o permit e...

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

    EPA Science Inventory

    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 ...

  6. Draft Genome Sequence of the Versatile Alkane-Degrading Bacterium Aquabacterium sp. Strain NJ1

    PubMed Central

    Shiwa, Yuh; Yoshikawa, Hirofumi; Zylstra, Gerben J.

    2014-01-01

    The draft genome sequence of a soil bacterium, Aquabacterium sp. strain NJ1, capable of utilizing both liquid and solid alkanes, was deciphered. This is the first report of an Aquabacterium genome sequence. PMID:25477416

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

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES... mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  8. Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohydrates

    NASA Astrophysics Data System (ADS)

    Huber, George W.; Chheda, Juben N.; Barrett, Christopher J.; Dumesic, James A.

    2005-06-01

    Liquid alkanes with the number of carbon atoms ranging from C7 to C15 were selectively produced from biomass-derived carbohydrates by acid-catalyzed dehydration, which was followed by aldol condensation over solid base catalysts to form large organic compounds. These molecules were then converted into alkanes by dehydration/hydrogenation over bifunctional catalysts that contained acid and metal sites in a four-phase reactor, in which the aqueous organic reactant becomes more hydrophobic and a hexadecane alkane stream removes hydrophobic species from the catalyst before they go on further to form coke. These liquid alkanes are of the appropriate molecular weight to be used as transportation fuel components, and they contain 90% of the energy of the carbohydrate and H2 feeds.

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

    DOEpatents

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

    1998-06-23

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

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

    DOEpatents

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

    1998-01-01

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

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

    PubMed Central

    2014-01-01

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

  12. Regulation of the Alkane Hydroxylase CYP153 Gene in a Gram-Positive Alkane-Degrading Bacterium, Dietzia sp. Strain DQ12-45-1b

    PubMed Central

    Liang, Jie-Liang; JiangYang, Jing-Hong

    2015-01-01

    CYP153, one of the most common medium-chain n-alkane hydroxylases belonging to the cytochrome P450 superfamily, is widely expressed in n-alkane-degrading bacteria. CYP153 is also thought to cooperate with AlkB in degrading various n-alkanes. However, the mechanisms regulating the expression of the protein remain largely unknown. In this paper, we studied CYP153 gene transcription regulation by the potential AraC family regulator (CypR) located upstream of the CYP153 gene cluster in a broad-spectrum n-alkane-degrading Gram-positive bacterium, Dietzia sp. strain DQ12-45-1b. We first identified the transcriptional start site and the promoter of the CYP153 gene cluster. Sequence alignment of upstream regions of CYP153 gene clusters revealed high conservation in the −10 and −35 regions in Actinobacteria. Further analysis of the β-galactosidase activity in the CYP153 gene promoter-lacZ fusion cell indicated that the CYP153 gene promoter was induced by n-alkanes comprised of 8 to 14 carbon atoms, but not by derived decanol and decanic acid. Moreover, we constructed a cypR mutant strain and found that the CYP153 gene promoter activities and CYP153 gene transcriptional levels in the mutant strain were depressed compared with those in the wild-type strain in the presence of n-alkanes, suggesting that CypR served as an activator for the CYP153 gene promoter. By comparing CYP153 gene arrangements in Actinobacteria and Proteobacteria, we found that the AraC family regulator is ubiquitously located upstream of the CYP153 gene, suggesting its universal regulatory role in CYP153 gene transcription. We further hypothesize that the observed mode of CYP153 gene regulation is shared by many Actinobacteria. PMID:26567302

  13. Second NASA Conference on Laser Energy Conversion

    NASA Technical Reports Server (NTRS)

    Billman, K. W. (Editor)

    1976-01-01

    The possible transmission of high power laser beams over long distances and their conversion to thrust, electricity, or other useful forms of energy is considered. Specific topics discussed include: laser induced chemistry; developments in photovoltaics, including modification of the Schottky barrier devices and generation of high voltage emf'sby laser radiation of piezoelectric ceramics; the thermo electronic laser energy converter and the laser plasmadynamics converters; harmonic conversion of infrared laser radiation in molecular gases; and photon engines.

  14. The Number of High-Energy Bands in the Photoelectron Spectrum of Alkanes

    NASA Astrophysics Data System (ADS)

    Merris, Russell; Gutman, Ivan

    2000-12-01

    It was observed that within the Bieri-Dill-Heilbronner-Schmelzer model for the calculation of the ion-ization energies of alkanes CnH2n+2, there are exactly n C2s -electron energy levels lying below the degenerate α-ß manifold. We now show that, indeed, this regularity is obeyed by practically all alkane species. Exceptions do exist, but they must possess a (chemically infeasible) group of more than six mutually connected quaternary carbon atoms.

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

    NASA Astrophysics Data System (ADS)

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

    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 ion distribution and sensitivity is a function of drift conditions. At 80 Td the most abundant ion fragments from C10 to C16 n-alkanes were m/z 57, 71 and 85. The mass spectrum of gasoline and diesel fuel at 80 Td displayed ion group patterns that can be related to known fuel constituents, such as alkanes, alkylbenzenes and cycloalkanes, and other compound groups that are inferred from molecular weight distributions such as dihydronapthalenes and naphthenic monoaromatics. It is shown that thermal desorption sampling of gasoline and diesel engine exhausts at 80 Td allows for discrimination against volatile organic compounds, allowing for quantification of long chain alkanes from the abundance of CnH2n+1 fragment ions. The total abundance of long chain alkanes in diesel engine exhaust was measured to be similar to the total abundance of C1-C4 alkylbenzene compounds. The abundance patterns of compounds determined by thermal desorption sampling may allow for emission profiles to be developed to better quantify the relative contributions of diesel and gasoline exhaust emissions on organic compounds concentrations in urban air.

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

    PubMed Central

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

    2011-01-01

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

  17. Chemistry Experiments

    NASA Technical Reports Server (NTRS)

    Brasseur, Guy; Remsberg, Ellis; Purcell, Patrick; Bhatt, Praful; Sage, Karen H.; Brown, Donald E.; Scott, Courtney J.; Ko, Malcolm K. W.; Tie, Xue-Xi; Huang, Theresa

    1999-01-01

    The purpose of the chemistry component of the model comparison is to assess to what extent differences in the formulation of chemical processes explain the variance between model results. Observed concentrations of chemical compounds are used to estimate to what degree the various models represent realistic situations. For readability, the materials for the chemistry experiment are reported in three separate sections. This section discussed the data used to evaluate the models in their simulation of the source gases and the Nitrogen compounds (NO(y)) and Chlorine compounds (Cl(y)) species.

  18. Tropospheric chemistry

    NASA Technical Reports Server (NTRS)

    Mohnen, V. A.; Chameides, W.; Demerjian, K. L.; Lenschow, D. H.; Logan, J. A.; Mcneal, R. J.; Penkett, S. A.; Platt, U.; Schurath, U.; Dias, P. D.

    1985-01-01

    The chemistry of the background troposphere, the source region, and the transition regions are discussed. The troposphere is governed by heterogeneous chemistry far more so than the stratosphere. Heterogeneous processes of interest involve scavenging of trace gases by aerosols, cloud and precipitation elements leading to aqueous phase chemical reactions and to temporary and permanent removal of material from the gas phase. Dry deposition is a major removal process for ozone, as well as for other gases of importance in tropospheric photochemistry. These processes are also discussed.

  19. Polymer Chemistry

    NASA Technical Reports Server (NTRS)

    Williams, Martha; Roberson, Luke; Caraccio, Anne

    2010-01-01

    This viewgraph presentation describes new technologies in polymer and material chemistry that benefits NASA programs and missions. The topics include: 1) What are Polymers?; 2) History of Polymer Chemistry; 3) Composites/Materials Development at KSC; 4) Why Wiring; 5) Next Generation Wiring Materials; 6) Wire System Materials and Integration; 7) Self-Healing Wire Repair; 8) Smart Wiring Summary; 9) Fire and Polymers; 10) Aerogel Technology; 11) Aerogel Composites; 12) Aerogels for Oil Remediation; 13) KSC's Solution; 14) Chemochromic Hydrogen Sensors; 15) STS-130 and 131 Operations; 16) HyperPigment; 17) Antimicrobial Materials; 18) Conductive Inks Formulations for Multiple Applications; and 19) Testing and Processing Equipment.

  20. Energy conversion

    SciTech Connect

    Woodall, J.M.

    1982-02-16

    Energy conversion capable of receiving input energy in thermal or radiant form at a variable rate and releasing energy in thermal, radiant or electrical form independent of rate is accomplished by providing a buffer member of a material that has three criteria: a melting temperature above 1300/sup degree/ K, a thermal conductance greater than 0.1 in calories per square centimeter per centimeter per degree per second and a latent heat of fusion of the order of 1 kilocalorie per mole. The converter can absorb energy of multiple types, store it and then release it in a form compatible with the prospective use. Sunlight of daylight duration and varying intensity is converted to steady 24 hour a day electrical output.

  1. Marine hydrocarbonoclastic bacteria as whole-cell biosensors for n-alkanes

    PubMed Central

    Sevilla, Emma; Yuste, Luis; Rojo, Fernando

    2015-01-01

    Whole-cell biosensors offer potentially useful, cost-effective systems for the in-situ monitoring of seawater for hydrocarbons derived from accidental spills. The present work compares the performance of a biosensor system for the detection of alkanes in seawater, hosted in either Escherichia coli (commonly employed in whole-cell biosensors but not optimized for alkane assimilation) or different marine bacteria specialized in assimilating alkanes. The sensor system was based on the Pseudomonas putida AlkS regulatory protein and the PalkB promoter fused to a gene encoding the green fluorescent protein. While the E. coli sensor provided the fastest response to pure alkanes (25-fold induction after 2 h under the conditions used), a sensor based on Alcanivorax borkumensis was slower, requiring 3–4 h to reach similar induction values. However, the A. borkumensis sensor showed a fourfold lower detection threshold for octane (0.5 μM), and was also better at sensing the alkanes present in petrol. At petrol concentrations of 0.0125%, the A. borkumensis sensor rendered a sevenfold induction, while E. coli sensor showed no response. We discuss possible explanations to this behaviour in terms of the cellular adaptations to alkane uptake and the basal fluorescence produced by each bacterial strain, which was lowest for A. borkumensis. PMID:25874658

  2. Two distinct monooxygenases for alkane oxidation in Nocardioides sp. strain CF8.

    PubMed

    Hamamura, N; Yeager, C M; Arp, D J

    2001-11-01

    Alkane monooxygenases in Nocardioides sp. strain CF8 were examined at the physiological and genetic levels. Strain CF8 can utilize alkanes ranging in chain length from C(2) to C(16). Butane degradation by butane-grown cells was strongly inhibited by allylthiourea, a copper-selective chelator, while hexane-, octane-, and decane-grown cells showed detectable butane degradation activity in the presence of allylthiourea. Growth on butane and hexane was strongly inhibited by 1-hexyne, while 1-hexyne did not affect growth on octane or decane. A specific 30-kDa acetylene-binding polypeptide was observed for butane-, hexane-, octane-, and decane-grown cells but was absent from cells grown with octane or decane in the presence of 1-hexyne. These results suggest the presence of two monooxygenases in strain CF8. Degenerate primers designed for PCR amplification of genes related to the binuclear-iron-containing alkane hydroxylase from Pseudomonas oleovorans were used to clone a related gene from strain CF8. Reverse transcription-PCR and Northern blot analysis showed that this gene encoding a binuclear-iron-containing alkane hydroxylase was expressed in cells grown on alkanes above C(6). These results indicate the presence of two distinct monooxygenases for alkane oxidation in Nocardioides sp. strain CF8. PMID:11679317

  3. Alkanes in flower surface waxes of Momordica cochinchinensis influence attraction to Aulacophora foveicollis Lucas (Coleoptera: Chrysomelidae).

    PubMed

    Mukherjee, A; Sarkar, N; Barik, A

    2013-08-01

    Extraction, thin-layer chromatography, and gas chromatography-mass spectrophotometry analyses revealed 15 alkanes representing 97.14% of the total alkanes in the surface waxes of Momordica cochinchinensis Spreng flowers. Nonacosane was the prevailing alkane followed by hexatriacontane, nonadecane, heptacosane, and hentriacontane, accounting for 39.08%, 24.24%, 13.52%, 6.32%, and 5.12%, respectively. The alkanes from flower surface waxes followed by a synthetic mixture of alkanes mimicking alkanes of flower surface waxes elicited attraction of the female insect, Aulacophora foveicollis Lucas (Coleoptera: Chrysomelidae) between 2 and 10-μg/mL concentrations in a Y-shaped glass tube olfactometer bioassay under laboratory conditions. Synthetic nonadecane from 178.28-891.37 ng, heptacosane from 118.14-590.72 ng, and nonacosane at 784.73 ng showed attraction of the insect. A synthetic mixture of 534.82 ng nonadecane, 354.43 ng heptacosane, and 2,354.18 ng nonacosane elicited highest attraction of A. foveicollis. PMID:23949856

  4. Combustion Characteristics of Liquid Normal Alkane Fuels in a Model Combustor of Supersonic Combustion Ramjet Engine

    NASA Astrophysics Data System (ADS)

    今村, 宰; 石川, 雄太; 鈴木, 俊介; 福本, 皓士郎; 西田, 俊介; 氏家, 康成; 津江, 光洋

    Effect of kinds of one-component n-alkane liquid fuels on combustion characteristics was investigated experimentally using a model combustor of scramjet engine. The inlet condition of a model combustor is 2.0 of Mach number, up to 2400K of total temperature, and 0.38MPa of total pressure. Five kinds of n-alkane are tested, of which carbon numbers are 7, 8, 10, 13, and 16. They are more chemically active and less volatile with an increase of alkane carbon number. Fuels are injected to the combustor in the upstream of cavity with barbotage nitrogen gas and self-ignition performance was investigated. The result shows that self-ignition occurs with less equivalence ratio when alkane carbon number is smaller. This indicates that physical characteristic of fuel, namely volatile of fuel, is dominant for self-ignition behavior. Effect on flame-holding performance is also examined with adding pilot hydrogen and combustion is kept after cutting off pilot hydrogen with the least equivalence ratio where alkane carbon number is from 8 to 10. These points are discussed qualitatively from the conflict effect of chemical and physical properties on alkane carbon number.

  5. Chemistry Notes

    ERIC Educational Resources Information Center

    School Science Review, 1972

    1972-01-01

    Short articles on the kinetics of the hydrogen peroxide-iodide ion reaction, simulation of fluidization catalysis, the use of Newman projection diagrams to represent steric relationships in organic chemistry, the use of synthetic substrates for proteolytic enzyme reactions, and two simple clock reactions"--hydrolysis of halogenoalkanes and…

  6. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1983

    1983-01-01

    Presents chemistry experiments, laboratory procedures, demonstrations, teaching suggestions, and classroom materials/activities. These include: game for teaching ionic formulas; method for balancing equations; description of useful redox series; computer programs (with listings) for water electrolysis simulation and for determining chemical…

  7. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1978

    1978-01-01

    Describes some laboratory apparatus, chemistry experiments and demonstrations, such as a Kofler block melting point apparatus, chromatographic investigation of the phosphoric acid, x-ray diffraction, the fountain experiment, endothermic sherbet, the measurement of viscosity, ionization energies and electronic configurations. (GA)

  8. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1982

    1982-01-01

    Presents procedures, experiments, demonstrations, teaching suggestions, and information on a variety of chemistry topics including, for example, inert gases, light-induced reactions, calculators, identification of substituted acetophenones, the elements, analysis of copper minerals, extraction of metallic strontium, equilibrium, halogens, and…

  9. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1980

    1980-01-01

    Presents 12 chemistry notes for British secondary school teachers. Some of these notes are: (1) a simple device for testing pH-meters; (2) portable fume cupboard safety screen; and (3) Mass spectroscopy-analysis of a mass peak. (HM)

  10. Chemistry Notes

    ERIC Educational Resources Information Center

    School Science Review, 1976

    1976-01-01

    Describes several chemistry projects, including solubility, formula for magnesium oxide, dissociation of dinitrogen tetroxide, use of 1-chloro-2, 4-dinitrobenzene, migration of ions, heats of neutralizations, use of pocket calculators, sonic cleaning, oxidation states of manganese, and cell potentials. Includes an extract from Chemical Age on…

  11. Chemistry Notes.

    ERIC Educational Resources Information Center

    School Science Review, 1983

    1983-01-01

    Presents chemistry experiments, laboratory procedures, demonstrations, and classroom materials/activities. These include: experiments on colloids, processing of uranium ore, action of heat on carbonates; color test for phenols and aromatic amines; solvent properties of non-electrolytes; stereoscopic applications/methods; a valency balance;…

  12. Chemistry Notes

    ERIC Educational Resources Information Center

    School Science Review, 1972

    1972-01-01

    Short articles on the alkylation of aniline, the preparation and properties of perbromate, using scrap copper in chemistry instruction, a safe method of burning hydrogen, and the use of an ion-charge model as an alternative to the mole concept in secondary school instruction. (AL)

  13. Selective catalytic process for conversion of light naphtha to aromatics

    SciTech Connect

    Law, D.V.; Tamm, P.W.; Detz, C.M.

    1987-01-01

    AROMAX catalyst represents a unique advance in the development of modern reforming catalysts. The catalyst employs a zeolite to take advantage of a conversion chemistry that is entirely different from that of conventional reforming catalysts. This process chemistry, however, can still be carried out under process conditions which are essentially identical to those of conventional reforming. The result is the use of conventional designs and hardware to achieve highly efficient conversion of previously undesirable light feedstocks to high value aromatics.

  14. Surveys of research in the Chemistry Division, Argonne National Laboratory

    SciTech Connect

    Grazis, B.M.

    1992-01-01

    Research reports are presented on reactive intermediates in condensed phase (radiation chemistry, photochemistry), electron transfer and energy conversion, photosynthesis and solar energy conversion, metal cluster chemistry, chemical dynamics in gas phase, photoionization-photoelectrons, characterization and reactivity of coal and coal macerals, premium coal sample program, chemical separations, heavy elements coordination chemistry, heavy elements photophysics/photochemistry, f-electron interactions, radiation chemistry of high-level wastes (gas generation in waste tanks), ultrafast molecular electronic devices, and nuclear medicine. Separate abstracts have been prepared. Accelerator activites and computer system/network services are also reported.

  15. Surveys of research in the Chemistry Division, Argonne National Laboratory

    SciTech Connect

    Grazis, B.M.

    1992-11-01

    Research reports are presented on reactive intermediates in condensed phase (radiation chemistry, photochemistry), electron transfer and energy conversion, photosynthesis and solar energy conversion, metal cluster chemistry, chemical dynamics in gas phase, photoionization-photoelectrons, characterization and reactivity of coal and coal macerals, premium coal sample program, chemical separations, heavy elements coordination chemistry, heavy elements photophysics/photochemistry, f-electron interactions, radiation chemistry of high-level wastes (gas generation in waste tanks), ultrafast molecular electronic devices, and nuclear medicine. Separate abstracts have been prepared. Accelerator activites and computer system/network services are also reported.

  16. Berberine cation: A fluorescent chemosensor for alkanes and other low-polarity compounds. An explanation of this phenomenon

    PubMed

    Cossio; Arrieta; Cebolla; Membrado; Vela; Garriga; Domingo

    2000-07-27

    Alkanes in the presence of berberine sulfate provide an enhancement of fluorescent signal, which depends on alkane concentration and structure, when the system is irradiated with monochromatic UV light. Computational analysis suggests that an ion-induced dipole between alkanes and berberine sulfate is responsible for this phenomenon. This interaction can properly model the experimentally obtained fluorescent response. The proposed explanation allows other interacting systems to be designed, which have been experimentally confirmed. PMID:10930271

  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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  19. Anaerobic alkane biodegradation by cultures enriched from oil sands tailings ponds involves multiple species capable of fumarate addition.

    PubMed

    Tan, BoonFei; Semple, Kathleen; Foght, Julia

    2015-05-01

    A methanogenic short-chain alkane-degrading culture (SCADC) was enriched from oil sands tailings and transferred several times with a mixture of C6, C7, C8 and C10 n-alkanes as the predominant organic carbon source, plus 2-methylpentane, 3-methylpentane and methylcyclopentane as minor components. Cultures produced ∼40% of the maximum theoretical methane during 18 months incubation while depleting the n-alkanes, 2-methylpentane and methylcyclopentane. Substrate depletion correlated with detection of metabolites characteristic of fumarate activation of 2-methylpentane and methylcyclopentane, but not n-alkane metabolites. During active methanogenesis with the mixed alkanes, reverse-transcription PCR confirmed the expression of functional genes (assA and bssA) associated with hydrocarbon addition to fumarate. Pyrosequencing of 16S rRNA genes amplified during active alkane degradation revealed enrichment of Clostridia (particularly Peptococcaceae) and methanogenic Archaea (Methanosaetaceae and Methanomicrobiaceae). Methanogenic cultures transferred into medium containing sulphate produced sulphide, depleted n-alkanes and produced the corresponding succinylated alkane metabolites, but were slow to degrade 2-methylpentane and methylcyclopentane; these cultures were enriched in Deltaproteobacteria rather than Clostridia. 3-Methylpentane was not degraded by any cultures. Thus, nominally methanogenic oil sands tailings harbour dynamic and versatile hydrocarbon-degrading fermentative syntrophs and sulphate reducers capable of degrading n-, iso- and cyclo-alkanes by addition to fumarate. PMID:25873461

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

    PubMed

    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

  1. Computational chemistry

    NASA Technical Reports Server (NTRS)

    Arnold, J. O.

    1987-01-01

    With the advent of supercomputers, modern computational chemistry algorithms and codes, a powerful tool was created to help fill NASA's continuing need for information on the properties of matter in hostile or unusual environments. Computational resources provided under the National Aerodynamics Simulator (NAS) program were a cornerstone for recent advancements in this field. Properties of gases, materials, and their interactions can be determined from solutions of the governing equations. In the case of gases, for example, radiative transition probabilites per particle, bond-dissociation energies, and rates of simple chemical reactions can be determined computationally as reliably as from experiment. The data are proving to be quite valuable in providing inputs to real-gas flow simulation codes used to compute aerothermodynamic loads on NASA's aeroassist orbital transfer vehicles and a host of problems related to the National Aerospace Plane Program. Although more approximate, similar solutions can be obtained for ensembles of atoms simulating small particles of materials with and without the presence of gases. Computational chemistry has application in studying catalysis, properties of polymers, all of interest to various NASA missions, including those previously mentioned. In addition to discussing these applications of computational chemistry within NASA, the governing equations and the need for supercomputers for their solution is outlined.

  2. Leaf wax n-alkane distributions in and across modern plants: Implications for paleoecology and chemotaxonomy

    NASA Astrophysics Data System (ADS)

    Bush, Rosemary T.; McInerney, Francesca A.

    2013-09-01

    Long chain (C21 to C37) n-alkanes are among the most long-lived and widely utilized terrestrial plant biomarkers. Dozens of studies have examined the range and variation of n-alkane chain-length abundances in modern plants from around the world, and n-alkane distributions have been used for a variety of purposes in paleoclimatology and paleoecology as well as chemotaxonomy. However, most of the paleoecological applications of n-alkane distributions have been based on a narrow set of modern data that cannot address intra- and inter-plant variability. Here, we present the results of a study using trees from near Chicago, IL, USA, as well as a meta-analysis of published data on modern plant n-alkane distributions. First, we test the conformity of n-alkane distributions in mature leaves across the canopy of 38 individual plants from 24 species as well as across a single growing season and find no significant differences for either canopy position or time of leaf collection. Second, we compile 2093 observations from 86 sources, including the new data here, to examine the generalities of n-alkane parameters such as carbon preference index (CPI), average chain length (ACL), and chain-length ratios for different plant groups. We show that angiosperms generally produce more n-alkanes than do gymnosperms, supporting previous observations, and furthermore that CPI values show such variation in modern plants that it is prudent to discard the use of CPI as a quantitative indicator of n-alkane degradation in sediments. We also test the hypotheses that certain n-alkane chain lengths predominate in and therefore can be representative of particular plant groups, namely, C23 and C25 in Sphagnum mosses, C27 and C29 in woody plants, and C31 in graminoids (grasses). We find that chain-length distributions are highly variable within plant groups, such that chemotaxonomic distinctions between grasses and woody plants are difficult to make based on n-alkane abundances. In contrast

  3. Ubiquitous Presence and Novel Diversity of Anaerobic Alkane Degraders in Cold Marine Sediments

    PubMed Central

    Gittel, Antje; Donhauser, Johanna; Røy, Hans; Girguis, Peter R.; Jørgensen, Bo B.; Kjeldsen, Kasper U.

    2015-01-01

    Alkanes are major constituents of crude oil and are released to the marine environment by natural seepage and from anthropogenic sources. Due to their chemical inertness, their removal from anoxic marine sediments is primarily controlled by the activity of anaerobic alkane-degrading microorganisms. To facilitate comprehensive cultivation-independent surveys of the diversity and distribution of anaerobic alkane degraders, we designed novel PCR primers that cover all known diversity of the 1-methylalkyl succinate synthase gene (masD/assA), which catalyzes the initial activation of alkanes. We studied masD/assA gene diversity in pristine and seepage-impacted Danish coastal sediments, as well as in sediments and alkane-degrading enrichment cultures from the Middle Valley (MV) hydrothermal vent system in the Pacific Northwest. MasD/assA genes were ubiquitously present, and the primers captured the diversity of both known and previously undiscovered masD/assA gene diversity. Seepage sediments were dominated by a single masD/assA gene cluster, which is presumably indicative of a substrate-adapted community, while pristine sediments harbored a diverse range of masD/assA phylotypes including those present in seepage sediments. This rare biosphere of anaerobic alkane degraders will likely increase in abundance in the event of seepage or accidental oil spillage. Nanomolar concentrations of short-chain alkanes (SCA) were detected in pristine and seepage sediments. Interestingly, anaerobic alkane degraders closely related to strain BuS5, the only SCA degrader in pure culture, were found in mesophilic MV enrichments, but not in cold sediments from Danish waters. We propose that the new masD/assA gene lineages in these sediments represent novel phylotypes that are either fueled by naturally occurring low levels of SCA or that metabolize medium- to long-chain alkanes. Our study highlights that masD/assA genes are a relevant diagnostic marker to identify seepage and microseepage, e

  4. Ubiquitous Presence and Novel Diversity of Anaerobic Alkane Degraders in Cold Marine Sediments.

    PubMed

    Gittel, Antje; Donhauser, Johanna; Røy, Hans; Girguis, Peter R; Jørgensen, Bo B; Kjeldsen, Kasper U

    2015-01-01

    Alkanes are major constituents of crude oil and are released to the marine environment by natural seepage and from anthropogenic sources. Due to their chemical inertness, their removal from anoxic marine sediments is primarily controlled by the activity of anaerobic alkane-degrading microorganisms. To facilitate comprehensive cultivation-independent surveys of the diversity and distribution of anaerobic alkane degraders, we designed novel PCR primers that cover all known diversity of the 1-methylalkyl succinate synthase gene (masD/assA), which catalyzes the initial activation of alkanes. We studied masD/assA gene diversity in pristine and seepage-impacted Danish coastal sediments, as well as in sediments and alkane-degrading enrichment cultures from the Middle Valley (MV) hydrothermal vent system in the Pacific Northwest. MasD/assA genes were ubiquitously present, and the primers captured the diversity of both known and previously undiscovered masD/assA gene diversity. Seepage sediments were dominated by a single masD/assA gene cluster, which is presumably indicative of a substrate-adapted community, while pristine sediments harbored a diverse range of masD/assA phylotypes including those present in seepage sediments. This rare biosphere of anaerobic alkane degraders will likely increase in abundance in the event of seepage or accidental oil spillage. Nanomolar concentrations of short-chain alkanes (SCA) were detected in pristine and seepage sediments. Interestingly, anaerobic alkane degraders closely related to strain BuS5, the only SCA degrader in pure culture, were found in mesophilic MV enrichments, but not in cold sediments from Danish waters. We propose that the new masD/assA gene lineages in these sediments represent novel phylotypes that are either fueled by naturally occurring low levels of SCA or that metabolize medium- to long-chain alkanes. Our study highlights that masD/assA genes are a relevant diagnostic marker to identify seepage and microseepage, e

  5. Biodegradation of C7 and C8 iso-alkanes under methanogenic conditions.

    PubMed

    Abu Laban, Nidal; Dao, Anh; Semple, Kathleen; Foght, Julia

    2015-12-01

    Iso-alkanes comprise a substantial proportion of petroleum and refined products that impact the environment, but their fate is cryptic under methanogenic conditions. We investigated methanogenic biodegradation of C7 and C8 iso-alkanes found in naphtha, specifically 2-methylhexane, 3-methylhexane, 2-methylheptane, 4-methylheptane and 3-ethylhexane. These were incubated as a mixture or individually with enrichment cultures derived from oil sands tailings ponds that generate methane from naphtha components; substrate depletion and methane production were monitored for up to 663 days. 3-Methylhexane and 4-methylheptane were degraded both singly and in the mixture, whereas 2-methylhexane and 2-methylheptane resisted degradation as single substrates but were depleted in the iso-alkane mixture, suggesting co-metabolism. 3-Ethylhexane was degraded neither singly nor with co-substrates. Putative metabolites consistent with succinylated C7 and C8 were detected, suggesting activation by addition of iso-alkanes to fumarate and corresponding to detection of alkylsuccinate synthase-like genes. 454 pyrotag sequencing, cloning and terminal restriction fragment length polymorphism of 16S rRNA genes revealed predominance of a novel member of the family Peptococcaceae (order Clostridiales) and Archaea affiliated with Methanoregula and Methanosaeta. We report here isomer-specific metabolism of C7 -C8 iso-alkanes under methanogenic conditions and propose their activation by a novel Peptococcaceae via addition to fumarate. PMID:25331365

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

    SciTech Connect

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

    2008-04-15

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

  7. Whole‐cell bacterial bioreporter for actively searching and sensing of alkanes and oil spills

    PubMed Central

    Zhang, Dayi; He, Yi; Wang, Yun; Wang, Hui; Wu, Lin; Aries, Eric; Huang, Wei E.

    2012-01-01

    Summary Acinetobacter baylyi ADP1 was found to tolerate seawater and have a special ability of adhering to an oil–water interface of 10–80 µm emulsified mineral and crude oil droplets. These properties make ADP1 an ideal bacterial chassis for constructing bioreporters that are able to actively search and sense oil spill in water and soils. Acinetobacter baylyi bioreporter ADPWH_alk was developed and applied to the detection of alkanes and alkenes in water, seawater and soils. Bioreporter ADPWH_alk was able to detect a broad range of alkanes and alkenes with carbon chain length from C7 to C36. So far, ADPWH_alk is the only bioreporter that is able to detect alkane with carbon chain length greater than C18. This bioreporter responded to the alkanes in about 30 min and it was independent to the cell growth phase because of two point mutations in alkM promoter recognized by alkane regulatory protein ALKR. ADPWH_alk was applied to detect mineral oil, Brent, Chestnut and Sirri crude oils in water and seawater in the range 0.1–100 mg l−1, showing that the bioreporter oil detection was semi‐quantitative. This study demonstrates that ADPWH_alk is a rapid, sensitive and semi‐quantitative bioreporter that can be useful for environmental monitoring and assessment of oil spills in seawater and soils. PMID:21951420

  8. Toward aldehyde and alkane production by removing aldehyde reductase activity in Escherichia coli

    PubMed Central

    Rodriguez, Gabriel M.; Atsumi, Shota

    2015-01-01

    Advances in synthetic biology and metabolic engineering have enabled the construction of novel biological routes to valuable chemicals using suitable microbial hosts. Aldehydes serve as chemical feedstocks in the synthesis of rubbers, plastics, and other larger molecules. Microbial production of alkanes is dependent on the formation of a fatty aldehyde intermediate which is converted to an alkane by an aldehyde deformylating oxygenase (ADO). However, microbial hosts such as Escherichia coli are plagued by many highly active endogenous aldehyde reductases (ALRs) that convert aldehydes to alcohols, which greatly complicates strain engineering for aldehyde and alkane production. It has been shown that the endogenous ALR activity outcompetes the ADO enzyme for fatty aldehyde substrate. The large degree of ALR redundancy coupled with an incomplete database of ALRs represents a significant obstacle in engineering E. coli for either aldehyde or alkane production. In this study, we identified 44 ALR candidates encoded in the E. coli genome using bioinformatics tools, and undertook a comprehensive screening by measuring the ability of these enzymes to produce isobutanol. From the pool of 44 candidates, we found five new ALRs using this screening method (YahK, DkgA, GldA, YbbO, and YghA). Combined deletions of all 13 known ALRs resulted in a 90–99% reduction in endogenous ALR activity for a wide range of aldehyde substrates (C2–C12). Elucidation of the ALRs found in E. coli could guide one in reducing competing alcohol formation during alkane or aldehyde production. PMID:25108218

  9. Biogeographic variation of foliar n-alkanes of Juniperus communis var. saxatilis Pallas from the Balkans.

    PubMed

    Rajčević, Nemanja; Janaćković, Pedja; Dodoš, Tanja; Tešević, Vele; Marin, Petar D

    2014-12-01

    The composition of the epicuticular n-alkanes isolated from the leaves of ten populations of Juniperus communis L. var. saxatilis Pallas from central (continental) and western (coastal) areas of the Balkan Peninsula was characterized by GC-FID and GC/MS analyses. In the leaf waxes, 14 n-alkane homologues with chain-lengths ranging from C22 to C35 were identified. All samples were dominated by n-tritriacontane (C33 ), but differences in two other dominant n-alkanes allowed separating the coastal from the continental populations. Several statistical methods (ANOVA, principal component, discriminant, and cluster analyses as well as the Mantel test) were deployed to analyze the diversity and variability of the epicuticular-leaf-n-alkane patterns of the ten natural populations of J. communis var. saxatilis and their relation to different geographic and bioclimatic parameters. Cluster analysis showed a high correlation of the leaf-n-alkane patterns with the geographical distribution of the investigated samples, differentiating the coastal from the continental populations of this taxon. Several bioclimatic parameters related to aridity were highly correlated with this differentiation. PMID:25491336

  10. Abiotic Organic Chemistry in Hydrothermal Systems.

    NASA Astrophysics Data System (ADS)

    Simoneit, B. R.; Rushdi, A. I.

    2004-12-01

    Abiotic organic chemistry in hydrothermal systems is of interest to biologists, geochemists and oceanographers. This chemistry consists of thermal alteration of organic matter and minor prebiotic synthesis of organic compounds. Thermal alteration has been extensively documented to yield petroleum and heavy bitumen products from contemporary organic detritus. Carbon dioxide, carbon monoxide, ammonia and sulfur species have been used as precursors in prebiotic synthesis experiments to organic compounds. These inorganic species are common components of hot spring gases and marine hydrothermal systems. It is of interest to further test their reactivities in reductive aqueous thermolysis. We have synthesized organic compounds (lipids) in aqueous solutions of oxalic acid, and with carbon disulfide or ammonium bicarbonate at temperatures from 175-400° C. The synthetic lipids from oxalic acid solutions consisted of n-alkanols, n-alkanoic acids, n-alkyl formates, n-alkanones, n-alkenes and n-alkanes, typically to C30 with no carbon number preferences. The products from CS2 in acidic aqueous solutions yielded cyclic thioalkanes, alkyl polysulfides, and thioesters with other numerous minor compounds. The synthesis products from oxalic acid and ammonium bicarbonate solutions were homologous series of n-alkyl amides, n-alkyl amines, n-alkanes and n-alkanoic acids, also to C30 with no carbon number predominance. Condensation (dehydration) reactions also occur under elevated temperatures in aqueous medium as tested by model reactions to form amide, ester and nitrile bonds. It is concluded that the abiotic formation of aliphatic lipids, condensation products (amides, esters, nitriles, and CS2 derivatives (alkyl polysulfides, cyclic polysulfides) is possible under hydrothermal conditions and warrants further studies.

  11. Effect of Different Types of Small-Group Activities on Students' Conversations

    ERIC Educational Resources Information Center

    Young, Krista K.; Talanquer, Vicente

    2013-01-01

    Teaching reform efforts in chemistry education often involve engaging students in small-group activities of different types. This study focused on the analysis of how activity type affected the nature of group conversations. In particular, we analyzed the small-group conversations of students enrolled in a chemistry course for nonscience majors.…

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

    SciTech Connect

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

    2013-05-14

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

  13. (Pesticide chemistry)

    SciTech Connect

    Barnthouse, L.W.

    1990-09-04

    This report summarizes a trip by L. W. Barnthouse of the Environmental Sciences Division (ESD), Oak Ridge National Laboratory (ORNL), to Hamburg, Federal Republic of Germany (FRG), where he participated in the 7th International Congress of Pesticide Chemistry. He chaired a workshop on experimental systems for determining effects of pesticides on nontarget organisms and gave an oral presentation at a symposium on pesticide risk assessment. Before returning to the United States, Dr. Barnthouse visited the Netherlands Institute for Sea Research in Texel, the Netherlands.

  14. Oxidation of alkanes by cobalt(II) salts of weakly coordinating anions

    SciTech Connect

    Goldstein, A.S.; Drago, R.S. )

    1991-11-27

    Catalysts which effect the selective oxidation of alkanes under mild reaction conditions are highly desired. Commercial processes exist which involve the oxidation of alkanes by O{sub 2} with cobalt carboxylate catalysts. Elevated temperatures and pressures are required, and the metal ion function is to decompose hydroperoxides formed in a radical-chain process. The authors have demonstrated that a weakly solvated cobalt-acetonitrile complex (Co(NCCH{sub 3}){sub 4})(PF{sub 6}){sub 2}, with a weakly coordinating anion catalyzes the air oxidation of alkanes under mild conditions (75C and 3 atm). Cyclohexane and adamantane are converted to the corresponding alcohol and ketone products. The commercial catalyst for cyclohexane oxidation does not function under these milder conditions. Experiments indicate a mechanism in which the metal ion functions both as an initiator and as a hydroperoxide decomposition catalyst.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  16. The low temperature phase transition in octane and its possible generalisation to other n-alkanes

    NASA Astrophysics Data System (ADS)

    Neumann, M. A.; Johnson, M. R.; Radaelli, P. G.

    2001-05-01

    A neutron powder diffraction study of three n-alkanes, octane, nonane and pentadecane, down to 2 K is presented. The temperature dependence of the octane diffraction pattern reveals a solid state phase transition between 40 and 55 K, which involves a doubling of the unit cell in the b direction, the space group remaining P 1¯. Confirmation of the phase transition, which results in a doubling of the number of crystallographically inequivalent methyl groups, is sought in the published NMR, tunnelling data and neutron scattering, vibrational data. Density functional theory and force field techniques are used to simulate spectroscopic data based on the measured structures. While no unequivocal evidence is found in spectroscopic data, the published data does not rule out the existence of energetically inequivalent methyl groups. Indeed close inspection of the spectroscopic data for other n-alkanes suggests that the phase transition may be common to many alkanes.

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    Surface sediments collected from 19 stations along Visakhapatnam harbour were analysed for organic carbon (OC), δ 13Coc, total lipids (TL), total hydrocarbon (THC), n-alkane concentration and composition. OC, δ 13Coc, TL and THC ranged from 0.6% to 7.6%, -29.3 to -23.8‰, 300 to 14,948 \\upmu g g - 1 dw, and 0.2 to 2,277 \\upmu g g - 1 dw, respectively. Predominance of even carbon numbers n-alkanes C12-C21 with carbon preference index (CPI) of <1 suggests major microbial influence. Fair abundance of odd carbon number n-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.

  19. Modeling SOA formation from alkanes and alkenes in chamber experiments: effect of gas/wall partitioning of organic vapors.

    NASA Astrophysics Data System (ADS)

    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

  20. Cyanobacterial alkane biosynthesis further expands the catalytic repertoire of the ferritin-like “di-iron-carboxylate” proteins

    PubMed Central

    Krebs, Carsten; Bollinger, J. Martin; Booker, Squire J.

    2011-01-01

    Summary Enzymes that activate dioxygen at carboxylate-bridged non-heme diiron clusters residing within ferritin-like, four-helix-bundle protein architectures have crucial roles in, among other processes, the global carbon cycle (e.g., soluble methane monooxygenase), fatty acid biosynthesis [plant fatty acyl-acyl carrier protein (ACP) desaturases], DNA biosynthesis [the R2 or β2 subunits of class Ia ribonucleotide reductases (RNRs)], and cellular iron trafficking (ferritins). Classic studies on class Ia RNRs showed long ago how this obligatorily oxidative di-iron/O2 chemistry can be used to activate an enzyme for even a reduction reaction, and more recent investigations of class Ib and Ic RNRs, coupled with earlier studies on dimanganese catalases, have shown that members of this protein family can also incorporate either one or two Mn ions and use them in place of iron for redox catalysis. These two strategies – oxidative activation for non-oxidative reactions and use of alternative metal ions – expand the catalytic repertoire of the family, probably to include activities that remain to be discovered. Indeed, a recent study has suggested that fatty aldehyde decarbonylases (ADs) from cyanobacteria, purported to catalyze a redox-neutral cleavage of a Cn aldehyde to the Cn−1 alkane (or alkene) and CO, also belong to this enzyme family and are most similar in structure to two other members with heterodinuclear (Mn-Fe) cofactors. Here, we first briefly review both the chemical principles underlying the O2-dependent oxidative chemistry of the “classical” di-iron-carboxylate proteins and the two aforementioned strategies that have expanded their functional range, and then consider what metal ion(s) and what chemical mechanism(s) might be employed by the newly discovered cyanobacterial ADs. PMID:21440485

  1. Leaf-wax n-alkanes record the plant–water environment at leaf flush

    PubMed Central

    Tipple, Brett J.; Berke, Melissa A.; Doman, Christine E.; Khachaturyan, Susanna; Ehleringer, James R.

    2013-01-01

    Leaf-wax n-alkanes 2H/1H ratios are widely used as a proxy in climate reconstruction. Although the broad nature of the relationship between n-alkanes δ2H values and climate is appreciated, the quantitative details of the proxy remain elusive. To examine these details under natural environmental conditions, we studied a riparian broadleaf angiosperm species, Populus angustifolia, growing on water with a constant δ2H value and monitored the δ2H values of leaf-wax n-alkanes and of stem, leaf, stream, and atmospheric waters throughout the entire growing season. Here we found the δ2H values of leaf-wax n-alkanes recorded only a 2-wk period during leaf flush and did not vary for the 19 weeks thereafter when leaves remained active. We found δ2H values of leaf-wax n-alkanes of P. angustifolia record conditions earlier in the season rather than fully integrating the entire growing season. Using these data, we modeled precipitation δ2H values during the time of wax synthesis. We observed that the isotope ratios of this precipitation generally were 2H-enriched compared with mean annual precipitation. This model provides a mechanistic basis of the often-observed 2H-enrichment from the expected fractionation values in studies of broadleaf angiosperm leaf-wax δ2H. In addition, these findings may have implications for the spatial and temporal uses of n-alkane δ2H values in paleoapplications; when both plant community and growth form are known, this study allows the isolation of the precipitation dynamics of individual periods of the growing season. PMID:23359675

  2. Structure and Mass Transport Characteristics at the Intrinsic Liquid-Vapor Interfaces of Alkanes.

    PubMed

    Chilukoti, Hari Krishna; Kikugawa, Gota; Ohara, Taku

    2016-07-28

    In this paper, an instantaneous interface definition has been used to study the intrinsic structure and self-diffusion coefficient in the vicinity of the liquid-vapor interfaces of decane and tetracosane at three different temperatures using molecular dynamics simulations, and the results have been compared with those obtained on the basis of the conventional Gibbs dividing surface (time- and space-averaged interface). The alkane molecules were modeled using the united atom NERD force field. Partial layered structures of alkane molecules at the liquid-vapor interface are observed as a pinned structure of alkane liquids based on the intrinsic interface. This kind of characteristic has not been observed in the density profiles obtained based on the Gibbs dividing surface. By examining the orientation order parameter and radius of gyration of the alkane molecules, it was observed that the alkane molecules were preferentially oriented to be more parallel to the intrinsic interface than to the Gibbs dividing surface, and the shape of the alkane molecules is slightly changed in the vicinity of the liquid-vapor interfaces. The self-diffusion coefficient parallel to the intrinsic interface was examined using the Green-Kubo relation, where the projection of the velocity in the parallel direction to the local intrinsic interface is used in the velocity correlation function. It was found that the self-diffusion coefficient in the direction parallel to the intrinsic interface changes as the position approaches the interface in a more obvious manner as compared with the self-diffusion coefficient obtained with respect to the Gibbs dividing surface. These results suggest that the use of an instantaneous interface definition allowed us to capture sharp variations in transport properties which are originating due to steeper structure at the liquid-vapor interfaces. PMID:27387788

  3. Isomerization of alkanes on sulfated zirconia: Promotion by Pt and by adamantyl hydride transfer species

    SciTech Connect

    Iglesia, E.; Soled, S.L.; Kramer, G.M. )

    1993-11-01

    The work shows that hydride transfer species, such as adamantane, increase isomerization rates and inhibit C-C scission reactions. n-Heptane isomerization rates show positive hydrogen kinetic orders, suggesting that the reaction proceeds on Pt/ZrO[sub 2]-SO[sub 4] via chain transfer pathways, in which carbenium ions propagate, after a chain initiation step involvings loss of hydrogen from alkanes, by hydride transfer from neutral species to carbonations. These pathways contrast with those involved in the bifunctional (metal-acid) catalytic sequences usually required for alkane isomerization, in which metal sites catalyze alkane dehydrogenation and acid sites catalyze skeletal rearrangements of alkenes. Rate-limiting hydride transfer steps are consistent with the strong influence of molecular hydride transfer agents such as adamantane, which act as co-catalysts and increase isomerization rate and selectivity. The addition of small amounts of adamantane (0.1-0.8 wt%) to n-heptane increases isomerizations rates by a factor of 3 and inhibits undesirable cracking reactions. Adamantane increases hydride transfer and carbenium ion termination rates, thus reducing the surface residence time required for a catalytic turnover. As a result, desorption occurs before secondary cracking of isomerized carbenium ions. Less effective hydride transfer agents (n-alkanes, isoalkanes) also increase n-alkanes isomerization rate and selectivity, but require much higher concentrations than adamantane. Dihydrogen also acts as a hydride source in alkane isomerization catalysis, but it requires the additional presence of metals or reducible oxides, which catalyze H[sub 2] dissociation and the formation of hydridic and protonic forms of hydrogen. 40 refs., 10 figs., 4 tabs.

  4. n-Alkane assimilation and tert-butyl alcohol (TBA) oxidation capacity in Mycobacterium austroafricanum strains.

    PubMed

    Lopes Ferreira, Nicolas; Mathis, Hugues; Labbé, Diane; Monot, Frédéric; Greer, Charles W; Fayolle-Guichard, Françoise

    2007-06-01

    Mycobacterium austroafricanum IFP 2012, which grows on methyl tert-butyl ether (MTBE) and on tert-butyl alcohol (TBA), the main intermediate of MTBE degradation, also grows on a broad range of n-alkanes (C2 to C16). A single alkB gene copy, encoding a non-heme alkane monooxygenase, was partially amplified from the genome of this bacterium. Its expression was induced after growth on n-propane, n-hexane, n-hexadecane and on TBA but not after growth on LB. The capacity of other fast-growing mycobacteria to grow on n-alkanes (C1 to C16) and to degrade TBA after growth on n-alkanes was compared to that of M. austroafricanum IFP 2012. We studied M. austroafricanum IFP 2012 and IFP 2015 able to grow on MTBE, M. austroafricanum IFP 2173 able to grow on isooctane, Mycobacterium sp. IFP 2009 able to grow on ethyl tert-butyl ether (ETBE), M. vaccae JOB5 (M. austroaafricanum ATCC 29678) able to degrade MTBE and TBA and M. smegmatis mc2 155 with no known degradation capacity towards fuel oxygenates. The M. austroafricanum strains grew on a broad range of n-alkanes and three were able to degrade TBA after growth on propane, hexane and hexadecane. An alkB gene was partially amplified from the genome of all mycobacteria and a sequence comparison demonstrated a close relationship among the M. austroafricanum strains. This is the first report suggesting the involvement of an alkane hydroxylase in TBA oxidation, a key step during MTBE metabolism. PMID:17347817

  5. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  6. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  7. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  8. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

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

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  10. 40 CFR 721.10625 - Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Distillation bottoms, alkylated... Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic). (a... generically as distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane...

  11. 40 CFR 721.10625 - Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Distillation bottoms, alkylated... Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic). (a... generically as distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane...

  12. Photolytic formation of free radicals and their effect on hydrocarbon pyrolysis chemistry in a concentrated solar environment: Final report

    SciTech Connect

    Hunjan, M.; Mok, W.S.; Antal, M.J. Jr.

    1987-01-01

    The objective of this research was two-fold: (1) to determine whether uv photons available in a concentrated solar environment can be used as a photolytic source to dissociate vapor phase acetone; and (2) to explore the effects of photolysis on rate and selectivity of free radical reactions. The experiments were conducted in a 1 kW arc image furnace/tubular flow reactor system. The results obtained conclusively showed that acetone readily photodissociates in a 1000 sun environment, leading to the formation of free radicals. It was further observed that Beer-Lambert law can be used to predict the rate of photolysis of acetone. Furthermore, acetone, when used as source of methyl radicals, sensitized the reaction chemistry of alkanes and alkenes at a temperature of 350/sup 0/C. The methyl radicals from photolysis of acetone enhanced the cracking reactions of the alkanes yielding smaller alkanes and alkenes. When the initial hydrocarbon reactant was an alkene, a sensitization of the addition reaction was observed leading to formation of next higher alkene. To gain a theoretical insight into the reaction chemistry of alkanes, a numerical simulation model was developed to study the photosensitized decomposition of n-butane and the simulation results thus obtained were found to be in close agreement with experimental results. 64 refs., 10 figs., 22 tabs.

  13. Regioselective alkane hydroxylation with a mutant CYP153A6 enzyme

    DOEpatents

    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.

  14. Thermodynamic functions of formation of n-alkane complexes with crystalline urea

    SciTech Connect

    Tolmachev, V.V.; Semenov, L.V.; Gaile, A.A.; Proskuryakov, V.A.

    1987-07-10

    For optimization of the conditions of deparaffination of petroleum fractions with the aid of urea, with the composition of the feedstock taken into account, it is important to know the equilibrium constants of formation of complexes of urea with n-alkanes differing in the number of carbon atoms in their molecules, as functions of temperature. In this investigation they obtained experimental data necessary for calculating the thermodynamic functions of formation of n-alkane complexes with crystalline urea up to the decomposition temperature, using Kirchhoff's equations.

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

    NASA Technical Reports Server (NTRS)

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

    1976-01-01

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

  16. Mass effect on the Soret coefficient in n-alkane mixtures.

    PubMed

    Alonso de Mezquia, David; Bou-Ali, M Mounir; Madariaga, J Antonio; Santamaría, Carlos

    2014-02-28

    We have determined the Soret coefficient of different equimolar and non equimolar n-alkane mixtures from measurements of the molecular diffusion and thermal diffusion coefficients. It is shown that equimolar mixtures behave as isotopic-like mixtures in which only the mass effect contributes to the Soret effect. In non equimolar mixtures, a small linear dependence with the molar fraction is observed. Finally, we have obtained a new correlation, which allows the determination of the Soret coefficient of n-alkane mixtures using the data of viscosity, the thermal expansion coefficient of the pure components, and the density of the equimolar mixture. PMID:24588181

  17. Determination of n-alkane content in middle and heavy distillates by gas chromatography

    SciTech Connect

    Fadeev, V.S.; Shteingardt, N.S.

    1987-07-01

    The authors have modified a procedure of determination of n-alkane content in middle and heavy distillates by gas chromatography. The zeolite is replaced by a surface-layer absorbent consisting of grains of diatomite on which there has been deposited a surface layer of MgA zeolite particles, and the helium is replaced by hydrogen. A special chromatograph attachment is described and the chromatograms are calculated on the basis of the heights or areas of the peaks of the charge and the impurity hydrocarbons which are not n-alkanes.

  18. Evaluation of NO+ reagent ion chemistry for online measurements of atmospheric volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Koss, Abigail R.; Warneke, Carsten; Yuan, Bin; Coggon, Matthew M.; Veres, Patrick R.; de Gouw, Joost A.

    2016-07-01

    NO+ chemical ionization mass spectrometry (NO+ CIMS) can achieve fast (1 Hz and faster) online measurement of trace atmospheric volatile organic compounds (VOCs) that cannot be ionized with H3O+ ions (e.g., in a PTR-MS or H3O+ CIMS instrument). Here we describe the adaptation of a high-resolution time-of-flight H3O+ CIMS instrument to use NO+ primary ion chemistry. We evaluate the NO+ technique with respect to compound specificity, sensitivity, and VOC species measured compared to H3O+. The evaluation is established by a series of experiments including laboratory investigation using a gas-chromatography (GC) interface, in situ measurement of urban air using a GC interface, and direct in situ measurement of urban air. The main findings are that (1) NO+ is useful for isomerically resolved measurements of carbonyl species; (2) NO+ can achieve sensitive detection of small (C4-C8) branched alkanes but is not unambiguous for most; and (3) compound-specific measurement of some alkanes, especially isopentane, methylpentane, and high-mass (C12-C15) n-alkanes, is possible with NO+. We also demonstrate fast in situ chemically specific measurements of C12 to C15 alkanes in ambient air.

  19. Detailed chemical kinetic models for large n-alkanes and iso-alkanes found in conventional and F-T diesel fuels

    SciTech Connect

    Westbrook, C K; Pitz, W J; Mehl, M; Curran, H J

    2009-03-09

    n-Hexadecane and 2,2,4,4,6,8,8-heptamethylnonane represent the primary reference fuels for diesel that are used to determine cetane number, a measure of the ignition property of diesel fuel. With the development of chemical kinetics models for both primary reference fuels, a new capability is now available to model diesel fuel ignition. Additionally, we have developed chemical kinetic models for a whole series of large n-alkanes and a large iso-alkane to represent these chemical classes in fuel surrogates for conventional and future fuels. These chemical kinetic models are used to predict the effect of the aforementioned fuel components on ignition characteristics under conditions found in internal combustion engines.

  20. Infrared spectra and structure of alkane- and cycloalkanecarbonitriles and of their carbanions: An ab initio force field treatment

    NASA Astrophysics Data System (ADS)

    Juchnovski, I. N.; Tsenov, J. A.; Binev, I. G.

    1996-08-01

    The structure of alkane- and cycloalkanecarbonitriles (seven compounds) and of their carbanions has been studied by both infrared spectrometry and ab initio force field calculations. The carbanions (counter ions Li +, Na + and K +) have been found to exist mainly as ionic aggregates in hexamethylphosphoric triamide solutions. The calculations describe well the marked decrease, by 124-214 cm -1, in the nitrile band frequencies and also the strong increase, by 1-2 orders, in the nitrile band integrated intensities which accompany the conversion of the parent neutral molecules into carbanions. Cyclopropanecarbonitrile is remarkable as having the highest nitrile band intensity among all the neutral molecules and the lowest one among all the carbanions studied. This result has also been predicted by the calculations, and it can be explained by certain peculiarities in the structure of the particles. The conjugation of the carbanionic charge with the cyano group in the cyclopropanecarbonitrile carbanion is greatly hindered by the considerable deviation (estimated at 56°) of the cyano group from the ring plane. The carbanionic charges of the carbanions studied are delocalized over the cyano groups (0.30-0.41 e -), carbanionic centres (0.08-0.29 e -) and hydrocarbon moieties (0.34-0.63 e -).

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

    PubMed

    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

  2. Adiabatic Coupling Constant of Nitrobenzene- n-Alkane Critical Mixtures. Evidence from Ultrasonic Spectra and Thermodynamic Data

    NASA Astrophysics Data System (ADS)

    Mirzaev, Sirojiddin Z.; Kaatze, Udo

    2016-09-01

    Ultrasonic spectra of mixtures of nitrobenzene with n-alkanes, from n-hexane to n-nonane, are analyzed. They feature up to two Debye-type relaxation terms with discrete relaxation times and, near the critical point, an additional relaxation term due to the fluctuations in the local concentration. The latter can be well represented by the dynamic scaling theory. Its amplitude parameter reveals the adiabatic coupling constant of the mixtures of critical composition. The dependence of this thermodynamic parameter upon the length of the n-alkanes corresponds to that of the slope in the pressure dependence of the critical temperature and is thus taken another confirmation of the dynamic scaling model. The change in the variation of the coupling constant and of several other mixture parameters with alkane length probably reflects a structural change in the nitrobenzene- n-alkane mixtures when the number of carbon atoms per alkane exceeds eight.

  3. Combustion chemistry

    SciTech Connect

    Brown, N.J.

    1993-12-01

    This research is concerned with the development and use of sensitivity analysis tools to probe the response of dependent variables to model input variables. Sensitivity analysis is important at all levels of combustion modeling. This group`s research continues to be focused on elucidating the interrelationship between features in the underlying potential energy surface (obtained from ab initio quantum chemistry calculations) and their responses in the quantum dynamics, e.g., reactive transition probabilities, cross sections, and thermal rate coefficients. The goals of this research are: (i) to provide feedback information to quantum chemists in their potential surface refinement efforts, and (ii) to gain a better understanding of how various regions in the potential influence the dynamics. These investigations are carried out with the methodology of quantum functional sensitivity analysis (QFSA).

  4. Changes in iso- and n-alkane distribution during biodegradation of crude oil under nitrate and sulphate reducing conditions.

    PubMed

    Hasinger, Marion; Scherr, Kerstin E; Lundaa, Tserennyam; Bräuer, Leopold; Zach, Clemens; Loibner, Andreas Paul

    2012-02-20

    Crude oil consists of a large number of hydrocarbons with different susceptibility to microbial degradation. The influence of hydrocarbon structure and molecular weight on hydrocarbon biodegradation under anaerobic conditions is not fully explored. In this study oxygen, nitrate and sulphate served as terminal electron acceptors (TEAs) for the microbial degradation of a paraffin-rich crude oil in a freshly contaminated soil. During 185 days of incubation, alkanes from n-C11 to n-C39, three n- to iso-alkane ratios commonly used as weathering indicators and the unresolved complex mixture (UCM) were quantified and statistically analyzed. The use of different TEAs for hydrocarbon degradation resulted in dissimilar degradative patterns for n- and iso-alkanes. While n-alkane biodegradation followed well-established patterns under aerobic conditions, lower molecular weight alkanes were found to be more recalcitrant than mid- to high-molecular weight alkanes under nitrate-reducing conditions. Biodegradation with sulphate as the TEA was most pronounced for long-chain (n-C32 to n-C39) alkanes. The observation of increasing ratios of n-C17 to pristane and of n-C18 to phytane provides first evidence of the preferential degradation of branched over normal alkanes under sulphate reducing conditions. The formation of distinctly different n- and iso-alkane biodegradation fingerprints under different electron accepting conditions may be used to assess the occurrence of specific degradation processes at a contaminated site. The use of n- to iso-alkane ratios for this purpose may require adjustment if applied for anaerobic sites. PMID:22001845

  5. Document Conversion Methodology.

    ERIC Educational Resources Information Center

    Bovee, Donna

    1990-01-01

    Discusses digital imaging technology and examines document database conversion considerations. Two types of document imaging systems are described: (1) a work in process system, and (2) a storage and retrieval system. Conversion methodology is outlined, and a document conversion scenario is presented as a practical guide to conversion. (LRW)

  6. Why Teach Environmental Chemistry?

    ERIC Educational Resources Information Center

    Gardner, Marjorie H.

    1974-01-01

    Discusses the importance of teaching environmental chemistry in secondary school science classes, and outlines five examples of environmental chemistry problems that focus on major concepts of chemistry and have critical implications for human survival and well-being. (JR)

  7. Science Update: Inorganic Chemistry

    ERIC Educational Resources Information Center

    Rawls, Rebecca

    1978-01-01

    This first in a series of articles describing the state of the art of various branches of chemistry reviews inorganic chemistry, including bioinorganic, photochemistry, organometallic, and solid state chemistries. (SL)

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

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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

  9. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

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

  10. A Microporous Metal-Organic Framework for Gas Chromatographic Separation of Alkanes

    SciTech Connect

    Chen, Banglin; Liang, Chengdu; Yang, Jun; Contreras, Damacio; Clancy, Yvette; Lobkovsky, Emil B.; Yaghi, Omar; Dai, Sheng

    2006-01-01

    A zinc-based metal-organic framework (MOF) can be transformed reversibly from an open (a) to a dense (b) configuration. The microporous solid is the first example of a MOF that is highly selective in the gas-chromatographic separation of alkanes.

  11. Stable isotopic studies of n-alkane metabolism by a sulfate-reducing bacterial enrichment culture.

    PubMed

    Davidova, Irene A; Gieg, Lisa M; Nanny, Mark; Kropp, Kevin G; Suflita, Joseph M

    2005-12-01

    Gas chromatography-mass spectrometry and nuclear magnetic resonance spectroscopy were used to study the metabolism of deuterated n-alkanes (C6 to C12) and 1-13C-labeled n-hexane by a highly enriched sulfate-reducing bacterial culture. All substrates were activated via fumarate addition to form the corresponding alkylsuccinic acid derivatives as transient metabolites. Formation of d14-hexylsuccinic acid in cell extracts from exogenously added, fully deuterated n-hexane confirmed that this reaction was the initial step in anaerobic alkane metabolism. Analysis of resting cell suspensions amended with 1-13C-labeled n-hexane confirmed that addition of the fumarate occurred at the C-2 carbon of the parent substrate. Subsequent metabolism of hexylsuccinic acid resulted in the formation of 4-methyloctanoic acid, and 3-hydroxy-4-methyloctanoic acid was tentatively identified. We also found that 13C nuclei from 1-13C-labeled n-hexane became incorporated into the succinyl portion of the initial metabolite in a manner that indicated that 13C-labeled fumarate was formed and recycled during alkane metabolism. Collectively, the findings obtained with a sulfate-reducing culture using isotopically labeled alkanes augment and support the previously proposed pathway (H. Wilkes, R. Rabus, T. Fischer, A. Armstroff, A. Behrends, and F. Widdel, Arch. Microbiol. 177:235-243, 2002) for metabolism of deuterated n-hexane by a denitrifying bacterium. PMID:16332800

  12. Biosurfactant-mediated biodegradation of straight and methyl-branched alkanes by Pseudomonas aeruginosa ATCC 55925

    PubMed Central

    2011-01-01

    Accidental oil spills and waste disposal are important sources for environmental pollution. We investigated the biodegradation of alkanes by Pseudomonas aeruginosa ATCC 55925 in relation to a rhamnolipid surfactant produced by the same bacterial strain. Results showed that the linear C11-C21 compounds in a heating oil sample degraded from 6% to 100%, whereas the iso-alkanes tended to be recalcitrant unless they were exposed to the biosurfactant; under such condition total biodegradation was achieved. Only the biodegradation of the commercial C12-C19 alkanes could be demonstrated, ranging from 23% to 100%, depending on the experimental conditions. Pristane (a C19 branched alkane) only biodegraded when present alone with the biosurfactant and when included in an artificial mixture even without the biosurfactant. In all cases the biosurfactant significantly enhanced biodegradation. The electron scanning microscopy showed that cells depicted several adaptations to growth on hydrocarbons, such as biopolymeric spheres with embedded cells distributed over different layers on the spherical surfaces and cells linked to each other by extracellular appendages. Electron transmission microscopy revealed transparent inclusions, which were associated with hydrocarbon based-culture cells. These patterns of hydrocarbon biodegradation and cell adaptations depended on the substrate bioavailability, type and length of hydrocarbon. PMID:21906343

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 ...

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

    NASA Astrophysics Data System (ADS)

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  16. Petrodiesel-like straight chain alkane and fatty alcohol production by the microalga Chlorella sorokiniana.

    PubMed

    Yang, Xuewei; Dai, Xin; Guo, Hui; Geng, Shu; Wang, Gangyi

    2013-05-01

    This study was to investigate the composition and characteristics of long-straight chain alkane and fatty alcohols from the microalga Chlorella Sorokiniana 21, isolated from the coastal water of Pearl River Delta, China. Under the optimized aeration growth condition, this strain yielded up to 1.44 g L(-1) biomass and 24.90% extracts of dry weight. The major compounds of the extracts were identified to be alkanes (35.93%) and alcohols (53.73%). Of the extracts, long-straight chain alkanes accounted for 30.54% with heptadecane (21.13%) as a predominant component. Furthermore, a large amount of fatty alcohols (53.73%) were identified in the algal extracts with 29.09% of 3-(2-methoxyethyl)-1-nonanol. Thus, this algal species is a promising feedstock for the production of supplement for petrodiesel-like fuels and biochemicals used in the cosmetics and food industries. This study represents the first report of long-straight chain alkane and fatty alcohols from microalgae isolated from coastal water of the region. PMID:23567672

  17. Anaerobic biodegradation of long-chain n-alkanes under sulfate-reducing conditions

    SciTech Connect

    Caldwell, M.E.; Suflita, J.M.; Garrett, R.M.; Prince, R.C.

    1998-07-15

    The ability of anaerobic microorganisms to degrade a wide variety of crude oil components was investigated using chronically hydrocarbon-contaminated marine sediments as the source of inoculum. When sulfate reduction was the predominant electron-accepting process, gas chromatographic analysis revealed almost complete n-alkane removal (C{sub 15}-C{sub 34}) from a weathered oil within 201 d of incubation. No alteration of the oil was detected in sterile control incubations or when nitrate served as an alternate electron acceptor. The amount of sulfate reduced in the oil-amended nonsterile incubations was more than enough to account for the complete mineralization of the n-alkane fraction of the oil; no loss of this anion was observed in sterile control incubations. The mineralization of the alkanes was confirmed using {sup 14}C-14,15-octacosane (C{sub 28}H{sub 58}), with 97% of the radioactivity recovered as {sup 14}CO{sub 2}. These findings extend the range of hydrocarbons known to be amenable to anaerobic biodegradation. Moreover, the rapid and extensive alteration in the n-alkanes can no longer be considered a defining characteristic of aerobic oil biodegradation processes alone.

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

    NASA Astrophysics Data System (ADS)

    Zech, M.; Kreutzer, S.; Goslar, T.; Meszner, S.; Krause, T.; Faust, D.; Fuchs, M.

    2012-07-01

    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.

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

    NASA Astrophysics Data System (ADS)

    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

  20. n-Alkane lipid biomarkers in loess: post-sedimentary or syn-sedimentary?

    NASA Astrophysics Data System (ADS)

    Zech, Michael; Kreutzer, Sebastian; Goslar, Tomasz; Meszner, Sascha; Krause, Tobias; Faust, Dominik; Fuchs, Markus

    2013-04-01

    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 (Zech et al., 2012, 2013; Wiesenberg and Gocke, 2013). 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 calBP 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 calBP, 22.1 ± 0.7 kyr calBP and 29.8 ± 1.4 kyr calBP) 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 (modern, last decades, 3 kyr, 6 kyr and 9 kyr). Accordingly, modern and last decadal 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. Zech, M., Kreutzer, S., Goslar, T., Meszner, S

  1. Science Update: Inorganic Chemistry.

    ERIC Educational Resources Information Center

    Rawls, Rebecca

    1981-01-01

    Describes areas of inorganic chemistry which have changed dramatically in the past year or two, including photochemistry, electrochemistry, organometallic complexes, inorganic reaction theory, and solid state chemistry. (DS)

  2. Trace Chemistry

    NASA Technical Reports Server (NTRS)

    Radhakrishnan, Krishnan; Whitefield, Philip

    1999-01-01

    The goals of the trace chemistry group were to identify the processes relevant to aerosol and aerosol precursor formation occurring within aircraft gas turbine engines; that is, within the combustor, turbine, and nozzle. The topics of discussion focused on whether the chemistry of aerosol formation is homogeneous or heterogeneous; what species are important for aerosol and aerosol precursor formation; what modeling/theoretical activities to pursue; what experiments to carry out that both support modeling activities and elucidate fundamental processes; and the role of particulates in aerosol and aerosol precursor formation. The consensus of the group was that attention should be focused on SO2, SO3, and aerosols. Of immediate concern is the measurement of the concentration of the species SO3, SO2, H2SO4 OH, HO2, H2O2, O, NO, NO2, HONO, HNO3, CO, and CO2 and particulates in various engines, both those currently in use and those in development. The recommendation was that concentration measurements should be made at both the combustor exit and the engine exit. At each location the above species were classified into one of four categories of decreasing importance, Priority I through IV, as follows: Combustor exit: Priority I species - SO3:SO2 ratio, SO3, SO2, and particulates; Priority II species: OH and O; Priority III species - NO and NO2; and Priority IV species - CO and CO2. For the Engine exit: Priority I species - SO3:SO2 ratio, SO3, SO2,H2SO4, and particulates; Priority II species: OH,HO2, H2O2, and O; Priority III species - NO, NO2, HONO, and HNO3; and Priority IV species - CO and CO2. Table I summarizes the anticipated concentration range of each of these species. For particulate matter, the quantities of interest are the number density, size distribution, and composition. In order to provide data for validating multidimensional reacting flow models, it would be desirable to make 2-D, time-resolved measurements of the concentrations of the above species and

  3. Diverse Bacterial Groups Contribute to the Alkane Degradation Potential of Chronically Polluted Subantarctic Coastal Sediments.

    PubMed

    Guibert, Lilian M; Loviso, Claudia L; Borglin, Sharon; Jansson, Janet K; Dionisi, Hebe M; Lozada, Mariana

    2016-01-01

    We aimed to gain insight into the alkane degradation potential of microbial communities from chronically polluted sediments of a subantarctic coastal environment using a combination of metagenomic approaches. A total of 6178 sequences annotated as alkane-1-monooxygenases (EC 1.14.15.3) were retrieved from a shotgun metagenomic dataset that included two sites analyzed in triplicate. The majority of the sequences binned with AlkB described in Bacteroidetes (32 ± 13 %) or Proteobacteria (29 ± 7 %), although a large proportion remained unclassified at the phylum level. Operational taxonomic unit (OTU)-based analyses showed small differences in AlkB distribution among samples that could be correlated with alkane concentrations, as well as with site-specific variations in pH and salinity. A number of low-abundance OTUs, mostly affiliated with Actinobacterial sequences, were found to be only present in the most contaminated samples. On the other hand, the molecular screening of a large-insert metagenomic library of intertidal sediments from one of the sampling sites identified two genomic fragments containing novel alkB gene sequences, as well as various contiguous genes related to lipid metabolism. Both genomic fragments were affiliated with the phylum Planctomycetes, and one could be further assigned to the genus Rhodopirellula due to the presence of a partial sequence of the 23S ribosomal RNA (rRNA) gene. This work highlights the diversity of bacterial groups contributing to the alkane degradation potential and reveals patterns of functional diversity in relation with environmental stressors in a chronically polluted, high-latitude coastal environment. In addition, alkane biodegradation genes are described for the first time in members of Planctomycetes. PMID:26547568

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

    PubMed

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

    2016-01-01

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

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

    PubMed Central

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

    2016-01-01

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

  6. Oxidative methane conversion in dielectric barrier discharge

    NASA Astrophysics Data System (ADS)

    Krawczyk, Krzysztof; Młotek, Michał; Ulejczyk, Bogdan; Pryciak, Krzysztof; Schmidt-Szałowski, Krzysztof

    2013-02-01

    A dielectric barrier discharge was used for the oxidative coupling of methane (OCM) with oxygen at the pressure of 1.2 bar. A dielectric barrier discharge (DBD) reactor was powered at the frequency of about 6 kHz. Molar ratio CH4/O2 in the inlet gas containing 50% or 25% of argon was 3, 6 and 12. The effects of temperature (110, 150 and 340 ◦C), gas flow rate, molar ratio of methane to oxygen on the overall methane and oxygen conversion and methane conversion to methanol, ethanol, hydrocarbons, carbon oxides and water were studied. In the studied system the increase of the temperature decreases the conversion of methane to methanol. The increase of the molar ratio of methane to oxygen increased the methane conversion to hydrocarbons and strongly decreased the methane conversion to alcohols. The conversion of methane to hydrocarbons increased and the conversion of methane to methanol decreased with the decrease of the gas flow rate from 2 to 1 NL/h. Contribution to the Topical Issue "13th International Symposium on High Pressure Low Temperature Plasma Chemistry (Hakone XIII)", Edited by Nicolas Gherardi, Henryca Danuta Stryczewska and Yvan Ségui.

  7. Pashto Conversation Manual and Pashto Conversation Tapescript.

    ERIC Educational Resources Information Center

    Tegey, Habibullah; Robson, Barbara

    This conversation manual and tapescript are part of a set of materials that have been developed to teach oral and written Afghan Pashto to English speakers. In addition to the conversation manual and tapescript, the set consists of a beginning textbook, an intermediate textbook, a reader, and a set of taped lessons that correlate with the…

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

    PubMed Central

    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/mass spectrometry allowed us to identify saturated 2-, 4-, 6-, and 8-methyl- and monounsaturated 6-methyl-branched fatty acids, with chain lengths that specifically correlated with those of the alkane. Growth of D. aliphaticivorans on perdeuterated hexadecane demonstrated that those methyl-branched fatty acids were directly derived from the substrate. In addition, cultures on pentadecane and hexadecane produced (1-methyltetradecyl)succinate and (1-methylpentadecyl)succinate, respectively. These results indicate that D. aliphaticivorans strain CV2803T oxidizes n-alkanes into fatty acids anaerobically, via the addition of fumarate at C-2. Based on our observations and on literature data, a pathway for anaerobic n-alkane metabolism by D. aliphaticivorans is proposed. This involves the transformation of the initial alkylsuccinate into a 4-methyl-branched fatty acid which, in addition to catabolic reactions, can alternatively undergo chain elongation and desaturation to form storage fatty acids. PMID:16000749

  9. Chemistry of the outer planets

    NASA Technical Reports Server (NTRS)

    Scattergood, Thomas W.

    1992-01-01

    Various aspects were studied of past or present chemistry in the atmospheres of the outer planets and their satellites using lab simulations. Three areas were studied: (1) organic chemistry induced by kinetically hot hydrogen atoms in the region of Jupiter's atmosphere containing the ammonia cirrus clouds; (2) the conversion of NH3 into N2 by plasmas associated with entry of meteors and other objects into the atmosphere of early Titan; and (3) the synthesis of simple hydrocarbons and HCN by lightning in mixtures containing N2, CH4, and NH3 representing the atmospheres of Titan and the outer planets. The results showed that: (1) hot H2 atoms formed from the photodissociation of NH3 in Jupiter's atmosphere could account for some of the atmospheric chemistry in the ammonia cirrus cloud region; (2) the thermalization of hot H2 atoms in atmospheres predominated by molecular H is not as rapid as predicted by elastic collision theory; (3) the net quantum loss of NH3 in the presence of a 200 fold excess of H2 is 0.02, much higher than was expected from the amount of H2 present; (4) the conversion of NH3 into N2 in plasmas associated with infalling meteors is very efficient and rapid, and could account for most of the N2 present on Titan; (5) the yields of C2H2 and HCN from lightning induced chemistry in mixtures of CH4 and N2 is consistent with quenched thermodynamic models of the discharge core; and (6) photolysis induced by the UV light emitted by the gases in the hot plasmas may account for some, if not most, of the excess production of C2H6 and the more complex hydrocarbons.

  10. PEROXYNITRITE CHEMISTRY

    SciTech Connect

    Lymar, S.V.

    2000-11-29

    This century old area of research has been experiencing a renaissance during the last decade, with the annual number of publications on the subject increasing from only one in 1990 to nearly 200 in the late-1990s. This renewed interest is stimulated by the discovery of biological roles of nitric oxide, distinguished by the 1998 Nobel prize, and the recognition that the conversion of nitric oxide into peroxynitrite may play major roles in human diseases associated with oxidative stress and in cellular defense against invading pathogens. Peroxynitrite (ONOO{sup {minus}})is a structural isomer of nitrate (NO{sub 3}{sup {minus}}) that contains a peroxo bond. The physiological route to ONOO{sup {minus}} is provided by the combination of nitric oxide ({center_dot}NO) with superoxide ({center_dot}O{sub 2}{sup {minus}}), an extremely rapid reaction occurring upon every encounter of these radicals (the upper dot denotes radical species). Both {center_dot}NO and {center_dot}O{sub 2}{sup {minus}} are the oxygen metabolic products simultaneously generated in a number of cell types within a human body. Compared to its precursors, peroxynitrite is a much stronger oxidant capable of oxidizing proteins, nucleic acids, and lipids.

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

    PubMed

    Shahimin, Mohd Faidz Mohamad; 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 ~600 d. Microbes in Albian MFT began methane production by ~80 d, 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 ~80 d lag but exhibited a lag of ~360 d 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

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

    PubMed Central

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

    2011-01-01

    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)-encoding systems of other alkane-degrading actinobacteria. Quantitative reverse transcription-PCR showed that the genes encoding AlkB (alkane 1-monooxygenase), RubA3 (rubredoxin), RubA4 (rubredoxin), and RubB (rubredoxin reductase) were induced by both n-hexadecane and n-triacontane, which were chosen as representative long-chain liquid and solid n-alkane molecules, respectively. Biotransformation of n-hexadecane into the corresponding 1-hexadecanol was detected by solid-phase microextraction coupled with gas chromatography-mass spectrometry (SPME/GC-MS) analysis. The Gordonia SoCg alkB was heterologously expressed in Escherichia coli BL21 and in Streptomyces coelicolor M145, and both hosts acquired the ability to transform n-hexadecane into 1-hexadecanol, but the corresponding long-chain alcohol was never detected on n-triacontane. However, the recombinant S. coelicolor M145-AH, expressing the Gordonia alkB gene, was able to grow on n-triacontane as the sole C source. A SoCg alkB disruption mutant that is completely unable to grow on n-triacontane was obtained, demonstrating the role of an AlkB-type AH system in degradation of solid n-alkanes. PMID:21183636

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

    PubMed

    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

  14. Biotechnology of biomass conversion

    SciTech Connect

    Wayman, M.; Parekh, S.R.

    1990-01-01

    This book covers: An introduction to biomass crops; The microbiology of fermentation processes; The production of ethanol from biomass crops, such as sugar cane and rubbers; The energy of biomass conversion; and The economics of biomass conversion.

  15. Multimetallic catalysed radical oxidative C(sp3)–H/C(sp)–H cross-coupling between unactivated alkanes and terminal alkynes

    PubMed Central

    Tang, Shan; Wang, Pan; Li, Haoran; Lei, Aiwen

    2016-01-01

    Radical involved transformations are now considered as extremely important processes in modern organic synthetic chemistry. According to the demand by atom-economic and sustainable chemistry, direct C(sp3)–H functionalization through radical oxidative coupling represents an appealing strategy for C–C bond formations. However, the selectivity control of reactive radical intermediates is still a great challenge in these transformations. Here we show a selective radical oxidative C(sp3)–H/C(sp)–H cross-coupling of unactivated alkanes with terminal alkynes by using a combined Cu/Ni/Ag catalytic system. It provides a new way to access substituted alkynes from readily available materials. Preliminary mechanistic studies suggest that this reaction proceeds through a radical process and the C(sp3)–H bond cleavage is the rate-limiting step. This study may have significant implications for controlling selective C–C bond formation of reactive radical intermediates by using multimetallic catalytic systems. PMID:27339161

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

    DOE PAGESBeta

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

    2016-02-08

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

  17. Direct Conversion of Energy.

    ERIC Educational Resources Information Center

    Corliss, William R.

    This publication is one of a series of information booklets for the general public published by the United States Atomic Energy Commission. Direct energy conversion involves energy transformation without moving parts. The concepts of direct and dynamic energy conversion plus the laws governing energy conversion are investigated. Among the topics…

  18. Industrial Chemistry and School Chemistry: Making Chemistry Studies More Relevant

    ERIC Educational Resources Information Center

    Hofstein, Avi; Kesner, Miri

    2006-01-01

    In this paper, we present the development and implementation over the period of more than 15 years of learning materials focusing on industrial chemistry as the main theme. The work was conducted in the Department of Science Teaching at the Weizmann Institute of Science, Israel. The project's general goal was to teach chemistry concepts in the…

  19. Iterated multidimensional wave conversion

    NASA Astrophysics Data System (ADS)

    Brizard, A. J.; Tracy, E. R.; Johnston, D.; Kaufman, A. N.; Richardson, A. S.; Zobin, N.

    2011-12-01

    Mode conversion can occur repeatedly in a two-dimensional cavity (e.g., the poloidal cross section of an axisymmetric tokamak). We report on two novel concepts that allow for a complete and global visualization of the ray evolution under iterated conversions. First, iterated conversion is discussed in terms of ray-induced maps from the two-dimensional conversion surface to itself (which can be visualized in terms of three-dimensional rooms). Second, the two-dimensional conversion surface is shown to possess a symplectic structure derived from Dirac constraints associated with the two dispersion surfaces of the interacting waves.

  20. The Role of Water Chemistry in Marine Aquarium Design: A Model System for a General Chemistry Class

    NASA Astrophysics Data System (ADS)

    Keaffaber, Jeffrey J.; Palma, Ramiro; Williams, Kathryn R.

    2008-02-01

    Water chemistry is central to aquarium design, and it provides many potential applications for discussion in undergraduate chemistry and engineering courses. Marine aquaria and their life support systems feature many chemical processes. A life support system consists of the entire recirculation system, as well as the habitat tank and all ancillary water treatment processes. Many fundamental concepts learned in general chemistry, for example, unit conversion, solution concentrations, stoichiometry, redox reactions, and acid-base chemistry are all key to understanding the life support system. This article uses a hypothetical tank to house ocean sunfish as a model to show students the calculations and other considerations that are needed when designing a marine aquarium.

  1. 40 CFR 721.10626 - 1,4-Butanediol, polymer with substituted alkane and substituted methylene biscarbomonocycle, 2...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... activities. Requirements as specified in § 721.80(o) and (y)(1). (ii) (b) Specific requirements. The... substituted alkane and substituted methylene biscarbomonocycle, 2-hydroxyalkyl acrylate-blocked (PMN...

  2. n-Alkane hydroconversion on Zeogrid and colloidal ZSM-5 assembled from aluminosilicate nanoslabs of MFI framework type.

    PubMed

    Aerts, Alexander; Huybrechts, Ward; Kremer, Sebastien P B; Kirschhock, Christine E A; Theunissen, Elisabeth; Van Isacker, Annabel; Denayer, Joeri F M; Baron, Gino V; Thybaut, Joris W; Marin, Guy B; Jacobs, Pierre A; Martens, Johan A

    2003-08-01

    n-Alkane hydroisomerisation and hydrocracking experiments reveal that ZSM-5 materials synthesized by self-assembly of nanoslabs show different molecular shape selectivity than ZSM-5 synthesized by hydrothermal methods. PMID:12932017

  3. Energy conversion & storage program. 1995 annual report

    SciTech Connect

    Cairns, E.J.

    1996-06-01

    The 1995 annual report discusses laboratory activities in the Energy Conversion and Storage (EC&S) Program. The report is divided into three categories: electrochemistry, chemical applications, and material applications. Research performed in each category during 1995 is described. Specific research topics relate to the development of high-performance rechargeable batteries and fuel cells, the development of high-efficiency thermochemical processes for energy conversion, the characterization of new chemical processes and complex chemical species, and the study and application of novel materials related to energy conversion and transmission. Research projects focus on transport-process principles, chemical kinetics, thermodynamics, separation processes, organic and physical chemistry, novel materials and deposition technologies, and advanced methods of analysis.

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

    NASA Astrophysics Data System (ADS)

    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

  5. Revisiting Mt. Kilimanjaro: Do n-alkane biomarkers in soils reflect the δ2H isotopic composition of precipitation?

    NASA Astrophysics Data System (ADS)

    Zech, M.; Zech, R.; Rozanski, K.; Hemp, A.; Gleixner, G.; Zech, W.

    2014-06-01

    During the last decade compound-specific deuterium (δ2H) analysis of plant leaf wax-derived n-alkanes has become a promising and popular tool in paleoclimate research. This is based on the widely accepted assumption that n-alkanes in soils and sediments generally reflect δ2H of precipitation (δ2Hprec). Recently, several authors suggested that δ2H of n-alkanes (δ2H,sub>n-alkanes) can also be used as proxy in paleoaltimetry studies. Here we present results from a δ2H transect study (~1500 to 4000 m a.s.l.) carried out on precipitation and soil samples taken from the humid southern slopes of Mt. Kilimanjaro. Contrary to earlier suggestions, a distinct altitude effect in δ2Hprec is present above ~2000 m a.s.l., i.e. δ2Hprec values become more negative with increasing altitude. The compound-specific δ2H values of nC27 and nC29 do not confirm this altitudinal trend, but rather become more positive both in the O-layers (organic layers) and the Ah-horizons (mineral topsoils). Although our δ2Hn-alkane results are in agreement with previously published results from the southern slopes of Mt. Kilimanjaro (Peterse et al., 2009, BG, 6, 2799-2807), a major re-interpretation is required given that the δ2Hn-alkane results do not reflect the δ2Hprec results. The theoretical framework for this re-interpretation is based on the evaporative isotopic enrichment of leaf water associated with transpiration process. Modelling results show that relative humidity, decreasing considerably along the southern slopes of Mt. Kilimanjaro (from 78% at ~ 2000 m a.s.l. to 51% at 4000 m a.s.l.), strongly controls δ2Hleaf water. The modelled δ2H leaf water enrichment along the altitudinal transect matches well the measured 2H leaf water enrichment as assessed by using the δ2Hprec and δ2Hn-alkane results and biosynthetic fractionation during n-alkane biosynthesis in leaves. Given that our results clearly demonstrate that n-alkanes in soils do not simply reflect δ2Hprec but rather δ2

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed Central

    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

  9. Different response of δD values of n-alkanes, isoprenoids, and kerogen during thermal maturation

    NASA Astrophysics Data System (ADS)

    Pedentchouk, Nikolai; Freeman, Katherine H.; Harris, Nicholas B.

    2006-04-01

    This study investigates the extent of post-depositional alteration of δD values of n-alkyl lipids, isoprenoids, and kerogen isolated from a continuous 450 m core that covers the transition from thermally immature to early mature sediments in the lacustrine Kissenda Formation, Lower Cretaceous, Gabon Basin. Large variations in δD values (up to 40‰ for nC 17 and up to 30‰ for nC 29 alkanes as well as up to 10‰ for kerogen) in closely spaced samples are evident throughout the core and remain preserved even at the bottom of the section. δD values of individual n-alkanes show a slight overall D-enrichment with depth, and a general trend of increasing δD values with increasing n-alkane chain length characterizes all samples, particularly in those below 600 m depth. Hydrogen isotopic compositions of kerogen samples overlap with those of n-alkanes throughout the section. δD values of pristane and phytane are more negative than those of nC 17 alkane by as much as 120‰ at shallow depths but increase dramatically and approach δD values of nC 17 alkane in the samples closest to the oil window. Integration of analytical and computational results indicates that: (1) n-alkanes and isoprenoids have the potential to preserve the original biological signal before the onset of oil generation; (2) isomeric and structural rearrangements taking place at the beginning stages of oil generation do not influence significantly the δD values of n-alkanes and kerogen. However, these processes have a major effect on the isotopic composition of isoprenoids, causing isotopic D-enrichment up to 90‰.

  10. Liquid-vapor equilibria and interfacial properties of n-alkanes and perfluoroalkanes by molecular simulation.

    PubMed

    Amat, Miguel A; Rutledge, Gregory C

    2010-03-21

    A molecular dynamics study is presented to assess the performance of a united-atom model in the prediction of liquid-vapor interfacial properties for short-chain perfluoroalkanes and their alkane counterparts. In particular, the ability of this model to discriminate between the surface-energy values of these two types of compounds was investigated over a wide temperature range corresponding to the liquid-vapor region. Comparisons with available experimental data and surface-tension predictions given by other force-field parameterizations, including those based on the more computationally demanding all-atom method, were performed to gauge the viability of this model. It was found that the model used in this study captures qualitatively the expected behavior of surface energy between alkanes and perfluoroalkanes and yields values that are in excellent agreement with experimental data, especially in the high-temperature limit as the critical temperature is approached. PMID:20331313

  11. Liquid-vapor equilibria and interfacial properties of n-alkanes and perfluoroalkanes by molecular simulation

    NASA Astrophysics Data System (ADS)

    Amat, Miguel A.; Rutledge, Gregory C.

    2010-03-01

    A molecular dynamics study is presented to assess the performance of a united-atom model in the prediction of liquid-vapor interfacial properties for short-chain perfluoroalkanes and their alkane counterparts. In particular, the ability of this model to discriminate between the surface-energy values of these two types of compounds was investigated over a wide temperature range corresponding to the liquid-vapor region. Comparisons with available experimental data and surface-tension predictions given by other force-field parameterizations, including those based on the more computationally demanding all-atom method, were performed to gauge the viability of this model. It was found that the model used in this study captures qualitatively the expected behavior of surface energy between alkanes and perfluoroalkanes and yields values that are in excellent agreement with experimental data, especially in the high-temperature limit as the critical temperature is approached.

  12. Isolation and characterization of a novel thermophilic Bacillus strain degrading long-chain n-alkanes.

    PubMed

    Wang, Lei; Tang, Yun; Wang, Shuo; Liu, Ru-Lin; Liu, Mu-Zhi; Zhang, Yan; Liang, Feng-Lai; Feng, Lu

    2006-08-01

    A thermophilic Bacillus strain NG80-2 growing within the temperature range of 45-73 degrees C (optimum at 65 degrees C) was isolated from a deep subterranean oil-reservoir in northern China. The strain was able to utilize crude oil and liquid paraffin as the sole carbon sources for growth, and the growth with crude oil was accompanied by the production of an unknown emulsifying agent. Further examination showed that NG80-2 degraded and utilized only long-chain (C15-C36) n-alkanes, but not short-chain (C8-C14) n-alkanes and those longer than C40. Based on phenotypic and phylogenic analyses, NG80-2 was identified as Geobacillus thermodenitrificans. The strain NG80-2 may be potentially used for oily-waste treatment at elevated temperature, a condition which greatly accelerates the biodegradation rate, and for microbial enhancing oil recovery process. PMID:16604274

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

    Zahed, Mohammad Ali; Aziz, Hamidi Abdul; Mohajeri, Leila; Mohajeri, Soraya; Kutty, Shamsul Rahman Mohamed; Isa, Mohamed Hasnain

    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. PMID:20837377

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

    NASA Astrophysics Data System (ADS)

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

    PubMed

    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

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

    SciTech Connect

    Shi, Yuanyuan; Kamasah, Alexander; Joalland, Baptiste; Suits, Arthur G.

    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. Comparison of bulk and n-alkane PETM carbon isotope trends from the Bighorn Basin, Wyoming

    NASA Astrophysics Data System (ADS)

    Baczynski, A. A.; McInerney, F. A.; Kraus, M. J.; Wing, S.

    2010-12-01

    The Paleocene-Eocene Thermal Maximum (PETM), a period of abrupt, short-term, and large-scale global warming fueled by a large release of isotopically light carbon, is recorded in terrestrial and marine carbonates and organic carbon as a prominent negative carbon isotope excursion (CIE). Here we present a composite stable carbon isotope record from n-alkanes and four bulk organic carbon records from individual sections spanning the PETM interval in the Cabin Fork area of the southeastern Bighorn Basin, Wyoming. The n-alkane curve shows an abrupt, negative shift in δ13C values, an extended CIE body, and a rapid recovery to pre-PETM δ13C values. While the bulk organic carbon records show similarly abrupt negative shifts in δ13C values, the CIE appears to be compressed as well as smaller in magnitude, and the return to more positive δ13C values is often more gradual. Furthermore, the stratigraphic thickness of the most negative CIE values and the pattern of the recovery phase are not consistent among the four bulk organic carbon records. The discrepancy between the bulk organic matter and n-alkane CIE may arise because of changes in soil organic matter cycling during the PETM. Bulk soil organic matter δ13C values are influenced by degradation and selective preservation whereas n-alkanes are resistant to diagenesis. Variations in sediment accumulation rates across the basin may be responsible for the differences between the four bulk organic carbon δ13C records. Sites with extended CIE bodies likely present more complete isotope records with greater time resolution and less time averaging than those with reduced CIEs. The shape of the high-resolution n-alkane curve presented here is similar to the newest 3He-based timescale for the PETM using data from Walvis Ridge, IODP site 1266 (Murphy et al., 2010). The most significant difference between this revised PETM timescale and previously published age models is the allocation of time within the PETM event. Murphy et

  19. A unified single-event microkinetic model for alkane hydroconversion in different aggregation states on Pt/H-USY-zeolites.

    PubMed

    Laxmi Narasimhan, C S; Thybaut, Joris W; Martens, Johan A; Jacobs, Pierre A; Denayer, Joeri F; Marin, Guy B

    2006-04-01

    A single-event microkinetic model for the catalytic hydroconversion of hydrocarbons on Pt/H-US-Y bifunctional zeolite catalysts developed for low-pressure vapor phase conditions was extended to cover high-pressure vapor phase and liquid phase conditions. The effect of the density of the bulk hydrocarbon phase on the physisorption as well as on the protonation steps of the reaction network was accounted for explicitly and can be interpreted in terms of "compression" of the hydrocarbon sorbate inside the zeolite pores and "solvation" of the catalyst framework by the dense bulk hydrocarbon phase. The bulk phase density effect on the physisorbed state is described via a single excess free enthalpy of physisorption. A dense bulk hydrocarbon phase destabilizes the sorbate molecules inside the catalyst pores. An expression of the excess free enthalpy of physisorption involving the fugacity coefficient and a zeolite dependent factor allows description of physisorption data. Typical excess free enthalpy values are in the range 1.5-5.1 kJ mol(-1) increasing with carbon number in the series of C5-C16 alkanes. At high-pressure vapor phase and liquid phase conditions, the excess standard protonation enthalpy is estimated at -7.8 kJ mol(-1) leading to relatively more stable carbenium ions at dense bulk phase conditions. As a result of the excess physisorption and protonation properties, the lightest hydrocarbons in mixtures are more competitive at dense phase conditions and their conversion is enhanced compared to low-density conditions. PMID:16570981

  20. Angiosperm n-alkane distribution patterns and the geologic record of C4 grassland evolution

    NASA Astrophysics Data System (ADS)

    Henderson, A.; Graham, H. V.; Patzkowsky, M.; Fox, D. L.; Freeman, K. H.

    2012-12-01

    n-Alkane average chain-length (ACL) patterns vary regionally with community composition and climate. To clarify the influence of phylogenetic and community patterns, we compiled and analyzed a global database of published n-alkane abundance for n-C27 to C35 homologs in modern plant specimens (n=205). ACL for waxes in C4 non-woody plants are longer than for woody plants, suggesting ACL can serve as an indicator of the three-dimensional structure of local vegetation. Further, these findings suggest compound-specific isotopic data for longer alkane homologs (C31, C33, C35) will proportionately represent non-woody vegetation and isotope measurements of C29 are more representative of woody vegetation. Thus, the combination of ACL and carbon isotope compositions should allow us to disentangle C3 woody, C3 non-woody, and C4 non-woody signals in terrestrial paleorecords. Application of this approach to the geologic record of Miocene C4 grassland expansion in the US Great Plains and the Siwaliks in Pakistan illustrate two very different transition scenarios. Alkane-specific isotopic data indicate C4 grasslands appeared 2.5 Ma in the Great Plains and 6.5 Ma in the Siwaliks, and ACL analysis indicates that this transition involved the replacement of woody vegetation in the US and the replacement of C3 grasses in Pakistan. Our analysis illustrates that, consistent with differences in the timing of C4 grassland, the drivers of change were likely not the same in these regions. Oxygen isotope records suggest that the more recent transition in the Great Plains was associated with climate cooling and possibly changes in disturbance regimes and that the transition in the Siwaliks was likely associated with warming and drying.

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

    SciTech Connect

    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.

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

    SciTech Connect

    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.

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

    PubMed Central

    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

  4. Iridium complexes of new NCP pincer ligands: catalytic alkane dehydrogenation and alkene isomerization.

    PubMed

    Jia, Xiangqing; Zhang, Lei; Qin, Chuan; Leng, Xuebing; Huang, Zheng

    2014-09-28

    Iridium complexes of novel NCP pincer ligands containing pyridine and phosphinite arms have been synthesized. One Ir complex shows good catalytic activity for alkane dehydrogenation, and all complexes are highly active for olefin isomerization. A combination of the Ir complex and a (PNN)Fe pincer complex catalyzes the formation of linear alkylboronates selectively from internal olefins via sequential olefin isomerization-hydroboration. PMID:25101950

  5. Carboxylic acid reductase is a versatile enzyme for the conversion of fatty acids into fuels and chemical commodities.

    PubMed

    Akhtar, M Kalim; Turner, Nicholas J; Jones, Patrik R

    2013-01-01

    Aliphatic hydrocarbons such as fatty alcohols and petroleum-derived alkanes have numerous applications in the chemical industry. In recent years, the renewable synthesis of aliphatic hydrocarbons has been made possible by engineering microbes to overaccumulate fatty acids. However, to generate end products with the desired physicochemical properties (e.g., fatty aldehydes, alkanes, and alcohols), further conversion of the fatty acid is necessary. A carboxylic acid reductase (CAR) from Mycobacterium marinum was found to convert a wide range of aliphatic fatty acids (C(6)-C(18)) into corresponding aldehydes. Together with the broad-substrate specificity of an aldehyde reductase or an aldehyde decarbonylase, the catalytic conversion of fatty acids to fatty alcohols (C(8)-C(16)) or fatty alkanes (C(7)-C(15)) was reconstituted in vitro. This concept was applied in vivo, in combination with a chain-length-specific thioesterase, to engineer Escherichia coli BL21(DE3) strains that were capable of synthesizing fatty alcohols and alkanes. A fatty alcohol titer exceeding 350 mg·L(-1) was obtained in minimal media supplemented with glucose. Moreover, by combining the CAR-dependent pathway with an exogenous fatty acid-generating lipase, natural oils (coconut oil, palm oil, and algal oil bodies) were enzymatically converted into fatty alcohols across a broad chain-length range (C(8)-C(18)). Together with complementing enzymes, the broad substrate specificity and kinetic characteristics of CAR opens the road for direct and tailored enzyme-catalyzed conversion of lipids into user-ready chemical commodities. PMID:23248280

  6. Carboxylic acid reductase is a versatile enzyme for the conversion of fatty acids into fuels and chemical commodities

    PubMed Central

    Akhtar, M. Kalim; Turner, Nicholas J.; Jones, Patrik R.

    2013-01-01

    Aliphatic hydrocarbons such as fatty alcohols and petroleum-derived alkanes have numerous applications in the chemical industry. In recent years, the renewable synthesis of aliphatic hydrocarbons has been made possible by engineering microbes to overaccumulate fatty acids. However, to generate end products with the desired physicochemical properties (e.g., fatty aldehydes, alkanes, and alcohols), further conversion of the fatty acid is necessary. A carboxylic acid reductase (CAR) from Mycobacterium marinum was found to convert a wide range of aliphatic fatty acids (C6–C18) into corresponding aldehydes. Together with the broad-substrate specificity of an aldehyde reductase or an aldehyde decarbonylase, the catalytic conversion of fatty acids to fatty alcohols (C8–C16) or fatty alkanes (C7–C15) was reconstituted in vitro. This concept was applied in vivo, in combination with a chain-length-specific thioesterase, to engineer Escherichia coli BL21(DE3) strains that were capable of synthesizing fatty alcohols and alkanes. A fatty alcohol titer exceeding 350 mg·L−1 was obtained in minimal media supplemented with glucose. Moreover, by combining the CAR-dependent pathway with an exogenous fatty acid-generating lipase, natural oils (coconut oil, palm oil, and algal oil bodies) were enzymatically converted into fatty alcohols across a broad chain-length range (C8–C18). Together with complementing enzymes, the broad substrate specificity and kinetic characteristics of CAR opens the road for direct and tailored enzyme-catalyzed conversion of lipids into user-ready chemical commodities. PMID:23248280

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

    PubMed

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

    2016-05-01

    Microbial transformation of n-alkanes in anaerobic ecosystems plays a pivotal role in biogeochemical carbon cycling and bioremediation, but the requisite genetic machinery is not well elucidated.Desulfatibacillum alkenivorans AK-01 utilizes n-alkanes (C13 to 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 investigate ass-gene expression across AK-01's known substrate range, and microarray-based transcriptomic analysis served to investigate whole-cell responses to growth on n-hexadecane versus hexadecanoate. RT-qPCR revealed induction of ass gene cluster 1 during growth on all tested alkane substrates, and the transcriptional start sites in cluster 1 were determined via 5'RACE. Induction of ass gene 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

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

    PubMed

    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

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

    SciTech Connect

    Doskey, P. V.; Environmental Research

    2000-01-01

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

  10. Chemistry Rocks: Redox Chemistry as a Geologic Tool.

    ERIC Educational Resources Information Center

    Burns, Mary Sue

    2001-01-01

    Applies chemistry to earth science, uses rocks in chemistry laboratories, and teaches about transition metal chemistry, oxidation states, and oxidation-reduction reactions from firsthand experiences. (YDS)

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

    PubMed

    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

  12. Line tension of alkane lenses on aqueous surfactant solutions at phase transitions of coexisting interfaces.

    PubMed

    Matsubara, Hiroki; Ushijima, Baku; Law, Bruce M; Takiue, Takanori; Aratono, Makoto

    2014-04-01

    Alkane droplets on aqueous solutions of surfactants exhibit a first-order wetting transition as the concentration of surfactant is increased. The low-concentration or "partial wetting" state corresponds to an oil lens in equilibrium with a two-dimensional dilute gas of oil and surfactant molecules. The high-concentration or "pseudo-partial wetting" state consists of an oil lens in equilibrium with a mixed monolayer of surfactant and oil. Depending on the combination of surfactant and oil, these mixed monolayers undergo a thermal phase transition upon cooling, either to a frozen mixed monolayer or to an unusual bilayer structure in which the upper leaflet is a solid layer of pure alkane with hexagonal packing and upright chains while the lower leaflet remains a disordered liquid-like mixed monolayer. Additionally, certain long-chain alkanes exhibit a surface freezing transition at the air-oil interface where the top monolayer of oil freezes above its melting point. In this review, we summarize our previous studies and discuss how these wetting and surface freezing transitions influence the line tension of oil lenses from both an experimental and theoretical perspective. PMID:24007861

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

    PubMed

    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

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

    PubMed

    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

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

    SciTech Connect

    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.

  16. Effect of geometrical confinement on the nucleation and crystallization behavior of n-alkane mixtures.

    PubMed

    Jiang, Kai; Su, Yunlan; Xie, Baoquan; Jiang, Shichun; Zhao, Ying; Wang, Dujin

    2008-12-25

    The condensed structure of normal alkane (n-alkane) mixtures in confined geometry is an interesting topic concerning the difference in crystallization behavior of odd and even alkanes. In the present work, the crystallization of mixtures of normal octadecane (n-C18H38) and normal nonadecane (n-C19H40) in microcapsules with narrow size distribution was investigated using the combination of differential scanning calorimetry (DSC) and X-ray diffraction (XRD). A surface freezing monolayer for microencapsulated n-C18H38, n-C19H40, and their mixture was detected by DSC, which for the mixture is a mixed homogeneous crystalline phase with continuous change in the composition. A more stable rotator phase (RI) was observed for the microencapsulated n-C18H38/n-C19H40 = 95/5 (molar ratio) mixture, confirmed by an increased supercooling of the transition from RI to stable phase compared to that of the mixture in bulk. Two nucleation mechanisms were speculated as "liquid-to-solid" heterogeneous nucleation and "solid-to-solid" homogeneous nucleation, which occur at different crystallization stages in microcapsules and might be attributed to the surface effect and confinement effect, respectively, in the confined geometry. PMID:19367940

  17. A new mechanism for regional atmospheric chemistry modeling

    NASA Astrophysics Data System (ADS)

    Stockwell, William R.; Kirchner, Frank; Kuhn, Michael; Seefeld, Stephan

    1997-11-01

    A new gas-phase chemical mechanism for the modeling of regional atmospheric chemistry, the "Regional Atmospheric Chemistry Mechanism" (RACM) is presented. The mechanism is intended to be valid for remote to polluted conditions and from the Earth's surface through the upper troposphere. The RACM mechanism is based upon the earlier Regional Acid Deposition Model, version 2 (RADM2) mechanism [Stockwell et al., 1990] and the more detailed Euro-RADM mechanism [Stockwell and Kley, 1994]. The RACM mechanism includes rate constants and product yields from the most recent laboratory measurements, and it has been tested against environmental chamber data. A new condensed reaction mechanism is included for biogenic compounds: isoprene, α-pinene, and d-limonene. The branching ratios for alkane decay were reevaluated, and in the revised mechanism the aldehyde to ketone ratios were significantly reduced. The relatively large amounts of nitrates resulting from the reactions of unbranched alkenes with NO3 are now included, and the production of HO from the ozonolysis of alkenes has a much greater yield. The aromatic chemistry has been revised through the use of new laboratory data. The yield of cresol production from aromatics was reduced, while the reactions of HO, NO3, and O3 with unsaturated dicarbonyl species and unsaturated peroxynitrate are now included in the RACM mechanism. The peroxyacetyl nitrate chemistry and the organic peroxy radical-peroxy radical reactions were revised, and organic peroxy radical +NO3 reactions were added.

  18. Chemistry at the Organic-Mineral Interface Relevant to Titan

    NASA Astrophysics Data System (ADS)

    Abbott-Lyon, Heather; Dawley, M.; McLain, J.; Grieves, G.; Orlando, T.

    2010-10-01

    The observation of rivers and lakes on Titan has generated considerable interest with regard to prebiotic chemistry, since these fluvial features provide a liquid medium for reactions and a transportation mechanism for catalytic mineral deposits left behind by meteorite impacts similar to the one that caused the Sinlap crater. Although numerous laboratory measurements and theoretical models have been used to study atmospheric chemistry applicable to Titan's potential astrobiology, few experiments have been performed to understand gas-/liquid-surface reactions. We are exploring heterogeneous chemistry relevant to Titan using low energy electrons (5-50 eV) as an analog of the incident cosmic rays and secondary electrons they generate. Amorphous alkane/acetylene ices have been deposited on mineral and carbon substrates to simulate lake environments. In some cases, small amounts of amorphous water ice have been deposited at the organic-mineral boundary to model the interface of the hydrocarbon "soil” and the underlying water-ice "bedrock” of Titan. Preliminary results suggest that protonation occurs readily even at the low temperatures observed on Titan's surface ( 100 K). These experiments are some of the first aimed at understanding chemistry at the organic-mineral interface under conditions relevant to Titan, in particular at the edges of hydrocarbon lakes. This work has been performed as part of the NASA Astrobiology Institute "Titan as a Prebiotic System” at the Jet Propulsion Laboratory.

  19. Fidelity of fossil n-alkanes from leaf to paleosol and applications to the Paleocene-Eocene Thermal Maximum

    NASA Astrophysics Data System (ADS)

    Bush, R. T.; McInerney, F. A.; Baczynski, A. A.; Wing, S. L.

    2011-12-01

    Long chain n-alkanes (C21-C35) are well-known as biomarkers of terrestrial plants. They can be preserved across a wide range of terrestrial and marine environments, survive in the sedimentary record for millions of years, and can serve as proxies for ancient environments. Most n-alkane records are derived from sediments rather than directly from fossil leaves. However, little is known about the fidelity of the n-alkane record: how and where leaf preservation relates to n-alkane preservation and how patterns of n-alkane carbon isotope ratios (δ13C) compare to living relatives. To examine these questions, we analyzed n-alkanes from fluvial sediments and individual leaf fossils collected in the Bighorn Basin, Wyoming, across the Paleocene-Eocene Thermal Maximum (PETM) carbon isotope excursion. We assessed the fidelity of the n-alkane signature from individual fossil leaves via three separate means. 1) Spatial variations were assessed by comparing n-alkane concentrations on a fossil leaf and in sediments both directly adjacent to the leaf and farther away. Absolute concentrations were greater within the compression fossil than in the directly adjacent sediment, which were in turn greater than in more distant sediment. 2) n-Alkane abundances and distributions were examined in fossil leaves having a range of preservational quality, from fossils with intact cuticle to carbonized fossils lacking cuticle and higher-order venation. The best preserved fossils preserved a higher concentration of n-alkanes and showed the most similar n-alkane distribution to living relatives. However, a strong odd over even predominance suggests a relatively unmodified plant source occurred in all samples regardless of preservation state. 3) n-Alkane δ13C values were measured for both fossil leaves and their living relatives. Both the saw-tooth pattern of δ13C values between odd and even chain lengths and the general decrease in δ13C values with increasing chain length are consistent with

  20. CHEMISTRY IN EVAPORATING ICES-UNEXPLORED TERRITORY

    SciTech Connect

    Cecchi-Pestellini, Cesare; Rawlings, Jonathan M. C.; Viti, Serena; Williams, David A. E-mail: jcr@star.ucl.ac.u E-mail: daw@star.ucl.ac.u

    2010-12-20

    We suggest that three-body chemistry may occur in warm high-density gas evaporating in transient co-desorption events on interstellar ices. Using a highly idealized computational model we explore the chemical conversion from simple species of the ice to more complex species containing several heavy atoms, as a function of density and of adopted three-body rate coefficients. We predict that there is a wide range of densities and rate coefficients in which a significant chemical conversion may occur. We discuss the implications of this idea for the astrochemistry of hot cores.

  1. Environmental swap energy and role of configurational entropy in transfer of small molecules from water into alkanes

    NASA Astrophysics Data System (ADS)

    Smejtek, Pavel; Word, Robert C.

    2004-01-01

    We studied the effect of segmented solvent molecules on the free energy of transfer of small molecules from water into alkanes (hexane, heptane, octane, decane, dodecane, tetradecane, and hexadecane). For these alkanes we measured partition coefficients of benzene, 3-methylindole (3MI), 2,3,4,6-tetrachlorophenol (TeCP), and 2,4,6-tribromophenol (TriBP) at 3, 11, 20, 3, and 47 °C. For 3MI, TeCP, and TriBP the dependence of free energy of transfer on length of alkane chains was found to be very different from that for benzene. In contrast to benzene, the energy of transfer for 3MI, TeCP, and TriBP was independent of the number of carbons in alkanes. To interpret data, we used the classic Flory-Huggins (FH) theory of concentrated polymer solutions for the alkane phase. For benzene, the measured dependence of energy of transfer on the number of carbons in alkanes agreed well with predictions based on FH model in which the size of alkane segments was obtained from the ratio of molar volumes of alkanes and the solute. We show that for benzene, the energy of transfer can be divided into two components, one called environmental swap energy (ESE), and one representing the contribution of configurational entropy of alkane chains. For 3MI, TeCP, and TriBP the contribution of configurational entropy was not measurable even though the magnitude of the effect predicted from the FH model for short chain alkanes was as much as 20 times greater than experimental uncertainties. From the temperature dependence of ESE we obtained enthalpy and entropy of transfer for benzene, 3MI, TeCP, and TriBP. Experimental results are discussed in terms of a thermodynamic cycle considering creation of cavity, insertion of solute, and activation of solute-medium attractive interactions. Our results suggest that correcting experimental free energy of transfer by Flory-Huggins configurational entropy term is not generally appropriate and cannot be applied indiscriminately.

  2. Conversing with Computers

    NASA Technical Reports Server (NTRS)

    2004-01-01

    I/NET, Inc., is making the dream of natural human-computer conversation a practical reality. Through a combination of advanced artificial intelligence research and practical software design, I/NET has taken the complexity out of developing advanced, natural language interfaces. Conversational capabilities like pronoun resolution, anaphora and ellipsis processing, and dialog management that were once available only in the laboratory can now be brought to any application with any speech recognition system using I/NET s conversational engine middleware.

  3. Environmental chemistry: Volume A

    SciTech Connect

    Yen, T.F.

    1999-08-01

    This is an extensive introduction to environmental chemistry for engineering and chemical professionals. The contents of Volume A include a brief review of basic chemistry prior to coverage of litho, atmo, hydro, pedo, and biospheres.

  4. Special Report: Brain Chemistry.

    ERIC Educational Resources Information Center

    Krassner, Michael B.

    1983-01-01

    Chemical actions in the brain result in cognitive, emotional, neuroendocrine, neuromuscular, and/or neurocirculatory effects. Developments in understanding brain chemistry are discussed, considering among others, neurotransmitter chemistry, neuropeptides, drugs and the brain, antidepressants, and actions of minor tranquilizers. (JN)

  5. Chemistry for Potters.

    ERIC Educational Resources Information Center

    Denio, Allen A.

    1980-01-01

    Relates pottery making to chemistry by providing chemical information about clay, its origin, composition, properties, and changes that occur during firing; also describes glaze compositions, examples of redox chemistry, salt glazing, crystalline glazes, and problems in toxicity. (CS)

  6. Organometallic Chemistry of Molybdenum.

    ERIC Educational Resources Information Center

    Lucas, C. Robert; Walsh, Kelly A.

    1987-01-01

    Suggests ways to avoid some of the problems students have learning the principles of organometallic chemistry. Provides a description of an experiment used in a third-year college chemistry laboratory on molybdenum. (TW)

  7. Chemistry and Art.

    ERIC Educational Resources Information Center

    Berry, Martyn

    1999-01-01

    Describes a Chemistry and Art project developed for secondary students and teachers sponsored by the National Gallery and The Royal Society of Chemistry in the United Kingdom. Discusses aspects of the techniques used in creating five paintings as well as the chemistry involved in their making, deterioration, conservation, and restoration.…

  8. Teaching School Chemistry.

    ERIC Educational Resources Information Center

    Waddington, D. J., Ed.

    This eight-chapter book is intended for use by chemistry teachers, curriculum developers, teacher educators, and other key personnel working in the field of chemical education. The chapters are: (1) "The Changing Face of Chemistry" (J. A. Campbell); (2) "Curriculum Innovation in School Chemistry" (R. B. Ingel and A. M. Ranaweera); (3) "Some…

  9. Green Chemistry and Education.

    ERIC Educational Resources Information Center

    Hjeresen, Dennis L.; Schutt, David L.; Boese, Janet M.

    2000-01-01

    Many students today are profoundly interested in the sustainability of their world. Introduces Green Chemistry and its principles with teaching materials. Green Chemistry is the use of chemistry for pollution prevention and the design of chemical products and processes that are environmentally benign. (ASK)

  10. Environmental Chemistry Activities.

    ERIC Educational Resources Information Center

    Jackland, Thomas; And Others

    The authors of this curriculum supplement believe in a laboratory approach to chemistry and express the feeling that environmental chemistry provides the students an opportunity to apply theoretical chemistry to important practical problems. There are eighteen activities presented, each accompanied with behavioral objectives, one or more suggested…

  11. Chemistry on Stamps.

    ERIC Educational Resources Information Center

    Schreck, James O.

    1986-01-01

    Suggests how postage stamps can be incorporated into chemistry teaching. Categories considered include emergence of chemistry as a science, metric system, atoms (and molecules and ions), stoichiometry, energy relationships in chemical systems, chemical bonding, nuclear chemistry, biochemistry, geochemistry, matter (gases, liquids, and solids),…

  12. Chemistry as General Education

    ERIC Educational Resources Information Center

    Tro, Nivaldo J.

    2004-01-01

    The efficacy of different science and chemistry courses for science-major and non-major students, and the question of chemistry's contribution to general education are evaluated. Chemistry and science curriculum are too profession- and consumer-oriented, and to overcome this problem, it is advised that all disciplines must incorporate the major…

  13. History of Chemistry.

    ERIC Educational Resources Information Center

    Servos, John W.

    1985-01-01

    Discusses the development of chemistry in the United States by considering: (1) chemistry as an evolving body of ideas/techniques, and as a set of conceptual resources affecting and affected by the development of other sciences; and (2) chemistry related to the history of American social and economic institutions and practices. (JN)

  14. Conversion of biomass to selected chemical products.

    PubMed

    Gallezot, Pierre

    2012-02-21

    This critical review provides a survey illustrated by recent references of different strategies to achieve a sustainable conversion of biomass to bioproducts. Because of the huge number of chemical products that can be potentially manufactured, a selection of starting materials and targeted chemicals has been done. Also, thermochemical conversion processes such as biomass pyrolysis or gasification as well as the synthesis of biofuels were not considered. The synthesis of chemicals by conversion of platform molecules obtained by depolymerisation and fermentation of biopolymers is presently the most widely envisioned approach. Successful catalytic conversion of these building blocks into intermediates, specialties and fine chemicals will be examined. However, the platform molecule value chain is in competition with well-optimised, cost-effective synthesis routes from fossil resources to produce chemicals that have already a market. The literature covering alternative value chains whereby biopolymers are converted in one or few steps to functional materials will be analysed. This approach which does not require the use of isolated, pure chemicals is well adapted to produce high tonnage products, such as paper additives, paints, resins, foams, surfactants, lubricants, and plasticisers. Another objective of the review was to examine critically the green character of conversion processes because using renewables as raw materials does not exempt from abiding by green chemistry principles (368 references). PMID:21909591

  15. Evaluating the potential of long chain n-alkanes and n-carboxylic acids as biomarkers for past vegetation

    NASA Astrophysics Data System (ADS)

    Lanny, Verena; Zech, Roland; Eglinton, Timothy

    2014-05-01

    Leaf waxes, such as long chain n-alkanes and n-carboxylic acids, may have a great potential for the reconstruction of past environmental and climate conditions (e.g. (Zech R. et al., 2013). While n-C27 and n-C29 alkanes often predominantly occur in trees and shrubs, n-C31 and n-C33 are more abundant in grasses and herbs. However, little is known about chain-length distributions of n-carboxylic acids, and very few studies have systematically investigated leaf waxes in top soils. We analyzed n-alkanes and n-carboxylic acids in ~100 litter and topsoil samples from Southern Germany to Sweden. Our results show that sites under deciduous trees often contain a lot of C27 n-alkanes and C28 n-carboxylic acids. Coniferous sites are characterized by dominance in n-alkanes C29 and C31 and have relatively high concentrations of n-carboxylic acids C22 and C24. Grass sites show a Cmax at C31 for n-alkanes and at C24 or C26 for n-carboxylic acids. Differences in homologue patterns are most pronounced in the litter samples, but are well preserved also in the topsoils (0-3 cm depth, a little less in the lower topsoils from 3-10 cm). Our results illustrate the potential of combining n-alkane and n-carboxylic acid analyses for paleo-vegetation reconstructions, yet indicate that the degree of degradation may have to be taken into consideration (Zech M. et al., 2013). References: Zech, M. et al. (2013) Quat. Int. 296, 108-116. Zech, R. et al. (2013) Palaeo3, 387, 165-175.

  16. School Chemistry vs. Chemistry in Research: An Exploratory Experiment.

    ERIC Educational Resources Information Center

    Habraken, Clarisse L.; Buijs, Wim; Borkent, Hens; Ligeon, Willy; Wender, Harry; Meijer, Marijn

    2001-01-01

    Reports on a study exploring why students are not studying chemistry. Three groups of graduating high school students and their chemistry teachers stayed at a research institute working on molecular modeling and wrote essays on school chemistry versus chemistry in research. Concludes that school chemistry does not convey today's chemistry in…

  17. Light-Emitting Diodes for Analytical Chemistry

    NASA Astrophysics Data System (ADS)

    Macka, Mirek; Piasecki, Tomasz; Dasgupta, Purnendu K.

    2014-06-01

    Light-emitting diodes (LEDs) are playing increasingly important roles in analytical chemistry, from the final analysis stage to photoreactors for analyte conversion to actual fabrication of and incorporation in microdevices for analytical use. The extremely fast turn-on/off rates of LEDs have made possible simple approaches to fluorescence lifetime measurement. Although they are increasingly being used as detectors, their wavelength selectivity as detectors has rarely been exploited. From their first proposed use for absorbance measurement in 1970, LEDs have been used in analytical chemistry in too many ways to make a comprehensive review possible. Hence, we critically review here the more recent literature on their use in optical detection and measurement systems. Cloudy as our crystal ball may be, we express our views on the future applications of LEDs in analytical chemistry: The horizon will certainly become wider as LEDs in the deep UV with sufficient intensity become available.

  18. Chemistry and physics of coal utilization - 1980

    SciTech Connect

    Cooper, B.R.; Petrakis, L.

    1981-01-01

    The Conference on the Chemistry and Physics of Coal Utilization was designed as an interdisciplinary conference centered on the physics and chemistry phenomena involved in coal utilization, including the chemistry and physics of coal itself. The Conference was designated as a Topical Conference of the American Physical Society, and was held on June 2-4, 1980, at the Lakeview Inn in Morgantown, West Virginia. It was primarily intended as a working conference for those already engaged in, or at least technically informed on, coal conversion and utilization research. The program consisted of lectures by 23 invited speakers and two panel discussions by invited experts. In addition there were two sessions at which a total of 49 poster contributions were presented. This volume contains the invited papers (with one exception), reports of the panel discussions, and abstracts for the poster contributions. The individual papers are entered individually into EDB from a tape prepared by the American Institute of Physics. (LTN)

  19. American Association for Clinical Chemistry

    MedlinePlus

    ... indispensable patient care tool. Learn more IN CLINICAL CHEMISTRY ddPCR Quantification of Lymphoma Mutations Researchers have developed ... Online Harmonization.net Commission on Accreditation in Clinical Chemistry American Board of Clinical Chemistry Clinical Chemistry Trainee ...

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

    PubMed

    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

  1. Common conversion factors.

    PubMed

    2001-05-01

    This appendix presents tables of some of the more common conversion factors for units of measure used throughout Current Protocols manuals, as well as prefixes indicating powers of ten for SI units. Another table gives conversions between temperatures on the Celsius (Centigrade) and Fahrenheit scales. PMID:18770653

  2. Assessment through Conversation.

    ERIC Educational Resources Information Center

    Fu, Danling; Lamme, Linda L.

    2002-01-01

    Presents conversations with parents, teachers, and children around portfolios that provide a better picture of a child's growth and understanding than standardized test scores ever can. Concludes that the involvement of students, teachers, and parents in conversation about children's literacy development brings the potential of a common vision and…

  3. Marathi Conversational Situations.

    ERIC Educational Resources Information Center

    Berntsen, Maxine; Nimbkar, Jai

    This volume is an elementary Marathi conversation text for adult learners of Marathi, both foreign and Indian. Designed to be used in conjunction with "Marathi Structural Patterns. Book One," the volume presents over 80 conversations that include material required in everyday situations. Each section contains basic and more difficult…

  4. Energy conversion alternatives study

    NASA Technical Reports Server (NTRS)

    Shure, L. T.

    1979-01-01

    Comparison of coal based energy systems is given. Study identifies and compares various advanced energy conversion systems using coal or coal derived fuels for baselaoad electric power generation. Energy Conversion Alternatives Study (ECAS) reports provede government, industry, and general public with technically consistent basis for comparison of system's options of interest for fossilfired electric-utility application.

  5. NUCLEAR CONVERSION APPARATUS

    DOEpatents

    Seaborg, G.T.

    1960-09-13

    A nuclear conversion apparatus is described which comprises a body of neutron moderator, tubes extending therethrough, uranium in the tubes, a fluid- circulating system associated with the tubes, a thorium-containing fluid coolant in the system and tubes, and means for withdrawing the fluid from the system and replacing it in the system whereby thorium conversion products may be recovered.

  6. Changing Our Conversations

    ERIC Educational Resources Information Center

    Porto, Mark

    2007-01-01

    In this article, a principal is inspired to change the conversations with students and staff members from discipline and deficit to hope and planning for future achievement. He wants conversations to be more about academic goals and decision making and less about discipline and random acceptance of postsecondary plans. He has asked all staff…

  7. The Renaissance of Non-Aqueous Uranium Chemistry.

    PubMed

    Liddle, Stephen T

    2015-07-20

    Prior to the year 2000, non-aqueous uranium chemistry mainly involved metallocene and classical alkyl, amide, or alkoxide compounds as well as established carbene, imido, and oxo derivatives. Since then, there has been a resurgence of the area, and dramatic developments of supporting ligands and multiply bonded ligand types, small-molecule activation, and magnetism have been reported. This Review 1) introduces the reader to some of the specialist theories of the area, 2) covers all-important starting materials, 3) surveys contemporary ligand classes installed at uranium, including alkyl, aryl, arene, carbene, amide, imide, nitride, alkoxide, aryloxide, and oxo compounds, 4) describes advances in the area of single-molecule magnetism, and 5) summarizes the coordination and activation of small molecules, including carbon monoxide, carbon dioxide, nitric oxide, dinitrogen, white phosphorus, and alkanes. PMID:26079536

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    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

  10. Conversion of methane to higher hydrocarbons in ac nonequilibrium plasmas

    SciTech Connect

    Thanyachotpaiboon, K.; Chavadej; Caldwell, T.A.; Lobban, L.L.; Mallinson, R.G.

    1998-10-01

    The effects of plasma chemistry on the conversion of methane were studied using a dielectric barrier discharge reactor at ambient temperatures. A dielectric barrier discharge reactor generates a nonequilibrium plasma when a sufficiently high voltage is applied across the reactor`s electrodes. Methane molecules are activated at this temperature and coupled to form C{sub 2} hydrocarbons, higher hydrocarbons, and hydrogen. The study on the effect of voltage, residence time and third bodies on methane conversion and product selectivity shows that methane conversion initially increases with increasing voltage and residence time above the breakdown voltage, and product selectivities are essentially independent of the voltage. Production of hydrogen during the reaction limits olefin production. Methane conversion also increases when helium and ethane are in the feed stream. Helium and ethane both appear to be more easily activated than methane and enhance methane activation and conversion.

  11. Alkanes and alkenes in Mediterranean volcanic-hydrothermal systems: origins and geothermometry

    NASA Astrophysics Data System (ADS)

    Fiebig, Jens; D'Alessandro, Walter; Tassi, Franco; Woodland, Alan

    2010-05-01

    It is still a matter of debate if nature provides conditions for abiogenic production of hydrocarbons. Methane (C1) and the C2+ alkanes emanating from ultramafic hydrothermal systems such as Lost City have been considered to be abiogenic in origin, mainly because of the occurrence of an isotopic reversal between methane and the C2+hydrocarbons and C1/C2+ ratios >1000 [1]. Abiogenic production of methane has been postulated to occur under the relatively oxidizing redox conditions of continental-hydrothermal systems, too. It was observed that temperatures received from the H2-H2O-CO-CO2-CH4 geoindicator were coincident with temperatures derived from carbon isotope partitioning between CO2 and CH4in gases released from the Mediterranean volcanic-hydrothermal systems of Nisyros (Greece), Vesuvio and Ischia (both Italy) [2]. Such equilibrium pattern, if not fortuitous, can only be obtained if mantle- and marine limestone-derived CO2 is reduced to CH4. At Nisyros, observed C1/C2+ ratios from 300-4000 are in agreement with an abiogenic origin of the methane. Ethane and propane, however, were shown to be non-genetic with CO2 and methane. C1/C2 and C2/C3 distribution ratios may point to the admixture of small amounts of hydrocarbons deriving from the thermal decomposition of organic matter along with abiogenically equilibrated methane essentially devoid of the higher hydrocarbons [3]. Here, we provide new isotopic and hydrocarbon concentration data on several Mediterranean volcanic-hydrothermal systems, including Nisyros, Vesuvio, Ischia, Vulcano, Solfatara and Pantelleria. Wherever possible, we have extended our data set for the hydrogen isotope composition of CH4 and H2, n-alkane- and alkene/alkane-distribution ratios. At Nisyros, measured alkene/alkane- and H2/H2O concentration ratios confirm the attainment of equilibrium between CO2 and CH4. CO2 and CH4 appear to have equilibrated in the liquid phase at temperatures of ~360° C and redox conditions closely corresponding

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

    SciTech Connect

    Bruheim, P.; Bredholt, H.; Eimhjellen, K.

    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.

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

    PubMed

    Ingrid, Lenoir; Lounès-Hadj Sahraoui, Anissa; Frédéric, Laruelle; Yolande, Dalpé; Joël, Fontaine

    2016-06-01

    Very few studies reported the potential of arbuscular mycorrhizal symbiosis to dissipate hydrocarbons in aged polluted soils. The present work aims to study the efficiency of arbuscular mycorrhizal colonized wheat plants in the dissipation of alkanes and polycyclic aromatic hydrocarbons (PAHs). Our results demonstrated that the inoculation of wheat with Rhizophagus irregularis allowed a better dissipation of PAHs and alkanes after 16 weeks of culture by comparison to non-inoculated condition. These dissipations observed in the inoculated soil resulted from several processes: (i) a light adsorption on roots (0.5% for PAHs), (ii) a bioaccumulation in roots (5.7% for PAHs and 6.6% for alkanes), (iii) a transfer in shoots (0.4 for PAHs and 0.5% for alkanes) and mainly a biodegradation. Whereas PAHs and alkanes degradation rates were respectively estimated to 12 and 47% with non-inoculated wheat, their degradation rates reached 18 and 48% with inoculated wheat. The mycorrhizal inoculation induced an increase of Gram-positive and Gram-negative bacteria by 56 and 37% compared to the non-inoculated wheat. Moreover, an increase of peroxidase activity was assessed in mycorrhizal roots. Taken together, our findings suggested that mycorrhization led to a better hydrocarbon biodegradation in the aged-contaminated soil thanks to a stimulation of telluric bacteria and hydrocarbon metabolization in mycorrhizal roots. PMID:26995451

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

    PubMed

    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

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

    PubMed

    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

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

    PubMed

    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

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

    PubMed Central

    Hayashi, Yuuki; Yasugi, Fumitaka; Arai, Munehito

    2015-01-01

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

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

    PubMed

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

    2015-07-01

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

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

    PubMed Central

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

    2014-01-01

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

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

    SciTech Connect

    Jeong, Cheol; Douglas, Jack F.

    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.

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

    NASA Astrophysics Data System (ADS)

    Jeong, Cheol; Douglas, Jack F.

    2015-10-01

    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.

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

    PubMed

    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

  3. New covalent modifications of phosphatidylethanolamine by alkanals: mass spectrometry based structural characterization and biological effects

    PubMed Central

    Annibal, Andrea; Schubert, Kristin; Wagner, Ulf; Hoffmann, Ralf; Schiller, Jürgen; Fedorova, Maria

    2014-01-01

    The pathophysiology of numerous human disorders, such as atherosclerosis, diabetes, obesity and Alzheimer's disease, is accompanied by increased production of reactive oxygen species (ROS). ROS can oxidatively damage nearly all biomolecules, including lipids, proteins and nucleic acids. In particular, (poly)unsaturated fatty acids within the phospholipid (PL) structure are easily oxidized by ROS to lipid peroxidation products (LPP) carrying reactive carbonyl groups. Carbonylated LPP are characterized by high in vivo toxicity due to their reactivity with nucleophilic substrates (Lys-, Cys-and His-residues in proteins or amino groups of phosphatidylethanolamines [PE]). Adducts of unsaturated LPP with PE amino groups have been reported before, whereas less is known about the reactivity of saturated alkanals – which are significantly increased in vivo under oxidative stress conditions – towards nucleophilic groups of PLs. Here, we present a study of new alkanal-dipalmitoyl-phosphatidylethanolamine (DPPE) adducts by MS-based approaches, using consecutive fragmentation (MSn) and multiple reaction monitoring techniques. At least eight different DPPE–hexanal adducts were identified, including Schiff base and amide adducts, six of which have not been reported before. The structures of these new compounds were determined by their fragmentation patterns using MSn experiments. The new PE-hexanal adducts contained dimeric and trimeric hexanal conjugates, including cyclic adducts. A new pyridine ring containing adduct of DPPE and hexanal was purified by HPLC, and its biological effects were investigated. Incubation of peripheral blood mononuclear cells and monocytes with modified DPPE did not result in increased production of TNF-α as one selected inflammation marker. However, incorporation of modified DPPE into 1,2-dipalmitoleoyl-sn-phosphatidylethanolamine multilamellar vesicles resulted in a negative shift of the transition temperature, indicating a possible role of

  4. Dependence on chain length of NMR relaxation times in mixtures of alkanes

    NASA Astrophysics Data System (ADS)

    Freed, Denise E.

    2007-05-01

    Many naturally occurring fluids, such as crude oils, consist of a very large number of components. It is often of interest to determine the composition of the fluids in situ. Diffusion coefficients and nuclear magnetic resonance (NMR) relaxation times can be measured in situ and depend on the size of the molecules. It has been shown [D. E. Freed et al., Phys. Rev. Lett. 94, 067602 (2005)] that the diffusion coefficient of each component in a mixture of alkanes follows a scaling law in the chain length of that molecule and in the mean chain length of the mixture, and these relations were used to determine the chain length distribution of crude oils from NMR diffusion measurements. In this paper, the behavior of NMR relaxation times in mixtures of chain molecules is addressed. The author explains why one would expect scaling laws for the transverse and longitudinal relaxation times of mixtures of short chain molecules and mixtures of alkanes, in particular. It is shown how the power law dependence on the chain length can be calculated from the scaling laws for the translational diffusion coefficients. The author fits the literature data for NMR relaxation in binary mixtures of alkanes and finds that its dependence on chain length agrees with the theory. Lastly, it is shown how the scaling laws in the chain length and the mean chain length can be used to determine the chain length distribution in crude oils that are high in saturates. A good fit is obtained between the NMR-derived chain length distributions and the ones from gas chromatography.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Quantification of hydrogen peroxide during the low-temperature oxidation of alkanes

    PubMed Central

    Bahrini, Chiheb; Herbinet, Olivier; Glaude, Pierre-Alexandre; Schoemaecker, Coralie; Fittschen, Christa; Battin-Leclerc, Frédérique

    2013-01-01

    The first reliable quantification of hydrogen peroxide (H2O2) formed during the low temperature oxidation of an organic compound has been achieved thanks to a new system that couples a jet stirred reactor to a detection by continuous wave cavity ring-down spectroscopy (cw-CRDS) in the near infrared. The quantification of this key compound for hydrocarbon low-temperature oxidation regime has been obtained under conditions close to those actually observed before the autoignition. The studied hydrocarbon was n-butane, the smallest alkane which has an oxidation behaviour close to that of the species present in gasoline and diesel fuels. PMID:22746212

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  8. Reprint of "Stable hydrogen and carbon isotopic compositions of long-chain (C21-C33) n-alkanes and n-alkenes in insects"

    NASA Astrophysics Data System (ADS)

    Chikaraishi, Yoshito; Kaneko, Masanori; Ohkouchi, Naohiko

    2013-06-01

    We report the molecular and stable isotopic (δD and δ13C) compositions of long-chain n-alkanes in common insects including the cabbage butterfly, swallowtail, wasp, hornet, grasshopper, and ladybug. Insect n-alkanes are potential candidates of the contamination of soil and sedimentary n-alkanes that are believed to be derived from vascular plant waxes. Long-chain n-alkanes (range C21-33; maximum C23-C29) are found to be abundant in the insects (31-781 μg/dry g), with a carbon preference index (CPI) of 5.1-31.5 and an average chain length (ACL) of 24.9-29.3. The isotopic compositions (mean ± 1σ, n = 33) of the n-alkanes are -195 ± 16‰ for hydrogen and -30.6 ± 2.4‰ for carbon. The insect n-alkanes are depleted in D by approximately 30-40‰ compared with wax n-alkanes from C3 (-155 ± 25‰) and C4 vascular plants (-167 ± 13‰), whereas their δ13C values fall between those of C3 (-36.2 ± 2.4‰) and C4 plants (-20.3 ± 2.4‰). Thus, the contribution of insect-derived n-alkanes to soil and sediment could potentially shift δD records of n-alkanes toward more negative values and potentially muddle the assumed original C3/C4 balance in the δ13C records of the soil and sedimentary n-alkanes. n-Alkenes are also found in three insects (swallowtail, wasp and hornet). They are more depleted in D relative to the same carbon numbered n-alkanes (δDn-alkene - δDn-alkane = -17 ± 16‰), but the δ13C values are almost identical to those of the n-alkanes (δ13Cn-alkene - δ13Cn-alkane = 0.1 ± 0.2‰). These results suggest that these n-alkenes are desaturated products of the same carbon numbered n-alkanes.

  9. Stable hydrogen and carbon isotopic compositions of long-chain (C21-C33) n-alkanes and n-alkenes in insects

    NASA Astrophysics Data System (ADS)

    Chikaraishi, Yoshito; Kaneko, Masanori; Ohkouchi, Naohiko

    2012-10-01

    We report the molecular and stable isotopic (δD and δ13C) compositions of long-chain n-alkanes in common insects including the cabbage butterfly, swallowtail, wasp, hornet, grasshopper, and ladybug. Insect n-alkanes are potential candidates of the contamination of soil and sedimentary n-alkanes that are believed to be derived from vascular plant waxes. Long-chain n-alkanes (range C21-33; maximum C23-C29) are found to be abundant in the insects (31-781 μg/dry g), with a carbon preference index (CPI) of 5.1-31.5 and an average chain length (ACL) of 24.9-29.3. The isotopic compositions (mean ± 1σ, n = 33) of the n-alkanes are -195 ± 16‰ for hydrogen and -30.6 ± 2.4‰ for carbon. The insect n-alkanes are depleted in D by approximately 30-40‰ compared with wax n-alkanes from C3 (-155 ± 25‰) and C4 vascular plants (-167 ± 13‰), whereas their δ13C values fall between those of C3 (-36.2 ± 2.4‰) and C4 plants (-20.3 ± 2.4‰). Thus, the contribution of insect-derived n-alkanes to soil and sediment could potentially shift δD records of n-alkanes toward more negative values and potentially muddle the assumed original C3/C4 balance in the δ13C records of the soil and sedimentary n-alkanes. n-Alkenes are also found in three insects (swallowtail, wasp and hornet). They are more depleted in D relative to the same carbon numbered n-alkanes (δDn-alkene - δDn-alkane = -17 ± 16‰), but the δ13C values are almost identical to those of the n-alkanes (δ13Cn-alkene - δ13Cn-alkane = 0.1 ± 0.2‰). These results suggest that these n-alkenes are desaturated products of the same carbon numbered n-alkanes.

  10. Postoperative conversion disorder.

    PubMed

    Afolabi, Kola; Ali, Sameer; Gahtan, Vivian; Gorji, Reza; Li, Fenghua; Nussmeier, Nancy A

    2016-05-01

    Conversion disorder is a psychiatric disorder in which psychological stress causes neurologic deficits. A 28-year-old female surgical patient had uneventful general anesthesia and emergence but developed conversion disorder 1 hour postoperatively. She reported difficulty speaking, right-hand numbness and weakness, and right-leg paralysis. Neurologic examination and imaging revealed no neuronal damage, herniation, hemorrhage, or stroke. The patient mentioned failing examinations the day before surgery and discontinuing her prescribed antidepressant medication, leading us to diagnose conversion disorder, with eventual confirmation by neuroimaging and follow-up examinations. PMID:27041258

  11. LTE plasma reactors for materials conversion

    NASA Astrophysics Data System (ADS)

    Kolacinski, Zbigniew; Szymanski, Lukasz; Raniszewski, Grzegorz

    2013-02-01

    Plasma aided materials conversion is the use of charged particles for producing new materials with unusual and superior properties or to convert unwanted materials such as waste into environmentally friendly products. The near LTE plasma (in atmospheric or reduced pressure) is a nice tool for engineering of materials which in consequence upgrades the performance of most of the consumer goods. The paper presents a few samples of the own research results related to the design and use of some plasma reactors for synthesis of nanomaterials and hazardous materials destruction with their conversion into valuable products. Contribution to the Topical Issue "13th International Symposium on High Pressure Low Temperature Plasma Chemistry (Hakone XIII)", Edited by Nicolas Gherardi, Henryca Danuta Stryczewska and Yvan Ségui.

  12. Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

    SciTech Connect

    Lee-Taylor, J.; Madronich, Sasha; Aumont, B.; Baker, A.; Camredon, M.; Hodzic, Alma; Tyndall, G. S.; Apel, Eric; Zaveri, Rahul A.

    2011-12-21

    The evolution of organic aerosols (OA) in Mexico City and its outflow is investigated with the nearly explicit gas phase photochemistry model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), wherein precursor hydrocarbons are oxidized to numerous intermediate species for which vapor pressures are computed and used to determine gas/particle partitioning in a chemical box model. Precursor emissions included observed C3-10 alkanes, alkenes, and light aromatics, as well as larger n-alkanes (up to C25) not directly observed but estimated by scaling to particulate emissions according to their volatility. Conditions were selected for comparison with observations made in March 2006 (MILAGRO). The model successfully reproduces the magnitude and diurnal shape for both primary (POA) and secondary (SOA) organic aerosols, with POA peaking in the early morning at 15-20 ug m-3, and SOA peaking at 10-15 μg m-3 during mid-day. The majority (> 75%) of the model SOA stems from the large n-alkanes, with the remainder mostly from the light aromatics. Simulated OA elemental composition reproduces observed H/C and O/C ratios reasonably well, although modeled ratios develop more slowly than observations suggest. SOA chemical composition is initially dominated by *- hydroxy ketones and nitrates from the large alkanes, with contributions from peroxy acyl nitrates and, at later times when NOx is lower, organic hydroperoxides. The simulated plume-integrated OA mass continues to increase for several days downwind despite dilution-induced particle evaporation, since oxidation chemistry leading to SOA formation remains strong. In this model, the plume SOA burden several days downwind exceeds that leaving the city by a factor of >3. These results suggest significant regional radiative impacts of SOA.

  13. Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J.; Madronich, S.; Aumont, B.; Baker, A.; Camredon, M.; Hodzic, A.; Tyndall, G. S.; Apel, E.; Zaveri, R. A.

    2011-12-01

    The evolution of organic aerosols (OA) in Mexico City and its outflow is investigated with the nearly explicit gas phase photochemistry model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), wherein precursor hydrocarbons are oxidized to numerous intermediate species for which vapor pressures are computed and used to determine gas/particle partitioning in a chemical box model. Precursor emissions included observed C3-10 alkanes, alkenes, and light aromatics, as well as larger n-alkanes (up to C25) not directly observed but estimated by scaling to particulate emissions according to their volatility. Conditions were selected for comparison with observations made in March 2006 (MILAGRO). The model successfully reproduces the magnitude and diurnal shape for both primary (POA) and secondary (SOA) organic aerosols, with POA peaking in the early morning at 15-20 μg m-3, and SOA peaking at 10-15 μg m-3 during mid-day. The majority (≥75%) of the model SOA stems from reaction products of the large n-alkanes, used here as surrogates for all emitted hydrocarbons of similar volatility, with the remaining SOA originating mostly from the light aromatics. Simulated OA elemental composition reproduces observed H/C and O/C ratios reasonably well, although modeled ratios develop more slowly than observations suggest. SOA chemical composition is initially dominated by δ-hydroxy ketones and nitrates from the large alkanes, with contributions from peroxy acyl nitrates and, at later times when NOx is lower, organic hydroperoxides. The simulated plume-integrated OA mass continues to increase for several days downwind despite dilution-induced particle evaporation, since oxidation chemistry leading to SOA formation remains strong. In this model, the plume SOA burden several days downwind exceeds that leaving the city by a factor of >3. These results suggest significant regional radiative impacts of SOA.

  14. Axial Chiral Bisbenzophenazines: Solid-State Self-Assembly via Halide Hydrogen Bonds Triggered by Linear Alkanes

    PubMed Central

    2015-01-01

    An axial chiral tetrachlorinated bisbenzo[a]phenazine has been discovered that undergoes an alkane-induced shift in the solid state from a disordered amorphous form to an ordered polycrystalline form. This phase transition is caused by the formation of pores that accommodate linear alkanes of varying lengths with a very strong affinity as judged by differential scanning calorimetry. Single crystal X-ray structure analysis revealed that a series of weak phenolic OH···Cl hydrogen bonds dictates the pore structure. These weak interactions can be disrupted mechanically, causing the material to revert to the amorphous form. Notably, the interchange between the amorphous and crystalline forms is readily reversible and is easily observed by characteristic colorimetric changes. Measurements via photoimage processing reveal that the degree of color change is dictated by the type of alkane employed. PMID:25019179

  15. Industrial Chemistry and School Chemistry: Making chemistry studies more relevant

    NASA Astrophysics Data System (ADS)

    Hofstein, Avi; Kesner, Miri

    2006-07-01

    In this paper, we present the development and implementation over the period of more than 15 years of learning materials focusing on industrial chemistry as the main theme. The work was conducted in the Department of Science Teaching at the Weizmann Institute of Science, Israel. The project’s general goal was to teach chemistry concepts in the context of industrial chemistry in order to present chemistry as a relevant topic both to the students personally as well as to the society in which they live. The learning materials that were developed during this period were in alignment with the changes and reforms that were conducted in the Israeli educational system. These developments were accompanied with intensive and comprehensive professional development courses and workshops. In addition, several research and evaluation projects were conducted with the goal to assess students’ achievements and to probe into the students’ perceptions regarding the classroom learning environment and the teachers’ and students’ attitudes towards the various instructional and learning materials techniques that were implemented in the programme throughout these years. This paper is structured attempting to describe the curricular cycle in alignment with Goodlad’s and Van den Akker’s curriculum representations.

  16. Responsive Teaching through Conversation

    ERIC Educational Resources Information Center

    Dozier, Cheryl; Garnett, Susan; Tabatabai, Simeen

    2011-01-01

    Conversations are the heart of responsive teaching. By talking with struggling learners, teachers can find out about their interests in order to design effective, personalized instruction; build relationships; work through complexities in teaching and learning; and celebrate successes.

  17. The chemistry of Venus' atmosphere

    NASA Technical Reports Server (NTRS)

    Sze, N. D.; Smith, W. H.

    1978-01-01

    A model for the Venus atmosphere involving photochemistry of oxygen, hydrogen, chlorine and sulfur species is presented. Sulfur reaction schemes and hydrogen and chlorine reaction schemes were included. The impact of sulfur on the oxygen budget and the subsequent production of H2SO4 molecules for the Venus cloud deck were explored. A major new reaction scheme for production of H2SO4 molecules involving sulfur and oxygen chemistry was established shown to dominate over the odd hydrogen scheme proposed earlier. The efficiency of the scheme in formation of H2SO4 is only about 50%, with the remaining sulfur residing in SO2 molecules. The calculated downward flux of H2SO4 may be sufficient to maintain a steady state sulfuric acid cloud if the resident time of H2SO4 droplets in the cloud is as long as a few years. If however, the resident time is half a year or shorter, additional chemistry capable of more efficient conversion of SO2 to SO3 is required.

  18. Structured luminescence conversion layer

    DOEpatents

    Berben, Dirk; Antoniadis, Homer; Jermann, Frank; Krummacher, Benjamin Claus; Von Malm, Norwin; Zachau, Martin

    2012-12-11

    An apparatus device such as a light source is disclosed which has an OLED device and a structured luminescence conversion layer deposited on the substrate or transparent electrode of said OLED device and on the exterior of said OLED device. The structured luminescence conversion layer contains regions such as color-changing and non-color-changing regions with particular shapes arranged in a particular pattern.

  19. Conversion of solar energy

    NASA Astrophysics Data System (ADS)

    Semenov, N. N.; Shilov, A. E.

    The papers presented in this volume provide an overview of current theoretical and experimental research related to the conversion and practical utilization of solar energy. Topics discussed include semiconductor photovoltaic cells, orbital solar power stations, chemical and biological methods of solar energy conversion, and solar energy applications. Papers are included on new theoretical models of solar cells and prospects for increasing their efficiency, metrology and optical studies of solar cells, and some problems related to the thermally induced deformations of large space structures.

  20. The Use of a Combination of alkB Primers to Better Characterize the Distribution of Alkane-Degrading Bacteria

    PubMed Central

    Jurelevicius, Diogo; Alvarez, Vanessa Marques; Peixoto, Raquel; Rosado, Alexandre S.; Seldin, Lucy

    2013-01-01

    The alkane monooxygenase AlkB, which is encoded by the alkB gene, is a key enzyme involved in bacterial alkane degradation. To study the alkB gene within bacterial communities, researchers need to be aware of the variations in alkB nucleotide sequences; a failure to consider the sequence variations results in the low representation of the diversity and richness of alkane-degrading bacteria. To minimize this shortcoming, the use of a combination of three alkB-targeting primers to enhance the detection of the alkB gene in previously isolated alkane-degrading bacteria was proposed. Using this approach, alkB-related PCR products were detected in 79% of the strains tested. Furthermore, the chosen set of primers was used to study alkB richness and diversity in different soils sampled in Carmópolis, Brazil and King George Island, Antarctica. The DNA extracted from the different soils was PCR amplified with each set of alkB-targeting primers, and clone libraries were constructed, sequenced and analyzed. A total of 255 alkB phylotypes were detected. Venn diagram analyses revealed that only low numbers of alkB phylotypes were shared among the different libraries derived from each primer pair. Therefore, the combination of three alkB-targeting primers enhanced the richness of alkB phylotypes detected in the different soils by 45% to 139%, when compared to the use of a single alkB-targeting primer. In addition, a dendrogram analysis and beta diversity comparison of the alkB composition showed that each of the sampling sites studied had a particular set of alkane-degrading bacteria. The use of a combination of alkB primers was an efficient strategy for enhancing the detection of the alkB gene in cultivable bacteria and for better characterizing the distribution of alkane-degrading bacteria in different soil environments. PMID:23825163