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Sample records for alkanes computational evidence

  1. Hydrogen Bonding to Alkanes: Computational Evidence

    DEFF Research Database (Denmark)

    Hammerum, Steen; Olesen, Solveig Gaarn

    2009-01-01

    The structural, vibrational, and energetic properties of adducts of alkanes and strong cationic proton donors were studied with composite ab initio calculations. Hydrogen bonding in [D-H+ H-alkyl] adducts contributes to a significant degree to the interactions between the two components, which...... are stronger in adducts of isobutane and in adducts of stronger acids. Intramolecular hydrogen bonding in protonated long-chain alcohols manifests itself in the same manner as intermolecular hydrogen bonding and can be equally strong. Udgivelsesdato: 12 juni 2009...

  2. Fully atomistic molecular-mechanical model of liquid alkane oils: Computational validation.

    Science.gov (United States)

    Zahariev, Tsvetan K; Slavchov, Radomir I; Tadjer, Alia V; Ivanova, Anela N

    2014-04-15

    Fully atomistic molecular dynamics simulations were performed on liquid n-pentane, n-hexane, and n-heptane to derive an atomistic model for middle-chain-length alkanes. All simulations were based on existing molecular-mechanical parameters for alkanes. The computational protocol was optimized, for example, in terms of thermo- and barostat, to reproduce properly the properties of the liquids. The model was validated by comparison of thermal, structural, and dynamic properties of the normal alkane liquids to experimental data. Two different combinations of temperature and pressure coupling algorithms were tested. A simple differential approach was applied to evaluate fluctuation-related properties with sufficient accuracy. Analysis of the data reveals a satisfactory representation of the hydrophobic systems behavior. Thermodynamic parameters are close to the experimental values and exhibit correct temperature dependence. The observed intramolecular geometry corresponds to extended conformations domination, whereas the intermolecular structure demonstrates all characteristics of liquid systems. Cavity size distribution function was calculated from coordinates analysis and was applied to study the solubility of gases in hexane and heptane oils. This study provides a platform for further in-depth research on hydrophobic solutions and multicomponent systems. Copyright © 2014 Wiley Periodicals, Inc.

  3. Semifluorinated alkanes and alkanes

    DEFF Research Database (Denmark)

    Runnsjo, Anna; Kocherbitov, Vitaly; Graf, Gesche

    2017-01-01

    The binary system perfluorohexyloctane (F6H8)–tetradecane (C14) was investigated in order to increase understanding of interactions of semifluorinated alkanes (SFAs) with hydrophobic molecules. The thermal phase behavior for F6H8 and C14 and their mixtures was determined using DSC. The activity...

  4. Oxidative dehydrogenation reaction of short alkanes on nanostructured carbon catalysts: a computational account.

    Science.gov (United States)

    Sun, XiaoYing; Han, Peng; Li, Bo; Mao, ShanJun; Liu, TianFu; Ali, Sajjad; Lian, Zan; Su, DangSheng

    2018-01-23

    Recent progress from first principles computational studies is presented for catalytic properties of nanostructured carbon catalysts in the oxidative dehydrogenation (ODH) reaction of short alkanes. Firstly, a brief introduction is given on the development of carbon catalysts in ODH since 1970. Oxygen functional groups have pivotal importance for ODH on nanostructured carbon catalysts. We discuss the oxidation process by HNO 3 on pristine and defective carbon materials. The interactions between the oxygen molecule (oxidant) and the nanostructured carbon catalysts are quantitatively calibrated. Moreover the different nucleophilic abilities of oxygen functional groups are carefully compared and the strongest nucleophilic sites are proposed. The active sites and detailed reaction pathway are revealed from several computational studies. Diketone/quinone groups are generally considered to be the active centers in ODH. A reaction pathway via radical formation is considered as the favorable path. Furthermore, single ketone and carbon sites are verified to be active in ODH from the analysis of aromaticity. Heteroatom doping effects in ODH are examined. Nitrogen doping is found to be very reactive towards oxygen molecule activation. Other dopants such as boron, phosphorous and sulfur also have positive effects on the reactivity of ODH. Extensive calculations suggest that the BEP relation is applicable for the doped nanostructured carbon catalysts. In the end, an outlook for the future direction of the computational study is supplied.

  5. Abundance of macroalgal organic matter in biofilms: Evidence from n-alkane biomarkers

    Digital Repository Service at National Institute of Oceanography (India)

    Garg, A.; Bhosle, N.B.

    Biofilm development on titanium panels immersed in the surface waters of Dona Paula Bay, Goa, India was investigated using molecular biomarkers such as n-alkanes and other chemical and biological parameters. Biofilm biomass measured as organic...

  6. Alkane Metathesis

    KAUST Repository

    Basset, Jean-Marie

    2015-03-29

    Catalytic activation of alkanes which directly transforms light alkanes into higher homologs is a major area in organometallic chemistry and petrochemical chemistry. This transformation is a chemical challenge considering the inertness of the sp3 carbon-hydrogen bond. It is generally accepted that this catalytic process involves the formation of olefins. This reaction is defined as alkane metathesis. To date, two catalytic systems of alkane metathesis exist: (i) a single catalytic system prepared by surface organometallic chemistry, acting as multifunctional-supported catalyst which transforms any alkanes into a mixture of their lower and higher homologs and (ii) the other catalytic systems employing a tandem strategy with two different metals, one metal for alkane (de)hydrogenation and another for olefin metathesis in which the activity of these catalysts is essentially driven by the performance of the (de)hydrogenation steps. In this book chapter, we would focus on the evolution of these two classes of catalysts by looking at their specific reactivity of the catalysts towards alkanes, comparing their performances and studying the mechanism.

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

    Czech Academy of Sciences Publication Activity Database

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

    2014-01-01

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

  8. Even-odd alternation of the formation of dimer isomers in irradiated polycrystalline alkanes: evidence from product analysis

    International Nuclear Information System (INIS)

    Baudson, T.; Tilquin, B.

    1984-01-01

    Recent ESR studies on n-alkanes from n-C 11 to n-C 25 have shown that a prominent chain end (-CH 2 -CH 2 ) alkyl radical is formed in odd members of the series. In this preliminary discussion of our study, we shall report the capillary chromatogram in the dimer isomers range for n-alkanes ranging from n-C 11 to n-C 17 irradiated at 80 kGy. Dimer isomers, produced in part by the combination of chain end radicals, are eluted at the end chromatogram. The combination of two chain end radicals gives the dimer (D 11 ) isomer eluted at the last place. It is shown that dimers produced by the combination of chain end alkyl radicals are more important for the odd members of the series than for the even members. (author)

  9. Alkane dimers interaction

    DEFF Research Database (Denmark)

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

    2010-01-01

    The interaction energies of a series of n-alkane dimers, from methane to decane, have been investigated with Density Functional Theory (DFT), using the MGGA-M06-L density functional. The results are compared both to the available wavefunction-based values as well as to dispersion corrected DFT...... values. The MGGA-M06-L density functional is a semi-local functional designed and has proven to provide accurate estimates of dispersion interactions for several systems at moderate computational cost. In the present application, it reproduces the trends obtained by the more expensive wavefunction...

  10. Transcriptome response to alkane biofuels in Saccharomyces cerevisiae: identification of efflux pumps involved in alkane tolerance

    Science.gov (United States)

    2013-01-01

    Background Hydrocarbon alkanes have been recently considered as important next-generation biofuels because microbial production of alkane biofuels was demonstrated. However, the toxicity of alkanes to microbial hosts can possibly be a bottleneck for high productivity of alkane biofuels. To tackle this toxicity issue, it is essential to understand molecular mechanisms of interactions between alkanes and microbial hosts, and to harness these mechanisms to develop microbial host strains with improved tolerance against alkanes. In this study, we aimed to improve the tolerance of Saccharomyces cerevisiae, a model eukaryotic host of industrial significance, to alkane biofuels by exploiting cellular mechanisms underlying alkane response. Results To this end, we first confirmed that nonane (C9), decane (C10), and undecane (C11) were significantly toxic and accumulated in S. cerevisiae. Transcriptome analyses suggested that C9 and C10 induced a range of cellular mechanisms such as efflux pumps, membrane modification, radical detoxification, and energy supply. Since efflux pumps could possibly aid in alkane secretion, thereby reducing the cytotoxicity, we formed the hypothesis that those induced efflux pumps could contribute to alkane export and tolerance. In support of this hypothesis, we demonstrated the roles of the efflux pumps Snq2p and Pdr5p in reducing intracellular levels of C10 and C11, as well as enhancing tolerance levels against C10 and C11. This result provided the evidence that Snq2p and Pdr5p were associated with alkane export and tolerance in S. cerevisiae. Conclusions Here, we investigated the cellular mechanisms of S. cerevisiae response to alkane biofuels at a systems level through transcriptome analyses. Based on these mechanisms, we identified efflux pumps involved in alkane export and tolerance in S. cerevisiae. We believe that the results here provide valuable insights into designing microbial engineering strategies to improve cellular tolerance for

  11. Diastereomeric and isotopic scrambling in (hydrido)alkyliridium complexes. Evidence for the presence of a common `alkane complex` intermediate

    Energy Technology Data Exchange (ETDEWEB)

    Mobley, T.A.; Schade, C.; Bergman, R.G. [Univ. of California, Berkeley, CA (United States)

    1995-07-26

    An alternative explanation for the scrambling of isotopic labels in the alkylmetal hydride complexes is the direct dyotropic rearrangement over the transition state. In an attempt to clarify the mechanism involved in these deuterium-scrambling reactions we have carried out kinetic investigations of the interconversion of diastereomeric (hydrido)(dimethylcyclopropyl)iridium complexes 1a and 1b and the deuterium scrambling of their {alpha}-deuterio analogs. A dramatic difference in behavior of the Rh and Ir systems yields significant conclusions regarding the reaction coordinate for alkane oxidative addition reactions to metal centers. Comparison of the results from the iridium system discussed here and the analogous rhodium system studied earlier yields the following interesting conclusion: with iridium, the barrier for interconversion of 4a and 4b is comparable to the barrier for C-H insertion to re-form 1a,b whereas the corresponding barrier for interconversion of the rhodium analogs of 4a and 4b is high compared to the barrier for C-H insertion. This difference may be caused by the different temperatures at which the two reactions are run; another possibility, however, is that deuterium scrambling in the rhodium system occurs by a dyotropic rearrangement. 27 refs., 3 figs.

  12. C14–22 n-Alkanes in Soil from the Freetown Layered Intrusion, Sierra Leone: Products of Pt Catalytic Breakdown of Natural Longer Chain n-Alkanes?

    Directory of Open Access Journals (Sweden)

    John F. W. Bowles

    2018-03-01

    Full Text Available Soil above a platinum-group element (PGE-bearing horizon within the Freetown Layered Intrusion, Sierra Leone, contains anomalous concentrations of n-alkanes (CnH2n+2 in the range C14 to C22 not readily attributable to an algal or lacustrine origin. Longer chain n-alkanes (C23 to C31 in the soil were derived from the breakdown of leaf litter beneath the closed canopy humid tropical forest. Spontaneous breakdown of the longer chain n-alkanes to form C14–22 n-alkanes without biogenic or abiogenic catalysts is unlikely as the n-alkanes are stable. In the Freetown soil, the catalytic properties of the PGE (Pt in particular may lower the temperature at which oxidation of the longer chain n-alkanes can occur. Reaction between these n-alkanes and Pt species, such as Pt2+(H2O2(OH2 and Pt4+(H2O2(OH4 can bend and twist the alkanes, and significantly lower the Heat of Formation. Microbial catalysis is a possibility. Since a direct organic geochemical source of the lighter n-alkanes has not yet been identified, this paper explores the theoretical potential for abiogenic Pt species catalysis as a mechanism of breakdown of the longer n-alkanes to form C14–22 alkanes. This novel mechanism could offer additional evidence for the presence of the PGE in solution, as predicted by soil geochemistry.

  13. Nanorheology of Liquid Alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, S.A., Cochran, H.D., Cummings, P.T. [Tennessee Univ., Knoxville, TN (United States). Dept. of Chemical Engineering], [Oak Ridge National Lab., TN (United States)

    1997-09-01

    We report molecular dynamics simulations of liquid alkanes, squalane and tetracosane, confined between moving walls to which butane chains are tethered, effectively screening the details of the wall. As in an experiment, heat is removed by thermostatting the tethered molecules. Results obtained at high strain rates, typical of practical applications, suggest little or no difference between the bulk rheology and confined flow, and the occurrence of a high degree of slip at the wall-fluid interface at the conditions studied. At relatively low velocities and high densities, tetracosane shows the formation of fully-extended chains at certain wall spacings.

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

    KAUST Repository

    Riache, Nassima

    2015-01-01

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

  15. Electron paramagnetic resonance evidence for the occurrence of hydrogen and/or proton transfer between C7, C8 and C11 n-alkanes and their cations in irradiated CCl3F matrices at 77 K

    International Nuclear Information System (INIS)

    Luyckx, G.; Ceulemans, J.

    1991-01-01

    After γ-irradiation of heptane and octane at low concentration in CCI 3 F at 77 K, only the EPR spectrum of the corresponding radical cations is observed. At higher concentrations, the spectrum of alkyl radicals also appears. Clear alkyl radical features are also observed after irradiation of 1 mol% undecane in CCI 3 F. In contrast, alkane radical cations but no alkyl radicals are observed after irradiation of heptane, octane and undecane in CCI 3 CF 3 and other saturated chlorofluorocarbon matrices at concentrations where alkyl radicals are already very prominent in CCI 3 F. Different mechanisms for the formation of these alkyl radicals are considered, viz. direct radiolysis of the alkane solutes, formation as a result of electronic excitation energy transfer and formation via the corresponding alkane radical cations that are formed by hole transfer from matrix cations. In the latter case, unimolecular deprotonation, charge neutralization by electron tunnelling and hydrogen/proton transfer with alkane molecules are taken into consideration. It is concluded that the hydrogen/proton transfer reaction (RH dot+ + RH→R dot + RH + 2 ) mainly accounts for the observed alkyl radicals. The results further indicate that in CCI 3 F at 77 K alkanes are present as small aggregates, to which hole transfer from matrix cations still occurs efficiently. (author)

  16. An Introduction to Computer Forensics: Gathering Evidence in a Computing Environment

    Directory of Open Access Journals (Sweden)

    Henry B. Wolfe

    2001-01-01

    Full Text Available Business has become increasingly dependent on the Internet and computing to operate. It has become apparent that there are issues of evidence gathering in a computing environment, which by their nature are technical and different to other forms of evidence gathering, that must be addressed. This paper offers an introduction to some of the technical issues surrounding this new and specialized field of Computer Forensics. It attempts to identify and describe sources of evidence that can be found on disk data storage devices in the course of an investigation. It also considers sources of copies of email, which can be used in evidence, as well as case building.

  17. Alkane oxidation by osmium tetroxide.

    Science.gov (United States)

    Bales, Brian C; Brown, Peter; Dehestani, Ahmad; Mayer, James M

    2005-03-09

    Aqueous alkaline OsO4 at 85 degrees C oxidizes saturated alkanes, including primary, secondary, and tertiary C-H bonds. Isobutane affords tert-butanol in quantitative yield based on consumed OsO4. Cyclohexane is oxidized to a mixture of adipate and succinate. Ethane and propane are oxidized to acetate, which itself is further oxidized under the reaction conditions. A few turnovers of isobutane oxidation have been accomplished using NaIO4 as the terminal oxidant. The alkane oxidation is an example of ligand accelerated catalysis, as hydroxide binding to OsO4 is required for reaction. A concerted mechanism involving [3+2] addition of a C-H bond to two oxo groups of OsO4(OH)- is suggested, analogous to the pathways for dihydroxylation of alkenes by OsO4(L) and for addition of H2 to OsO4(L).

  18. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.

    1992-06-30

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

  19. Reactivity of C-Amino-1,2,4-triazoles toward Electrophiles: A Combined Computational and Experimental Study of Alkylation by Halogen Alkanes.

    Science.gov (United States)

    Chernyshev, Victor M; Vlasova, Anna G; Astakhov, Alexander V; Shishkina, Svitlana V; Shishkin, Oleg V

    2015-01-02

    A combination of computational and experimental methods was used to examine the structure-reactivity relationships in the reactions of C-amino-1H-1,2,4-triazoles with electrophiles. The global nucleophilicity of 3-amino- and 3,5-diamino-1H-1,2,4-triazoles was predicted to be higher than that of 5-amino-1H-1,2,4-triazoles. Fukui functions and molecular electrostatic potential indicate that reactions involving an amino group should occur more easily for the 3-amino- than for the 5-amino-1H-1,2,4-triazoles. Increasing electrophile hardness should increase the probability of attack at the N-4 atom of the triazole ring, whereas increasing softness should enhance the probability of attack at the N-2 atom and 3-NH2 group. Calculated transition state energies of model SN2 reactions and experimental studies showed that quaternization of 1-substituted 3-amino- and 3,5-diamino-1H-1,2,4-triazoles by many alkyl halides proceeds with low selectivity and can involve the N-2 and N-4 atoms as well as the 3-NH2 group as reaction centers. A new method for the selective synthesis of 1,4-disubstituted 3-amino- and 3,5-diamino-1,2,4-triazoles based on quaternization of readily available 1-substituted 3-acetylamino-1,2,4-triazoles with subsequent removal of the acetyl protecting group by acid hydrolysis was developed.

  20. ELECTRONIC EVIDENCE IN THE JUDICIAL PROCEEDINGS AND COMPUTER FORENSIC ANALYSIS

    Directory of Open Access Journals (Sweden)

    Marija Boban

    2017-01-01

    Full Text Available Today’s perspective of the information society is characterized by the terminology of modern dictionaries of globalization including the terms such as convergence, digitization (media, technology and/or telecommunications and mobility of people or technology. Each word with progress, development, a positive sign of the rise of the information society. On the other hand in a virtual environment traditional evidence in judicial proceedings with the document on paper substrate, are becoming electronic evidence, and their management processes and criteria for admissibility are changing over traditional evidence. The rapid growth of computer data created new opportunities and the growth of new forms of computing, and cyber crime, but also the new ways of proof in court cases, which were unavailable just a few decades. The authors of this paper describe new trends in the development of the information society and the emergence of electronic evidence, with emphasis on the impact of the development of computer crime on electronic evidence; the concept, legal regulation and probative value of electronic evidence, and in particular of electronic documents; and the issue of electronic evidence expertise and electronic documents in court proceedings.

  1. Local computations in Dempster-Shafer theory of evidence

    Czech Academy of Sciences Publication Activity Database

    Jiroušek, Radim

    2012-01-01

    Roč. 53, č. 8 (2012), s. 1155-1167 ISSN 0888-613X Grant - others:GA ČR(CZ) GAP403/12/2175 Program:GA Institutional support: RVO:67985556 Keywords : Discrete belief functions * Dempster-Shafer theory * conditional independence * decomposable model Subject RIV: IN - Informatics, Computer Science Impact factor: 1.729, year: 2012 http://library.utia.cas.cz/separaty/2012/MTR/jirousek-local computations in dempster–shafer theory of evidence.pdf

  2. Biocatalysis of azidolysis of epoxides: Computational evidences on ...

    Indian Academy of Sciences (India)

    279–290. c Indian Academy of Sciences. Biocatalysis of azidolysis of epoxides: Computational evidences on the role of halohydrin dehalogenase (HheC). DHURAIRAJAN SENTHILNATHANa, VENKATACHALAM TAMILMANIb and. PONNAMBALAM VENUVANALINGAMa,∗. aSchool of Chemistry, Bharathidasan University ...

  3. Biocatalysis of azidolysis of epoxides: Computational evidences on ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 3. Biocatalysis of azidolysis of epoxides: Computational evidences on the role of halohydrin dehalogenase (HheC). Dhurairajan senthilnathan Venkatachalam Tamilmani Ponnambalam Venuvanalingam. Volume 123 Issue 3 May 2011 pp 279-290 ...

  4. [Forensic evidence-based medicine in computer communication networks].

    Science.gov (United States)

    Qiu, Yun-Liang; Peng, Ming-Qi

    2013-12-01

    As an important component of judicial expertise, forensic science is broad and highly specialized. With development of network technology, increasement of information resources, and improvement of people's legal consciousness, forensic scientists encounter many new problems, and have been required to meet higher evidentiary standards in litigation. In view of this, evidence-based concept should be established in forensic medicine. We should find the most suitable method in forensic science field and other related area to solve specific problems in the evidence-based mode. Evidence-based practice can solve the problems in legal medical field, and it will play a great role in promoting the progress and development of forensic science. This article reviews the basic theory of evidence-based medicine and its effect, way, method, and evaluation in the forensic medicine in order to discuss the application value of forensic evidence-based medicine in computer communication networks.

  5. Conformational problem of alkanes in liquid crystals by NMR spectroscopy: a mini-review.

    Science.gov (United States)

    Weber, Adrian C J; Chen, Daniel H J

    2014-10-01

    Recent discoveries of the role of alkane flexibility in determining liquid-crystal behaviour are surveyed. With the impetus for understanding the alkane conformational problem established, recent model dependent (1)H NMR work on the topic will be reviewed where progress is made but the need to circumvent models eventually becomes evident. A closer look at the rigid basic units of alkanes will provide the way forward where it is shown that the orientational ordering and anisotropic potentials of these molecules dissolved in liquid crystals scale with each other. Once this relationship is established, a series of works using anisotropic and isotropic (1)H NMR spectroscopy to study alkane conformational statistics will be covered, wherein the influence of the gas, isotropic condensed and anisotropic condensed phases will be described. Copyright © 2014 John Wiley & Sons, Ltd.

  6. Excessive computer game playing: evidence for addiction and aggression?

    Science.gov (United States)

    Grüsser, S M; Thalemann, R; Griffiths, M D

    2007-04-01

    Computer games have become an ever-increasing part of many adolescents' day-to-day lives. Coupled with this phenomenon, reports of excessive gaming (computer game playing) denominated as "computer/video game addiction" have been discussed in the popular press as well as in recent scientific research. The aim of the present study was the investigation of the addictive potential of gaming as well as the relationship between excessive gaming and aggressive attitudes and behavior. A sample comprising of 7069 gamers answered two questionnaires online. Data revealed that 11.9% of participants (840 gamers) fulfilled diagnostic criteria of addiction concerning their gaming behavior, while there is only weak evidence for the assumption that aggressive behavior is interrelated with excessive gaming in general. Results of this study contribute to the assumption that also playing games without monetary reward meets criteria of addiction. Hence, an addictive potential of gaming should be taken into consideration regarding prevention and intervention.

  7. Search of computers for discovery of electronic evidence

    Directory of Open Access Journals (Sweden)

    Pisarić Milana M.

    2015-01-01

    Full Text Available In order to address the specific nature of criminal activities committed using computer networks and systems, the efforts of states to adapt or complement the existing criminal law with purposeful provisions is understandable. To create an appropriate legal framework for supressing cybercrime, except the rules of substantive criminal law predict certain behavior as criminal offenses against the confidentiality, integrity and availability of computer data, computer systems and networks, it is essential that the provisions of the criminal procedure law contain adequate powers of competent authorities for detecting sources of illegal activities, or the collection of data on the committed criminal offense and offender, which can be used as evidence in criminal proceedings, taking into account the specificities of cyber crime and the environment within which the illegal activity is undertaken. Accordingly, the provisions of the criminal procedural law should be designed to be able to overcome certain challenges in discovering and proving high technology crime, and the provisions governing search of computer for discovery of electronic evidence is of special importance.

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

    Directory of Open Access Journals (Sweden)

    Melissa M Adams

    2013-05-01

    Full Text Available 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-C4 alkanes with AOM for available oxidants and the influence on the fate of C1 derived from these hydrothermal systems.

  9. Supported organoiridium catalysts for alkane dehydrogenation

    Science.gov (United States)

    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.

  10. Metathesis of alkanes and related reactions

    KAUST Repository

    Basset, Jean-Marie

    2010-02-16

    (Figure Presented) The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, (=SiO)2TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of aluminasupported tungsten hydride, W(H)3/Al 2O3, which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis of

  11. The Roles of Microbial Communities in n-Alkane Distribution of The Nanjenshan Lowland Subtropical Rainforest in Taiwan

    Science.gov (United States)

    Chen, Y. W.; Huang, T. Y.; Fan, C. W.; Chao, W. C.; Yang, T. N.; Huang, C. P.; Hsu, B. M.

    2016-12-01

    Analysis of total organic carbon in Nanjenshan, a lowland subtropical rainforest in southern Taiwan, revealed that the carbon storage of litter-layer was about 35% lower in ravine area than in windward and leeward areas, while the soil storage in these areas were similar. In this one year follow-up study, we aimed to investigate the kinetic changes of n-alkane (C14-C35) concentration from litter fall, litter-layer, surface soil, soil in -10 cm depth, and soil in -30 cm depth by a GC-FID method. The n-alkane distribution and n-alkane flux of these areas were also analyzed. Next generation sequencing was carried out to examine the metagenomics of uncultured microbial community in litter-layer of these areas. Our results showed that the net weight of one year-litter fall in ravine area was 30% higher than the others. The average concentration of n-alkane in leaves in ravine was 90% and 50% higher than in windward area and leeward area, respectively. Although the n-alkane flux in ravine area was twice higher than the other areas, the n-alkane concentrations in litter-layer and soils of different layers were similar among all areas, suggesting a rapid degradation of n-alkane in liter layer in ravine area. Interestingly, the character of odd over even predominance of n-alkane was gradually lost in soil layer in ravine area. Metagenomic data have showed that the structure of microbial abundance in ravine area was different from windward and leeward areas. In ravine area, the numbers in phyla of Bacteroidetes, Actinobacteria, and Proteobacteria, were higher than the other areas, while in phyla of Acidobacteria and Planctomycetes were lower. Our data provided evidence that microbial communities may not only play a role on n-alkane degradation but also change the profile in abundance of high-chain length n-alkanes.

  12. Constructing Scientific Arguments Using Evidence from Dynamic Computational Climate Models

    Science.gov (United States)

    Pallant, Amy; Lee, Hee-Sun

    2015-04-01

    Modeling and argumentation are two important scientific practices students need to develop throughout school years. In this paper, we investigated how middle and high school students ( N = 512) construct a scientific argument based on evidence from computational models with which they simulated climate change. We designed scientific argumentation tasks with three increasingly complex dynamic climate models. Each scientific argumentation task consisted of four parts: multiple-choice claim, openended explanation, five-point Likert scale uncertainty rating, and open-ended uncertainty rationale. We coded 1,294 scientific arguments in terms of a claim's consistency with current scientific consensus, whether explanations were model based or knowledge based and categorized the sources of uncertainty (personal vs. scientific). We used chi-square and ANOVA tests to identify significant patterns. Results indicate that (1) a majority of students incorporated models as evidence to support their claims, (2) most students used model output results shown on graphs to confirm their claim rather than to explain simulated molecular processes, (3) students' dependence on model results and their uncertainty rating diminished as the dynamic climate models became more and more complex, (4) some students' misconceptions interfered with observing and interpreting model results or simulated processes, and (5) students' uncertainty sources reflected more frequently on their assessment of personal knowledge or abilities related to the tasks than on their critical examination of scientific evidence resulting from models. These findings have implications for teaching and research related to the integration of scientific argumentation and modeling practices to address complex Earth systems.

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

    International Nuclear Information System (INIS)

    Alan Riga, D.

    1998-01-01

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

  14. Alkane Energy plc annual report 2001

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2002-04-01

    Alkane Energy plc (Alkane) is the UK's leading commercial producer of methane gas from abandoned coal mines. It currently operates five Green Energy Parks in the East Midlands and Yorkshire two of which were opened in the reporting year. Two agreements have been signed to develop sites to supply sites with a capacity of 50 MW of electricity. The annual report outlines achievements and plans and describes the technologies developed to capture methane. It discusses the environmental benefits of producing coal mine methane (CMM), particularly in reducing global warming, and benefits to the deprived former mining communities of the UK.

  15. Alkane Energy plc annual report 2002

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2003-04-01

    Alkane Energy plc (Alkane) is the UK's leading commercial producer of methane gas from abandoned coal mines. It currently operates five Green Energy Parks in the East Midlands and Yorkshire two of which began delivering gas in the reporting year. In March 2003 a contract was signed to develop a 2.7 MW generation facility in Gelsenkirchen, Germany. The annual report outlines achievements and plans and describes the technologies developed to capture methane. It discusses the environmental benefits of producing coal mine methane (CMM), particularly in reducing global warming, and benefits to the deprived former mining communities of the UK.

  16. Enzymes and Genes Involved in Aerobic Alkane Degradation

    Directory of Open Access Journals (Sweden)

    Zongze eShao

    2013-05-01

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

  17. A chemotaxonomic approach to the alkane content of three species ...

    African Journals Online (AJOL)

    The chemotaxonomic significance of leaf wax n-alkanes was studied in three species of Anthocleista Afzel. Identification of alkane components were determined by gas chromatography (GC) and gas chromatography – mass spectrometry (GC-MS) data. In all, fourteen alkanes were identified, ranging from tetracosane ...

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

    Science.gov (United States)

    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.

  19. Semantics guide infants' vowel learning: Computational and experimental evidence.

    Science.gov (United States)

    Ter Schure, S M M; Junge, C M M; Boersma, P P G

    2016-05-01

    In their first year, infants' perceptual abilities zoom in on only those speech sound contrasts that are relevant for their language. Infants' lexicons do not yet contain sufficient minimal pairs to explain this phonetic categorization process. Therefore, researchers suggested a bottom-up learning mechanism: infants create categories aligned with the frequency distributions of sounds in their input. Recent evidence shows that this bottom-up mechanism may be complemented by the semantic context in which speech sounds occur, such as simultaneously present objects. To test this hypothesis, we investigated whether discrimination of a non-native vowel contrast improves when sounds from the contrast were paired consistently or randomly with two distinct visually presented objects, while the distribution of speech tokens suggested a single broad category. This was assessed in two ways: computationally, namely in a neural network simulation, and experimentally, namely in a group of 8-month-old infants. The neural network, trained with a large set of sound-meaning pairs, revealed that two categories emerge only if sounds are consistently paired with objects. A group of 49 real 8-month-old infants did not immediately show sensitivity to the pairing condition; a later test at 18 months with some of the same infants, however, showed that this sensitivity at 8 months interacted with their vocabulary size at 18 months. This interaction can be explained by the idea that infants with larger future vocabularies are more positively influenced by consistent training (and/or more negatively influenced by inconsistent training) than infants with smaller future vocabularies. This suggests that consistent pairing with distinct visual objects can help infants to discriminate speech sounds even when the auditory information does not signal a distinction. Together our results give computational as well as experimental support for the idea that semantic context plays a role in disambiguating

  20. Evidence Report: Risk of Inadequate Human-Computer Interaction

    Science.gov (United States)

    Holden, Kritina; Ezer, Neta; Vos, Gordon

    2013-01-01

    Human-computer interaction (HCI) encompasses all the methods by which humans and computer-based systems communicate, share information, and accomplish tasks. When HCI is poorly designed, crews have difficulty entering, navigating, accessing, and understanding information. HCI has rarely been studied in an operational spaceflight context, and detailed performance data that would support evaluation of HCI have not been collected; thus, we draw much of our evidence from post-spaceflight crew comments, and from other safety-critical domains like ground-based power plants, and aviation. Additionally, there is a concern that any potential or real issues to date may have been masked by the fact that crews have near constant access to ground controllers, who monitor for errors, correct mistakes, and provide additional information needed to complete tasks. We do not know what types of HCI issues might arise without this "safety net". Exploration missions will test this concern, as crews may be operating autonomously due to communication delays and blackouts. Crew survival will be heavily dependent on available electronic information for just-in-time training, procedure execution, and vehicle or system maintenance; hence, the criticality of the Risk of Inadequate HCI. Future work must focus on identifying the most important contributing risk factors, evaluating their contribution to the overall risk, and developing appropriate mitigations. The Risk of Inadequate HCI includes eight core contributing factors based on the Human Factors Analysis and Classification System (HFACS): (1) Requirements, policies, and design processes, (2) Information resources and support, (3) Allocation of attention, (4) Cognitive overload, (5) Environmentally induced perceptual changes, (6) Misperception and misinterpretation of displayed information, (7) Spatial disorientation, and (8) Displays and controls.

  1. Reflectance spectroscopy of organic compounds: 1. Alkanes

    Science.gov (United States)

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

    2009-01-01

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

  2. Nitrated metalloporphyrins as catalysts for alkane oxidation

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2012-12-01

    hydrocarbon species characteristic of these metalliferous sediments. These systems are also characterized by sharp physicochemical gradients that have been shown to have a pronounced effect on microbial ecology and activity. Sediments were collected from a Middle Valley field with relatively high concentrations of short-chain alkanes and incubated in anaerobic batch reactors with each individual alkane (C1, C2, C3 and C4, respectively) at a range of temperatures (25, 55 and 75 °C) to mimic environmental physico-chemical conditions in a closed system. Stable carbon isotope ratios and radiotracer incubations provide clear evidence for C2-C4 alkane oxidation in the sediments over time. Upon identifying sediments with anaerobic alkane oxidation activity, microbial communities were screened via 16S rRNA pyrosequencing, and key phylotypes were then quantified using both molecular and microscopic methods. There were shifts in overall community composition and putative alkane-oxidizing phylotypes after the incubation period with the alkane substrates. These are the first evidence to date indicating that anaerobic C2-C4 alkane oxidation occurs across a broad range of temperatures in metalliferous sediments.

  4. The Calculation of Standard Enthalpies of Formation of Alkanes: Illustrating Molecular Mechanics and Spreadsheet Programs

    Science.gov (United States)

    Hawk, Eric Leigh

    1999-02-01

    How group increment methods may be used to predict standard enthalpies of formation of alkanes is outlined as an undergraduate computational chemistry experiment. The experiment requires input and output data sets. Although users may create their own data sets, both sets are provided. The input data set contains experimentally determined gas-phase standard enthalpies of formation and calculated steric energies for 10 alkanes. The steric energy for an alkane is calculated via a Molecular Mechanics approach employing Allinger's MM3 force field. Linear regression analysis on data contained in the input data set generates the coefficients that are used with the output data set to calculate standard enthalpies of formation for 15 alkanes. The average absolute error for the calculated standard enthalpies of formation is 1.22 kcal/mol. The experiment is highly suited to those interested in incorporating more computational chemistry in their curricula. In this regard, it is ideally suited for a physical chemistry laboratory, but it may be used in an organic chemistry course as well.

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

    Science.gov (United States)

    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

  6. On the large σ-hyperconjugation in alkanes and alkenes.

    Science.gov (United States)

    Wu, Judy I-Chia; Wang, Changwei; McKee, William Chadwick; Schleyer, Paul von Ragué; Wu, Wei; Mo, Yirong

    2014-06-01

    The conventional view that the σCC and σCH bonds in alkanes and unsaturated hydrocarbons are so highly localized that their non-steric interactions are negligible is scrutinized by the block-localized wavefunction (BLW) method. Even molecules considered conventionally to be "strain free" and "unperturbed" have surprisingly large and quite significant total σ-BLW-delocalization energies (DEs) due to their geminal and vicinal hyperconjugative interactions. Thus, the computed BLW-DEs (in kcal mol(-1)) for the antiperiplanar conformations of the n-alkanes (C(N)H(2N+2), N = 1-10) range from 11.6 for ethane to 82.2 for n-decane and are 50.9 for cyclohexane and 91.0 for adamantane. Although σ-electron delocalization in unsaturated hydrocarbons usually is ignored, the σ-BLW-DEs (in kcal mol(-1)) are substantial, as exemplified by D2h ethylene (9.0), triplet D2d ethylene (16.4), allene (19.3), butadiene (19.0), hexatriene (28.3), benzene (28.1), and cyclobutadiene (21.1). While each individual geminal and vicinal hyperconjugative interaction between hydrocarbon σ-bonding and σ-antibonding orbitals tends to be smaller than an individual π conjugative interaction (e.g., 10.2 kcal mol(-1) in anti-1,3-butadiene, the presence of many σ-hyperconjugative interactions (e.g., a total of 12 in anti-1,3-butadiene, see text), result in substantial total σ-stabilization energies (e.g., 19.0 kcal mol(-1) for butadiene), which may surpass those from the π interactions. Although large in magnitude, σ-electron delocalization energies often are obscured by cancellation when two hydrocarbons are compared. Rather than being strain-free, cyclohexane, adamantane, and diamantane suffer from their increasing number of intramolecular 1,4-C…C repulsions resulting in elongated C-C bond lengths and reduced σ-hyperconjugation, compared to the (skew-free) antiperiplanar n-alkane conformers. Instead of being inconsequential, σ-bond interactions are important and merit consideration.

  7. Heritability in Cognitive Performance: Evidence Using Computer-Based Testing

    Science.gov (United States)

    Hervey, Aaron S.; Greenfield, Kathryn; Gualtieri, C. Thomas

    2012-01-01

    There is overwhelming evidence of genetic influence on cognition. The effect is seen in general cognitive ability, as well as in specific cognitive domains. A conventional assessment approach using face-to-face paper and pencil testing is difficult for large-scale studies. Computerized neurocognitive testing is a suitable alternative. A total of…

  8. Visualising the scene: computer graphics and evidence presentation

    OpenAIRE

    Noond, Jez; Schofield, Damian; March, Jack; Evison, Martin

    2002-01-01

    In the UK forensic animations are becoming an increasingly important visual aid in courtroom situations, where complex data relating to a sequence of events is being visualised before a general public who may have little or no understanding of established forensic procedure or methodology. This paper will introduce and discuss a spectrum of new technologies that utilise new developments in Computer Graphics (CG) and Virtual Reality (VR) for a range of incident investigation and presentation s...

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

    DEFF Research Database (Denmark)

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

    2014-01-01

    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...

  10. Evidence-based guidelines for the wise use of computers by children: physical development guidelines.

    Science.gov (United States)

    Straker, L; Maslen, B; Burgess-Limerick, R; Johnson, P; Dennerlein, J

    2010-04-01

    Computer use by children is common and there is concern over the potential impact of this exposure on child physical development. Recently principles for child-specific evidence-based guidelines for wise use of computers have been published and these included one concerning the facilitation of appropriate physical development. This paper reviews the evidence and presents detailed guidelines for this principle. The guidelines include encouraging a mix of sedentary and whole body movement tasks, encouraging reasonable postures during computing tasks through workstation, chair, desk, display and input device selection and adjustment and special issues regarding notebook computer use and carriage, computing skills and responding to discomfort. The evidence limitations highlight opportunities for future research. The guidelines themselves can inform parents and teachers, equipment designers and suppliers and form the basis of content for teaching children the wise use of computers. STATEMENT OF RELEVANCE: Many children use computers and computer-use habits formed in childhood may track into adulthood. Therefore child-computer interaction needs to be carefully managed. These guidelines inform those responsible for children to assist in the wise use of computers.

  11. A Systematic Literature Review of Empirical Evidence on Computer Games and Serious Games

    Science.gov (United States)

    Connolly, Thomas M.; Boyle, Elizabeth A.; MacArthur, Ewan; Hainey, Thomas; Boyle, James M.

    2012-01-01

    This paper examines the literature on computer games and serious games in regard to the potential positive impacts of gaming on users aged 14 years or above, especially with respect to learning, skill enhancement and engagement. Search terms identified 129 papers reporting empirical evidence about the impacts and outcomes of computer games and…

  12. Evidence of nonuniqueness and oscillatory solutions in computational fluid mechanics

    International Nuclear Information System (INIS)

    Nunziato, J.W.; Gartling, D.K.; Kipp, M.E.

    1985-01-01

    We will review some of our recent experiences in computing solutions for nonlinear fluids in relatively simple, two-dimensional geometries. The purpose of this discussion will be to display by example some of the interesting but difficult questions that arise when ill-behaved solutions are obtained numerically. We will consider two examples. As the first example, we will consider a nonlinear elastic (compressible) fluid with chemical reactions and discuss solutions for detonation and detonation failure in a two-dimensional cylinder. In this case, the numerical algorithm utilizes a finite-difference method with artificial viscosity (von Neumann-Richtmyer method) and leads to two, distinctly different, stable solutions depending on the time step criterion used. The second example to be considered involves the convection of a viscous fluid in a rectangular container as a result of an exothermic polymerization reaction. A solidification front develops near the top of the container and propagates down through the fluid, changing the aspect ratio of the region ahead of the front. Using a Galerkin-based finite element method, a numerical solution of the partial differential equations is obtained which tracks the front and correctly predicts the fluid temperatures near the walls. However, the solution also exhibits oscillatory behavior with regard to the number of cells in the fluid ahead of the front and in the strength of the cells. More definitive experiments and analysis are required to determine whether this oscillatory phenomena is a numerical artifact or a physical reality. 20 refs., 14 figs

  13. Evidence of effectiveness of health care professionals using handheld computers: a scoping review of systematic reviews.

    Science.gov (United States)

    Mickan, Sharon; Tilson, Julie K; Atherton, Helen; Roberts, Nia Wyn; Heneghan, Carl

    2013-10-28

    Handheld computers and mobile devices provide instant access to vast amounts and types of useful information for health care professionals. Their reduced size and increased processing speed has led to rapid adoption in health care. Thus, it is important to identify whether handheld computers are actually effective in clinical practice. A scoping review of systematic reviews was designed to provide a quick overview of the documented evidence of effectiveness for health care professionals using handheld computers in their clinical work. A detailed search, sensitive for systematic reviews was applied for Cochrane, Medline, EMBASE, PsycINFO, Allied and Complementary Medicine Database (AMED), Global Health, and Cumulative Index to Nursing and Allied Health Literature (CINAHL) databases. All outcomes that demonstrated effectiveness in clinical practice were included. Classroom learning and patient use of handheld computers were excluded. Quality was assessed using the Assessment of Multiple Systematic Reviews (AMSTAR) tool. A previously published conceptual framework was used as the basis for dual data extraction. Reported outcomes were summarized according to the primary function of the handheld computer. Five systematic reviews met the inclusion and quality criteria. Together, they reviewed 138 unique primary studies. Most reviewed descriptive intervention studies, where physicians, pharmacists, or medical students used personal digital assistants. Effectiveness was demonstrated across four distinct functions of handheld computers: patient documentation, patient care, information seeking, and professional work patterns. Within each of these functions, a range of positive outcomes were reported using both objective and self-report measures. The use of handheld computers improved patient documentation through more complete recording, fewer documentation errors, and increased efficiency. Handheld computers provided easy access to clinical decision support systems and

  14. Computer models and the evidence of anthropogenic climate change: An epistemology of variety-of-evidence inferences and robustness analysis.

    Science.gov (United States)

    Vezér, Martin A

    2016-04-01

    To study climate change, scientists employ computer models, which approximate target systems with various levels of skill. Given the imperfection of climate models, how do scientists use simulations to generate knowledge about the causes of observed climate change? Addressing a similar question in the context of biological modelling, Levins (1966) proposed an account grounded in robustness analysis. Recent philosophical discussions dispute the confirmatory power of robustness, raising the question of how the results of computer modelling studies contribute to the body of evidence supporting hypotheses about climate change. Expanding on Staley's (2004) distinction between evidential strength and security, and Lloyd's (2015) argument connecting variety-of-evidence inferences and robustness analysis, I address this question with respect to recent challenges to the epistemology robustness analysis. Applying this epistemology to case studies of climate change, I argue that, despite imperfections in climate models, and epistemic constraints on variety-of-evidence reasoning and robustness analysis, this framework accounts for the strength and security of evidence supporting climatological inferences, including the finding that global warming is occurring and its primary causes are anthropogenic. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Alkane oxidation by Pseudomonas oleovorans : genes and proteins

    NARCIS (Netherlands)

    van Beilen, Jan Berthold

    1994-01-01

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

  16. Succession of Alkane Conformational Motifs Bound within Hydrophobic Supramolecular Capsular Assemblies.

    Science.gov (United States)

    Barnett, J Wesley; Gibb, Bruce C; Ashbaugh, Henry S

    2016-10-06

    n-Alkane encapsulation experiments within dimeric octa-acid cavitand capsules in water reveal a succession of packing motifs from extended, to helical, to hairpin, to spinning top structures with increasing chain length. Here, we report a molecular simulation study of alkane conformational preferences within these host-guest assemblies to uncover the factors stabilizing distinct conformers. The simulated alkane conformers follow the trends inferred from 1 H NMR experiments, while guest proton chemical shifts evaluated from Gauge Invariant Atomic Orbital calculations provide further evidence our simulations capture guest packing within these assemblies. Analysis of chain length and dihedral distributions indicates that packing under confinement to minimize nonpolar guest and host interior contact with water largely drives the transitions. Mean intramolecular distance maps and transfer free energy differences suggest the extended and helical motifs are members of a larger family of linear guest structures, for which the guest gauche population increases with increasing chain length to accommodate the chains within the complex. Breaks observed between the helical/hairpin and hairpin/spinning top motifs, on the other hand, indicate the hairpin and spinning top conformations are distinct from the linear family. Our results represent the first bridging of empirical and simulation data for flexible guests encapsulated within confined nanospaces, and constitute an effective strategy by which guest packing motifs within artificial or natural compartments can be rationalized and/or predicted a priori.

  17. Exchange of alkanes with deuterium over γ-alumina

    International Nuclear Information System (INIS)

    John, C.S.; Kemball, C.; Pearce, E.A.; Pearman, A.J.

    1979-01-01

    Exchange reactions of hydrocarbons with deuterium over γ-alumina have been extensively studied but less attention has been directed to the effect of catalyst activation temperature. It has been shown that activity for propane/D 2 exchange passes through a sharp maximum at approximately 823 K and similar behaviour has been shown for the various exchange processes of propene. In this work, the first objective was to examine the effect of varying catalyst activation temperature, Tsub(a), on the subsequent activity of γ-alumina for the exchange of cyclopentane with D 2 ; the effect of chloriding the alumina was also studied. The second objective was to study the influence on the activity for cyclopentane/D 2 exchange of pretreating the catalyst with alkene at various temperatures to determine whether poisoning occurred. The literature indicates that for alkene exchange with deuterium on alumina reaction occurs preferentially for the vinyl hydrogen atoms as opposed to the hydrogen atoms attached to saturated carbon atoms. On this evidence one might expect the presence of alkene to interfere with the exchange of alkanes and indeed there is work which reports that alkene poisons both CH 4 /D 2 and H 2 /D 2 exchange. Finally, the effect of chain-length on the relative rates of methylene and methyl exchange in straight-chain hydrocarbons was examined to follow up previous work on propane and butane. The results are presented and discussed. (author)

  18. Reaction of atomic oxygen with alkanes. Regioselective alcohol formation on γ-radiolysis of liquid carbon dioxide solutions of alkanes

    International Nuclear Information System (INIS)

    Hori, A.; Takamuku, S.; Sakurai, H.

    1977-01-01

    Gamma-radiolysis of liquid carbon dioxide in the presence of cyclohexane, methylcyclohexane, and cis- or trans-decalin has been studied at 0 0 C. The main products were corresponding alcohols and carbonyl compounds. The oxidizing species from carbon dioxide apparently shows selective attack on C--H bonds of alkane in the order tertiary greater than secondary greater than primary. The observed tendency could be rationalized in terms of the reaction of ground state triplet oxygen atoms, O( 3 P), with alkane in liquid carbon dioxide. In the case of cis- and trans-decalin, highly configurational retention of decalol-9 was observed. The formation of a dimer of alkane was negligibly small. The rapid recombination of radical pairs initially formed by the reaction of O( 3 P) atoms with alkane in a solvent cage is proposed. In addition, the production of cyclohexanone from cyclohexanol is described

  19. Gathering Empirical Evidence Concerning Links between Computer Aided Design (CAD) and Creativity

    Science.gov (United States)

    Musta'amal, Aede Hatib; Norman, Eddie; Hodgson, Tony

    2009-01-01

    Discussion is often reported concerning potential links between computer-aided designing and creativity, but there is a lack of systematic enquiry to gather empirical evidence concerning such links. This paper reports an indication of findings from other research studies carried out in contexts beyond general education that have sought evidence…

  20. Persistence of Learning Gains from Computer Assisted Learning: Experimental Evidence from China

    Science.gov (United States)

    Mo, D.; Zhang, L.; Wang, J.; Huang, W.; Shi, Y.; Boswell, M.; Rozelle, S.

    2015-01-01

    Computer assisted learning (CAL) programs have been shown to be effective in improving educational outcomes. However, the existing studies on CAL have almost all been conducted over a short period of time. There is very little evidence on how the impact evolves over time. In response, we conducted a clustered randomized experiment involving 2741…

  1. A new and selective cycle for dehydrogenation of linear and cyclic alkanes under mild conditions using a base metal

    Science.gov (United States)

    Solowey, Douglas P.; Mane, Manoj V.; Kurogi, Takashi; Carroll, Patrick J.; Manor, Brian C.; Baik, Mu-Hyun; Mindiola, Daniel J.

    2017-11-01

    Selectively converting linear alkanes to α-olefins under mild conditions is a highly desirable transformation given the abundance of alkanes as well as the use of olefins as building blocks in the chemical community. Until now, this reaction has been primarily the remit of noble-metal catalysts, despite extensive work showing that base-metal alkylidenes can mediate the reaction in a stoichiometric fashion. Here, we show how the presence of a hydrogen acceptor, such as the phosphorus ylide, when combined with the alkylidene complex (PNP)Ti=CHtBu(CH3) (PNP=N[2-P(CHMe2)2-4-methylphenyl]2-), catalyses the dehydrogenation of cycloalkanes to cyclic alkenes, and linear alkanes with chain lengths of C4 to C8 to terminal olefins under mild conditions. This Article represents the first example of a homogeneous and selective alkane dehydrogenation reaction using a base-metal titanium catalyst. We also propose a unique mechanism for the transfer dehydrogenation of hydrocarbons to olefins and discuss a complete cycle based on a combined experimental and computational study.

  2. Alkane inducible proteins in Geobacillus thermoleovorans B23

    Directory of Open Access Journals (Sweden)

    Kato Tomohisa

    2009-03-01

    Full Text Available Abstract 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.

  3. Evidence-based ergonomics education: Promoting risk factor awareness among office computer workers.

    Science.gov (United States)

    Mani, Karthik; Provident, Ingrid; Eckel, Emily

    2016-01-01

    Work-related musculoskeletal disorders (WMSDs) related to computer work have become a serious public health concern. Literature revealed a positive association between computer use and WMSDs. The purpose of this evidence-based pilot project was to provide a series of evidence-based educational sessions on ergonomics to office computer workers to enhance the awareness of risk factors of WMSDs. Seventeen office computer workers who work for the National Board of Certification in Occupational Therapy volunteered for this project. Each participant completed a baseline and post-intervention ergonomics questionnaire and attended six educational sessions. The Rapid Office Strain Assessment and an ergonomics questionnaire were used for data collection. The post-intervention data revealed that 89% of participants were able to identify a greater number of risk factors and answer more questions correctly in knowledge tests of the ergonomics questionnaire. Pre- and post-intervention comparisons showed changes in work posture and behaviors (taking rest breaks, participating in exercise, adjusting workstation) of participants. The findings have implications for injury prevention in office settings and suggest that ergonomics education may yield positive knowledge and behavioral changes among computer workers.

  4. Evidence-based pathology in its second decade: toward probabilistic cognitive computing.

    Science.gov (United States)

    Marchevsky, Alberto M; Walts, Ann E; Wick, Mark R

    2017-03-01

    Evidence-based pathology advocates using a combination of best available data ("evidence") from the literature and personal experience for the diagnosis, estimation of prognosis, and assessment of other variables that impact individual patient care. Evidence-based pathology relies on systematic reviews of the literature, evaluation of the quality of evidence as categorized by evidence levels and statistical tools such as meta-analyses, estimates of probabilities and odds, and others. However, it is well known that previously "statistically significant" information usually does not accurately forecast the future for individual patients. There is great interest in "cognitive computing" in which "data mining" is combined with "predictive analytics" designed to forecast future events and estimate the strength of those predictions. This study demonstrates the use of IBM Watson Analytics software to evaluate and predict the prognosis of 101 patients with typical and atypical pulmonary carcinoid tumors in which Ki-67 indices have been determined. The results obtained with this system are compared with those previously reported using "routine" statistical software and the help of a professional statistician. IBM Watson Analytics interactively provides statistical results that are comparable to those obtained with routine statistical tools but much more rapidly, with considerably less effort and with interactive graphics that are intuitively easy to apply. It also enables analysis of natural language variables and yields detailed survival predictions for patient subgroups selected by the user. Potential applications of this tool and basic concepts of cognitive computing are discussed. Copyright © 2016 Elsevier Inc. All rights reserved.

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

    DEFF Research Database (Denmark)

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

    2004-01-01

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

  6. Regioselective alkane hydroxylation with a mutant AlkB enzyme

    Science.gov (United States)

    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.

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

    KAUST Repository

    Szeto, Kaï Chung

    2012-01-01

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

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

    Directory of Open Access Journals (Sweden)

    SLOBODAN P. SERBANOVIC

    2005-03-01

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

  9. Solid acid catalysts in heterogeneous n-alkanes hydroisomerisation ...

    African Journals Online (AJOL)

    As the current global environmental concerns have prompted regulations to reduce the level of aromatic compounds, particularly benzene and its derivatives in gasoline, ydroisomerisation of n-alkanes is becoming a major alternative for enhancing octane number. Series of solid acid catalysts comprising of Freidel crafts, ...

  10. n-Alkanes in surficial sediments of Visakhapatnam harbour, east ...

    Indian Academy of Sciences (India)

    characterised at molecular level, they provide valu- able information on the sources of OM (Meyers. 2003; Volkman 2006). For example, lipid com- pounds such as n-alkanes, sterols, alcohols and fatty acids are used to assess sources of OM in marine and terrestrial sediments (Volkman et al. 1992; Tolosa et al. 2009).

  11. Catalytic dehydrogenation of light alkanes on metals and metal oxides

    NARCIS (Netherlands)

    Sattler, Jesper J H B|info:eu-repo/dai/nl/328235601; Ruiz-Martinez, Javier|info:eu-repo/dai/nl/341386405; Santillan-Jimenez, Eduardo|info:eu-repo/dai/nl/323171958; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

    2014-01-01

    A study is conducted to demonstrate catalytic dehydrogenation of light alkanes on metals and metal oxides. The study provides a complete overview of the materials used to catalyze this reaction, as dehydrogenation for the production of light olefins has become extremely relevant. Relevant factors,

  12. Aerobic Oxidations of Light Alkanes over Solid Metal Oxide Catalysts.

    Science.gov (United States)

    Grant, Joseph T; Venegas, Juan M; McDermott, William P; Hermans, Ive

    2017-11-07

    Heterogeneous metal oxide catalysts are widely studied for the aerobic oxidations of C 1 -C 4 alkanes to form olefins and oxygenates. In this review, we outline the properties of supported metal oxides, mixed-metal oxides, and zeolites and detail their most common applications as catalysts for partial oxidations of light alkanes. By doing this we establish similarities between different classes of metal oxides and identify common themes in reaction mechanisms and research strategies for catalyst improvement. For example, almost all partial alkane oxidations, regardless of the metal oxide, follow Mars-van Krevelen reaction kinetics, which utilize lattice oxygen atoms to reoxidize the reduced metal centers while the gaseous O 2 reactant replenishes these lattice oxygen vacancies. Many of the most-promising metal oxide catalysts include V 5+ surface species as a necessary constituent to convert the alkane. Transformations involving sequential oxidation steps (i.e., propane to acrylic acid) require specific reaction sites for each oxidation step and benefit from site isolation provided by spectator species. These themes, and others, are discussed in the text.

  13. Thermodynamic parameters for the adsorption of volatile n-alkane ...

    African Journals Online (AJOL)

    user

    Thermodynamic parameters for the adsorption of volatile n-alkane hydrocarbons on water hyacinth. (Eichhornia crassipes) root biomass: Effect of organic solvent and mineral acid treatment. Netai Mukaratirwa-Muchanyereyi1,2, Jameson Kugara1 and Mark Fungayi Zaranyika1*. 1Chemistry Department, University of ...

  14. Thermodynamic parameters for the adsorption of volatile n-alkane ...

    African Journals Online (AJOL)

    alkanes hexane to nonane on ground dried water hyacinth (E. crassipes) root biomass were studied between 40 and 70°C column temperature using inverse gas chromatography, before and after treatment of the root biomass with mineral acid ...

  15. Further Evidence in Support of the Universal Nilpotent Grammatical Computational Paradigm of Quantum Physics

    Science.gov (United States)

    Marcer, Peter J.; Rowlands, Peter

    2010-12-01

    Further evidence is presented in favour of the computational paradigm, conceived and constructed by Rowlands and Diaz, as detailed in Rowlands' book Zero to Infinity (2007) [2], and in particular the authors' paper `The Grammatical Universe: the Laws of Thermodynamics and Quantum Entanglement' [1]. The paradigm, which has isomorphic group and algebraic quantum mechanical language interpretations, not only predicts the well-established facts of quantum physics, the periodic table, chemistry / valence and of molecular biology, whose understanding it extends; it also provides an elegant, simple solution to the unresolved quantum measurement problem. In this fundamental paradigm, all the computational constructs / predictions that emerge, follow from the simple fact, that, as in quantum mechanics, the wave function is defined only up to an arbitrary fixed phase. This fixed phase provides a simple physical understanding of the quantum vacuum in quantum field theory, where only relative phases, known to be able to encode 3+1 relativistic space-time geometries, can be measured. It is the arbitrary fixed measurement standard, against which everything that follows is to be measured, even though the standard itself cannot be, since nothing exists against which to measure it. The standard, as an arbitrary fixed reference phase, functions as the holographic basis for a self-organized universal quantum process of emergent novel fermion states of matter where, following each emergence, the arbitrary standard is re-fixed anew so as to provide a complete history / holographic record or hologram of the current fixed past, advancing an unending irreversible evolution, such as is the evidence of our senses. The fermion states, in accord with the Pauli exclusion principle, each correspond to a unique nilpotent symbol in the infinite alphabet (which specifies the grammar in this nilpotent universal computational rewrite system (NUCRS) paradigm); and the alphabet, as Hill and Rowlands

  16. Further Evidence in Support of the Universal Nilpotent Grammatical Computational Paradigm of Quantum Physics

    International Nuclear Information System (INIS)

    Marcer, Peter J.; Rowlands, Peter

    2010-01-01

    Further evidence is presented in favour of the computational paradigm, conceived and constructed by Rowlands and Diaz, as detailed in Rowlands' book Zero to Infinity (2007), and in particular the authors' paper 'The Grammatical Universe: the Laws of Thermodynamics and Quantum Entanglement'. The paradigm, which has isomorphic group and algebraic quantum mechanical language interpretations, not only predicts the well-established facts of quantum physics, the periodic table, chemistry / valence and of molecular biology, whose understanding it extends; it also provides an elegant, simple solution to the unresolved quantum measurement problem. In this fundamental paradigm, all the computational constructs / predictions that emerge, follow from the simple fact, that, as in quantum mechanics, the wave function is defined only up to an arbitrary fixed phase. This fixed phase provides a simple physical understanding of the quantum vacuum in quantum field theory, where only relative phases, known to be able to encode 3+1 relativistic space-time geometries, can be measured. It is the arbitrary fixed measurement standard, against which everything that follows is to be measured, even though the standard itself cannot be, since nothing exists against which to measure it. The standard, as an arbitrary fixed reference phase, functions as the holographic basis for a self-organized universal quantum process of emergent novel fermion states of matter where, following each emergence, the arbitrary standard is re-fixed anew so as to provide a complete history / holographic record or hologram of the current fixed past, advancing an unending irreversible evolution, such as is the evidence of our senses. The fermion states, in accord with the Pauli exclusion principle, each correspond to a unique nilpotent symbol in the infinite alphabet (which specifies the grammar in this nilpotent universal computational rewrite system (NUCRS) paradigm); and the alphabet, as Hill and Rowlands

  17. Sentence-based attention mechanisms in word learning: Evidence from a computational model

    Directory of Open Access Journals (Sweden)

    Afra eAlishahi

    2012-07-01

    Full Text Available When looking for the referents of nouns, adults and young children are sensitive to cross- situational statistics (Yu & Smith, 2007; Smith & Yu, 2008. In addition, the linguistic context that a word appears in has been shown to act as a powerful attention mechanism for guiding sentence processing and word learning (Landau & Gleitman, 1985; Altmann & Kamide, 1999; Kako & Trueswell, 2000. Koehne & Crocker (2010, 2011 investigate the interaction between cross-situational evidence and guidance from the sentential context in an adult language learning scenario. Their studies reveal that these learning mechanisms interact in a complex manner: they can be used in a complementary way when context helps reduce referential uncertainty; they influence word learning about equally strongly when cross-situational and contextual evidence are in conflict; and contextual cues block aspects of cross-situational learning when both mechanisms are independently applicable. To address this complex pattern of findings, we present a probabilistic computational model of word learning which extends a previous cross-situational model (Fazly et al., 2010 with an attention mechanism based on sentential cues. Our model uses a framework that seamlessly combines the two sources of evidence in order to study their emerging pattern of interaction during the process of word learning. Simulations of the experiments of Koehne & Crocker (2010, 2011 reveal an overall patterns of results that are in line with their findings. Importantly, we demonstrate that our model does not need to explicitly assign priority to either source of evidence in order to produce these results: learning patterns emerge as a result of a probabilistic interaction between the two types of cues. Moreover, using a computational model allows us to examine the developmental trajectory of the differential roles of cross-situational and sentential cues in word learning.

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

    Directory of Open Access Journals (Sweden)

    Yu Yunlong

    2016-03-01

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

  19. A Detailed Chemical Kinetic Reaction Mechanism for n-Alkane Hydrocarbons From n-Octane to n-Hexadecane

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-02-08

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

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

    Directory of Open Access Journals (Sweden)

    Kirill A. Emelyanenko

    2016-03-01

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

  1. Plant n-alkane production from litterfall altered the diversity and community structure of alkane degrading bacteria in litter layer in lowland subtropical rainforest in Taiwan

    Science.gov (United States)

    Huang, Tung-Yi; Hsu, Bing-Mu; Chao, Wei-Chun; Fan, Cheng-Wei

    2018-03-01

    n-Alkane and alkane-degrading bacteria have long been used as crucial biological indicators of paleoecology, petroleum pollution, and oil and gas prospecting. However, the relationship between n-alkane and alkane-degrading bacteria in natural forests is still poorly understood. In this study, long-chain n-alkane (C14-C35) concentrations in litterfall, litter layer, and topsoil as well as the diversity and abundance of n-alkane-degrading bacterial communities in litter layers were investigated in three habitats across a lowland subtropical rainforest in southern Taiwan: ravine, windward, and leeward habitats in Nanjenshan. Our results demonstrate that the litterfall yield and productivity of long-chain n-alkane were highest in the ravine habitats. However, long-chain n-alkane concentrations in all habitats were decreased drastically to a similar low level from the litterfall to the bulk soil, suggesting a higher rate of long-chain n-alkane degradation in the ravine habitat. Operational taxonomic unit (OTU) analysis using next-generation sequencing data revealed that the relative abundances of microbial communities in the windward and leeward habitats were similar and different from that in the ravine habitat. Data mining of community amplicon sequencing using the NCBI database revealed that alkB-gene-associated bacteria (95 % DNA sequence similarity to alkB-containing bacteria) were most abundant in the ravine habitat. Empirical testing of litter layer samples using semi-quantitative polymerase chain reaction for determining alkB gene levels confirmed that the ravine habitat had higher alkB gene levels than the windward and leeward habitats. Heat map analysis revealed parallels in pattern color between the plant and microbial species compositions of the habitats, suggesting a causal relationship between the plant n-alkane production and microbial community diversity. This finding indicates that the diversity and relative abundance of microbial communities in the

  2. Using tablet computers to teach evidence-based medicine to pediatrics residents: a prospective study.

    Science.gov (United States)

    Soma, David B; Homme, Jason H; Jacobson, Robert M

    2013-01-01

    We sought to determine if tablet computers-supported by a laboratory experience focused upon skill-development-would improve not only evidence-based medicine (EBM) knowledge but also skills and behavior. We conducted a prospective cohort study where we provided tablet computers to our pediatric residents and then held a series of laboratory sessions focused on speed and efficiency in performing EBM at the bedside. We evaluated the intervention with pre- and postintervention tests and surveys based on a validated tool available for use on MedEdPORTAL. The attending pediatric hospitalists also completed surveys regarding their observations of the residents' behavior. All 38 pediatric residents completed the preintervention test and the pre- and postintervention surveys. All but one completed the posttest. All 7 attending pediatric hospitalists completed their surveys. The testing, targeted to assess EBM knowledge, revealed a median increase of 16 points out of a possible 60 points (P computer and laboratory sessions designed to teach the quick and efficient application of EBM at the bedside. Copyright © 2013 Academic Pediatric Association. Published by Elsevier Inc. All rights reserved.

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

    Science.gov (United States)

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

    2015-11-19

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

  4. "Insufficient evidence of effectiveness" is not "evidence of no effectiveness:" evaluating computer-based education for patients with severe mental illness.

    Science.gov (United States)

    Stoltz, Peter; Skärsäter, Ingela; Willman, Ania

    2009-01-01

    This article reports on commissioned research funded by the Swedish Council of Technology Assessment in Health Care (SBU) and the Swedish Nursing Society (SSF). The objective was to review computer-based education programs. However, as the review produced insufficient evidence of effectiveness, the publication was withheld due to a previous incident where such evidence was misunderstood by Swedish policy and health care decision makers. This article highlights the concept of evidence with regard to the consequences of insufficient evidence of effectiveness being mistaken for evidence of no effectiveness. The aim is also to present a systematic review evaluating a computer-based education program for patients suffering from severe mental illness. Systematic database searches in Medline, CINAHL, PsycINFO and the Cochrane Library identified a total of 131 potentially relevant references. Thereafter, 27 references were retrieved as full-text documents, of which 5 were finally included and co-reviewed by two independent researchers. The review found no decisive evidence of effectiveness regarding computer-based education programs designed to assist persons suffering from severe mental illness. Failing to see the difference between insufficient evidence and evidence of no effectiveness may have unexpected consequences. As a result, practice may be misguided and treatments withheld, which at worse may have harmful consequences for patients. In the end, it is of utmost importance that researchers do good quality research by ensuring statistical power and quality of outcome measurement. For example, this review of computer-based education programs could have revealed effective ways of dealing with severe mental illness if the studies included had been conducted using more sophisticated designs.

  5. Alkane Biosynthesis Genes in Cyanobacteria and Their Transcriptional Organization

    Energy Technology Data Exchange (ETDEWEB)

    Klähn, Stephan; Baumgartner, Desirée; Pfreundt, Ulrike; Voigt, Karsten; Schön, Verena; Steglich, Claudia; Hess, Wolfgang R., E-mail: wolfgang.hess@biologie.uni-freiburg.de [Genetics and Experimental Bioinformatics, Institute of Biology 3, Faculty of Biology, University of Freiburg, Freiburg (Germany)

    2014-07-14

    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.

  6. Alkane Biosynthesis Genes in Cyanobacteria and Their Transcriptional Organization

    International Nuclear Information System (INIS)

    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.

  7. Alkane biosynthesis genes in cyanobacteria and their transcriptional organization

    Directory of Open Access Journals (Sweden)

    Stephan eKlähn

    2014-07-01

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

  8. Chromium oxide catalysts in the dehydrogenation of alkanes

    OpenAIRE

    Airaksinen, Sanna

    2005-01-01

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

  9. Safety of intravenous tissue plasminogen activator administration with computed tomography evidence of prior infarction.

    Science.gov (United States)

    Lyerly, Michael J; Houston, J Thomas; Boehme, Amelia K; Albright, Karen C; Bavarsad Shahripour, Reza; Palazzo, Paola; Alvi, Muhammed; Rawal, Pawan V; Kapoor, Niren; Sisson, April; Alexandrov, Anne W; Alexandrov, Andrei V

    2014-07-01

    Prior stroke within 3 months excludes patients from thrombolysis; however, patients may have computed tomography (CT) evidence of prior infarct, often of unknown time of origin. We aimed to determine if the presence of a previous infarct on pretreatment CT is a predictor of hemorrhagic complications and functional outcomes after the administration of intravenous (IV) tissue plasminogen activator (tPA). We retrospectively analyzed consecutive patients treated with IV tPA at our institution from 2009-2011. Pretreatment CTs were reviewed for evidence of any prior infarct. Further review determined if any hemorrhagic transformation (HT) or symptomatic intracerebral hemorrhage (sICH) were present on repeat CT or magnetic resonance imaging. Outcomes included sICH, any HT, poor functional outcome (modified Rankin Scale score of 4-6), and discharge disposition. Of 212 IV tPA-treated patients, 84 (40%) had evidence of prior infarct on pretreatment CT. Patients with prior infarcts on CT were older (median age, 72 versus 65 years; P=.001) and had higher pretreatment National Institutes of Health Stroke Scale scores (median, 10 versus 7; P=.023). Patients with prior infarcts on CT did not experience more sICH (4% versus 2%; P=.221) or any HT (18% versus 14%; P=.471). These patients did have a higher frequency of poor functional outcome at discharge (82% versus 50%; P<.001) and were less often discharged to home or inpatient rehabilitation center (61% versus 73%; P=.065). Visualization of prior infarcts on pretreatment CT did not predict an increased risk of sICH in our study and should not be viewed as a reason to withhold systemic tPA treatment after clinically evident strokes within 3 months were excluded. Published by Elsevier Inc.

  10. Irrelevant sensory stimuli interfere with working memory storage: evidence from a computational model of prefrontal neurons.

    Science.gov (United States)

    Bancroft, Tyler D; Hockley, William E; Servos, Philip

    2013-03-01

    The encoding of irrelevant stimuli into the memory store has previously been suggested as a mechanism of interference in working memory (e.g., Lange & Oberauer, Memory, 13, 333-339, 2005; Nairne, Memory & Cognition, 18, 251-269, 1990). Recently, Bancroft and Servos (Experimental Brain Research, 208, 529-532, 2011) used a tactile working memory task to provide experimental evidence that irrelevant stimuli were, in fact, encoded into working memory. In the present study, we replicated Bancroft and Servos's experimental findings using a biologically based computational model of prefrontal neurons, providing a neurocomputational model of overwriting in working memory. Furthermore, our modeling results show that inhibition acts to protect the contents of working memory, and they suggest a need for further experimental research into the capacity of vibrotactile working memory.

  11. Fluorine as a hydrogen-bond acceptor: experimental evidence and computational calculations.

    Science.gov (United States)

    Dalvit, Claudio; Invernizzi, Christian; Vulpetti, Anna

    2014-08-25

    Hydrogen-bonding interactions play an important role in many chemical and biological systems. Fluorine acting as a hydrogen-bond acceptor in intermolecular and intramolecular interactions has been the subject of many controversial discussions and there are different opinions about it. Recently, we have proposed a correlation between the propensity of fluorine to be involved in hydrogen bonds and its (19)F NMR chemical shift. We now provide additional experimental and computational evidence for this correlation. The strength of hydrogen-bond complexes involving the fluorine moieties CH2F, CHF2, and CF3 was measured and characterized in simple systems by using established and novel NMR methods and compared to the known hydrogen-bond complex formed between acetophenone and p-fluorophenol. Implications of these results for (19)F NMR screening are analyzed in detail. Computed values of the molecular electrostatic potential at the different fluorine atoms and the analysis of the electron density topology at bond critical points correlate well with the NMR results. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Computer-aided analyses of transport protein sequences: gleaning evidence concerning function, structure, biogenesis, and evolution.

    Science.gov (United States)

    Saier, M H

    1994-03-01

    Three-dimensional structures have been elucidated for very few integral membrane proteins. Computer methods can be used as guides for estimation of solute transport protein structure, function, biogenesis, and evolution. In this paper the application of currently available computer programs to over a dozen distinct families of transport proteins is reviewed. The reliability of sequence-based topological and localization analyses and the importance of sequence and residue conservation to structure and function are evaluated. Evidence concerning the nature and frequency of occurrence of domain shuffling, splicing, fusion, deletion, and duplication during evolution of specific transport protein families is also evaluated. Channel proteins are proposed to be functionally related to carriers. It is argued that energy coupling to transport was a late occurrence, superimposed on preexisting mechanisms of solute facilitation. It is shown that several transport protein families have evolved independently of each other, employing different routes, at different times in evolutionary history, to give topologically similar transmembrane protein complexes. The possible significance of this apparent topological convergence is discussed.

  13. Cone-beam computed tomography: time for an evidence-based approach.

    Science.gov (United States)

    Horner, Keith

    2013-01-01

    Cone-beam computed tomography (CBCT) is an imaging technology that has revolutionised dental imaging in the last decade. Although of particular value to specialists performing implant treatment, it is increasingly being adopted by general dental practitioners. As the radiation dose is higher than that of conventional radiography, it is important to consider its diagnostic efficacy for the common tasks performed in general dental practice, such as caries diagnosis, endodontics and the detection of periapical pathosis. Any new imaging technique needs to have proven advantages over existing techniques before it is adopted, yet the evidence remains quite limited. Furthermore, image quality and radiation doses vary enormously between different manufacturers' equipment, so that extrapolating results of one piece of research from one CBCT machine to another is fraught with pitfalls. Radiation doses with CBCT are typically an order of magnitude higher than conventional radiography. There is scope, however, for reducing these doses by judicious adjustment of exposure factors and limiting the field of view to the smallest dimensions consistent with the clinical situation. There is still a long way to go before we understand the value of CBCT in dentistry. High quality research evidence is needed, particularly with regard to assessing whether using BCT improves patient outcomes.

  14. Model comparison using Bayes factors computed from MCMC samples: evidence for four planets orbiting GJ 876

    Science.gov (United States)

    Nelson, Benjamin Earl; Robertson, Paul; Pritchard, Seth

    2015-08-01

    As planet hunters are pushing radial velocity (RV) precision to the sub-meter per second regime, it is becoming increasingly necessary to disentangle periodic signals of stellar magnetic activity from those of real exoplanets. Statistically robust model comparison algorithms are key in addressing this challenge and complementing more traditional observationally focused methods of planet validation. We develop an algorithm to compute the fully marginalized likelihood (FML, i.e. Bayesian evidence) of a finite set of high-dimensional (~30-40 parameter) models, whose ratios yield Bayes factors for model comparison. The code combines a simple importance sampling algorithm with a Markov chain Monte Carlo posterior sample to produce an accurate estimate of the FML. We apply this algorithm to RV observations of the GJ 876, an M dwarf harboring four supposed planets, three of which are undergoing strong dynamical interactions. Our analysis finds overwhelming Bayesian evidence for the inner three planets and a fourth periodicity due to either the putative planet "e" or stellar activity. Combining our Doppler analysis with a separate stellar activity analysis favors the four-planet model.

  15. Evident?

    DEFF Research Database (Denmark)

    Plant, Peter

    2012-01-01

    Quality assurance and evidence in career guidance in Europe are often seen as self-evident approaches, but particular interests lie behind......Quality assurance and evidence in career guidance in Europe are often seen as self-evident approaches, but particular interests lie behind...

  16. A sampling-based computational strategy for the representation of epistemic uncertainty in model predictions with evidence theory.

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, J. D. (Prostat, Mesa, AZ); Oberkampf, William Louis; Helton, Jon Craig (Arizona State University, Tempe, AZ); Storlie, Curtis B. (North Carolina State University, Raleigh, NC)

    2006-10-01

    Evidence theory provides an alternative to probability theory for the representation of epistemic uncertainty in model predictions that derives from epistemic uncertainty in model inputs, where the descriptor epistemic is used to indicate uncertainty that derives from a lack of knowledge with respect to the appropriate values to use for various inputs to the model. The potential benefit, and hence appeal, of evidence theory is that it allows a less restrictive specification of uncertainty than is possible within the axiomatic structure on which probability theory is based. Unfortunately, the propagation of an evidence theory representation for uncertainty through a model is more computationally demanding than the propagation of a probabilistic representation for uncertainty, with this difficulty constituting a serious obstacle to the use of evidence theory in the representation of uncertainty in predictions obtained from computationally intensive models. This presentation describes and illustrates a sampling-based computational strategy for the representation of epistemic uncertainty in model predictions with evidence theory. Preliminary trials indicate that the presented strategy can be used to propagate uncertainty representations based on evidence theory in analysis situations where naive sampling-based (i.e., unsophisticated Monte Carlo) procedures are impracticable due to computational cost.

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

    DEFF Research Database (Denmark)

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

    1996-01-01

    UNIQUAC interaction parameters have been successfully determined for three alkane/primary amine systems using a Molecular Mechanics method called the Consistent Force Field. Interaction parameters for alkane/alkane and alkane/ketone systems had been determined previously using this method...... and in this contribution the method has been extended to polar systems with extensive hydrogen bonding. It is thus possible to predict reliable vapor liquid equilibrium data using pure component data only. A method for finding the global minimum on the potential energy surface of a pair of molecules was developed. Good...

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

    Science.gov (United States)

    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.

  19. Angry facial expressions bias gender categorization in children and adults: behavioral and computational evidence

    Science.gov (United States)

    Bayet, Laurie; Pascalis, Olivier; Quinn, Paul C.; Lee, Kang; Gentaz, Édouard; Tanaka, James W.

    2015-01-01

    Angry faces are perceived as more masculine by adults. However, the developmental course and underlying mechanism (bottom-up stimulus driven or top-down belief driven) associated with the angry-male bias remain unclear. Here we report that anger biases face gender categorization toward “male” responding in children as young as 5–6 years. The bias is observed for both own- and other-race faces, and is remarkably unchanged across development (into adulthood) as revealed by signal detection analyses (Experiments 1–2). The developmental course of the angry-male bias, along with its extension to other-race faces, combine to suggest that it is not rooted in extensive experience, e.g., observing males engaging in aggressive acts during the school years. Based on several computational simulations of gender categorization (Experiment 3), we further conclude that (1) the angry-male bias results, at least partially, from a strategy of attending to facial features or their second-order relations when categorizing face gender, and (2) any single choice of computational representation (e.g., Principal Component Analysis) is insufficient to assess resemblances between face categories, as different representations of the very same faces suggest different bases for the angry-male bias. Our findings are thus consistent with stimulus-and stereotyped-belief driven accounts of the angry-male bias. Taken together, the evidence suggests considerable stability in the interaction between some facial dimensions in social categorization that is present prior to the onset of formal schooling. PMID:25859238

  20. Angry facial expressions bias gender categorization in children and adults: behavioral and computational evidence

    Directory of Open Access Journals (Sweden)

    Laurie eBayet

    2015-03-01

    Full Text Available Angry faces are perceived as more masculine by adults. However, the developmental course and underlying mechanism (bottom-up stimulus driven or top-down belief driven associated with the angry-male bias remain unclear. Here we report that anger biases face gender categorization towards male responding in children as young as 5-6 years. The bias is observed for both own- and other-race faces, and is remarkably unchanged across development (into adulthood as revealed by signal detection analyses (Experiments 1-2. The developmental course of the angry-male bias, along with its extension to other-race faces, combine to suggest that it is not rooted in extensive experience, e.g. observing males engaging in aggressive acts during the school years. Based on several computational simulations of gender categorization (Experiment 3, we further conclude that (1 the angry-male bias results, at least partially, from a strategy of attending to facial features or their second-order relations when categorizing face gender, and (2 any single choice of computational representation (e.g., Principal Component Analysis is insufficient to assess resemblances between face categories, as different representations of the very same faces suggest different bases for the angry-male bias. Our findings are thus consistent with stimulus-and stereotyped-belief driven accounts of the angry-male bias. Taken together, the evidence suggests considerable stability in the interaction between some facial dimensions in social categorization that is present prior to the onset of formal schooling.

  1. Two novel alkane hydroxylase-rubredoxin fusion genes isolated from a Dietzia bacterium and the functions of fused rubredoxin domains in long-chain n-alkane degradation.

    Science.gov (United States)

    Nie, Yong; Liang, Jieliang; Fang, Hui; Tang, Yue-Qin; Wu, Xiao-Lei

    2011-10-01

    Two alkane hydroxylase-rubredoxin fusion gene homologs (alkW1 and alkW2) were cloned from a Dietzia strain, designated DQ12-45-1b, which can grow on crude oil and n-alkanes ranging in length from 6 to 40 carbon atoms as sole carbon sources. Both AlkW1 and AlkW2 have an integral-membrane alkane monooxygenase (AlkB) conserved domain and a rubredoxin (Rd) conserved domain which are fused together. Phylogenetic analysis showed that these two AlkB-fused Rd domains formed a novel third cluster with all the Rds from the alkane hydroxylase-rubredoxin fusion gene clusters in Gram-positive bacteria and that this third cluster was distant from the known AlkG1- and AlkG2-type Rds. Expression of the alkW1 gene in DQ12-45-1b was induced when cells were grown on C(8) to C(32) n-alkanes as sole carbon sources, but expression of the alkW2 gene was not detected. Functional heterologous expression in an alkB deletion mutant of Pseudomonas fluorescens KOB2Δ1 suggested the alkW1 could restore the growth of KOB2Δ1 on C(14) and C(16) n-alkanes and induce faster growth on C(18) to C(32) n-alkanes than alkW1ΔRd, the Rd domain deletion mutant gene of alkW1, which also caused faster growth than KOB2Δ1 itself. In addition, the artificial fusion of AlkB from the Gram-negative P. fluorescens CHA0 and the Rds from both Gram-negative P. fluorescens CHA0 and Gram-positive Dietzia sp. DQ12-45-1b significantly increased the degradation of C(32) alkane compared to that seen with AlkB itself. In conclusion, the alkW1 gene cloned from Dietzia species encoded an alkane hydroxylase which increased growth on and degradation of n-alkanes up to C(32) in length, with its fused rubredoxin domain being necessary to maintain the functions. In addition, the fusion of alkane hydroxylase and rubredoxin genes from both Gram-positive and -negative bacteria can increase the degradation of long-chain n-alkanes (such as C(32)) in the Gram-negative bacterium.

  2. TrueAllele casework on Virginia DNA mixture evidence: computer and manual interpretation in 72 reported criminal cases.

    Directory of Open Access Journals (Sweden)

    Mark W Perlin

    Full Text Available Mixtures are a commonly encountered form of biological evidence that contain DNA from two or more contributors. Laboratory analysis of mixtures produces data signals that usually cannot be separated into distinct contributor genotypes. Computer modeling can resolve the genotypes up to probability, reflecting the uncertainty inherent in the data. Human analysts address the problem by simplifying the quantitative data in a threshold process that discards considerable identification information. Elevated stochastic threshold levels potentially discard more information. This study examines three different mixture interpretation methods. In 72 criminal cases, 111 genotype comparisons were made between 92 mixture items and relevant reference samples. TrueAllele computer modeling was done on all the evidence samples, and documented in DNA match reports that were provided as evidence for each case. Threshold-based Combined Probability of Inclusion (CPI and stochastically modified CPI (mCPI analyses were performed as well. TrueAllele's identification information in 101 positive matches was used to assess the reliability of its modeling approach. Comparison was made with 81 CPI and 53 mCPI DNA match statistics that were manually derived from the same data. There were statistically significant differences between the DNA interpretation methods. TrueAllele gave an average match statistic of 113 billion, CPI averaged 6.68 million, and mCPI averaged 140. The computer was highly specific, with a false positive rate under 0.005%. The modeling approach was precise, having a factor of two within-group standard deviation. TrueAllele accuracy was indicated by having uniformly distributed match statistics over the data set. The computer could make genotype comparisons that were impossible or impractical using manual methods. TrueAllele computer interpretation of DNA mixture evidence is sensitive, specific, precise, accurate and more informative than manual

  3. Optimized reaction mechanism rate rules for ignition of normal alkanes

    KAUST Repository

    Cai, Liming

    2016-08-11

    The increasing demand for cleaner combustion and reduced greenhouse gas emissions motivates research on the combustion of hydrocarbon fuels and their surrogates. Accurate detailed chemical kinetic models are an important prerequisite for high fidelity reacting flow simulations capable of improving combustor design and operation. The development of such models for many new fuel components and/or surrogate molecules is greatly facilitated by the application of reaction classes and rate rules. Accurate and versatile rate rules are desirable to improve the predictive accuracy of kinetic models. A major contribution in the literature is the recent work by Bugler et al. (2015), which has significantly improved rate rules and thermochemical parameters used in kinetic modeling of alkanes. In the present study, it is demonstrated that rate rules can be used and consistently optimized for a set of normal alkanes including n-heptane, n-octane, n-nonane, n-decane, and n-undecane, thereby improving the predictive accuracy for all the considered fuels. A Bayesian framework is applied in the calibration of the rate rules. The optimized rate rules are subsequently applied to generate a mechanism for n-dodecane, which was not part of the training set for the optimized rate rules. The developed mechanism shows accurate predictions compared with published well-validated mechanisms for a wide range of conditions.

  4. The Effect of Compositional Changes of Binary Mixtures of n-alkane ...

    African Journals Online (AJOL)

    The Effect of Compositional Changes of Binary Mixtures of n-alkane solvents on the Precipitation of Heavy Organics from a Solution of Crude Oil Residue. ... The results have shown that the quantity of HO precipitate decreases with increasing quantity of higher carbon number of n-alkane solvent to a minimum value at 2:1 ...

  5. The use of n-alkane markers to estimate the intake and apparent ...

    African Journals Online (AJOL)

    The n-alkane marker (dosed marker, dotriacontane, C32, herbage markers C31, C33 and C35) technique was evaluated for use in feed intake and digestibility studies with horses. The mean retention time of digesta in the digestive tract was determined in horses following a single dose of C32. The n-alkane technique was ...

  6. Thermal, Catalytic Conversion of Alkanes to Linear Aldehydes and Linear Amines.

    Science.gov (United States)

    Tang, Xinxin; Jia, Xiangqing; Huang, Zheng

    2018-03-21

    Alkanes, the main constituents of petroleum, are attractive feedstocks for producing value-added chemicals. Linear aldehydes and amines are two of the most important building blocks in the chemical industry. To date, there have been no effective methods for directly converting n-alkanes to linear aldehydes and linear amines. Here, we report a molecular dual-catalyst system for production of linear aldehydes via regioselective carbonylation of n-alkanes. The system is comprised of a pincer iridium catalyst for transfer-dehydrogenation of the alkane using t-butylethylene or ethylene as a hydrogen acceptor working sequentially with a rhodium catalyst for olefin isomerization-hydroformylation with syngas. The system exhibits high regioselectivity for linear aldehydes and gives high catalytic turnover numbers when using ethylene as the acceptor. In addition, the direct conversion of light alkanes, n-pentane and n-hexane, to siloxy-terminated alkyl aldehydes through a sequence of Ir/Fe-catalyzed alkane silylation and Ir/Rh-catalyzed alkane carbonylation, is described. Finally, the Ir/Rh dual-catalyst strategy has been successfully applied to regioselective alkane aminomethylation to form linear alkyl amines.

  7. Crystallisation and chain conformation of long chain n-alkanes

    International Nuclear Information System (INIS)

    Gorce, J.

    2000-06-01

    Hydrocarbon chains are a basic component in a number of systems as diverse as biological membranes, phospholipids and polymers. A better understanding of the physical properties of n-alkane chains should provide a better understanding of these more complex systems. With this aim, vibrational spectroscopy has been extensively used. This technique, sensitive to molecular details, is the only one able to both identify and quantify conformational disorder present in paraffinic systems. To achieve this, methyl deformations have been widely used as ''internal standards'' for the normalisation of peak areas. However, in the case of n-alkanes with short chain length, such as n-C 44 H 90 for example, the infrared spectra recorded at liquid nitrogen temperature and reported here show the sensitivity of these latter peaks to the various crystal structures formed. Indeed, the main frequencies of the symmetric methyl bending mode were found between 1384 cm -1 and 1368 cm -1 as a function of the crystal form. Changes in the frequency of the first order of the L.A.M. present in the Raman spectra were also observed. At higher temperatures, non all-trans conformers, inferred from different infrared bands present in the wagging mode region, were found to be essentially placed at the end of the n-alkane chains. At the monoclinic phase transition, the concentration of end-gauche conformers, proportional to the area of the infrared band at 1342 cm -1 , increases abruptly. On the contrary, in the spectra recorded at liquid nitrogen temperature no such band is observed. We also studied the degree of disorder in two purely monodisperse long chain n-alkanes, namely n-C 198 H 398 and n-C 246 H 494 . The chain conformation as well as the tilt angle of the chains from the crystal surfaces were determined by means of low frequency Raman spectroscopy and S.A.X.S. measurements on solution-crystallised samples. The increase in the number of end-gauche conformers which was expected to occur with

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

    Directory of Open Access Journals (Sweden)

    Arpita eBose

    2013-12-01

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

  9. Functional screening of aldehyde decarbonylases for long-chain alkane production by Saccharomyces cerevisiae

    DEFF Research Database (Denmark)

    Kang, Min-Kyoung; Zhou, Yongjin J.; Buijs, Nicolaas A.

    2017-01-01

    performed functional screening to identify efficient ADs that can improve alkane production by S. cerevisiae. Results: A comparative study of ADs originated from a plant, insects, and cyanobacteria were conducted in S. cerevisiae. As a result, expression of aldehyde deformylating oxygenases (ADOs), which......Background: Low catalytic activities of pathway enzymes are often a limitation when using microbial based chemical production. Recent studies indicated that the enzyme activity of aldehyde decarbonylase (AD) is a critical bottleneck for alkane biosynthesis in Saccharomyces cerevisiae. We therefore...... are cyanobacterial ADs, from Synechococcus elongatus and Crocosphaera watsonii converted fatty aldehydes to corresponding Cn-1 alkanes and alkenes. The CwADO showed the highest alkane titer (0.13 mg/L/OD600) and the lowest fatty alcohol production (0.55 mg/L/OD600). However, no measurable alkanes and alkenes were...

  10. An integrative computational analysis provides evidence for FBN1-associated network deregulation in trisomy 21

    Directory of Open Access Journals (Sweden)

    Mireia Vilardell

    2013-06-01

    Although approximately 50% of Down Syndrome (DS patients have heart abnormalities, they exhibit an overprotection against cardiac abnormalities related with the connective tissue, for example a lower risk of coronary artery disease. A recent study reported a case of a person affected by DS who carried mutations in FBN1, the gene causative for a connective tissue disorder called Marfan Syndrome (MFS. The fact that the person did not have any cardiac alterations suggested compensation effects due to DS. This observation is supported by a previous DS meta-analysis at the molecular level where we have found an overall upregulation of FBN1 (which is usually downregulated in MFS. Additionally, that result was cross-validated with independent expression data from DS heart tissue. The aim of this work is to elucidate the role of FBN1 in DS and to establish a molecular link to MFS and MFS-related syndromes using a computational approach. To reach that, we conducted different analytical approaches over two DS studies (our previous meta-analysis and independent expression data from DS heart tissue and revealed expression alterations in the FBN1 interaction network, in FBN1 co-expressed genes and FBN1-related pathways. After merging the significant results from different datasets with a Bayesian approach, we prioritized 85 genes that were able to distinguish control from DS cases. We further found evidence for several of these genes (47%, such as FBN1, DCN, and COL1A2, being dysregulated in MFS and MFS-related diseases. Consequently, we further encourage the scientific community to take into account FBN1 and its related network for the study of DS cardiovascular characteristics.

  11. Deciding not to decide: computational and neural evidence for hidden behavior in sequential choice.

    Directory of Open Access Journals (Sweden)

    Sebastian Gluth

    2013-10-01

    Full Text Available Understanding the cognitive and neural processes that underlie human decision making requires the successful prediction of how, but also of when, people choose. Sequential sampling models (SSMs have greatly advanced the decision sciences by assuming decisions to emerge from a bounded evidence accumulation process so that response times (RTs become predictable. Here, we demonstrate a difficulty of SSMs that occurs when people are not forced to respond at once but are allowed to sample information sequentially: The decision maker might decide to delay the choice and terminate the accumulation process temporarily, a scenario not accounted for by the standard SSM approach. We developed several SSMs for predicting RTs from two independent samples of an electroencephalography (EEG and a functional magnetic resonance imaging (fMRI study. In these studies, participants bought or rejected fictitious stocks based on sequentially presented cues and were free to respond at any time. Standard SSM implementations did not describe RT distributions adequately. However, by adding a mechanism for postponing decisions to the model we obtained an accurate fit to the data. Time-frequency analysis of EEG data revealed alternating states of de- and increasing oscillatory power in beta-band frequencies (14-30 Hz, indicating that responses were repeatedly prepared and inhibited and thus lending further support for the existence of a decision not to decide. Finally, the extended model accounted for the results of an adapted version of our paradigm in which participants had to press a button for sampling more information. Our results show how computational modeling of decisions and RTs support a deeper understanding of the hidden dynamics in cognition.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-04-15

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

  13. n-Alkane distributions as palaeoclimatic proxies in ombrotrophic peat: The role of decomposition and dominant vegetation

    NARCIS (Netherlands)

    Schellekens, J.; Buurman, P.

    2011-01-01

    n-Alkane distributions are frequently used as palaeoclimate proxies in ombrotrophic peat deposits. Although n-alkane distributions differ strongly between plant species, n-alkanes are not species-specific molecules. For a proper interpretation, it is important to understand the different abundances

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

    Science.gov (United States)

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

    2015-12-01

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

  15. Computer simulation, rhetoric, and the scientific imagination how virtual evidence shapes science in the making and in the news

    CERN Document Server

    Roundtree, Aimee Kendall

    2013-01-01

    Computer simulations help advance climatology, astrophysics, and other scientific disciplines. They are also at the crux of several high-profile cases of science in the news. How do simulation scientists, with little or no direct observations, make decisions about what to represent? What is the nature of simulated evidence, and how do we evaluate its strength? Aimee Kendall Roundtree suggests answers in Computer Simulation, Rhetoric, and the Scientific Imagination. She interprets simulations in the sciences by uncovering the argumentative strategies that underpin the production and disseminati

  16. On the Need for Research Evidence to Guide the Design of Computer Games for Learning

    Science.gov (United States)

    Mayer, Richard E.

    2015-01-01

    Computer games for learning (also called video games or digital games) have potential to improve education. This is the intriguing idea that motivates this special issue of the "Educational Psychologist" on "Psychological Perspectives on Digital Games and Learning." Computer games for learning are games delivered via computer…

  17. Measurement and Evidence of Computer-Based Task Switching and Multitasking by "Net Generation" Students

    Science.gov (United States)

    Judd, Terry; Kennedy, Gregor

    2011-01-01

    Logs of on-campus computer and Internet usage were used to conduct a study of computer-based task switching and multitasking by undergraduate medical students. A detailed analysis of over 6000 individual sessions revealed that while a majority of students engaged in both task switching and multitasking behaviours, they did so less frequently than…

  18. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    Energy Technology Data Exchange (ETDEWEB)

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

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

    Science.gov (United States)

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

    1998-01-01

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

  20. Efficacy of individual computer-based auditory training for people with hearing loss: a systematic review of the evidence.

    Science.gov (United States)

    Henshaw, Helen; Ferguson, Melanie A

    2013-01-01

    Auditory training involves active listening to auditory stimuli and aims to improve performance in auditory tasks. As such, auditory training is a potential intervention for the management of people with hearing loss. This systematic review (PROSPERO 2011: CRD42011001406) evaluated the published evidence-base for the efficacy of individual computer-based auditory training to improve speech intelligibility, cognition and communication abilities in adults with hearing loss, with or without hearing aids or cochlear implants. A systematic search of eight databases and key journals identified 229 articles published since 1996, 13 of which met the inclusion criteria. Data were independently extracted and reviewed by the two authors. Study quality was assessed using ten pre-defined scientific and intervention-specific measures. Auditory training resulted in improved performance for trained tasks in 9/10 articles that reported on-task outcomes. Although significant generalisation of learning was shown to untrained measures of speech intelligibility (11/13 articles), cognition (1/1 articles) and self-reported hearing abilities (1/2 articles), improvements were small and not robust. Where reported, compliance with computer-based auditory training was high, and retention of learning was shown at post-training follow-ups. Published evidence was of very-low to moderate study quality. Our findings demonstrate that published evidence for the efficacy of individual computer-based auditory training for adults with hearing loss is not robust and therefore cannot be reliably used to guide intervention at this time. We identify a need for high-quality evidence to further examine the efficacy of computer-based auditory training for people with hearing loss.

  1. Efficacy of individual computer-based auditory training for people with hearing loss: a systematic review of the evidence.

    Directory of Open Access Journals (Sweden)

    Helen Henshaw

    Full Text Available BACKGROUND: Auditory training involves active listening to auditory stimuli and aims to improve performance in auditory tasks. As such, auditory training is a potential intervention for the management of people with hearing loss. OBJECTIVE: This systematic review (PROSPERO 2011: CRD42011001406 evaluated the published evidence-base for the efficacy of individual computer-based auditory training to improve speech intelligibility, cognition and communication abilities in adults with hearing loss, with or without hearing aids or cochlear implants. METHODS: A systematic search of eight databases and key journals identified 229 articles published since 1996, 13 of which met the inclusion criteria. Data were independently extracted and reviewed by the two authors. Study quality was assessed using ten pre-defined scientific and intervention-specific measures. RESULTS: Auditory training resulted in improved performance for trained tasks in 9/10 articles that reported on-task outcomes. Although significant generalisation of learning was shown to untrained measures of speech intelligibility (11/13 articles, cognition (1/1 articles and self-reported hearing abilities (1/2 articles, improvements were small and not robust. Where reported, compliance with computer-based auditory training was high, and retention of learning was shown at post-training follow-ups. Published evidence was of very-low to moderate study quality. CONCLUSIONS: Our findings demonstrate that published evidence for the efficacy of individual computer-based auditory training for adults with hearing loss is not robust and therefore cannot be reliably used to guide intervention at this time. We identify a need for high-quality evidence to further examine the efficacy of computer-based auditory training for people with hearing loss.

  2. Effect of nanoparticles on the RII -RI -RV rotator phase transitions of alkanes

    Science.gov (United States)

    Mukherjee, Prabir K.

    2017-08-01

    Experimental studies have shown that nanoparticles play an important role on the rotator phase transitions of n-alkanes. A phenomenological model for predicting the RII -RI -RV phase transitions in mixtures of alkanes and nanoparticles has been proposed by combining Flory-Huggins free energy of isotropic mixing and Landau free energy. The impact of nanoparticles on the RII -RI -RV phase transitions and their transition temperatures is discussed by means of phenomenological theory. The possibility of the tricritical behavior of the RI -RV phase transition in the mixtures of alkanes and nanoparticles is discussed. The theoretical predictions are in good qualitative agreement with available experimental results.

  3. A Case for Tamper-Resistant and Tamper-Evident Computer Systems

    National Research Council Canada - National Science Library

    Solihin, Yan

    2007-01-01

    .... These attacks attempt to snoop or modify data transfer between various chips in a computer system such as between the processor and memory, and between processors in a multiprocessor interconnect network...

  4. The role of beliefs in lexical alignment: evidence from dialogs with humans and computers.

    Science.gov (United States)

    Branigan, Holly P; Pickering, Martin J; Pearson, Jamie; McLean, Janet F; Brown, Ash

    2011-10-01

    Five experiments examined the extent to which speakers' alignment (i.e., convergence) on words in dialog is mediated by beliefs about their interlocutor. To do this, we told participants that they were interacting with another person or a computer in a task in which they alternated between selecting pictures that matched their 'partner's' descriptions and naming pictures themselves (though in reality all responses were scripted). In both text- and speech-based dialog, participants tended to repeat their partner's choice of referring expression. However, they showed a stronger tendency to align with 'computer' than with 'human' partners, and with computers that were presented as less capable than with computers that were presented as more capable. The tendency to align therefore appears to be mediated by beliefs, with the relevant beliefs relating to an interlocutor's perceived communicative capacity. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. Anomaly in the Chain Length Dependence of n-Alkane Diffusion in ZIF-4 Metal-Organic Frameworks.

    Science.gov (United States)

    Hwang, Seungtaik; Gopalan, Arun; Hovestadt, Maximilian; Piepenbreier, Frank; Chmelik, Christian; Hartmann, Martin; Snurr, Randall Q; Kärger, Jörg

    2018-03-15

    Molecular diffusion is commonly found to slow down with increasing molecular size. Deviations from this pattern occur in some host materials with pore sizes approaching the diameters of the guest molecules. A variety of theoretical models have been suggested to explain deviations from this pattern, but robust experimental data are scarcely available. Here, we present such data, obtained by monitoring the chain length dependence of the uptake of n- alkanes in the zeolitic imidazolate framework ZIF-4. A monotonic decrease in diffusivity from ethane to n- butane was observed, followed by an increase for n- pentane, and another decrease for n- hexane. This observation was confirmed by uptake measurements with n- butane/ n -pentane mixtures, which yield faster uptake of n- pentane. Further evidence is provided by the observation of overshooting effects, i.e., by transient n- pentane concentrations exceeding the (eventually attained) equilibrium value. Accompanying grand canonical Monte Carlo simulations reveal, for the larger n- alkanes, significant differences between the adsorbed and gas phase molecular configurations, indicating strong confinement effects within ZIF-4, which, with increasing chain length, may be expected to give rise to configurational shifts facilitating molecular propagation at particular chain lengths.

  6. Anomaly in the Chain Length Dependence of n-Alkane Diffusion in ZIF-4 Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Seungtaik Hwang

    2018-03-01

    Full Text Available Molecular diffusion is commonly found to slow down with increasing molecular size. Deviations from this pattern occur in some host materials with pore sizes approaching the diameters of the guest molecules. A variety of theoretical models have been suggested to explain deviations from this pattern, but robust experimental data are scarcely available. Here, we present such data, obtained by monitoring the chain length dependence of the uptake of n-alkanes in the zeolitic imidazolate framework ZIF-4. A monotonic decrease in diffusivity from ethane to n-butane was observed, followed by an increase for n-pentane, and another decrease for n-hexane. This observation was confirmed by uptake measurements with n-butane/n-pentane mixtures, which yield faster uptake of n-pentane. Further evidence is provided by the observation of overshooting effects, i.e., by transient n-pentane concentrations exceeding the (eventually attained equilibrium value. Accompanying grand canonical Monte Carlo simulations reveal, for the larger n-alkanes, significant differences between the adsorbed and gas phase molecular configurations, indicating strong confinement effects within ZIF-4, which, with increasing chain length, may be expected to give rise to configurational shifts facilitating molecular propagation at particular chain lengths.

  7. Chromium oxide catalysts in the dehydrogenation of alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Airaksinen, S.

    2005-07-01

    Light alkenes, such as propene and butenes, are important intermediates in the manufacture of fuel components and chemicals. The direct catalytic dehydrogenation of the corresponding alkanes is a selective way to produce these alkenes and is frequently carried out using chromia/alumina catalysts. The aim of this work was to obtain structure-activity information, which could be utilised in the optimisation of this catalytic system. The properties of chromia/alumina catalysts were investigated by advanced in situ and ex situ spectroscopic methods, and the activities were measured in the dehydrogenation of isobutane. The dehydrogenation activity of chromia/alumina was attributed to coordinatively unsaturated redox and non- redox Cr{sup 3+} ions at all chromium loadings. In addition, the oxygen ions in the catalyst appeared to participate in the reaction. The reduction of chromia/alumina resulted in formation of adsorbed surface species: hydroxyl groups bonded to chromia and alumina were formed in reduction by hydrogen and alkanes, and carbon- containing species in reduction by carbon monoxide and alkanes. Prereduction with hydrogen or carbon monoxide decreased the dehydrogenation activity. The effect by hydrogen was suggested to be related to the amount of OH/H species on the reduced surface affecting the number of coordinatively unsaturated chromium sites, and the effect by carbon monoxide to the formation of unselective chromium sites and carboncontaining species. The chromia/alumina catalysts were deactivated with time on stream and in cycles of (pre)reduction- dehydrogenation-regeneration. The deactivation with time on stream was caused mainly by coke formation. The nature of the coke species changed during dehydrogenation. Carboxylates and aliphatic hydrocarbon species formed at the beginning of the reaction and unsaturated/aromatic hydrocarbons and graphite- like species with increasing time on stream. The deactivation in several dehydrogenation- regeneration

  8. ESR and electronic spectra of alkane radical cations formed in γ-irradiated 3-methylpentane and 3-methylhexane glasses containing alkane solutes

    International Nuclear Information System (INIS)

    Ichikawa, T.; Ohta, N.

    1987-01-01

    Electron spin resonance (ESR) and optical difference spectra of photobleaching are measured, and the radical cations from some higher alkanes (C 9 -C 11 ) and some methyl-branched butanes are found to be trapped in 3-methylpentane or 3-methylhexane matrices at 77 K. The ESR spectra show close agreement with those of radical cations produced in CCl 2 FCClF 2 matrices. The cations of methyl-branched butanes give the absorption bands with λ/sub max/ ranging from 300 to 260 nm and the bands are attributed to σ-localized cations, while the higher alkane cation bands appearing in the near-IR region are ascribed to σ-delocalized cations. The cations of higher alkanes are found to be mobilized by light with λ > 900 nm to recombine with the negative ions formed by electron scavenging

  9. Causal evidence for retina-dependent and -independent visual motion computations in mouse cortex.

    Science.gov (United States)

    Hillier, Daniel; Fiscella, Michele; Drinnenberg, Antonia; Trenholm, Stuart; Rompani, Santiago B; Raics, Zoltan; Katona, Gergely; Juettner, Josephine; Hierlemann, Andreas; Rozsa, Balazs; Roska, Botond

    2017-07-01

    How neuronal computations in the sensory periphery contribute to computations in the cortex is not well understood. We examined this question in the context of visual-motion processing in the retina and primary visual cortex (V1) of mice. We disrupted retinal direction selectivity, either exclusively along the horizontal axis using FRMD7 mutants or along all directions by ablating starburst amacrine cells, and monitored neuronal activity in layer 2/3 of V1 during stimulation with visual motion. In control mice, we found an over-representation of cortical cells preferring posterior visual motion, the dominant motion direction an animal experiences when it moves forward. In mice with disrupted retinal direction selectivity, the over-representation of posterior-motion-preferring cortical cells disappeared, and their responses at higher stimulus speeds were reduced. This work reveals the existence of two functionally distinct, sensory-periphery-dependent and -independent computations of visual motion in the cortex.

  10. Causal evidence for retina dependent and independent visual motion computations in mouse cortex

    Science.gov (United States)

    Hillier, Daniel; Fiscella, Michele; Drinnenberg, Antonia; Trenholm, Stuart; Rompani, Santiago B.; Raics, Zoltan; Katona, Gergely; Juettner, Josephine; Hierlemann, Andreas; Rozsa, Balazs; Roska, Botond

    2017-01-01

    How neuronal computations in the sensory periphery contribute to computations in the cortex is not well understood. We examined this question in the context of visual-motion processing in the retina and primary visual cortex (V1) of mice. We disrupted retinal direction selectivity – either exclusively along the horizontal axis using FRMD7 mutants or along all directions by ablating starburst amacrine cells – and monitored neuronal activity in layer 2/3 of V1 during stimulation with visual motion. In control mice, we found an overrepresentation of cortical cells preferring posterior visual motion, the dominant motion direction an animal experiences when it moves forward. In mice with disrupted retinal direction selectivity, the overrepresentation of posterior-motion-preferring cortical cells disappeared, and their response at higher stimulus speeds was reduced. This work reveals the existence of two functionally distinct, sensory-periphery-dependent and -independent computations of visual motion in the cortex. PMID:28530661

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

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Dimitrios, Tassios

    1997-01-01

    Several methods for the estimation of the critical temperature T-c, the critical pressure P-c, and the acentric factor omega for long-chain n-alkanes are reviewed and evaluated for the prediction of vapor pressures using Corresponding States (CS) methods, like the Lee-Kesler equation and the cubic...... equations of state. Most reliable and recent literature methods proposed for the estimation of the acentric factor of heavy alkanes yield similar values and the emphasis is, thus, given to the determination of the best sets of T-c and P-c. Various extrapolation schemes proposed for this purpose and several....... Anselme, Correlation of the critical properties of alkanes and alkanols, Fluid Phase Equilibria, 56 (1990) 153-169; W. Hu, J. Lovland and P. Vonka. Generalized vapor pressure equations for n-alkanes, 1-alkenes, and 1-alkanols, Presented at the 11th Int. Congress of Chemical Engineering, Chemical Equipment...

  12. Biobased production of alkanes and alkenes through metabolic engineering of microorganisms

    DEFF Research Database (Denmark)

    Kang, Min Kyoung; Nielsen, Jens

    2017-01-01

    Advancement in metabolic engineering of microorganisms has enabled bio-based production of a range of chemicals, and such engineered microorganism can be used for sustainable production leading to reduced carbon dioxide emission there. One area that has attained much interest is microbial...... hydrocarbon biosynthesis, and in particular, alkanes and alkenes are important high-value chemicals as they can be utilized for a broad range of industrial purposes as well as ‘drop-in’ biofuels. Some microorganisms have the ability to biosynthesize alkanes and alkenes naturally, but their production level...... is extremely low. Therefore, there have been various attempts to recruit other microbial cell factories for production of alkanes and alkenes by applying metabolic engineering strategies. Here we review different pathways and involved enzymes for alkane and alkene production and discuss bottlenecks...

  13. Simulation studies on structural and thermal properties of alkane thiol capped gold nanoparticles.

    Science.gov (United States)

    Devi, J Meena

    2017-06-01

    The structural and thermal properties of the passivated gold nanoparticles were explored employing molecular dynamics simulation for the different surface coverage densities of the self-assembled monolayer (SAM) of alkane thiol. The structural properties of the monolayer protected gold nanoparticles such us overall shape, organization and conformation of the capping alkane thiol chains were found to be influenced by the capping density. The structural order of the thiol capped gold nanoparticles enhances with the increase in the surface coverage density. The specific heat capacity of the alkane thiol capped gold nanoparticles was found to increase linearly with the thiol coverage density. This may be attributed to the enhancement in the lattice vibrational energy. The present simulation results suggest, that the structural and thermal properties of the alkane thiol capped gold nanoparticles may be modified by the suitable selection of the SAM coverage density. Copyright © 2017 Elsevier Inc. All rights reserved.

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

    Science.gov (United States)

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

    2011-11-01

    Libraries of 16S rRNA genes cloned from methanogenic oil degrading microcosms amended with North Sea crude oil and inoculated with estuarine sediment indicated that bacteria from the genera Smithella (Deltaproteobacteria, Syntrophaceace) and Marinobacter sp. (Gammaproteobacteria) were enriched during degradation. Growth yields and doubling times (36 days for both Smithella and Marinobacter) were determined using qPCR and quantitative data on alkanes, which were the predominant hydrocarbons degraded. The growth yield of the Smithella sp. [0.020 g(cell-C)/g(alkane-C)], assuming it utilized all alkanes removed was consistent with yields of bacteria that degrade hydrocarbons and other organic compounds in methanogenic consortia. Over 450 days of incubation predominance and exponential growth of Smithella was coincident with alkane removal and exponential accumulation of methane. This growth is consistent with Smithella's occurrence in near surface anoxic hydrocarbon degrading systems and their complete oxidation of crude oil alkanes to acetate and/or hydrogen in syntrophic partnership with methanogens in such systems. The calculated growth yield of the Marinobacter sp., assuming it grew on alkanes, was [0.0005 g(cell-C)/g(alkane-C)] suggesting that it played a minor role in alkane degradation. The dominant methanogens were hydrogenotrophs (Methanocalculus spp. from the Methanomicrobiales). Enrichment of hydrogen-oxidizing methanogens relative to acetoclastic methanogens was consistent with syntrophic acetate oxidation measured in methanogenic crude oil degrading enrichment cultures. qPCR of the Methanomicrobiales indicated growth characteristics consistent with measured rates of methane production and growth in partnership with Smithella. © 2011 Society for Applied Microbiology and Blackwell Publishing Ltd.

  15. Microaerophilic alkane degradation in Pseudomonas extremaustralis: a transcriptomic and physiological approach

    DEFF Research Database (Denmark)

    Tribelli, Paula Maria; Rossi, Leticia; Ricardi, Martiniano M

    2017-01-01

    Diesel fuel is one of the most important sources of hydrocarbon contamination worldwide. Its composition consists of a complex mixture of n-alkanes, branched alkanes and aromatic compounds. Hydrocarbon degradation in Pseudomonas species has been mostly studied under aerobic conditions; however, a...... conditions for cell maintenance or slow growth in a Pseudomonas species and this metabolism could represent an adaptive advantage in polluted environments....

  16. Estimating valence from the sound of a word : Computational, experimental, and cross-linguistic evidence

    NARCIS (Netherlands)

    Louwerse, Max; Qu, Zhan

    2017-01-01

    It is assumed linguistic symbols must be grounded in perceptual information to attain meaning, because the sound of a word in a language has an arbitrary relation with its referent. This paper demonstrates that a strong arbitrariness claim should be reconsidered. In a computational study, we showed

  17. The heart of patients with aortic aneurysms: evidence from cardiac computed tomography.

    NARCIS (Netherlands)

    Stolzmann, P.; Phan, C.; Desbiolles, L.; Lachat, M.; Pfammatter, T.; Marincek, B.; Prokop, M.; Alkadhi, H.

    2009-01-01

    To determine in patients with abdominal aortic aneurysm (AAA) the coronary calcium burden and prevalence of coronary artery disease (CAD) in relation to cardiovascular risk factors, and to assess the left ventricular (LV) function using cardiac computed tomography (CT). Sixty consecutive patients

  18. Application of a Crossover Equation of State to Describe Phase Equilibrium and Critical Properties of n-Alkanes and Methane/n-Alkane Mixtures

    DEFF Research Database (Denmark)

    P. C. M. Vinhal, Andre; Yan, Wei; Kontogeorgis, Georgios M.

    2017-01-01

    and the asymptotic one near the critical point. Although several crossover EOSs have been developed in the last decades their use in modeling industrial processes is rather limited. In this work, we use the crossover Soave–Redlich–Kwong (CSRK) to describe phase equilibrium and critical properties of pure n......-alkanes and methane/n-alkane binary mixtures and compare the results to two other modeling approaches of the SRK EOS. In the case of the pure fluids, CSRK gives an accurate overall description of the phase equilibrium and critical properties; nevertheless, a minor increase in the deviation of the saturation pressure...

  19. Perspectives on Games, Computers, and Mental Health: Questions about Paradoxes, Evidences, and Challenges.

    Science.gov (United States)

    Desseilles, Martin

    2016-01-01

    In the field of mental health, games and computerized games present questions about paradoxes, evidences, and challenges. This perspective article offers perspectives and personal opinion about these questions, evidences, and challenges with an objective of presenting several ideas and issues in this rapidly developing field. First, games raise some questions in the sense of the paradox between a game and an issue, as well as the paradox of using an amusing game to treat a serious pathology. Second, games also present evidence in the sense that they involve relationships with others, as well as learning, communication, language, emotional regulation, and hedonism. Third, games present challenges, such as the risk of abuse, the critical temporal period that may be limited to childhood, their important influence on sociocognitive learning and the establishment of social norms, and the risk of misuse of games.

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

    International Nuclear Information System (INIS)

    Megeed, A.A.

    2011-01-01

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

  1. Optimization of linear and branched alkane interactions with water to simulate hydrophobic hydration

    Science.gov (United States)

    Ashbaugh, Henry S.; Liu, Lixin; Surampudi, Lalitanand N.

    2011-08-01

    Previous studies of simple gas hydration have demonstrated that the accuracy of molecular simulations at capturing the thermodynamic signatures of hydrophobic hydration is linked both to the fidelity of the water model at replicating the experimental liquid density at ambient pressure and an accounting of polarization interactions between the solute and water. We extend those studies to examine alkane hydration using the transferable potentials for phase equilibria united-atom model for linear and branched alkanes, developed to reproduce alkane phase behavior, and the TIP4P/2005 model for water, which provides one of the best descriptions of liquid water for the available fixed-point charge models. Alkane site/water oxygen Lennard-Jones cross interactions were optimized to reproduce the experimental alkane hydration free energies over a range of temperatures. The optimized model reproduces the hydration free energies of the fitted alkanes with a root mean square difference between simulation and experiment of 0.06 kcal/mol over a wide temperature range, compared to 0.44 kcal/mol for the parent model. The optimized model accurately reproduces the temperature dependence of hydrophobic hydration, as characterized by the hydration enthalpies, entropies, and heat capacities, as well as the pressure response, as characterized by partial molar volumes.

  2. Effect of pore confinement on the adsorption of mono-branched alkanes of naphtha in ZSM-5 and Y zeolites

    Science.gov (United States)

    Fu, Jia; Feng, Xiang; Liu, Yibin; Yang, Chaohe

    2017-11-01

    Branched alkanes are important parts of naphtha, and their conversions are related to the adsorption stabilities in the pore of zeolites. In this work, the adsorption stabilities of C7-C10 mono-branched alkanes in the pores of HY (ca. 0.74 nm) and HZSM-5 (ca. 0.55 nm) zeolites are investigated using DFT calculation. After excluding the effect of Brønsted acid by subtracting the adsorption energy on 8T cluster from the total adsorption energy, it is found that confinement effect plays an essential role in stabilizing mono-branched alkanes. With the increase in the carbon number of alkanes, there is gradual increase of adsorption energy on both HZSM-5 and HY zeolites. Moreover, in the narrow channel of HZSM-5 zeolite, the change of adsorption energy (ethyl-alkane methyl-alkane > n-alkane), which is mainly due to confinement effect rather than effect of Brønsted acid. Methyl-alkanes prefer to stay in the pore of HZSM-5, while ethyl-alkanes and propyl-alkanes are more likely absorbed in the pore of HY zeolite. By analyzing the total electron densities of adsorbates, it is concluded that only when there is a certain distance between zeolite fragment and the adsorbate and low electron density region occupies the remaining space of the pore, the confinement effect is the strongest.

  3. Degradation of Hydrocarbons by Members of the Genus Candida II. Oxidation of n-Alkanes and 1-Alkenes by Candida lipolytica

    Science.gov (United States)

    Klug, M. J.; Markovetz, A. J.

    1967-01-01

    Candida lipolytica ATCC 8661 was grown in a mineral-salts hydrocarbon medium. n-Alkanes and 1-alkenes with 14 through 18 carbon atoms were used as substrates. Ether extracts of culture fluids and cells obtained from cultures grown on the various substrates were analyzed by thin-layer and gas-liquid chromatography. Analyses of fluids from cultures grown on n-alkanes indicated a predominance of fatty acids and alcohols of the same chain length as the substrate. In addition, numerous other fatty acids and alcohols were present. Analyses of saponifiable and nonsaponifiable material obtained from the cells revealed essentially the same products. The presence of primary and secondary alcohols, as well as fatty acids, of the same chain length as the n-alkane substrate suggested that attack on both the methyl and α-methylene group was occurring. The significance of these two mechanisms in the degradation of n-alkanes by this organism was not evident from the data presented. Analyses of fluids from cultures grown on 1-alkenes indicated the presence of 1,2-diols, as well as ω-unsaturated fatty acids, of the same chain length as the substrate. Alcohols present were all unsaturated. Saponifiable and nonsaponifiable material obtained from cells contained essentially the same products. The presence of 1,2-diols and ω-unsaturated fatty acids of the same chain length as the substrate from cultures grown on 1-alkenes indicated that both the terminal methyl group and the terminal double bond were being attacked. PMID:6025303

  4. Emulsification of crude oil by an alkane-oxidizing Rhodococcus species isolated from seawater

    Energy Technology Data Exchange (ETDEWEB)

    Bredholt, H.; Bruheim, P.; Eimhjellen, K. [Norwegian Univ. of Scince and Technology, Trondheim (Norway); Josefsen, K.; Vatland, A. [SINTEF SI, Oslo (Norway). Industrial Chemistry Div.

    1998-04-01

    A Rhodococcus species, which has proven to be the best of 99 oil-emulsifying bacteria isolated from seawater, was characterized. This bacterium produced very stable oil-in-water emulsions from different crude oils with various content of aliphatic and aromatic compounds, by utilizing C{sub 1}1 and C{sub 3}3 n-alkanes as carbon and energy sources. Bacteria that produce stable emulsions are often able to adhere strongly to hydrocarbons or hydrophobic surfaces. It was at these surfaces that extensive emulsification of the residual oil and accumulation of acidic oxidation products occurred. The acidic products were consumed in a second step. This step was characterized by linear growth and an increasing number of cells growing in the water phase. The most extensive emulsification occurred at the end of the exponential phase. There was no evidence of surfactants at the end of the exponential phase, however, a polymeric compound with emulsifying activity, tightly bound to the oil droplets, was isolated, suggesting that the emulsification resulted from the release of the hydrophobic cell surface discarded during growth limitations. 38 refs., 7 figs.

  5. COMPUTING

    CERN Document Server

    M. Kasemann

    Overview In autumn the main focus was to process and handle CRAFT data and to perform the Summer08 MC production. The operational aspects were well covered by regular Computing Shifts, experts on duty and Computing Run Coordination. At the Computing Resource Board (CRB) in October a model to account for service work at Tier 2s was approved. The computing resources for 2009 were reviewed for presentation at the C-RRB. The quarterly resource monitoring is continuing. Facilities/Infrastructure operations Operations during CRAFT data taking ran fine. This proved to be a very valuable experience for T0 workflows and operations. The transfers of custodial data to most T1s went smoothly. A first round of reprocessing started at the Tier-1 centers end of November; it will take about two weeks. The Computing Shifts procedure was tested full scale during this period and proved to be very efficient: 30 Computing Shifts Persons (CSP) and 10 Computing Resources Coordinators (CRC). The shift program for the shut down w...

  6. The evidence of personal computer waste quantity in the territory of Serbia -statistical estimation

    Directory of Open Access Journals (Sweden)

    Tadić Branko

    2006-01-01

    Full Text Available In recent years, the state-of-the-art research has been dealing with putting into traffic, withdrawing and freeing the environment from electrical and electronic equipment waste-WEEE. In our country there has been no serious research so far concerning this problem, although current and future members of the European Union (EU are obligated to conduct WEEE directive based on individual responsibility of each "waste manufacturer". The Ministry of Science and Environmental Protection of Serbia has accepted the financing of scientific research project called "The development of electrical and electronic equipment recycling system". In this paper, statistical estimation method of quantity and diffusion of computer waste (which according to the EU classification, belongs to the third category WEEE-devices for computer and communication technique in the territory of Serbia is described. The implications of the problem on our country are also presented.

  7. Auditors’ Usage of Computer Assisted Audit Tools and Techniques: Empirical Evidence from Nigeria

    OpenAIRE

    Appah Ebimobowei; G.N. Ogbonna; Zuokemefa P. Enebraye

    2013-01-01

    This study examines use of computer assisted audit tool and techniques in audit practice in the Niger Delta of Nigeria. To achieve this objective, data was collected from primary and secondary sources. The secondary sources were from scholarly books and journals while the primary source involved a well structured questionnaire of three sections of thirty seven items with an average reliability of 0.838. The data collected from the questionnaire were analyzed using relevant descriptive statist...

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

    Science.gov (United States)

    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

  9. COMPUTING

    CERN Multimedia

    I. Fisk

    2011-01-01

    Introduction CMS distributed computing system performed well during the 2011 start-up. The events in 2011 have more pile-up and are more complex than last year; this results in longer reconstruction times and harder events to simulate. Significant increases in computing capacity were delivered in April for all computing tiers, and the utilisation and load is close to the planning predictions. All computing centre tiers performed their expected functionalities. Heavy-Ion Programme The CMS Heavy-Ion Programme had a very strong showing at the Quark Matter conference. A large number of analyses were shown. The dedicated heavy-ion reconstruction facility at the Vanderbilt Tier-2 is still involved in some commissioning activities, but is available for processing and analysis. Facilities and Infrastructure Operations Facility and Infrastructure operations have been active with operations and several important deployment tasks. Facilities participated in the testing and deployment of WMAgent and WorkQueue+Request...

  10. COMPUTING

    CERN Multimedia

    M. Kasemann

    Overview During the past three months activities were focused on data operations, testing and re-enforcing shift and operational procedures for data production and transfer, MC production and on user support. Planning of the computing resources in view of the new LHC calendar in ongoing. Two new task forces were created for supporting the integration work: Site Commissioning, which develops tools helping distributed sites to monitor job and data workflows, and Analysis Support, collecting the user experience and feedback during analysis activities and developing tools to increase efficiency. The development plan for DMWM for 2009/2011 was developed at the beginning of the year, based on the requirements from the Physics, Computing and Offline groups (see Offline section). The Computing management meeting at FermiLab on February 19th and 20th was an excellent opportunity discussing the impact and for addressing issues and solutions to the main challenges facing CMS computing. The lack of manpower is particul...

  11. COMPUTING

    CERN Multimedia

    P. McBride

    The Computing Project is preparing for a busy year where the primary emphasis of the project moves towards steady operations. Following the very successful completion of Computing Software and Analysis challenge, CSA06, last fall, we have reorganized and established four groups in computing area: Commissioning, User Support, Facility/Infrastructure Operations and Data Operations. These groups work closely together with groups from the Offline Project in planning for data processing and operations. Monte Carlo production has continued since CSA06, with about 30M events produced each month to be used for HLT studies and physics validation. Monte Carlo production will continue throughout the year in the preparation of large samples for physics and detector studies ramping to 50 M events/month for CSA07. Commissioning of the full CMS computing system is a major goal for 2007. Site monitoring is an important commissioning component and work is ongoing to devise CMS specific tests to be included in Service Availa...

  12. Evidence in clinical reasoning: a computational linguistics analysis of 789,712 medical case summaries 1983-2012.

    Science.gov (United States)

    Seidel, Bastian M; Campbell, Steven; Bell, Erica

    2015-03-21

    Better understanding of clinical reasoning could reduce diagnostic error linked to 8% of adverse medical events and 30% of malpractice cases. To a greater extent than the evidence-based movement, the clinical reasoning literature asserts the importance of practitioner intuition—unconscious elements of diagnostic reasoning. The study aimed to analyse the content of case report summaries in ways that explored the importance of an evidence concept, not only in relation to research literature but also intuition. The study sample comprised all 789,712 abstracts in English for case reports contained in the database PUBMED for the period 1 January 1983 to 31 December 2012. It was hypothesised that, if evidence and intuition concepts were viewed by these clinical authors as essential to understanding their case reports, they would be more likely to be found in the abstracts. Computational linguistics software was used in 1) concept mapping of 21,631,481 instances of 201 concepts, and 2) specific concept analyses examining 200 paired co-occurrences for 'evidence' and research 'literature' concepts. 'Evidence' is a fundamentally patient-centred, intuitive concept linked to less common concepts about underlying processes, suspected disease mechanisms and diagnostic hunches. In contrast, the use of research literature in clinical reasoning is linked to more common reasoning concepts about specific knowledge and descriptions or presenting features of cases. 'Literature' is by far the most dominant concept, increasing in relevance since 2003, with an overall relevance of 13% versus 5% for 'evidence' which has remained static. The fact that the least present types of reasoning concepts relate to diagnostic hunches to do with underlying processes, such as what is suspected, raises questions about whether intuitive practitioner evidence-making, found in a constellation of dynamic, process concepts, has become less important. The study adds support to the existing corpus of

  13. Validation of a δ2Hn-alkane-δ18Ohemicellulose based paleohygrometer: Implications from a climate chamber experiment

    Science.gov (United States)

    Hepp, Johannes; Kathrin Schäfer, Imke; Tuthorn, Mario; Wüthrich, Lorenz; Zech, Jana; Glaser, Bruno; Juchelka, Dieter; Rozanski, Kazimierz; Zech, Roland; Mayr, Christoph; Zech, Michael

    2017-04-01

    biomarker fractionation factors from temperature and relative humidity of the climate chamber, as well as from the measured transpiration rate of the plants are evident from the data. As an outlook, the proposed coupled δ2Hn-alkane-δ18Ohemicellulose approach allows (i) more robust δ2H/δ18Oprecipitation reconstructions and (ii) paleohygrometry studies in future paleoclimate research. References Mayr, C., 2003. Möglichkeiten der Klimarekonstruktion im Holozän mit δ13C- und δ2H-Werten von Baum-Jahrringen auf der Basis von Klimakammerversuchen und Rezentstudien. Ludwig-Maximilians-Universität München. Tuthorn, M., Zech, R., Ruppenthal, M., Oelmann, Y., Kahmen, A., del Valle, H.F., Eglinton, T., Rozanski, K., Zech, M., 2015. Coupling δ2H and δ18O biomarker results yields information on relative humidity and isotopic composition of precipitation - a climate transect validation study. Biogeosciences 12, 3913-3924. Zech, M., Tuthorn, M., Detsch, F., Rozanski, K., Zech, R., Zöller, L., Zech, W., Glaser, B., 2013. A 220 ka terrestrial δ18O and deuterium excess biomarker record from an eolian permafrost paleosol sequence, NE-Siberia. Chemical Geology.

  14. Left fronto-temporal dynamics during agreement processing: evidence for feature-specific computations.

    Science.gov (United States)

    Molinaro, Nicola; Barber, Horacio A; Pérez, Alejandro; Parkkonen, Lauri; Carreiras, Manuel

    2013-09-01

    Grammatical agreement is a widespread language phenomenon that indicates formal syntactic relations between words; however, it also conveys basic lexical (e.g. grammatical gender) or semantic (e.g. numerosity) information about a discourse referent. In this study, we focus on the reading of Spanish noun phrases, violating either number or gender determiner-noun agreement compared to grammatical controls. Magnetoencephalographic activity time-locked to the onset of the noun in both types of violation revealed a left-lateralized brain network involving anterior temporal regions (~220 ms) and, later in time, ventro-lateral prefrontal regions (>300 ms). These activations coexist with dependency-specific effects: in an initial step (~170 ms), occipito-temporal regions are employed for fine-grained analysis of the number marking (in Spanish, presence or absence of the suffix '-s'), while anterior temporal regions show increased activation for gender mismatches compared to grammatical controls. The semantic relevance of number agreement dependencies was mainly reflected by left superior temporal increased activity around 340 ms. These findings offer a detailed perspective on the multi-level analyses involved in the initial computation of agreement dependencies, and theoretically support a derivational approach to agreement computation. Copyright © 2013 Elsevier Inc. All rights reserved.

  15. The integration of social influence and reward: Computational approaches and neural evidence.

    Science.gov (United States)

    Tomlin, Damon; Nedic, Andrea; Prentice, Deborah A; Holmes, Philip; Cohen, Jonathan D

    2017-08-01

    Decades of research have established that decision-making is dramatically impacted by both the rewards an individual receives and the behavior of others. How do these distinct influences exert their influence on an individual's actions, and can the resulting behavior be effectively captured in a computational model? To address this question, we employed a novel spatial foraging game in which groups of three participants sought to find the most rewarding location in an unfamiliar two-dimensional space. As the game transitioned from one block to the next, the availability of information regarding other group members was varied systematically, revealing the relative impacts of feedback from the environment and information from other group members on individual decision-making. Both reward-based and socially-based sources of information exerted a significant influence on behavior, and a computational model incorporating these effects was able to recapitulate several key trends in the behavioral data. In addition, our findings suggest how these sources were processed and combined during decision-making. Analysis of reaction time, location of gaze, and functional magnetic resonance imaging (fMRI) data indicated that these distinct sources of information were integrated simultaneously for each decision, rather than exerting their influence in a separate, all-or-none fashion across separate subsets of trials. These findings add to our understanding of how the separate influences of reward from the environment and information derived from other social agents are combined to produce decisions.

  16. Estimating valence from the sound of a word: Computational, experimental, and cross-linguistic evidence.

    Science.gov (United States)

    Louwerse, Max; Qu, Zhan

    2017-06-01

    It is assumed linguistic symbols must be grounded in perceptual information to attain meaning, because the sound of a word in a language has an arbitrary relation with its referent. This paper demonstrates that a strong arbitrariness claim should be reconsidered. In a computational study, we showed that one phonological feature (nasals in the beginning of a word) predicted negative valence in three European languages (English, Dutch, and German) and positive valence in Chinese. In three experiments, we tested whether participants used this feature in estimating the valence of a word. In Experiment 1, Chinese and Dutch participants rated the valence of written valence-neutral words, with Chinese participants rating the nasal-first neutral-valence words more positive and the Dutch participants rating nasal-first neutral-valence words more negative. In Experiment 2, Chinese (and Dutch) participants rated the valence of Dutch (and Chinese) written valence-neutral words without being able to understand the meaning of these words. The patterns replicated the valence patterns from Experiment 1. When the written words from Experiment 2 were transformed into spoken words, results in Experiment 3 again showed that participants estimated the valence of words on the basis of the sound of the word. The computational study and psycholinguistic experiments indicated that language users can bootstrap meaning from the sound of a word.

  17. Chemotaxonomic significance of distribution and stable carbon isotopic composition of long-chain alkanes and alkan-1-ols in C{sub 4} grass waxes

    Energy Technology Data Exchange (ETDEWEB)

    Rommerskirchen, F.; Plader, A. [Carl von Ossietzky University, Oldenburg (Germany). Institute of Chemistry and Biology of the Marine Environment; Eglinton, G. [Hanse Institute for Advanced Study, Delmenhorst (Germany); Chikaraishii, Yoshito [Japan Agency for Marine-Earth Science and Technology, Yokosuka (Japan). Institute for Research on Earth Evolution

    2006-10-15

    Grasses (Poaceae) are distributed across the world in broad latitudinal belts and are an important source of C4 biomass in the geological record of soils as well as lake and marine sediments. We examined long-chain leaf wax components of thirty-five C{sub 4} grasses of the subfamilies Aristidoideae, Chloridoideae and Panicoideae from the southern African grasslands and savannas and three C{sub 3} grasses of the subfamily Pooideae from Peru and Australia and review the relevant botanical, phytogeographic and leaf wax compositional background information. Contents, distribution patterns and molecular stable carbon isotopic compositions of long-chain n-alkanes (n-C{sub 27} to n-C{sub 35}) and n-alkan-1-ols (n-C{sub 22} to n-C{sub 32}) were used to estimate the chemotaxonomic relevance of wax signatures of whole plants, separately for different subfamilies and for members of the three C{sub 4} subtypes (NADP-ME, NAD-ME and PCK). Two grass species were separated into flower heads, leaves and stems and the parts analysed separately. Grass flowers contain remarkable amounts of short-chain n-alkanes, which may have a significant influence on the chemical signature of the whole plant, whereas n-alkanol distribution patterns exhibit no systematics. The stable carbon isotopic composition of both biomarker types in different plant parts is remarkably uniform. Chemotaxonomic differentiation was not possible on a species level based on whole plant samples, but was more successful for averages of subfamily and photosynthetic subtype data. Wax signatures of C{sub 4} grasses are generally distinguishable from those of C{sub 3} species by heavier isotopic values, higher contents of n-C{sub 31} and n-C{sub 33} alkanes and the abundance of the n-C{sub 32} n-alkanol, which is largely absent in C{sub 3} grass waxes. Especially the waxes of the NAD-ME and PCK C{sub 4}-subtype grasses, which thrive in extremely arid tropical and subtropical areas, contain high relative amounts of longer

  18. Theoretical investigation of the structure and nature of the interaction in metal-alkane σ-complexes of the type [M(CO)5(C2H6)] (M = Cr, Mo, and W)

    International Nuclear Information System (INIS)

    Da Silva, Julio C.S.; De Almeida, Wagner B.; Rocha, Willian R.

    2009-01-01

    Density Functional Theory calculations were carried out to study the structure, energetics of the interactions and nature of the bonds in the metal-alkane σ-complexes of the type M(CO) 5 (C 2 H 6 ) M = Cr, Mo, and W. Only the η 1 coordination mode through hydrogen is obtained. The vibrational frequencies showed that upon coordination the ν(C-H) asym mode has an important red shift of 273 cm -1 and thus may be an important mode to characterize and follow the alkane coordination to the metallic fragment. TD-DFT calculations of the electronic transitions show that the coordination of the alkane affects drastically the metal to ligand charge transfer (MLCT) band of the metallic fragment, showing a blue shift of 163 nm. The computed AIM local properties (ρ(r), ∇ 2 (ρ), G(r), V(r) and H(r)) in conjunction with the Morokuma energy decomposition analysis (EDA) and also comparisons with the water dimer, suggest that this metal-alkane interaction may also be viewed as an unconventional hydrogen bond, with significant charge transfer and polarization contribution.

  19. Theoretical investigation of the structure and nature of the interaction in metal-alkane {sigma}-complexes of the type [M(CO){sub 5}(C{sub 2}H{sub 6})] (M = Cr, Mo, and W)

    Energy Technology Data Exchange (ETDEWEB)

    Da Silva, Julio C.S.; De Almeida, Wagner B. [LQC-MM: Laboratorio de Quimica Computacional e Modelagem Molecular, Departamento de Quimica, ICEx, Universidade Federal de Minas Gerais, Campus Universitario Pampulha, 31270-901 Belo Horizonte, MG (Brazil); Rocha, Willian R., E-mail: wrocha@ufmg.br [LQC-MM: Laboratorio de Quimica Computacional e Modelagem Molecular, Departamento de Quimica, ICEx, Universidade Federal de Minas Gerais, Campus Universitario Pampulha, 31270-901 Belo Horizonte, MG (Brazil)

    2009-11-18

    Density Functional Theory calculations were carried out to study the structure, energetics of the interactions and nature of the bonds in the metal-alkane {sigma}-complexes of the type M(CO){sub 5}(C{sub 2}H{sub 6}) M = Cr, Mo, and W. Only the {eta}{sup 1} coordination mode through hydrogen is obtained. The vibrational frequencies showed that upon coordination the {nu}(C-H){sub asym} mode has an important red shift of 273 cm{sup -1} and thus may be an important mode to characterize and follow the alkane coordination to the metallic fragment. TD-DFT calculations of the electronic transitions show that the coordination of the alkane affects drastically the metal to ligand charge transfer (MLCT) band of the metallic fragment, showing a blue shift of 163 nm. The computed AIM local properties ({rho}(r), {nabla}{sup 2}({rho}), G(r), V(r) and H(r)) in conjunction with the Morokuma energy decomposition analysis (EDA) and also comparisons with the water dimer, suggest that this metal-alkane interaction may also be viewed as an unconventional hydrogen bond, with significant charge transfer and polarization contribution.

  20. COMPUTING

    CERN Multimedia

    I. Fisk

    2013-01-01

    Computing activity had ramped down after the completion of the reprocessing of the 2012 data and parked data, but is increasing with new simulation samples for analysis and upgrade studies. Much of the Computing effort is currently involved in activities to improve the computing system in preparation for 2015. Operations Office Since the beginning of 2013, the Computing Operations team successfully re-processed the 2012 data in record time, not only by using opportunistic resources like the San Diego Supercomputer Center which was accessible, to re-process the primary datasets HTMHT and MultiJet in Run2012D much earlier than planned. The Heavy-Ion data-taking period was successfully concluded in February collecting almost 500 T. Figure 3: Number of events per month (data) In LS1, our emphasis is to increase efficiency and flexibility of the infrastructure and operation. Computing Operations is working on separating disk and tape at the Tier-1 sites and the full implementation of the xrootd federation ...

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

    Directory of Open Access Journals (Sweden)

    Florin Musat

    2015-01-01

    Full Text Available 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.

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

    Directory of Open Access Journals (Sweden)

    Conor Blake Smith

    2013-12-01

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

  3. Cervical Spinal Cord Injury without Computed Tomography Evidence of Trauma in Adults: Magnetic Resonance Imaging Prognostic Factors.

    Science.gov (United States)

    Martinez-Perez, Rafael; Munarriz, Pablo M; Paredes, Igor; Cotrina, Javier; Lagares, Alfonso

    2017-03-01

    Spinal cord injury (SCI) without computed tomography evidence of trauma is underreported in adults and is considered a subtype of SCI with relatively good outcome. Despite this, few studies have been performed to determine specific imaging-related prognostic factors. Our objective is to describe the imaging characteristics of patients experiencing blunt cervical spine trauma with neurologic deficits, but without radiologic abnormalities and associated prognostic factors. A retrospective review of all adult patients with cervical SCI admitted to the emergency room of 2 university hospitals from January 2004 to December 2013 was performed. Only patients with a magnetic resonance imaging (MRI) performed within 72 hours after trauma were included for further analysis. All patients with bony injury or traumatic malalignment were excluded. Data gathered on the remaining patients included demographics, mechanism of injury, severity of SCI, long-term patient outcome, improvement in neurologic condition, and MRI results. There were 48 patients who met the inclusion and exclusion criteria, and 40 who demonstrated improvement in the neurologic examination at follow-up. Disruption of either the anterior longitudinal ligament or ligamentum flavum and larger lesions in the MRI were predictors of lack of neurologic improvement. Early MRI has prognostic value in patients suffering SCI without computed tomography evidence of trauma. Lesion length is a powerful predictor of outcome in this subgroup of patients. Soft tissue injury plays a role in the severity of injury and the ability to recover in this subgroups of patients. Copyright © 2016 Elsevier Inc. All rights reserved.

  4. Judgement heuristics and bias in evidence interpretation: The effects of computer generated exhibits.

    Science.gov (United States)

    Norris, Gareth

    2015-01-01

    The increasing use of multi-media applications, trial presentation software and computer generated exhibits (CGE) has raised questions as to the potential impact of the use of presentation technology on juror decision making. A significant amount of the commentary on the manner in which CGE exerts legal influence is largely anecdotal; empirical examinations too are often devoid of established theoretical rationalisations. This paper will examine a range of established judgement heuristics (for example, the attribution error, representativeness, simulation), in order to establish their appropriate application for comprehending legal decisions. Analysis of both past cases and empirical studies will highlight the potential for heuristics and biases to be restricted or confounded by the use of CGE. The paper will conclude with some wider discussion on admissibility, access to justice, and emerging issues in the use of multi-media in court. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Extending peripersonal space representation without tool-use: evidence from a combined behavioural-computational approach

    Directory of Open Access Journals (Sweden)

    Andrea eSerino

    2015-02-01

    Full Text Available Stimuli from different sensory modalities occurring on or close to the body are integrated in a multisensory representation of the space surrounding the body, i.e. peripersonal space (PPS. PPS dynamically modifies depending on experience, e.g. it extends after using a tool to reach far objects. However, the neural mechanism underlying PPS plasticity after tool use is largely unknown. Here we use a combined computational-behavioural approach to propose and test a possible mechanism accounting for PPS extension. We first present a neural network model simulating audio-tactile representation in the PPS around one hand. Simulation experiments showed that our model reproduced the main property of PPS neurons, i.e. selective multisensory response for stimuli occurring close to the hand. We used the neural network model to simulate the effects of a tool-use training. In terms of sensory inputs, tool use was conceptualized as a concurrent tactile stimulation from the hand, due to holding the tool, and an auditory stimulation from the far space, due to tool-mediated action. Results showed that after exposure to those inputs, PPS neurons responded also to multisensory stimuli far from the hand. The model thus suggests that synchronous pairing of tactile hand stimulation and auditory stimulation from the far space is sufficient to extend PPS, such as after tool-use. Such prediction was confirmed by a behavioural experiment, where we used an audio-tactile interaction paradigm to measure the boundaries of PPS representation. We found that PPS extended after synchronous tactile-hand stimulation and auditory-far stimulation in a group of healthy volunteers. Control experiments both in simulation and behavioural settings showed that asynchronous tactile and auditory inputs did not change PPS. We conclude by proposing a biological-plausible model to explain plasticity in PPS representation after tool-use, supported by computational and behavioural data.

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

    KAUST Repository

    Riache, Nassima

    2014-10-03

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

  7. COMPUTING

    CERN Multimedia

    M. Kasemann P. McBride Edited by M-C. Sawley with contributions from: P. Kreuzer D. Bonacorsi S. Belforte F. Wuerthwein L. Bauerdick K. Lassila-Perini M-C. Sawley

    Introduction More than seventy CMS collaborators attended the Computing and Offline Workshop in San Diego, California, April 20-24th to discuss the state of readiness of software and computing for collisions. Focus and priority were given to preparations for data taking and providing room for ample dialog between groups involved in Commissioning, Data Operations, Analysis and MC Production. Throughout the workshop, aspects of software, operating procedures and issues addressing all parts of the computing model were discussed. Plans for the CMS participation in STEP’09, the combined scale testing for all four experiments due in June 2009, were refined. The article in CMS Times by Frank Wuerthwein gave a good recap of the highly collaborative atmosphere of the workshop. Many thanks to UCSD and to the organizers for taking care of this workshop, which resulted in a long list of action items and was definitely a success. A considerable amount of effort and care is invested in the estimate of the comput...

  8. COMPUTING

    CERN Multimedia

    I. Fisk

    2010-01-01

    Introduction It has been a very active quarter in Computing with interesting progress in all areas. The activity level at the computing facilities, driven by both organised processing from data operations and user analysis, has been steadily increasing. The large-scale production of simulated events that has been progressing throughout the fall is wrapping-up and reprocessing with pile-up will continue. A large reprocessing of all the proton-proton data has just been released and another will follow shortly. The number of analysis jobs by users each day, that was already hitting the computing model expectations at the time of ICHEP, is now 33% higher. We are expecting a busy holiday break to ensure samples are ready in time for the winter conferences. Heavy Ion An activity that is still in progress is computing for the heavy-ion program. The heavy-ion events are collected without zero suppression, so the event size is much large at roughly 11 MB per event of RAW. The central collisions are more complex and...

  9. Investigation of the computer experiences and attitudes of pre-service mathematics teachers: new evidence from Turkey.

    Science.gov (United States)

    Birgin, Osman; Catlioğlu, Hakan; Gürbüz, Ramazan; Aydin, Serhat

    2010-10-01

    This study aimed to investigate the experiences of pre-service mathematics (PSM) teachers with computers and their attitudes toward them. The Computer Attitude Scale, Computer Competency Survey, and Computer Use Information Form were administered to 180 Turkish PSM teachers. Results revealed that most PSM teachers used computers at home and at Internet cafes, and that their competency was generally intermediate and upper level. The study concludes that PSM teachers' attitudes about computers differ according to their years of study, computer ownership, level of computer competency, frequency of computer use, computer experience, and whether they had attended a computer-aided instruction course. However, computer attitudes were not affected by gender.

  10. Synthesis of Renewable Lubricant Alkanes from Biomass-Derived Platform Chemicals.

    Science.gov (United States)

    Gu, Mengyuan; Xia, Qineng; Liu, Xiaohui; Guo, Yong; Wang, Yanqin

    2017-10-23

    The catalytic synthesis of liquid alkanes from renewable biomass has received tremendous attention in recent years. However, bio-based platform chemicals have not to date been exploited for the synthesis of highly branched lubricant alkanes, which are currently produced by hydrocracking and hydroisomerization of long-chain n-paraffins. A selective catalytic synthetic route has been developed for the production of highly branched C 23 alkanes as lubricant base oil components from biomass-derived furfural and acetone through a sequential four-step process, including aldol condensation of furfural with acetone to produce a C 13 double adduct, selective hydrogenation of the adduct to a C 13 ketone, followed by a second condensation of the C 13 ketone with furfural to generate a C 23 aldol adduct, and finally hydrodeoxygenation to give highly branched C 23 alkanes in 50.6 % overall yield from furfural. This work opens a general strategy for the synthesis of high-quality lubricant alkanes from renewable biomass. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Alkanes as Components of Soil Hydrocarbon Status: Behavior and Indication Significance

    Science.gov (United States)

    Gennadiev, A. N.; Zavgorodnyaya, Yu. A.; Pikovskii, Yu. I.; Smirnova, M. A.

    2018-01-01

    Studies of soils on three key plots with different climatic conditions and technogenic impacts in Volgograd, Moscow, and Arkhangelsk oblasts have showed that alkanes in the soil exchange complex have some indication potential for the identification of soil processes. The following combinations of soil-forming factors and processes have been studied: (a) self-purification of soil after oil pollution; (b) accumulation of hydrocarbons coming from the atmosphere to soils of different land use patterns; and (c) changes in the soil hydrocarbon complex beyond the zone of technogenic impact due to the input of free hydrocarbon-containing gases. At the injection input of hydrocarbon pollutants, changes in the composition and proportions of alkanes allow tracing the degradation trend of pollutants in the soil from their initial content to the final stage of soil self-purification, when the background concentrations of hydrocarbons are reached. Upon atmospheric deposition of hydrocarbons onto the soil, from the composition and mass distribution of alkanes, conclusions can be drawn about the effect of toxicants on biogeochemical processes in the soil, including their manifestation under different land uses. Composition analysis of soil alkanes in natural landscapes can reveal signs of hydrocarbon emanation fluxes in soils. The indication potentials of alkanes in combination with polycyclic aromatic hydrocarbons and other components of soil hydrocarbon complex can also be used for the solution of other soil-geochemical problems.

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

    International Nuclear Information System (INIS)

    Alonso, Victor; Garcia, Mario; Gonzalez, Juan Antonio; Garcia De La Fuente, Isaias; Cobos, Jose Carlos

    2011-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-10

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

  14. The fate of primary cations in radiolysis of alkanes as studied by ESR

    International Nuclear Information System (INIS)

    Iwasaki, M.; Toriyama, K.; Nunome, K.

    1983-01-01

    The structures and reactions of alkane cations (RH + ) have been studied by ESR to elucidate the fate of primary cations in radiolysis of alkanes. Radical cations of prototype alkanes such as C 2 H 6 , C 3 H 8 , iso-C 4 H 10 and neo-C 5 H 12 etc. as well as their partially deuterated analogues were stabilized in irradiated frozen matrices such as SF 6 , CFCl 2 CF 2 Cl and CFCl 3 having a higher ionization potential than that of these alkanes contained as dilute solutes. RH + in SF 6 and in CFCl 2 CF 2 Cl converts into alkyl radicals by deprotonation probably through bimolecular reactions, whereas RH + in CFCl 3 unimolecularily decomposes into olefinic cations by H 2 and/or CH 4 elimination reactions. It is further found that the electronic structures of propane and isobutane cations in halocarbon matrices are different from those in SF 6 and the difference is drastically reflected in the site preference of their deprotonation reactions. The results are discussed in relation to the mechanisms of pairwise formation of alkyl radicals in low temperature radiolysis of neat alkanes and its suppression by addition of electron scavengers. (author)

  15. ERP evidence for on-line syntactic computations in 2-year-olds

    Directory of Open Access Journals (Sweden)

    Perrine Brusini

    2016-06-01

    Full Text Available Syntax allows human beings to build an infinite number of sentences from a finite number of words. How this unique, productive power of human language unfolds over the course of language development is still hotly debated. When they listen to sentences comprising newly-learned words, do children generalize from their knowledge of the legal combinations of word categories or do they instead rely on strings of words stored in memory to detect syntactic errors? Using novel words taught in the lab, we recorded Evoked Response Potentials (ERPs in two-year-olds and adults listening to grammatical and ungrammatical sentences containing syntactic contexts that had not been used during training. In toddlers, the ungrammatical use of words, even when they have been just learned, induced an early left anterior negativity (surfacing 100–400 ms after target word onset followed by a late posterior positivity (surfacing 700–900 ms after target word onset that was not observed in grammatical sentences. This late effect was remarkably similar to the P600 displayed by adults, suggesting that toddlers and adults perform similar syntactic computations. Our results thus show that toddlers build on-line expectations regarding the syntactic category of upcoming words in a sentence.

  16. Holistic Processing and Right Hemisphere Lateralization Do Not Always Go Together—Evidence from Computational Modeling

    Directory of Open Access Journals (Sweden)

    Janet H. Hsiao

    2011-05-01

    Full Text Available Studies on face recognition have suggested a relationship between holistic processing and right hemisphere (RH lateralization. Thus, it has long been assumed that holistic processing is a property of RH processing. Nevertheless, recent studies showed reduced holistic processing and increased RH lateralization in Chinese character recognition expertise, suggesting that these two effects may be separate processes. Through computational modeling, in which we implement a theory of hemispheric asymmetry in perception that posits a low spatial frequency bias in the RH and a high spatial frequency bias in the left hemisphere (i.e. the Double Filtering by Frequency Theory, Ivry & Robertson, 1998, here we show that when the recognition task relies purely on featural information, holistic processing increases whereas RH lateralization decreases with increasing stimulus similarity, and there is a negative correlation between them. In contrast, when the recognition task relies purely on configural information, although holistic processing also increases whereas RH lateralization decreases with increasing stimulus similarity, there is no correlation between them. This result suggests that holistic processing and RH lateralization are separate processes that can be influenced differentially by task requirements.

  17. COMPUTING

    CERN Multimedia

    P. McBride

    It has been a very active year for the computing project with strong contributions from members of the global community. The project has focused on site preparation and Monte Carlo production. The operations group has begun processing data from P5 as part of the global data commissioning. Improvements in transfer rates and site availability have been seen as computing sites across the globe prepare for large scale production and analysis as part of CSA07. Preparations for the upcoming Computing Software and Analysis Challenge CSA07 are progressing. Ian Fisk and Neil Geddes have been appointed as coordinators for the challenge. CSA07 will include production tests of the Tier-0 production system, reprocessing at the Tier-1 sites and Monte Carlo production at the Tier-2 sites. At the same time there will be a large analysis exercise at the Tier-2 centres. Pre-production simulation of the Monte Carlo events for the challenge is beginning. Scale tests of the Tier-0 will begin in mid-July and the challenge it...

  18. COMPUTING

    CERN Multimedia

    M. Kasemann

    CCRC’08 challenges and CSA08 During the February campaign of the Common Computing readiness challenges (CCRC’08), the CMS computing team had achieved very good results. The link between the detector site and the Tier0 was tested by gradually increasing the number of parallel transfer streams well beyond the target. Tests covered the global robustness at the Tier0, processing a massive number of very large files and with a high writing speed to tapes.  Other tests covered the links between the different Tiers of the distributed infrastructure and the pre-staging and reprocessing capacity of the Tier1’s: response time, data transfer rate and success rate for Tape to Buffer staging of files kept exclusively on Tape were measured. In all cases, coordination with the sites was efficient and no serious problem was found. These successful preparations prepared the ground for the second phase of the CCRC’08 campaign, in May. The Computing Software and Analysis challen...

  19. COMPUTING

    CERN Multimedia

    I. Fisk

    2011-01-01

    Introduction It has been a very active quarter in Computing with interesting progress in all areas. The activity level at the computing facilities, driven by both organised processing from data operations and user analysis, has been steadily increasing. The large-scale production of simulated events that has been progressing throughout the fall is wrapping-up and reprocessing with pile-up will continue. A large reprocessing of all the proton-proton data has just been released and another will follow shortly. The number of analysis jobs by users each day, that was already hitting the computing model expectations at the time of ICHEP, is now 33% higher. We are expecting a busy holiday break to ensure samples are ready in time for the winter conferences. Heavy Ion The Tier 0 infrastructure was able to repack and promptly reconstruct heavy-ion collision data. Two copies were made of the data at CERN using a large CASTOR disk pool, and the core physics sample was replicated ...

  20. COMPUTING

    CERN Multimedia

    M. Kasemann

    Introduction More than seventy CMS collaborators attended the Computing and Offline Workshop in San Diego, California, April 20-24th to discuss the state of readiness of software and computing for collisions. Focus and priority were given to preparations for data taking and providing room for ample dialog between groups involved in Commissioning, Data Operations, Analysis and MC Production. Throughout the workshop, aspects of software, operating procedures and issues addressing all parts of the computing model were discussed. Plans for the CMS participation in STEP’09, the combined scale testing for all four experiments due in June 2009, were refined. The article in CMS Times by Frank Wuerthwein gave a good recap of the highly collaborative atmosphere of the workshop. Many thanks to UCSD and to the organizers for taking care of this workshop, which resulted in a long list of action items and was definitely a success. A considerable amount of effort and care is invested in the estimate of the co...

  1. COMPUTING

    CERN Multimedia

    I. Fisk

    2012-01-01

    Introduction Computing continued with a high level of activity over the winter in preparation for conferences and the start of the 2012 run. 2012 brings new challenges with a new energy, more complex events, and the need to make the best use of the available time before the Long Shutdown. We expect to be resource constrained on all tiers of the computing system in 2012 and are working to ensure the high-priority goals of CMS are not impacted. Heavy ions After a successful 2011 heavy-ion run, the programme is moving to analysis. During the run, the CAF resources were well used for prompt analysis. Since then in 2012 on average 200 job slots have been used continuously at Vanderbilt for analysis workflows. Operations Office As of 2012, the Computing Project emphasis has moved from commissioning to operation of the various systems. This is reflected in the new organisation structure where the Facilities and Data Operations tasks have been merged into a common Operations Office, which now covers everything ...

  2. COMPUTING

    CERN Multimedia

    M. Kasemann

    Introduction During the past six months, Computing participated in the STEP09 exercise, had a major involvement in the October exercise and has been working with CMS sites on improving open issues relevant for data taking. At the same time operations for MC production, real data reconstruction and re-reconstructions and data transfers at large scales were performed. STEP09 was successfully conducted in June as a joint exercise with ATLAS and the other experiments. It gave good indication about the readiness of the WLCG infrastructure with the two major LHC experiments stressing the reading, writing and processing of physics data. The October Exercise, in contrast, was conducted as an all-CMS exercise, where Physics, Computing and Offline worked on a common plan to exercise all steps to efficiently access and analyze data. As one of the major results, the CMS Tier-2s demonstrated to be fully capable for performing data analysis. In recent weeks, efforts were devoted to CMS Computing readiness. All th...

  3. COMPUTING

    CERN Multimedia

    I. Fisk

    2010-01-01

    Introduction The first data taking period of November produced a first scientific paper, and this is a very satisfactory step for Computing. It also gave the invaluable opportunity to learn and debrief from this first, intense period, and make the necessary adaptations. The alarm procedures between different groups (DAQ, Physics, T0 processing, Alignment/calibration, T1 and T2 communications) have been reinforced. A major effort has also been invested into remodeling and optimizing operator tasks in all activities in Computing, in parallel with the recruitment of new Cat A operators. The teams are being completed and by mid year the new tasks will have been assigned. CRB (Computing Resource Board) The Board met twice since last CMS week. In December it reviewed the experience of the November data-taking period and could measure the positive improvements made for the site readiness. It also reviewed the policy under which Tier-2 are associated with Physics Groups. Such associations are decided twice per ye...

  4. Predictions of homogeneous nucleation rates for n-alkanes accounting for the diffuse phase interface and capillary waves.

    Science.gov (United States)

    Planková, Barbora; Vinš, Václav; Hrubý, Jan

    2017-10-28

    Homogeneous droplet nucleation has been studied for almost a century but has not yet been fully understood. In this work, we used the density gradient theory (DGT) and considered the influence of capillary waves (CWs) on the predicted size-dependent surface tensions and nucleation rates for selected n-alkanes. The DGT model was completed by an equation of state (EoS) based on the perturbed-chain statistical associating fluid theory and compared to the classical nucleation theory and the Peng-Robinson EoS. It was found that the critical clusters are practically free of CWs because they are so small that even the smallest wavelengths of CWs do not fit into their finite dimensions. The CWs contribute to the entropy of the system and thus decrease the surface tension. A correction for the effect of CWs on the surface tension is presented. The effect of the different EoSs is relatively small because by a fortuitous coincidence their predictions are similar in the relevant range of critical cluster sizes. The difference of the DGT predictions to the classical nucleation theory computations is important but not decisive. Of the effects investigated, the most pronounced is the suppression of CWs which causes a sizable decrease of the predicted nucleation rates. The major difference between experimental nucleation rate data and theoretical predictions remains in the temperature dependence. For normal alkanes, this discrepancy is much stronger than observed, e.g., for water. Theoretical corrections developed here have a minor influence on the temperature dependency. We provide empirical equations correcting the predicted nucleation rates to values comparable with experiments.

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

    Energy Technology Data Exchange (ETDEWEB)

    Bruheim, Per

    1998-12-31

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

  6. Liquid + liquid equilibria for ternary mixtures of (solvent + aromatic hydrocarbon + alkane)

    International Nuclear Information System (INIS)

    Mohsen-Nia, M.; Modarress, H.; Doulabi, F.; Bagheri, H.

    2005-01-01

    Liquid + liquid equilibrium (LLE) results for the ternary mixtures of (solvent + aromatic hydrocarbon + alkane) at different temperatures from (298.15 to 313.15) K are reported, where the aromatic hydrocarbon is toluene or m-xylene and the alkane is n-heptane or n-octane or cyclohexane and the solvent is tetramethylene sulfone (i.e., sulfolane) or dimethyl sulfoxide (DMSO) or ethylene carbonate. The data were correlated with the UNIQUAC and NRTL equations. The partition coefficients and the selectivity factor of the solvents are calculated. Then, the selectivity of solvents for the extraction of aromatic hydrocarbons from alkanes has been compared. The phase diagrams for the ternary mixtures are presented and the correlated tie line results have been compared with the experimental data. The comparisons indicate the applicability of the UNIQUAC and NRTL activity coefficients model for liquid + liquid equilibrium calculations of the studied mixtures

  7. Hydrogenation and hydrodeoxygenation of biomass-derived oxygenates to liquid alkanes for transportation fuels

    Directory of Open Access Journals (Sweden)

    Shaohui Sun

    2018-04-01

    Full Text Available An attractive approach for the production of transportation fuels from renewable biomass resources is to convert oxygenates into alkanes. In this paper, C5–C20 alkanes formed via the hydrogenation and hydrodeoxygenation of the oligomers of furfuryl alcohol(FA can be used as gasoline, diesel and jet fuel fraction. The first step of the process is the oligomers of FA convert into hydrogenated products over Raney Ni catalyst in a batch reactor. The second step of the process converts hydrogenated products to alkanes via hydrodeoxygenation over different bi-functional catalysts include hydrogenation and acidic deoxidization active sites. After this process, the oxygen content decreased from 22.1 wt% in the oligomers of FA to 0.58 wt% in the hydrodeoxygenation products.

  8. Carbon Isotopes of Alkanes in Hydrothermal Abiotic Organic Synthesis Processes at High Temperatures and Pressures: An Experimental Study

    Science.gov (United States)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2010-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques [1-4]. With more evidence showing extensive water-rock interaction in Martian history [5-7], abiotic formation by Fischer-Tropsch Type (FTT) synthesis during serpentization reactions may be one possible process responsible for methane generation on Mars [8, 9]. While the experimental studies performed to date leave little doubt that chemical reactions exist for the abiotic synthesis of organic compounds by mineral surface-catalyzed reactions [10-12], little is known about the reaction pathways by which CO2 and/or CO are reduced under hydrothermal conditions. Carbon and hydrogen isotope measurements of alkanes have been used as an effective tool to constrain the origin and reaction pathways of hydrocarbon formation. Alkanes generated by thermal breakdown of high molecular weight organic compounds have carbon and hydrogen isotopic signatures completely distinct from those formed abiotically [13-15]. Recent experimental studies, however, showed that different abiogenic hydrocarbon formation processes (e.g., polymerization vs. depolymerization) may have different carbon and hydrogen isotopic patterns [16]. Results from previous experiments studying decomposition of higher molecular weight organic compounds (lignite) also suggested that pressure could be a crucial factor affecting fractionation of carbon isotopes [17]. Under high pressure conditions, no experimental data are available describing fractionation of carbon isotope during mineral catalyzed FTT synthesis. Thus, hydrothermal experiments present an excellent opportunity to provide the requisite carbon isotope data. Such data can also be used to identify reaction pathways of abiotic organic synthesis under experimental conditions.

  9. COMPUTING

    CERN Multimedia

    Matthias Kasemann

    Overview The main focus during the summer was to handle data coming from the detector and to perform Monte Carlo production. The lessons learned during the CCRC and CSA08 challenges in May were addressed by dedicated PADA campaigns lead by the Integration team. Big improvements were achieved in the stability and reliability of the CMS Tier1 and Tier2 centres by regular and systematic follow-up of faults and errors with the help of the Savannah bug tracking system. In preparation for data taking the roles of a Computing Run Coordinator and regular computing shifts monitoring the services and infrastructure as well as interfacing to the data operations tasks are being defined. The shift plan until the end of 2008 is being put together. User support worked on documentation and organized several training sessions. The ECoM task force delivered the report on “Use Cases for Start-up of pp Data-Taking” with recommendations and a set of tests to be performed for trigger rates much higher than the ...

  10. COMPUTING

    CERN Multimedia

    P. MacBride

    The Computing Software and Analysis Challenge CSA07 has been the main focus of the Computing Project for the past few months. Activities began over the summer with the preparation of the Monte Carlo data sets for the challenge and tests of the new production system at the Tier-0 at CERN. The pre-challenge Monte Carlo production was done in several steps: physics generation, detector simulation, digitization, conversion to RAW format and the samples were run through the High Level Trigger (HLT). The data was then merged into three "Soups": Chowder (ALPGEN), Stew (Filtered Pythia) and Gumbo (Pythia). The challenge officially started when the first Chowder events were reconstructed on the Tier-0 on October 3rd. The data operations teams were very busy during the the challenge period. The MC production teams continued with signal production and processing while the Tier-0 and Tier-1 teams worked on splitting the Soups into Primary Data Sets (PDS), reconstruction and skimming. The storage sys...

  11. COMPUTING

    CERN Document Server

    2010-01-01

    Introduction Just two months after the “LHC First Physics” event of 30th March, the analysis of the O(200) million 7 TeV collision events in CMS accumulated during the first 60 days is well under way. The consistency of the CMS computing model has been confirmed during these first weeks of data taking. This model is based on a hierarchy of use-cases deployed between the different tiers and, in particular, the distribution of RECO data to T1s, who then serve data on request to T2s, along a topology known as “fat tree”. Indeed, during this period this model was further extended by almost full “mesh” commissioning, meaning that RECO data were shipped to T2s whenever possible, enabling additional physics analyses compared with the “fat tree” model. Computing activities at the CMS Analysis Facility (CAF) have been marked by a good time response for a load almost evenly shared between ALCA (Alignment and Calibration tasks - highest p...

  12. COMPUTING

    CERN Multimedia

    I. Fisk

    2013-01-01

    Computing operation has been lower as the Run 1 samples are completing and smaller samples for upgrades and preparations are ramping up. Much of the computing activity is focusing on preparations for Run 2 and improvements in data access and flexibility of using resources. Operations Office Data processing was slow in the second half of 2013 with only the legacy re-reconstruction pass of 2011 data being processed at the sites.   Figure 1: MC production and processing was more in demand with a peak of over 750 Million GEN-SIM events in a single month.   Figure 2: The transfer system worked reliably and efficiently and transferred on average close to 520 TB per week with peaks at close to 1.2 PB.   Figure 3: The volume of data moved between CMS sites in the last six months   The tape utilisation was a focus for the operation teams with frequent deletion campaigns from deprecated 7 TeV MC GEN-SIM samples to INVALID datasets, which could be cleaned up...

  13. COMPUTING

    CERN Multimedia

    I. Fisk

    2012-01-01

      Introduction Computing activity has been running at a sustained, high rate as we collect data at high luminosity, process simulation, and begin to process the parked data. The system is functional, though a number of improvements are planned during LS1. Many of the changes will impact users, we hope only in positive ways. We are trying to improve the distributed analysis tools as well as the ability to access more data samples more transparently.  Operations Office Figure 2: Number of events per month, for 2012 Since the June CMS Week, Computing Operations teams successfully completed data re-reconstruction passes and finished the CMSSW_53X MC campaign with over three billion events available in AOD format. Recorded data was successfully processed in parallel, exceeding 1.2 billion raw physics events per month for the first time in October 2012 due to the increase in data-parking rate. In parallel, large efforts were dedicated to WMAgent development and integrati...

  14. COMPUTING

    CERN Multimedia

    M. Kasemann

    Introduction A large fraction of the effort was focused during the last period into the preparation and monitoring of the February tests of Common VO Computing Readiness Challenge 08. CCRC08 is being run by the WLCG collaboration in two phases, between the centres and all experiments. The February test is dedicated to functionality tests, while the May challenge will consist of running at all centres and with full workflows. For this first period, a number of functionality checks of the computing power, data repositories and archives as well as network links are planned. This will help assess the reliability of the systems under a variety of loads, and identifying possible bottlenecks. Many tests are scheduled together with other VOs, allowing the full scale stress test. The data rates (writing, accessing and transfer¬ring) are being checked under a variety of loads and operating conditions, as well as the reliability and transfer rates of the links between Tier-0 and Tier-1s. In addition, the capa...

  15. COMPUTING

    CERN Multimedia

    Contributions from I. Fisk

    2012-01-01

    Introduction The start of the 2012 run has been busy for Computing. We have reconstructed, archived, and served a larger sample of new data than in 2011, and we are in the process of producing an even larger new sample of simulations at 8 TeV. The running conditions and system performance are largely what was anticipated in the plan, thanks to the hard work and preparation of many people. Heavy ions Heavy Ions has been actively analysing data and preparing for conferences.  Operations Office Figure 6: Transfers from all sites in the last 90 days For ICHEP and the Upgrade efforts, we needed to produce and process record amounts of MC samples while supporting the very successful data-taking. This was a large burden, especially on the team members. Nevertheless the last three months were very successful and the total output was phenomenal, thanks to our dedicated site admins who keep the sites operational and the computing project members who spend countless hours nursing the...

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

    KAUST Repository

    Wang, Zhandong

    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. 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. © 2015 The Combustion Institute.

  17. Evidence for Neural Computations of Temporal Coherence in an Auditory Scene and Their Enhancement during Active Listening.

    Science.gov (United States)

    O'Sullivan, James A; Shamma, Shihab A; Lalor, Edmund C

    2015-05-06

    The human brain has evolved to operate effectively in highly complex acoustic environments, segregating multiple sound sources into perceptually distinct auditory objects. A recent theory seeks to explain this ability by arguing that stream segregation occurs primarily due to the temporal coherence of the neural populations that encode the various features of an individual acoustic source. This theory has received support from both psychoacoustic and functional magnetic resonance imaging (fMRI) studies that use stimuli which model complex acoustic environments. Termed stochastic figure-ground (SFG) stimuli, they are composed of a "figure" and background that overlap in spectrotemporal space, such that the only way to segregate the figure is by computing the coherence of its frequency components over time. Here, we extend these psychoacoustic and fMRI findings by using the greater temporal resolution of electroencephalography to investigate the neural computation of temporal coherence. We present subjects with modified SFG stimuli wherein the temporal coherence of the figure is modulated stochastically over time, which allows us to use linear regression methods to extract a signature of the neural processing of this temporal coherence. We do this under both active and passive listening conditions. Our findings show an early effect of coherence during passive listening, lasting from ∼115 to 185 ms post-stimulus. When subjects are actively listening to the stimuli, these responses are larger and last longer, up to ∼265 ms. These findings provide evidence for early and preattentive neural computations of temporal coherence that are enhanced by active analysis of an auditory scene. Copyright © 2015 the authors 0270-6474/15/357256-08$15.00/0.

  18. Necessary, yet dissociable contributions of the insular and ventromedial prefrontal cortices to norm adaptation: computational and lesion evidence in humans.

    Science.gov (United States)

    Gu, Xiaosi; Wang, Xingchao; Hula, Andreas; Wang, Shiwei; Xu, Shuai; Lohrenz, Terry M; Knight, Robert T; Gao, Zhixian; Dayan, Peter; Montague, P Read

    2015-01-14

    Social norms and their enforcement are fundamental to human societies. The ability to detect deviations from norms and to adapt to norms in a changing environment is therefore important to individuals' normal social functioning. Previous neuroimaging studies have highlighted the involvement of the insular and ventromedial prefrontal (vmPFC) cortices in representing norms. However, the necessity and dissociability of their involvement remain unclear. Using model-based computational modeling and neuropsychological lesion approaches, we examined the contributions of the insula and vmPFC to norm adaptation in seven human patients with focal insula lesions and six patients with focal vmPFC lesions, in comparison with forty neurologically intact controls and six brain-damaged controls. There were three computational signals of interest as participants played a fairness game (ultimatum game): sensitivity to the fairness of offers, sensitivity to deviations from expected norms, and the speed at which people adapt to norms. Significant group differences were assessed using bootstrapping methods. Patients with insula lesions displayed abnormally low adaptation speed to norms, yet detected norm violations with greater sensitivity than controls. Patients with vmPFC lesions did not have such abnormalities, but displayed reduced sensitivity to fairness and were more likely to accept the most unfair offers. These findings provide compelling computational and lesion evidence supporting the necessary, yet dissociable roles of the insula and vmPFC in norm adaptation in humans: the insula is critical for learning to adapt when reality deviates from norm expectations, and that the vmPFC is important for valuation of fairness during social exchange. Copyright © 2015 Gu et al.

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

    Directory of Open Access Journals (Sweden)

    Renata Janaína Carvalho de Souza

    2010-11-01

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

  20. Toxics release inventory: List of toxic chemicals within the polychlorinated alkanes category and guidance for reporting

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-02-01

    Section 313 of the Emergency Planning and Community Right-to-Know Act of 1986 (EPCRA) requires certain facilities manufacturing, processing, or otherwise using listed toxic chemicals to report their environmental releases of such chemicals annually. On November 30, 1994 EPA added 286 chemicals and chemical categories. Six chemical categories (nicotine and salts, strychnine and salts, polycyclic aromatic compounds, water dissociable nitrate compounds, diisocyanates, and polychlorinated alkanes) are included in these additions. At the time of the addition, EPA indicated that the Agency would develop, as appropriate, interpretations and guidance that the Agency determines are necessary to facilitate accurate reporting for these categories. This document constitutes such guidance for the polychlorinated alkanes category.

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

    DEFF Research Database (Denmark)

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

    1996-01-01

    -liquid equilibrium of n-alkanes ranging from n-C_20 to n-C_40.The model is further modified to achieve a more correct temperature dependence because it severely underestimates the excess enthalpy. It is shown that the ratio of excess enthalpy and entropy for n-alkane solid solutions, as happens for other solid...... mixtures, is related with the values of the melting temperatures by a function common to the entire homologous series. When applied to systems with a symmetric behavior, this yields a correct description of both the enthalpic and entropic parts of the excess Gibbs free energy with the CDLP model...

  2. Regioselective alkane hydroxylation with a mutant CYP153A6 enzyme

    Science.gov (United States)

    Koch, Daniel J.; Arnold, Frances H.

    2013-01-29

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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  4. Stable isotope labeled n-alkanes to assess digesta passage kinetics through the digestive tract of ruminants

    NARCIS (Netherlands)

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

    2013-01-01

    We describe the use of carbon stable isotope (13C) labeled n-alkanes as a potential internal tracer to assess passage kinetics of ingested nutrients in ruminants. Plant cuticular n-alkanes originating from intrinsically 13C labeled ryegrass plants were pulse dosed intraruminally in four

  5. QSPR models based on molecular mechanics and quantum chemical calculations. 2. Thermodynamic properties of alkanes, alcohols, polyols, and ethers

    DEFF Research Database (Denmark)

    Dyekjær, Jane Dannow; Jonsdottir, Svava Osk

    2003-01-01

    for alkanes, alcohols, diols, ethers, and oxyalcohols, including cyclic alkanes and alcohols. Several good models, having good predictability, have been developed. To enhance the applicability of the QSPR models, simpler expressions for each descriptor have also been developed. This allows for the prediction...

  6. Data from: Stable isotope labeled n-alkanes to assess digesta passage kinetics through the digestive tract of ruminants

    NARCIS (Netherlands)

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

    2013-01-01

    We describe the use of carbon stable isotope (13C) labeled n-alkanes as a potential internal tracer to assess passage kinetics of ingested nutrients in ruminants. Plant cuticular n-alkanes originating from intrinsically 13C labeled ryegrass plants were pulse dosed intraruminally in four

  7. Evaluation of n-alkanes and their carbon isotope enrichments (d13C) as diet composition markers

    NARCIS (Netherlands)

    Derseh, M.B.; Pellikaan, W.F.; Tolera, A.; Hendriks, W.H.

    2011-01-01

    Plant cuticular n-alkanes have been successfully used as markers to estimate diet composition and intake of grazing herbivores. However, additional markers may be required under grazing conditions in botanically diverse vegetation. This study was conducted to describe the n-alkane profiles and the

  8. 40 CFR 721.10178 - Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction. 721.10178 Section 721.10178 Protection of Environment...), hydroisomerized middle, C10-13-branched alkane fraction. (a) Chemical substance and significant new uses subject...

  9. Alkane-degrading bacteria at the soil-litter interface: comparing isolates with T-RFLP-based community profiles.

    Science.gov (United States)

    Giebler, Julia; Wick, Lukas Y; Chatzinotas, Antonis; Harms, Hauke

    2013-10-01

    Alkane-degrading bacteria were isolated from uncontaminated soil microcosms, which had been incubated with maize litter as natural alkane source. The isolates served to understand spatio-temporal community changes at the soil-litter interface, which had been detected using alkB as a functional marker gene for bacterial alkane degraders. To obtain a large spectrum of isolates, liquid subcultivation was combined with a matrix-assisted enrichment (Teflon membranes, litter). Elevated cell numbers of alkane degraders were detected by most probable number counting indicating enhanced alkane degradation potential in soil in response to litter treatment. Partial 16S rRNA gene sequencing of 395 isolates revealed forty different phylogenetic groups [operational taxonomic units (OTUs)] and spatio-temporal shifts in community composition. Ten OTUs comprised so far unknown alkane degraders, and five OTUs represented putative new bacterial genera. The combination of enrichment methods yielded a higher diversity of isolates than liquid subcultivation alone. Comparison of 16S rRNA gene T-RFLP profiles indicated that many alkane degraders present in the enrichments were not detectable in the DNA extracts from soil microcosms. These possibly rare specialists might represent a seed bank for the alkane degradation capacity in uncontaminated soil. This relevant ecosystem function can be fostered by the formation of the soil-litter interface. © 2013 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

  10. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Science.gov (United States)

    2010-07-01

    ...-alkane, branched and linear. 721.10103 Section 721.10103 Protection of Environment ENVIRONMENTAL..., branched and linear. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS No...

  11. Hydrocarbons biodegradation and evidence of mixed petroleum ...

    African Journals Online (AJOL)

    Chromatographic analysis of extracts from the Cross River system show evidence of variable composition of biogenic n-alkane profile with dominance of terrigenous over aquatic organic matter present (LHC/SHC-0.36-10.57) at upstream location reflecting the natural background levels and marked levels of petroleum ...

  12. Evidence-based guidelines for the informal use of computers by children to promote the development of academic, cognitive and social skills.

    Science.gov (United States)

    Tran, Phuoc; Subrahmanyam, Kaveri

    2013-01-01

    The use of computers in the home has become very common among young children. This paper reviews research on the effects of informal computer use and identifies potential pathways through which computers may impact children's development. Based on the evidence reviewed, we present the following guidelines to arrange informal computer experiences that will promote the development of children's academic, cognitive and social skills: (1) children should be encouraged to use computers for moderate amounts of time (2-3 days a week for an hour or two per day) and (2) children's use of computers should (a) include non-violent action-based computer games as well as educational games, (b) not displace social activities but should instead be arranged to provide opportunities for social engagement with peers and family members and (c) involve content with pro-social and non-violent themes. We conclude the paper with questions that must be addressed in future research. This paper reviews research on the effects of informal computer use on children's academic, cognitive and social skills. Based on the evidence presented, we have presented guidelines to enable parents, teachers and other adults to arrange informal computer experiences so as to maximise their potential benefit for children's development.

  13. COMPUTING

    CERN Multimedia

    I. Fisk

    2011-01-01

    Introduction The Computing Team successfully completed the storage, initial processing, and distribution for analysis of proton-proton data in 2011. There are still a variety of activities ongoing to support winter conference activities and preparations for 2012. Heavy ions The heavy-ion run for 2011 started in early November and has already demonstrated good machine performance and success of some of the more advanced workflows planned for 2011. Data collection will continue until early December. Facilities and Infrastructure Operations Operational and deployment support for WMAgent and WorkQueue+Request Manager components, routinely used in production by Data Operations, are provided. The GlideInWMS and components installation are now deployed at CERN, which is added to the GlideInWMS factory placed in the US. There has been new operational collaboration between the CERN team and the UCSD GlideIn factory operators, covering each others time zones by monitoring/debugging pilot jobs sent from the facto...

  14. Distribution and variability of n-alkanes in epicuticular waxes of sedum species from the central Balkan Peninsula: chemotaxonomic importance.

    Science.gov (United States)

    Jovanović, Snežana Č; Zlatković, Bojan K; Stojanović, Gordana S

    2015-05-01

    For the first time, the n-alkane distribution and variability of the epicuticular waxes within 22 Sedum taxa was reported with focus on the chemotaxonomy of native Sedum representatives from the central Balkan Peninsula, compared to their relations with four other species of the Crassulaceae family. By GC/MS and GC-FID identification and quantification, it was established that n-alkanes C27 , C29 , C31 , C33 , and C35 were the dominant constituents of the examined epicuticular wax samples. Applying multivariate statistical analyses including agglomerative hierarchical clustering (AHC) and principal component analysis (PCA), the relation according to the n-alkane composition between the examined samples was established. It was shown that the n-alkane variability of the central Balkan Sedum species was considerable and that n-alkanes might not be very reliable taxonomic markers for these species. Copyright © 2015 Verlag Helvetica Chimica Acta AG, Zürich.

  15. Diversity of alkane degrading bacteria associated with plants in a petroleum oil-contaminated environment and expression of alkane monooxygenase (alkB) genes

    Science.gov (United States)

    Andria, V.; Yousaf, S.; Reichenauer, T. G.; Smalla, K.; Sessitsch, A.

    2009-04-01

    Among twenty-six different plant species, Italian ryegrass (Lolium multiflorum var. Taurus), Birdsfoot trefoil (Lotus corniculatus var. Leo), and the combination of both plants performed well in a petroleum oil contaminated soil. Hydrocarbon degrading bacteria were isolated from the rhizosphere, root interior and shoot interior and subjected to the analysis of 16S rRNA, the 16S and 23S rRNA intergenic spacer region and alkane hydroxylase genes. Higher numbers of culturable, degrading bacteria were associated with Italian ryegrass, which were also characterized by a higher diversity, particularly in the plant interior. Only half of the isolated bacteria hosted known alkane hydroxylase genes (alkB and cytochrome P153-like). Our results indicated that alkB genes have spread through horizontal gene transfer, particularly in the Italian ryegrass rhizosphere, and suggested mobility of catabolic genes between Gram-negative and Gram-positive bacteria. We furthermore studied the colonization behaviour of selected hydrocarbon-degrading strains (comprising an endopyhte and a rhizosphere strain) as well as the expression of their alkane monooxygenase genes in association with Italian ryegrass. Results showed that the endophyte strain better colonized the plant, particularly the plant interior, and also showed higher expression of alkB genes suggesting a more efficient degradation of the pollutant. Furthermore, plants inoculated with the endophyte were better able to grow in the presence of diesel. The rhizosphere strain colonized primarily the rhizosphere and showed low alkB gene expression in the plant interior.

  16. Alkane activation at ambient temperature - Unusual selectivities, C-C, C-H bond scission vs C-C bond coupling

    NARCIS (Netherlands)

    Trionfetti, C.; Agiral, A.; Gardeniers, Han J G E; Lefferts, L.; Seshan, K.

    2008-01-01

    Availability and low cost of light alkanes make them interesting as feedstock for commercial fuels and chemicals. However, direct conversion of lower alkanes for such purposes is a challenging problem. A discussion covers the oxidative conversion of light alkanes in the presence of cold plasma in a

  17. COMPUTING

    CERN Multimedia

    M. Kasemann

    CMS relies on a well functioning, distributed computing infrastructure. The Site Availability Monitoring (SAM) and the Job Robot submission have been very instrumental for site commissioning in order to increase availability of more sites such that they are available to participate in CSA07 and are ready to be used for analysis. The commissioning process has been further developed, including "lessons learned" documentation via the CMS twiki. Recently the visualization, presentation and summarizing of SAM tests for sites has been redesigned, it is now developed by the central ARDA project of WLCG. Work to test the new gLite Workload Management System was performed; a 4 times increase in throughput with respect to LCG Resource Broker is observed. CMS has designed and launched a new-generation traffic load generator called "LoadTest" to commission and to keep exercised all data transfer routes in the CMS PhE-DEx topology. Since mid-February, a transfer volume of about 12 P...

  18. Interrogation of Chesapeake Bay sediment microbial communities for intrinsic alkane-utilizing potential under anaerobic conditions.

    Science.gov (United States)

    Johnson, Jamie M; Wawrik, Boris; Isom, Catherine; Boling, Wilford B; Callaghan, Amy V

    2015-02-01

    Based on the transient exposure of Chesapeake Bay sediments to hydrocarbons and the metabolic versatility of known anaerobic alkane-degrading microorganisms, it was hypothesized that distinct Bay sediment communities, governed by geochemical gradients, would have intrinsic alkane-utilizing potential under sulfate-reducing and/or methanogenic conditions. Sediment cores were collected along a transect of the Bay. Community DNA was interrogated via pyrosequencing of 16S rRNA genes, PCR of anaerobic hydrocarbon activation genes, and qPCR of 16S rRNA genes and genes involved in sulfate reduction/methanogenesis. Site sediments were used to establish microcosms amended with n-hexadecane under sulfate-reducing and methanogenic conditions. Sequencing of 16S rRNA genes indicated that sediments associated with hypoxic water columns contained significantly greater proportions of Bacteria and Archaea consistent with syntrophic degradation of organic matter and methanogenesis compared to less reduced sediments. Microbial taxa frequently associated with hydrocarbon-degrading communities were found throughout the Bay, and the genetic potential for hydrocarbon metabolism was demonstrated via the detection of benzyl-(bssA) and alkylsuccinate synthase (assA) genes. Although microcosm studies did not indicate sulfidogenic alkane degradation, the data suggested that methanogenic conversion of alkanes was occurring. These findings highlight the potential role that anaerobic microorganisms could play in the bioremediation of hydrocarbons in the Bay. © FEMS 2014. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

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

    Czech Academy of Sciences Publication Activity Database

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

    2012-01-01

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

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

    Science.gov (United States)

    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

  1. The influence of extra framework aluminium on H-fak catalyzed cracking of light alkanes

    NARCIS (Netherlands)

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

    1996-01-01

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

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

    International Nuclear Information System (INIS)

    Dardour, H.; Mazouz, S.; Reneaume, J.-M.; Cézac, P.; Bourouis, M.; Bellagi, A.

    2015-01-01

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

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

    DEFF Research Database (Denmark)

    Wang, S. K.; Mamontov, E.; Bai, M.

    2010-01-01

    High-energy-resolution quasielastic neutron scattering on three complementary spectrometers has been used to investigate molecular diffusive motion in solid nano- to bulk-sized particles of the alkane n-C32H66. The crystalline-to-plastic and plastic-to-fluid phase transition temperatures are obse...

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

    Czech Academy of Sciences Publication Activity Database

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

    2001-01-01

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

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

    DEFF Research Database (Denmark)

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

    2001-01-01

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

  6. Ashwagandha derived withanone targets TPX2-Aurora A complex: computational and experimental evidence to its anticancer activity.

    Directory of Open Access Journals (Sweden)

    Abhinav Grover

    Full Text Available Cancer is largely marked by genetic instability. Specific inhibition of individual proteins or signalling pathways that regulate genetic stability during cell division thus hold a great potential for cancer therapy. The Aurora A kinase is a Ser/Thr kinase that plays a critical role during mitosis and cytokinesis and is found upregulated in several cancer types. It is functionally regulated by its interactions with TPX2, a candidate oncogene. Aurora A inhibitors have been proposed as anticancer drugs that work by blocking its ATP binding site. This site is common to other kinases and hence these inhibitors lack specificity for Aurora A inhibition in particular, thus advocating the need of some alternative inhibition route. Previously, we identified TPX2 as a cellular target for withanone that selectively kill cancer cells. By computational approach, we found here that withanone binds to TPX2-Aurora A complex. In experiment, withanone treatment to cancer cells indeed resulted in dissociation of TPX2-Aurora A complex and disruption of mitotic spindle apparatus proposing this as a mechanism of the anticancer activity of withanone. From docking analysis, non-formation/disruption of the active TPX2-Aurora A association complex could be discerned. Our MD simulation results suggesting the thermodynamic and structural stability of TPX2-Aurora A in complex with withanone further substantiates the binding. We report a computational rationale of the ability of naturally occurring withanone to alter the kinase signalling pathway in an ATP-independent manner and experimental evidence in which withanone cause inactivation of the TPX2-Aurora A complex. The study demonstrated that TPX2-Aurora A complex is a target of withanone, a potential natural anticancer drug.

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

    Science.gov (United States)

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

    2014-12-01

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

  8. Intermolecular Forces in Introductory Chemistry Studied by Gas Chromatography, Computer Models, and Viscometry

    Science.gov (United States)

    Wedvik, Jonathan C.; McManaman, Charity; Anderson, Janet S.; Carroll, Mary K.

    1998-07-01

    An experiment on intermolecular forces for first-term introductory college chemistry is presented. The experiment integrates traditional viscometry-based measurements with modern chromatographic analysis and use of computer-based molecular models. Students performing gas chromatographic (GC) analyses of mixtures of n-alkanes and samples that simulate crime scene evidence discover that liquid mixtures can be separated rapidly into their components based upon intermolecular forces. Each group of students is given a liquid sample that simulates one collected at an arson scene, and the group is required to determine the identity of the accelerant. Students also examine computer models to better visualize how molecular structure affects intermolecular forces: London forces, dipole-dipole interactions, and hydrogen bonding. The relative viscosities of organic liquids are also measured to relate physical properties to intermolecular forces.

  9. Pure and Au nanoparticles doped higher alkanes for an optical fiber temperature threshold sensor

    Science.gov (United States)

    Przybysz, Natalia; Marć, Paweł; Tomaszewska, Emilia; Grobelny, Jarosław; Jaroszewicz, Leszek R.

    2017-05-01

    Development of photonic crystal fibers (PCFs) technology has created new research fields for optical sensors and telecommunication. The cross section geometry modifications of this type of fibers allow to influence their optical parameters. These modifications are not limited to change sizes and arrangements of an air holes' lattice, but also replacing air with another material. In the paper we have shown how to change thermo-optical properties of a large mode area commercially available LMA-10 PCF by filling it with different chemical substances. Our previous research has led us to develop a class of optical fiber temperature threshold sensor transducers based on a partially filled PCF with higher alkanes. The principle of work of such a sensor transducer is to use a temperature bi-stability of a filling material because when the higher alkane is in the solid state light cannot pass through the transducer, and when it is in the liquid state light can be transmitted. One of the most important advantages of higher alkanes we used in the experiments are their different melting points, but the most important disadvantage is discrepancy between melting and crystallization temperatures and the sensor switches on and off for different temperatures. This effect called supercoiling appears due to the lack of nucleation centers. To reduce this effect the gold nanoparticels (NPs) in hexane colloid were used. We have prepared samples with three higher alkanes doped with 1% of Au NPs and we have shown their temperature and time responses. The proper selection of melting points of higher alkanes allows to design the multilevel temperature threshold sensor which can cover the temperature range from -20°C up to 70°C, and can be applied in chemical, oil, gas and energy industry.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-11-07

    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.

  11. Pulse radiolysis of alkanes: a time-resolved EPR study - Part I. Alkyl radicals

    International Nuclear Information System (INIS)

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

    1995-01-01

    Time-resolved EPR was applied to detect short-lived alkyl radicals in pulse radiolysis of liquid alkanes. Two problems were addressed: (i) the mechanism of radical formation and (ii) the mechanism of chemically-induced spin polarization in these radicals. (i) The ratio of yields of penultimate and interior radicals in n-alkanes at the instant of their generation was found to be ≅ 1.25 times greater than the statistical quantity. This higher-than-statistical production of penultimate radicals indicates that the proton transfer reaction involving excited radical cations must be a prevailing route of radical generation. The relative yields of hydrogen abstraction and fragmentation for various branched alkanes are estimated. It is concluded that the fragmentation occurs prior to the formation of radicals in an excited precursor species. (ii) The analysis of spin-echo kinetics in n-alkanes suggests that the alkyl radicals gain the emissive polarization in spur reactions. This initial polarization increases with shortening of the aliphatic chain. We suggest that the origin of this polarization is the ST mechanism operating in the pairs of alkyl radicals and hydrogen atoms generated in dissociation of excited alkane molecules. It is also found that a long-chain structure of alkyl radicals results in much higher rate of Heisenberg spin exchange relative to the recombination rate (up to 30 times). That suggests prominent steric effects in recombination or the occurrence of through-chain electron exchange. The significance of these results in the context of cross-linking in polyethylene and higher paraffins is discussed. (Author)

  12. Variability of n-alkanes and nonacosan-10-ol in natural populations of Picea omorika.

    Science.gov (United States)

    Nikolić, Biljana; Tešević, Vele; Ðorđević, Iris; Todosijević, Marina; Jadranin, Milka; Bojović, Srdjan; Marin, Petar D

    2013-03-01

    This is the first report of population variability of the contents of n-alkanes and nonacosan-10-ol in the needle epicuticular waxes of Serbian spruce (Picea omorika). The hexane extracts of needle samples originated from three natural populations in Serbia (Vranjak, Zmajevački potok, and Mileševka Canyon) were investigated by GC and GC/MS analyses. The amount of nonacosan-10-ol varied individually from 50.05 to 74.42% (65.74% in average), but the differences between the three investigated populations were not statistically confirmed. The results exhibited variability of the composition of n-alkanes in the epicuticular waxes with their size ranging from C(18) to C(35). The most abundant n-alkanes were C(29), C(31), and C(27) (35.22, 13.77, and 12.28% in average, resp.). The carbon preference index of all the n-alkanes (CPI(total)) of the P. omorika populations (average of populations I-III) ranged from 3.3 to 11.5 (mean of 5.9), while the average chain length (ACL) ranged from 26.6 to 29.2. The principal component and cluster analyses of the contents of nine n-alkanes showed the greatest difference for the population growing in the Mileševka Canyon. The obtained results were compared with previous literature data given for other Picea species, and this comparison was briefly discussed. Copyright © 2013 Verlag Helvetica Chimica Acta AG, Zürich.

  13. Enhanced biodegradation of alkane hydrocarbons and crude oil by mixed strains and bacterial community analysis.

    Science.gov (United States)

    Chen, Yu; Li, Chen; Zhou, Zhengxi; Wen, Jianping; You, Xueyi; Mao, Youzhi; Lu, Chunzhe; Huo, Guangxin; Jia, Xiaoqiang

    2014-04-01

    In this study, two strains, Acinetobacter sp. XM-02 and Pseudomonas sp. XM-01, were isolated from soil samples polluted by crude oil at Bohai offshore. The former one could degrade alkane hydrocarbons (crude oil and diesel, 1:4 (v/v)) and crude oil efficiently; the latter one failed to grow on alkane hydrocarbons but could produce rhamnolipid (a biosurfactant) with glycerol as sole carbon source. Compared with pure culture, mixed culture of the two strains showed higher capability in degrading alkane hydrocarbons and crude oil of which degradation rate were increased from 89.35 and 74.32 ± 4.09 to 97.41 and 87.29 ± 2.41 %, respectively. In the mixed culture, Acinetobacter sp. XM-02 grew fast with sufficient carbon source and produced intermediates which were subsequently utilized for the growth of Pseudomonas sp. XM-01 and then, rhamnolipid was produced by Pseudomonas sp. XM-01. Till the end of the process, Acinetobacter sp. XM-02 was inhibited by the rapid growth of Pseudomonas sp. XM-01. In addition, alkane hydrocarbon degradation rate of the mixed culture increased by 8.06 to 97.41 % compared with 87.29 % of the pure culture. The surface tension of medium dropping from 73.2 × 10(-3) to 28.6 × 10(-3) N/m. Based on newly found cooperation between the degrader and the coworking strain, rational investigations and optimal strategies to alkane hydrocarbons biodegradation were utilized for enhancing crude oil biodegradation.

  14. Even-odd alternation of near-infrared spectra of alkane-α,ω-diols in their solid states.

    Science.gov (United States)

    Toyama, Yuta; Murakami, Kohei; Yoshimura, Norio; Takayanagi, Masao

    2018-05-15

    Even-odd alternation of the melting points of α,ω-disubstituted linear alkanes such as alkane-α,ω-diols, alkane-α,ω-dinitriles and α,ω-diaminoalkanes is well known. Melting points for compounds with an even number of carbons in their alkyl chains are systematically higher than those for compounds with an odd number of carbons. In order to clarify the origin of this alternation, near-infrared absorption spectra of linear alkane-α,ω-diols with 3 to 9 carbon atoms in their alkyl chains were measured in the liquid and solid states. The band due to the first overtone of the OH stretching mode was investigated. The temperature-dependent spectra of all alkane-α,ω-diols in their liquid states were found to be similar; no even-odd alternation was observed. In the solid state, however, spectra of alkane-α,ω-diols with even and odd numbers of carbon atoms differed greatly. Spectra of alkane-α,ω-diols with an odd number of carbon atoms in their solid states were similar to those in the liquid states, although the variation of spectra observed upon lowering the temperature of liquid seemed to continue when the liquids were frozen. In contrast, spectra of alkane-α,ω-diols with an even number of carbon atoms in their liquid and solid states were found to be quite different. New bands appeared upon freezing. The observed even-odd alternation of the spectra observed for alkane-α,ω-diols in their solid states is presumably caused by their even-odd alternation of crystal structures. Copyright © 2018 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, Frances H.

    2012-02-27

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

  16. Relevance of carbon structure to formation of tar and liquid alkane during coal pyrolysis

    International Nuclear Information System (INIS)

    Liu, Peng; Le, Jiawei; Wang, Lanlan; Pan, Tieying; Lu, Xilan; Zhang, Dexiang

    2016-01-01

    Highlights: • Curve-fitting method was used to quantify the accurate contents of structural carbon. • Effect of carbon structure in coal with different rank on formation of pyrolysis tar was studied. • Numerical interrelation between carbon types in coal structure and tar yield is elaborated. • Effect of carbon structure on formation of liquid alkane during coal pyrolysis is discussed. - Abstract: The relevance of carbon structure to formation of tar and liquid alkane during coal pyrolysis were discussed extensively. The pyrolysis tests were carried out in a tube reactor at 873 K and keep 15 min. The carbon distribution in coals was investigated by solid state 13 C nuclear magnetic resonance (N.M.R.). The curve-fitting method was used to quantify the accurate contents of structural carbon. The alkanes in coal tar were analyzed by Gas Chromatograph–Mass Spectrometer (GC–MS). The results show that oxygen-linked aromatic carbon decreases with the increasing of coal rank. The aliphatic carbon contents of Huainan (HN) coal are 44.20%, the highest among the four coals. The carbon types in coal structure have a significant influence on the formation of tar and liquid alkane. The coal tar yields are related to the aliphatic substituted aromatic carbon, CH 2 /CH 3 ratio and oxygen-linked carbon in coal so that the increasing order of tar yield is Inner Mongolia lignite (IM, 6.30 wt.%) < Sinkiang coal (SK, 7.55 wt.%) < Shenmu coal (SM, 12.84 wt.%) < HN (16.29 wt.%). The highest contents of oxygen-linked aromatic carbon in IM lead to phenolic compound of 41.06% in IM-tar. The contents of alkane in SM-tar are the highest because the appropriate CH 2 /CH 3 ratio and the highest aliphatic side chains on aromatic rings in SM leading to generate aliphatic hydrocarbon with medium molecular weight easily. The mechanism on formation of tar and liquid alkane plays an important role in guiding the industrialization of pyrolysis-based poly-generation producing tar with high

  17. Carbon and Hydrogen Isotopic Composition of Plant Wax n-Alkanes: A Tool for Characterizing Soil Provenance in Forensic Science

    Science.gov (United States)

    Pedentchouk, N.; Wagner, T.; Jones, M.

    2009-04-01

    Forensic science is an integrative discipline that requires material evidence from diverse sources. Geochemical evidence derived from inorganic and organic substances is becoming increasingly popular among law enforcement agencies in industrialized countries. Previous investigations indicate that the relative distributions of individual plant-derived biomarkers found in soils are linked to the biomarker patterns found in the overlying vegetation. However, identification of soil provenance based on the distribution of plant-derived biomarkers for forensic purposes is inhibited by the fact that a significant number of terrestrial plant species have overlapping biomarker distributions. In order to enhance the resolving power of plant-derived biomarker signal, we propose to enhance the molecular approach by adding a stable isotope component, i.e. the delta13C/deltaD values of individual biomarkers. The first objective of this project is to determine the delta13C/deltaD signatures of n-alkanes derived from various higher plant types commonly growing in the UK. The second objective is to investigate whether the same species/plant types differ isotopically between two locations affected by different weather patterns in the UK: a relatively warmer and drier Norwich, Norfolk and a cooler and wetter Newcastle-upon-Tyne in NE England. The n-C29 alkane data from 14 tree species sampled during July 2007 and August 2008 in Newcastle show a clear negative trend between delta13C and deltaD values. When these data are plotted against each other, the six deciduous angiosperms (delta13C: c. -39 to -35 per mil; deltaD: c. -155 to -130 per mil) are completely separated from four evergreen angiosperms (delta13C: c. -33 to -28 per mil; deltaD: c. -195 to -165 per mil). The four gymnosperm species data plot between those of the deciduous and evergreen angiosperms. Because all 14 species in Newcastle experience the same environmental conditions, we suggest that the observed isotopic

  18. Motor imagery for severely motor-impaired patients: evidence for brain-computer interfacing as superior control solution.

    Directory of Open Access Journals (Sweden)

    Johannes Höhne

    Full Text Available Brain-Computer Interfaces (BCIs strive to decode brain signals into control commands for severely handicapped people with no means of muscular control. These potential users of noninvasive BCIs display a large range of physical and mental conditions. Prior studies have shown the general applicability of BCI with patients, with the conflict of either using many training sessions or studying only moderately restricted patients. We present a BCI system designed to establish external control for severely motor-impaired patients within a very short time. Within only six experimental sessions, three out of four patients were able to gain significant control over the BCI, which was based on motor imagery or attempted execution. For the most affected patient, we found evidence that the BCI could outperform the best assistive technology (AT of the patient in terms of control accuracy, reaction time and information transfer rate. We credit this success to the applied user-centered design approach and to a highly flexible technical setup. State-of-the art machine learning methods allowed the exploitation and combination of multiple relevant features contained in the EEG, which rapidly enabled the patients to gain substantial BCI control. Thus, we could show the feasibility of a flexible and tailorable BCI application in severely disabled users. This can be considered a significant success for two reasons: Firstly, the results were obtained within a short period of time, matching the tight clinical requirements. Secondly, the participating patients showed, compared to most other studies, very severe communication deficits. They were dependent on everyday use of AT and two patients were in a locked-in state. For the most affected patient a reliable communication was rarely possible with existing AT.

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

    DEFF Research Database (Denmark)

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

    2003-01-01

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

  20. Paleoclimatic implications of the hydrogen isotopic composition of terrigenous n-alkanes from Lake Yamzho, southern Tibetan Plateau

    International Nuclear Information System (INIS)

    Xia Zhonghuan; Xu Baiqing; Wu Guangjian; Zhu Liping; Muegler Ines; Gleixner, Gerd; Sachse, Dirk

    2009-01-01

    The hydrogen isotopic composition (δD) of leaf water used for biosynthesis of n-alkanes can be modified by climate. Therefore, the δD can be considered as potential paleolimatic proxy to explore. We compared measured δD values of alkanes (n-C 25 to n-C 31 ) extracted from a short sediment profile spanning the past 50 years with a 7-year resolution from Lake Yamzho, southern Tibetan Plateau. Climatic control was reconstructed using meteorological records of the nearby Langkazi and Lhasa weather stations. We found that the δD values of the n-alkanes correlated with the mean annular air temperature and significantly correlated with the mean growing season air temperature. On the other hand, the δD values show poor correlations with both rainfall amount and relative humidity. These results indicate that stable isotope composition of n-alkanes could be an excellent proxy for paleotemperature reconstruction. (author)

  1. Selectivity of alkyl radical formation from branched alkanes studied by electron spin resonance and electron spin echo spectroscopy

    International Nuclear Information System (INIS)

    Tsuneki, Ichikawa; Hiroshi, Yoshida

    1992-01-01

    Alkyl radicals generated from branched alkanes by γ radiation are being measuring by electron spin resonance and electron spin echo spectroscopy. This research is being conducted to determine the mechanism of selective alkyl radical formation in low-temperature solids

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

    DEFF Research Database (Denmark)

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

    2007-01-01

    their backbone and squalane has, in addition, six methyl side groups. Upon adsorption, there are significant differences as well as similarities in the behavior of these molecular films. Both molecules form ordered structures at low temperatures; however, while the melting point of the two-dimensional (2D......The structure of a monolayer film of the branched alkane squalane (C30H62) adsorbed on graphite has been studied by neutron diffraction and molecular dynamics (MD) simulations and compared with a similar study of the n-alkane tetracosane (n-C24H52). Both molecules have 24 carbon atoms along...... temperature. The neutron diffraction data show that the translational order in the squalane monolayer is significantly less than in the tetracosane monolayer. The authors' MD simulations suggest that this is caused by a distortion of the squalane molecules upon adsorption on the graphite surface. When...

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

    International Nuclear Information System (INIS)

    Elshafie, Abdulkadir; AlKindi, Abdulaziz Yahya; Al-Busaidi, Sultan; Bakheit, Charles; Albahry, S.N.

    2007-01-01

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

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

    DEFF Research Database (Denmark)

    von Solms, Nicolas; Jensen, Lars; Kofod, Jonas L.

    2007-01-01

    Two equations of state (simplified PC-SAFT and CPA) are used to predict the monomer fraction of 1-alkanols in binary mixtures with n-alkanes. It is found that the choice of parameters and association schemes significantly affects the ability of a model to predict hydrogen bonding in mixtures, eve...... studies, which is clarified in the present work. New hydrogen bonding data based on infrared spectroscopy are reported for seven binary mixtures of alcohols and alkanes. (C) 2007 Elsevier B.V. All rights reserved....... though pure-component liquid densities and vapour pressures are predicted equally accurately for the associating compound. As was the case in the study of pure components, there exists some confusion in the literature about the correct interpretation and comparison of experimental data and theoretical...

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

    KAUST Repository

    Sun, Miao

    2014-01-22

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

  6. Experimental measurements and prediction of liquid densities for n-alkane mixtures

    International Nuclear Information System (INIS)

    Ramos-Estrada, Mariana; Iglesias-Silva, Gustavo A.; Hall, Kenneth R.

    2006-01-01

    We present experimental liquid densities for n-pentane, n-hexane and n-heptane and their binary mixtures from (273.15 to 363.15) K over the entire composition range (for the mixtures) at atmospheric pressure. A vibrating tube densimeter produces the experimental densities. Also, we present a generalized correlation to predict the liquid densities of n-alkanes and their mixtures. We have combined the principle of congruence with the Tait equation to obtain an equation that uses as variables: temperature, pressure and the equivalent carbon number of the mixture. Also, we present a generalized correlation for the atmospheric liquid densities of n-alkanes. The average absolute percentage deviation of this equation from the literature experimental density values is 0.26%. The Tait equation has an average percentage deviation of 0.15% from experimental density measurements

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

    Science.gov (United States)

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

    2013-12-01

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

  8. Developing Selective Oxidation Catalysts of Light Alkanes:. from Fundamental Understanding to Rational Design

    Science.gov (United States)

    Fu, Gang; Yi, Xiaodong; Huang, Chuanjing; Xu, Xin; Weng, Weizheng; Xia, Wensheng; Wan, Hui-Lin

    Selective oxidation of light alkanes remains to be a great challenge for the wider use of alkanes as feedstocks. To achieve high activity and at the same time high selectivity, some key issues have to be addressed: (1) the stability of the desired products with respect to the reactants; (2) the roles of the active components in the catalysts, the structure and the functionality of the active centers; (3) the reducibility of the metal cations, the Lewis acid sites and their synergic effects with the basic sites of the lattice oxygen anions; (4) spatial isolation of the active centers; and (5) the mechanisms for the formation and transformation of the intermediates and their kinetic controls. In this contribution, we took selective oxidation of propane to acrolein as our target reaction, and reviewed mainly our own work, trying to provide some thinking and answers to these five questions.

  9. High Selectivity of Alkanes Production by Calcium Basic Soap Thermal Decarboxylation

    Directory of Open Access Journals (Sweden)

    Neonufa Godlief F.

    2018-01-01

    Full Text Available Renewable fuel production from vegetable oil and fat or its fatty acids by direct decarboxylation has been widely reported. An innovative approach to produce drop-in fuel via thermal catalytic decarboxylation of basic soap derived from palm stearin reported in this research. The catalytic effect of the calcium and magnesium metals in the basic soap and its decarboxylation on drop-in fuel yield and product distribution was studied. The catalytic effect was tested in the temperature range up to 370°C and atmospheric pressure for 5 hours in a batch reactor. It has been proved that the calcium basic soap decarboxylation, effectively produce the drop-in fuel in carbon ranges C8 – C20, in which more than 78% selectivity toward alkane. Whereas, only 70% selectivity toward alkane has been resulted from the magnesium basic soap decarboxylation.

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

    International Nuclear Information System (INIS)

    Wang, S.-K.; Mamontov, Eugene; Bai, M.; Hansen, F.Y.; Taub, H.; Copley, J.R.D.; Garcia Sakai, V.; Gasparovic, Goran; Jenkins, Timothy; Tyagi, M.; Herwig, Kenneth W.; Neumann, D.A.; Montfrooij, W.; Volkmann, U.G.

    2010-01-01

    High-energy-resolution quasielastic neutron scattering on three complementary spectrometers has been used to investigate molecular diffusive motion in solid nano- to bulk-sized particles of the alkane n-C32H66. The crystalline-to-plastic and plastic-to-fluid phase transition temperatures are observed to decrease as the particle size decreases. In all samples, localized molecular diffusive motion in the plastic phase occurs on two different time scales: a 'fast' motion corresponding to uniaxial rotation about the long molecular axis; and a 'slow' motion attributed to conformational changes of the molecule. Contrary to the conventional interpretation in bulk alkanes, the fast uniaxial rotation begins in the low-temperature crystalline phase.

  11. Light scattering by low-frequency excitations in quasi-periodic n-alkane/urea adducts

    Science.gov (United States)

    Ollivier, J.; Ecolivet, C.; Beaufils, S.; Guillaume, F.; Breczewski, T.

    1998-09-01

    High-resolution light scattering spectroscopy has been performed on a series of n-alkane CnH2n + 2/urea inclusion compounds with n = 12,14,17 - 19. The elastic constants of these incommensurate composite crystals have been determined and found to be independent of the chain length of the guest molecules. In addition, no extraneous acoustic-like mode appeared in all spectra. However, quasi-elastic components with different widths are observed for different polarizations. In one of them the characteristics of the scattered light suggest that the quasi-elastic broadening could be generated by a sliding mode, whereas the other detected component is assigned to the reorientational motions of the n-alkane chains about their long axis.

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

    International Nuclear Information System (INIS)

    Ortega, J.; Navas, A.; Sabater, G.; Ascanio, M.; Placido, J.

    2007-01-01

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

  13. Stable isotope labeled n-alkanes to assess digesta passage kinetics through the digestive tract of ruminants.

    Directory of Open Access Journals (Sweden)

    Daniel Warner

    Full Text Available 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 δ(13C (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 (K 1 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. K 1 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 δ(13C signature of digestible feed nutrients as a tool to measure nutrient-specific passage kinetics.

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

    Directory of Open Access Journals (Sweden)

    Haidong Zhang

    2016-01-01

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

  15. The effect of environmental factors on stable isotopic composition of n-alkanes in Mediterranean olive oils

    Science.gov (United States)

    Pedentchouk, Nikolai; Mihailova, Alina; Abbado, Dimitri

    2014-05-01

    Traceability of the geographic origin of olive oils is an important issue from both commercial and health perspectives. This study evaluates the impact of environmental factors on stable C and H isotope compositions of n-alkanes in extra virgin olive oils from Croatia, France, Greece, Italy, Morocco, Portugal, Slovenia, and Spain. The data are used to investigate the applicability of stable isotope methodology for olive oil regional classification in the Mediterranean region. Analysis of stable C isotope composition of n-C29 alkane showed that extra virgin olive oils from Portugal and Spain have the most positive n-C29 alkane delta13C values. Conversely, olive oils from Slovenia, northern and central Italy are characterized by the most negative values. Overall, the n-C29 alkane delta13C values show a positive correlation with the mean air temperature during August-December and a negative correlation with the mean relative humidity during these months. Analysis of stable H isotope composition of n-C29 alkane revealed that the deltaD values are the most positive in olive oils from Greece and Morocco and the most negative in oils from northern Italy. The deltaD values of oils show significant correlation with all the analyses geographical parameters: the mean air temperature and relative humidity during August-December, the total amount of rainfall (the same months) and the annual deltaD values of precipitation. As predictor variables in the Categorical Data Analysis, the n-C29 alkane deltaD values show the most significant discriminative power, followed by the n-C29 alkane delta13C values. Overall, 93.4% of olive oil samples have been classified correctly into one of the production regions. Our findings suggest that an integrated analysis of C and H isotope compositions of n-alkanes extracted from extra virgin olive oil could become a useful tool for geographical provenancing of this highly popular food commodity.

  16. Angiosperm n-alkane distribution patterns and the geologic record of C4 grassland evolution

    Science.gov (United States)

    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.

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

    DEFF Research Database (Denmark)

    Mo, H.; Taub, H.; Volkmann, U.G.

    2003-01-01

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

  18. Enabling the synthesis of medium chain alkanes and 1-alkenes in yeast

    DEFF Research Database (Denmark)

    Zhu, Zhiwei; Zhou, Yongjin J.; Kang, Min Kyoung

    2017-01-01

    Microbial synthesis of medium chain aliphatic hydrocarbons, attractive drop-in molecules to gasoline and jet fuels, is a promising way to reduce our reliance on petroleum-based fuels. In this study, we enabled the synthesis of straight chain hydrocarbons (C7–C13) by yeast Saccharomyces cerevisiae...... of fatty acids to 1-alkenes, which could be synthesized at a level of 3 mg/L, 25-fold higher than that of alkanes produced via aldehydes....

  19. Alkane and polycyclic aromatic hydrocarbons in sediments and benthic invertebrates of the northern Chukchi Sea

    Science.gov (United States)

    Harvey, H. Rodger; Taylor, Karen A.

    2017-10-01

    The Hanna Shoal region represents an important northern gateway for transport and deposition in the Chukchi Sea. This study determined the concentration and distribution of organic contaminants (aliphatic hydrocarbon and polycyclic aromatic hydrocarbons, PAHs) in surface sediments from 34 sites across Hanna Shoal. Up to 31 total PAHs, including parent and alkyl homologues were detected with total concentrations ranging from a low of 168 ng g-1 the western flank of Hanna Shoal (station H34) to 1147 ng g-1 at station in Barrow Canyon (station BarC5). Alkyl PAHs were more abundant than parent structures and accounted for 53-64% of the summed concentrations suggesting overall at background levels (< 1600 ng g-1) in sediments. Alkane (C15-C33) hydrocarbons ranged from 4.3 μg g-1 on the southern flank of Hanna shoal to 31 μg g-1 at a northern station. Sediments were often dominated by short chain (C15-C22) alkanes with overall terrestrial aquatic ratios (TAR) for the region averaging 0.20. Based on the ratio of Fl/(Fl+ Py) and BaF/(Baf+BeP) verses (BA/BA+Ch) in sediments, PAHs are largely derived from petrogenic sources with minor amounts of mixed combustion sources. A diversity of PAHs were detected in the northern whelk Neptunea heros foot muscle with total concentrations ranging from 0.14 to 1.5 μg g-1 dry tissue wt. Larger (and presumably older) animals showed higher levels of PAH per unit muscle tissue, suggesting that animals may bioaccumulate PAHs over time, with low but increasing concentrations also present in internal and external eggs. Alkane hydrocarbons were also higher in whelks with distributions similar to that seen in sediments. The mussel Muscularus discors collected in Barrow Canyon showed constrained distributions and substantially lower concentrations of both PAHs and alkanes than the surrounding surface sediments.

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

    Directory of Open Access Journals (Sweden)

    F. C. PEIXOTO

    1999-09-01

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

  1. Practicing evidence based medicine at the bedside: a randomized controlled pilot study in undergraduate medical students assessing the practicality of tablets, smartphones, and computers in clinical life.

    Science.gov (United States)

    Friederichs, Hendrik; Marschall, Bernhard; Weissenstein, Anne

    2014-12-05

    Practicing evidence-based medicine is an important aspect of providing good medical care. Accessing external information through literature searches on computer-based systems can effectively achieve integration in clinical care. We conducted a pilot study using smartphones, tablets, and stationary computers as search devices at the bedside. The objective was to determine possible differences between the various devices and assess students' internet use habits. In a randomized controlled pilot study, 120 students were divided in three groups. One control group solved clinical problems on a computer and two intervention groups used mobile devices at the bedside. In a questionnaire, students were asked to report their internet use habits as well as their satisfaction with their respective search tool using a 5-point Likert scale. Of 120 surveys, 94 (78.3%) complete data sets were analyzed. The mobility of the tablet (3.90) and the smartphone (4.39) was seen as a significant advantage over the computer (2.38, p computer (3.22) was rated superior to both tablet computers (2.13) and smartphones (1.68). No significant differences were detected between tablets and smartphones except satisfaction with screen size (tablet 4.10, smartphone 2.00, p computers. However, mobility is regarded as a substantial advantage, and therefore future applications might facilitate quick and simple searches at the bedside.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-10-15

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

  3. Distribution and sources of n-alkanes and polycyclic aromatic hydrocarbons in shellfish of the Egyptian Red Sea coast

    Directory of Open Access Journals (Sweden)

    Ahmed El Nemr

    2016-06-01

    Full Text Available Aromatic hydrocarbons and n-alkanes were analyzed in shellfish collected from 13 different sites along the Egyptian Red Sea coast. All samples were analyzed for n-alkanes (C8–C40 and polycyclic aromatic hydrocarbons (EPA list of PAHs. n-Alkanes in shellfish samples from 13 locations were found to be in the range of 71.0–701.1 ng/g with a mean value of 242.2 ± 192.1 ng/g dry wt. Different indices were calculated for the n-alkanes to assess their sources. These were carbon preference index (CPI, average chain length (ACL, terrigenous/aquatic ratio (TAR, natural n-alkane ratio (NAR and proxy ratio (Paq. Most of the collected samples of n-alkanes were discovered to be from natural sources. Aromatic hydrocarbons (16 PAHs from 13 sites varied between 1.3 and 160.9 ng/g with an average of 47.9 ± 45.5 ng/g dry wt. Benzo(apyrine (BaP, a cancer risk assessment, was calculated for the PAHs and resulted in ranges between 0.08 and 4.47 with an average of 1.25 ng/g dry wt.

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

    Science.gov (United States)

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

    2016-05-01

    Aqueous solubility is a fundamental physical-chemical substance property that strongly influences the distribution, fate and effects of chemicals upon release into the environment. Experimental water solubility was determined for 18 selected C9-C18 normal, branched and cyclic alkanes. A slow-stir technique was applied to obviate emulsion formation, which historically has resulted in significant overestimation of the aqueous solubility of such hydrophobic liquid compounds. Sensitive GC-MS based methods coupled with contemporary sample extraction techniques were employed to enable reproducible analysis of low parts-per billion aqueous concentrations. Water solubility measurements for most of the compounds investigated, are reported for the first time expanding available data for branched and cyclic alkanes. Measured water solubilities spanned four orders of magnitude ranging from 0.3 μg/L to 250 μg/L. Good agreement was observed for selected alkanes tested in this work and reported in earlier literature demonstrating the robustness of the slow-stir water solubility technique. Comparisons of measured alkane water solubilities were also made with those predicted by commonly used quantitative structure-property relationship models (e.g. SPARC, EPIWIN, ACD/Labs). Correlations are also presented between alkane measured water solubilities and molecular size parameters (e.g. molar volume, solvent accessible molar volume) affirming a mechanistic description of empirical aqueous solubility results and prediction previously reported for a more limited set of alkanes. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Electron-stimulated desorption from condensed branched alkanes

    International Nuclear Information System (INIS)

    Kelber, J.A.; Knotek, M.L.

    1982-01-01

    Desorption of H + , CH 3+ , H 2+ , and D + have been measured as a function of electron excitation energy for solid neopentane, tetramethylsilane and two deuterated isomers of isobutane. The evidence shows that C-C (or Si-C) and C-H bonds are broken by electronic excitations localized on methyl groups, in contrast to CH 3+ production in gas-phase neopentane, and that these excitations are the final states of decay processes initiated by creation of a hole in the C2s level, or, in tetramethylsilane, the C2s/Si3s level. This is in accord with other evidence which shows that localized multi-valence hole states result in C-H, C-C, Si-C and Si-H dissociation, and that such states may be excited either directly or by shakeup, by decay from a C2s hole, or by decay for a C1s core hole. It is apparent then, that dissociation and desorption of ions from covalent materials is a multi (electron) hole mechanism, and that the means of localizing the excitation energy in such systems involves multi-hole correlation

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-10-15

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

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

    International Nuclear Information System (INIS)

    Yousaf, Sohail; Afzal, Muhammad; Reichenauer, Thomas G.; Brady, Carrie L.; Sessitsch, Angela

    2011-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.

    1992-06-30

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

  10. Theory and Experiment of Binary Diffusion Coefficient of n-Alkanes in Dilute Gases.

    Science.gov (United States)

    Liu, Changran; McGivern, W Sean; Manion, Jeffrey A; Wang, Hai

    2016-10-10

    Binary diffusion coefficients were measured for n-pentane, n-hexane, and n-octane in helium and of n-pentane in nitrogen over the temperature range of 300 to 600 K, using reversed-flow gas chromatography. A generalized, analytical theory is proposed for the binary diffusion coefficients of long-chain molecules in simple diluent gases, taking advantage of a recently developed gas-kinetic theory of the transport properties of nanoslender bodies in dilute free-molecular flows. The theory addresses the long-standing question about the applicability of the Chapman-Enskog theory in describing the transport properties of nonspherical molecular structures, or equivalently, the use of isotropic potentials of interaction for a roughly cylindrical molecular structure such as large normal alkanes. An approximate potential energy function is proposed for the intermolecular interaction of long-chain n-alkane with typical bath gases. Using this potential and the analytical theory for nanoslender bodies, we show that the diffusion coefficients of n-alkanes in typical bath gases can be treated by the resulting analytical model accurately, especially for compounds larger than n-butane.

  11. Structural Exploration of the Two HBI Alkanes in the Chinese Maoming Oil Shale

    Science.gov (United States)

    Liao, J.; Lu, H.; Wang, Q.; Zhou, Y., Sr.

    2017-12-01

    The Maoming oil shale is notable for its high rate of oil production and abundant biomarker compounds. Apart from the odd-numbered C31 and C33botryococcanes dominant and characteristic, two highly branched isoprenoid (HBI) alkanes (Fig. 1) were exclusively occurred (Brassell et al., 1986). The first identification of the two HBI alkanes in the Maoming oil shale was based on a comparison with the mass spectrum of C20 HBI (2,6,10-trimethyl-7-(3-methylbutyl)dodecane) (Yon et al., 1982; Rowland et al., 1985 ) from Rozel Point crude oil. Brassell et al (1986) thought that the characteristic ions at m/z 308 and 336 could be indicative of an additional C10 alkyl side chain on top of the characteristic ions of m/z 168 and 197 for the C20-HBI. However, the structural speculation seemed suspicious for not only their mass spectrum but also their co-chromatography results were not identical to the later synthesized C30 HBI alkane (Rowland and Robson, 1990). In addition, the source attribution of diatoms indicated by two C30 HBIs was inconsistent with the species of B race of Botryococcus braunii indicated by the dominant distribution of botryococcanes. Thus, the thirty-year-old structural assignment of the two C30 HBI alkanes may require confirmation. At first, the monomers of two HBIs were prepared by preparative gas chromatography. The HR-EI MS (436.5003) illustrated a formula of C31H64 rather than carbon numbered C30 HBIs. Moreover, two novel polymethyl alkane structures (I, II) could be yielded by 1D and 2D NMR results (Fig. 2), which completely different from that of previously speculated C30-HBIs (Fig. 2). According to the elucidated structure, the characteristic ions at m/z 308, 336, 434 and other irons at m/z 127, 211, 225, 281, 336 were mainly corresponded to relevant cleavages. Hence, their mass spectra were basically consistent with the structure determined from the NMR data. The new structural skeleton in our results for the two compounds does not support the

  12. Digital evidence

    Directory of Open Access Journals (Sweden)

    Lukić Tatjana

    2012-01-01

    Full Text Available Although computer makes human activities faster and easier, innovating and creating new forms of work and other kinds of activities, it also influenced the criminal activity. The development of information technology directly affects the development of computer forensics without which, it can not even imagine the discovering and proving the computer offences and apprehending the perpetrator. Information technology and computer forensic allows us to detect and prove the crimes committed by computer and capture the perpetrators. Computer forensics is a type of forensics which can be defined as a process of collecting, preserving, analyzing and presenting digital evidence in court proceedings. Bearing in mind, that combat against crime, in which computers appear as an asset or object of the offense, requires knowledge of digital evidence as well as specific rules and procedures, the author in this article specifically addresses the issues of digital evidence, forensic (computer investigation, specific rules and procedures for detecting, fixing and collecting digital evidence and use of this type of evidence in criminal proceedings. The author also delas with international standards regarding digital evidence and cyber-space investigation.

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

    OpenAIRE

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

    2014-01-01

    Should iron and copper be added to the environment to stimulate the natural bioremediation of marine oil spills? The key enzymes that catalyze the oxidation of alkanes require either iron or copper, and the concentration of these ions in seawater is vanishingly low. Nevertheless, the dependence of alkane oxidation activity on external metal concentrations remains unclear. This perspective will summarize what is known about the co-regulation of alkane oxidation and metal acquisition and pose a...

  14. Biodegradation of n-alkanes on oil-seawater interfaces at different temperatures and microbial communities associated with the degradation.

    Science.gov (United States)

    Lofthus, Synnøve; Netzer, Roman; Lewin, Anna S; Heggeset, Tonje M B; Haugen, Tone; Brakstad, Odd Gunnar

    2018-04-01

    Oil biodegradation studies have mainly focused on microbial processes in dispersions, not specifically on the interfaces between the oil and the seawater in the dispersions. In this study, a hydrophobic adsorbent system, consisting of Fluortex fabrics, was used to investigate biodegradation of n-alkanes and microbial communities on oil-seawater interfaces in natural non-amended seawater. The study was performed over a temperature range from 0 to 20 °C, to determine how temperature affected biodegradation at the oil-seawater interfaces. Biodegradation of n-alkanes were influenced both by seawater temperature and chain-length. Biotransformation rates of n-alkanes decreased by reduced seawater temperature. Low rate coefficients at a seawater temperature of 0 °C were probably associated with changes in physical-chemical properties of alkanes. The primary bacterial colonization of the interfaces was predominated by the family Oceanospirillaceae at all temperatures, demonstrating the wide temperature range of these hydrocarbonoclastic bacteria. The mesophilic genus Oleibacter was predominant at the seawater temperature of 20 °C, and the psychrophilic genus Oleispira at 5 and 0 °C. Upon completion of n-alkane biotransformation, other oil-degrading and heterotrophic bacteria became abundant, including Piscirickettsiaceae (Cycloclasticus), Colwelliaceae (Colwellia), Altermonadaceae (Altermonas), and Rhodobacteraceae. This is one of a few studies that describe the biodegradation of oil, and the microbial communities associated with the degradation, directly at the oil-seawater interfaces over a large temperature interval.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-03-16

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

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

    Science.gov (United States)

    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'.

  17. Cuticular n-alkane in leaves of seven Neotropical species of the family Lecythidaceae: a contribution to chemotaxonomy

    Directory of Open Access Journals (Sweden)

    Rejane Maria da Silva

    Full Text Available ABSTRACT Biosynthesized from very long-chain fatty acid wax precursors, n-alkanes make a valuable contribution to the taxonomy of plants. The alkane components of foliar epicuticles of seven Neotropical species of Lecythidaceae were investigated: Bertholletia excelsa, Cariniana legalis, Couroupita guianensis, Eschweilera alvimii, Eschweilera ovata, Gustavia augusta and Lecythis pisonis. Specimens were collected in the metropolitan area of Recife, Pernambuco, and their n-alkane fractions were analyzed by gas chromatography. The chemical relationships among the species were then evaluated using cophenetic correlation and UPGMA. Among the seven species, a total of 15 n-alkanes, with 21-35 carbon atoms, were identified and formed a consistent group of B. excelsa, C. guianensis, E. ovata, G. augusta, and L. pisonis with n-C31. The greatest similarities were found between B. excelsa and L. pisonis, and between C. guianensis and G. augusta. Nevertheless, a phenetic analysis based on a larger number of species is needed to better understand the chemotaxonomic value of epicuticular n-alkanes within the Lecythidaceae.

  18. Molecular dynamics simulation studies of mid-size liquid n-Alkanes, C12–C160

    International Nuclear Information System (INIS)

    Kwon, Tae Woo; Lee, Song Hi

    2015-01-01

    In this study, we report the results of molecular dynamics simulations (MD) for model systems of mid-size liquid n-alkanes (C 12 –C 160 ) at several temperatures (⁓2700 K) in canonical ensembles to calculate structural and dynamic properties (viscosity η, self-diffusion constant D, and monomeric friction constant ζ). For the small n-alkanes for n ≤ 80, the chains are clearly ≥ 1, which leads to the conclusion that the liquid n-alkanes are far away from the Rouse regime, but for the n-alkanes for n ≥ 120, the chains are ⁓ 1 and they are Gaussian. It is found that the long chains of these n-alkanes at high temperatures show abnormalities in density, viscosity, and monomeric friction constant. The mass and temperature dependences of structural and dynamic properties (η, D, and ζ) are discussed

  19. Role of cysteine residues in the structure, stability, and alkane producing activity of cyanobacterial aldehyde deformylating oxygenase.

    Directory of Open Access Journals (Sweden)

    Yuuki Hayashi

    Full Text Available 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-04-01

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

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

    Science.gov (United States)

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

    Energy Technology Data Exchange (ETDEWEB)

    Ragil, K.

    1996-10-18

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

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

    Science.gov (United States)

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

    2015-12-01

    Mixtures of light hydrocarbon gases are common in deep Gulf of Mexico cold-seep sediments, and are typically dissolved in pore fluids, adsorbed to sediment particles, trapped in methane ice, or as free gas. The dominant component in these natural gas mixtures is usually methane (>80% C1), but ethane (C2) and propane (C3) are nearly always present in trace amounts (95% of the methane produced at depth never reaches the water column. Production of C1 and C2 in deep-sea sediments has been historically attributed only to thermocatalytic processes, though limited data suggests production of C2/C3 compounds through the activity of archaea at depth. Furthermore, carbon isotopic data on ethane and propane from deep cores of Gulf of Mexico sediments suggest alkanogenesis at >3 m depth in the sediment column and alkane oxidation in uppermost oxidant-rich sediments. Additional studies have also isolated microorganisms capable of oxidizing ethane and propane in the laboratory, but field studies of microbial-driven dynamics of C2/C3 gases in cold-seep sediments are rare. Here, we present the results of a series of incubation experiments using sediment slurries culled from surface sediments from one of the most prolific natural oil and gas seeps in the Gulf of Mexico. Rates of alkane oxidation were measured under a variety of conditions to assess the surface-driven microbial controls on C2/C3 cycling in cold-seep environments. Such microbial processes are important in terms of the possible 'oxidative overprinting' of alkane isotopic signatures produced at depth, possibly obscuring typical microbial isotopic signals.

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

    Directory of Open Access Journals (Sweden)

    Michael eSchloter

    2014-03-01

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

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

    Science.gov (United States)

    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.

  6. Can Children Construct Inverse Relations in Arithmetic? Evidence for Individual Differences in the Development of Conceptual Understanding and Computational Skill

    Science.gov (United States)

    Gilmore, Camilla K.; Bryant, Peter

    2008-01-01

    Understanding conceptual relationships is an important aspect of learning arithmetic. Most studies of arithmetic, however, do not distinguish between children's understanding of a concept and their ability to identify situations in which it might be relevant. We compared 8- to 9-year-old children's use of a computational shortcut based on the…

  7. Interaction between Promoters Mn/Fe, Sulfate, and Zirconia in Accordingly Composed Alkane Isomerization Catalysts

    OpenAIRE

    Jentoft, F.; Hahn, A.; Wild, U.; Klose, B.; Jentoft, R.; Ressler, T.; Schlögl, R.; Häßner, C.; Köhler, K.

    2004-01-01

    Interaction between Promoters Mn/Fe, Sulfate, and Zirconia in Accordingly Composed Alkane Isomerization Catalysts F.C. Jentoft, A. Hahn, U. Wild, B.S. Klose, R.E. Jentoft, T. Ressler, R. Schlögl Department of Inorganic Chemistry, Fritz Haber Institute, Max Planck Society, Faradayweg 4-6, 14195 Berlin, Germany C. Häßner, K. Köhler Anorganisch-Chemisches Institut, Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany Introduction Promotion of sulfated zirconia (SZ) with man...

  8. Interaction between Promoters Mn/Fe, Sulfate, and Zirconia in Accordingly Composed Alkane Isomerization Catalysts

    OpenAIRE

    Jentoft, Friederike C.; Hahn, Alexander; Wild, Ute; Klose, Barbara S.; Jentoft, Rolf E.; Ressler, Thorsten; Schlögl, Robert; Häßner, Christian; Köhler, Klaus

    2004-01-01

    Interaction between Promoters Mn/Fe, Sulfate, and Zirconia in Accordingly Composed Alkane Isomerization Catalysts F.C. Jentoft, A. Hahn, U. Wild, B.S. Klose, R.E. Jentoft, T. Ressler, R. Schlögl Department of Inorganic Chemistry, Fritz Haber Institute, Max Planck Society, Faradayweg 4-6, 14195 Berlin, Germany C. Häßner, K. Köhler Anorganisch-Chemisches Institut, Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany Introduction Promotion of sulfated zi...

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

    Science.gov (United States)

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

    2011-12-01

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

  10. Pediatric hydrocephalus: systematic literature review and evidence-based guidelines. Part 3: Endoscopic computer-assisted electromagnetic navigation and ultrasonography as technical adjuvants for shunt placement.

    Science.gov (United States)

    Flannery, Ann Marie; Duhaime, Ann-Christine; Tamber, Mandeep S; Kemp, Joanna

    2014-11-01

    This systematic review was undertaken to answer the following question: Do technical adjuvants such as ventricular endoscopic placement, computer-assisted electromagnetic guidance, or ultrasound guidance improve ventricular shunt function and survival? The US National Library of Medicine PubMed/MEDLINE database and the Cochrane Database of Systematic Reviews were queried using MeSH headings and key words specifically chosen to identify published articles detailing the use of cerebrospinal fluid shunts for the treatment of pediatric hydrocephalus. Articles meeting specific criteria that had been delineated a priori were then examined, and data were abstracted and compiled in evidentiary tables. These data were then analyzed by the Pediatric Hydrocephalus Systematic Review and Evidence-Based Guidelines Task Force to consider evidence-based treatment recommendations. The search yielded 163 abstracts, which were screened for potential relevance to the application of technical adjuvants in shunt placement. Fourteen articles were selected for full-text review. One additional article was selected during a review of literature citations. Eight of these articles were included in the final recommendations concerning the use of endoscopy, ultrasonography, and electromagnetic image guidance during shunt placement, whereas the remaining articles were excluded due to poor evidence or lack of relevance. The evidence included 1 Class I, 1 Class II, and 6 Class III papers. An evidentiary table of relevant articles was created. CONCLUSIONS/RECOMMENDATION: There is insufficient evidence to recommend the use of endoscopic guidance for routine ventricular catheter placement. Level I, high degree of clinical certainty. The routine use of ultrasound-assisted catheter placement is an option. Level III, unclear clinical certainty. The routine use of computer-assisted electromagnetic (EM) navigation is an option. Level III, unclear clinical certainty.

  11. Upgrading light hydrocarbons via tandem catalysis: a dual homogeneous Ta/Ir system for alkane/alkene coupling.

    Science.gov (United States)

    Leitch, David C; Lam, Yan Choi; Labinger, Jay A; Bercaw, John E

    2013-07-17

    Light alkanes and alkenes are abundant but are underutilized as energy carriers because of their high volatility and low energy density. A tandem catalytic approach for the coupling of alkanes and alkenes has been developed in order to upgrade these light hydrocarbons into heavier fuel molecules. This process involves alkane dehydrogenation by a pincer-ligated iridium complex and alkene dimerization by a Cp*TaCl2(alkene) catalyst. These two homogeneous catalysts operate with up to 60/30 cooperative turnovers (Ir/Ta) in the dimerization of 1-hexene/n-heptane, giving C13/C14 products in 40% yield. This dual system can also effect the catalytic dimerization of n-heptane (neohexene as the H2 acceptor) with cooperative turnover numbers of 22/3 (Ir/Ta).

  12. Effect of solid phase on the selectivity of alkyl radical formation by gamma-irradiation of branched alkanes

    International Nuclear Information System (INIS)

    Koizumi, Hitoshi; Hashino, Masatoshi; Ichikawa, Tsuneki; Yoshida, Hiroshi

    1992-01-01

    ESR and electron spin echo measurements of alkyl radicals generated by γ-irradiation of glassy and crystalline branched alkanes C 10 ∼ C 13 have been carried out to elucidate the effect of molecular structure and solid phase on the selectivity of alkyl radical formation. Alkyl radicals generated and stabilized at 77 K in the glassy alkanes are secondary penultimate radicals. Tertiary radicals and secondary radicals other than the penultimate one are not generated either by hydrogen abstraction or from ionized or excited molecules. In the crystalline alkanes, however, a small amount of secondary internal radicals are generated in addition to the predominant formation of the secondary penultimate radicals. It is concluded that the detachment of C-H hydrogen preferentially takes place at the location where the motion of carbon atoms assisting the detachment of the C-H hydrogen easily occurs. (author)

  13. Influence of N-alkanes on adhesion of an air bubble to the surface of low-rank coals

    Energy Technology Data Exchange (ETDEWEB)

    Janczuk, B.; Wojcik, W.; Bialopiotrowicz, T. (Maria Curie-Sklodowska University, Lublin (Poland). Dept. of Physical Chemistry)

    1989-10-10

    Measurements of the detachment force of an air bubble from the surface of coals of the ranks: 31.1, 31.2, 32.1 and 32.2 were carried out. The coal surface was precovered with n-alkane film in the homologous series from n-hexane to n-hexadecane. The forces were compared with those calculated theoretically on the basis of the previously determined values of the surface free energy components and of the contact angles measured in a coal/n-alkane film-air bubble-water system. On the basis of the conducted measurements and calculations it was confirmed that the stability of the coal/n-alkane film-air bubble-water systems depends on the rank of the coal studied, the thickness and kind of the hydrocarbon film present on the coal surface, and on the water film pressure under the air bubble. The stability of n-alkane films on the surface of the coals studied is confirmed as smaller than the stability of these films on the surface of typical hydrophobic solids. By comparison of the measured and calculated stabilities of the coal/n-alkane film-air bubble-water system it appeared that the stabilities of such systems may be predicted on the basis of the contact angle of the coal/n-alkane film-air bubble-water system and of the dispersion and nondispersion components of the surface free energy of coal. 28 refs., 3 figs., 3 tabs.

  14. Biosynthesis of medium chain length alkanes for bio-aviation fuel by metabolic engineered Escherichia coli.

    Science.gov (United States)

    Wang, Meng; Nie, Kaili; Cao, Hao; Xu, Haijun; Fang, Yunming; Tan, Tianwei; Baeyens, Jan; Liu, Luo

    2017-09-01

    The aim of this work was to study the synthesis of medium-chain length alkanes (MCLA), as bio-aviation product. To control the chain length of alkanes and increase the production of MCLA, Escherichia coli cells were engineered by incorporating (i) a chain length specific thioesterase from Umbellularia californica (UC), (ii) a plant origin acyl carrier protein (ACP) gene and (iii) the whole fatty acid synthesis system (FASs) from Jatropha curcas (JC). The genetic combination was designed to control the product spectrum towards optimum MCLA. Decanoic, lauric and myristic acid were produced at concentrations of 0.011, 0.093 and 1.657mg/g, respectively. The concentration of final products nonane, undecane and tridecane were 0.00062mg/g, 0.0052mg/g, and 0.249mg/g respectively. Thioesterase from UC controlled the fatty acid chain length in a range of 10-14 carbons and the ACP gene with whole FASs from JC significantly increased the production of MCLA. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Recommended Vapor-Liquid Equilibrium Data. Part 2: Binary Alkanol-Alkane Systems

    Science.gov (United States)

    Góral, Marian; Oracz, Paweł; Skrzecz, Adam; Bok, Andrzej; Ma̧czyński, Andrzej

    2003-12-01

    The recommended vapor-liquid equilibrium (VLE) data for 36 binary systems involving primary, secondary, and tertiary alcohols with n-alkanes and isoalkanes [with the exception of 1-alkanols-n-alkane systems, which were presented in Part 1 of this series—J. Phys. Chem. Ref. Data 31(3), 702 (2002)] have been obtained after critical evaluation of all data (744 data sets) reported in the open literature up to the middle of 2002. The evaluation procedure consisted in combining the thermodynamic consistency tests, data correlation, comparison with enthalpy of mixing data, and comparison of VLE data for various mixtures. The data were correlated with equations based on local compositions concept as well as with equation of state appended with chemical term (EoSC) proposed by Góral. The recommended data are presented in the form of sheets containing tables of data, figures and auxiliary information. Each sheet corresponds to one system and contains three isotherms (spaced by at least 15 K) and one isobar (preferably at 101.32 kPa). Experimental gaps were completed with the predicted data.

  16. Jet-stirred reactor oxidation of alkane-rich FACE gasoline fuels

    KAUST Repository

    Chen, Bingjie

    2016-06-23

    Understanding species evolution upon gasoline fuel oxidation can aid in mitigating harmful emissions and improving combustion efficiency. Experimentally measured speciation profiles are also important targets for surrogate fuel kinetic models. This work presents the low- and high-temperature oxidation of two alkane-rich FACE gasolines (A and C, Fuels for Advanced Combustion Engines) in a jet-stirred reactor at 10. bar and equivalence ratios from 0.5 to 2 by probe sampling combined with gas chromatography and Fourier Transformed Infrared Spectrometry analysis. Detailed speciation profiles as a function of temperature are presented and compared to understand the combustion chemistry of these two real fuels. Simulations were conducted using three surrogates (i.e., FGA2, FGC2, and FRF 84), which have similar physical and chemical properties as the two gasolines. The experimental results reveal that the reactivity and major product distributions of these two alkane-rich FACE fuels are very similar, indicating that they have similar global reactivity despite their different compositions. The simulation results using all the surrogates capture the two-stage oxidation behavior of the two FACE gasolines, but the extent of low temperature reactivity is over-predicted. The simulations were analyzed, with a focus on the n-heptane and n-butane sub-mechanisms, to help direct the future model development and surrogate fuel formulation strategies.

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

    KAUST Repository

    Sarathy, Mani

    2015-01-01

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

  18. The upper explosion limit of lower alkanes and alkenes in air at elevated pressures and temperatures.

    Science.gov (United States)

    Van den Schoor, F; Verplaetsen, F

    2006-01-16

    The upper explosion limit (UEL) of ethane-air, propane-air, n-butane-air, ethylene-air and propylene-air mixtures is determined experimentally at initial pressures up to 30 bar and temperatures up to 250 degrees C. The experiments are performed in a closed spherical vessel with an internal diameter of 200 mm. The mixtures are ignited by fusing a coiled tungsten wire, placed at the centre of the vessel, by electric current. Flame propagation is said to have taken place if there is a pressure rise of at least 1% of the initial pressure after ignition of the mixture. In the pressure-temperature range investigated, a linear dependence of UEL on temperature and a bilinear dependence on pressure are found except in the vicinity of the auto-ignition range. A comparison of the UEL data of the lower alkanes shows that the UEL expressed as equivalence ratio (the actual fuel/air ratio divided by the stoichiometric fuel/air ratio) increases with increasing carbon number in the homologous series of alkanes.

  19. Chemical characterization of organosulfates in secondary organic aerosol derived from the photooxidation of alkanes

    Science.gov (United States)

    Riva, Matthieu; Da Silva Barbosa, Thais; Lin, Ying-Hsuan; Stone, Elizabeth A.; Gold, Avram; Surratt, Jason D.

    2016-09-01

    We report the formation of aliphatic organosulfates (OSs) in secondary organic aerosol (SOA) from the photooxidation of C10-C12 alkanes. The results complement those from our laboratories reporting the formation of OSs and sulfonates from gas-phase oxidation of polycyclic aromatic hydrocarbons (PAHs). Both studies strongly support the formation of OSs from the gas-phase oxidation of anthropogenic precursors, as hypothesized on the basis of recent field studies in which aromatic and aliphatic OSs were detected in fine aerosol collected from several major urban locations. In this study, dodecane, cyclodecane and decalin, considered to be important SOA precursors in urban areas, were photochemically oxidized in an outdoor smog chamber in the presence of either non-acidified or acidified ammonium sulfate seed aerosol. Effects of acidity and relative humidity on OS formation were examined. Aerosols collected from all experiments were characterized by ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS). Most of the OSs identified could be explained by formation of gaseous epoxide precursors with subsequent acid-catalyzed reactive uptake onto sulfate aerosol and/or heterogeneous reactions of hydroperoxides. The OSs identified here were also observed and quantified in fine urban aerosol samples collected in Lahore, Pakistan, and Pasadena, CA, USA. Several OSs identified from the photooxidation of decalin and cyclodecane are isobars of known monoterpene organosulfates, and thus care must be taken in the analysis of alkane-derived organosulfates in urban aerosol.

  20. Equivalent Alkane Carbon Number of Live Crude Oil: A Predictive Model Based on Thermodynamics

    Directory of Open Access Journals (Sweden)

    Creton Benoit

    2016-09-01

    Full Text Available We took advantage of recently published works and new experimental data to propose a model for the prediction of the Equivalent Alkane Carbon Number of live crude oil (EACNlo for EOR processes. The model necessitates the a priori knowledge of reservoir pressure and temperature conditions as well as the initial gas to oil ratio. Additionally, some required volumetric properties for hydrocarbons were predicted using an equation of state. The model has been validated both on our own experimental data and data from the literature. These various case studies cover broad ranges of conditions in terms of API gravity index, gas to oil ratio, reservoir pressure and temperature, and composition of representative gas. The predicted EACNlo values reasonably agree with experimental EACN values, i.e. determined by comparison with salinity scans for a series of n-alkanes from nC8 to nC18. The model has been used to generate high pressure high temperature data, showing competing effects of the gas to oil ratio, pressure and temperature. The proposed model allows to strongly narrow down the spectrum of possibilities in terms of EACNlo values, and thus a more rational use of equipments.

  1. Optimizing catalysis conditions to decrease aromatic hydrocarbons and increase alkanes for improving jet biofuel quality.

    Science.gov (United States)

    Cheng, Jun; Li, Tao; Huang, Rui; Zhou, Junhu; Cen, Kefa

    2014-04-01

    To produce quality jet biofuel with high amount of alkanes and low amount of aromatic hydrocarbons, two zeolites of HY and HZSM-5 supporting Ni and Mo were used as catalysts to convert soybean oil into jet fuel. Zeolite HY exhibited higher jet range alkane selectivity (40.3%) and lower jet range aromatic hydrocarbon selectivity (23.8%) than zeolite HZSM-5 (13.8% and 58.9%). When reaction temperature increased from 330 to 390°C, yield of jet fuel over Ni-Mo/HY catalyst at 4 MPa hydrogen pressure increased from 0% to 49.1% due to the shift of reaction pathway from oligomerization to cracking reaction. Further increase of reaction temperature from 390 to 410°C resulted in increased yield of jet range aromatic hydrocarbons from 18.7% to 30%, which decreased jet fuel quality. A high yield of jet fuel (48.2%) was obtained at 1 MPa low hydrogen pressure over Ni (8 wt.%)-Mo (12 wt.%)/HY catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Monisha Rastogi

    2015-05-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-15

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

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

    Directory of Open Access Journals (Sweden)

    Yasushi Kawashima

    2013-05-01

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

  5. Artificial Neural Network Modeling of Liquid Thermal Conductivity for alkanes, ketones and silanes

    Science.gov (United States)

    Latini, G.; Di Nicola, G.; Pierantozzi, M.; Coccia, G.; Tomassetti, S.

    2017-11-01

    The values of thermal conductivity λ at different temperatures for organic and inorganic compounds in the liquid phase is essential in the study of numerous processes, but experimental data are frequently not available with acceptable reliability or not available at all, since rigorous theoretical or semi-theoretical models of the liquid state are usually of poor practical use for engineering purposes. The Artificial Neural Network (ANN) approach is a very powerful tool and it can be a good indicator of the lowest limit achievable with a selected database and with a selected set of inputs. This study investigates the applicability of the ANN as an efficient tool for the prediction of pure organic compounds’ thermal conductivity of three important families such as alkanes, ketones and silanes, for a wide range of temperatures. The families of n-alkanes, ketones and silanes were chosen to verify the general reliability of the proposed method when used in large temperature ranges for very different organic families, above all the silanes (compounds containing silicon), whose liquid thermal conductivity is experimentally investigated in very few cases. This method appears to be successful: in all reduced temperature range, along or near the saturation line, the average absolute deviations between calculated and experimental thermal conductivity data are 0.19% and the maximum absolute ones 2.44%

  6. Tetradentate Schiff base ligands and their complexes: Synthesis, structural characterization, thermal, electrochemical and alkane oxidation

    Science.gov (United States)

    Ceyhan, Gökhan; Köse, Muhammet; McKee, Vickie; Uruş, Serhan; Gölcü, Ayşegül; Tümer, Mehmet

    Three Schiff base ligands (H2L1-H2L3) with N2O2 donor sites were synthesized by condensation of 1,5-diaminonapthalene with benzaldehyde derivatives. A series of Cu(II), Co(II), Ni(II), Mn(II) and Cr(III) complexes were prepared and characterized by spectroscopic and analytical methods. Thermal, electrochemical and alkane oxidation reactions of the ligands and their metal complexes were investigated. Extensive application of 1D (1H, 13C NMR) and 2D (COSY, HETCOR, HMBC and TOSCY) NMR techniques were used to characterize the structures of the ligands and establish the 1H and 13C resonance assignments of the three ligands. Ligands H2L1 and H2L3 were obtained as single crystals from THF solution and characterized by X-ray diffraction. Both molecules are centrosymmetric and asymmetric unit contains one half of the molecule. Catalytic alkane oxidation reactions with the transition metal complexes investigated using cyclohexane and cyclooctane as substrates. The Cu(II) and Cr(III) complexes showed good catalytic activity in the oxidation of cyclohexane and cyclooctane to desired oxidized products. Electrochemical and thermal properties of the compounds were also investigated.

  7. Catalytic conversion of light alkanes -- research and proof-of-concept stages

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.; Hancock, A.W. II

    1993-12-31

    Objective is to find new catalysts for direct reaction of methane, ethane, propane, butanes with O{sub 2} to form alcohols, and to develop practical processes for direct oxidative conversion of natural gas and its C{sub 1}-C{sub 4} components to produce alcohol-rich liquid oxygenates for use as alternative transportation fuels/environmentally superior reformulated gasolines. The proposed mechanism for oxidation activity of cytochrome P-450 and methane monoxygenase suggested that a catalyst able to reductively bind oxygen, not between Fe(III) center and a proton, but between two Fe(III) centers, might give the desired dioxygenase activity for alkane hydroxylation. Selective oxidation of light alkanes could be done by oxidation-active metal (Fe) centers in electron-deficient prophyrin-like macrocycles, polyoxoanions, and zeolites. In the isobutane conversion to tert-butanol proof-of-concept, it was found that nitro groups on the periphery of Fe porphyrin complexes give the greatest increase in Fe(III)/(II) reduction potential. 8 figs, 6 tabs, 40 refs.

  8. Prediction of the Flash Point of Binary and Ternary Straight-Chain Alkane Mixtures

    Directory of Open Access Journals (Sweden)

    X. Li

    2014-01-01

    Full Text Available The flash point is an important physical property used to estimate the fire hazard of a flammable liquid. To avoid the occurrence of fire or explosion, many models are used to predict the flash point; however, these models are complex, and the calculation process is cumbersome. For pure flammable substances, the research for predicting the flash point is systematic and comprehensive. For multicomponent mixtures, especially a hydrocarbon mixture, the current research is insufficient to predict the flash point. In this study, a model was developed to predict the flash point of straight-chain alkane mixtures using a simple calculation process. The pressure, activity coefficient, and other associated physicochemical parameters are not required for the calculation in the proposed model. A series of flash points of binary and ternary mixtures of straight-chain alkanes were determined. The results of the model present consistent experimental results with an average absolute deviation for the binary mixtures of 0.7% or lower and an average absolute deviation for the ternary mixtures of 1.03% or lower.

  9. Light alkane (mixed feed selective dehydrogenation using bi-metallic zeolite supported catalyst

    Directory of Open Access Journals (Sweden)

    Zeeshan Nawaz

    2009-12-01

    Full Text Available Light alkanes are the important intermediates of many refinery processes and their catalytic dehydrogenation gives corresponding alkenes. The aim behind this experimentation is to investigate reaction behavior of mixed alkanes during direct catalytic dehydrogenation and emphasis has been given to enhance propene. Bi-metallic zeolite supported catalyst Pt-Sn/ZSM-5 was prepared by sequentional impregnation method and characterized by BET, EDS and XRD. Direct dehydrogenation reaction is highly endothermic and its conversion is thermodynamically limited. Results showed that the increase in temperature increases the conversion to some extent but there is no overall effect on selectivity of propene. Increase in time-on-stream (TOS remarkably improves propene selectivity at the expense of lower conversion. The performances of bi-metallic zeolite based catalyst largely affected by coke deposition. The presence of butane and ethane adversely affected propane conversion. Optimum propene selectivity is about 48 %, obtained at 600 oC and time-on-stream 10 h.

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

    Science.gov (United States)

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

    2012-12-01

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

  11. Olefin metathesis over silica-supported molybdena catalysts activated by UV-irradiation in the presence of alkanes

    International Nuclear Information System (INIS)

    Subbotina, I.R.; Shelimov, B.N.; Kazanskij, V.B.

    1997-01-01

    It is established that molybdenum-silica catalysts (MoO 3 /SiO 2 ) applied after their irradiation by UV-light in the alkanes atmosphere acquire high activity in the reaction of propylen and hexene metathesis at the temperature of 293 K. The efficiency of photoactivated catalysts during these reactions is determined. It is shown that by UV-irradiation of MoO 3 /SiO 2 in presence of alkanes there take place the Mo 6+ ions conversion to Mo 5+ and Mo 4+ , formation the of Mo 4+ solid π-complexes with olefins and, probably, the surface carbene complexes Mo=CH-R

  12. The effect of initial diameter on rainbow positions and temperature distributions of burning single-component n-Alkane droplets

    Science.gov (United States)

    Li, Haipeng; Rosebrock, Christopher D.; Wriedt, Thomas; Mädler, Lutz

    2017-07-01

    The effect of initial diameter on rainbow positions of burning single-component n-Alkane droplets has been investigated experimentally for the first time. The droplet diameters are determined with interferometric laser imaging for droplet sizing, and the temperature distributions inside burning droplets are assessed by rainbow refractometry together with a droplet combustion model developed in our previous work. Temperature gradients inside burning droplets influence rainbow positions, which first make the experimental scattering angles of the rainbow maxima increase and then decrease. The variations of initial diameter lead to variations of both experimental rainbow maxima and simulated temperature of n-Alkane burning droplets.

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

    Science.gov (United States)

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

  14. Biooxidation of n-octane by a recombinant Escherichia coli in a two-liquid-phase system: Effect of medium components on cell growth and alkane oxidation activity

    NARCIS (Netherlands)

    FAVREBULLE, O; Witholt, Bernard

    1992-01-01

    When Escherichia coli hosts are transformed with the alk genes, which encode the alkane oxidation pathway of Pseudomonas oleovorans, the recombinants are capable of converting alkanes to alkanoic acids during growth in two-liquid-phase (aqueous-organic) media. In such media, the cells grow on

  15. Level-2 perspectives computed quickly and spontaneously: Evidence from eight- to 9.5-year-old children.

    Science.gov (United States)

    Elekes, Fruzsina; Varga, Máté; Király, Ildikó

    2017-11-01

    It has been widely assumed that computing how a scene looks from another perspective (level-2 perspective taking, PT) is an effortful process, as opposed to the automatic capacity of tracking visual access to objects (level-1 PT). Recently, adults have been found to compute both forms of visual perspectives in a quick but context-sensitive way, indicating that the two functions share more features than previously assumed. However, the developmental literature still shows the dissociation between automatic level-1 and effortful level-2 PT. In the current paper, we report an experiment showing that in a minimally social situation, participating in a number verification task with an adult confederate, eight- to 9.5-year-old children demonstrate similar online level-2 PT capacities as adults. Future studies need to address whether online PT shows selectivity in children as well and develop paradigms that are adequate to test preschoolers' online level-2 PT abilities. Statement of Contribution What is already known on this subject? Adults can access how objects appear to others (level-2 perspective) spontaneously and online Online level-1, but not level-2 perspective taking (PT) has been documented in school-aged children What the present study adds? Eight- to 9.5-year-olds performed a number verification task with a confederate who had the same task Children showed similar perspective interference as adults, indicating spontaneous level-2 PT Not only agent-object relations but also object appearances are computed online by eight- to 9.5-year-olds. © 2017 The British Psychological Society.

  16. On the evidence of extra mixing in models of 8 M⊙ computed with the new solar abundances

    Directory of Open Access Journals (Sweden)

    Scuflaire R.

    2013-03-01

    Full Text Available Stars more massive than about 3M⊙ are known to experience loops in the HR diagram during their core helium burning phase. Except for very massive stars the extent of their loops increases with the stellar mass. We show that a stellar evolution track for a 8M⊙ star computed with the new solar abundances [2] shows only a very tiny loop located near the red giant branch. An overshooting below the convective envelope is required to obtain a H-discontinuity located deep enough in the μ-gradient region and thus to allow the development of a loop in the HR diagram.

  17. Standoffish perhaps, but successful as well: evidence that avoidant attachment can be beneficial in professional tennis and computer science.

    Science.gov (United States)

    Ein-Dor, Tsachi; Reizer, Abira; Shaver, Phillip R; Dotan, Eyal

    2012-06-01

    Attachment-related avoidance and anxiety have repeatedly been associated with poorer adjustment in various social, emotional, and behavioral domains. We examined 2 domains in which avoidant individuals might be better equipped than their less avoidant peers to succeed and be satisfied--professional singles tennis and computer science. These fields may reward self-reliance, independence, and the ability to work without proximal social support from loved ones. In study 1, we followed 58 professional singles tennis players for 16 months and found that scores on attachment-related avoidance predicted a higher ranking, above and beyond the contributions of training and coping resources. In study 2, we sampled 100 students and found that those who scored higher on avoidance were happier with their choice of computer science as a career than those who scored lower on avoidance. Results are discussed in relation to the possible adaptive functions of certain personality characteristics often viewed as undesirable. © 2011 The Authors. Journal of Personality © 2011, Wiley Periodicals, Inc.

  18. Sensitive detection of n-alkanes using a mixed ionization mode proton-transfer-reaction mass spectrometer

    Directory of Open Access Journals (Sweden)

    O. Amador-Muñoz

    2016-11-01

    Full Text Available Proton-transfer-reaction mass spectrometry (PTR-MS is a technique that is widely used to detect volatile organic compounds (VOCs with proton affinities higher than water. However, n-alkanes generally have a lower proton affinity than water and therefore proton transfer (PT by reaction with H3O+ is not an effective mechanism for their detection. In this study, we developed a method using a conventional PTR-MS to detect n-alkanes by optimizing ion source and drift tube conditions to vary the relative amounts of different primary ions (H3O+, O2+, NO+ in the reaction chamber (drift tube. There are very few studies on O2+ detection of alkanes and the mixed mode has never been proposed before. We determined the optimum conditions and the resulting reaction mechanisms, allowing detection of n-alkanes from n-pentane to n-tridecane. These compounds are mostly emitted by evaporative/combustion process from fossil fuel use. The charge transfer (CT mechanism observed with O2+ was the main reaction channel for n-heptane and longer n-alkanes, while for n-pentane and n-hexane the main reaction channel was hydride abstraction (HA. Maximum sensitivities were obtained at low E ∕ N ratios (83 Td, low water flow (2 sccm and high O2+ ∕ NO+ ratios (Uso =  180 V. Isotopic 13C contribution was taken into account by subtracting fractions of the preceding 12C ion signal based on the number of carbon atoms and the natural abundance of 13C (i.e., 5.6 % for n-pentane and 14.5 % for n-tridecane. After accounting for isotopic distributions, we found that PT cannot be observed for n-alkanes smaller than n-decane. Instead, protonated water clusters of n-alkanes (M  ⋅  H3O+ species were observed with higher abundance using lower O2+ and higher water cluster fractions. M  ⋅  H3O+ species are probably the source for the M + H+ species observed from n-decane to n-tridecane. Normalized sensitivities to O2+ or to the sum of O2++

  19. Hydrogen isotope ratios of terrestrial leaf wax n-alkanes from the Tibetan Plateau: Controls on apparent enrichment factors, effect of vapor sources and implication for altimetry

    Science.gov (United States)

    Zhang, Xiaolong; Xu, Baiqing; Günther, Franziska; Mügler, Ines; Lange, Markus; Zhao, Huabiao; Li, Jiule; Gleixner, Gerd

    2017-08-01

    Empirical evidence suggested that the altitudinal dependence of hydrogen isotope ratios of leaf wax n-alkanes (δDwax) can be used to estimate paleoaltitudinal changes. However, the application of δDwax-based paleoaltimetry remains difficult, as the impacts of evaporative, transpirative and biosynthetic processes on hydrogen isotope fractionations in changing environments and the influence of likely changing water vapor sources are not well explored. For this study, we sampled stream waters, soils and plant leaves along two transects spanning large gradients of altitude, precipitation amount, vapor source, temperature and vegetation type on the Tibetan Plateau (TP). δD values of stream water (as an approximation for δDp), soil water (δDsw) and plant leaf water (δDlw) as well as leaf wax n-alkanes were measured in order to quantify isotopic fractionations in the formation of leaf waxes. Most interestingly, we found a strong negative correlation between the evapotranspirative enrichment of leaf water against precipitation (εlw-p), which combines the effects of soil evaporation and leaf transpiration, and the biosynthetic hydrogen isotope fractionation (εwax-lw), which describes isotopic enrichment between leaf wax and leaf water. The relationship yields a steady apparent isotopic enrichment factor (εwax-p) between leaf wax and precipitation, which is independent from climatic parameters and has an average value of -107 ± 26‰ for grasses (monocotyledons) and -77 ± 22‰ for trees (dicotyledons). Since the terrestrial n-alkanes, especially n-C27 and n-C29, in sediments are derived from trees and grasses, the likely change of the vegetation type in the uplift of mountains can change the isotopic estimates by about ±30‰, which corresponds to an altitudinal change of ∼1600 m. We, therefore, suggest that hydrogen isotope ratio of sedimentary n-C31 alkane, which is mainly derived from grasses might be better proxies to reconstruct paleoaltitudes. Our large

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

    KAUST Repository

    Badra, Jihad

    2015-01-01

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

  1. Reconstructing tropical cyclone frequency using hydrogen isotope ratios of sedimentary n-alkanes in northern Queensland, Australia

    NARCIS (Netherlands)

    Soelen, E.E. van; Wagner-Cremer, F.; Sinninghe Damsté, J.S.; Reichart, G.-J.

    2013-01-01

    A peat record from Quincan Crater (Queensland, Australia), spanning the past 200 years, was used to test if hydrogen isotope ratios of leaf wax long-chain n-alkanes derived of higher plants can be used to reconstruct past tropical cyclone activity. Queensland is frequently impacted by tropical

  2. Isolation and characterization of alkane degrading bacteria from petroleum reservoir waste water in Iran (Kerman and Tehran provenances).

    Science.gov (United States)

    Hassanshahian, Mehdi; Ahmadinejad, Mohammad; Tebyanian, Hamid; Kariminik, Ashraf

    2013-08-15

    Petroleum products spill and leakage have become two major environmental challenges in Iran. Sampling was performed in the petroleum reservoir waste water of Tehran and Kerman Provinces of Iran. Alkane degrading bacteria were isolated by enrichment in a Bushnel-Hass medium, with hexadecane as sole source of carbon and energy. The isolated strains were identified by amplification of 16S rDNA gene and sequencing. Specific primers were used for identification of alkane hydroxylase gene. Fifteen alkane degrading bacteria were isolated and 8 strains were selected as powerful degradative bacteria. These 8 strains relate to Rhodococcus jostii, Stenotrophomonas maltophilia, Achromobacter piechaudii, Tsukamurella tyrosinosolvens, Pseudomonas fluorescens, Rhodococcus erythropolis, Stenotrophomonas maltophilia, Pseudomonas aeruginosa genera. The optimum concentration of hexadecane that allowed high growth was 2.5%. Gas chromatography results show that all strains can degrade approximately half of hexadecane in one week of incubation. All of the strains have alkane hydroxylase gene which are important for biodegradation. As a result, this study indicates that there is a high diversity of degradative bacteria in petroleum reservoir waste water in Iran. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

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

    DEFF Research Database (Denmark)

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

    2002-01-01

    to the interface. At still higher coverages and at temperatures below the bulk melting point at T-b=341 K, solid bulk particles coexist on top of the "perpendicular film." For higher temperatures in the range T-bT-s, a uniformly thick fluid film wets to the parallel film phase. This structure of the alkane/SiO2...

  5. A nonequilibrium simulation method for calculating tracer diffusion coefficients of small solutes in n-alkane liquids and polymers

    NARCIS (Netherlands)

    van der Vegt, N.F.A.; Briels, Willem J.; Wessling, Matthias; Strathmann, H.

    1998-01-01

    The tracer diffusion coefficients of methane in n-alkane liquids of increasing chain length were calculated by measuring the friction from short time nonequilibrium molecular dynamics simulations. The frictional constant was calculated from the exponentially decaying distance between two methane

  6. Carbon isotope analysis of n-alkanes in dust from the lower atmosphere over the eastern Atlantic

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Schefuß, E.; Ratmeyer, V.; Stuut, J-B.W.; Jansen, J.H.F.

    2003-01-01

    Atmospheric dust samples collected along a transect off the West African coast have been investigated for their lipid content and compound-specific stable carbon isotope compositions. The saturated hydrocarbon fractions of the organic solvent extracts consist mainly of long-chain n-alkanes derived

  7. Spectroscopic Analyses on Reaction Intermediates Formed during Chlorination of Alkanes with NaOCl Catalyzed by a Nickel Complex

    NARCIS (Netherlands)

    Draksharapu, Apparao; Codolà, Zoel; Gómez, Laura; Lloret-Fillol, Julio; Browne, Wesley R; Costas, Miquel

    2015-01-01

    The spectroscopic, electrochemical, and crystallographic characterization of [((Me,H)PyTACN)Ni(II)(CH3CN)2](OTf)2 (1) ((Me,H)PyTACN = 1-(2-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane, OTf = CF3SO3) is described together with its reactivity with NaOCl. 1 catalyzes the chlorination of alkanes

  8. Oil contamination in surface sediment of Anzali Wetland in Iran is primarily even carbon number n-alkanes.

    Science.gov (United States)

    Azimi-Yancheshmeh, Rokhsareh; Riyahi-Bakhtiari, Alireza; Savabieasfahani, Mozhgan

    2017-10-29

    To determine the extent of oil contamination and biodegradation in Anzali Wetland of Iran, we examined aliphatic hydrocarbons in surface sediment of this area (n=20). Petroleum hydrocarbon levels (mean 1585 ± 1117; range 316 to 4358 μg g- 1 dry weight) were similar in value to reports from other highly contaminated areas, such as New York Bight, Saudi and Kuwaiti coasts of the Persian Gulf, and Dubai shorelines. Even carbon homologs dominated distribution of n-alkanes in surface sediment of Anzali, which is rarely reported elsewhere. Multiple factors used in our study point to petrogenic source for n-alkanes in Anzali Wetland. Anzali receives multiple industrial and agricultural runoffs from the surrounding area. Shipping industry and oil industry are responsible for a major portion of pollutants entering Anzali. Municipal wastewater discharges are another source of Anzali pollution. To determine why even carbon number n-alkanes predominate in Anzali, we examined the following indices: existence of unresolved complex mixtures (UCM), ratio of UCM to resolved alkanes (RA), ratio of low-molecular weight to high-molecular weight molecules, presence of degraded oil residue, high-relative biodegradation, and the degree of hydrocarbon weathering in the surface sediment of the area. Our findings corroborate with such predominance.

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

    DEFF Research Database (Denmark)

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

    1996-01-01

    The predictive local composition model is applied to multicomponent hydrocarbon systems with long-chain n-alkanes as solutes. The results show that it can successfully be extended to highorder systems and accurately predict the solid appearance temperature, also known as cloud point, in solutions...

  10. Striatal disorders dissociate mechanisms of enhanced and impaired response selection — Evidence from cognitive neurophysiology and computational modelling

    Directory of Open Access Journals (Sweden)

    Christian Beste

    2014-01-01

    Full Text Available Paradoxically enhanced cognitive processes in neurological disorders provide vital clues to understanding neural function. However, what determines whether the neurological damage is impairing or enhancing is unclear. Here we use the performance of patients with two disorders of the striatum to dissociate mechanisms underlying cognitive enhancement and impairment resulting from damage to the same system. In a two-choice decision task, Huntington's disease patients were faster and less error prone than controls, yet a patient with the rare condition of benign hereditary chorea (BHC was both slower and more error prone. EEG recordings confirmed significant differences in neural processing between the groups. Analysis of a computational model revealed that the common loss of connectivity between striatal neurons in BHC and Huntington's disease impairs response selection, but the increased sensitivity of NMDA receptors in Huntington's disease potentially enhances response selection. Crucially the model shows that there is a critical threshold for increased sensitivity: below that threshold, impaired response selection results. Our data and model thus predict that specific striatal malfunctions can contribute to either impaired or enhanced selection, and provide clues to solving the paradox of how Huntington's disease can lead to both impaired and enhanced cognitive processes.

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

    DEFF Research Database (Denmark)

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

    2005-01-01

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

  12. Recommended Vapor-Liquid Equilibrium Data. Part 1: Binary n-Alkanol-n-Alkane Systems

    Science.gov (United States)

    Góral, Marian; Oracz, Paweł; Skrzecz, Adam; Bok, Andrzej; Ma̧czyński, Andrzej

    2002-09-01

    The recommended vapor-liquid equilibrium (VLE) data for 39 binary n-alcohol-n-alkane systems have been obtained after critical evaluation of all data (490 data sets) reported in the open literature up to the middle of 2001. The evaluation procedure consisted in combining the thermodynamic consistency tests, data correlation, comparison with enthalpy of mixing data, and comparison of VLE data for various mixtures. The data were correlated with equations based on the local compositions concept as well as with the equation of state appended with a chemical term (EoSC) proposed by Góral. The recommended data are presented in the form of individual pages containing tables of data, figures, and auxiliary information. Each page corresponds to one system and contains three isotherms (spaced by at least 15 K) and one isobar (preferably at 101.32 kPa). Experimental gaps were completed with the predicted data.

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

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    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.

  14. Effect of Thermal Maturation on n-alkanes and Kerogen in Preserved Organic Matter: Implications for Paleoenvironment Biomarkers

    Science.gov (United States)

    Craven, O. D.; Longbottom, T. L.; Hockaday, W. C.; Blackaby, E.

    2017-12-01

    Understanding the effects of maturity on biomarkers is vital in assessing biomarker reliability in mature sediments. It is well known for n-alkanes that increased maturity shortens chain lengths and decreases the odd over even preference however, the amount of change in these variables has not been determined for different maturities and types of preserved organic matter. For this reason, it is difficult to judge the trustworthiness of even lightly matured samples for paleoenvironment reconstruction. Another complication is the difficulty of accurately determining maturity as many maturity indicators are error-prone or not appropriate at low maturities. Using hydrous pyrolysis, we artificially matured black shale samples with type I (lacustrine) and type II (marine) kerogen to measure changes in n-alkane length and odd over even preference. Whole rock samples underwent hydrous pyrolysis for 72 hours, at 250 °C, 300 °C, 325 °C, 350 °C, and 375 °C to cover a wide maturity range. From the immature and artificially matured samples, the bitumen was extracted and the saturate fraction was separated using column chromatography. The saturate fraction was analyzed for n-alkanes using gas chromatography-mass spectroscopy. Kerogen structural changes were also measured using solid-state 13C NMR to relate changes in n-alkane biomarkers to changes in kerogen structure. Results show that for type I bitumen the n-alkanes did not change at low maturities considered premature in terms of oil generation (FaC) decreases greatly from immature to low maturities, leveling off between 300 °C and 325 °C, allowing FaC to be a tool for determining low maturities.

  15. Temperature-Dependent Oxygen Effect on NMR D-[Formula: see text] Relaxation-Diffusion Correlation of n-Alkanes.

    Science.gov (United States)

    Shikhov, Igor; Arns, Christoph H

    2016-01-01

    Nuclear magnetic resonance (NMR) diffusion-relaxation correlation experiments ( D -[Formula: see text]) are widely used for the petrophysical characterisation of rocks saturated with petroleum fluids both in situ and for laboratory analyses. The encoding for both diffusion and relaxation offers increased fluid typing contrast by discriminating fluids based on their self-diffusion coefficients, while relaxation times provide information about the interaction of solid and fluid phases and associated confinement geometry (if NMR responses of pure fluids at particular temperature and pressure are known). Petrophysical interpretation of D -[Formula: see text] correlation maps is typically assisted by the "standard alkane line"-a relaxation-diffusion correlation valid for pure normal alkanes and their mixtures in the absence of restrictions to diffusing molecules and effects of internal gradients. This correlation assumes fluids are free from paramagnetic impurities. In situations where fluid samples cannot be maintained at air-free state the diffusion-relaxation response of fluids shift towards shorter relaxation times due to oxygen paramagnetic relaxation enhancement. Interpretation of such a response using the "standard alkane line" would be erroneous and is further complicated by the temperature-dependence of oxygen solubility for each component of the alkane mixture. We propose a diffusion-relaxation correlation suitable for interpretation of low-field NMR D -[Formula: see text] responses of normal alkanes and their mixtures saturating rocks over a broad temperature range, in equilibrium with atmospheric air. We review and where necessary revise existing viscosity-relaxation correlations. Findings are applied to diffusion-relaxation dependencies taking into account the temperature dependence of oxygen solubility and solvent vapour pressure. The effect is demonstrated on a partially saturated carbonate rock.

  16. [Eco-environmental evolution inferred from n-alkanes and delta13C records in the sediments of Shijiu Lake].

    Science.gov (United States)

    Ou, Jie; Wang, Yan-Hua; Yang, Hao; Hu, Jian-Fang; Chen, Xia; Zou, Jun; Xie, Yun

    2013-02-01

    The study of global changes has focused on the reconstruction of paleovegetation and paleoclimate by n-alkanes and delta13C. 210Pb contents were measured for dating. The distribution characteristics of n-alkanes and delta13C were used to indicate the source of the organic matter in the sediments of Shijiu Lake. The relationship between modern eco-environmental evolution and human behaviors was discussed in this paper. The combination characteristics of n-alkanes showed a significant odd-even predominance in high-carbon number and main peak at C29, suggesting that the organic matter in the sediments were mainly derived from macrophytes and terrestrial higher plants. The delta13C contents of C27, C29 and C31 n-alkanes were analyzed. Results indicated that C3 plants are the dominant species. The distribution characteristics of n-alkanes and delta13C in different periods revealed the impact of human behaviors on Shijiu Lake. From 1862 to 1970, the low relative content of TOC, TN, C17-C25 and the light delta13C25-31 values showed that there were less human behaviors effects on Shijiu Lake and the eco-environment around the lake was stable. From 1970 to 1983, the relative content of TOC, TN and C17-C25 increased significantly, the delta13C25-31 values became weight. In this period, large areas of Shijiu Lake turned into farmland; pollution by fertilizers and pesticides was serious; large amounts of industrial and domestic wastewater were discharged into the lake. All these human behaviors resulted in the degradation of terrestrial higher plants around the lake. Meanwhile, the eutrophication levels were significantly increased. From 1983 to 2010, the relative contents of TOC, TN and C17-C25 were still in high-value ranges, the problem of eutrophication was not effectively controlled and the eco-environment of Shijiu Lake was relatively degradated.

  17. Evidence of neurofibromatosis type 1 in a multi-morbid Inca child mummy: A paleoradiological investigation using computed tomography.

    Science.gov (United States)

    Panzer, Stephanie; Wittig, Holger; Zesch, Stephanie; Rosendahl, Wilfried; Blache, Sandra; Müller-Gerbl, Magdalena; Hotz, Gerhard

    2017-01-01

    In this study, an Inca bundle was examined using computed tomography (CT). The primary aim was to determine the preservation status of bony and soft tissues, the sex, the age at the time of death, possible indicators for disease or even the cause of death, as well as the kind of mummification. A secondary aim was to obtain a brief overview of the wrapping in order to gain additional information on the cultural background. The bundle belongs to the Museum of Cultures in Basel, Switzerland, and was bought in Munich, Germany, in 1921. Radiocarbon dating of the superficial textile yielded a calibrated age between 1480 and 1650 AD. The mummy was investigated using multi-slice CT with slice thickness of 0.75 mm and 110 kilovolt. For standardized assessment of soft tissue preservation, a recently developed checklist was applied. CT revealed the mummy of a seven to nine year old boy with superior preservation of bony and soft tissues allowing detailed assessment. Indicators of neurofibromatosis type 1 (paravertebral and cutaneous neurofibromas, a breast neurofibroma, sphenoid wing dysplasia), Chagas disease (dilatation of the esophagus, stomach, rectum, and large amounts of feces), and lung infection (pleural adherence, calcifications), probably due to tuberculosis, were found. Furthermore, signs of peri-mortem violence (transection of the chest and a defect in the abdominal wall) were detected. CT images revealed a carefully performed wrapping. CT examination of the Inca bundle proved to be an important non-destructive examination method. Standardized assessment, especially of the soft tissue structures, allowed for diagnoses of several diseases, indicating a multi-morbid child at the time of death. The careful wrapping pointed to a ceremonial burial. Within the cultural background, the signs of fatal violence were discussed as a possible result of war, murder, accident, or human sacrifice.

  18. Human computation as a new method for evidence-based knowledge transfer in Web-based guideline development groups: proof of concept randomized controlled trial.

    Science.gov (United States)

    Heselmans, Annemie; Aertgeerts, Bert; Donceel, Peter; Van de Velde, Stijn; Vanbrabant, Peter; Ramaekers, Dirk

    2013-01-17

    Guideline developers use different consensus methods to develop evidence-based clinical practice guidelines. Previous research suggests that existing guideline development techniques are subject to methodological problems and are logistically demanding. Guideline developers welcome new methods that facilitate a methodologically sound decision-making process. Systems that aggregate knowledge while participants play a game are one class of human computation applications. Researchers have already proven that these games with a purpose are effective in building common sense knowledge databases. We aimed to evaluate the feasibility of a new consensus method based on human computation techniques compared to an informal face-to-face consensus method. We set up a randomized design to study 2 different methods for guideline development within a group of advanced students completing a master of nursing and obstetrics. Students who participated in the trial were enrolled in an evidence-based health care course. We compared the Web-based method of human-based computation (HC) with an informal face-to-face consensus method (IC). We used 4 clinical scenarios of lower back pain as the subject of the consensus process. These scenarios concerned the following topics: (1) medical imaging, (2) therapeutic options, (3) drugs use, and (4) sick leave. Outcomes were expressed as the amount of group (dis)agreement and the concordance of answers with clinical evidence. We estimated within-group and between-group effect sizes by calculating Cohen's d. We calculated within-group effect sizes as the absolute difference between the outcome value at round 3 and the baseline outcome value, divided by the pooled standard deviation. We calculated between-group effect sizes as the absolute difference between the mean change in outcome value across rounds in HC and the mean change in outcome value across rounds in IC, divided by the pooled standard deviation. We analyzed statistical significance of

  19. Dehalogenimonas alkenigignens sp. nov., a chlorinated-alkane-dehalogenating bacterium isolated from groundwater.

    Science.gov (United States)

    Bowman, Kimberly S; Nobre, M Fernanda; da Costa, Milton S; Rainey, Fred A; Moe, William M

    2013-04-01

    Two strictly anaerobic bacterial strains, designated IP3-3(T) and SBP-1, were isolated from groundwater contaminated by chlorinated alkanes and alkenes at a Superfund Site located near Baton Rouge, Louisiana (USA). Both strains reductively dehalogenate a variety of polychlorinated aliphatic alkanes, including 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane and 1,2,3-trichloropropane, when provided with hydrogen as the electron donor. To clarify their taxonomic position, strains IP3-3(T) and SBP-1 were characterized using a polyphasic approach. Both IP3-3(T) and SBP-1 are mesophilic, non-spore-forming, non-motile and Gram-stain-negative. Cells of both strains are irregular cocci with diameters of 0.4-1.1 µm. Both are resistant to ampicillin and vancomycin. The genomic DNA G+C contents of strains IP3-3(T) and SBP-1 are 55.5±0.4 and 56.2±0.2 mol% (HPLC), respectively. Major cellular fatty acids include C18 : 1ω9c, C16 : 0, C14 : 0 and C16 : 1ω9c. 16S rRNA gene sequence based phylogenetic analyses indicated that the strains cluster within the phylum Chloroflexi most closely related to but distinct from the species Dehalogenimonas lykanthroporepellens (96.2 % pairwise similarity) and Dehalococcoides mccartyi (90.6 % pairwise similarity). Physiological and chemotaxonomic traits as well as phylogenetic analysis support the conclusion that these strains represent a novel species within the genus Dehalogenimonas for which the name Dehalogenimonas alkenigignens sp. nov. is proposed. The type strain is IP3-3(T) ( = JCM 17062(T) = NRRL B-59545(T)).

  20. Subnanometer-sized Pt/Sn alloy cluster catalysts for the dehydrogenation of linear alkanes.

    Science.gov (United States)

    Hauser, Andreas W; Gomes, Joseph; Bajdich, Michal; Head-Gordon, Martin; Bell, Alexis T

    2013-12-21

    The reaction pathways for the dehydrogenation of ethane, propane, and butane, over Pt are analyzed using density functional theory (DFT). Pt nanoparticles are represented by a tetrahedral Pt4 cluster. The objectives of this work were to establish which step is rate limiting and which one controls the selectivity for forming alkenes as opposed to causing further dehydrogenation of adsorbed alkenes to produce precursors responsible for catalyst deactivation due to coking. Further objectives of this work are to identify the role of adsorbed hydrogen, derived from H2 fed together with the alkane, on the reaction pathway, and the role of replacing one of the four Pt atoms by a Sn atom. A comparison of Gibbs free energies shows that in all cases the rate-determining step is cleavage of a C-H bond upon alkane adsorption. The selectivity to alkene formation versus precursors to coking is dictated by the relative magnitudes of the activation energies for alkene desorption and dehydrogenation of the adsorbed alkene. The presence of an adsorbed H atom on the cluster facilitates alkene desorption relative to dehydrogenation of the adsorbed alkene. Substitution of a Sn atom in the cluster to produce a Pt3Sn cluster leads to a downward shift of the potential energy surface for the reaction and causes an increase of the activity of the catalyst as suggested by recent experiments due to the lower net activation barrier for the rate limiting step. However, the introduction of Sn does not alter the relative activation barriers for gas-phase alkene formation versus loss of hydrogen from the adsorbed alkene, the process leading to the formation of coke precursors.

  1. Quantifying alkane emissions in the Eagle Ford Shale using boundary layer enhancement

    Science.gov (United States)

    Roest, Geoffrey; Schade, Gunnar

    2017-09-01

    The Eagle Ford Shale in southern Texas is home to a booming unconventional oil and gas industry, the climate and air quality impacts of which remain poorly quantified due to uncertain emission estimates. We used the atmospheric enhancement of alkanes from Texas Commission on Environmental Quality volatile organic compound monitors across the shale, in combination with back trajectory and dispersion modeling, to quantify C2-C4 alkane emissions for a region in southern Texas, including the core of the Eagle Ford, for a set of 68 days from July 2013 to December 2015. Emissions were partitioned into raw natural gas and liquid storage tank sources using gas and headspace composition data, respectively, and observed enhancement ratios. We also estimate methane emissions based on typical ethane-to-methane ratios in gaseous emissions. The median emission rate from raw natural gas sources in the shale, calculated as a percentage of the total produced natural gas in the upwind region, was 0.7 % with an interquartile range (IQR) of 0.5-1.3 %, below the US Environmental Protection Agency's (EPA) current estimates. However, storage tanks contributed 17 % of methane emissions, 55 % of ethane, 82 % percent of propane, 90 % of n-butane, and 83 % of isobutane emissions. The inclusion of liquid storage tank emissions results in a median emission rate of 1.0 % (IQR of 0.7-1.6 %) relative to produced natural gas, overlapping the current EPA estimate of roughly 1.6 %. We conclude that emissions from liquid storage tanks are likely a major source for the observed non-methane hydrocarbon enhancements in the Northern Hemisphere.

  2. Nutrient-enhanced n-alkanes biodegradation and succession of bacterial communities

    Science.gov (United States)

    Sun, Yanyu; Wang, Hui; Li, Junde; Wang, Bin; Qi, Cancan; Hu, Xiaoke

    2017-11-01

    Bioremediation, is an effective and environment-friendly method of cleaning up crude oil pollution after an oil spill. However, the in situ bioremediation of crude oil is usually inhibited by deficiency of inorganic nutrients. To understand the effects of nutrient addition on the bioremediation of crude oil and the succession of bacterial communities during process of bioremediation, microcosms containing oil-contaminated sediments were constructed and biodegradation of crude oil was assessed based on the depletion of different ingredients. We used two culture-independent methods, denaturing gradient gel electrophoresis and a 16S rRNA gene based clone library, to analyze the succession of bacterial communities. The results suggested n-alkanes were degraded after 30 days and that nutrient amendments significantly improved the efficiency of their biodegradation. Moreover, oil contamination and nutrient amendments could dramatically change bacterial community structures. Lower diversity was detected after being contaminated with oil. For instance, bacterial clones affiliated with the phylum Armatimonadetes, Firmicutes, Gemmatimonadetes, and Planctomycetes and the class Deltaproteobacteria and Epsilonproteobacteria could not be identified after 30 days of incubation with crude oil. However, "professional hydrocarbonocastic bacteria" became abundant in samples treated with oil during the bioremediation period, while these clones were almost completely absent from the control plots. Interestingly, bioinformatics analysis showed that even when dramatic differences in oil biodegradation efficiency were observed, bacterial communities in the plots with nutrient amendments were not significantly different from those in plots treated with oil alone. These findings indicated that nutrient amendments could stimulate the process of biodegradation but had less impact on bacterial communities. Overall, nutrient amendments might be able to stimulate the growth of n-alkane degrading

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

    International Nuclear Information System (INIS)

    Bravo-Perez, Graciela; Alvarez-Idaboy, J. Raul; Jimenez, Annia Galano; Cruz-Torres, Armando

    2005-01-01

    Reactions of OH with methane, ethane, propane, i-butane, and n-butane have been modeled using ab initio (MP2) and hybrid DFT (BHandHLYP) methods, and the 6-311G(d,p) basis set. Furthermore, single-point calculations at the CCSD(T) level were carried out at the optimized geometries. The rate constants have been calculated using the conventional transition-state theory (CTST). Arrhenius equations are proposed in the temperature range of 250-650 K. Hindered Internal Rotation partition functions calculations were explicitly carried out and included in the total partition functions. These corrections showed to be relevant in the determination of the pre-exponential parameters, although not so important as in the NO 3 + alkane reactions [G. Bravo-Perez, J.R. Alvarez-Idaboy, A. Cruz-Torres, M.E. Ruiz, J. Phys. Chem. A 106 (2002) 4645]. The explicit participation of the tunnel effect has been taken into account. The calculated rate coefficients provide a very good agreement with the experimental data. The best agreement for the overall alkane + OH reactions seemed to occur when the BHandHLYP geometries and partition functions are used. For propane and i-butane, in addition to the respective secondary and tertiary H-abstraction channels, the primary one has been considered. These pathways are confirmed to be significant in spite of the large differences in activation energies between primary and secondary or primary and tertiary channels, respectively of propane and i-butane reactions and should not be disregarded

  4. review of the archaeological evidence for food plants from the British Isles: an example of the use of the Archaeobotanical Computer Database (ABCD

    Directory of Open Access Journals (Sweden)

    Philippa Tomlinson

    1996-09-01

    Full Text Available The Archaeobotanical Computer Database is an electronic compilation of information about remains of plants from archaeological deposits throughout the British Isles. For the first time, this wealth of published data, much of it post-dating Godwin's (1975 History of the British Flora has been brought together in a form in which the user can explore the history of a particular species or group of plants, or investigate the flora and vegetation of a particular archaeological period or part of the British Isles. The database contains information about the sites, deposits and samples from which the remains in question have been recovered, together with details of the plant parts identified and their mode of preservation. It also provides some interpretative guidance concerning the integrity of contexts and the reliability of dating as an aid to judging the quality of the data available. In this paper the compilers of the ABCD make use of the database in order to review the archaeological evidence for food plants in the British Isles. The paper begins with a definition of its scope, examining the concept of a "food plant" and the taphonomy of plant remains on British archaeological sites. It then summarises the principal changes in food plants from the prehistoric period to post-medieval times. The body of the paper is a detailed discussion of the evidence for the use of berries, other fruits, vegetables, pulses, herbs and flavourings, oil plants, cereals and nuts. Finally, the paper compares the archaeological evidence with that known from documentary sources. Readers will be able to view the archaeological evidence as distribution maps and will be able to explore aspects of the database online, enabling queries by taxa, site or worker. Instructions on obtaining electronic copies of the database tables and registering as an ABCD user are also included.

  5. The evidence-policy divide: a 'critical computational linguistics' approach to the language of 18 health agency CEOs from 9 countries.

    Science.gov (United States)

    Bell, Erica; Seidel, Bastian M

    2012-10-30

    There is an emerging body of literature suggesting that the evidence-practice divide in health policy is complex and multi-factorial but less is known about the processes by which health policy-makers use evidence and their views about the specific features of useful evidence. This study aimed to contribute to understandings of how the most influential health policy-makers view useful evidence, in ways that help explore and question how the evidence-policy divide is understood and what research might be supported to help overcome this divide. A purposeful sample of 18 national and state health agency CEOs from 9 countries was obtained. Participants were interviewed using open-ended questions that asked them to define specific features of useful evidence. The analysis involved two main approaches 1)quantitative mapping of interview transcripts using Bayesian-based computational linguistics software 2)qualitative critical discourse analysis to explore the nuances of language extracts so identified. The decision-making, conclusions-oriented world of policy-making is constructed separately, but not exclusively, by policy-makers from the world of research. Research is not so much devalued by them as described as too technical- yet at the same time not methodologically complex enough to engage with localised policy-making contexts. It is not that policy-makers are negative about academics or universities, it is that they struggle to find complexity-oriented methodologies for understanding their stakeholder communities and improving systems. They did not describe themselves as having a more positive role in solving this challenge than academics. These interviews do not support simplistic definitions of policy-makers and researchers as coming from two irreconcilable worlds. They suggest that qualitative and quantitative research is valued by policy-makers but that to be policy-relevant health research may need to focus on building complexity-oriented research methods for

  6. The evidence-policy divide: a ‘critical computational linguistics’ approach to the language of 18 health agency CEOs from 9 countries

    Directory of Open Access Journals (Sweden)

    Bell Erica

    2012-10-01

    Full Text Available Abstract Background There is an emerging body of literature suggesting that the evidence-practice divide in health policy is complex and multi-factorial but less is known about the processes by which health policy-makers use evidence and their views about the specific features of useful evidence. This study aimed to contribute to understandings of how the most influential health policy-makers view useful evidence, in ways that help explore and question how the evidence-policy divide is understood and what research might be supported to help overcome this divide. Methods A purposeful sample of 18 national and state health agency CEOs from 9 countries was obtained. Participants were interviewed using open-ended questions that asked them to define specific features of useful evidence. The analysis involved two main approaches 1quantitative mapping of interview transcripts using Bayesian-based computational linguistics software 2qualitative critical discourse analysis to explore the nuances of language extracts so identified. Results The decision-making, conclusions-oriented world of policy-making is constructed separately, but not exclusively, by policy-makers from the world of research. Research is not so much devalued by them as described as too technical— yet at the same time not methodologically complex enough to engage with localised policy-making contexts. It is not that policy-makers are negative about academics or universities, it is that they struggle to find complexity-oriented methodologies for understanding their stakeholder communities and improving systems. They did not describe themselves as having a more positive role in solving this challenge than academics. Conclusions These interviews do not support simplistic definitions of policy-makers and researchers as coming from two irreconcilable worlds. They suggest that qualitative and quantitative research is valued by policy-makers but that to be policy-relevant health research may

  7. Technology-enabled academic detailing: computer-mediated education between pharmacists and physicians for evidence-based prescribing.

    Science.gov (United States)

    Ho, Kendall; Nguyen, Anne; Jarvis-Selinger, Sandra; Novak Lauscher, Helen; Cressman, Céline; Zibrik, Lindsay

    2013-09-01

    Academic detailing (AD) is the practice of specially trained pharmacists with detailed medication knowledge meeting with physicians to share best practices of prescribing. AD has demonstrated efficacy in positively influencing physicians' prescribing behavior. Nevertheless, a key challenge has been that physicians in rural and remote locations, or physicians who are time challenged, have limited ability to participate in face-to-face meetings with academic detailers, as these specially trained academic detailers are primarily urban-based and limited in numbers. To determine the feasibility of using information technologies to facilitate communication between academic detailers and physicians (known as Technology-Enabled Academic Detailing or TEAD) through a comparison to traditional face-to-face academic detailing (AD). Specifically, TEAD is compared to AD in terms of the ability to aid physicians in acquiring evidence-informed prescribing information on diabetes-related medications, measured in terms of time efficiency, satisfaction of both physicians and pharmacists, and quality of knowledge exchange. General Practitioner Physicians (n=105) and pharmacists (n=12) were recruited from across British Columbia. Pharmacists were trained to be academic detailers on diabetes medication usage. Physicians were assigned to one of four intervention groups to receive four academic detailing sessions from trained pharmacists. Intervention groups included: (1) AD only, (2) TEAD only, (3) TEAD crossed over to AD at midpoint, and (4) AD crossed over to TEAD at midpoint. Evaluation included physician-completed surveys before and after each session, pharmacist logs after each detailing session, interviews and focus groups with physicians and pharmacists at study completion, as well as a technical support log to record all phone calls and emails from physicians and pharmacists regarding any technical challenges during the TEAD sessions, or usage of the web portal. Because

  8. Evidence-based investigation of the influence of computer-aided detection of polyps on screening of colon cancer with CT colonography

    International Nuclear Information System (INIS)

    Yoshida, Hiroyuki

    2008-01-01

    Computed tomographic colonography (CTC), also known as virtual colonoscopy, is a CT examination of the colon for colorectal neoplasms. Recent large-scale clinical trials have demonstrated that CTC yields sensitivity comparable to optical colonoscopy in the detection of clinically significant polyps in a screening population, making CTC a promising technique for screening of colon cancer. For CTC to be a clinically practical means of screening, it must reliably and consistently detect polyps with high accuracy. However, high-level expertise is required to interpret the resulting CT images to find polyps, resulting in variable diagnostic accuracy among radiologists in the detection of polyps. A key technology to overcome this problem and to bring CTC to prime time for screening of colorectal cancer is computer-aided detection (CAD) of polyps. CAD automatically detects the locations of suspicious polyps in CTC images and presents them to radiologists. CAD has the potential to increase diagnostic performance in the detection of polyps as well as to reduce variability of the diagnostic accuracy among radiologists. This paper presents an evidence-based investigation of the influence of CAD on screening of colon cancer with CTC by describing the benefits of using CAD in the diagnosis of CTC, the fundamental CAD scheme for the detection of polyps in CTC, its detection performance, the effect on the improvement of detection performance, as well as the current and future challenges in CAD. (author)

  9. Automatic construction and validation of models of combustion of alkanes and ethers; Construction automatique et validation de modeles cinetiques de combustion d'alcanes et d'ethers

    Energy Technology Data Exchange (ETDEWEB)

    Glaude, P.A.

    1999-07-01

    The reformulation of fuels for the abatement of pollutants emission requires the construction of detailed chemical models of the combustion of hydrocarbons. The manual writing of these chemical mechanisms is complex. Thus, an automatic generator of alkanes and ethers combustion models has been developed. The models include a base of the small species reactions, a detailed and exhaustive primary mechanism of the reagents consumption and a simplified secondary mechanism. The necessary kinetic and thermodynamic data are supplied. Beside this computer code development, the kinetic schemes and the velocity constants used have been defined. The validations of this system were performed with the simulation of the combustion of n-butane, n-heptane and iso-octane, pure and in mixtures, of n-octane and n-decane for the alkanes. MTBE, ETBE and their mixtures with n-heptane were studied in the case of ethers. The analysis of the models allows to show the expert-system characteristic of the generator by proposing a-priori simplification rules for the mechanisms. The reaction ways of the different species are studied, together with the formation of the products. The most sensible parameters of the models and the reactions that determine the global behaviour of the chemical systems are examined. Finally, some explanations are proposed to explain the differences in the behaviour of molecules, in particular with respect to self-ignition. (J.S.)

  10. Immaterial Evidence

    Directory of Open Access Journals (Sweden)

    Ivanov N. A.

    2012-11-01

    Full Text Available It is substantiated in the article that some of the objects which either could serve as instruments of a crime for criminal actions, or they were obtained through the commission of a crime, are immaterial objects, and they may be conditionally designated as evidence. The author relates to immaterial evidence physical fields, radiation, undocumented information, computer programs, property rights, intangible benefits, heat and electric power, and information processes.

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

    Science.gov (United States)

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

    2014-06-01

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

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

    Science.gov (United States)

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

    2012-12-01

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

  13. Chemotaxonomic implications of the n-alkane composition and the nonacosan-10-ol content in Picea omorika, Pinus heldreichii, and Pinus peuce.

    Science.gov (United States)

    Nikolić, Biljana; Tešević, Vele; Bojović, Srdjan; Marin, Petar D

    2013-04-01

    The n-alkane composition and the nonacosan-10-ol content in the needle cuticular waxes of Serbian spruce (Picea omorika), Bosnian pine (Pinus heldreichii), and Macedonian pine (Pinus peuce) were compared. The amount of nonacosan-10-ol in the needle waxes of P. omorika was higher than those in P. heldreichii and P. peuce. The range of n-alkanes was also wider in P. omorika (C18 -C35 ) than in P. heldreichii and P. peuce (C18 -C33 ). The dominant n-alkanes were C29 in the needle waxes of P. omorika, C23 , C27 , and C25 in those of P. heldreichii, and C29 , C25 , C27 , and C23 in those of P. peuce. The waxes of P. omorika contained higher amounts of n-alkanes C29 , C31 , and C33 , while those of P. heldreichii and P. peuce had higher contents of n-alkanes C21 , C22 , C23 , C24 , and C26 . The principal component analysis of the contents of nine n-alkanes showed a clear separation of the Serbian spruce populations from those of the two investigated pine species, which partially overlapped. The separation of the species was due to high contents of the n-alkanes C29 and C31 (P. omorika), C19 , C20 , C21 , C22 , C23 , and C24 (P. heldreichii), and C28 (P. peuce). Cluster analysis also showed a clear separation between the P. omorika populations on one side and the P. heldreichii and P. peuce populations on the other side. The n-alkane and terpene compositions are discussed in the light of their usefulness in chemotaxonomy as well as with regard to the biogeography and phylogeny of these rare and endemic conifers. Copyright © 2013 Verlag Helvetica Chimica Acta AG, Zürich.

  14. Physiological Adaptations Involved in Alkane Assimilation at a Low Temperature by Rhodococcus sp. Strain Q15†

    Science.gov (United States)

    Whyte, L. G.; Slagman, S. J.; Pietrantonio, F.; Bourbonnière, L.; Koval, S. F.; Lawrence, J. R.; Inniss, W. E.; Greer, C. W.

    1999-01-01

    We examined physiological adaptations which allow the psychrotroph Rhodococcus sp. strain Q15 to assimilate alkanes at a low temperature (alkanes are contaminants which are generally insoluble and/or solid at low temperatures). During growth at 5°C on hexadecane or diesel fuel, strain Q15 produced a cell surface-associated biosurfactant(s) and, compared to glucose-acetate-grown cells, exhibited increased cell surface hydrophobicity. A transmission electron microscopy examination of strain Q15 grown at 5°C revealed the presence of intracellular electron-transparent inclusions and flocs of cells connected by an extracellular polymeric substance (EPS) when cells were grown on a hydrocarbon and morphological differences between the EPS of glucose-acetate-grown and diesel fuel-grown cells. A lectin binding analysis performed by using confocal scanning laser microscopy (CSLM) showed that the EPS contained a complex mixture of glycoconjugates, depending on both the growth temperature and the carbon source. Two glycoconjugates [β-d-Gal-(1-3)-d-GlcNAc and α-l-fucose] were detected only on the surfaces of cells grown on diesel fuel at 5°C. Using scanning electron microscopy, we observed strain Q15 cells on the surfaces of octacosane crystals, and using CSLM, we observed strain Q15 cells covering the surfaces of diesel fuel microdroplets; these findings indicate that this organism assimilates both solid and liquid alkane substrates at a low temperature by adhering to the alkane phase. Membrane fatty acid analysis demonstrated that strain Q15 adapted to growth at a low temperature by decreasing the degree of saturation of membrane lipid fatty acids, but it did so to a lesser extent when it was grown on hydrocarbons at 5°C; these findings suggest that strain Q15 modulates membrane fluidity in response to the counteracting influences of low temperature and hydrocarbon toxicity. PMID:10388690

  15. Excess enthalpies of binary mixtures of 1-hexene with some branched alkanes at the temperature 298.15 K

    International Nuclear Information System (INIS)

    Wang, Zhaohui; Benson, George C.; Lu, Benjamin C.-Y.

    2004-01-01

    Measurements of excess molar enthalpies at the temperature 298.15 K in a flow microcalorimeter are reported for the five binary mixtures formed by mixing 1-hexene with the branched alkanes: 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, and 2,2,4-trimethylpentane. Smooth Redlich-Kister representations of the results are described. It was found that the Liebermann-Fried model also provided good representations of the results

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

    Directory of Open Access Journals (Sweden)

    Amy V. Callaghan

    2013-05-01

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

  17. Substrate specificity and reaction mechanism of purified alkane hydroxylase from the hydrocarbonoclastus bacterium Alcanivorax borkumensis (AbAlkB)

    Science.gov (United States)

    Naing, Swe-Htet; Parvez, Saba; Pender-Cudlip, Marilla; Groves, John T.

    2013-01-01

    An alkane hydroxylase from the marine organism Alcanivorax borkumensis (AbAlkB) was purified. The purified protein retained high activity in an assay with purified rubredoxin (AlkG), purified maize ferridoxin reductase, NADPH, and selected substrates. The reaction mechanism of the purified protein was probed using the radical clock substrates bicyclo[4.1.0]heptane (norcarane), bicyclo[3.1.0]hexane (bicyclohexane), methylphenylcyclopropane and deuterated and non-deuterated cyclohexane. The distribution of products from the radical clock substrates supports the hypothesis that purified AbAlkB hydroxylates substrates by forming a substrate radical. Experiments with deuterated cyclohexane indicate that the rate-determining step has significant C-H bond breaking character. The products formed from a number of differently shaped and sized substrates were characterized to determine the active site constraints of this AlkB. AbAlkB can catalyze the hydroxylation of a large number of aromatic compounds and linear and cyclic alkanes. It does not catalyze the hydroxylation of alkanes with a chain length longer than 15 carbons, nor does it hydroxylate sterically hindered C-H bonds. PMID:23337786

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-01

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

  19. Similarity and Scaling of Turbulent Flame Speeds for Expanding Premixed Flames of C4-C8 n -alkanes

    Science.gov (United States)

    Wu, Fujia; Saha, Abhishek; Chaudhuri, Swetaprovo; Yang, Sheng; Law, Chung K.

    2013-11-01

    We experimentally investigated the propagation speed of constant-pressure expanding flames in near isotropic turbulence using a dual-chamber, fan-stirred vessel. The motivation is to test whether the fuel similarity concept among C4-C8 n-alkanes on laminar flames also holds for turbulent flames. Previously it was found that the laminar flame speed and Markstein length are almost identical for C4-C8 n-alkanes. If this fuel similarity concept can also be shown for turbulent flames, it will suggest a canonical flame structure for large hydrocarbon fuels, i . e . , large fuels always decompose to small C0-C4 fuel fragments before being oxidized, and would significantly simplify the description of the flames. Preliminary results show that in the flamelet and thin-reaction zone, turbulent flame speeds of C4-C8 n-alkanes are indeed largely similar at various conditions, thereby suggesting the fuel similarity for turbulent flames. In addition, it is found that the normalized turbulent flame speed also approximately scales with the square root of an appropriately-defined Reynolds number recently found for C0-C4 fuels. This work was supported by the AFOSR under the technical monitoring of Dr. Chiping Li.

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

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

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

  1. Observation of Weak C-H...O Hydrogen Bonding by Unactivated Alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xue B.; Woo, Hin-koon; Boggavarapu, Kiran; Wang, Lai S.

    2005-08-12

    Weak C-H...O hydrogen bonding has been recognized to play a major role in biological molecular structures and functions. A newly developed low-temperature photoelectron spectroscopy apparatus is used here to study the C-H...O hydrogen bonding between unactivated alkanes and the carboxylate functional group. We observed that gaseous linear carboxylates, CH3(CH2)nCO2-, assume folded structures at low temperatures due to weak C-H...O hydrogen bonding between the terminal CH3 and CO2- groups for n-5. Temperature-dependent studies showed that the folding transition depends on both the temperature and the aliphatic chain length. Theoretical calculations revealed that for n = 3-8, the folded conformations are more stable than the linear structures, but C-H...O hydrogen bonding only forms for species with n-5 due to steric constraint in the smaller species. One C-H...O hydrogen-bond is formed in the n = 5 and 6 species, whereas two C-H...O hydrogen-bonds are formed for n = 7 and 8. Comparison of the photoelectron spectral shifts for the folded relative to the linear conformations yielded lower limits for the strength of the C-H...O hydrogen-bonds in CH3(CH2)nCO2-, ranging from 1.2 kcal/mol for n = 5 to 4.4 kcal/mol for n = 8.

  2. The effect of the naphthenic ring on the VLE of (carbon dioxide + alkane) mixtures

    International Nuclear Information System (INIS)

    Sima, Sergiu; Milanesio, Juan Manuel; Ramello, Juan Ignacio; Cismondi, Martin; Secuianu, Catinca; Feroiu, Viorel; Geană, Dan

    2016-01-01

    Highlights: • Isothermal VLE data are reported for CO 2 + cyclopentane, +cyclohexane binary systems. • Critical points were measured for the carbon (dioxide + cyclopentane) system. • The phase behaviour of systems is predicted by RKPR and PR EoS. • Double retrograde behaviour phenomenon is predicted by RKPR model. - Abstract: Isothermal (vapour + liquid) equilibrium (VLE) data for the binary systems (carbon dioxide + cyclopentane) and (carbon dioxide + cyclohexane) were determined using a (static + analytical) method with phases sampling by rapid online sample injectors (ROLSI) coupled to a gas chromatograph (GC) for analysis. The VLE behaviour for these systems was also analysed based on the PR and RKPR equations of state (EoS) and different available data from the literature, both critical and subcritical. It is clearly shown how CO 2 is more soluble and miscible with normal alkanes than with the corresponding cycloalkanes. Predictions based on the general correlation of available data in wide ranges of conditions suggest the appearance of double retrograde behaviour at least for (CO 2 + cyclohexane) mixtures with very low contents of the hydrocarbon in CO 2 , being this phenomenon very much related to asymmetry of the system. The existence of this phenomenon has not been experimentally confirmed yet for these systems and should be explored.

  3. Heat capacities and thermal diffusivities of n-alkane acid ethyl esters—biodiesel fuel components

    Science.gov (United States)

    Bogatishcheva, N. S.; Faizullin, M. Z.; Nikitin, E. D.

    2017-09-01

    The heat capacities and thermal diffusivities of ethyl esters of liquid n-alkane acids C n H2 n-1O2C2H5 with the number of carbon atoms in the parent acid n = 10, 11, 12, 14, and 16 are measured. The heat capacities are measured using a DSC 204 F1 Phoenix heat flux differential scanning calorimeter (Netzsch, Germany) in the temperature range of 305-375 K. Thermal diffusivities are measured by means of laser flash method on an LFA-457 instrument (Netzsch, Germany) at temperatures of 305-400 K. An equation is derived for the dependence of the molar heat capacities of the investigated esters on temperature. It is shown that the dependence of molar heat capacity C p,m (298.15 K) on n ( n = 1-6) is close to linear. The dependence of thermal diffusivity on temperature in the investigated temperature range is described by a first-degree polynomial, but thermal diffusivity a (298.15 K) as a function of n has a minimum at n = 5.

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

    Science.gov (United States)

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

    2013-05-01

    A new methodology has been developed for the determination of secondary alkane sulfonates (SAS), an anionic surfactant, in environmental matrices. Sediment and sludge samples were extracted using pressurized liquid extraction and sonication, whereas wastewater and surface water samples were processed using solid-phase extraction. Extraction recoveries were acceptable for both aqueous (78-120%) and solid samples (83-100%). Determination of SAS was carried out by high or ultra performance liquid chromatography - mass spectrometry using ion trap and time-of-flight detectors. The methodology was applied to samples from Guadalete River (SW Spain), where SAS concentrations below 1 μg L(-1) were measured in surface water, and from 72 to 9737 μg kg(-1) in sediments. Differential partitioning was observed for SAS homologues as those having a longer hydrocarbon chain which preferentially sorbed onto particulate matter. A preliminary environmental risk assessment also showed that SAS measured levels were not harmful to the aquatic community in the sampling area. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Thermodynamics of the hydrophobic effect. III. Condensation and aggregation of alkanes, alcohols, and alkylamines.

    Science.gov (United States)

    Matulis, D

    2001-10-18

    Knowledge of the energetics of the low solubility of non-polar compounds in water is critical for the understanding of such phenomena as protein folding and biomembrane formation. Solubility in water can be considered as one leg of the three-part thermodynamic cycle - vaporization from the pure liquid, hydration of the vapor in aqueous solution, and aggregation of the substance back into initial pure form as an immiscible phase. Previous studies on the model compounds n-alkanes, 1-alcohols, and 1-aminoalkanes have noted that the thermodynamic parameters (Gibbs free energy, DeltaG; enthalpy, DeltaH; entropy, DeltaS; and heat capacity, DeltaC(p)) associated with these three processes are generally linear functions of the number of carbons in the alkyl chains. Here we assess the accuracy and limitations of the assumption of additivity of CH(2) group contributions to the thermodynamic parameters for vaporization, hydration, and aggregation. Processes of condensation from pure gas to liquid and aqueous solution to aggregate are compared. Hydroxy, amino, and methyl headgroup contributions are estimated, liquid and solid aggregates are distinguished. Most data in the literature were obtained for compounds with short aliphatic hydrocarbon tails. Here we emphasize long aliphatic chain behavior and include our recent experimental data on long chain alkylamine aggregation in aqueous solution obtained by titration calorimetry and van't Hoff analysis. Contrary to what is observed for short compounds, long aliphatic compound aggregation has a large exothermic enthalpy and negative entropy.

  6. Laboratory spectroscopic analyses of electron irradiated alkanes and alkenes in solar system ices

    Science.gov (United States)

    Hand, K. P.; Carlson, R. W.

    2012-03-01

    We report results from laboratory experiments of 10 keV electron irradiation of thin ice films of water and short-chain hydrocarbons at ˜10-8 Torr and temperatures ranging from 70-100 K. Hydrocarbon mixtures include water with C3H8, C3H6, C4H10 (butane and isobutane), and C4H8, (1-butene and cis/trans-2-butene). The double bonds of the alkenes in our initial mixtures were rapidly destroyed or converted to single carbon bonds, covalent bonds with hydrogen, bonds with -OH (hydroxyl), bonds with oxygen (C-O), or double bonds with oxygen (carbonyl). Spectra resulting from irradiation of alkane and alkene ices are largely indistinguishable; the initial differences in film composition are destroyed and the resulting mixture includes long-chain, branched aliphatics, aldehydes, ketones, esters, and alcohols. Methane was observed as a product during radiolysis but CO was largely absent. We find that while some of the carbon is oxidized and lost to CO2 formation, some carbon is sequestered into highly refractory, long-chain aliphatic compounds that remain as a thin residue even after the ice film has been raised to standard temperature and pressure. We conclude that the high availability of hydrogen in our experiments leads to the formation of the formyl radical which then serves as the precursor for formaldehyde and polymerization of longer hydrocarbon chains.

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

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1992-12-31

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

  8. SAXS study of transient pre-melting in chain-folded alkanes

    International Nuclear Information System (INIS)

    Ungar, G.; Wills, H.H.

    1990-01-01

    A pronounced pre-melting effect is observed in chain-folded crystals of pure monodisperse n-alkane C 246 H 494 . The effect is reversible on a short time scale, but at longer times the once-folded chain crystals are irreversibly lost as slow chain extension proceeds by solid diffusion well below the melting point. The melting process is thus monitored by rapid time-resolved small-angle X-ray (SAXS) measurements, using synchrotron radiation. The results show that the observed pronounced broadening of the DSC melting endotherm for chain-folded crystals is entirely due to genuine pre-melting of lamellar surfaces. Although a significant portion of material is already molten below the final melting point of chain-folded crystals T F , no recrystallization in the chain-extended form can occur until the cores of the crystalline lamellae melt at T F . Pre-melting of extended chain crystals is significantly less pronounced than that of folded chain crystals

  9. An investigation of heat effects in N-alkanes and asphaltenes systems

    Energy Technology Data Exchange (ETDEWEB)

    Stachowiak, C.; Grolier, J.P.E.; Randzio, S.L. [Univ. Blaise Pascal, Lab. de Thermodynamiqueet Genie Chimique, Aubiere (France); Achard, C.; Rogalski, M.; Voguie, J.R. [Univ. de Metz, Lab. de Thermodynamique et d' Analyse Chimique, Metz (France)

    2000-08-01

    We report results of studies carried out on the heat effects observed during the dilution of asphaltenic crude oil by n-alkanes. The dilution process induces aspheltene flocculation. However, the flocculation is not a first order phase transition and no strong heat effect is expected. The experimental results show that significant endo- and exo-thermic effects occur in this case. Titration calorimetry and inverse chromatography were used to elucidate the nature and the intensity of these thermal phenomena. The calorimetric titration of two crude oils by n-heptane was performed at ambient temperature. Then, the two oils were stabilised with behenic and titrated by n-heptane. Behenic acid, CH{sub 3}(CH{sub 2}){sub 20} CO{sub 2}H, has dispersing effect on asphaltenes and influences the flocculation onset. The chromatographic study was performed using columns coated with asphaltenes or with mixtures containing asphaltenes, in the temperature range between 340 and 520 K. Indirect enthalpic data obtained by this method over wide temperature ranges complete the direct calorimetric measurements. It can be hypothesised that observed heat effects are mainly due to the modifications of the asphaltenes structure. The objective of this work is to evaluate the possibility of using calorimetric methods to controlling flocculation processes in crude oils. (ln)

  10. Modification by SiO2 of Alumina Support for Light Alkane Dehydrogenation Catalysts

    Directory of Open Access Journals (Sweden)

    Giyjaz E. Bekmukhamedov

    2016-10-01

    Full Text Available Due to the continuously rising demand for C3–C5 olefins it is important to improve the performance of catalysts for dehydrogenation of light alkanes. In this work the effect of modification by SiO2 on the properties of the alumina support and the chromia-alumina catalyst was studied. SiO2 was introduced by impregnation of the support with a silica sol. To characterize the supports and the catalysts the following techniques were used: low-temperature nitrogen adsorption; IR-spectroscopy; magic angle spinning 29Si nuclear magnetic resonance; temperature programmed desorption and reduction; UV-Vis-, Raman- and electron paramagnetic resonance (EPR-spectroscopy. It was shown that the modifier in amounts of 2.5–7.5 wt % distributed on the support surface in the form of SiOx-islands diminishes the interaction between the alumina support and the chromate ions (precursor of the active component. As a result, polychromates are the compounds predominantly stabilized on the surface of the modified support; under thermal activation of the catalyst and are reduced to the amorphous Cr2O3. This in turn leads to an increase in the activity of the catalyst in the dehydrogenation of isobutane.

  11. Decimal representations are not distinct from natural number representations – Evidence from a combined eye-tracking and computational modelling approach

    Directory of Open Access Journals (Sweden)

    Stefan eHuber

    2014-04-01

    Full Text Available Decimal fractions comply with the base-10 notational system of natural Arabic numbers. Nevertheless, recent research suggested that decimal fractions may be represented differently than natural numbers because two number processing effects (i.e., semantic interference and compatibility effects differed in their size between decimal fractions and natural numbers. In the present study, we examined whether these differences indeed indicate that decimal fractions are represented differently from natural numbers. Therefore, we provided an alternative explanation for the semantic congruity effect, namely a string length congruity effect. Moreover, we suggest that the smaller compatibility effect for decimal fractions compared to natural numbers was driven by differences in processing strategy (sequential vs. parallel.To evaluate this claim, we manipulated the tenth and hundredth digits in a magnitude comparison task with participants' eye movements recorded, while the unit digits remained identical. In addition, we evaluated whether our empirical findings could be simulated by an extended version of our computational model originally developed to simulate magnitude comparisons of two-digit natural numbers. In the eye-tracking study, we found evidence that participants processed decimal fractions more sequentially than natural numbers because of the identical leading digit. Importantly, our model was able to account for the smaller compatibility effect found for decimal fractions. Moreover, string length congruity was an alternative account for the prolonged reaction times for incongruent decimal pairs. Consequently, we suggest that representations of natural numbers and decimal fractions do not differ.

  12. n-alkanes from Paepalanthus Mart. species (Eriocaulaceae n-alcanos de espécies de Paepalanthus Mart. (Eriocaulaceae

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    Lourdes Campaner dos Santos

    2005-12-01

    Full Text Available This work presents the study of nonpolar compounds from plants belonging to the genus Paepalanthus Mart. (Eriocaulaceae. Long-chain linear aliphatic hydrocarbons were identified by GC-FID and GC-MS. The results indicate that Paepalanthus subg. Platycaulon species present a very homogenous profile, with carbon chains of n-alkanes ranging from C25 to C31, most samples presenting higher frequencies of C27 and C29 homologues. Paepalanthus subg. Paepalocephalus species may be distinguished from one another by the distribution of main n-alkanes. P. macrocephalus, subsect. Aphorocaulon species, presents alkanes with odd-carbon numbers and P. denudatus and P. polyanthus, Actinocephalus species, present alkanes with quite distinctive profiles, with many shorter chains and a high frequency of even-carbon number, especially P. polyanthus. The results obtained indicate that the distribution of alkanes can be a useful taxonomic character, as do polar compounds like flavonoid glycosides.Este trabalho apresenta o estudo de substâncias apolares obtidas a partir de plantas pertencentes ao gênero Paepalanthus Mart. (Eriocaulaceae. Hidrocarbonetos alifáticos de cadeias longas lineares foram identificados por CG-DIC e CG-EM. Os resultados indicam que as espécies de Paepalanthus subg. Platycaulon apresentam perfil homogêneo, com cadeias carbônicas de n-alcanos variando de C25 a C31, com a maioria das amostras apresentando freqüências maiores dos homólogos C27 e C29. As espécies do subgênero Paepalocephalus podem ser diferenciadas pela distribuição dos n-alcanos principais. P. macrocephalus, uma espécie da subseção Aphorocaulon, apresenta perfil com alcanos de cadeia ímpar, enquanto P. denudatus e P. polyanthus, espécies da seção Actinocephalus, apresentam perfil bem distinto, com grande número de cadeias mais curtas e alta freqüência de cadeias com número par de carbonos, especialmente P. polyanthus. Os resultados obtidos indicam que a

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

    Science.gov (United States)

    Gamarra, Bruno; Sachse, Dirk; Kahmen, Ansgar

    2013-04-01

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

  14. Podemos prever a taxa de cambio brasileira? Evidência empírica utilizando inteligência computacional e modelos econométricos Can we forecast Brazilian exchange rates? Empirical evidences using computational intelligence and econometric models

    Directory of Open Access Journals (Sweden)

    Leandro dos Santos Coelho

    2008-12-01

    Full Text Available As abordagens de inteligência computacional, tais como sistemas nebulosos e redes neurais artificiais, têm-se gradualmente estabelecido como ferramentas robustas para a tarefa de aproximação de sistemas não-lineares complexos e previsão de séries temporais. Em aplicações envolvendo a área de Finanças, evidências empíricas anteriores indicam que modelos de inteligência computacional são mais precisos, dada sua maior capacidade em capturar não-linearidades e outros fatos estilizados presentes em séries financeiras. Nesse sentido, este artigo investiga a hipótese de que os modelos matemáticos de redes neurais perceptron multicamadas, redes neurais função de base radial e o sistema nebuloso Takagi-Sugeno (TAKAGI; SUGENO, 1985 são capazes de fornecer uma previsão fora-da-amostra mais acurada que os modelos auto-regressivos de médias móveis (ARMA e auto-regressivo de médias móveis supondo heterocedasticidade condicional auto-regressiva (ARMA-GARCH. O desempenho de previsão um-passo-à-frente dos modelos foi comparado utilizando-se séries de retorno da taxa de câmbio real/dólar (R$/US$ com freqüências de 15 minutos, 60 minutos, 120 minutos, diária e semanal. Resultados indicam que o desempenho dos modelos está diretamente relacionado à freqüência observada das séries. Além disso, os modelos de redes neurais obtiveram um desempenho superior em relação aos demais modelos considerados. A avaliação da estratégia de negociação estabelecida com base nas previsões geradas pelos modelos indicou que estratégias baseadas em modelos de redes neurais forneceram retornos superiores em relação àquelas baseadas em modelos ARMA e ARMA-GARCH e também em relação à estratégia buy-and-hold.Computational intelligence approaches, such as artificial neural networks and fuzzy systems, have become popular tools in approximating complicated nonlinear systems and time series forecasting. In Finance applications, there is

  15. Evaluation of the organic matter sources using the δ13C composition of individual n-alkanes in sediments from Brazilian estuarine systems by GC/C/IRMS

    Science.gov (United States)

    Maioli, Otávio Luiz Gusso; de Oliveira, Cristiane Rossi; Dal Sasso, Marco Aurélio; Madureira, Luiz Augusto dos Santos; Azevedo, Débora de Almeida; de Aquino Neto, Francisco Radler

    2012-12-01

    The δ13C composition of individual n-alkanes (from C16 to C34) was measured from surface sediments of five Brazilian estuarine systems affected by different organic matter sources, such as harbor area, industries, urban centers and sugar cane crops, in order to determine the origins of the organic matter. The aliphatic hydrocarbon fraction was analyzed by gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS). The levels of n-alkanes in the studied areas ranged from 0.34 to 18.14 μg kg-1, being relatively low in comparison to high polluted environments. The Carbon Preference Index (CPI) calculated in the C23-C34 range indicates that n-alkanes are mainly inherited from cuticular waxes of higher plants. The δ13C composition of all n-alkanes detected in the sediment samples ranged from -39.6 to -18.3‰ showing different sources for the studied estuarine systems. Through Principal Component Analysis (PCA) it was possible to verify the petrogenic influence in the n-alkane sources, especially in the Paraíba do Sul sediment samples. Differences up to 15‰ of the δ13C values between n-alkanes of odd and even carbon number (C26 and C27) also indicated mixture of petrogenic and biogenic sources in Paraíba do Sul River. High (less negative) δ13C n-alkane values of odd carbon number were obtained from two sampling sites located close to an ethanol plant, indicating residues discharge of sugar cane (C4 plant). Influence of C3 plants that are the main components of dense ombrophile forest was observed in the Itajaí-Açu sediments by the decrease of δ13C (about 10‰ compared to the Paraíba do Sul River δ13C).

  16. Emission of Methane and Heavier Alkanes From the La Brea Tar Pits Seepage Area, Los Angeles

    Science.gov (United States)

    Etiope, G.; Doezema, L. A.; Pacheco, C.

    2017-11-01

    Natural hydrocarbon (oil and gas) seeps are widespread in Los Angeles, California, due to gas migration, along faults, from numerous subsurface petroleum fields. These seeps may represent important natural contributors of methane (CH4) and heavier alkanes (C2-C4) to the atmosphere, in addition to anthropogenic fossil fuel and biogenic sources. We measured the CH4 flux by closed-chamber method from the La Brea Tar Pits park (0.1 km2), one of the largest seepage sites in Los Angeles. The gas seepage occurs throughout the park, not only from visible oil-asphalt seeps but also diffusely from the soil, affecting grass physiology. About 500 kg CH4 d-1 is emitted from the park, especially along a belt of enhanced degassing that corresponds to the 6th Street Fault. Additional emissions are from bubble plumes in the lake within the park (order of 102-103 kg d-1) and at the intersection of Wilshire Boulevard and Curson Avenue (>130 kg d-1), along the same fault. The investigated area has the highest natural gas flux measured thus far for any onshore seepage zone in the USA. Gas migration, oil biodegradation, and secondary methanogenesis altered the molecular composition of the original gas accumulated in the Salt Lake Oil Field (>300 m deep), leading to high C1/C2+ and i-butane/n-butane ratios. These molecular alterations can be important tracers of natural seepage and should be considered in the atmospheric modeling of the relative contribution of fossil fuel (anthropogenic fugitive emission and natural geologic sources) versus biogenic sources of methane, on local and global scales.

  17. Molecular Simulation of Flow-Enhanced Crystal Nucleation in Alkane Melts

    Science.gov (United States)

    Nicholson, David; Rutledge, Gregory

    Under typical processing conditions, the crystallization of polymer materials occurs far from equilibrium. In particular, the application of a flow field is known to drastically accelerate the kinetics of crystallization, and in turn alter the morphology and properties of the resulting material. It remains a significant challenge to establish the processing-structure-property relationships associated with crystallization under flow. Non-equilibrium molecular dynamics simulation has proven to be a useful investigative tool for the study of the early stages of flow-induced crystallization, known as flow-enhanced nucleation. Using this technique, nucleation studies were performed under shear and uniaxial extension for monodisperse melts of short (C20) and long (C150) alkanes, as well as for bimodal mixtures composed of both short and long chains. Through the application of a mean first-passage time-based analysis method, the effect of flow on the nucleation kinetics was quantified and classified in terms of an increase in the driving force for crystallization, reflected in the reduction of the free energy barrier, as well as a diffusive enhancement, reflected in the increase of the monomer attachment pre-factor. In bimodal blends with C150 fractions of 3-9 wt% chains, a drastic acceleration in the nucleation kinetics relative to monodisperse C20 was observed for strain rates intermediate to the inverse Rouse times of C20 and C150. For this range of strain rates, the long chains were found to preferentially participate in the formation of small clusters, and therefore serve as templates for the crystallization of the short chain fraction.

  18. Dehalogenimonas formicexedens sp. nov., a chlorinated alkane-respiring bacterium isolated from contaminated groundwater.

    Science.gov (United States)

    Key, Trent A; Bowman, Kimberly S; Lee, Imchang; Chun, Jongsik; Albuquerque, Luciana; da Costa, Milton S; Rainey, Fred A; Moe, William M

    2017-05-01

    A strictly anaerobic, Gram-stain-negative, non-spore-forming bacterium designated NSZ-14T, isolated from contaminated groundwater in Louisiana (USA), was characterized using a polyphasic approach. Strain NSZ-14T reductively dehalogenated a variety of polychlorinated aliphatic alkanes, producing ethene from 1,2-dichloroethane, propene from 1,2-dichloropropane, a mixture of cis- and trans-1,2-dichloroethene from 1,1,2,2-tetrachloroethane, vinyl chloride from 1,1,2-trichloroethane and allyl chloride (3-chloro-1-propene) from 1,2,3-trichloropropane. Formate or hydrogen could both serve as electron donors. Dechlorination occurred between pH 5.5 and 7.5 and over a temperature range of 20-37 °C. Major cellular fatty acids included C18 : 1ω9c, C14 : 0 and C16 : 0. 16S rRNA gene sequence-based phylogenetic analysis indicated that the strain clusters within the class Dehalococcoidia of the phylum Chloroflexi, most closely related to but distinct from type strains of the species Dehalogenimonas alkenigignens (97.63 % similarity) and Dehalogenimonas lykanthroporepellens (95.05 %). A complete genome sequence determined for strain NSZ-14T revealed a DNA G+C content of 53.96 mol%, which was corroborated by HPLC (54.1±0.2 mol% G+C). Genome-wide comparisons based on average nucleotide identity by orthology and estimated DNA-DNA hybridization values combined with phenotypic and chemotaxonomic traits and phylogenetic analysis indicate that strain NSZ-14T represents a novel species within the genus Dehalogenimonas, for which the name Dehalogenimonas formicexedens sp. nov. is proposed. The type strain is NSZ-14T (=HAMBI 3672T=JCM 19277T=VKM B-3058T). An emended description of Dehalogenimonas alkenigignens is also provided.

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

    Science.gov (United States)

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

    2015-10-01

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

  20. Semifluorinated Alkane Eye Drops for Treatment of Dry Eye Disease Due to Meibomian Gland Disease.

    Science.gov (United States)

    Steven, Philipp; Augustin, Albert J; Geerling, Gerd; Kaercher, Thomas; Kretz, Florian; Kunert, Kathleen; Menzel-Severing, Johannes; Schrage, Norbert; Schrems, Wolfgang; Krösser, Sonja; Beckert, Michael; Messmer, Elisabeth M

    2017-11-01

    Meibomian gland disease is generally accepted as the leading cause for evaporative dry eye disease (DED). In a previous study, perfluorohexyloctane, a semifluorinated alkane, has been demonstrated to significantly increase tear film breakup time and to reduce corneal fluorescein staining in patients with evaporative DED, thereby vastly reducing dry eye-related symptoms. This study was set up to evaluate perfluorohexyloctane in a larger population of patients with Meibomian gland dysfunction. Seventy-two patients with Meibomian gland disease and associated dry eye received 1 drop of perfluorohexyloctane 4 times daily during an observational, prospective, multicenter, 6-8-week study. Clinical assessment included best-corrected visual acuity, intraocular pressure, Schirmer test I, tear film breakup time, anterior and posterior blepharitis assessment, number of expressible Meibomian glands, meibum quality and quantity, ocular surface fluorescein staining, lid margin and symptom assessment, and Ocular Surface Disease Index (OSDI © ). From the 72 patients recruited, 61 completed the trial per protocol. Nine patients did not apply the medication as recommended and 2 patients were lost to follow-up. Tear film breakup time, corneal and conjunctival fluorescein staining, number of expressible Meibomian glands, and severity of anterior and posterior blepharitis significantly improved after 6-8 weeks of perfluorohexyloctane application. In addition, symptoms improved as demonstrated by a significant decrease of OSDI-values from 37 (±13) to 26 (±16). In concordance with previous findings, 6-8 weeks of topical application of perfluorohexyloctane significantly improves clinical signs of Meibomian gland disease and associated mild to moderate DED.

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

    Science.gov (United States)

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

    2015-01-01

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

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

    International Nuclear Information System (INIS)

    Dongen, Bart E. van; Rowland, Helen A.L.; Gault, Andrew G.; Polya, David A.; Bryant, Charlotte; Pancost, Richard D.

    2008-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-09-15

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

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

    Science.gov (United States)

    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. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

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

    Science.gov (United States)

    2015-01-01

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

  6. Structures of butyl ions formed by electron impact ionization of isomeric butyl halides and alkanes

    International Nuclear Information System (INIS)

    Shold, D.M.; Ausloos, P.

    1978-01-01

    Using a pulsed ion cyclotron resonance (ICR) spectrometer, it is demonstrated that at pressures of about 10 -6 Torr and at observation times ranging from 10 -3 to 0.5 s, isobutane, neopentane, 2,2-dimethylbutane, isobutyl halides, and tert-butyl halides form C 4 H 9 + ions having the tertiary structure. In n-alkanes, 2-methylbutane, 3-methylpentane, n-butyl halides, and sec-butyl halides, both sec-C 4 H 9 + and t-C 4 H 9 + ions are observed, the sec-C 4 H 9 + ions surviving without rearrangement for at least 0.1 s. However, in the case of the halides, a collision-induced isomerization of the sec-C 4 H 9 + to the t-C 4 H 9 + ions occurs. The efficiency of this process increases with the basicity of the alkyl halide. Radiolysis experiments carried out at atmospheric pressures indicate, in agreement with ICR and solution experiments, that at times as short as 10 -10 s the majority of the i-C 4 H 9 + ions from isobutyl bromide rearrange to the t-C 4 H 9 + structure. On the other hand, in the radiolysis of both n-hexane and 3-methylpentane, the abundance of t-C 4 H 9 + relative to sec-C 4 H 9 + is substantially smaller than that observed in the ICR experiments, and decreases with decreasing collision interval. It is suggested that about 90% of the i-C 4 H 9 + can rearrange to t-C 4 H 9 + by simple 1,2-hydride shift without involving secondary or protonated methylcyclopropane structures as intermediates. 4 figures, 2 tables

  7. Kinetics and mechanistic study of n-alkane hydroisomerization reaction on Pt-doped γ-alumina catalyst

    Directory of Open Access Journals (Sweden)

    Abhishek Dhar

    2017-12-01

    Full Text Available The catalysts γ-alumina (GA, the reference catalyst and Pt doped γ-alumina (PGA-s were synthesized using a simple sol-gel technique, in which at first preparation of porous base (GA, then impregnation of platinum salt over the base and finally reduction of platinum in the surface of the support were done. These catalysts prepared in different mole ratios of Pt:Al as 2:1, 1:1 and 1:2 are named as PGA-1, PGA-2 and PGA-3 respectively. The isomerization of n-alkanes (n-hexane, n-heptane and n-octane were investigated over the synthesized catalysts. The 2-methyl pentane (2-MP, 2,2-dimethyl pentane (2,2-DMP and 2,3-dimethyl hexane (2,3-DMH are the major products of respective isomerization of n-hexane, n-heptane and n-octane, besides a small amount of other branched isomers are also produced. The product distribution is comparable to that reported for Pt based other catalysts. The optimal mole ratios of Pt:Al is 1:1 (PGA-2 gives quite good catalytic activity for isomerization of n-alkane. Even through in reusability study, PGA-2 gives better performance than others. We have mainly focused on kinetic study, reaction mechanism behind isomerization and calculated the order of reactions and activation energies of the isomerization reactions in the present work. Keywords: Isomerization, n-alkanes, Catalyst, Reaction mechanism, Kinetics study, Activation energy

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

    Science.gov (United States)

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

    2012-05-15

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

  9. The detection and phylogenetic analysis of the alkane 1-monooxygenase gene of members of the genus Rhodococcus.

    Science.gov (United States)

    Táncsics, András; Benedek, Tibor; Szoboszlay, Sándor; Veres, Péter G; Farkas, Milán; Máthé, István; Márialigeti, Károly; Kukolya, József; Lányi, Szabolcs; Kriszt, Balázs

    2015-02-01

    Naturally occurring and anthropogenic petroleum hydrocarbons are potential carbon sources for many bacteria. The AlkB-related alkane hydroxylases, which are integral membrane non-heme iron enzymes, play a key role in the microbial degradation of many of these hydrocarbons. Several members of the genus Rhodococcus are well-known alkane degraders and are known to harbor multiple alkB genes encoding for different alkane 1-monooxygenases. In the present study, 48 Rhodococcus strains, representing 35 species of the genus, were investigated to find out whether there was a dominant type of alkB gene widespread among species of the genus that could be used as a phylogenetic marker. Phylogenetic analysis of rhodococcal alkB gene sequences indicated that a certain type of alkB gene was present in almost every member of the genus Rhodococcus. These alkB genes were common in a unique nucleotide sequence stretch absent from other types of rhodococcal alkB genes that encoded a conserved amino acid motif: WLG(I/V/L)D(G/D)GL. The sequence identity of the targeted alkB gene in Rhodococcus ranged from 78.5 to 99.2% and showed higher nucleotide sequence variation at the inter-species level compared to the 16S rRNA gene (93.9-99.8%). The results indicated that the alkB gene type investigated might be applicable for: (i) differentiating closely related Rhodococcus species, (ii) properly assigning environmental isolates to existing Rhodococcus species, and finally (iii) assessing whether a new Rhodococcus isolate represents a novel species of the genus. Copyright © 2014 Elsevier GmbH. All rights reserved.

  10. [Bis(TrimethylsilylMethyl]Lithium and -Sodium: Solubility in Alkanes and Complexes with O- and N- Donor Ligands

    Directory of Open Access Journals (Sweden)

    Markus von Pilgrim

    2017-06-01

    Full Text Available In contrast to alkyl compounds of lithium, which play an important role in organometallic chemistry, the corresponding heavier alkali metal compounds are less investigated. These compounds are mostly insoluble in inert solvents or undergo solvolysis in coordinating solvents due to their high reactivity. An exception from this typical behavior is demonstrated by bis(trimethylsilylmethylsodium. This study examines alkane solutions of bis(trimethylsilylmethyllithium and -sodium by NMR spectroscopic and cryoscopic methods. In addition, structural studies by X-ray crystallography of the corresponding compounds coordinated by O- and N- ligands (tetrahydrofuran and tetramethylethylenediamine present possible structural motifs of the uncoordinated compounds in solution.

  11. Re-evaluating the isotopic divide between angiosperms and gymnosperms using n-alkane δ13C values

    Science.gov (United States)

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

    2009-12-01

    Angiosperm δ13C values are typically 1-3‰ more negative than those of co-occurring gymnosperms. This is known for both bulk leaf and compound-specific values from n-alkanes, which are stable, straight-chain hydrocarbons (C23-C35) found in the epicuticular leaf wax of vascular plants. For n-alkanes, there is a second distinction between the δ13C values of angiosperms and gymnosperms—δ13C values generally decrease with increasing chain-length in angiosperms, while in gymnosperms they increase. These two distinctions have been used to support the ‘plant community change hypothesis’ explaining the difference between the terrestrial and marine carbon isotope excursions during the Paleocene-Eocene Thermal Maximum (PETM.) Preserved n-alkanes from terrestrial paleosols in the Bighorn Basin, Wyoming reveal a negative carbon isotope excursion during the PETM of 4-5‰, which is 1-2‰ greater than the excursion recorded by marine carbonates. The local plant community, known from macrofossils as well as palynoflora, shifted from a deciduous, mixed angiosperm/gymnosperm flora to a suite of evergreen angiosperm species during the PETM. At the end of the PETM, the community returned to a mixed deciduous flora very similar to the original. This change in the plant community could thus magnify the terrestrial negative carbon isotope excursion to the degree necessary to explain its divergence from the marine record. However, the comparison between modern angiosperms and gymnosperms has been made mostly between broadleaf, deciduous angiosperms and evergreen, coniferous gymnosperms. New data analyzing deciduous, coniferous gymnosperms, including Metasequoia glyptostroboides and Taxodium distichum, suggests that the division previously ascribed to taxonomy may actually be based on leaf habit and physiology, specifically broadleaf, deciduous versus needle-leaf, evergreen plants. If differences in n-alkane δ13C values can be described not as angiosperms versus gymnosperms

  12. Particle size distribution of n-alkanes and polycyclic aromatic hydrocarbons (PAHS) in urban and industrial aerosol of Algiers, Algeria.

    Science.gov (United States)

    Ladji, R; Yassaa, N; Balducci, C; Cecinato, A

    2014-02-01

    The distribution of ambient air n-alkanes and polycyclic aromatic hydrocarbons (PAHs) associated to particles with aerodynamic diameters lesser than 10 μm (PM(10)) into six fractions (five stages and a backup filter) was studied for the first time in Algeria. Investigation took place during September of 2007 at an urban and industrial site of Algiers. Size-resolved samples (<0.49, 0.49-0.95, 0.95-1.5, 1.5-3.0, 3.0-7.2, and 7.2-10 μm) were concurrently collected at the two sampling sites using five-stage high-volume cascade impactors. Most of n-alkanes (~72 %) and PAHs (~90 %) were associated with fine particles ≤ 1.5 μm in both urban and industrial atmosphere. In both cases, the n-alkane contents exhibited bimodal or weakly bimodal distribution peaking at the 0.95-1.5-μm size range within the fine mode and at 7.3-10 μm in the coarse mode. Low molecular weight PAHs displayed bimodal patterns peaking at 0.49-0.95 and 7.3-10 μm, while high molecular weight PAHs exhibited mono-modal distribution with maximum in the <0.49-μm fraction. While the mass mean diameter of total n-alkanes in the urban and industrial sites was 0.70 and 0.84 μm, respectively, it did not exceed 0.49 μm for PAHs. Carbon preference index (~1.1), wax% (10.1-12.8), and the diagnostic ratios for PAHs all revealed that vehicular emission was the major source of these organic compounds in PM(10) during the study periods and that the contribution of epicuticular waxes emitted by terrestrial plants was minor. According to benzo[a]pyrene-equivalent carcinogenic power rates, ca. 90 % of overall PAH toxicity across PM(10) was found in particles ≤ 0.95 μm in diameter which could induce adverse health effects to the population living in these areas.

  13. Collisional energy transfer in polyatomic molecules at high temperatures: Master equation analysis of vibrational relaxation of shock-heated alkanes

    Science.gov (United States)

    Matsugi, Akira

    2015-08-01

    Collisional energy transfer plays an important role in unimolecular reaction kinetics. This Letter presents classical trajectory calculations of the energy transfer processes in collisions between selected alkanes (ethane, propane, isobutane, and neopentane) and krypton at high temperature. The primary aim of this study was to elucidate the validity of the predicted energy transfer parameters by performing master equation analyses of their vibrational relaxation times and comparing the predicted values with the available experimental data. The results demonstrate the ability of classical trajectory calculations to accurately predict the parameters for vibrational energy transfer.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-09-15

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

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

    International Nuclear Information System (INIS)

    Ortega, J.; Espiau, F.; Toledo, F.J.; Dieppa, R.

    2005-01-01

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

  16. Thermodynamic properties of (an ester + an alkane). XVI. Experimental HmE and VmE values and a new correlation method for (an alkyl ethanoate + an n-alkane) at 318.15 K

    International Nuclear Information System (INIS)

    Ortega, J.; Espiau, F.; Toledo, F.J.

    2004-01-01

    This work presents the measurements of H m E and V m E , obtained at a temperature of T=318.15 K and atmospheric pressure for a set of 30 binary mixtures composed of five alkyl ethanoates (methyl to pentyl) with six odd n-alkanes (C 7 to C 17 ). The results show that the mixing processes are endothermic in all cases, with regular increases in H m E with the molecular weight of the saturated hydrocarbon and diminishing with the alkanolic part of the ester. The change in V m E is also regular and similar to that of H m E . For data correlation, a new form of polynomial equation is used. In this, the so-called active fraction is used as a variable which, in turn, depends on the concentration of the mixture, giving acceptable estimations of the Gibbs function obtained in the isobaric (liquid + vapor) equilibria for some of the mixtures studied. Finally, a molecular model which interprets the behavior of mixtures of alkyl ethanoates + n-alkanes and the results of residual quantities is proposed. To these binary systems some group contribution models are applied. A modified version of the UNIFAC model gives satisfactory results for enthalpies

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-11-15

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

  18. The Gas-Phase Heats of Formation of n-Alkanes as a Function of the Electrostatic Potential Extrema on their Molecular Surfaces

    Directory of Open Access Journals (Sweden)

    Fakhr M. Abu-Awwad

    2004-01-01

    Full Text Available The hybrid density functional B3LYP is employed to map the molecular electrostatic potentials on the surfaces of twenty normal alkanes, (Cn H2n+2, n = 1-20. It is shown that gas-phase heats of formation of the alkanes can be represented quantitatively in terms of the potential, where a general equation of the heat of formation is introduced as a function of potentials' extrema, VS,min and VS,max with average absolute error of 0.028 kcal/mol and a standard deviation of 0.048 kcal/mol. This should be viewed as a success of the B3LYP functional and the molecular surface electrostatic potential as tools of chemistry. The predicted gas-phase heats of formation of thirty normal alkanes (n = 21-50 are reproduced and compared to their experimental counterparts when available.

  19. Rhodococcus rhodochrous ATCC12674 becomes alkane-tolerant upon GroEL2 overexpression and survives in the n-octane phase in two phase culture.

    Science.gov (United States)

    Takihara, Hayato; Matsuura, Chiaki; Ogihara, Jun; Iwabuchi, Noriyuki; Sunairi, Michio

    2014-01-01

    We recently reported that the overexpression of GroEL2 played an important role in increasing the alkane tolerance of Rhodococcus erythropolis PR4. In the present study, we examined the effects of the introduction of groEL2 on the alkane tolerance of other Rhodococcus strains. The introduction of groEL2 into Rhodococcus strains led to increased alkane tolerance. The translocation of R. rhodochrous ATCC12674 cells to and survival in the n-octane (C8) phase in two phase culture were significantly enhanced by the introduction of groEL2 derived from strain PR4, suggesting that engineering cells to overexpress GroEL2 represents an effective strategy for enhancing organic solvent tolerance in Rhodococcus.

  20. Terrestrial environmental changes around the Gulf of Aden over the last 210 kyr deduced from the sediment n-alkane record: Implications for the dispersal of Homo sapiens

    Science.gov (United States)

    Isaji, Yuta; Kawahata, Hodaka; Ohkouchi, Naohiko; Murayama, Masafumi; Tamaki, Kensaku

    2015-03-01

    We analyzed long-chain (C25-C36) n-alkanes and pollen grains in sediments from the Gulf of Aden covering the last 212 kyr to reconstruct the surrounding terrestrial environment, a critical region for the dispersal of Homo sapiens. Substantial increases in the flux of n-alkanes during 200-185, 120-95, and 70-50 ka were interpreted to indicate enhanced vegetation biomass in the Arabian Peninsula and the northern part of the Horn of Africa or increase in lithogenic material inputs. Periods of enhanced n-alkane flux occurred during or immediately after pluvial episodes, indicating that the increased precipitation may have induced substantially enhanced vegetation biomass, creating favorable conditions for Homo sapiens. Additionally, vegetation may have increased due to moderate precipitation unrecorded by speleothems or in accordance with the lowering of sea level, indicating that the dispersal might have been possible even after the shift to an arid environment indicated by the speleothems.

  1. Anaerobic Coculture of Microalgae with Thermosipho globiformans and Methanocaldococcus jannaschii at 68°C Enhances Generation of n-Alkane-Rich Biofuels after Pyrolysis

    Science.gov (United States)

    Matsuyama, Shigeru; Igarashi, Kensuke; Utsumi, Motoo; Shiraiwa, Yoshihiro; Kuwabara, Tomohiko

    2013-01-01

    We tested different alga-bacterium-archaeon consortia to investigate the production of oil-like mixtures, expecting that n-alkane-rich biofuels might be synthesized after pyrolysis. Thermosipho globiformans and Methanocaldococcus jannaschii were cocultured at 68°C with microalgae for 9 days under two anaerobic conditions, followed by pyrolysis at 300°C for 4 days. Arthrospira platensis (Cyanobacteria), Dunaliella tertiolecta (Chlorophyta), Emiliania huxleyi (Haptophyta), and Euglena gracilis (Euglenophyta) served as microalgal raw materials. D. tertiolecta, E. huxleyi, and E. gracilis cocultured with the bacterium and archaeon inhibited their growth and CH4 production. E. huxleyi had the strongest inhibitory effect. Biofuel generation was enhanced by reducing impurities containing alkanenitriles during pyrolysis. The composition and amounts of n-alkanes produced by pyrolysis were closely related to the lipid contents and composition of the microalgae. Pyrolysis of A. platensis and D. tertiolecta containing mainly phospholipids and glycolipids generated short-carbon-chain n-alkanes (n-tridecane to n-nonadecane) and considerable amounts of isoprenoids. E. gracilis also produced mainly short n-alkanes. In contrast, E. huxleyi containing long-chain (31 and 33 carbon atoms) alkenes and very long-chain (37 to 39 carbon atoms) alkenones, in addition to phospholipids and glycolipids, generated a high yield of n-alkanes of various lengths (n-tridecane to n-pentatriacontane). The gas chromatography-mass spectrometry (GC-MS) profiles of these n-alkanes were similar to those of native petroleum crude oils despite containing a considerable amount of n-hentriacontane. The ratio of phytane to n-octadecane was also similar to that of native crude oils. PMID:23183975

  2. Geochemical characteristics of n-alkanes and isoprenoids in coal seams from Zhuji coal mine, Huainan coalfield, China, and their relationship with coal-forming environment.

    Science.gov (United States)

    Wang, Shanshan; Liu, Guijian; Liu, Jingjing

    2018-01-26

    Ten coal seams in Upper Shihezi Formation, Lower Shihezi Formation, and Shanxi Formation from the Zhuji mine, Huainan coalfield, China, were analyzed for n-alkanes and isoprenoids (pristine and phytane) using gas chromatography-mass spectrometry (GC-MS), with an aim of reconstructing the coal-forming plants and depositional environments along with organic carbon isotope analyses. The total n-alkane concentrations ranged from 34.1 to 481 mg/kg. Values of organic carbon isotope (δ 13 C org ) ranged from - 24.6 to - 23.7‰. The calorific value (Q b,d ), maximum vitrinite reflectance (Ro max ), proximate, and ultimate analysis were also determined but showed no correlation with n-alkane concentrations. Carbon Preference Index (CPI) values ranged from 0.945 to 1.30, suggesting no obvious odd/even predominance of n-alkane. The predominance of C 11 and C 17 n-alkanes implied that the coal may be deposited in the fresh and mildly brackish environment. According to the contrary changing trend of pristine/phytane (Pr/Ph) ratio and boron concentrations, Pr/Ph can be used as an indicator to reconstruct the marine transgression-regression in sedimentary environment of coal formation. The influence of marine transgression may lead to the enrichment of pyrite sulfur in the coal seam 4-2. C3 plants (- 32 to - 21‰) and marine algae (- 23 to - 16‰) were probably the main coal-forming plants in the studied coal seams. No correlation of the n-alkane concentration and redox condition of the depositional environment with organic carbon isotope composition were found.

  3. Hydrodeoxygenation of water-insoluble bio-oil to alkanes using a highly dispersed Pd-Mo catalyst.

    Science.gov (United States)

    Duan, Haohong; Dong, Juncai; Gu, Xianrui; Peng, Yung-Kang; Chen, Wenxing; Issariyakul, Titipong; Myers, William K; Li, Meng-Jung; Yi, Ni; Kilpatrick, Alexander F R; Wang, Yu; Zheng, Xusheng; Ji, Shufang; Wang, Qian; Feng, Junting; Chen, Dongliang; Li, Yadong; Buffet, Jean-Charles; Liu, Haichao; Tsang, Shik Chi Edman; O'Hare, Dermot

    2017-09-19

    Bio-oil, produced by the destructive distillation of cheap and renewable lignocellulosic biomass, contains high energy density oligomers in the water-insoluble fraction that can be utilized for diesel and valuable fine chemicals productions. Here, we show an efficient hydrodeoxygenation catalyst that combines highly dispersed palladium and ultrafine molybdenum phosphate nanoparticles on silica. Using phenol as a model substrate this catalyst is 100% effective and 97.5% selective for hydrodeoxygenation to cyclohexane under mild conditions in a batch reaction; this catalyst also demonstrates regeneration ability in long-term continuous flow tests. Detailed investigations into the nature of the catalyst show that it combines hydrogenation activity of Pd and high density of both Brønsted and Lewis acid sites; we believe these are key features for efficient catalytic hydrodeoxygenation behavior. Using a wood and bark-derived feedstock, this catalyst performs hydrodeoxygenation of lignin, cellulose, and hemicellulose-derived oligomers into liquid alkanes with high efficiency and yield.Bio-oil is a potential major source of renewable fuels and chemicals. Here, the authors report a palladium-molybdenum mixed catalyst for the selective hydrodeoxygenation of water-insoluble bio-oil to mixtures of alkanes with high carbon yield.

  4. An overview of dehydration, aldol-condensation and hydrogenation processes for production of liquid alkanes from biomass-derived carbohydrates

    Energy Technology Data Exchange (ETDEWEB)

    Chheda, Juben N.; Dumesic, James A. [University of Wisconsin-Madison, Department of Chemical and Biological Engineering, Madison, WI 53706 (United States)

    2007-05-30

    We present results for the conversion of carbohydrate feedstocks to liquid alkanes by the combination of dehydration, aldol-condensation/hydrogenation, and dehydration/hydrogenation processing. With respect to the first dehydration step, we demonstrate that HMF can be produced in good selectivity from abundantly available polysaccharides (such as inulin, sucrose) containing fructose monomer units using a biphasic batch reactor system. The reaction system can be optimized to achieve good yields to 5-hydroxymethylfurfural (HMF) from fructose by varying the contents of aqueous-phase modifiers such as dimethylsulfoxide (DMSO) and 1-methyl-2-pyrrolidinone (NMP). Regarding the aldol-condensation/hydrogenation step, we present the development of stable, solid base catalysts in aqueous environments. We address the effects of various reaction parameters such as the molar ratio of reactants and temperature on overall product yield for sequential aldol-condensation and hydrogenation steps. Overall, our results show that it is technically possible to convert carbohydrate feedstocks to produce liquid alkanes by the combination of dehydration, aldol-condensation/hydrogenation, and dehydration/hydrogenation processing; however, further optimization of these processes is required to decrease the overall number of separate steps (and reactors) required in this conversion. (author)

  5. High pressure phase equilibrium of ternary and multicomponent alkane mixtures in the temperature range from (283–473) K

    DEFF Research Database (Denmark)

    Regueira Muñiz, Teresa; Liu, Yiqun; Wibowo, Ahmad A.

    2017-01-01

    Asymmetric multicomponent alkane mixtures can be used as model systems for reservoir fluids. We have prepared two ternary mixtures, methane/n-butane/n-decane and methane/n-butane/n-dodecane, and two multicomponent mixtures composed of methane/n-butane/n-octane/n-dodecane/n-hexadecane/n-eicosane a......Asymmetric multicomponent alkane mixtures can be used as model systems for reservoir fluids. We have prepared two ternary mixtures, methane/n-butane/n-decane and methane/n-butane/n-dodecane, and two multicomponent mixtures composed of methane......-Redlich-Kwong (SRK), Peng-Robinson (PR), Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT), and Soave-Benedict-Webb-Rubin (Soave-BWR), have been used to predict phase equilibrium of the measured systems. PR and PC-SAFT give better results than others and Soave-BWR gives poor phase envelope predictions...... the fractions just below the saturation pressures are difficult to predict. Moreover GERG-2008 has also been tested with the measured methane/n-butane/n-decane system. It over predicts the saturation pressures but predicts low pressure liquid fractions quite accurately....

  6. Investigation on the light alkanes aromatization over Zn and Ga modified HZSM-5 catalysts in the presence of methane

    Energy Technology Data Exchange (ETDEWEB)

    Li, Qingyin; Zhang, Fengqi; Jarvis, Jack; He, Peng; Yung, Matthew M.; Wang, Aiguo; Zhao, Kai; Song, Hua

    2018-05-01

    The catalytic co-aromatization of methane and paraffin-rich raffinate oil was investigated along with hexane, heptane and octane as its model compounds over zinc and gallium modified ZSM-5 zeolite catalysts. The benzene, toluene and xylene (BTX) components derived from light alkane aromatization were highly promoted with the assistance of methane. The co-existence of Zn and Ga metal species has a positive effect on the formation of BTX components, whereas the individual metal loaded catalyst resulted in the production of heavy aromatics, suggesting that zinc and gallium have a synergistic effect on the formation of BTX under the methane environment. When concerned with gaseous analysis, the introduced methane might interact with smaller intermediates and then transform into larger hydrocarbons. From the DRIFT observation, it was witnessed that the interaction between light alkane and methane occurred on the surface of the charged Zn-Ga/ZSM-5 catalyst. According to the comprehensive catalyst characterizations, the excellent catalytic performance may be closely associated with greatly dispersed metal species on the zeolite support, improved microporous characteristic, moderate Bronsted and increased Lewis acidic sites during the paraffin-rich liquid feedstock aromatization under methane environment. This research provides a promising pathway for the highly effective and profitable utilization of petrochemical resources and natural gas.

  7. Methanogenic paraffin degradation proceeds via alkane addition to fumarate by 'Smithella' spp. mediated by a syntrophic coupling with hydrogenotrophic methanogens.

    Science.gov (United States)

    Wawrik, Boris; Marks, Christopher R; Davidova, Irene A; McInerney, Michael J; Pruitt, Shane; Duncan, Kathleen E; Suflita, Joseph M; Callaghan, Amy V

    2016-09-01

    Anaerobic microbial biodegradation of recalcitrant, water-insoluble substrates, such as paraffins, presents unique metabolic challenges. To elucidate this process, a methanogenic consortium capable of mineralizing long-chain n-paraffins (C28 -C50 ) was enriched from San Diego Bay sediment. Analysis of 16S rRNA genes indicated the dominance of Syntrophobacterales (43%) and Methanomicrobiales (26%). Metagenomic sequencing allowed draft genome assembly of dominant uncultivated community members belonging to the bacterial genus Smithella and the archaeal genera Methanoculleus and Methanosaeta. Five contigs encoding homologs of the catalytic subunit of alkylsuccinate synthase (assA) were detected. Additionally, mRNA transcripts for these genes, including a homolog binned within the 'Smithella' sp. SDB genome scaffold, were detected via RT-PCR, implying that paraffins are activated via 'fumarate addition'. Metabolic reconstruction and comparison with genome scaffolds of uncultivated n-alkane degrading 'Smithella' spp. are consistent with the hypothesis that syntrophically growing 'Smithella' spp. may achieve reverse electron transfer by coupling the reoxidation of ETFred to a membrane-bound FeS oxidoreductase functioning as an ETF:menaquinone oxidoreductase. Subsequent electron transfer could proceed via a periplasmic formate dehydrogenase and/or hydrogenase, allowing energetic coupling to hydrogenotrophic methanogens such as Methanoculleus. Ultimately, these data provide fundamental insight into the energy conservation mechanisms that dictate interspecies interactions salient to methanogenic alkane mineralization. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

  8. Modeling of asphaltene precipitation due to steam and n-alkane co-injection in the ES-SAGD process

    Energy Technology Data Exchange (ETDEWEB)

    Badamchizadeh, A.; Kohse, Bruce F.; Kumar, A. [Computer Modelling Group Ltd (Canada)

    2011-07-01

    This paper provides an insight into the SAGD process in general, and the formation of asphaltene participates in the hybrid ES-SAGD process in particular. The objective of this work was to build an EoS model able to calculate the physical and chemical properties of the bitumen and n-alkane mixture, develop a model to quantify asphaltene participates in bitumen due to n-alkane injection, and investigate their effect on the ES-SAGD process. Athabasca bitumen properties identified under various test conditions and from the results of previous efforts, mainly the SimDist experimental data, were illustrated. These data were used to develop the EoS model, which in turn was used to generate the STARS thermal simulator. Overall, the EoS model was successfully developed and hence was able to predict bitumen and n-heptane properties. Moreover, asphaltene deposition in the ES-SAGD process was modeled in the thermal simulator its effect in causing oil blockage and restrictions in the steam chamber over a long run of the process was demonstrated.

  9. Third O2 addition reactions promote the low-temperature auto-ignition of n-alkanes

    KAUST Repository

    Wang, Zhandong

    2016-01-20

    Comprehensive low-temperature oxidation mechanisms are needed to accurately predict fuel auto-ignition properties. This paper studies the effects of a previously unconsidered third O2 addition reaction scheme on the simulated auto-ignition of n-alkanes. We demonstrate that this extended low-temperature oxidation scheme has a minor effect on the simulation of n-pentane ignition; however, its addition significantly improves the prediction of n-hexane auto-ignition under low-temperature rapid compression machine conditions. Additional simulations of n-hexane in a homogeneous charge compression ignition engine show that engine-operating parameters (e.g., intake temperature and combustion phasing) are significantly altered when the third O2 addition kinetic mechanism is considered. The advanced combustion phasing is initiated by the formation and destruction of additional radical chain-branching intermediates produced in the third O2 addition process, e.g. keto-dihydroperoxides and/or keto-hydroperoxy cyclic ethers. Our results indicate that third O2 addition reactions accelerate low-temperature radical chain branching at conditions of relevance to advance engine technologies, and therefore these chemical pathways should also be considered for n-alkanes with 6 or more carbon atoms. © 2015 The Combustion Institute.

  10. Complete genome sequence of Tsukamurella sp. MH1: A wide-chain length alkane-degrading actinomycete.

    Science.gov (United States)

    Chiciudean, Iulia; Nie, Yong; Tănase, Ana-Maria; Stoica, Ileana; Wu, Xiao-Lei

    2018-02-20

    Tsukamurella sp. strain MH1, capable to use a wide range of n-alkanes as the only carbon source, was isolated from petroleum-contaminated soil (Pitești, Romania) and its complete genome was sequenced. The 4,922,396 bp genome contains only one circular chromosome with a G + C content of 71.12%, much higher than the type strains of this genus (68.4%). Based on the 16S rRNA genes sequence similarity, strain MH1 was taxonomically identified as Tsukamurella carboxydivorans. Genome analyses revealed that strain MH1 is harboring only one gene encoding for the alkB-like hydroxylase, arranged in a complete alkane monooxygenase operon. This is the first complete genome of the specie T. carboxydivorans, which will provide insights into the potential of Tsukamurella sp. MH1 and related strains for bioremediation of petroleum hydrocarbons-contaminated sites and into the environmental role of these bacteria. Copyright © 2017. Published by Elsevier B.V.

  11. Products and Kinetics of the Reactions of an Alkane Monolayer and a Terminal Alkene Monolayer with NO₃ Radicals

    Energy Technology Data Exchange (ETDEWEB)

    Gross, Simone; Bertram, Allan K.

    2009-01-27

    The reactions of an alkanethiol and a terminal alkenethiol self-assembled monolayer with NO₃ radicals (in the presence of NO₂ and O₂) were studied. For the alkane monolayer, infrared (IR) spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed the formation of organonitrates (RONO₂). The observation of organonitrates is in contrast to the recent X-ray photoelectron spectroscopy (XPS) data, which showed very little nitrogen-containing surface species. The identification of organonitrates may help explain why significant volatilization of the organic chain was not observed in recent studies of alkane monolayer oxidation by NO₃ radicals. The reactive uptake coefficient (g) of NO₃ on alkene monolayers determined in our study is higher than the values obtained in a recent study using liquid and solid alkene bulk films. A possible reason for this difference may be the location of the double bond at the interface. Using the g value determined in our studies, we show that under conditions where NO₃ is high the lifetime of an alkene monolayer in the atmosphere may be short (approximately 20 min). XPS, IR, and ToF-SIMS were used to identify surface functional groups after the oxidation of the alkene monolayers by NO₃. The results are consistent with the formation of C-O, aldehyde/ketone, carboxylic groups, and nitrogen containing species.

  12. Heritability of the Structures and 13C Fractionation in Tomato Leaf Wax Alkanes: A Genetic Model System to Inform Paleoenvironmental Reconstructions

    Directory of Open Access Journals (Sweden)

    Amanda L. D. Bender

    2017-06-01

    Full Text Available Leaf wax n-alkanes are broadly used to reconstruct paleoenvironmental information. However, the utility of n-alkanes as a paleoenvironmental proxy may be modulated by the extent to which biological as well as environmental factors influence the structural and isotopic variability of leaf waxes. In paleoclimate applications, there is usually an implicit assumption that most variation of leaf wax traits through a time series can be attributed to environmental change and that biological sources of variability within plant communities are small. For example, changes in hydrology affect the δ2H of waxes via rainwater and the δ13C of leaf waxes by changing plant communities. We measured the degree of genetic control over δ13C variation in leaf waxes within closely related species with an experimental greenhouse growth study. We measured the proportion of variability in structural and isotopic leaf wax traits that is attributable to genetic variation using a set of 76 introgression lines (ILs between two interfertile Solanum (tomato species: S. lycopersicum cv M82 (hereafter cv M82 and S. pennellii. Leaves of S. pennellii, a wild desert tomato relative, produced significantly more iso-alkanes than cv M82, a domesticated tomato cultivar adapted to water-replete conditions. We report a methylation index to summarize the ratio of branched (iso- and anteiso- to total alkanes. Between Solanum pennellii and cv M82, the iso-alkanes were found to be enriched in 13C by 1.2–1.4‰ over n-alkanes. The broad-sense heritability values (H2 of leaf wax traits describe the degree to which genetic variation contributes to variation of these traits. Variation of individual carbon isotopic compositions of alkanes were of low heritability (H2 = 0.13–0.19, suggesting that most variation in δ13C of leaf waxes in this study can be attributed to environmental variance. This supports the interpretation that variation in the δ13C of wax compounds recorded in sediments

  13. Simple addition of silica to an alkane solution of Wilkinson WMe6 or Schrock W alkylidyne complex give active complex for saturated and unsaturated hydrocarbons metathesis

    KAUST Repository

    Callens, Emmanuel

    2015-08-24

    Addition of PDA silica to a solution of the Wilkinson WMe6 as well as the Schrock W neopentilidyne tris neopentyl complex catalyzes linear or cyclic alkanes to produce respectively a distribution of linear alkanes from methane up to triacontane or a mixture of cyclic and macrocyclic hydrocarbons. This single catalytic system transforms also linear α-olefins into higher and lower homologues via isomerization/metathesis mechanism (ISOMET). This complex is also efficient towards functionalized olefins. Unsaturated fatty acid esters (FAEs) are converted into diesters corresponding to self-metathesis products.

  14. Heritability of the structures and 13C fractionation in tomato leaf wax alkanes: a genetic model system to inform paleoenvironmental reconstructions

    Science.gov (United States)

    Bender, Amanda L. D.; Chitwood, Daniel H.; Bradley, Alexander S.

    2017-06-01

    Leaf wax n-alkanes are broadly used to reconstruct paleoenvironmental information. However, the utility of n-alkanes as a paleoenvironmental proxy may be modulated by the extent to which biological as well as environmental factors influence the structural and isotopic variability of leaf waxes. In paleoclimate applications, there is usually an implicit assumption that most variation of leaf wax traits through a time series can be attributed to environmental change and that biological sources of variability within plant communities are small. For example, changes in hydrology affect the δ2H of waxes via rainwater and the δ13C of leaf waxes by changing plant communities. We measured the degree of genetic control over δ13C variation in leaf waxes within closely related species with an experimental greenhouse growth study. We measured the proportion of variability in structural and isotopic leaf wax traits that is attributable to genetic variation using a set of 76 introgression lines (ILs) between two interfertile Solanum (tomato) species: S. lycopersicum cv M82 (hereafter cv M82) and S. pennellii. Leaves of S. pennellii, a wild desert tomato relative, produced significantly more iso-alkanes than cv M82, a domesticated tomato cultivar adapted to water-replete conditions. We report a methylation index to summarize the ratio of branched (iso- and anteiso-) to total alkanes. Between S. pennellii and cv M82, the iso-alkanes were found to be enriched in 13C by 1.2-1.4‰ over n-alkanes. The broad-sense heritability values (H2) of leaf wax traits describe the degree to which genetic variation contributes to variation of these traits. Variation of individual carbon isotopic compositions of alkanes were of low heritability (H2 = 0.13-0.19), suggesting that most variation in δ13C of leaf waxes in this study can be attributed to environmental variance. This supports the interpretation that variation in the δ13C of wax compounds recorded in sediments reflects

  15. Changes in the n-alkane composition of avocado pulp oil ( Persea americana, Mill. during fruit ripening

    Directory of Open Access Journals (Sweden)

    Giuffrè, A. M.

    2005-03-01

    Full Text Available The n-alkane composition of Avocado pulp oil (cv. Hass was investigated during fruit ripening. Three samples of fruit were harvested on March 3, 2003, March 18, 2003 and April 2, 2003. Glass gravity column chromatography was employed to separate n-alkanes from other minor components contained in the unsaponifiable fraction. Gas chromatography was used to analyze the eluate. Fourteen compounds were detected ranging from n -C21 to n -C34; mainly n -C24, followed by n -C25 and then by n -C23. Quantities of n -C21, n -C22, n -C23, n -C27 and n -C28 progressively increased during ripening, whereas n -C24, n -C25, n -C26, n -C29, n -C30 and n -C34 decreased from the first harvest date to the third harvest date. While odd-numbered carbon n-alkanes increased (52.38 %, 52.85 % and 53.06 % for the three samples respectively, even-numbered carbon n-alkanes decreased as the fruit ripened (47.62 %, 47.15 % and 46.94 %. The total n-alkane content decreased during ripening, from 25.20 mg/Kg (first harvest date to 16.77 mg/Kg (third harvest date. In order to minimize.Se ha analizado la composición en hidrocarburos lineales saturados del aceite de la pulpa de aguacate (variedad Hass. Tres muestras fueron recolectadas: el 3 de marzo 2003, el 18 de marzo 2003 y el 2 de abril 2003. La separación de los hidrocarburos lineales saturados se realizó mediante fraccionamiento del insaponificable por cromatografía gravimétrica de adsorción en columna y la determinación de los mismos hidrocarburos por cromatografía gaseosa. 14 compuestos fueron detectados del n- C21 al n- C34. El n- C24 fue el mayoritario, seguido del n- C25 y el n- C23. El porcentaje de n- C21, n- C22, n- C23, n- C27 y n- C28, aumentó durante la maduración, mientras que el porcentaje de n- C24, n- C25, n- C26, n- C29, n- C30 y C34 disminuyó desde el 3 de marzo 2003 hasta el 2 de abril 2003. Los hidrocarburos lineales saturados con número impar de átomos de carbono aumentaron (52.38 %, 52

  16. CHARACTERIZATION OF THE ALKANE-INDUCIBLE CYTOCHROME P450 (P450ALK) GENE FROM THE YEAST CANDIDA TROPICALIS: IDENTIFICATION OF A NEW P450 FAMILY

    Science.gov (United States)

    The P450alk gene, which is inducible by the assimilation of alkane in Candida tropicalis, was sequenced and characterized. Structural features described in promoter and terminator regions of Saccharomyces yeast genes are present in the P450alk gene and some particular structures ...

  17. Heat capacity and Joule-Thomson coefficient of selected n-alkanes at 0.1 and 10 MPa in broad temperature ranges

    DEFF Research Database (Denmark)

    Regueira Muñiz, Teresa; Varzandeh, Farhad; Stenby, Erling Halfdan

    2017-01-01

    Isobaric heat capacity of six n-alkanes, i.e. n-hexane, n-octane, n-decane, n-dodecane, n-tetradecane and n-hexadecane, was determined with a Calvet type differential heat-flux calorimeter at 0.1 and 10 MPa in a broad temperature range. The measured isobaric heat capacity data were combined...

  18. Modelling the phase equilibria of multicomponent mixtures containing CO2, alkanes, water, and/or alcohols using the quadrupolar CPA equation of state

    DEFF Research Database (Denmark)

    Bjørner, Martin Gamel; Kontogeorgis, Georgios

    2016-01-01

    In this work, a quadrupolar cubic plus association (qCPA) equation of state is evaluated for its ability to predict the phase equilibria of multicomponent mixtures containing CO2 and alkanes, alcohols, and/or water. A single binary interaction parameter is employed in qCPA for all binary...

  19. Distribution and origins of n-alkanes, hopanes, and steranes in rivers and marine sediments from Southwest Caspian coast, Iran: implications for identifying petroleum hydrocarbon inputs.

    Science.gov (United States)

    Shirneshan, Golshan; Bakhtiari, Alireza Riyahi; Memariani, Mahmoud

    2016-09-01

    The occurrence of n-alkanes and biomarkers (hopane and sterane) in surface sediments from Southwestern coasts of Caspian Sea and 28 rivers arriving to this lake, determined with a gas chromatography-mass spectrometry method, was used to assess the impacts of anthropogenic activities in the studied area. The concentrations of total n-alkanes (Σ21 n-alkane) in costal and riverine sediments varied from 249.2 to 3899.5 and 56 to 1622.4 μg g(-1), respectively. An evaluation of the source diagnostic indices indicated that petroleum related sources (petrogenic) were mainly contributed to n-alkanes in costal and most riverine sediments. Only the hydrocarbons in sediment of 3 rivers were found to be mainly of biogenic origin. Principal component analysis using hopane diagnostic ratios in costal and riverine sediments, and Anzali, Turkmenistan, and Azerbaijan oils were used to identify the sources of hydrocarbons in sediments. It was indicated that the anthropogenic contributions in most of the costal sediment samples are dominated with inputs of oil spills from Turkmenistan and Azerbaijan countries.

  20. Mechanism of Alkene, Alkane, and Alcohol Oxidation with H2O2 by an in Situ Prepared Mn-II/Pyridine-2-carboxylic Acid Catalyst

    NARCIS (Netherlands)

    Saisaha, Pattama; Dong, Jia Jia; Meinds, Tim G.; de Boer, Johannes W.; Hage, Ronald; Mecozzi, Francesco; Kasper, Johann B.; Browne, Wesley R.

    The oxidation of alkenes, alkanes, and alcohols with H2O2 is catalyzed efficiently using an in situ prepared catalyst comprised of a MnII salt and pyridine-2-carboxylic acid (PCA) together with a ketone in a wide range of solvents. The mechanism by which these reactions proceed is elucidated, with a

  1. Characterization of polychlorinated n-alkanes using comprehensive two-dimensional gas chromatography-electron-capture negative ionization time-of-flight mass spectrometry

    NARCIS (Netherlands)

    Korytar, P.; Parera, J.; Leonards, P.E.G.; Santos, F.J.; Boer, de J.; Brinkman, U.A.Th.

    2005-01-01

    Comprehensive two-dimensional gas chromatography with electron-capture negative ionization time-of-flight mass spectrometry (GC × GC¿ECNI-TOF-MS) is used to study the composition and characteristics of short-, medium- and long-chain polychlorinated n-alkane (PCA) mixtures. Distinct ordered

  2. The Effect of Using XO Computers on Students' Mathematics and Reading Abilities: Evidences from Learning Achievement Tests Conducted in Primary Education Schools in Mongolia

    Science.gov (United States)

    Yamaguchi, Shinobu; Sukhbaatar, Javzan; Takada, Jun-ichi; Dayan-Ochir, Khishigbuyan

    2014-01-01

    In 2008, Mongolia took part in One Laptop per Child (OLPC) project. Since that time, over 10,000 students in grades 2-5 in 43 primary education schools are using XO computers. This paper presents the findings of a study conducted in 2012 to evaluate the impact of the OLPC initiatives on students' literacy and math skills. This study covered 14…

  3. Optimizing the Noticing of Recasts via Computer-Delivered Feedback: Evidence That Oral Input Enhancement and Working Memory Help Second Language Learning

    Science.gov (United States)

    Sagarra, Nuria; Abbuhl, Rebekha

    2013-01-01

    This study investigates whether practice with computer-administered feedback in the absence of meaning-focused interaction can help second language learners notice the corrective intent of recasts and develop linguistic accuracy. A group of 218 beginning Anglophone learners of Spanish received 1 of 4 types of automated feedback (no feedback,…

  4. Source apportionment of PAHs and n-alkanes bound to PM1 collected near the Venice highway.

    Science.gov (United States)

    Valotto, Gabrio; Rampazzo, Giancarlo; Gonella, Francesco; Formenton, Gianni; Ficotto, Silvia; Giraldo, Giorgia

    2017-04-01

    n-Alkanes and polycyclic aromatic hydrocarbons (PAHs) bound to atmospheric particulate matter (PM 1 ) were investigated in a traffic site located in an urban area of Venice Province (Eastern Po Valley, Italy) during the cold season. Considering the critical situation affecting the Veneto Region concerning the atmospheric pollution and the general lack of information on PM 1 composition and emission in this area, this experimental study aims at determining the source profile, their relative contributions and the dispersion of finer particles. Four sources were identified and quantified using the Positive Matrix Factorization receptor model: (1) mixed combustions related to the residential activities, (2) agricultural biomass burning in addition to the resuspension of anthropogenic and natural debris carried by the wind, (3) gasoline and (4) diesel traffic-related combustions. The role of local atmospheric circulation was also investigated to identify the pollutant sources. Copyright © 2016. Published by Elsevier B.V.

  5. Elevation-dependent changes in n-alkane δD and soil GDGTs across the South Central Andes

    Science.gov (United States)

    Nieto-Moreno, Vanesa; Rohrmann, Alexander; van der Meer, Marcel T. J.; Sinninghe Damsté, Jaap S.; Sachse, Dirk; Tofelde, Stefanie; Niedermeyer, Eva M.; Strecker, Manfred R.; Mulch, Andreas

    2016-11-01

    Surface uplift of large plateaus may significantly influence regional climate and more specifically precipitation patterns and temperature, sometimes complicating paleoaltimetry interpretations. Thus, understanding the topographic evolution of tectonically active mountain belts benefits from continued development of reliable proxies to reduce uncertainties in paleoaltimetry reconstructions. Lipid biomarker-based proxies provide a novel approach to stable isotope paleoaltimetry and complement authigenic or pedogenic mineral proxy materials, in particular outside semi-arid climate zones where soil carbonates are not abundant but (soil) organic matter has a high preservation potential. Here we present δD values of soil-derived n-alkanes and mean annual air temperature (MAT) estimates based on branched glycerol dialkyl glycerol tetraether (brGDGT) distributions to assess their potential for paleoelevation reconstructions in the southern central Andes. We analyzed soil samples across two environmental and hydrological gradients that include a hillslope (26-28°S) and a valley (22-24°S) transect on the windward flanks of Central Andean Eastern Cordillera in NW Argentina. Our results show that present-day n-alkane δD values and brGDGT-based MAT estimates are both linearly related with elevation and in good agreement with present-day climate conditions. Soil n-alkanes show a δD lapse rate (Δ (δD)) of - 1.64 ‰ / 100 m (R2 = 0.91, p Colombia and Bolivia and the Equatorial and Peruvian Andes. BrGDGT-derived soil temperatures are similar to monitored winter temperatures in the region and show a lapse rate of ΔT = - 0.51 °C / 100 m (R2 = 0.91, p < 0.01), comparable with lapse rates from in situ soil temperature measurements, satellite-derived land-surface temperatures at this transect, and weather stations from the Eastern Cordillera at similar latitude. As a result of an increasing leeward sampling position along the valley transect lapse rates are biased towards

  6. Stable Hydrogen Isotopes of Terrestrial n-alkanes record the Mid Younger Dryas Event in European Lakes

    Science.gov (United States)

    Muegler, I.; Gleixner, G.; Sachse, D.; Grafenstein, U. V.

    2007-12-01

    Compound-specific hydrogen isotope measurements (expressed as δD values) on lacustrine long- chained n-alkanes are a potentially promising means of reconstructing variations in the isotopic composition of continental precipitation in the geological past. Long-chain n-alkanes are produced in the leaf waxes of terrestrial higher plants and have been shown to preserve the hydrogen isotope composition of precipitation being influenced by atmospheric moisture source, evaporation as well as plant physiology. Since δD values are determined directly on carbon-bound hydrogen, which is non-exchangeable even at higher temperatures biological and environmental source conditions can be preserved over geological timescales. Here, we present a record of n-alkane δD values, \\( nC27 - nC31 \\), from the Ammersee, southern Germany and Lac d'Annecy, French Alps spanning the time period from the Oldest Dryas to Preboreal (14 ka to 11 ka BP). We compare biomarker hydrogen isotopic signatures to oxygen-isotope ratios of precipitation inferred from deep-lake ostracods from the Ammersee as well to GRIP \\(δ18\\)O values. The remarkable climate shift at the onset of the Younger Dryas (YD) (12.9 to 11.6 ka BP) is recorded in the \\(δ18\\)O values as well as the hydrogen isotope signal with a pronounced drop of approx. - 40‰ in D at the Ammersee and a minor negative excursion of - (20‰) in D at Lac d'Annecy. This depletion is consistent with a colder and dryer climate and the expansion of grasslands in the lake catchments as recorded in a significant increase of grass-derived \\( nC31 \\). A sudden remarkable deuterium enrichment of about 100‰ in D is apparent in both lakes and marks the mid-Younger Dryas event (MYDE), which is also reflected in the GRIP and Ammersee \\(δ18\\)O values. δD values during this event reach or even exceed the following Holocene level. The simultaneous appearance of this event in different locations suggests a climate driven by mechanisms like the

  7. Efficient Hydrogenolysis of Alkanes at Low Temperature and Pressure Using Tantalum Hydride on MCM-41, and a Quantum Chemical Study

    KAUST Repository

    Polshettiwar, Vivek

    2012-02-10

    Hydrogenolysis of hydrocarbons is of considerable technological importance for applications such as the hydroprocessing of petrochemical feedstocks to generate high-value and useful chemicals and fuels. We studied the catalytic activity of tantalum hydride supported on MCM-41 for the hydrogenolysis of alkanes at low temperature and low atmospheric pressure in a dynamic reactor. The reactions proceed with good turnover numbers, and the catalyst could be reused for several times, which makes the overall catalytic process sustainable. We derived the plausible mechanism by using DFT calculations and identified the preferred pathways by the analysis of potential energy surface. Our results and the proposed reaction mechanism demonstrate the viability of the "catalyst-by-design" approach. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1994-12-31

    During the course of the first three years of the Cooperative Agreement, the authors uncovered a family of metal perhaloporphyrin complexes which had unprecedented activity for the selective air-oxidation of light alkanes to alcohols. The reactivity of light hydrocarbon substrates with air or oxygen was in the order: isobutane > propane > ethane > methane, in accord with their homolytic bond dissociation energies. Isobutane was so reactive that the proof-of-concept stage of a process for producing tert-butyl alcohol from isobutane was begun (Phase 5). It was proposed that as more active catalytic systems were developed (Phases 4, 6), propane, then ethane and finally methane oxidations will move into this stage (Phases 7 through 9). As of this writing, however, the program has been terminated during the later stages of Phase 5 and 6 so that further work is not anticipated. 72 refs.

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

    Science.gov (United States)

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

    2011-10-01

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

  10. Oh Magadi! Interpreting isoGDGTs and n-alkanes in a saline tropical lake: Lake Magadi, Kenya

    Science.gov (United States)

    Ferland, T. M.; Werne, J. P.; Castañeda, I. S.; Cohen, A. S.; Lowenstein, T. K.; Deocampo, D.; Renaut, R.; Bernhart, O. R.

    2017-12-01

    The Hominin Sites and Paleolakes Drilling Project (HSPDP) seeks to understand the paleoclimatic and paleoenvironmental context of hominin adaptation and evolution by analysis of paleolacustrine cores taken near key hominin fossil and artifact localities in Kenya and Ethiopia. We present biomarker and compound specific isotope data from a 200 m drill core from Lake Magadi, Kenya. Located 20 km from the Koora Plain in the southern Kenya Rift, and adjacent to the Olorgesailie basin, Lake Magadi is in one of the richest Early-Late Pleistocene archaeological localities in Africa, a region that has been key in debates about the relationship between climate and evolution. Present-day Lake Magadi is a saline pan, a descendant of a series of paleolakes that have occupied its drainage basin and progressively dried for approximately one million years. Nearly 70% of samples analyzed for n-alkanes recorded a robust terrestrial signal. The majority of samples did not contain the complete suite of branched GDGTs necessary to reconstruct temperature from the Methylation of Branched Tetraethers and Cyclisation of Branched Tetraethers (MBT/CBT; Weijers et al., 2007) proxy. The TetraEther indeX with 86 carbon atoms (TEX86; Schouten et al., 2002) temperature proxy was established for 90% of samples analyzed for isoGDGTs, however the Methane and Ring Indices (Zhang et al., 2011; Zhang et al., 2016) suggest that the TEX86 is not applicable to temperature reconstruction at Magadi. Despite this, the Magadi TEX86 temperature reconstruction appears to agree with not only the trends in our n-alkane data but with other regional and global records, including the GRIP-2 δ18O record. We compare our temperature data to other records in the region, and investigate influences on our TEX86 data including microbial community turnover and lake drying.

  11. Diversity of crude oil-degrading bacteria and alkane hydroxylase (alkB) genes from the Qinghai-Tibet Plateau.

    Science.gov (United States)

    Long, Haozhi; Wang, Yilin; Chang, Sijing; Liu, Guangxiu; Chen, Tuo; Huo, Guanghua; Zhang, Wei; Wu, Xiukun; Tai, Xisheng; Sun, Likun; Zhang, Baogui

    2017-03-01

    The aim of this study was to survey the response of the microbial community to crude oil and the diversity of alkane hydroxylase (alkB) genes in soil samples from the Qinghai-Tibet Plateau (QTP). The enrichment cultures and clone libraries were used. Finally, 53 isolates and 94 alkB sequences were obtained from 10 pristine soil samples after enrichment at 10 °C with crude oil as sole carbon source. The isolates fell into the phyla Proteobacteria, Actinobacteria, and Bacteroidetes, with the dominance of Pseudomonas and Acinetobacter. The composition of degraders was different from polar habitats where Acinetobacter sp. is not a predominant responder of alkane degradative microbial communities. Phylogenetic analysis showed that the alkB genes from isolates and enrichment communities formed eight clusters and mainly related with alkB genes of Pseudomonas, Rhodococcus, and Acinetobacter. The alkB gene diversity in the QTP was lower than marine environments and polar soil samples. In particular, a total of 10 isolates exhibiting vigorous growth with crude oil could detect no crude oil degradation-related gene sequences, such as alkB, P450, almA, ndoB, and xylE genes. The Shannon-Wiener index of the alkB clone libraries from the QTP ranged from 1.00 to 2.24 which is similar with polar pristine soil samples but lower than that of contaminated soils. These results indicated that the Pseudomonas, Acinetobacter, and Rhodococcus genera are the candidate for in situ bioremediation, and the environment of QTP may be still relatively uncontaminated by crude oil.

  12. Portraits of Middle School Students Constructing Evidence-Based Arguments during Problem-Based Learning: The Impact of Computer-Based Scaffolds

    Science.gov (United States)

    Belland, Brian R.

    2010-01-01

    A critical step in problem-based learning (PBL) units occurs when groups present their solution to the central problem. This is challenging for middle school students because it involves the creation of an evidence-based argument (Krajcik et al., "Journal of the Learning Sciences" 7:313-350, 1998). Using a mixed method design, this study…

  13. Hydrogen isotopes of n-alkanes and n-alkanoic acids as tracers of precipitation in a temperate forest and implications for paleorecords

    Science.gov (United States)

    Freimuth, Erika J.; Diefendorf, Aaron F.; Lowell, Thomas V.

    2017-06-01

    The hydrogen isotopic composition of leaf waxes (δDwax) primarily reflects that of plant source water. Therefore, sedimentary δDwax records are increasingly used to reconstruct the δD of past precipitation (δDp) and to investigate paleohydrologic changes. Such reconstructions rely on estimates of apparent fractionation (εapp) between δDp and the resulting δDwax. However, εapp values are modified by numerous environmental and biological factors during leaf wax production. As a result, εapp can vary widely among plant species and growth forms. This complicates estimation of accurate εapp values and presents a central challenge to quantitative leaf wax paleohydrology. During the 2014 growing season, we examined εapp in the five deciduous angiosperm tree species (Prunus serotina, Acer saccharinum, Quercus rubra, Quercus alba, and Ulmus americana) that dominate the temperate forest at Brown's Lake Bog, Ohio, USA. We sampled individuals of each species at weekly to monthly intervals from March to October and report δD values of n-C29 alkanes (δDn-C29 alkane) and n-C28 alkanoic acids (δDn-C28 acid), as well as xylem (δDxw) and leaf water (δDlw). n-Alkane synthesis was most intense 2-3 weeks after leaf emergence and ceased thereafter, whereas n-alkanoic acid synthesis continued throughout the entire growing season. During bud swell and leaf emergence, δDlw was a primary control on δDn-C29 alkane and δDn-C28 acid values, which stabilized once leaves became fully expanded. Metabolic shifts between young and mature leaves may be an important secondary driver of δDwax changes during leaf development. In mature autumn leaves of all species, the mean εapp for n-C29 alkane (-107‰) was offset by approximately -19‰ from the mean εapp for n-C28 alkanoic acid (-88‰). These results indicate that in temperate settings n-alkanes and n-alkanoic acids from deciduous trees are distinct with respect to their abundance, timing of synthesis, and εapp values.

  14. Predominance of even carbon-numbered n-alkanes from lacustrine sediments in Linxia Basin, NE Tibetan Plateau: Implications for climate change

    Energy Technology Data Exchange (ETDEWEB)

    Wang Yongli [Key Laboratory of Petroleum Resources Research, Institute of Geology and Geophysics, Chinese Academy of Sciences, Lanzhou 730000 (China)] [Institute of Tibetan and Plateau Research, Chinese Academy of Sciences, Beijing 100085 (China); Fang Xiaomin, E-mail: fangxm@itpcas.ac.cn [Institute of Tibetan and Plateau Research, Chinese Academy of Sciences, Beijing 100085 (China)] [Key Laboratory of Western Resources and Environment of Education Ministry, College at Earth and Environment Sciences, University of Lanzhou, Lanzhou 730000 (China); Zhang Tongwei [Key Laboratory of Western Resources and Environment of Education Ministry, College at Earth and Environment Sciences, University of Lanzhou, Lanzhou 730000 (China); Li Yuanmao; Wu Yingqin; He Daxiang; Wang Youxiao [Key Laboratory of Petroleum Resources Research, Institute of Geology and Geophysics, Chinese Academy of Sciences, Lanzhou 730000 (China)

    2010-10-15

    Research highlights: {yields} This study reports the first observation of predominant even carbon-numbered n-alkanes of sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. {yields} Certain types of special autochthonous bacteria are a possible source for the special distribution of even carbon-numbered n-alkanes in lacustrine sediments. {yields} These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change. {yields} A close correspondence among the low ratio of n-C{sub 27}/n-C{sub 31}, the heavy {delta}{sup 13}C values of TOC and a strong even carbon-number predominance (low OEP{sub 16-20} values) from approximately 6.5 to 4.4 Ma and at approximately 8 Ma in the studied section suggests that n-alkanes with a high predominance of even carbon-numbers may be treated as geochemical proxies for arid climate. - Abstract: This study reports the first observation of predominant even C-numbered n-alkanes from sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. The n-alkanes showed a bimodal distribution that is characterised by a centre at n-C{sub 16}-n-C{sub 20} with maximum values at n-C{sub 18} and n-C{sub 27}-n-C{sub 31} as well as at n-C{sub 29}. The first mode shows a strong even C-number predominance (OEP{sub 16-20} 0.34-0.66). In contrast, the second mode has a strong odd C-number predominance (OEP{sub 27-31} 1.20-2.45). Certain types of special autochthonous bacteria are a possible source for this distribution of even C-numbered n-alkanes in lacustrine sediments. These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded

  15. Predominance of even carbon-numbered n-alkanes from lacustrine sediments in Linxia Basin, NE Tibetan Plateau: Implications for climate change

    International Nuclear Information System (INIS)

    Wang Yongli; Fang Xiaomin; Zhang Tongwei; Li Yuanmao; Wu Yingqin; He Daxiang; Wang Youxiao

    2010-01-01

    Research highlights: → This study reports the first observation of predominant even carbon-numbered n-alkanes of sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. → Certain types of special autochthonous bacteria are a possible source for the special distribution of even carbon-numbered n-alkanes in lacustrine sediments. → These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change. → A close correspondence among the low ratio of n-C 27 /n-C 31 , the heavy δ 13 C values of TOC and a strong even carbon-number predominance (low OEP 16-20 values) from approximately 6.5 to 4.4 Ma and at approximately 8 Ma in the studied section suggests that n-alkanes with a high predominance of even carbon-numbers may be treated as geochemical proxies for arid climate. - Abstract: This study reports the first observation of predominant even C-numbered n-alkanes from sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. The n-alkanes showed a bimodal distribution that is characterised by a centre at n-C 16 -n-C 20 with maximum values at n-C 18 and n-C 27 -n-C 31 as well as at n-C 29 . The first mode shows a strong even C-number predominance (OEP 16-20 0.34-0.66). In contrast, the second mode has a strong odd C-number predominance (OEP 27-31 1.20-2.45). Certain types of special autochthonous bacteria are a possible source for this distribution of even C-numbered n-alkanes in lacustrine sediments. These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change.

  16. Examination of forensic entomology evidence using computed tomography scanning: case studies and refinement of techniques for estimating maggot mass volumes in bodies.

    Science.gov (United States)

    Johnson, Aidan; Archer, Melanie; Leigh-Shaw, Lyndie; Pais, Mike; O'Donnell, Chris; Wallman, James

    2012-09-01

    A new technique has recently been developed for estimating the volume of maggot masses on deceased persons using post-mortem CT scans. This allows volume to be measured non-invasively and factored into maggot mass temperature calculations for both casework and research. Examination of admission scans also allows exploration of entomological evidence in anatomical areas not usually exposed by autopsy (e.g. nasal cavities and facial sinuses), and before autopsy disrupts the maggot distribution on a body. This paper expands on work already completed by providing the x-ray attenuation coefficient by way of Hounsfield unit (HU) values for various maggot species, maggot masses and human tissue adjacent to masses. Specifically, this study looked at the HU values for four forensically important blowfly larvae: Lucilia cuprina, L. sericata, Calliphora stygia and C. vicina. The Calliphora species had significantly lower HU values than the Lucilia species. This might be explained by histological analysis, which revealed a non-significant trend, suggesting that Calliphora maggots have a higher fat content than the Lucilia maggots. It is apparent that the variation in the x-ray attenuation coefficient usually precludes its use as a tool for delineating the maggot mass from human tissue and that morphology is the dominant method for delineating a mass. This paper also includes three case studies, which reveal different applications for interpreting entomological evidence using post-mortem CT scans.

  17. The Sex and Race Specific Relationship between Anthropometry and Body Fat Composition Determined from Computed Tomography: Evidence from the Multi-Ethnic Study of Atherosclerosis.

    Science.gov (United States)

    Mongraw-Chaffin, Morgana; Golden, Sherita Hill; Allison, Matthew A; Ding, Jingzhong; Ouyang, Pamela; Schreiner, Pamela J; Szklo, Moyses; Woodward, Mark; Young, Jeffery Hunter; Anderson, Cheryl A M

    2015-01-01

    Few studies have investigated the relationship of anthropometric measurements with computed tomography (CT) body fat composition, and even fewer determined if these relationships differ by sex and race. CT scans from 1,851 participants in the population based Multi-Ethnic Study of Atherosclerosis were assessed for visceral and subcutaneous fat areas by semi-automated segmentation of body compartments. Regression models were used to investigate relationships for anthropometry with visceral and subcutaneous fat separately by sex and race/ethnicity. Participants were 50% female, 41% Caucasian, 13% Asian, 21% African American, and 25% Hispanic. For visceral fat, the positive relationship with weight (p = 0.028), waist circumference (panthropometry and underlying adiposity differs by sex and race/ethnicity. When anthropometry is used as a proxy for visceral fat in research, sex-specific models should be used.

  18. An arsenate-reducing and alkane-metabolizing novel bacterium, Rhizobium arsenicireducens sp. nov., isolated from arsenic-rich groundwater.

    Science.gov (United States)

    Mohapatra, Balaram; Sarkar, Angana; Joshi, Swati; Chatterjee, Atrayee; Kazy, Sufia Khannam; Maiti, Mrinal Kumar; Satyanarayana, Tulasi; Sar, Pinaki

    2017-03-01

    A novel arsenic (As)-resistant, arsenate-respiring, alkane-metabolizing bacterium KAs 5-22 T , isolated from As-rich groundwater of West Bengal was characterized by physiological and genomic properties. Cells of strain KAs 5-22 T were Gram-stain-negative, rod-shaped, motile, and facultative anaerobic. Growth occurred at optimum of pH 6.0-7.0, temperature 30 °C. 16S rRNA gene affiliated the strain KAs 5-22 T to the genus Rhizobium showing maximum similarity (98.4 %) with the type strain of Rhizobium naphthalenivorans TSY03b T followed by (98.0 % similarity) Rhizobium selenitireducens B1 T . The genomic G + C content was 59.4 mol%, and DNA-DNA relatedness with its closest phylogenetic neighbors was 50.2 %. Chemotaxonomy indicated UQ-10 as the major quinone; phosphatidylethanolamine, phosphatidylglycerol, and diphosphatidylglycerol as major polar lipids; C 16:0 , C 17:0 , 2-OH C 10:0 , 3-OH C 16:0 , and unresolved C 18:1 ɷ7C/ɷ9C as predominant fatty acids. The cells were found to reduce O 2 , As 5+ , NO 3 - , SO 4 2- and Fe 3+ as alternate electron acceptors. The strain's ability to metabolize dodecane or other alkanes as sole carbon source using As 5+ as terminal electron acceptor was supported by the presence of genes encoding benzyl succinate synthase (bssA like) and molybdopterin-binding site (mopB) of As 5+ respiratory reductase (arrA). Differential phenotypic, chemotaxonomic, genotypic as well as physiological properties revealed that the strain KAs 5-22 T is separated from its nearest recognized Rhizobium species. On the basis of the data presented, strain KAs 5-22 T is considered to represent a novel species of the genus Rhizobium, for which the name Rhizobium arsenicireducens sp. nov. is proposed as type strain (=LMG 28795 T =MTCC 12115 T ).

  19. H-Abstraction by OH from Large Branched Alkanes: Overall Rate Measurements and Site-Specific Tertiary Rate Calculations

    KAUST Repository

    Liu, Dapeng

    2017-01-10

    Reaction rate coefficients for the reaction of hydroxyl (OH) radicals with nine large branched alkanes (i.e., 2-methyl-3-ethyl-pentane, 2,3-dimethyl-pentane, 2,2,3-trimethylbutane, 2,2,3-trimethyl-pentane, 2,3,4-trimethyl-pentane, 3-ethyl-pentane, 2,2,3,4-tetramethyl-pentane, 2,2-dimethyl-3-ethyl-pentane, and 2,4-dimethyl-3-ethyl-pentane) are measured at high temperatures (900-1300 K) using a shock tube and narrow-line-width OH absorption diagnostic in the UV region. In addition, room-temperature measurements of six out of these nine rate coefficients are performed in a photolysis cell using high repetition laser-induced fluorescence of OH radicals. Our experimental results are combined with previous literature measurements to obtain three-parameter Arrhenius expressions valid over a wide temperature range (300-1300 K). The rate coefficients are analyzed using the next-nearest-neighbor (N-N-N) methodology to derive nine tertiary (T003, T012, T013, T022, T023, T111, T112, T113, and T122) site-specific rate coefficients for the abstraction of H atoms by OH radicals from branched alkanes. Derived Arrhenius expressions, valid over 950-1300 K, are given as (the subscripts denote the number of carbon atoms connected to the next-nearest-neighbor carbon): T003 = 1.80 × 10-10 exp(-2971 K/T) cm3 molecule-1 s-1; T012 = 9.36 × 10-11 exp(-3024 K/T) cm3 molecule-1 s-1; T013 = 4.40 × 10-10 exp(-4162 K/T) cm3 molecule-1 s-1; T022 = 1.47 × 10-10 exp(-3587 K/T) cm3 molecule-1 s-1; T023 = 6.06 × 10-11 exp(-3010 K/T) cm3 molecule-1 s-1; T111 = 3.98 × 10-11 exp(-1617 K/T) cm3 molecule-1 s-1; T112 = 9.08 × 10-12 exp(-3661 K/T) cm3 molecule-1 s-1; T113 = 6.74 × 10-9 exp(-7547 K/T) cm3 molecule-1 s-1; T122 = 3.47 × 10-11 exp(-1802 K/T) cm3 molecule-1 s-1.

  20. Literature study and experimental investigations into the production of organic iodine compounds from alkane-vapour/air mixtures with radioiodine in the radiation field

    International Nuclear Information System (INIS)

    Leskopf, W.; Holl, S.; Bleier, K.

    1992-01-01

    It was assumed in these investigations that these compounds originated in the gas phase by irradiation induced reactions with radioiodine. Alkane(methane, ethane, propane, n-butane) vapour/air mixtures were radiolysed with iodine in a Co-60 gamma source. The parameter varied were the concentrations of iodine (6.85 E-09 mol/ml - 3.43 E-06 mol/ml) and of the alkanes (1.81 E-05 mol/ml - 3.72 E-10 mol/ml) as well as the irradiation doses (4.45 E + 02 Gy - 1.17 E + 05 Gy). The gaseous reaction mixtures were analysed qualitatively and quantitatively by an ECD- and a MSD-detector for iodine compounds difficult to separate. (orig.) [de

  1. Calculation for liquid-liquid equilibria of quaternary alkane-ethyl acetate-methanol-water systems used in counter-current chromatography.

    Science.gov (United States)

    Chen, Jian; Zhao, Mengqiang; Yu, Yanmei; Li, Zongcheng

    2007-06-01

    The calculation of liquid-liquid equilibrium compositions of solvent systems is very important for the work on counter-current chromatography (CCC), especially the phase composition and volume ratio obtained from liquid-liquid equilibrium calculation. In this work, liquid-liquid equilibria of quaternary Arizona solvent systems, alkane-ethyl acetate-methanol-water, and related ternary systems are correlated and predicted using the non-random two-liquid model (NRTL). Hexane, heptane and isooctane are the used alkanes. The parameters in the model are regressed only with the special systems considered. Detailed comparison with experimental data shows that liquid-liquid equilibria of these systems can be predicted with greatly improved accuracy as compared to the group contribution method (UNIFAC).

  2. An efficient nitration of light alkanes and the alkyl side-chain of aromatic compounds with nitrogen dioxide and nitric acid catalyzed by N-hydroxyphthalimide.

    Science.gov (United States)

    Nishiwaki, Yoshiki; Sakaguchi, Satoshi; Ishii, Yasutaka

    2002-08-09

    Nitration of light alkanes and the alkyl side-chain of aromatic compounds with NO(2) and HNO(3) was successfully achieved by the use of N-hydroxyphthalimide (NHPI) as a catalyst under relatively mild conditions. For example, the nitration of propane with NO(2) catalyzed by NHPI at 100 degrees C for 14 h gave 2-nitropropane in good yield without formation of 1-nitropropane and cleaved products such as nitroethane and nitromethane. Various aliphatic nitroalkanes, which are difficult to prepare by conventional methods, could be selectively obtained by means of the present methodology by using NHPI as the key catalyst. In addition, the side-chain nitration of alkylbenzenes such as toluene was selectively carried out to lead to alpha-nitrotoluene without the ring nitration. The present reaction provides an efficient selective method for the nitration of light alkanes and alkylbenzenes, which has been very difficult to carry out so far.

  3. Rationalization and Prediction of the Equivalent Alkane Carbon Number (EACN) of Polar Hydrocarbon Oils with COSMO-RS σ-Moments.

    Science.gov (United States)

    Lukowicz, Thomas; Benazzouz, Adrien; Nardello-Rataj, Véronique; Aubry, Jean-Marie

    2015-10-20

    The equivalent alkane carbon numbers (EACNs) of 20 polar hydrocarbon oils are determined by the fishtail method. These values supplemented by 43 already reported EACNs of other hydrocarbons are rationalized by using the COSMO-RS σ-moments as descriptors for a QSPR analysis. A reliable model, with only two meaningful physicochemical parameters, namely the surface area (M0(X)) and the overall polarity (M2(X)) of the oil X, is able to predict the EACN values of a large variety of oils including (cyclo)alkanes, (cyclo)alkenes, terpenes, aromatics, alkynes, and chloroalkanes and to rationalize structural effects on EACNs. Furthermore, the dependence of the EACN of homologous oils on the chain length provides some molecular insight into how the different oils penetrate into the interfacial film of surfactants.

  4. Reconstruction of palaeoenvironmental change in a late Miocene peatland, as deduced from distribution patterns of lipid biomarkers and the carbon isotopic composition of individual n-alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Johnny Briggs; David Large [University of Nottingham, Nottingham (United Kingdom). School of Chemical, Environmental and Mining Engineering

    2007-07-01

    In order to comprehend the processes of peatland evolution, and to make projections concerning the long-term response of the peatland carbon reservoir to environmental change, we consider thick lignite deposits formed over periods of 1 my. To explore the long-term response of peatland to changing climate, we have investigated the reaction of peatland plant communities to changes in the exogenic carbon cycle on timescales exceeding 100 ky. This was achieved by examining variations in bulk {delta}{sup 13}C, biomarker distributions, and compound specific {delta}{sup 13}C compositions of plant derived n-alkanes, from orbitally tuned early Miocene lignite. 21 samples were analysed from the Morwell 1B lignite, Gippsland Basin, Australia. These samples encompassed 27.8 m of lignite, thought to correspond to the time interval of 22.29 - 22.68 Ma. Prior to analysis by GC-IR-MS, the n-alkanes were purified using urea adduction. Analysis of the relative distributions of n-alkanes and aliphatic Terpenoid biomarkers was undertaken by GC-MS. The distributions of Terpenoid biomarkers indicated that no correlation exists between bulk {delta}{sup 13}C and the relative contribution of angiosperm to gymnosperm type vegetation. The n-alkane distributions demonstrated a link between bulk {delta}{sup 13}C and aquatic macrophytes, (greatest contributor to the C{sub 29} homologue in peat forming vegetation is terrestrial plants, whereas the C{sub 25} homologue is a proxy for aquatic macrophytes). This suggests that after accounting for atmospheric {delta}{sup 13}C, bulk carbon isotopes carry a signature for the hydrological conditions of plant growth. 22 refs., 4 figs.

  5. Fusing catalase to an alkane-producing enzyme maintains enzymatic activity by converting the inhibitory byproduct H2O2 to the cosubstrate O2.

    Science.gov (United States)

    Andre, Carl; Kim, Sung Won; Yu, Xiao-Hong; Shanklin, John

    2013-02-19

    Biologically produced alkanes represent potential renewable alternatives to petroleum-derived chemicals. A cyanobacterial pathway consisting of acyl-Acyl Carrier Protein reductase and an aldehyde-deformylating oxygenase (ADO) converts acyl-Acyl Carrier Proteins into corresponding n-1 alkanes via aldehyde intermediates in an oxygen-dependent manner (K(m) for O(2), 84 ± 9 µM). In vitro, ADO turned over only three times, but addition of more ADO to exhausted assays resulted in additional product formation. While evaluating the peroxide shunt to drive ADO catalysis, we discovered that ADO is inhibited by hydrogen peroxide (H(2)O(2)) with an apparent K(i) of 16 ± 6 µM and that H(2)O(2) inhibition is of mixed-type with respect to O(2). Supplementing exhausted assays with catalase (CAT) restored ADO activity, demonstrating that inhibition was reversible and dependent on H(2)O(2), which originated from poor coupling of reductant consumption with alkane formation. Kinetic analysis showed that long-chain (C14-C18) substrates follow Michaelis-Menten kinetics, whereas short and medium chains (C8-C12) exhibit substrate inhibition. A bifunctional protein comprising an N-terminal CAT coupled to a C-terminal ADO (CAT-ADO) prevents H(2)O(2) inhibition by converting it to the cosubstrate O(2). Indeed, alkane production by the fusion protein is observed upon addition of H(2)O(2) to an anaerobic reaction mix. In assays, CAT-ADO turns over 225 times versus three times for the native ADO, and its expression in Escherichia coli increases catalytic turnovers per active site by fivefold relative to the expression of native ADO. We propose the term "protection via inhibitor metabolism" for fusion proteins designed to metabolize inhibitors into noninhibitory compounds.

  6. Preferential activation of primary C–H bonds in the reactions of small alkanes with the diatomic MgO+. cation

    Czech Academy of Sciences Publication Activity Database

    Schröder, Detlef; Roithová, J.; Alikhani, E.; Kwapien, K.; Sauer, J.

    2010-01-01

    Roč. 16, č. 13 (2010), s. 4110-4119 ISSN 0947-6539 R&D Projects: GA AV ČR KJB400550704; GA ČR GA203/08/1487 Grant - others: ERC (XE) HORIZOMS AdG226373 Institutional research plan: CEZ:AV0Z40550506 Keywords : alkanes * C-H activation * density functional calculations * magnesium oxide Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.476, year: 2010

  7. Using Odd-Alkanes as a Carbon Source to Increase the Content of Nutritionally Important Fatty Acids in Candida krusei, Trichosporon cutaneum, and Yarrowia lipolytica

    Czech Academy of Sciences Publication Activity Database

    Matátková, O.; Gharwalová, L.; Zimola, M.; Řezanka, Tomáš; Masák, J.; Kolouchová, I.

    2017-01-01

    Roč. 2017, October (2017), s. 1-9, č. článku 8195329. ISSN 1687-8760 R&D Projects: GA ČR(CZ) GA17-00027S Institutional support: RVO:61388971 Keywords : HYDROCARBON-UTILIZING MICROORGANISMS * CHAIN N-ALKANES * POTENTIAL APPLICATIONS Subject RIV: EE - Microbiology, Virology OBOR OECD: Microbiology Impact factor: 0.901, year: 2016

  8. Can an evidence-based book club intervention delivered via a tablet computer improve physical activity in middle-aged women?

    Science.gov (United States)

    Ehlers, Diane K; Huberty, Jennifer L; de Vreede, Gert-Jan

    2015-02-01

    Fewer than 50% of middle-aged women participate in regular physical activity (PA). Innovative approaches that engage women who may not otherwise participate in PA programs are warranted. The purpose of this study was to explore the acceptability and feasibility of a 12-week tablet-based book club for improving middle-aged women's PA. Thirty women (35-64 years of age) were randomized to the Fit Minded Tablet (n=15) and the Standard Fit Minded (i.e., face-to-face intervention) (n=15) groups. The Fit Minded Tablet was adapted from the Standard Fit Minded, a previously tested, theory-based book club intervention using books as a platform for discussion and group support to help women adopt regular PA. Both interventions met weekly for 3 months, for a total of 12 sessions. Tablet group participants accessed materials (e.g., e-books, workbook, live/recorded videoconferencing) via a tablet computer; Standard group participants received materials (e.g., printed books, workbook, live face-to-face meetings) in person. Feasibility (i.e., implementation and expansion) was assessed using process evaluation, qualitative interviews, satisfaction surveys, and quantitative outcome assessments. Women in the Tablet group attended fewer meetings (mean, 8.25) than women in the Standard group (mean, 9.9). Videoconferencing, digital literacy, and participant engagement limitations were observed in the Tablet group. Tablet participants enjoyed the e-books but thought technology barriers hindered their engagement during meetings. Women in both groups valued the support they received from other group members. Standard participants cited this support as a key contributor to their PA changes, whereas Tablet participants reported needing in-person contact to feel more connected. Given the popularity of tablet computers and the value that middle-aged women place on group interaction to support their PA behaviors, additional research is warranted to determine best strategies for optimizing

  9. Complex regulation of Hsf1-Skn7 activities by the catalytic subunits of PKA in Saccharomyces cerevisiae: experimental and computational evidences.

    Science.gov (United States)

    Pérez-Landero, Sergio; Sandoval-Motta, Santiago; Martínez-Anaya, Claudia; Yang, Runying; Folch-Mallol, Jorge Luis; Martínez, Luz María; Ventura, Larissa; Guillén-Navarro, Karina; Aldana-González, Maximino; Nieto-Sotelo, Jorge

    2015-07-27

    The cAMP-dependent protein kinase regulatory network (PKA-RN) regulates metabolism, memory, learning, development, and response to stress. Previous models of this network considered the catalytic subunits (CS) as a single entity, overlooking their functional individualities. Furthermore, PKA-RN dynamics are often measured through cAMP levels in nutrient-depleted cells shortly after being fed with glucose, dismissing downstream physiological processes. Here we show that temperature stress, along with deletion of PKA-RN genes, significantly affected HSE-dependent gene expression and the dynamics of the PKA-RN in cells growing in exponential phase. Our genetic analysis revealed complex regulatory interactions between the CS that influenced the inhibition of Hsf1/Skn7 transcription factors. Accordingly, we found new roles in growth control and stress response for Hsf1/Skn7 when PKA activity was low (cdc25Δ cells). Experimental results were used to propose an interaction scheme for the PKA-RN and to build an extension of a classic synchronous discrete modeling framework. Our computational model reproduced the experimental data and predicted complex interactions between the CS and the existence of a repressor of Hsf1/Skn7 that is activated by the CS. Additional genetic analysis identified Ssa1 and Ssa2 chaperones as such repressors. Further modeling of the new data foresaw a third repressor of Hsf1/Skn7, active only in the absence of Tpk2. By averaging the network state over all its attractors, a good quantitative agreement between computational and experimental results was obtained, as the averages reflected more accurately the population measurements. The assumption of PKA being one molecular entity has hindered the study of a wide range of behaviors. Additionally, the dynamics of HSE-dependent gene expression cannot be simulated accurately by considering the activity of single PKA-RN components (i.e., cAMP, individual CS, Bcy1, etc.). We show that the differential

  10. Succinimide Formation from an NGR-Containing Cyclic Peptide: Computational Evidence for Catalytic Roles of Phosphate Buffer and the Arginine Side Chain

    Directory of Open Access Journals (Sweden)

    Ryota Kirikoshi

    2017-02-01

    Full Text Available The Asn-Gly-Arg (NGR motif and its deamidation product isoAsp-Gly-Arg (isoDGR have recently attracted considerable attention as tumor-targeting ligands. Because an NGR-containing peptide and the corresponding isoDGR-containing peptide target different receptors, the spontaneous NGR deamidation can be used in dual targeting strategies. It is well known that the Asn deamidation proceeds via a succinimide derivative. In the present study, we computationally investigated the mechanism of succinimide formation from a cyclic peptide, c[CH2CO-NGRC]-NH2, which has recently been shown to undergo rapid deamidation in a phosphate buffer. An H2PO4− ion was explicitly included in the calculations. We employed the density functional theory using the B3LYP functional. While geometry optimizations were performed in the gas phase, hydration Gibbs energies were calculated by the SM8 (solvation model 8 continuum model. We have found a pathway leading to the five-membered ring tetrahedral intermediate in which both the H2PO4− ion and the Arg side chain act as catalyst. This intermediate, once protonated at the NH2 group on the five-membered ring, was shown to easily undergo NH3 elimination leading to the succinimide formation. This study is the first to propose a possible catalytic role for the Arg side chain in the NGR deamidation.

  11. Concurrent La and A-Site Vacancy Doping Modulates the Thermoelectric Response of SrTiO3: Experimental and Computational Evidence.

    Science.gov (United States)

    Azough, Feridoon; Jackson, Samuel S; Ekren, Dursun; Freer, Robert; Molinari, Marco; Yeandel, Stephen R; Panchmatia, Pooja M; Parker, Stephen C; Maldonado, David Hernandez; Kepaptsoglou, Demie M; Ramasse, Quentin M

    2017-12-06

    To help understand the factors controlling the performance of one of the most promising n-type oxide thermoelectric SrTiO 3 , we need to explore structural control at the atomic level. In Sr 1-x La 2x/3 TiO 3 ceramics (0.0 ≤ x ≤ 0.9), we determined that the thermal conductivity can be reduced and controlled through an interplay of La-substitution and A-site vacancies and the formation of a layered structure. The decrease in thermal conductivity with La and A-site vacancy substitution dominates the trend in the overall thermoelectric response. The maximum dimensionless figure of merit is 0.27 at 1070 K for composition x = 0.50 where half of the A-sites are occupied with La and vacancies. Atomic resolution Z-contrast imaging and atomic scale chemical analysis show that as the La content increases, A-site vacancies initially distribute randomly (x thermal conductivity, an important route to enhancement of the thermoelectric performance. A computational study confirmed that the thermal conductivity of SrTiO 3 is lowered by the introduction of La and A-site vacancies as shown by the experiments. The modeling supports that a critical mass of A-site vacancies is needed to reduce thermal conductivity and that the arrangement of La, Sr, and A-site vacancies has a significant impact on thermal conductivity only at high La concentration.

  12. Normal alkanes and the unresolved complex mixture as diagnostic indicators of hydrocarbon source contributions to marine sediments of the Northern Gulf of Alaska

    International Nuclear Information System (INIS)

    Short, J.W.; Heintz, R.A.

    2003-01-01

    Coal beds, hydrocarbon source rocks, and natural oil seeps represent potentially significant sources of hydrocarbons contamination of marine sediments in the northern Gulf of Alaska. Intensive studies of several supposedly diagnostic polycyclic aromatic (PAH) and aliphatic hydrocarbon compounds have been conducted to solve the controversy of whether the hydrocarbons come from natural or anthropogenic sources. These hydrocarbons could be associated with a refractory matrix not biologically available, as strongly suggested by the n-alkane profile characteristic of the marine sediments. There are similarities between the unresolved complex mixture (UCM) profile of the marine sediments and those of eroding coals and source rocks. However, there were differences with the UCM of seep oils entering the Gulf of Alaska. The seep-oils possess low concentrations of n-alkanes due to biodegradation before entering the Gulf of Alaska, and have large UCM and PAH concentrations. Additional strong constraints are placed on hydrocarbon contributions from natural sources to the marine sediments of the northern portion of the Gulf of Alaska as a result of inclusion of n-alkane and UCM results into hydrocarbon source allocation models. The authors indicated that seep-oils are unlikely to be significant contributors. 19 refs., 1 tab., 6 figs

  13. Whole-cell bio-oxidation of n-dodecane using the alkane hydroxylase system of P. putida GPo1 expressed in E. coli

    DEFF Research Database (Denmark)

    Grant, Chris; Woodley, John; Baganz, Frank

    2011-01-01

    , successful n-dodecane oxidation for the production of 1-dodecanol or dodecanoic acid has proven elusive in the past when using alkB-expressing recombinants. This article demonstrates, for the first time in vivo, by using the Escherichia coli GEC137 pGEc47ΔJ strain, that n-dodecane oxidation using this enzyme......The alkane-1-monoxygenase (alkB) complex of Pseudomonas putida GPo1 has been extensively studied in the past and shown to be capable of oxidising aliphatic C5–C12 alkanes to primary alcohols both in the wild-type organism by growth on C5–C12 alkanes as sole carbon source and in vitro. Despite this...... aqueous phase and 200mL of n-dodecane as a second phase. The maximum volumetric rate of combined alcohol and acid production achieved was 1.9g/Lorganic/h (0.35g/Ltotal/h). The maximum specific activity of combined alcohol and acid production was 7-fold lower on n-dodecane (3.5μmol/min/gdcw) than on n...

  14. Threshold Ionization Spectroscopy of La(CH_{3}CN) and La(C_{4}H_{9}CN) Radicals Formed by la Reactions with Alkane Nitriles

    Science.gov (United States)

    Ullah, Ahamed; Kim, Jong Hyun; Cao, Wenjin; Yang, Dong-Sheng

    2017-06-01

    La atom reactions with acetonitrile (CH_{3}CN) and pentanenitrile (C_{4}H_{9}CN) are carried out in a laser-vaporization supersonic molecular beam source. Metal-containing species are observed using time-of-flight mass spectrometry. In this talk, we report the mass-analyzed threshold ionization (MATI) spectroscopic characterization of two metal-containing radicals, La(CH_{3}CN) and La(C_{4}H_{9}CN), formed by La associations with acetonitrile and pentanenitrile, respectively. Adiabatic ionization energies of the two La-alkane nitrile species and their vibrational frequencies are measured from the MATI spectra. Metal-ligand binding modes and molecular structures are investigated by comparing the spectroscopic measurements with density functional theory calculations and spectral simulations. For both alkane nitriles, the preferred La binding site is identified to be the nitrile group with a π-bind mode, the resultant metal complexes are three-membered metallacycles. While a single isomer is observed for La(CH_{3}CN), two rotational conformers are identified for La(C_{4}H_{9}CN). The binding and structures of these metal-alkane nitrile radicals are different from those formed by metal ion reactions, where metal ions were reported to favor σ binding with the nitrogen atom. K. Eller, W. Zummack, H. Schwarz, L. M. Roth, B. S. Freiser, J. Am. Chem. Soc., 1991, 113, 833-839

  15. Plant Wax n-Alkane and n-Alkanoic Acid Signatures Overprinted by Microbial Contributions and Old Carbon in Meromictic Lake Sediments

    Science.gov (United States)

    Makou, Matthew; Eglinton, Timothy; McIntyre, Cameron; Montluçon, Daniel; Antheaume, Ingrid; Grossi, Vincent

    2018-01-01

    Specific n-alkanes and n-alkanoic acids are commonly used as biomarkers in paleoenvironmental reconstruction, yet any individual homologue may originate from multiple biological sources. Here we improve source and age controls for these compounds in meromictic systems by measuring the radiocarbon (14C) ages of specific homologues preserved in twentieth century Lake Pavin (France) sediments. In contrast to many studies, 14C ages generally decreased with increasing carbon chain length, from 7.3 to 2.6 ka for the C14-C30 n-alkanoic acids and from 9.2 to 0.3 ka for the C21-C33 n-alkanes. Given a known hard water effect, these values suggest that aquatic microbial sources predominate and contributed to most of the homologues measured. Only the longest chain n-alkanes exclusively represent inputs of higher plant waxes, which were previously sequestered in soils over centennial to millennial timescales prior to transport and deposition. These findings suggest that biomarker source and age should be carefully established for lacustrine settings.

  16. The phase behavior of a hard sphere chain model of a binary n-alkane mixture

    International Nuclear Information System (INIS)

    Malanoski, A. P.; Monson, P. A.

    2000-01-01

    Monte Carlo computer simulations have been used to study the solid and fluid phase properties as well as phase equilibrium in a flexible, united atom, hard sphere chain model of n-heptane/n-octane mixtures. We describe a methodology for calculating the chemical potentials for the components in the mixture based on a technique used previously for atomic mixtures. The mixture was found to conform accurately to ideal solution behavior in the fluid phase. However, much greater nonidealities were seen in the solid phase. Phase equilibrium calculations indicate a phase diagram with solid-fluid phase equilibrium and a eutectic point. The components are only miscible in the solid phase for dilute solutions of the shorter chains in the longer chains. (c) 2000 American Institute of Physics

  17. Analysis of rotator phase transitions in the linear alkanes hexacosane to triacontane by adiabatic scanning calorimetry and by photopyroelectric calorimetry

    Science.gov (United States)

    Paoloni, S.; Mercuri, F.; Zammit, U.; Leys, J.; Glorieux, C.; Thoen, J.

    2018-03-01

    The study of the nature of various phase transitions between rotator phases in several linear alkanes was performed by analyzing the hysteretic behavior of the specific heat between heating and cooling measurements. The investigations have been carried out by both adiabatic scanning calorimetry and photopyroelectric calorimetry techniques, whose combined use has provided complementary information concerning the changes occurring in the samples' structure during their temperature change. The study enabled to establish that, unlike what previously reported, the Riii-Riv and the Rii-Riv transitions are of first order, despite them not showing any sharp peak profile in the temperature dependence of the specific heat. The first order of the Rv-Rii transition was confirmed also in the present study and, finally the Rv-Riii transition could be observed by calorimetric detection for the first time and shown to be of second order. The obtained results were discussed in terms of order parameters power terms in the Landau free energy expansion.

  18. Directed assembly of optoelectronically active alkyl-π-conjugated molecules by adding n-alkanes or π-conjugated species

    Science.gov (United States)

    Hollamby, Martin J.; Karny, Maciej; Bomans, Paul H. H.; Sommerdjik, Nico A. J. M.; Saeki, Akinori; Seki, Shu; Minamikawa, Hiroyuki; Grillo, Isabelle; Pauw, Brian R.; Brown, Paul; Eastoe, Julian; Möhwald, Helmuth; Nakanishi, Takashi

    2014-08-01

    Supramolecular assembly can yield ordered structures by taking advantage of the cumulative effect of multiple non-covalent interactions between adjacent molecules. The thermodynamic origin of many self-assembled structures in water is the balance between the hydrophilic and hydrophobic segments of the molecule. Here, we show that this approach can be generalized to use solvophobic and solvophilic segments of fully hydrophobic alkylated fullerene molecules. Addition of n-alkanes results in their assembly—due to the antipathy of C60 towards n-alkanes—into micelles and hexagonally packed gel-fibres containing insulated C60 nanowires. The addition of pristine C60 instead directs the assembly into lamellar mesophases by increasing the proportion of π-conjugated material in the mixture. The assembled structures contain a large fraction of optoelectronically active material and exhibit comparably high photoconductivities. This method is shown to be applicable to several alkyl-π-conjugated molecules, and can be used to construct organized functional materials with π-conjugated sections.

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

    Science.gov (United States)

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

    2016-04-01

    Alumina-supported Pt is one of the major industrial catalysts for light alkane dehydrogenation. This catalyst loses activity during reaction, with coke formation often considered as the reason for deactivation. As we show in this study, the amount and nature of carbon deposits do not directly correlate with the loss of activity. Rather, it is the transformation of subnanometer Pt species into larger Pt nanoparticles that appears to be responsible for the loss of catalytic activity. Surprisingly, a portion of the Sn remains atomically dispersed on the alumina surface in the spent catalyst and helps in the redispersion of the Pt. In the absence of Sn on the alumina support, the larger Pt nanoparticles formed during reaction are not redispersed during oxidative regeneration. It is known that Sn is added as a promoter in the industrial catalyst to help in achieving high propene selectivity and to minimize coke formation. This work shows that an important role of Sn is to help in the regeneration of Pt, by providing nucleation sites on the alumina surface. Aberration-corrected scanning transmission electron microscopy helps to provide unique insights into the operating characteristics of an industrially important catalyst by demonstrating the role of promoter elements, such as Sn, in the oxidative regeneration of Pt on γ-Al 2 O 3 .

  20. Microwave-assisted extraction versus Soxhlet extraction for the analysis of short-chain chlorinated alkanes in sediments.

    Science.gov (United States)

    Parera, J; Santos, F J; Galceran, M T

    2004-08-13

    Microwave-assisted extraction (MAE) was evaluated as a possible alternative to Soxhlet extraction for analysing short-chain chlorinated alkanes (commonly called short-chain chlorinated paraffins, SCCPs) in river sediment samples, using gas chromatography coupled to negative chemical ionisation mass spectrometry. For MAE optimisation, several extraction parameters such as solvent extraction mixture, extraction time and extraction temperature were studied. Maximum extraction efficiencies for SCCPs (90%) and for 12 polychlorinated biphenyl (PCB) congeners (91-95%) were achieved using 5 g of sediment sample, 30 ml of n-hexane-acetone (1:1, v/v) as solvent extraction, and 15 min and 115 degrees C of extraction time and temperature, respectively. Activated Florisil was used to clean-up the extracts, allowing highly selective separation of SCCPs from other organic contaminants such as PCBs. MAE was compared with a conventional extraction technique such as Soxhlet and good agreement in the results was obtained. Quality parameters of the optimised MAE method such as run-to-run (R.S.D. 7%) and day-to-day precision (R.S.D. 9%) were determined using spiked river sediment samples, with LODs of 1.5 ng g(-1). This method was successfully applied to the analysis of SCCPs in river sediment samples at concentrations below the ng g(-1) level. O 2004 Elsevier B.V. All rights reserved.

  1. Physical properties of {anisole + n-alkanes} at temperatures between (293.15 and 303.15) K

    International Nuclear Information System (INIS)

    Al-Jimaz, Adel S.; Al-Kandary, Jasem A.; Abdul-latif, Abdul-Haq M.; Al-Zanki, Adnan M.

    2005-01-01

    Density ρ, viscosity η, and refractive index n D , values of {anisole + hexane, or heptane, or octane, or nonane, or decane, or dodecane} binary mixtures over the entire range of mole fraction at temperatures (293.15, 298.15, and 303.15) K, have been investigated at atmospheric pressure. The excess molar volume V E , has been calculated from the experimental measurements. These results were fitted to Redlich and Kister polynomial equation to estimate the binary interaction parameters. The viscosity data were correlated with equations of Grunberg and Nissan, and McAllister. The refractive indices data were used to calculate the specific refractivity R 12 , and also correlated with Lorentz-Lorenz equation. While the excess molar volumes of {anisole + hexane} are negative, and {anisole + heptane} are sigmoidal S-shaped, the remaining binary mixtures are positive. The effects of n-alkanes chain length as well as the temperature on the excess molar volume have been studied. The calculated values have been qualitatively used to explain the intermolecular interaction between the mixing components

  2. Viscosity and surface tension of binary systems of N,N-dimethylformamide with alkan-1-ols at different temperatures

    International Nuclear Information System (INIS)

    Mohammad, Abubaker A.; Alkhaldi, Khaled H.A.E.; AlTuwaim, Mohammad S.; Al-Jimaz, Adel S.

    2013-01-01

    Highlights: ► Physical properties of binary mixtures of DMF+1-pentanol, 1-hexanol, or 1-heptanol. ► Viscosity and surface tension were measured. ►Δη, Δσ σ and G ∗E were calculated using the experimental data. ► H σ and S σ were determined using the surface tension data. ► Semi-empirical relations were used to estimate the viscosity of liquid mixtures. - Abstract: Viscosity η and surface tension σ were measured for binary mixtures of N,N-dimethylformamide DMF with pentan-1-ol, hexan-1-ol, and heptan-1-ol at T = (298.15, 303.15, 308.15, and 313.15) K and atmospheric pressure over the entire mole fraction range. Deviations in viscosity Δη and surface tension Δσ were calculated using experimental results. Moreover, the values of the excess Gibbs free energy of activation G ∗E , surface enthalpy H σ and surface entropy S σ of these mixtures were determined. Viscosity measurements of the binary systems were correlated with Grunberg and Nissan, the three-body and four-body McAllister expressions. Viscosity deviation, surface tension deviation and excess Gibbs energy of activation functions were fitted to the method of Redlich–Kister (R–K) polynomial to estimate the coefficients and standard deviations. The effects of chain length of alkan-1-ols and temperature on the thermodynamic properties of binary systems were studied.

  3. Isolation and characterization of biosurfactant-producing Alcanivorax strains: hydrocarbon accession strategies and alkane hydroxylase gene analysis.

    Science.gov (United States)

    Olivera, Nelda L; Nievas, Marina L; Lozada, Mariana; Del Prado, Guillermo; Dionisi, Hebe M; Siñeriz, Faustino

    2009-01-01

    Biosurfactant-producing bacteria belonging to the genera Alcanivorax, Cobetia and Halomonas were isolated from marine sediments with a history of hydrocarbon exposure (Aristizábal and Gravina Peninsulas, Argentina). Two Alcanivorax isolates were found to form naturally occurring consortia with strains closely related to Pseudomonas putida and Microbacterium esteraromaticum. Alkane hydroxylase gene analysis in these two Alcanivorax strains resulted in the identification of two novel alkB genes, showing 86% and 60% deduced amino acid sequence identity with those of Alcanivorax sp. A-11-3 and Alcanivorax dieselolei P40, respectively. In addition, a gene homologous to alkB2 from Alcanivorax borkumensis was present in one of the strains. The consortium formed by this strain, Alcanivorax sp. PA2 (98.9% 16S rRNA gene sequence identity with A. borkumensis SK2(T)) and P. putida PA1 was characterized in detail. These strains form cell aggregates when growing as mixed culture, though only PA2 was responsible for biosurfactant activity. During exponential growth phase of PA2, cells showed high hydrophobicity and adherence to hydrocarbon droplets. Biosurfactant production was only detectable at late growth and stationary phases, suggesting that it is not involved in initiating oil degradation and that direct interfacial adhesion is the main hydrocarbon accession mode of PA2. This strain could be useful for biotechnological applications due to its biosurfactant production, catabolic and aggregation properties.

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

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

    This report details the research performed on Phase IV of the extended Cooperative Agreement. This Phase, entitled C{sub 1}-C{sub 4} Research, provides the research support which accompanies the C{sub 4} Proof-of-Concept Phase (Phase V) as the two major activities of the Cooperative Agreement during calendar 1993. It is the objective of this phase to understand the nature of the catalysts and catalytic activity of perhaloporphyrin complexes uncovered during Phases I-III in order that superior catalytic materials can be made and tested which meet commercial criteria for the oxidation of the C{sub 1}-C{sub 4} light alkane gases found in natural gas and other available hydrocarbon streams. During Phase IV, we have examined the physical and electronic structures of the very active perhaloporphyrin catalysts which we have developed, and have gained an understanding of the properties which make them active. This has led us to design and synthesize materials which are cheaper, more active, more robust and, in general superior for carrying out practical catalysis. Our early generation perhaloporphyrin catalysts, while exhibiting unprecedented catalytic activity, were far too expensive for use in converting natural gas or its C{sub 1}-C{sub 4} components.

  5. High Amounts of n-Alkanes in the Composition of Asphodelus aestivus Brot. Flower Essential Oil from Cyprus.

    Science.gov (United States)

    Polatoğlu, Kaan; Demirci, Betül; Can Başer, Kemal Hüsnü

    2016-10-01

    There is only a couple of reports indicating essential oil composition of Asphodelus species in the literature. However, from the members of this genus many non-volatile secondary metabolites were isolated. In Cyprus, Asphodelus aestivus Brot. can be found abundantly in all regions of the island. This plant has various ethnobotanical uses in Cyprus. There is no report on the volatiles nor the essential oil composition of A. aestivus. The smell of A. aestivus flowers resembles that of a cat pee which caught our attention. Therefore, we have carried out GC, GC/MS analysis of the essential oil (yield: 0.01 v/w) obtained from Asphodelus aestivus flowers. Seventeen compounds were identified in the essential oil comprising 96.2% of the oil. The major components of the essential oil were hexadecanoic acid 35.6%, pentacosane 17.4%, tricosane 13.4% and heptacosane 8.4%. In our results, we expected to see sulfur containing cat pee odorants due to the odor of the flower whereas high amounts of n-alkanes, saturated fatty acids and minor amounts of acyclic diterpenes were observed.

  6. Transport behavior of n-alkane penetrants into castor oil based polyurethane-polyester nonwoven fabric composites

    International Nuclear Information System (INIS)

    Satheesh Kumar, M.N.; Manjula, K.S.; Siddaramaiah

    2007-01-01

    Castor oil based polyurethane (PU)-polyester nonwoven fabric composites were fabricated by impregnating the polyester nonwoven fabric in a composition containing castor oil and diisocyanate. Composites were fabricated with two different isocyanates such as toluene-2,4-diisocyanate (TDI) and hexamethylene diisocyanate (HMDI). Transport behavior of n-alkane penetrants (pentane, hexane and heptane) into both PUs and PU-polyester nonwoven fabric composites were studied. Sorption studies were carried out at different temperatures. From the sorption results, the diffusion (D) and permeation (P) coefficients of penetrants have been calculated. Significant increase in the diffusion and permeation coefficients was observed with increase in the temperature of sorption experiments. Drastical reduction in diffusion and permeation coefficients was noticed in the composites compared to neat PUs. Attempts were made to estimate the empirical parameters like n, which suggests the mode of transport and K is a constant depends on the structural characteristics of the composite in addition to its interaction with penetrants. The temperature dependence of the transport coefficients has been used to estimate the activation energy parameter for diffusion (E D ) and permeation (E P ) processes from Arrhenius plots. Furthermore, the sorption results have been interpreted in terms of the thermodynamic parameters such as enthalpy (ΔH) and entropy (ΔS)

  7. Identification of In-Chain-Functionalized Compounds and Methyl-Branched Alkanes in Cuticular Waxes of Triticum aestivum cv. Bethlehem.

    Directory of Open Access Journals (Sweden)

    Radu C Racovita

    Full Text Available In this work, cuticular waxes from flag leaf blades and peduncles of Triticum aestivum cv. Bethlehem were investigated in search for novel wax compounds. Seven wax compound classes were detected that had previously not been reported, and their structures were elucidated using gas chromatography-mass spectrometry of various derivatives. Six of the classes were identified as series of homologs differing by two methylene units, while the seventh was a homologous series with homologs with single methylene unit differences. In the waxes of flag leaf blades, secondary alcohols (predominantly C27 and C33, primary/secondary diols (predominantly C28 and esters of primary/secondary diols (predominantly C50, combining C28 diol with C22 acid were found, all sharing similar secondary hydroxyl group positions at and around C-12 or ω-12. 7- and 8-hydroxy-2-alkanol esters (predominantly C35, 7- and 8-oxo-2-alkanol esters (predominantly C35, and 4-alkylbutan-4-olides (predominantly C28 were found both in flag leaf and peduncle wax mixtures. Finally, a series of even- and odd-numbered alkane homologs was identified in both leaf and peduncle waxes, with an internal methyl branch preferentially on C-11 and C-13 of homologs with even total carbon number and on C-12 of odd-numbered homologs. Biosynthetic pathways are suggested for all compounds, based on common structural features and matching chain length profiles with other wheat wax compound classes.

  8. Fabrication, thermal properties and thermal stabilities of microencapsulated n-alkane with poly(lauryl methacrylate) as shell

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Xiaolin, E-mail: shirleyqiu2009@gmail.com [Jiangsu Key Laboratory of Advanced Food Manufacturing Equipment and Technology, School of Mechanical Engineering, Jiangnan University, Wuxi 214122 (China); Lu, Lixin; Wang, Ju [Jiangsu Key Laboratory of Advanced Food Manufacturing Equipment and Technology, School of Mechanical Engineering, Jiangnan University, Wuxi 214122 (China); Tang, Guoyi [Advanced Materials Institute and Clearer Production Key Laboratory, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Key Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Haidian District, Beijing 100084 (China); Song, Guolin [Advanced Materials Institute and Clearer Production Key Laboratory, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China)

    2015-11-20

    Highlights: • Microencapsulation of octadecane and paraffin by crosslinked poly(lauryl methacrylate). • Octadecane microcapsules have a melting enthalpy of about 118 J g{sup −1}. • Weight loss temperatures of the microcapsules were increased by 67 °C and 28 °C. • Phase change enthalpies decreased by around 10 wt% after 500 thermal cycles. • Foams with microcapsules can be applied for passive temperature control. - Abstract: Microencapsulation of n-octadecane or paraffin with poly(lauryl methacrylate) (PLMA) shell was performed by a suspension-like polymerization. The polymer shell was crosslinked by pentaerythritol tetraacrylate (PETRA). The surface morphologies of microcapsules were investigated by scanning electron microscopy (SEM). Phase change properties, thermal reliabilities and thermal stabilities of microcapsules were determined by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The n-octadecane microcapsule exhibits higher melting enthalpy (118.0 J g{sup −1}) and crystallization enthalpy (108.3 J g{sup −1}) compared with the paraffin microcapsule. The thermal resistant temperatures were enhanced by more than 25 °C when n-alkanes were microencapsulated by PLMA. The PCM contents of microcapsules decreased by less than 4 wt% and 6 wt% after 500 and 1000 thermal cycles, respectively. Heat-up experiments indicated that microcapsule-treated foams exhibited upgraded thermal regulation capacities. Consequently, microencapsulated n-octadecane or paraffin with PLMA as shell possesses good potentials for heat storage and thermal regulation.

  9. Fabrication, thermal properties and thermal stabilities of microencapsulated n-alkane with poly(lauryl methacrylate) as shell

    International Nuclear Information System (INIS)

    Qiu, Xiaolin; Lu, Lixin; Wang, Ju; Tang, Guoyi; Song, Guolin

    2015-01-01

    Highlights: • Microencapsulation of octadecane and paraffin by crosslinked poly(lauryl methacrylate). • Octadecane microcapsules have a melting enthalpy of about 118 J g −1 . • Weight loss temperatures of the microcapsules were increased by 67 °C and 28 °C. • Phase change enthalpies decreased by around 10 wt% after 500 thermal cycles. • Foams with microcapsules can be applied for passive temperature control. - Abstract: Microencapsulation of n-octadecane or paraffin with poly(lauryl methacrylate) (PLMA) shell was performed by a suspension-like polymerization. The polymer shell was crosslinked by pentaerythritol tetraacrylate (PETRA). The surface morphologies of microcapsules were investigated by scanning electron microscopy (SEM). Phase change properties, thermal reliabilities and thermal stabilities of microcapsules were determined by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The n-octadecane microcapsule exhibits higher melting enthalpy (118.0 J g −1 ) and crystallization enthalpy (108.3 J g −1 ) compared with the paraffin microcapsule. The thermal resistant temperatures were enhanced by more than 25 °C when n-alkanes were microencapsulated by PLMA. The PCM contents of microcapsules decreased by less than 4 wt% and 6 wt% after 500 and 1000 thermal cycles, respectively. Heat-up experiments indicated that microcapsule-treated foams exhibited upgraded thermal regulation capacities. Consequently, microencapsulated n-octadecane or paraffin with PLMA as shell possesses good potentials for heat storage and thermal regulation.

  10. The ORF slr0091 of Synechocystis sp. PCC6803 encodes a high-light induced aldehyde dehydrogenase converting apocarotenals and alkanals

    KAUST Repository

    Trautmann, Danika

    2013-07-05

    Oxidative cleavage of carotenoids and peroxidation of lipids lead to apocarotenals and aliphatic aldehydes called alkanals, which react with vitally important compounds, promoting cytotoxicity. Although many enzymes have been reported to deactivate alkanals by converting them into fatty acids, little is known about the mechanisms used to detoxify apocarotenals or the enzymes acting on them. Cyanobacteria and other photosynthetic organisms must cope with both classes of aldehydes. Here we report that the Synechocystis enzyme SynAlh1, encoded by the ORF slr0091, is an aldehyde dehydrogenase that mediates oxidation of both apocarotenals and alkanals into the corresponding acids. Using a crude lysate of SynAlh1-expressing Escherichia coli cells, we show that SynAlh1 converts a wide range of apocarotenals and alkanals, with a preference for apocarotenals with defined chain lengths. As suggested by in vitro incubations and using engineered retinal-forming E. coli cells, we found that retinal is not a substrate for SynAlh1, making involvement in Synechocystis retinoid metabolism unlikely. The transcript level of SynAlh1 is induced by high light and cold treatment, indicating a role in the stress response, and the corresponding gene is a constituent of a stress-related operon. The assumptions regarding the function of SynAlh are further supported by the surprisingly high homology to human and plant aldehyde dehydrogenase that have been assigned to aldehyde detoxification. SynAlh1 is the first aldehyde dehydrogenase that has been shown to form both apocarotenoic and fatty acids. This dual function suggests that its eukaryotic homologs may also be involved in apocarotenal metabolism, a function that has not been considered so far. Aldehyde dehydrogenases play an important role in detoxification of reactive aldehydes. Here, we report on a cyanbacterial enzyme capable in converting two classes of lipid-derived aldehydes, apocaotenals and alkanals. The corresponding gene is a

  11. Size-distributions of n-alkanes, PAHs and hopanes and their sources in the urban, mountain and marine atmospheres over East Asia

    Directory of Open Access Journals (Sweden)

    Z. Wang

    2009-11-01

    Full Text Available Size-segregated (9 stages n-alkanes, polycyclic aromatic hydrocarbons (PAHs and hopanes in the urban (Baoji city in inland China, mountain (Mt. Tai in east coastal China and marine (Okinawa Island, Japan atmospheres over East Asia were studied using a GC/MS technique. Ambient concentrations of n-alkanes (1698±568 ng m−3 in winter and 487±145 ng m−3 in spring, PAHs (536±80 and 161±39 ng m−3, and hopanes (65±24 and 20±2.4 ng m−3 in the urban air are 1–2 orders of magnitude higher than those in the mountain aerosols and 2–3 orders of magnitude higher than those in the marine samples. Mass ratios of n-alkanes, PAHs and hopanes clearly demonstrate coal-burning emissions as their major source. Size distributions of fossil fuel derived n-alkane, PAHs and hopanes were found to be unimodal in most cases, peaking at 0.7–1.1 μm size. In contrast, plant wax derived n-alkanes presented a bimodal distribution with two peaks at the sizes of 0.7–1.1 μm and >4.7 μm in the summer mountain and spring marine samples. Among the three types of samples, geometric mean diameter (GMD of the organics in fine mode (<2.1 μm was found to be smallest (av. 0.63 μm in spring for the urban samples and largest (1.01 μm for the marine samples, whereas the GMD in coarse mode (≥2.1 μm was found to be smallest (3.48 μm for the marine aerosols and largest (4.04 μm for the urban aerosols. The fine mode GMDs of the urban and mountain samples were larger in winter than in spring and summer. Moreover, GMDs of 3- and 4-ring PAHs were larger than those of 5- and 6-ring PAHs in the three types of atmospheres. Such differences in GMDs can be interpreted by the repartitioning of organic compounds and the coagulation and hygroscopic growth of particles during a long-range transport from the inland continent to the marine area, as well as the difference in their sources among the three regions.

  12. Oxidation of Alkane Rich Gasoline Fuels and their Surrogates in a Motored Engine

    KAUST Repository

    Shankar, Vijai S B

    2015-03-30

    The validation of surrogates formulated using a computational framework by Ahmed et al.[1]for two purely paraffinic gasoline fuels labelled FACE A and FACE C was undertaken in this study. The ability of these surrogate mixtures to be used in modelling LTC engines was accessed by comparison of their low temperature oxidation chemistry with that of the respective parent fuel as well as a PRF based on RON. This was done by testing the surrogate mixtures in a modified Cooperative Fuels Research (CFR) engine running in Controlled Autoignition Mode (CAI) mode. The engine was run at a constant speed of 600 rpm at an equivalence ratio of 0.5 with the intake temperature at 150 °C and a pressure of 98 kPa. The low temperature reactivity of the fuels were studied by varying the compression ratio of the engine from the point were very only small low temperature heat release was observed to a point beyond which auto-ignition of the fuel/air mixture occurred. The apparent heat release rates of different fuels was calculated from the pressure histories using first law analysis and the CA 50 times of the low temperature heat release (LTHR) were compared. The surrogates reproduced the cool flame behavior of the parent fuels better than the PRF across all compression ratios.

  13. Evidence for the blue 10 pi S62+ dication in solutions of S8(AsF6)2: a computational study including solvation energies.

    Science.gov (United States)

    Krossing, Ingo; Passmore, Jack

    2004-02-09

    The energetics of dissociation reactions of S(8)(2+) into stoichiometric mixtures of S(n)(+), n = 2-7, and S(m)(2+), m = 3, 4, 6, 10, were investigated by the B3PW91 method [6-311+G(3df)//6-311+G] in the gas phase and in solution, with solvation energies calculated using the SCIPCM model and in some cases also the COSMO model [B3PW91/6-311+G*, dielectric constants 2-30, 83, 110]. UV-vis spectra of all species were calculated at the CIS/6-311G(2df) level and for S(4)(2+) and S(6)(2+) also at the TD-DFT level (BP86/SV(P)). Standard enthalpies of formation at 298 K were derived for S(3)(2+) (2538 kJ/mol), S(6)(2+) (2238 kJ/mol), and S(10)(2+) (2146 kJ/mol). A comparison of the observed and calculated UV-vis spectra based on our calculated thermochemical data in solution suggests that, in the absence of traces of facilitating agent (such as dibromine Br(2)), S(8)(2+) dissociates in dilute SO(2) solution giving an equilibrium mixture of ca. 0.5S(6)(2+) and S(5)(+) (K approximately 8.0) while in the more polar HSO(3)F some S(8)(2+) remains (K approximately 0.4). According to our calculations, the blue color of this solution is likely due to the pi-pi transition of the previously unknown 10 pi S(6)(2+) dication, and the previously assigned S(5)(+) is a less important contributor. Although not strictly planar, S(6)(2+) may be viewed as a 10 pi electron Hückel-aromatic ring containing a thermodynamically stable 3p(pi)-3p(pi) bond [d(S-S) = 2.028 A; tau(S-S-S-S) = 47.6 degrees ]. The computations imply that the new radical cation S(4)(+) may be present in sulfur dioxide solutions given on reaction of sulfur oxidized by AsF(5) in the presence of a facilitating agent. The standard enthalpy of formation of S(6)(AsF(6))(2)(s) was estimated as -3103 kJ/mol, and the disproportionation enthalpy of 2S(6)(AsF(6))(2)(s) to S(8)(AsF(6))(2)(s) and S(4)(AsF(6))(2)(s) as exothermic by 6-17 kJ/mol. The final preference of the observed disproportionation products is due to the inclusion of

  14. Catalytic behavior of Pt nanoparticles dealuminated Y-zeolite for some n-alkane hydroisomerization

    Directory of Open Access Journals (Sweden)

    S.A. Hanafi

    2014-06-01

    Full Text Available Dealuminated zeolite Y-supported platinum was prepared adopting two dealumination methods, viz. fast (1, 3 and 6 h and slow method (18 h. The content of Pt was constant at 0.5 wt% in all investigated catalysts. The prepared samples were characterized using TGA/DSC, XRD, FTIR techniques, nitrogen adsorption at −196 °C and TEM-connected with energy dispersive spectroscopy (EDS. Surface acidity was investigated via pyridine adsorption using FT-IR spectroscopy. The parent and dealuminated Y-zeolite samples were characterized by their microporous system. By increasing the dealumination time to 6 h, the increased specific surface area and total pore volume indicated a sort of pore opening taking place with an increase in the accessibility of nitrogen molecules. DSC confirmed the thermal stability of the dealuminated zeolite samples up to 800 °C. The prepared catalysts were tested through hydroisomerization reactions of n-hexane and n-heptane using a micro-catalytic pulse technique. Different catalytic behaviors could be distinguished for the dealuminated samples based on competitive reactions; hydro-isomerization, hydrocracking and cyclization. Slow dealumination leads to the most selective catalysts for hydroisomerization. n-Heptane was converted to higher extent than n-hexane; cracking process was more evident when the former was fed to the reactor.

  15. Variation in the carbon isotopic composition of alkanes during shale gas desorption process and its geological significance

    Directory of Open Access Journals (Sweden)

    Qiang Meng

    2016-04-01

    Full Text Available Taking Chang 7 shale of the Yanchang Formation in the southeastern area of the Yishan slope of the Ordos Basin as our research subject, desorption experiments were performed on more than 30 shale samples that helped this study focus on the variation of carbon isotopic composition of alkanes during the desorption process of shale gas, the possible causes of this phenomenon and its geological significance will also be discussed as follows. It was found that carbon isotopic composition became higher by 9.2‰ (from −50.1‰ to −40.9‰ for methane desorbed gas (δ13C1, and it also became higher by 2.8‰ (from −35.5‰ to −32.7‰ for ethane (δ13C2, but there's barely any differences for propane during the desorption process. At room temperature or constant temperature, carbon isotopic composition for both methane and ethane (δ13C1 & δ13C2 increased continuously. The values of δ13C1 and δ13C2 were low at first and then it gradually became high whilst the desorption process of shale gas that was optimized with the aid of the increasing temperature. The reason for this phenomenon is most likely due to the main adsorption/desorption of shale gas and diffusion migration fractionation of isotope. Additionally, these variation characteristics of methane and ethane carbon isotope composition of shale gas may be a vital reason for the relatively low carbon isotopic composition of methane compared to δ13C calculated by means of the vitrinite reflectance (RO, and this may be applied to evaluate the remaining amount of shale gas resources.

  16. Orientation in metal-catalyzed hydrogen exchange between alkanes, naphthalene, or biphenyl and deuterium or deuterium oxide

    International Nuclear Information System (INIS)

    Long, M.A.; Moyes, R.B.; Wells, P.B.; Garnett, J.L.

    1978-01-01

    Hydrogen isotope exchange between deuterium gas and protium in hexane, pentane, 2-methyl-butane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, and 2,4-dimethylpentane has been catalyzed by clean platinum films (70--100 0 C). A selection of these reactions has been catalyzed by films of rhodium and iridium (typically -13 to -35 0 C). In all cases, multiple exchange occurred. Product analysis by mass and proton NMR spectroscopy showed that exchange in methylene and methine groups was more rapid than that in methyl groups. A similar orientation effect was observed in reactions over platinum powder but not over platinum-alumina. For exchange between deuterium oxide and hexane catalyzed by platinum films at 200 0 C, the rate of exchange in methyl groups exceeded that in methylene groups. It is proposed that preferential exchange in methylene and methine groups is normal behavior during alkane exchange with molecular deuterium over these platinum metals when their surfaces (i) are initially clean or (ii) contain several adjacent sites which are unperturbed by the presence of any electronegative adsorbed species. Preferential exchange in the methyl groups of hexane results from contamination of the surface by adsorbed D 2 O, OD, or O; this may be a geometric effect or an electronic effect, depending on the magnitude of the surface coverage of water, which is unknown. Orientation in the exchange between deuterium gas and naphthalene or biphenyl catalyzed by films of platinum and iridium does not differ from that observed in exchanges where the isotope source is deuterium oxide or deuterated solvent, but the M value calculated for exchange in naphthalene is higher than that previously reported

  17. Preparation and surface active properties of oxypropylated α-hydroxyacids, α-hydroxyesters and α-, β-alkane diols

    Directory of Open Access Journals (Sweden)

    Shaker, N. O.

    1994-10-01

    Full Text Available A series of a-hydroxyacids RCH(OHCO2H, α-hydroxyesters RCH(OHCO2CH3 and α, β-alkane diols was synthetized and condensed with 5-20 moles propylene oxide to obtain nonionic surfactants. Some of the physicochemical properties and the biodegradability of these products were examined. The results showed that the best wetting properties were obtained by the addition of 15 oxypropylene groups to methyl α-hydroxymyristate. The α-hydroxymyristic acid with 20 moles of propylene oxide gave the highest foam. Biodegradation studies indicated that increasing both the chain length of the hydrophobic alkyl chain or the number of oxypropylene groups in the adduct decreased biodegradation.

    Una serie de α-hidroxiácidos RCH(OHCO2H, α-hidroxiésteres RCH(OHCO2CH3 y α, β-alcanodioles se sintetizaron y condensaron con 5-20 moles de óxido de propileno para obtener tensioactivos no iónicos. Se examinaron algunas propiedades fisicoquímicas y de biodegradabilidad de estos productos. Los resultados mostraron que las mejores propiedades humectantes se obtuvieron por adición de 15 grupos oxipropilenos a α-hidroximiristato de metilo.
    El ácido α-hidroximirístico con 20 moles de óxido de propileno dio la espuma más poderosa. Estudios de biodegradación indicaron que tanto el aumento de la longitud de cadena de los grupos alquilo hidrofóbicos como el número de grupos oxipropilenos en el aducto disminuyeron la biodegradación.

  18. Leaf cuticular n-alkanes as markers in the chemotaxonomy of the eggplant (Solanum melongena L.) and related species.

    Science.gov (United States)

    Haliński, L P; Szafranek, J; Stepnowski, P

    2011-11-01

    The complex of species formed by eggplant (Solanum melongena L.) and its wild and weedy relatives (mainly S. incanum L. and S. insanum L.) is characterised by an extreme morphological divergence that is not always associated with genetic variation. The taxonomy of so-called 'spiny Solanum' species (subgenus Leptostemonum) is therefore extremely unclear. Cultivated eggplant lacks resistance to pests that frequently occur among the wild forms and species. As these wild plants are a potential gene pool for improvement of eggplant cultivars, knowledge of the characteristics of taxonomic relations between plants of different origin is crucial. We suggest using the leaf cuticular n-alkane chain length distribution pattern as an alternative taxonomic marker for eggplant and related species. The results are in good agreement with current knowledge of the systematics of these plants; at the same time, the method developed here is useful for verifying plant identification based on morphological traits. Analysis of 13 eggplant cultivars, five accessions of S. incanum and two lines of S. macrocarpon enabled the intraspecific variation within eggplant to be assessed as low. There was wide variability among S. incanum accessions, probably because plants described as S. incanum are members of a number of different species. Some Asian accessions (sometimes described as S. insanum) were found to be almost identical to S. melongena, while a truly wild African S. incanum plant showed extensive similarity. The usefulness of the chemotaxonomic approach in dealing with the S. melongena-S. incanum complex is discussed. © 2011 German Botanical Society and The Royal Botanical Society of the Netherlands.

  19. 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.

    Science.gov (United States)

    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

  20. Neural computation and the computational theory of cognition.

    Science.gov (United States)

    Piccinini, Gualtiero; Bahar, Sonya

    2013-04-01

    We begin by distinguishing computationalism from a number of other theses that are sometimes conflated with it. We also distinguish between several important kinds of computation: computation in a generic sense, digital computation, and analog computation. Then, we defend a weak version of computationalism-neural processes are computations in the generic sense. After that, we reject on empirical grounds the common assimilation of neural computation to either analog or digital computation, concluding that neural computation is sui generis. Analog computation requires continuous signals; digital computation requires strings of digits. But current neuroscientific evidence indicates that typical neural signals, such as spike trains, are graded like continuous signals but are constituted by discrete functional elements (spikes); thus, typical neural signals are neither continuous signals nor strings of digits. It follows that neural computation is sui generis. Finally, we highlight three important consequences of a proper understanding of neural computation for the theory of cognition. First, understanding neural computation requires a specially designed mathematical theory (or theories) rather than the mathematical theories of analog or digital computation. Second, several popular views about neural computation turn out to be incorrect. Third, computational theories of cognition that rely on non-neural notions of computation ought to be replaced or reinterpreted in terms of neural computation. Copyright © 2012 Cognitive Science Society, Inc.

  1. Programming in biomolecular computation

    DEFF Research Database (Denmark)

    Hartmann, Lars Røeboe; Jones, Neil; Simonsen, Jakob Grue

    2011-01-01

    Our goal is to provide a top-down approach to biomolecular computation. In spite of widespread discussion about connections between biology and computation, one question seems notable by its absence: Where are the programs? We identify a number of common features in programming that seem...... conspicuously absent from the literature on biomolecular computing; to partially redress this absence, we introduce a model of computation that is evidently programmable, by programs reminiscent of low-level computer machine code; and at the same time biologically plausible: its functioning is defined...... by a single and relatively small set of chemical-like reaction rules. Further properties: the model is stored-program: programs are the same as data, so programs are not only executable, but are also compilable and interpretable. It is universal: all computable functions can be computed (in natural ways...

  2. Programming in biomolecular computation

    DEFF Research Database (Denmark)

    Hartmann, Lars Røeboe; Jones, Neil; Simonsen, Jakob Grue

    2011-01-01

    conspicuously absent from the literature on biomolecular computing; to partially redress this absence, we introduce a model of computation that is evidently programmable, by programs reminiscent of low-level computer machine code; and at the same time biologically plausible: its functioning is defined...... by a single and relatively small set of chemical-like reaction rules. Further properties: the model is stored-program: programs are the same as data, so programs are not only executable, but are also compilable and interpretable. It is universal: all computable functions can be computed (in natural ways......Our goal is to provide a top-down approach to biomolecular computation. In spite of widespread discussion about connections between biology and computation, one question seems notable by its absence: Where are the programs? We identify a number of common features in programming that seem...

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

    Energy Technology Data Exchange (ETDEWEB)

    Yeston, Jake Simon [Univ. of California, Berkeley, CA (United States)

    2001-01-01

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

  4. Liquid–liquid extraction of toluene from alkane with pyridinium based ionic liquid ([BPy][NO3] and [HPy][NO3]) at 298.15 K and atmospheric pressure

    International Nuclear Information System (INIS)

    Enayati, Mobin; Mokhtarani, Babak; Sharifi, Ali; Anvari, Sanam; Mirzaei, Mojtaba

    2016-01-01

    Highlights: • Extraction of toluene from alkane with pyridinium based ionic liquid was studied. • The ionic liquids [BPy][NO 3 ] and [HPy][NO 3 ] were used. • The effect of alkane chain length on selectivity of toluene was evaluated. • The effect of alkyl chain length of ionic liquids on toluene selectivity was investigated. • The experimental data were correlated with the NRTL model. - Abstract: The focus of this paper is to study the liquid−liquid extraction process for the separation of toluene from alkane employing the ionic liquids N-butylpyridinium nitrate, [BPy][NO 3 ], and N-hexylpyridinium nitrate, [HPy][NO 3 ], as a new solvents. New experimental data for the ternary systems of {[BPy][NO 3 ] (1) + heptane, or octane, or decane (2) + toluene (3)} and {[HPy][NO 3 ] (1) + heptane, or octane, or decane (2) + toluene (3)} at T = 298.15 K and atmospheric pressure are reported. The Othmer-Tobias and Hand correlation are examined to check the reliability of the experimental LLE data. The toluene distribution ratios and selectivity were calculated form the experimental data. The selectivity values are higher than unity which indicates the ILs, [BPy][NO 3 ] and [HPy][NO 3 ], used in this work are potential solvents to separate toluene from alkane. Besides, the effect of the alkane chain length in the selectivity values was evaluated. In addition, the result of the NRTL thermodynamic modeling shows, the experimental data were satisfactorily correlated.

  5. Comment on "Changes in atmospheric CO2 levels recorded by the isotopic signature of n-alkanes from plants" from K.S. Machado and S. Froehner

    Science.gov (United States)

    Köhler, Peter; Nehrbass-Ahles, Christoph; Schmitt, Jochen; Stocker, Thomas F.; Fischer, Hubertus

    2017-09-01

    The recently published invited research article by Machado and Froehner (2017) is presenting δ13C values from sedimentary organic matter (n-alkane), measured on samples collected in the Barigui watershed (Brazil) covering the last 400 years. The derived δ13C time series based on C27n-alkane, beginning approximately in the calendar year 1600 (or 1600 CE; with CE for Common Era) until recent times is subsequently - in their Fig. 3 - compared with a record, which is believed to be a representative reconstruction of atmospheric CO2 concentrations covering approximately the last 650 years (with respect to the year 2005 CE). The final conclusion of this article, as reflected in its title, is that changes in atmospheric CO2 levels are recorded in isotopic signatures on n-alkane from plants. We argue, that this conclusion can not be drawn from the study of Machado and Froehner (2017), since what is shown in their Fig. 3 is not a time series of atmospheric CO2 concentration of the last 650 years. The authors show reconstructions of atmospheric CO2 concentrations based on Antarctic ice cores over the past 650,000 years and use them for the past 650 years by ignoring the fact that the time scale in IPCC (2007), from which, according to the caption of their Fig. 3, they took this CO2 time series, is in kyr (1 kyr = 1 kilo year = 1000 years). This is wrong and any conclusion based on this comparison is incorrect. Instead they should have used for a correct CO2 time series for the comparison with their measurements.

  6. Digital forensic evidence in computing, networking and cloud computing

    OpenAIRE

    Triana-Fuentes, José Javier; Secretaría de Educación de Boyacá; BALLESTEROS-RICAURTE, Javier Antonio; Universidad Pedagógica y Tecnológica de Colombia

    2016-01-01

    La informática forense se encarga de investigar los antecedentes por los cuales se pudo haber realizado un crimen utilizando dispositivos electrónicos con el objeto de descubrir y analizar la información disponible para que pueda servir como evidencia en un asunto legal. Hoy en día, con la posibilidad de almacenar y procesar la información a nivel local, remoto y en la nube, las empresas necesitan cada día mayor seguridad. Por medio de la informática forense y diferentes técnicas que han sido...

  7. Degradation of n-alkanes and PAHs from the heavy crude oil using salt-tolerant bacterial consortia and analysis of their catabolic genes.

    Science.gov (United States)

    Gurav, Ranjit; Lyu, Honghong; Ma, Jianli; Tang, Jingchun; Liu, Qinglong; Zhang, Hairong

    2017-04-01

    In the present study, salt-tolerant strains, Dietzia sp. HRJ2, Corynebacterium variabile HRJ4, Dietzia cinnamea HRJ5 and Bacillus tequilensis HRJ6 were isolated from the Dagang oil field, China. These strains degraded n-alkanes and polycyclic aromatic hydrocarbons (PAHs) aerobically from heavy crude oil (HCO) in an experiment at 37 °C and 140 rpm. The GC/MS investigation for degradation of different chain lengths of n-alkanes (C8-C40) by individual strains showed the highest degradation of C8-C19 (HRJ5), C20-C30 (HRJ4) and C31-C40 (HRJ5), respectively. Moreover, degradation of 16 PAHs with individual strains demonstrated that the bicyclic and pentacyclic aromatic hydrocarbons (AHs) were mostly degraded by HRJ5, tricyclic and tetracyclic AHs by HRJ6 and hexacyclic AHs by HRJ2. However, the highest degradation of total petroleum hydrocarbons (TPHs), total saturated hydrocarbons (TSH), total aromatic hydrocarbons (TAH), n-alkanes (C8-C40) and 16 PAHs was achieved by a four-membered consortium (HRJ2 + 4 + 5 + 6) within 12 days, with the predominance of HRJ4 and HRJ6 strains which was confirmed by denaturing gradient gel electrophoresis. The abundance of alkB and nah genes responsible for catabolism of n-alkanes and PAHs was quantified using the qPCR. Maximum copy numbers of genes were observed in HRJ2 + 4 + 5 + 6 consortium (gene copies l -1 ) 2.53 × 10 4 (alkB) and 3.47 × 10 3 (nah) at 12 days, which corresponded to higher degradation rates of petroleum hydrocarbons. The superoxide dismutase (SOD) (total SOD (T-SOD), Cu 2+ Zn 2+ -SOD), catalase (CAT) and ascorbate peroxidase (APX) activities in Allium sativum and Triticum aestivum were lower in the HRJ2 + 4 + 5 + 6-treated HCO as compared to the plantlets exposed directly to HCO. The present results revealed the effective degradation of HCO-contaminated saline medium using the microbial consortium having greater metabolic diversity.

  8. Vanderbilt University: Campus Computing Environment.

    Science.gov (United States)

    CAUSE/EFFECT, 1988

    1988-01-01

    Despite the decentralized nature of computing at Vanderbilt, there is significant evidence of cooperation and use of each other's resources by the various computing entities. Planning for computing occurs in every school and department. Caravan, a campus-wide network, is described. (MLW)

  9. Cone-Beam Computed Tomography and Interdisciplinary Dentofacial Therapy: An American Academy of Periodontology Best Evidence Review Focusing on Risk Assessment of the Dentoalveolar Bone Changes Influenced by Tooth Movement.

    Science.gov (United States)

    Mandelaris, George A; Neiva, Rodrigo; Chambrone, Leandro

    2017-10-01

    The aim of this systematic review is to evaluate whether cone-beam computed tomography (CBCT) imaging can be used to assess dentoalveolar anatomy critical to the periodontist when determining risk assessment for patients undergoing orthodontic therapy using fixed or removable appliances. Both observational and interventional trials reporting on the use of CBCT imaging assessing the impact of orthodontic/dentofacial orthopedic treatment on periodontal tissues (i.e., alveolar bone) were included. Changes in the alveolar bone thickness and height around natural teeth as well as treatment costs were evaluated. MEDLINE (via PubMed) and EMBASE databases were searched for articles published in the English language, up to and including July 2016, and extracted data were organized into evidence tables. Thirteen studies were included in this systematic review describing the positive or deleterious changes on the alveolar bone surrounding natural teeth undergoing orthodontic tooth movement or influenced by orthopedic forces through fixed appliances. Clinical recommendation summaries presenting the strengths and weaknesses of the evidence in terms of benefits and harms were generated. CBCT imaging can improve the periodontal diagnostic acumen regarding alveolar bone alterations influenced by orthodontic tooth movement and can help determine risk assessment prior to such intervention. Clinicians are also better informed to determine risk assessment and develop preventative or plan interceptive periodontal augmentation (soft tissue and/or bone augmentation) therapies for patients undergoing orthodontic tooth movement. These considerations are recognized as being especially critical for treatment approaches in patients where buccal tooth movement (expansion) is planned in the anterior mandible or involving the maxillary premolars.

  10. [Altered expressions of alkane monooxygenase and hypoxia inducible factor-1α expression in lung tissue of rat hypoxic pulmonary hypertension].

    Science.gov (United States)

    Deng, Hua-jun; Yuan, Ya-dong

    2013-10-29

    To explore the altered expressions of alkane monooxygenase (AlkB) and hypoxia-inducible factor-1α (HIF-1α) in a rat model of hypoxic pulmonary arterial hypertension. Twenty Wistar rats were divided randomly into normal control and hypoxia groups after 1-week adaptive feeding. Hypoxia group was raised in a homemade organic glass tank with a 24-h continuous supply of air and nitrogen atmospheric mixed gas. And the oxygen concentration of (10.0 ± 0.5)% was controlled by oxygen monitoring control system. The control group was maintained in room air. Both groups stayed in the same room with the same diet. After 8 weeks, the level of mean pulmonary pressure (mPAP) was measured by right-heart catheterization, right ventricular hypertrophy index (RVHI) calculated by the ratio of right ventricle to left ventricle plus septum and hypoxic pulmonary vascular remodeling (HPSR) observed under microscope. And the levels of AlkB and HIF-1α mRNA and protein in lungs were measured by reverse transcriptase-polymerase chain reaction (RT-PCR) and Western blot. At 8 weeks post-hypoxia, compared with the control group [11.0 ± 0.7 mm Hg (1 mm Hg = 0.133 kPa), 0.210 ± 0.035], the levels of mPAP and RVHI in hypoxia group (33.3 ± 1.3 mm Hg, 0.448 ± 0.013) increased significantly (both P < 0.05), the expressions of AlkB mRNA and protein in pulmonary tissue decreased significantly (0.338 ± 0.085 vs 0.688 ± 0.020, P < 0.01) (0.483 ± 0.052 vs 0.204 ± 0.010, P < 0.01), and the expressions of HIF-1α mRNA and protein increased significantly (0.790 ± 0.161 vs 0.422 ± 0.096, P < 0.01) (0.893 ± 0.080 vs 0.346 ± 0.008, P < 0.01). The down-regulation of AlkB in lung tissue may increase the activity of HIF-1 to participate in the occurrence and development of pulmonary hypertension.

  11. Premarital Sexual Practice among Unmarried First Year Undergraduate Students in Alkan University College in Addis Ababa, Ethiopia

    Directory of Open Access Journals (Sweden)

    Endalew Gemechu Sendo

    2014-03-01

    Full Text Available BACKGROUND: Premarital sexual practice among unmarried College students has markedly increased recently in Ethiopia. College students are recognized as one of the age groups most affected by sexually transmitted infections including HIV. However, little has been explored about the magnitude of premarital sexual activity and predisposing factors in the circumstance of private higher education institutions in Ethiopia. OBJECTIVE: To investigate the magnitude of premarital sexual practice and predisposing factors among unmarried undergraduate first year students in Alkan University College in Addis Ababa, Ethiopia. METHODS: A cross-sectional survey of college students was conducted in April-May 2013. Study participants were selected by stratified random sampling. A self-administered questionnaire was completed by 207 unmarried first year undergraduate students, and was analyzed using SPSS V.16.0. Multi-variate logistic regression was used to see association between variables. Results were summarized in frequencies and percentages and presented in tables. RESULTS: A total of 207 students took part in the survey. The mean age of respondents was 21.8 ±2.0 years. More than half of survey respondents (60.9% reported that they have had premarital sex. Multi-variate logistic regression analysis showed that male respondents were more than seven times to ever have sexual intercourse as compared to female respondents (AOR= 7.6; 95%CI: 4.51, 34.87. However, age less than 18 years was found to be protective against premarital sexual practice (AOR=0.42.; 95%CI: 0.27-0.73. Compared to respondents who do not use alcohol, those who are alcohol users after joining college were 3.8 times (AOR 3.05, 95% CI: 1.51-4.32 as likely to begin premarital sex. Similarly, ever chewing khat after joining college was found to be positively associated with premarital sex in this study. (AOR=2.60.; 95%CI: 0.62-1.43. CONCLUSION: A significant number of students had started

  12. Premarital Sexual Practice among Unmarried First Year Undergraduate Students in Alkan University College in Addis Ababa, Ethiopia

    Directory of Open Access Journals (Sweden)

    Endalew Gemechu Sendo

    2014-01-01

    Full Text Available BACKGROUND Premarital sexual practice among unmarried College students has markedly increased recently in Ethiopia. College students are recognized as one of the age groups most affected by sexually transmitted infections including HIV. However, little has been explored about the magnitude of premarital sexual activity and predisposing factors in the circumstance of private higher education institutions in Ethiopia. OBJECTIVE To investigate the magnitude of premarital sexual practice and predisposing factors among unmarried undergraduate first year students in Alkan University College in Addis Ababa, Ethiopia. METHODS A cross-sectional survey of college students was conducted in April-May 2013. Study participants were selected by stratified random sampling. A self-administered questionnaire was completed by 207 unmarried first year undergraduate students, and was analyzed using SPSS V.16.0. Multi-variate logistic regression was used to see association between variables. Results were summarized in frequencies and percentages and presented in tables. RESULTS A total of 207 students took part in the survey. The mean age of respondents was 21.8 ±2.0 years. More than half of survey respondents (60.9% reported that they have had premarital sex. Multi-variate logistic regression analysis showed that male respondents were more than seven times to ever have sexual intercourse as compared to female respondents (AOR= 7.6; 95%CI: 4.51, 34.87. However, age less than 18 years was found to be protective against premarital sexual practice (AOR=0.42.; 95%CI: 0.27- 0.73. Compared to respondents who do not use alcohol, those who are alcohol users after joining college were 3.8 times (AOR 3.05, 95% CI: 1.51- 4.32 as likely to begin premarital sex. Similarly, ever chewing khat after joining college was found to be positively associated with premarital sex in this study. (AOR=2.60.; 95%CI: 0.62-1.43. CONCLUSION A significant number of students had started pre

  13. The C32 alkane-1,15-diol as a proxy of late Quaternary riverine input in coastal margins

    Science.gov (United States)

    Lattaud, Julie; Dorhout, Denise; Schulz, Hartmut; Castañeda, Isla S.; Schefuß, Enno; Sinninghe Damsté, Jaap S.; Schouten, Stefan

    2017-08-01

    The study of past sedimentary records from coastal margins allows us to reconstruct variations in terrestrial input into the marine realm and to gain insight into continental climatic variability. There are numerous organic proxies for tracing terrestrial input into marine environments but none that strictly reflect the input of river-produced organic matter. Here, we test the fractional abundance of the C32 alkane 1,15-diol relative to all 1,13- and 1,15-long-chain diols (FC32 1, 15) as a tracer of input of river-produced organic matter in the marine realm in surface and Quaternary (0-45 ka) sediments on the shelf off the Zambezi and nearby smaller rivers in the Mozambique Channel (western Indian Ocean). A Quaternary (0-22 ka) sediment record off the Nile River mouth in the eastern Mediterranean was also studied for long-chain diols. For the Mozambique Channel, surface sediments of sites most proximal to Mozambique rivers showed the highest F1, 15 - C32 (up to 10 %). The sedimentary record shows high (15-35 %) pre-Holocene F1, 15 - C32 and low (soil and river-produced organic matter in the marine environment, which declines from 0.25 to 0.60 for the pre-Holocene to sea level, which caused the Zambezi River mouth to become more distal to our study site, thereby decreasing riverine input at the core location. Some small discrepancies are observed between the records of the BIT index and FC32 1, 15 for Heinrich Event 1 (H1) and the Younger Dryas (YD), which may be explained by a change in soil sources in the catchment area rather than a change in river influx. Like for the Mozambique Channel, a significant correlation between FC32 1, 15 and the BIT index (r2 = 0.38, p sea level rise. In general, the differences between the BIT index and FC32 1, 15 eastern Mediterranean Nile records can be explained by the fact that the BIT index is not only affected by riverine runoff but also by vegetation cover with increasing cover leading to lower soil erosion. Our results

  14. Grid Computing

    Indian Academy of Sciences (India)

    IAS Admin

    A computing grid interconnects resources such as high per- formance computers, scientific databases, and computer- controlled scientific instruments of cooperating organiza- tions each of which is autonomous. It precedes and is quite different from cloud computing, which provides computing resources by vendors to ...

  15. One-of-A-Kind: A Microporous Metal-Organic Framework Capable of Adsorptive Separation of Linear, Mono- and Di-branched Alkane Isomers via Temperature- and Adsorbate-Dependent Molecular Sieving

    KAUST Repository

    Wang, Hao

    2018-03-29

    Separation of alkane isomers represents a crucial process in the petrochemical industry in order to achieve high octane rating of gasoline. Herein, we report the first example of complete separation of linear, monobranched and dibranched alkane isomers by a single adsorbent. A calcium-based robust microporous metal-organic framework, Ca(H2tcpb) (tcpb = 1,2,4,5-tetrakis(4-carboxyphenyl)-benzene) exhibits unique molecular exclusion behavior which enables full separation of binary or ternary mixtures of alkane isomers into pure form of each isomerate. The successful separation of monobranched and dibranched hexane isomers will not only lead to the production of higher quality gasoline with maximum possible octane numbers but also fill the gap in the current separation technology. Exploration of separation mechanism indicates that structural flexibility and adsorbate-dependent structure change of the porous framework plays a vital role for the observed temperature-dependent molecular sieving property of the adsorbent.

  16. Programming in biomolecular computation

    DEFF Research Database (Denmark)

    Hartmann, Lars Røeboe; Jones, Neil; Simonsen, Jakob Grue

    2010-01-01

    , by programs reminiscent of low-level computer machine code; and at the same time biologically plausible: its functioning is defined by a single and relatively small set of chemical-like reaction rules. Further properties: the model is stored-program: programs are the same as data, so programs are not only......Our goal is to provide a top-down approach to biomolecular computation. In spite of widespread discussion about connections between biology and computation, one question seems notable by its absence: Where are the programs? We introduce a model of computation that is evidently programmable...... executable, but are also compilable and interpretable. It is universal: all computable functions can be computed (in natural ways and without arcane encodings of data and algorithm); it is also uniform: new “hardware” is not needed to solve new problems; and (last but not least) it is Turing complete...

  17. Indagini informatiche e acquisizione della prova nel processo penale / Enquêtes informatiques et acquisition d’éléments de preuve dans le procès pénal / Computer investigation and acquisition of evidence in criminal proceedings

    Directory of Open Access Journals (Sweden)

    Bravo Fabio

    2010-03-01

    Full Text Available This article aims to examine the new regulations introduced by the Budapest Convention on Cybercrime and the Italian Ratification Law No. 48/2008. Attention is focused primarily on the impact on computer investigation and the acquisition of evidence in criminal proceedings. The article also analyzes some relevant Italian Court decisions, in which we can find an uncertain and fluctuating trend as regards elements and principles of computer forensics. Although the Italian law has now implemented several articles of the Criminal Procedure Code, the principles of computer forensics, it will be necessary to verify how these principles will be implemented in practice.

  18. Process for functionalizing alkanes

    Science.gov (United States)

    Bergman, R.G.; Janowicz, A.H.; Periana-Pillai, R.A.

    1984-06-12

    Process for functionalizing saturated hydrocarbons selectively in the terminal position comprises: (a) reacting said saturated hydrocarbons with a metal complex CpRhPMe/sub 3/H/sub 2/ in the presence of ultraviolet radiation at -60/sup 0/ to -17/sup 0/C to form a hydridoalkyl complex CpRhPMe/sub 3/RH; (b) reacting said hydridoalkyl complex with a haloform CHX/sub 3/ at -60/sup 0/ to -17/sup 0/C to form the corresponding haloalkyl complex of step (a) CpRhPMe/sub 3/RX; and (c) reacting said haloalkyl complex with halogen -60 to 25/sup 0/C to form a functional haloalkyl compound.

  19. Computer group

    International Nuclear Information System (INIS)

    Bauer, H.; Black, I.; Heusler, A.; Hoeptner, G.; Krafft, F.; Lang, R.; Moellenkamp, R.; Mueller, W.; Mueller, W.F.; Schati, C.; Schmidt, A.; Schwind, D.; Weber, G.

    1983-01-01

    The computer groups has been reorganized to take charge for the general purpose computers DEC10 and VAX and the computer network (Dataswitch, DECnet, IBM - connections to GSI and IPP, preparation for Datex-P). (orig.)

  20. Computer Music

    Science.gov (United States)

    Cook, Perry R.

    This chapter covers algorithms, technologies, computer languages, and systems for computer music. Computer music involves the application of computers and other digital/electronic te