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Sample records for cyclopentanes

  1. Computational Chemistry of Cyclopentane Low Temperature Oxidation

    KAUST Repository

    El Rachidi, Mariam; Zá dor, Judit; Sarathy, Mani

    2015-01-01

    reactions occurring during low-temperature cyclopentane combustion using theoretical chemical kinetics. The reaction pathways of the cyclopentyl + O2 adduct is traced to alkylhydroperoxide, cyclic ether, β-scission and HO2 elimination products. The calculations are carried out at the UCCSD(T)-F12b/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory. The barrierless entrance channel is treated using variable-reaction-coordinate transition state theory (VRC-TST) at the CASPT2(7e,6o) level of theory, including basis set, geometry relaxation and ZPE corrections. 1-D time-dependent multiwell master equation analysis is used to determine pressure-and temperature-dependent rate parameters of all investigated reactions. Tunneling corrections are included using Eckart barriers. Comparison with cyclohexane is used to elucidate the effect of ring size on the low temperature reactivity of naphthenes. The rate coefficients reported herein are suitable for use in cyclopentane and methylcyclopentane combustion models, even below ~900 K, where ignition is particularly sensitive to these pressure-dependent values.

  2. Computational Chemistry of Cyclopentane Low Temperature Oxidation

    KAUST Repository

    El Rachidi, Mariam

    2015-03-30

    Cycloalkanes are significant constituents of conventional fossil fuels, but little is known concerning their combustion chemistry and kinetics, particularly at low temperatures. This study investigates the pressure dependent kinetics of several reactions occurring during low-temperature cyclopentane combustion using theoretical chemical kinetics. The reaction pathways of the cyclopentyl + O2 adduct is traced to alkylhydroperoxide, cyclic ether, β-scission and HO2 elimination products. The calculations are carried out at the UCCSD(T)-F12b/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory. The barrierless entrance channel is treated using variable-reaction-coordinate transition state theory (VRC-TST) at the CASPT2(7e,6o) level of theory, including basis set, geometry relaxation and ZPE corrections. 1-D time-dependent multiwell master equation analysis is used to determine pressure-and temperature-dependent rate parameters of all investigated reactions. Tunneling corrections are included using Eckart barriers. Comparison with cyclohexane is used to elucidate the effect of ring size on the low temperature reactivity of naphthenes. The rate coefficients reported herein are suitable for use in cyclopentane and methylcyclopentane combustion models, even below ~900 K, where ignition is particularly sensitive to these pressure-dependent values.

  3. Cyclopentane combustion. Part II. Ignition delay measurements and mechanism validation

    KAUST Repository

    Rachidi, Mariam El

    2017-06-12

    This study reports cyclopentane ignition delay measurements over a wide range of conditions. The measurements were obtained using two shock tubes and a rapid compression machine, and were used to test a detailed low- and high-temperature mechanism of cyclopentane oxidation that was presented in part I of this study (Al Rashidi et al., 2017). The ignition delay times of cyclopentane/air mixtures were measured over the temperature range of 650–1350K at pressures of 20 and 40atm and equivalence ratios of 0.5, 1.0 and 2.0. The ignition delay times simulated using the detailed chemical kinetic model of cyclopentane oxidation show very good agreement with the experimental measurements, as well as with the cyclopentane ignition and flame speed data available in the literature. The agreement is significantly improved compared to previous models developed and investigated at higher temperatures. Reaction path and sensitivity analyses were performed to provide insights into the ignition-controlling chemistry at low, intermediate and high temperatures. The results obtained in this study confirm that cycloalkanes are less reactive than their non-cyclic counterparts. Moreover, cyclopentane, a high octane number and high octane sensitivity fuel, exhibits minimal low-temperature chemistry and is considerably less reactive than cyclohexane. This study presents the first experimental low-temperature ignition delay data of cyclopentane, a potential fuel-blending component of particular interest due to its desirable antiknock characteristics.

  4. Cyclopentane combustion. Part II. Ignition delay measurements and mechanism validation

    KAUST Repository

    Rachidi, Mariam El; Má rmol, Juan C.; Banyon, Colin; Sajid, Muhammad Bilal; Mehl, Marco; Pitz, William J.; Mohamed, Samah; Alfazazi, Adamu; Lu, Tianfeng; Curran, Henry J.; Farooq, Aamir; Sarathy, Mani

    2017-01-01

    This study reports cyclopentane ignition delay measurements over a wide range of conditions. The measurements were obtained using two shock tubes and a rapid compression machine, and were used to test a detailed low- and high-temperature mechanism of cyclopentane oxidation that was presented in part I of this study (Al Rashidi et al., 2017). The ignition delay times of cyclopentane/air mixtures were measured over the temperature range of 650–1350K at pressures of 20 and 40atm and equivalence ratios of 0.5, 1.0 and 2.0. The ignition delay times simulated using the detailed chemical kinetic model of cyclopentane oxidation show very good agreement with the experimental measurements, as well as with the cyclopentane ignition and flame speed data available in the literature. The agreement is significantly improved compared to previous models developed and investigated at higher temperatures. Reaction path and sensitivity analyses were performed to provide insights into the ignition-controlling chemistry at low, intermediate and high temperatures. The results obtained in this study confirm that cycloalkanes are less reactive than their non-cyclic counterparts. Moreover, cyclopentane, a high octane number and high octane sensitivity fuel, exhibits minimal low-temperature chemistry and is considerably less reactive than cyclohexane. This study presents the first experimental low-temperature ignition delay data of cyclopentane, a potential fuel-blending component of particular interest due to its desirable antiknock characteristics.

  5. Enantiopure cyclopentane building blocks from iridoid glucosides

    DEFF Research Database (Denmark)

    Rasmussen, Jon Holbech

    .e. S. albida, S. woronowic, S. subvelutina, S. lateriflora, S. altissima, were investigated. It was found that in the water-soluble part of an ethanolic extract, a cinnamic ester of catalpol, scutellarioside I (348), was extractable into EtOAc. A method was developed in which the preparation of a water......-soluble extract of the plant material, extraction of 348 into EtOAc and acetylation of the crude EtOAc-extract, gave an acetylated crude product, from which scutellarioside I pentaacetate (351) was crystallised. Thus, 351 was obtained without the use of chromatography. Conversely, the purification of 5 was only......, pentaacetate 351 was transformed into an iridoid glucoside diacetonide 371. Ozonolysis of 371 followed by a reductive work-up procedure (NaBH4) led to the partially protected cyclopentane derivative 352. The ozonolysis/reduction sequence constitutes a new method in iridoid chemistry to obtain cyclopentanoid...

  6. Measuring and modelling of the combined thermodynamic promoting effect of tetrahydrofuran and cyclopentane on carbon dioxide hydrates

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen; Daraboina, Nagu; Thomsen, Kaj

    2014-01-01

    This work documents both experimental data, and by thermodynamic modelling, the synergistic effect occurring in promoted carbon dioxide hydrate systems at the simultaneous presence of tetrahydrofuran and cyclopentane.Cyclopentane has previously been considered a reference among gas hydrate promot...

  7. Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics

    KAUST Repository

    Rachidi, Mariam El

    2017-06-23

    Cycloalkanes are significant constituents of conventional fossil fuels, in which they are one of the main contributors to soot formation, but also significantly influence the ignition characteristics below ∼900K. This paper discusses the development of a detailed high- and low-temperature oxidation mechanism for cyclopentane, which is an important archetypical cycloalkane. The differences between cyclic and non-cyclic alkane chemistry, and thus the inapplicability of acyclic alkane analogies, required the detailed theoretical investigation of the kinetics of important cyclopentane oxidation reactions as part of the mechanism development. The cyclopentyl+O reaction was investigated at the UCCSD(T)-F12a/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory in a time-dependent master equation framework. Comparisons with analogous cyclohexane or non-cyclic alkane reactions are presented. Our study suggests that beyond accurate quantum chemistry the inclusion of pressure dependence and especially that of formally direct kinetics is crucial even at pressures relevant for practical application.

  8. Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics

    KAUST Repository

    Rachidi, Mariam El; Mehl, Marco; Pitz, William J.; Mohamed, Samah; Sarathy, Mani

    2017-01-01

    Cycloalkanes are significant constituents of conventional fossil fuels, in which they are one of the main contributors to soot formation, but also significantly influence the ignition characteristics below ∼900K. This paper discusses the development of a detailed high- and low-temperature oxidation mechanism for cyclopentane, which is an important archetypical cycloalkane. The differences between cyclic and non-cyclic alkane chemistry, and thus the inapplicability of acyclic alkane analogies, required the detailed theoretical investigation of the kinetics of important cyclopentane oxidation reactions as part of the mechanism development. The cyclopentyl+O reaction was investigated at the UCCSD(T)-F12a/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory in a time-dependent master equation framework. Comparisons with analogous cyclohexane or non-cyclic alkane reactions are presented. Our study suggests that beyond accurate quantum chemistry the inclusion of pressure dependence and especially that of formally direct kinetics is crucial even at pressures relevant for practical application.

  9. Highly Stereoselective Synthesis of Cyclopentanes bearing Four Stereocenters by a Rhodium Carbene–Initiated Domino Sequence

    Science.gov (United States)

    Parr, Brendan T.; Davies, Huw M. L.

    2014-01-01

    Stereoselective synthesis of a cyclopentane nucleus by convergent annulations constitutes a significant challenge for synthetic chemists. Though a number of biologically relevant cyclopentane natural products are known, more often than not, the cyclopentane core is assembled in a stepwise fashion due to lack of efficient annulation strategies. Herein, we report the rhodium-catalyzed reactions of vinyldiazoacetates with (E)-1,3-disubstituted 2-butenols generate cyclopentanes, containing four new stereogenic centers with very high levels of stereoselectivity (99% ee, >97 : 3 dr). The reaction proceeds by a carbene–initiated domino sequence consisting of five distinct steps: rhodium–bound oxonium ylide formation, [2,3]-sigmatropic rearrangement, oxy-Cope rearrangement, enol–keto tautomerization, and finally an intramolecular carbonyl ene reaction. A systematic study is presented detailing how to control chirality transfer in each of the four stereo-defining steps of the cascade, consummating in the development of a highly stereoselective process. PMID:25082301

  10. Density and temperature effects on electron mobilities in gaseous, critical and liquid n-hexane, cyclohexane, and cyclopentane

    International Nuclear Information System (INIS)

    Huang, S.S.-S.; Freeman, G.R.

    1978-01-01

    In the low density vapors the density normalized mobilities μn of thermal electrons decreased in the order n-hexane > cyclopentane > cyclohexane. Mobilities in the critical fluids were 16 cm 2 /V s in n-hexane, 23 in cyclohexane, and 22 in cyclopentane. Mobilities in the liquids were independent of field up to the highest value used, which was 1.5 Td in the hexanes and 0.9 Td in cyclopentane. The mobilities and their temperature dependences were interpreted in terms of a model

  11. Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling

    KAUST Repository

    Rachidi, Mariam El; Thion, Sé bastien; Togbé , Casimir; Dayma, Guillaume; Mehl, Marco; Dagaut, Philippe; Pitz, William J.; Zá dor, Judit; Sarathy, Mani

    2016-01-01

    This study is concerned with the identification and quantification of species generated during the combustion of cyclopentane in a jet stirred reactor (JSR). Experiments were carried out for temperatures between 740 and 1250K, equivalence ratios from 0.5 to 3.0, and at an operating pressure of 10atm. The fuel concentration was kept at 0.1% and the residence time of the fuel/O/N mixture was maintained at 0.7s. The reactant, product, and intermediate species concentration profiles were measured using gas chromatography and Fourier transform infrared spectroscopy. The concentration profiles of cyclopentane indicate inhibition of reactivity between 850-1000K for ϕ = 2.0 and ϕ = 3.0. This behavior is interesting, as it has not been observed previously for other fuel molecules, cyclic or non-cyclic. A kinetic model including both low- and high-temperature reaction pathways was developed and used to simulate the JSR experiments. The pressure-dependent rate coefficients of all relevant reactions lying on the PES of cyclopentyl+O, as well as the C-C and C-H scission reactions of the cyclopentyl radical were calculated at the UCCSD(T)-F12b/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory. The simulations reproduced the unique reactivity trend of cyclopentane and the measured concentration profiles of intermediate and product species. Sensitivity and reaction path analyses indicate that this reactivity trend may be attributed to differences in the reactivity of allyl radical at different conditions, and it is highly sensitive to the C-C/C-H scission branching ratio of the cyclopentyl radical decomposition.

  12. Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling

    KAUST Repository

    Rachidi, Mariam El

    2016-06-23

    This study is concerned with the identification and quantification of species generated during the combustion of cyclopentane in a jet stirred reactor (JSR). Experiments were carried out for temperatures between 740 and 1250K, equivalence ratios from 0.5 to 3.0, and at an operating pressure of 10atm. The fuel concentration was kept at 0.1% and the residence time of the fuel/O/N mixture was maintained at 0.7s. The reactant, product, and intermediate species concentration profiles were measured using gas chromatography and Fourier transform infrared spectroscopy. The concentration profiles of cyclopentane indicate inhibition of reactivity between 850-1000K for ϕ = 2.0 and ϕ = 3.0. This behavior is interesting, as it has not been observed previously for other fuel molecules, cyclic or non-cyclic. A kinetic model including both low- and high-temperature reaction pathways was developed and used to simulate the JSR experiments. The pressure-dependent rate coefficients of all relevant reactions lying on the PES of cyclopentyl+O, as well as the C-C and C-H scission reactions of the cyclopentyl radical were calculated at the UCCSD(T)-F12b/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory. The simulations reproduced the unique reactivity trend of cyclopentane and the measured concentration profiles of intermediate and product species. Sensitivity and reaction path analyses indicate that this reactivity trend may be attributed to differences in the reactivity of allyl radical at different conditions, and it is highly sensitive to the C-C/C-H scission branching ratio of the cyclopentyl radical decomposition.

  13. Chemoselective, Substrate-directed Fluorination of Functionalized Cyclopentane β-Amino Acids.

    Science.gov (United States)

    Kiss, Loránd; Nonn, Melinda; Sillanpää, Reijo; Haukka, Matti; Fustero, Santos; Fülöp, Ferenc

    2016-12-06

    This work describes a substrate-directed fluorination of some highly functionalized cyclopentane derivatives. The cyclic products incorporating CH 2 F or CHF 2 moieties in their structure have been synthesized from diexo- or diendo-norbornene β-amino acids following a stereocontrolled strategy. The synthetic study was based on an oxidative transformation of the ring carbon-carbon double bond of the norbornene β-amino acids, followed by transformation of the resulted "all cis" and "trans" diformyl intermediates by fluorination with "chemodifferentiation". © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Comparison of the linear energy transfer effect in the radiolysis of cyclopentane, cyclohexane and cyclooctane

    International Nuclear Information System (INIS)

    Wojnarovits, L.; La Verne, J.A.

    1998-01-01

    In the radiolysis of cyclopentane, cyclohexane and cyclooctane, changing the irradiating particles from γ-rays to heavy ions, there are indications for the increase of the proportion of the H atom forming reaction at the expense of the reactions leading to H 2 molecule elimination and to radical production without participation of H atoms. This shift is attributed to changes in charge recombination with the increasing LET from basically geminate recombination to predominantly cross combination. The iodine scavenging results are similar in the three systems which is attributed to the basically diffusion controlled character of the competing reactions. (author)

  15. Tribological Properties of a Pennzane(Registered Trademark)-Based Liquid Lubricant (Disubstituted Alkylated Cyclopentane) for Low Temperature Space Applications

    Science.gov (United States)

    Venier, Clifford; Casserly, Edward W.; Jones, William R., Jr.; Marchetti, Mario; Jansen, Mark J.; Predmore, Roamer E.

    2002-01-01

    The tribological properties of a disubstituted alkylated cyclopentane, Pennzane (registered) Synthesized Hydrocarbon Fluid X-1000, are presented. This compound is a lower molecular weight version of the commonly used multiply alkylated cyclopentane, Pennzane X-2000, currently used in many space mechanisms. New, lower temperature applications will require liquid lubricants with lower viscosities and pour points and acceptable vapor pressures. Properties reported include: friction and wear studies and lubricated lifetime in vacuum; additionally, typical physical properties (i.e., viscosity-temperature, pour point, flash and fire point, specific gravity, refractive index, thermal properties, volatility and vapor pressure) are reported.

  16. Thermodynamic promotion of carbon dioxide-clathrate hydrate formation by tetrahydrofuran, cyclopentane and their mixtures

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen; Thomsen, Kaj; Abildskov, Jens

    2013-01-01

    Gas clathrate hydrate dissociation pressures are reported for mixtures of carbon dioxide, water and thermodynamic promoters forming structure II hydrates.Hydrate (H)-aqueous liquid (Lw)-vapour (V) equilibrium pressures for the ternary system composed of water, tetrahydrofuran (THF), and carbon....... It is shown that upon adding THF to the pure aqueous phase to form a 4mass percent solution, the equilibrium pressure of the formed hydrates may be lowered compared to the ternary system of water, cyclopentane and carbon dioxide. © 2013 Elsevier Ltd....... dioxide (CO2), with 5.0mole percent THF in the initial aqueous phase, are presented in the temperature range from 283.3K to 285.2K. At 283.3K, the three-phase equilibrium pressure is determined to be 0.61MPa (absolute pressure).Four-phase hydrate (H)-aqueous liquid (Lw)-organic liquid (La)-vapour (V...

  17. Graphene with outstanding anti-irradiation capacity as multialkylated cyclopentanes additive toward space application

    Science.gov (United States)

    Fan, Xiaoqiang; Wang, Liping

    2015-07-01

    Multialkylated cyclopentanes (MACs), a class of synthetic hydrocarbon fluid have attracted intensive interest as possible space lubricants due to a series of unique physical and chemical properties. Here, we used graphene with high mechanical strength and chemical inertness as lubricant additive to explore its potential for space application. The effects of space irradiation on graphene and the tribological properties of graphene as lubricant additive were firstly investigated in detail under simulated space environment composed of high vacuum, high/low temperature and irradiation. Results demonstrate that graphene not only possesses outstanding anti-irradiation capacity but also significantly improves the space performance and tribological properties of MACs, which depends on the excellent physicochemical properties and high load-carrying ability of graphene as well as more effective separation of the sliding surfaces.

  18. Synthesis and pharmacology of 3-hydroxy-delta2-isoxazoline-cyclopentane analogues of glutamic acid

    DEFF Research Database (Denmark)

    Conti, P; De Amici, M; Bräuner-Osborne, Hans

    2002-01-01

    The synthesis and pharmacology of two potential glutamic acid receptor ligands are described. Preparation of the bicyclic 3-hydroxy-delta2-isoxazoline-cyclopentane derivatives (+/-)-7 and (+/-)-8 was accomplished via 1,3-dipolar cycloaddition of bromonitrile oxide to suitably protected 1-amino......-cyclopent-3-enecarboxylic acids. Their structure was established using a combination of 1H NMR spectroscopy and molecular mechanics calculations carried out on the intermediate cycloadducts (+/-)-11 and (+/-)-12. Amino acid derivatives (+/-)-7 and (+/-)-8 were assayed at ionotropic and metabotropic glutamic...... acid receptor subtypes and their activity compared with that of trans-ACPD and cis-ACPD. The results show that the replacement of the omega-carboxylic group of the model compounds with the 3-hydroxy-delta2-isoxazoline moiety abolishes or reduces drastically the activity at the metabotropic glutamate...

  19. Highly Functionalized and Potent Antiviral Cyclopentane Derivatives Formed by a Tandem Process Consisting of Organometallic, Transition-Metal-Catalyzed, and Radical Reaction Steps

    Czech Academy of Sciences Publication Activity Database

    Jagtap, Pratap; Ford, Leigh Robert; Deister, E.; Pohl, Radek; Císařová, I.; Hodek, Jan; Weber, Jan; Mackman, R.; Bahador, G.; Jahn, Ullrich

    2014-01-01

    Roč. 20, č. 33 (2014), s. 10298-10304 ISSN 0947-6539 R&D Projects: GA ČR GA203/09/1936 Institutional support: RVO:61388963 Keywords : antiviral activity * cyclopentanes * isomerization * organic synthesis * radicals Subject RIV: CC - Organic Chemistry Impact factor: 5.731, year: 2014

  20. Lifetimes of Multiply Alkylated Cyclopentane Oil in Contact with Various Metals, Evaluated with Vacuum Spiral Orbit Tribometer

    Science.gov (United States)

    Pepper, Stephen V.

    2018-01-01

    The dependence of the lifetimes of small quantities of a Multiply Alkylated Cyclopentane (MAC) lubricant oil, Pennzane (Registered Trademark) 2001A (Nye Lubricants, Inc.), in rolling and sliding contact with different metals was evaluated with a vacuum spiral orbit tribometer. The metals were the bearing alloys 52100 steel, 440C steel, 17-4 PH steel and Nitinol 60 and the elements chromium, vanadium and titanium. The lifetimes of the lubricant oil on different metals fell into distinct groups with 52100 greater than 440C approx. Nitinol 60 greater than 17-4 PH for the order of the lifetimes of the steels and chromium greater than vanadium greater than titanium for the order of the lifetimes for the elements. The limited life of the small quantities of oil is assumed to be due to its consumption by the tribochemical reaction of the oil with the different metal bearing materials. The lifetimes are then inversely related to the reaction rates of the oil molecules with the various metals: the longest life of 52100 steel having the lowest reaction rate and the shortest life of titanium having the highest reaction rate. Mechanisms for the tribochemical reactions are discussed.

  1. Effects of cyclopentane on CO2 hydrate formation and dissociation as a co-guest molecule for desalination

    International Nuclear Information System (INIS)

    Zheng, Jia-nan; Yang, Ming-jun; Liu, Yu; Wang, Da-yong; Song, Yong-chen

    2017-01-01

    Highlights: • CP decreases CO 2 hydrate phase equilibrium pressure by forming CO 2 -CP hydrates. • The increase of CP can’t decrease hydrates phase equilibrium pressure unlimitedly. • Higher CP concentration lowers CO 2 hydrate gas uptake. • The optimal CP molar ratio is 0.01 based on hydrate phase equilibrium and gas uptake. - Abstract: Cyclopentane (CP) is considered to be a potential co-guest molecule in carbon dioxide (CO 2 ) hydrate-based desalination. The experimental thermodynamic data of CO 2 -CP hydrates were measured for a salt solution, where CP was chosen as a hydrate promoter. Seven experimental cases (62 cycles) were studied with different molar ratios of CP/water (0, 0.0025, 0.005, 0.0075, 0.01, 0.02, and 0.03). Hydrate phase equilibrium data were generated using an isochoric method, and the hydrate saturations were calculated based on gas uptake. The results indicated that the increase in CP concentration significantly decreased the CO 2 hydrate equilibrium pressure to a certain limit; the hydrate saturation also decreased during this process. Also, it was determined that CP encouraged the formation of s-II double CO 2 -CP hydrates, which are different from s-I simple CO 2 hydrate. The CO 2 -CP guest provides a strengthened stability and moderate hydrate phase equilibrium conditions for hydrate-based desalination. The recommended optimal molar ratio of CP is 0.01 when the increase in equilibrium was more than 10 K, and the decrease in hydrate saturation was less than 2%.

  2. Production of 3-Oxo-2-(2'-pentenyl)-cyclopentane-1-octanoic Acid in the Fungus Aspergillus oryzae: A Step Towards Heterologous Production of Pyrethrins in Fungi.

    Science.gov (United States)

    Mohamed, Maged E; Pahirulzaman, Khomaizon A K; Lazarus, Colin M

    2016-03-01

    Pyrethrins are natural insecticides, which accumulate to high concentrations in pyrethrum (Chrysanthemum cinerariaefolium) flowers. Synthetic pyrethroids are more stable, more efficacious and cheaper, but contemporary requirements for safe and environmentally friendly pesticides encourage a return to the use of natural pyrethrins, and this would be favoured by development of an efficient route to their production by microbial fermentation. The biosynthesis of pyrethrins involves ester linkage between an acid moiety (chrysanthemoyl or pyrethroyl, synthesised via the mevalonic acid pathway from glucose), and an alcohol (pyrethrolone). Pyrethrolone is generated from 3-oxo-2-(2'-pentenyl)-cyclopentane-1-octanoic acid, which originates from α-linolenic acid via the jasmonic acid biosynthetic cascade. The first four genes in this cascade, encoding lipoxygenase 2, allene-oxide synthase, allene-oxide cyclase 2 and 12-oxophytodienoic acid reductase 3, were amplified from an Arabidopsis thaliana cDNA library, cloned in a purpose-built fungal multigene expression vector and expressed in Aspergillus oryzae. HPLC-MS analysis of the transgenic fungus homogenate gave good evidence for the presence of 3-oxo-2-(2'-pentenyl)-cyclopentane-1-octanoic acid.

  3. Development of a Henry's constant correlation and solubility measurements of n-pentane, i-pentane, cyclopentane, n-hexane, and toluene in water

    International Nuclear Information System (INIS)

    Chapoy, Antonin; Haghighi, Hooman; Tohidi, Bahman

    2008-01-01

    In this communication, we report new experimental data on n-pentane, i-pentane, cyclopentane, n-hexane, and toluene solubility in water at low temperature (below 298.15 K) and atmospheric pressure conditions. The new experimental data together with those reported in the literature have been used in developing a new equation for Henry's constants of normal alkanes (methane to decane), BETEX compounds, and acid gases in aqueous phase over a wide range of temperature (typically from 273.15 K to 373.15 K). The new equation is based on a thermodynamic model, which uses the Peng-Robinson equation of state combined with the classical quadratic mixing rules for modelling non-aqueous phases, while the NRTL model is used to calculate the water activity. The predictions of the developed thermodynamic model are compared to the experimental data and the results of a thermodynamic approach, which uses the Valderrama modification of the Patel-Teja equation of state and non-density dependent mixing rules for modelling all fluid phases. Good agreement is observed between the experimental data and the model predictions

  4. Study of pentane and cyclopentane radiolysis with the aid of radioactive iodine; Etude de la radiolyse du pentane et du cyclopentane a l'aide d'iode radioactif; Issledovanie radioliza pentana i tsiklopentana s pomoshch'yu radioaktivnogo joda; Estudio de la radiolisis del pentano y del ciclopentano con ayuda de yodo radiactivo

    Energy Technology Data Exchange (ETDEWEB)

    Dauphin, J [Laboratoire de Chimie-Physique, Faculte des Sciences de Paris (France)

    1962-03-15

    Irradiation of hydrocarbons by ionizing radiation such as Co{sup 60} gamma-rays produces, inter alia, free radicals. Analysis of these radicals may lead to at least a partial explanation of the phenomena occurring. For analysis, the ''isotopic dilution'' method is used: the iodine used for taking up the radicals is labelled with iodine-131, resulting in a whole series of labelled iodides when the reaction is completed. Separation is affected by means of distillation on a microcolumn after inactive carriers have been added and the mineral iodine has been extracted. The activity of each fraction is measured directly it leaves the column. A control is used to obtain absolute G values from the counting. Precautions are taken to prevent isotopic exchange during separation. This method has been applied to cyclopentane and n-pentane and has yielded a detailed radiolysis spectrum. (author) [French] Les hydrocarbures irradies par des rayonnements ionisants tels que les {gamma} du cobalt-60 produisent entre autres entites des radicaux libres, dont l'analyse peut amener a decouvrir une explication au moins partielle des phenomenes. Pour effectuer cette analyse, on utilise la technique de la : l'iode servant de capteur est marque par de l'iode-131, ce qui a pour resultat de donner toute une serie d'iodures marques en fin de reaction. La separation se fait par distillation sur une microcolonne, apres addition d'entraineurs inactifs et extraction de l'iode mineral. L'activite de chaque fraction est mesuree directement a la sortie de la colonne. Un temoin permet l'obtention de valeurs absolues de G a partir des comptages. Des precautions sont prises pour eviter l'echange isotopique en cours de separation. Appliquee au cyclopentane et au n-pentane, cette methode a permis d'obtenir un spectre detaille de radiolyse. (author) [Spanish] La exposicion de los hidrocarburos a la accion de radiaciones ionizantes tales como los rayos gamma del {sup 60}Co da lugar a la

  5. Synthesis of polyhydroxylated cyclopentanes from bromodeoxyaldonolactones

    DEFF Research Database (Denmark)

    Horneman, Anne Marie

    -azido-7-bromo-5,6-di-O-acetyl-2,3,7-trideoxy-D-arabino-hept-2-en ono-1,4-lactone (38) was prepared starting from 1. Additionally, compound 3 was converted into the C-4 epimer 35 by base catalysed epimerisation.The eight 7-bromo-7-deoxy-hept-2-enono-1,4-lactones were submitted to tributyltin hydride...

  6. (ajst) activation of cyclopentane in aqueous medium

    African Journals Online (AJOL)

    opiyo

    radiolysis in combination with absorption detection methods.1,2,3 In many of ... from the chloride salt, obtained from G.F. Smith chemical company. ... Total-ion chromatogram were obtained by using the HP 5890A gas chromatograph coupled to a vacuum-Generator Analytical. MS-12 mass spectrometer. pH measurements ...

  7. Synthesis of library from amino-hydroxy substituted cyclopentanes

    DEFF Research Database (Denmark)

    Bøjstrup, Marie; Lundt, Inge; Andrews, Robert

    -reaction followed by an opening of the lactone with an amine posed to be a suitable protocol for diversification (fig 2). Figure 2 Reactions performed on solid phase In this way several compounds were synthesized by parallel synthesis and cleaved off the resin. TransTech Pharma has tested these compounds...

  8. Modelling of cyclopentane promoted gas hydrate systems for carbon dioxide capture processes

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen; Thomsen, Kaj; Abildskov, Jens

    2014-01-01

    A thermodynamic model based on the Cubic-Plus-Association equation of state and the van der Waals-Platteeuw hydrate model is applied to perform a thermodynamic evaluation of gas hydrate forming systems relevant for post-combustion carbon dioxide capture.A modelling study of both fluid phase...... behaviour and hydrate phase behaviour is presented. Cycloalkanes ranging from cyclopropane to cyclohexane, represents a challenge for CPA, both in the description of the pure component densities and for liquid-liquid equilibrium (LLE) in the binary systems with water. It is concluded that an insufficient...

  9. Highly Functionalized Cyclopentane Derivatives by Tandem Michael Addition/Radical Cyclization/Oxygenation Reactions

    Czech Academy of Sciences Publication Activity Database

    Holan, Martin; Pohl, Radek; Císařová, I.; Klepetářová, Blanka; Jones, P. G.; Jahn, Ullrich

    2015-01-01

    Roč. 21, č. 27 (2015), s. 9877-9888 ISSN 0947-6539 R&D Projects: GA ČR GA13-40188S Institutional support: RVO:61388963 Keywords : cyclization * domino reactions * electron transfer * Michael addition * radical reactions Subject RIV: CC - Organic Chemistry Impact factor: 5.771, year: 2015

  10. Tandem Michael addition/radical cyclizations for the construction of highly functionalized cyclopentanes

    Czech Academy of Sciences Publication Activity Database

    Holan, Martin; Pohl, Radek; Císarová, I.; Jahn, Ullrich

    2012-01-01

    Roč. 106, - (2012), s1298-s1298 ISSN 0009-2770. [EuCheMS Chemistry Congress /4./. 26.08.2012-30.08.2012, Prague] Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclization * diastereoselectivity * Michael addiction * radical reactions * domino reactions Subject RIV: CC - Organic Chemistry

  11. Adsorption of Krypton and Cyclopentane on C.sub.60./sub.: An Experimental Study

    Czech Academy of Sciences Publication Activity Database

    Rathouský, Jiří; Zukal, Arnošt

    2000-01-01

    Roč. 8, 4/5 (2000), s. 337-350 ISSN 1064-122X R&D Projects: GA ČR GA203/95/1228 Institutional research plan: CEZ:AV0Z4040901; CEZ:A54/98:Z4-040-9-ii Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.846, year: 2000

  12. Tribochemistry of Multiply-Alkylated Cyclopentane Oils on DLC-Coated Thrust Bearings

    National Research Council Canada - National Science Library

    Lince, Jeffrey R; Bertrand, Patricia A

    2007-01-01

    In contrast to typical DLC coatings, hydrogenated DLC (H-DLC) coatings exhibit extremely low friction in vacuum and dry atmospheres, suggesting their potential importance for spacecraft applications...

  13. The combined effect of thermodynamic promoters tetrahydrofuran and cyclopentane on the kinetics of flue gas hydrate formation

    DEFF Research Database (Denmark)

    Daraboina, Nagu; von Solms, Nicolas

    2015-01-01

    ) hydrate formation using a rocking cell apparatus. Hydrate formation and decomposition kinetics were investigated by constant cooling (hydrate nucleation temperature) and isothermal (hydrate nucleation time) methods. Improved (synergistic) hydrate formation kinetics (hydrate nucleation and growth) were...... of these two promoters is favorable both thermodynamically and kinetically for hydrate formation from flue gas....

  14. Hydrate equilibrium data for the CO2 + N2 system with the use of tetra-n-butylammonium bromide (TBAB), cyclopentane (CP) and their mixture

    DEFF Research Database (Denmark)

    Tzirakis, Fragkiskos; Stringari, Paolo; von Solms, Nicolas

    2016-01-01

    Carbon Dioxide capture and sequestration (CCS) is nowadays an important area of research for decreasing CO2 emissions worldwide. Hydrates can become of great importance in the future as they form the basis for a new technology that can be used for CO2 capture from flue gases (hydrate...... crystallization). In this work hydrate equilibrium data are measured and compared with literature data. In particular, experimental results for hydrate dissociation with several promoters are presented. The isochoric method is used to determine the gas hydrate dissociation points. Different CO2 + N2 gas mixtures...

  15. A Novel Strategy Towards the Asymmetric Synthesis of Orthogonally Funtionalised 2-N-Benzyl-N-α-methylbenzylamino- 5-carboxymethyl-cyclopentane-1-carboxylic acid.

    Directory of Open Access Journals (Sweden)

    Julio G. Urones

    2004-04-01

    Full Text Available The asymmetric synthesis of the orthogonally funtionalised compounds tert-butyl 2-N-benzyl-N-α-methylbenzylamino-5-methoxycarbonylmethylcyclopentane- 1-carboxylate and methyl 2-N-benzyl-N-α-methylbenzylamino-5–carboxymethylcyclo- pentane-1-carboxylate by a domino reaction of tert-butyl methyl (E,E-octa-2,6- diendioate with lithium N-α-methylbenzyl-N-benzylamide initiated by a Michael addition, subsequent 5-exo-trig intramolecular cyclisation and posterior selective hydrolysis with trifluoroacetic acid is reported.

  16. Hydrate Equilibrium Data for CO2+N-2 System in the Presence of Tetra-n-butylammonium Fluoride (TBAF) and Mixture of TBAF and Cyclopentane (CP)

    DEFF Research Database (Denmark)

    Tzirakis, Fragkiskos; Stringari, Paolo; Coquelet, Christophe

    2016-01-01

    Hydrates can be used for CO2 capture from flue gases (hydrate crystallization). In this work, hydrate equilibrium data were measured and compared with literature data. The isochoric method was used to determine the gas hydrate dissociation points. Different CO2+N2 gas mixtures were used...

  17. Highly Functionalised Cyclopentanes by Radical Cyclisation of Unsaturated Bromolactones III. Preparation of Carbaaldohexofuranoses. - Determination of the Relative Configuration at C-4/C-5 of 2,3-Unsaturated heptono-1,4-lactones by Means of 1-H NMR Spectroscopy

    DEFF Research Database (Denmark)

    Lundt, Inge; Horneman, Anne Marie

    1999-01-01

    Two new carbaaldohexofuranoses, carba--D-glucofuranose and carba--L-mannofuranose have been prepared using 5,6-O-isopropylidene-D-glycero-L-galacto-heptono-1,4-lactone (6) as the starting material. The key step was a highly stereoselective intramolecular 5-exo-trig radical cyclisation of C-2......-substituted 2,3-unsaturated 7-bromo-7-deoxy-heptono-1,4-lactones promoted by tributyltin hydride. Assignment of the configuration of the unsaturated lactones was based upon NMR data of related compounds. The starting material, compound 6, was obtained by chain elongation of D-gulose, and a facile method...

  18. Carbon-Phenolic Cages for High-Speed Bearings. Part 1 - Friction and Wear Response of Phenolic Composite Impregnated with a Multiply-Alkylated Cyclopentane (MAC) Lubricant and MoS2 Solid Lubricant

    National Research Council Canada - National Science Library

    Forster, Nelson

    2003-01-01

    .... This portion covers characterization of flat panel specimens using thermal conductivity, tensile strength, coefficient of thermal expansion measurement, and friction and wear testing in a sliding contact...

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

    Science.gov (United States)

    DeMore, W.; Bayes, K.

    1998-01-01

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

  20. Raman spectroscopic study of reaction dynamics

    Science.gov (United States)

    MacPhail, R. A.

    1990-12-01

    The Raman spectra of reacting molecules in liquids can yield information about various aspects of the reaction dynamics. The author discusses the analysis of Raman spectra for three prototypical unimolecular reactions, the rotational isomerization of n-butane and 1,2-difluoroethane, and the barrierless exchange of axial and equatorial hydrogens in cyclopentane via pseudorotation. In the first two cases the spectra are sensitive to torsional oscillations of the gauche conformer, and yield estimates of the torsional solvent friction. In the case of cyclopentane, the spectra can be used to discriminate between different stochastic models of the pseudorotation dynamics, and to determine the relevant friction coefficients.

  1. 1H-cyclopentapyrimidine-2,4(1H,3H)-dione-related ionotropic glutamate receptors ligands. Structure-activity relationships and identification of potent and selective iGluR5 modulators

    DEFF Research Database (Denmark)

    Butini, Stefania; Pickering, Darryl S; Morelli, Elena

    2008-01-01

    (S)-CPW399 ((S)-1) is a potent and excitotoxic AMPA receptor partial agonist. Modifying the cyclopentane ring of (S)-1, we developed two of the most potent and selective functional antagonists (5 and 7) for kainate receptor (KA-R) subunit iGluR5. Derivatives 5 and 7, with their unique pharmacolog...

  2. Nickel-catalyzed cyclization of alpha, omega-dienes: formation vs. cleavage of C-C bonds

    Czech Academy of Sciences Publication Activity Database

    Nečas, D.; Turský, M.; Tišlerová, I.; Kotora, Martin

    2006-01-01

    Roč. 30, č. 4 (2006), s. 671-674 ISSN 1144-0546 R&D Projects: GA MŠk 1M0508; GA ČR GD203/03/H140 Institutional research plan: CEZ:AV0Z40550506 Keywords : catalysis * nickel * cyclization * diene * cyclopentane Subject RIV: CC - Organic Chemistry Impact factor: 2.647, year: 2006

  3. Phase equilibrium measurements of structure II clathrate hydrates of hydrogen with various promoters

    NARCIS (Netherlands)

    Torres Trueba, A.; Rovetto, L.J.; Florusse, L.J.; Kroon, M.C.; Peters, C.J.

    2011-01-01

    Phase equilibrium measurements of single and mixed organic clathrate hydrates with hydrogen were determined within a pressure range of 2.0–14.0 MPa. The organic compounds studied were furan, 2,5-dihydrofuran, tetrahydropyran, 1,3-dioxolane and cyclopentane. These organic compounds are known to form

  4. DFT-based inhibitor and promoter selection criteria for pentagonal ...

    Indian Academy of Sciences (India)

    Methane hydrate formation inhibition by methanol and ethylene glycol as well as methane hydrate stabilization by cyclopentane and tetrahydrofuran are critically analysed based on the interaction energy, free energy change, dipole moment and infrared frequency calculation. Calculation of free energy change for formation ...

  5. Dinesh

    Indian Academy of Sciences (India)

    Semiconductor applications of plasma immersion ion implantation technology ... X-ray analysis of 2-aniline benzo(2,3-) cyclopentane-1,3-dione .... entropy of activation and free energy of activation revealed the efficiency of the process. .... Phonon, magnon and electron contributions to low temperature specific heat in ...

  6. NATURAL CYCLOPENTANOID CYANOHYDRIN GLYCOSIDES .13. STRUCTURE DETERMINATION OF NATURAL EPOXYCYCLOPENTANES BY X-RAY CRYSTALLOGRAPHY AND NMR-SPECTROSCOPY

    DEFF Research Database (Denmark)

    Olafsdottir, E. S.; Sorensen, A. M.; Cornett, Claus

    1991-01-01

    nonannellated cyclopentane derivatives. The new glucosides were shown, by NMR spectroscopy (including NOE measurements), X-ray crystallography, and enzymatic hydrolysis to the corresponding cyanohydrins, to be (1R,2R,3R,4R)- and (1S,2S,3S,4S)-1-(beta-D-glucopyranosyloxy)-2,3-epoxy-4-hydroxycyclopenta ne-1...

  7. Synthesis of aminocyclopentanols: a-D-galacto configured sugar mimics

    DEFF Research Database (Denmark)

    Bøjstrup, Marie; Lundt, Inge

    2005-01-01

    Four aminocyclopentanols, as mimics of putative intermediates in hydrolysis of a-D-galactosides, have been synthesized through a number of stereoselective transformations, using the cis-fused cyclopentane-1,4-lactone (1R, 5S, 7R, 8R)-7,8-dihydroxy-2-oxabicyclo[3.3.0]oct-3-one 1 as a chiral buildi...

  8. Aminocyclopentanols as sugar mimics. Synthesis from unsaturated bicyclic lactones by Overman rearrangement

    DEFF Research Database (Denmark)

    Bøjstrup, Marie; Fanefjord, Mette; Lundt, Inge

    2007-01-01

    Bicyclic cyclopentane lactones, prepared from bromodeoxyaldonolactones, were transformed into aminocyclopentanols with an Overman rearrangement as the key step. Two of the compounds prepared, 7 and 19, were found to be good inhibitors of jack bean alpha-mannosidase and beta-D-N-acetylglucosaminid...

  9. Diffusive transport and evaporation to the atmosphere from a NAPL source in the vadose zone

    DEFF Research Database (Denmark)

    Holtegaard, L.E.; Bjerre, T.; Christophersen, Mette

    2002-01-01

    To evaluate the risks concerned with the presence of volatile organic compounds in the unsaturated zone it is important to know how the compounds are transported in the soil. In this project the effective diffusion coefficient of 3-methylpentane, hexane, methyl-cyclopentane, iso-octane and methyl...

  10. A Palladium-Catalyzed Vinylcyclopropane (3 + 2) Cycloaddition Approach to the Melodinus Alkaloids

    KAUST Repository

    Goldberg, Alexander F. G.

    2011-08-19

    A palladium-catalyzed (3+2) cycloaddition of a vinylcyclopropane and a β-nitrostyrene is employed to rapidly assemble the cyclopentane core of the Melodinus alkaloids. The ABCD ring system of the natural product family is prepared in six steps from commercially available materials.

  11. The Effects of Temperature and Growth Phase on the Lipidomes of Sulfolobus islandicus and Sulfolobus tokodaii

    DEFF Research Database (Denmark)

    Jensen, Sara Munk; Neesgaard, Vinnie Lund; Skjoldbjerg, Sandra Landbo Nedergaard

    2015-01-01

    at three different temperatures, with samples withdrawn during lag, exponential, and stationary phases. Three abundant tetraether lipid classes and one diether lipid class were monitored. Beside the expected increase in the number of cyclopentane moieties with higher temperature in both archaea, we......The functionality of the plasma membrane is essential for all organisms. Adaption to high growth temperatures imposes challenges and Bacteria, Eukarya, and Archaea have developed several mechanisms to cope with these. Hyperthermophilic archaea have earlier been shown to synthesize tetraether...... membrane lipids with an increased number of cyclopentane moieties at higher growth temperatures. Here we used shotgun lipidomics to study this effect as well as the influence of growth phase on the lipidomes of Sulfolobus islandicus and Sulfolobus tokodaii for the first time. Both species were cultivated...

  12. Natural gas storage in hydrates with the presence of promoters

    International Nuclear Information System (INIS)

    Sun Zhigao; Wang Ruzhu; Ma Rongsheng; Guo Kaihua; Fan Shuanshi

    2003-01-01

    Hydrate technology is being developed for the storage and transport of natural gas. Micellar surfectant solutions were found to increase the gas hydrate formation rate and storage capacity. An anionic surfactant, a nonionic surfactant, their mixtures and cyclopentane were used to improve the hydrate formation of a synthetic natural gas (methane=92.05 mol%, ethane=4.96 mol%, propane=2.99 mol%) in a quiescent system in this work. The effect of an anionic surfactant (sodium dodecyl sulfate) on natural gas storage in hydrates is more pronounced compared to the effect of a nonionic surfactant (dodecyl polysaccharide glycoside). Cyclopentane could reduce hydrate formation induction time but could not improve the hydrate formation rate and storage capacity

  13. The contribution of electronically excited states to the radiation chemistry of organic systems

    International Nuclear Information System (INIS)

    Lipsky, S.

    1990-01-01

    The photocurrent from anthracene in 2,2,4-trimethylpentane, 2.2- dimethylbutane, cyclohexane, cyclopentane, and tetramethylsilane has been studied as a function of excitation energy from the ionization threshold to the onset of strong solvent absorption. The fluroescence from solutions of hexafluorobenzene in cyclopentane, 2,2,4-trimethylpentane, 2,2-dimethylbutane and tetramethylsilane irradiated with β-particles has been studied as a function of the hexafluorobenzene concentration from c = 10 -3 -10 -1 M. The data are analyzed to permit extraction of the geminate ion-pair scavenging probability. The absorption of 160 nm light by cyclohexane in mixtures of cyclohexane, benzene and tetraphenylmethylenediamine results in an emission spectrum consisting of the simultaneous fluorescence from all three components. A mechanism for the development of this spectrum and its dependence on benzene concentration is constructed and shown to be quantitatively consistent with the results of independent measurements on the separate components. 55 refs

  14. Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

    KAUST Repository

    Cai, Yunfei

    2016-10-13

    The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields as well as excellent enantioselectivities and diastereoselectivities. The high value of the aza-Piancatelli rearrangement was demonstrated by the synthesis of a cyclopentane-based hNK1 antagonist analogue.

  15. Synthesis of Methylenebicyclo[3.2.1]octanol by a Sm(II)-Induced 1,2-Rearrangement Reaction with Ring Expansion of Methylenebicyclo[4.2.0]octanone.

    Science.gov (United States)

    Takatori, Kazuhiko; Ota, Shoya; Tendo, Kenta; Matsunaga, Kazuma; Nagasawa, Kokoro; Watanabe, Shinya; Kishida, Atsushi; Kogen, Hiroshi; Nagaoka, Hiroto

    2017-07-21

    Direct conversion of methylenebicyclo[4.2.0]octanone to methylenebicyclo[3.2.1]octanol by a Sm(II)-induced 1,2-rearrangement with ring expansion of the methylenecyclobutane is described. Three conditions were optimized to allow the adaptation of this approach to various substrates. A rearrangement mechanism is proposed involving the generation of a ketyl radical and cyclopentanation by ketyl-olefin cyclization, followed by radical fragmentation and subsequent protonation.

  16. Thermophysical study of 1,4-dioxane with cycloalkane mixtures

    International Nuclear Information System (INIS)

    Romero, C.; Giner, B.; Haro, M.; Artigas, H.; Lafuente, C.

    2006-01-01

    Densities, refractive indices, and surface tension for the binary mixtures 1,4-dioxane with cyclopentane or cylohexane have been determined at ambient pressure and at T = (283.15, 298.15, and 313.15) K. Excess volumes and refractive index and surface tension deviations have been calculated from the experimental data. Several relations between the thermophysical properties studied here have been tested using our experimental results

  17. Determination of the ionisation potential of certain hydrocarbons in the liquid phase

    International Nuclear Information System (INIS)

    Casanovas, J.; Grob, R.; Brunet, G.; Sabattier, R.; Guelfucci, J.P.; Blanc, D.

    1978-01-01

    The first results obtained are presented on the determination of the ionisation potential of four alkanes (n-hexane, n-pentane, cyclopentane and trimethyl-2,2,4 pentane) in the liquid phase. In the gaseous phase, the ionisation potential values of these hydrocarbons are respectively 10.18 eV for n-hexane, 10.35 eV for n-pentane, 10.53 eV for cyclopentane and 9.86 eV for trimethyl-2,2,4 pentane. Consequently rare gas resonance lamps (krypton and Xenon) were made, sealed and excited by an ultra-high frequency wave, which emit photons in the energy field concerned, i.e. from 8.5 eV to 11eV. The energy of the photons emitted by these lamps is respectively 8.44 eV (100%) and 9.57 eV (2%) for xenon and 10.03 eV (100%) and 10.64 eV (5%) for krypton. From the extent of the induced ionisation currents and particularly the value of the ratio of the currents induced by the photons of the krypton and xenon lamps, a minimum value of the ionisation potential drop can be deduced compared with the gas phase of 0.61 eV for n-hexane, 0.78 eV for n-pentane, 0.96 eV for cyclopentane and a maximum value of 1.42 eV for trimethyl-2,2,4 pentane [fr

  18. Thermal conductivity and rectification in asymmetric archaeal lipid membranes

    Science.gov (United States)

    Youssefian, Sina; Rahbar, Nima; Van Dessel, Steven

    2018-05-01

    Nature employs lipids to construct nanostructured membranes that self-assemble in an aqueous environment to separate the cell interior from the exterior environment. Membrane composition changes among species and according to environmental conditions, which allows organisms to occupy a wide variety of different habitats. Lipid bilayers are phase-change materials that exhibit strong thermotropic and lyotropic phase behavior in an aqueous environment, which may also cause thermal rectification. Among different types of lipids, archaeal lipids are of great interest due to their ability to withstand extreme conditions. In this paper, nonequilibrium molecular dynamics simulations were employed to study the nanostructures and thermal properties of different archaeols and to investigate thermal rectification effects in asymmetric archaeal membranes. In particular, we are interested in understanding the role of bridged phytanyl chains and cyclopentane groups in controlling the phase transition temperature and heat flow across the membrane. Our results indicate that the bridged phytanyl chains decrease the molecular packing of lipids, whereas the existence of cyclopentane rings on the tail groups increases the molecular packing by enhancing the interactions between isoprenoid chains. We found that macrocyclic archaeols have the highest thermal conductivity, whereas macrocyclic archaeols with two cyclopentane rings have the lowest. The effect of the temperature on the variation of thermal conductivity was found to be progressive. Our results further indicate that small thermal rectification effects occur in asymmetric archaeol bilayer membranes at around 25 K temperature gradient. The calculated thermal rectification factor was around 0.09 which is in the range of rectification factor obtained experimentally for nanostructures such as carbon nanotubes (0.07). Such phenomena may be of biological significance and could also be optimized for use in various engineering

  19. Total Synthesis and Absolute Configuration of the Marine Norditerpenoid Xestenone

    Directory of Open Access Journals (Sweden)

    Hiroaki Miyaoka

    2009-11-01

    Full Text Available Xestenone is a marine norditerpenoid found in the northeastern Pacific sponge Xestospongia vanilla. The relative configuration of C-3 and C-7 in xestenone was determined by NOESY spectral analysis. However the relative configuration of C-12 and the absolute configuration of this compound were not determined. The authors have now achieved the total synthesis of xestenone using their developed one-pot synthesis of cyclopentane derivatives employing allyl phenyl sulfone and an epoxy iodide as a key step. The relative and absolute configurations of xestenone were thus successfully determined by this synthesis.

  20. Forging Fluorine-Containing Quaternary Stereocenters by a Light-Driven Organocatalytic Aldol Desymmetrization Process.

    Science.gov (United States)

    Cuadros, Sara; Dell'Amico, Luca; Melchiorre, Paolo

    2017-09-18

    Reported herein is a light-triggered organocatalytic strategy for the desymmetrization of achiral 2-fluoro-substituted cyclopentane-1,3-diketones. The chemistry is based on an intermolecular aldol reaction of photochemically generated hydroxy-o-quinodimethanes and simultaneously forges two adjacent fully substituted carbon stereocenters, with one bearing a stereogenic carbon-fluorine unit. The method uses readily available substrates, a simple chiral organocatalyst, and mild reaction conditions to afford an array of highly functionalized chiral 2-fluoro-3-hydroxycyclopentanones. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  1. Modification of the performance of WO3-ZrO2 catalysts by metal addition in hydrocarbon reactions

    Directory of Open Access Journals (Sweden)

    Gerardo Carlos Torres

    2012-01-01

    Full Text Available A study of the different hydrocarbon reactions over Ni doped WO3-ZrO2 catalysts was performed. Ni was found as NiO at low Ni concentration while at high Ni concentrations a small fraction was present as a metal. For both cases, Ni strongly modified total acidity and concentration of strong acid sites. In the cyclohexane dehydrogenation reaction, Ni addition promotes both benzene and methyl cyclopentane production. The hydroconversion activity (n-butane and n-octane increases with the augment of total acidity produced by Ni. The selectivity to reaction products is modified according to the acid strength distribution changes produced by Ni addition.

  2. Modification of the performance of WO{sub 3}-ZrO{sub 2} catalysts by metal addition in hydrocarbon reactions

    Energy Technology Data Exchange (ETDEWEB)

    Torres, Gerardo Carlos; Manuale, Debora Laura; Benitez, Viviana Monica; Vera, Carlos Roman; Yori, Juan Carlos, E-mail: jyori@fiq.unl.edu.ar [Instituto de Investigaciones en Catalisis y Petroquimica, Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Consejo Nacional de Investigaciones Cientifica y Tecnicas, Santiago del Estero Santa Fe (Argentina)

    2012-07-01

    A study of the different hydrocarbon reactions over Ni doped WO{sub 3}-ZrO{sub 2} catalysts was performed. Ni was found as NiO at low Ni concentration while at high Ni concentrations a small fraction was present as a metal. For both cases, Ni strongly modified total acidity and concentration of strong acid sites. In the cyclohexane dehydrogenation reaction, Ni addition promotes both benzene and methyl cyclopentane production. The hydroconversion activity (n-butane and n-octane) increases with the augment of total acidity produced by Ni. The selectivity to reaction products is modified according to the acid strength distribution changes produced by Ni addition. (author)

  3. Synthesis of Carbasugars from Aldonolactones: Ritter-Type Epoxide Opening of Polyhydroxylated Aminocyclopentanes

    DEFF Research Database (Denmark)

    Lundt, Inge; Johansen, Steen Karsk; Kornø, Hanne Tøfting

    1999-01-01

    Using the cis-fused cyclopentane-1,4-lactone, 1(R),5(S)-7(R),8(R)-dihydroxy-2-oxabicyclo[3.3.0]oct-3-one (1), as starting material, 5-deoxycarba-*-L-xylo-hexofuranose (6) together with ?- (12) and ?-1-amino-1,5-dideoxycarba-L-xylo-hexofuranose (16) have been prepared using a number...... of stereoselective transformations. The key step was the regioselective opening of the epoxide 1(R),5(S)-7(R),8(R)-epoxy-2-oxabicyclo[3.3.0]oct-3-one (4) with different nucleophiles....

  4. (1R,2R,3R,4R,5S-2,3-Bis[(2S′-2-acetoxy-2-phenylacetoxy]-4-azido-1-[(2,4-dinitrophenylhydrazonomethyl]bicyclo[3.1.0]hexane

    Directory of Open Access Journals (Sweden)

    Robert McDonald

    2008-02-01

    Full Text Available In the title compound, C38H29N7O12, the five-membered ring adopts an envelope conformation in which the `flap' is cis to the cyclopropane group. This conformation is similar to those of other bicyclo[3.1.0]hexane analogues for which crystal structures have been reported. The absolute configuration of the stereogenic centers on the cyclopentane ring, as determined by comparison with the known configurations of the stereogenic centers in the (2S-2-acetoxy-2-phenylacetoxy groups, is 1(R, 2(R, 3(R, 4(R and 5(S. An intramolecular N—H...O hydrogen bond is present.

  5. Gaithersburg Nike Control and Launch Area Preliminary Assessment/Site Inspection Gaithersburg, Maryland

    Science.gov (United States)

    1990-01-01

    CYCLOPENTANE 1M7MEN 1-M4ETHYL-7- ( -METHYLETHYL) NAPHTHALENE 1MFLRE 1 -METHYL- 9H-FLUORENE INHP 1-NITROHEPTA14E MNONE 1-NITRO-2- OCTANONE 1OCTOL 1- OCTANOL ...iNuP 1-NITROHEPTANE 1NKCL 1.0 N POTASSIUM CHLORIDE 1NONE 1-NITRO-2- OCTANONE 1OCTOL 1-OCTAI4OL IPECHX 1-PROPENYLCYCLOHEXANE 1PNAP 1-PHENYLNAPHTHALENE...BROMO-1-CHLOROPROPANEI2B100L 2-BUTYL-1- OCTANOL 2B4MFU 2- (T-BUTYL) -4-METHYLFURAN 2CBMN 2-CHLOROBENZYLIDINEM-LONONITRILEI 2CECHO 2- (2-CYANOETHYL

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

    International Nuclear Information System (INIS)

    Bonnet, Jacques.

    1977-01-01

    This study deals with ionization of alkane-electron scavenger reactant mixtures, irradiated by 60 Co γ-rays. It is shown that the extrapolated free-ion yields (extrapolated yield method) decrease with the reactant concentration. On the basis of ONSAGER model and theoretical treatment of MOZUMDER, the cross sections of epithermal electron attachment in hexane, cyclohexane, 2,2-dimethylbutane, cyclopentane, 2,2,4-trimethylpentane for CCl 4 , C 7 F 14 , C 6 H 5 Br, C 6 H 5 Cl, C 6 F 14 , (C 6 H 5 ) 2 are determined. A comparison between gas-phase and liquid-phase cross sections is established [fr

  7. 13-Hydroxy-4,16-dimethyl-4,16-diazapentacyclo[12.3.1.01,5.05,13.07,12]octadeca-7(12,8,10-triene-6,18-dione

    Directory of Open Access Journals (Sweden)

    K. Gurunathan

    2009-05-01

    Full Text Available In the title compound, C18H20N2O3, the N-methylpiperidone ring adopts a chair conformation. The pyrrolidine ring and the five-membered cyclopentane rings adopt envelope conformations. The five-membered ring of the ninhydrin system adopts an envelope conformation with the central C atom deviating by 0.217 (1Å from the mean plane through the other atoms. The molecular packing is characterized by intermolecular C—H...O and intramolecular C—H...O and O—H...N interactions.

  8. Rhodomollanol A, a Highly Oxygenated Diterpenoid with a 5/7/5/5 Tetracyclic Carbon Skeleton from the Leaves of Rhododendron molle.

    Science.gov (United States)

    Zhou, Junfei; Zhan, Guanqun; Zhang, Hanqi; Zhang, Qihua; Li, Ying; Xue, Yongbo; Yao, Guangmin

    2017-07-21

    A novel diterpenoid with an unprecedented carbon skeleton, rhodomollanol A (1), and a new grayanane diterpenoid, rhodomollein XXXI (2), were isolated from the leaves of Rhododendron molle. Their structures were elucidated using comprehensive spectroscopic methods and single-crystal X-ray diffraction. Compound 1 possesses a unique cis/trans/trans/cis/cis-fused 3/5/7/5/5/5 hexacyclic ring system featuring a rare 7-oxabicyclo[4.2.1]nonane core decorated with three cyclopentane units. The plausible biosynthetic pathway for 1 was proposed. Compound 1 exhibited moderate PTP1B inhibitory activity.

  9. Adsorption of volatile hydrocarbons in iron polysulfide chalcogels

    KAUST Repository

    Ahmed, Ejaz

    2014-11-01

    We report the synthesis, characterization and possible applications of three new metal-chalcogenide aerogels KFe3Co3S 21, KFe3Y3S22 and KFe 3Eu3S22. Metal acetates react with the alkali metal polychalcogenides in formamide/water mixture to form extended polymeric frameworks that exhibit gelation phenomena. Amorphous aerogels obtained after supercritical CO2 drying have BET surface area from 461 to 573 m 2/g. Electron microscopy images and nitrogen adsorption measurements showed that pore sizes are found in micro (below 2 nm), meso (2-50 nm), and macro (above 50 nm) porous regions. These chalcogels possess optical bandgaps in the range of 1.55-2.70 eV. These aerogels have been studied for the adsorption of volatile hydrocarbons and gases. A much higher adsorption of toluene in comparison with cyclohexane and cyclopentane vapors have been observed. The adsorption capacities of the three volatile hydrocarbons are found in the following order: toluene > cyclohexane > cyclopentane. It has been observed that high selectivity in adsorption is feasible with high-surface-area metal chalcogenides. Similarly, almost an eight to ten times increase in adsorption selectivity towards CO2 over H2/CH4 was observed in the aerogels. Moreover, reversible ion-exchange properties for K+/Cs+ ions have also been demonstrated. © 2014 Elsevier Inc. All rights reserved.

  10. NMR studies of organic liquids confined in mesoporous materials: (1) Pore size distribution and (2) Phase behaviour and dynamic studies in restricted geometry

    International Nuclear Information System (INIS)

    Foerland, Kjersti

    2005-01-01

    In the thesis NMR spectroscopy is used for studying liquids confined in various porous materials. In the first part, pore size distributions of mesoporous silicas and controlled pore glasses were determined by measuring the 1H NMR signal from the non-frozen fraction of the confined liquid as a function of temperature, using benzene, acetonitrile and HMDS as probe molecules. In the second part, the molecular dynamics of acetonitrile, hexamethyldisilane, cyclohexane and cyclopentane confined in mesoporous materials were studied as a function of temperature. 6 papers are included with titles: 1) Pore-size determination of mesoporous materials by 1H NMR spectroscopy. 2) Pore-size distribution in mesoporous materials as studied by 1H NMR. 3) Dynamic 1H and 2H NMR investigations of acetonitrile confined in porous silica. 4) NMR investigations of hexamethyldisilane confined in controlled pore glasses: Pore size distribution and molecular dynamics studies. 5) 1H and 2H NMR studies of cyclohexane nano crystals in controlled pore glasses. 6) 1H NMR relaxation and diffusion studies of cyclohexane and cyclopentane confined in MCM-41

  11. Lipid Composition of methane-derived Carbonate Crusts and Sediments from Mud Volcanoes in the Sorokin Trough, NE Black Sea

    Science.gov (United States)

    Stadnitskaia, A.; Baas, M.; Hopmans, E.; van Weering, T.; Sinninghe Damsté, J.

    2003-04-01

    We investigated the distributions and d13C values of bacterial and archaeal lipids in four carbonate crusts and hosting sediments collected from three mud volcanoes in the Sorokin Trough during the 11th Training Through Research expedition in 2001. The lipid extract from carbonate crusts contains abundant archaeal and bacterial biomarkers such as pentamethylicosane (PMI), unsaturated PMIs, archaeol, hydroxyarchaeols (sn-2 and sn-3 isomers), diphytanyl glycerol diethers (DGDs). Hosting sediments also contain a diversity of bacterial and archaeal lipids, but their concentrations are significantly lower then those observed in the crusts. The stable isotopic signature of these compounds have established their biosynthesis by consortia of microorganisms performing anaerobic methanotrophy. Quantitatively, the most predominant group of archaeal core membrane lipids in the crusts and in the sediments is the glycerol dialkyl glycerol tetraethers (GDGTs). Besides, two carbonate crusts contained two archaeal core membrane macrocyclic diether lipids which have not been reported previously. These macrocyclic diethers are structurally related to GDGTs with one and two cyclopentane rings. Cyclopentane-bearing GDGTs are well known for different archaeal species thriving in different environments, while a macrocyclic diether was found only in the thermophilic methanogen Methanococcus jannaschi. Therefore, the molecular structure of novel macrocyclic DGDs unites ecologically contrasting archaeal groups. Strongly depleted carbon isotopic values of these diethers indicate that these diethers derived from archaea acting within anaerobic methane-oxidizing consortia in cold-water environments.

  12. Synthesis of high density aviation fuel with cyclopentanol derived from lignocellulose

    Science.gov (United States)

    Sheng, Xueru; Li, Ning; Li, Guangyi; Wang, Wentao; Yang, Jinfan; Cong, Yu; Wang, Aiqin; Wang, Xiaodong; Zhang, Tao

    2015-03-01

    For the first time, renewable high density aviation fuels were synthesized at high overall yield (95.6%) by the Guerbet reaction of cyclopentanol which can be derived from lignocellulose, followed by the hydrodeoxygenation (HDO). The solvent-free Guerbet reaction of cyclopentanol was carried out under the co-catalysis of solid bases and Raney metals. Among the investigated catalyst systems, the combinations of magnesium-aluminium hydrotalcite (MgAl-HT) and Raney Ni (or Raney Co) exhibited the best performances. Over them, high carbon yield (96.7%) of C10 and C15 oxygenates was achieved. The Guerbet reaction products were further hydrodeoxygenated to bi(cyclopentane) and tri(cyclopentane) over a series of Ni catalysts. These alkanes have high densities (0.86 g mL-1 and 0.91 g mL-1) and can be used as high density aviation fuels or additives to bio-jet fuel. Among the investigated HDO catalysts, the 35 wt.% Ni-SiO2-DP prepared by deposition-precipitation method exhibited the highest activity.

  13. NMR studies of organic liquids confined in mesoporous materials: (1) Pore size distribution and (2) Phase behaviour and dynamic studies in restricted geometry

    Energy Technology Data Exchange (ETDEWEB)

    Foerland, Kjersti

    2005-07-01

    In the thesis NMR spectroscopy is used for studying liquids confined in various porous materials. In the first part, pore size distributions of mesoporous silicas and controlled pore glasses were determined by measuring the 1H NMR signal from the non-frozen fraction of the confined liquid as a function of temperature, using benzene, acetonitrile and HMDS as probe molecules. In the second part, the molecular dynamics of acetonitrile, hexamethyldisilane, cyclohexane and cyclopentane confined in mesoporous materials were studied as a function of temperature. 6 papers are included with titles: 1) Pore-size determination of mesoporous materials by 1H NMR spectroscopy. 2) Pore-size distribution in mesoporous materials as studied by 1H NMR. 3) Dynamic 1H and 2H NMR investigations of acetonitrile confined in porous silica. 4) NMR investigations of hexamethyldisilane confined in controlled pore glasses: Pore size distribution and molecular dynamics studies. 5) 1H and 2H NMR studies of cyclohexane nano crystals in controlled pore glasses. 6) 1H NMR relaxation and diffusion studies of cyclohexane and cyclopentane confined in MCM-41.

  14. Evaluating Production of Cyclopentyl Tetraethers by Marine Group II Euryarchaeota in the Pearl River Estuary and Coastal South China Sea: Potential Impact on the TEX86 Paleothermometer

    Directory of Open Access Journals (Sweden)

    Jin-Xiang Wang

    2017-10-01

    Full Text Available TEX86 [TetraEther indeX of glycerol dialkyl glycerol tetraethers (GDGTs with 86 carbon atoms] has been widely applied to reconstruct (paleo- sea surface temperature. Marine Group I (MG-I Thaumarchaeota were thought to be the primary source of GDGTs constituting the TEX86 formula; however, recent research has suggested that Marine Group II (MG-II Euryarchaeota may also contribute significantly to the GDGT pool in the ocean. Little is known regarding the potential impact of MG-II Euryarchaeota-derived GDGTs on TEX86 values recorded in marine sediments. In this study, we assessed the relationship between distributions of GDGTs and MG-II Euryarchaeota and evaluated its potential effect on the TEX86 proxy. Lipid and DNA analyses were performed on suspended particulate matter and surface sediments collected along a salinity gradient from the lower Pearl River (river water and its estuary (mixing water to the coastal South China Sea (SCS, seawater. TEX86-derived temperatures from the water column and surface sediments were significantly correlated and both were lower than satellite-based temperatures. The ring index (RI values in these environments were higher than predicted from the calculated TEX86-RI correlation, indicating that the GDGT pool in the water column of the PR estuary and coastal SCS comprises relatively more cyclopentane rings, which thereby altered TEX86 values. Furthermore, the abundance of MG-II Euryarchaeota 16S rRNA gene in the mixing water was two to three orders of magnitude higher than those observed in the river or seawater. Significant linear correlations were observed between the gene abundance ratio of MG-II Euryarchaeota to total archaea and the fractional abundance of GDGTs with cyclopentane rings. Collectively, these results suggest that MG-II Euryarchaeota likely produce a large proportion of GDGTs with 1–4 cyclopentane moieties, which may bias TEX86 values in the water column and sediments. As such, valid

  15. Poisoning Experiments Aimed at Discriminating Active and Less-Active Sites of Silica-Supported Tantalum Hydride for Alkane Metathesis

    KAUST Repository

    Saggio, Guillaume

    2010-10-04

    Only 50% of the silica-supported tantalum hydride sites are active in the metathesis of propane. Indeed, more than 45% of the tantalum hydride can be eliminated by a selective oxygen poisoning of inactive sites with no significant decrease in the global turnover. Conversely, cyclopentane induces no such selective poisoning. Hence, the active tantalum hydride sites that show greater resistance to oxygen poisoning correspond to the νTa-H bands of higher wavenumbers, particularly that at 1860cm-1. These active tantalum hydride sites should correspond to tris- or monohydride species relatively far from silica surface oxygen atoms. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Thermodynamic and Process Modelling of Gas Hydrate Systems in CO2 Capture Processes

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen

    A novel gas separation technique based on gas hydrate formation (solid precipitation) is investigated by means of thermodynamic modeling and experimental investigations. This process has previously been proposed for application in post-combustion carbon dioxide capture from power station flue gases...... formation may be performed at pressures of approximately 20 MPa and temperatures below 280 K. Thermodynamic promoters are needed, to reduce the pressure requirement of the process, thereby making it competitive to existing capture technologies. A literature study is presented focusing mainly...... on thermodynamic gas hydrate promotion by hydrate formers stabilising the classical gas clathrate hydrate structures (sI, sII and sH) at low to moderate pressures. Much literature is available on this subject. Both experimental and theoretical studies presented in the literature have pointed out cyclopentane...

  17. Crystal structure of a bioactive sesquiterpene isolated from Artemisia reticulata

    Directory of Open Access Journals (Sweden)

    A. K. Bauri

    2016-04-01

    Full Text Available The title compound, C15H24O2 {systematic name: 1-[6-hydroxy-7-(propan-2-yl-4-methylidene-2,3,3a,4,5,6,7,7a-octahydro-1H-inden-1-yl]ethanone} was isolated from A. reticulata by column chromatography over silica gel by gradient solvent elution. The molecule comprises a bicyclo[4.3.0]nonane ring bearing acetoxy, hydroxy and isopropyl substituents, and an exocyclic double bond on the cyclohexane ring. In the bicyclic skeleton, the cyclohexane ring adopts a chair conformation ring and the cyclopentane ring is in an envelope conformation. In the crystal, molecules are linked by O—H...O hydrogen bonds, forming chains along [010]. These chains are cross-linked by C—H...O hydrogen bonds.

  18. Unimolecular H2 elimination during the liquid phase radiolysis and photolysis of alkane - alkane mixtures

    International Nuclear Information System (INIS)

    Wojnarovits, L.; Foeldiak, G.

    1980-01-01

    Unimolecular H 2 elimination from alkanes was investigated in cyclopentane-cyclohexane, n-hexane-cyclohexane and cyclohexane-cyclooctane mixtures during fluradiolysis and 7.6 eV photolysis. During the radiolysis of all systems, and when the fluorescence shift law allowed it, during the photolysis as well, inhibited H 2 detachment was observed from the first component and sensitized hydrogen molecule elimination from the second. It has been concluded that the same excited state (the lowest singlet, S 1 ) is responsible for the H 2 elimination during radiolysis and photolysis and this is that one that gives rise to fluorescence in the experiments of other authors. The H 2 and H elimination from alkanes generally have different excited precursors. The direct population of S 1 by γ-irradiation is of limited importance and this intermediate is mainly produced in ''charge neutralization'' processes. (author)

  19. Structural and physicochemical properties of polar lipids from thermophilic archaea.

    Science.gov (United States)

    Ulrih, Natasa Poklar; Gmajner, Dejan; Raspor, Peter

    2009-08-01

    The essential general features required for lipid membranes of extremophilic archaea to fulfill biological functions are that they are in the liquid crystalline phase and have extremely low permeability of solutes that is much less temperature sensitive due to a lack of lipid-phase transition and highly branched isoprenoid chains. Many accumulated data indicate that the organism's response to extremely low pH is the opposite of that to high temperature. The high temperature adaptation does not require the tetraether lipids, while the adaptation of thermophiles to acidic environment requires the tetraether polar lipids. The presence of cyclopentane rings and the role of polar heads are not so straightforward regarding the correlations between fluidity and permeability of the lipid membrane. Due to the unique lipid structures and properties of archaeal lipids, they are a valuable resource in the development of novel biotechnological processes. This microreview focuses primarily on structural and physicochemical properties of polar lipids of (hyper)thermophilic archaea.

  20. Tribological Performance of Some Pennzane(Registered Trademark) Based Greases for Vacuum Applications

    Science.gov (United States)

    Marchetti, Mario; Jones, William R., Jr.; Street, Kenneth W.; Wheeler, Donald; Dixon, Duane; Jansen, Mark J.; Kimura, Hiroshi

    2002-01-01

    Commercial greases for space applications usually fulfill the requirements imposed by the severe conditions of use. The main requirement is their ability to create an EHL film, boundary film, or both under speed, load and temperature conditions that the mechanisms will operate. Three greases, all based on a multiply alkylated cyclopentane (Pennzan(R)) base oil, were studied. The thickeners were an n-octadecylterephthalamate soap, a lithium soap, and a urea derivative. A Four-Ball Tribometer and a Spiral Orbit Tribometer were employed to evaluate the greases under ultrahigh vacuum. Results indicated that all three greases yielded very low wear rates and extended lifetimes. In addition, routine physical property data is reported for each grease.

  1. (3R,5S,7R,8R,9S,10S,12S,13R,14S-10,13-Dimethyl-17-[5-oxo-5-(prop-2-yn-1-yloxypentan-2-yl]hexadecahydro-1H-cyclopenta[a]phenanthrene-3,7,12-triyl triacetate

    Directory of Open Access Journals (Sweden)

    T. Kavitha

    2017-03-01

    Full Text Available In the title compound, C33H48O8, four terminal H atoms of cholic acid are replaced by three acetyl and one terminal alkyne group. All the acetyl residues are twisted with respect to the rings (A, B and C to which they are attached. The cyclopentane ring D adopts an envelope conformation with the methyl-substituted C atom as the flap. Rings A, B and C have chair conformations. The dihedral angle between the mean planes of rings C and D is 4.70 (11°. In the crystal, molecules are linked by C—H...O hydrogen bonds, forming a three-dimensional structure.

  2. Uncertainty assessment of equations of state with application to an organic Rankine cycle

    DEFF Research Database (Denmark)

    Frutiger, Jerome; Bell, Ian; O’Connell, John P.

    2017-01-01

    Evaluations of equations of state (EoS) should include uncertainty. This study presents a genericmethod to analyse EoS from a detailed uncertainty analysis of the mathematical form and the dataused to obtain EoS parameter values. The method is illustrated by comparison of Soave–Redlich–Kwong (SRK......) cubic EoS with perturbed-chain statistical associating fluid theory (PC-SAFT) EoS for anorganic Rankine cycle (ORC) for heat recovery to power fromthe exhaust gas of a marine diesel engineusing cyclopentane as working fluid. Uncertainties of the EoS input parameters including......Evaluations of equations of state (EoS) should include uncertainty. This study presents a genericmethod to analyse EoS from a detailed uncertainty analysis of the mathematical form and the dataused to obtain EoS parameter values. The method is illustrated by comparison of Soave–Redlich–Kwong (SRK...

  3. KFeSbTe3: A quaternary chalcogenide aerogel for preferential adsorption of polarizable hydrocarbons and gases

    KAUST Repository

    Ahmed, Ejaz

    2015-01-01

    The first telluride-based quaternary aerogel KFeSbTe3 is synthesized by a sol-gel metathesis reaction between Fe(OAc)2 and K3SbTe3 in dimethyl formamide. The aerogel has an exceptionally large surface area 652 m2 g-1 which is amongst the highest reported for chalcogenide-based aerogels. This predominantly mesoporous material shows preferential adsorption for toluene vapors over cyclohexane or cyclopentane and CO2 over CH4 or H2. The remarkably high adsorption capacity for toluene (9.31 mmol g-1) and high selectivity for gases (CO2/H2: 121 and CO2/CH4: 75) suggest a potential use of such materials in adsorption-based separation processes for the effective purification of hydrocarbons and gases. © The Royal Society of Chemistry 2015.

  4. Structural optimization and structure-functional selectivity relationship studies of G protein-biased EP2 receptor agonists.

    Science.gov (United States)

    Ogawa, Seiji; Watanabe, Toshihide; Moriyuki, Kazumi; Goto, Yoshikazu; Yamane, Shinsaku; Watanabe, Akio; Tsuboi, Kazuma; Kinoshita, Atsushi; Okada, Takuya; Takeda, Hiroyuki; Tani, Kousuke; Maruyama, Toru

    2016-05-15

    The modification of the novel G protein-biased EP2 agonist 1 has been investigated to improve its G protein activity and develop a better understanding of its structure-functional selectivity relationship (SFSR). The optimization of the substituents on the phenyl ring of 1, followed by the inversion of the hydroxyl group on the cyclopentane moiety led to compound 9, which showed a 100-fold increase in its G protein activity compared with 1 without any increase in β-arrestin recruitment. Furthermore, SFSR studies revealed that the combination of meta and para substituents on the phenyl moiety was crucial to the functional selectivity. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Uncertainty Assessment of Equations of State with Application to an Organic Rankine Cycle

    DEFF Research Database (Denmark)

    Frutiger, Jerome; Bell, Ian; O’Connell, John P.

    2017-01-01

    Evaluations of equations of state (EoS) with application to process systems should include uncertainty analysis. A generic method is presented for determining such uncertainties from both the mathematical formand the data for obtaining EoS parameter values. The method is implemented for the Soave......–Redlich–Kwong (SRK), the Peng-Robinson (PR) cubic EoS, and the perturbed-chain statistical associating fluid theory (PCSAFT) EoS, as applied to an organic Rankine cycle (ORC) power system to recover heat from the exhaust gas of a marine diesel engine with cyclopentane as the working fluid. Uncertainties of the Eo......S input parameters, including their corresponding correlation structure, are quantified from the data using a bootstrap method. A Monte Carlo procedure propagates parameter input uncertainties onto the process output. Regressions have been made of the three cubic EoS parameters from both critical point...

  6. Effects of gasoline components on MTBE and TBA cometabolism by Mycobacterium austroafricanum JOB5.

    Science.gov (United States)

    House, Alan J; Hyman, Michael R

    2010-07-01

    In this study we have examined the effects of individual gasoline hydrocarbons (C(5-10,12,14) n-alkanes, C(5-8) isoalkanes, alicyclics [cyclopentane and methylcyclopentane] and BTEX compounds [benzene, toluene, ethylbenzene, m-, o-, and p-xylene]) on cometabolism of methyl tertiary butyl ether (MTBE) and tertiary butyl alcohol (TBA) by Mycobacterium austroafricanum JOB5. All of the alkanes tested supported growth and both MTBE and TBA oxidation. Growth on C(5-8) n-alkanes and isoalkanes was inhibited by acetylene whereas growth on longer chain n-alkanes was largely unaffected by this gas. However, oxidation of both MTBE and TBA by resting cells was consistently inhibited by acetylene, irrespective of the alkane used as growth-supporting substrate. A model involving two separate but co-expressed alkane-oxidizing enzyme systems is proposed to account for these observations. Cyclopentane, methylcyclopentane, benzene and ethylbenzene did not support growth but these compounds all inhibited MTBE and TBA oxidation by alkane-grown cells. In the case of benzene, the inhibition was shown to be due to competitive interactions with both MTBE and TBA. Several aromatic compounds (p-xylene > toluene > m-xylene) did support growth and cells previously grown on these substrates also oxidized MTBE and TBA. Low concentrations of toluene (TBA oxidation by alkane-grown cells whereas higher concentrations were inhibitory. The effects of acetylene suggest strain JOB5 also has two distinct toluene-oxidizing activities. These results have been discussed in terms of their impact on our understanding of MTBE and TBA cometabolism and the enzymes involved in these processes in mycobacteria and other bacteria.

  7. Chemical characterization of exhaled breath to differentiate between patients with malignant plueral mesothelioma from subjects with similar professional asbestos exposure

    Energy Technology Data Exchange (ETDEWEB)

    Gennaro, G. de; Longobardi, F.; Stallone, G.; Trizio, L.; Tutino, M. [University of Bari Aldo Moro, Department of Chemistry, Bari (Italy); Dragonieri, S. [University of Bari Aldo Moro, Department of Pulmonology, Bari (Italy); Musti, M. [University of Bari Aldo Moro, Department of Occupational Medicine, Bari (Italy)

    2010-12-15

    Malignant pleural mesothelioma (MPM) is an aggressive tumour whose main aetiology is the long-term exposure to asbestos fibres. The diagnostic procedure of MPM is difficult and often requires invasive approaches; therefore, it is clinically important to find accurate markers for MPM by new noninvasive methods that may facilitate the diagnostic process and identify patients at an earlier stage. In the present study, the exhaled breath of 13 patients with histology-established diagnosis of MPM, 13 subjects with long-term certified professional exposure to asbestos (EXP) and 13 healthy subjects without exposure to asbestos (healthy controls, HC) were analysed. An analytical procedure to determine volatile organic compounds by sampling of air on a bed of solid sorbent and thermal desorption GC-MS analysis was developed in order to identify the compounds capable of discriminating among the three groups. The application of univariate (ANOVA) and multivariate statistical treatments (PCA, DFA and CP-ANN) showed that cyclopentane and cyclohexane were the dominant variables able to discriminate among the three groups. In particular, it was found that cyclohexane is the only compound able to differentiate the MPM group from the other two; therefore, it can be a possible marker of MPM. Cyclopentane is the dominant compound in the discrimination between EXP and the other groups (MPM and HC); then, it can be considered a good indicator for long-term asbestos exposure. This result suggests the need to perform frequent and thorough investigations on people exposed to asbestos in order to constantly monitor their state of health or possibly to study the evolution of disease over time. (orig.)

  8. NO{sub x} reduction by coke deposited on Pt/Al{sub 2}O{sub 3} in an oxidizing medium; Elimination des NO{sub x} par le coke depose sur Pt/Al{sub 2}O{sub 3} en milieu oxydant

    Energy Technology Data Exchange (ETDEWEB)

    Lunati, S

    1997-12-12

    NO{sub x} reduction by coke deposited on Pt/Al{sub 2}O{sub 3} was studied in excess oxygen. Continuous analysis of the effluent was performed with a mass spectrometer. The coking reaction was carried out under reducing conditions with two different coking agents: cyclopentane and heptanal. In general, NO{sub x} reduction by coke deposited on Pt/Al{sub 2}O{sub 3} occurs in a wide temperature range (200 deg Ccyclopentane which does not contain these functional groups. Based on our results, we proposed a `dual-site` reaction for NO{sub x} reduction on coked Pt/Al{sub 2}O{sub 3} catalyst. Platinum allows O{sub 2} activation by dissociative adsorption, and NO{sub 2} formation by oxidation of NO. NO{sub x} reduction occurs on carbon deposits. Reaction between NO{sub x} and coke leads to the formation of N-containing species which are decomposed in CI{sub 2}, H{sub 2}O, N{sub 2} and N{sub 2}O by reaction with activated O{sub 2}. (author) 205 refs.

  9. Cyclopentanone: A raw material for production of C15 and C17 fuel precursors

    International Nuclear Information System (INIS)

    Hronec, Milan; Fulajtárova, Katarína; Liptaj, Tibor; Štolcová, Magdaléna; Prónayová, Naďa; Soták, Tomáš

    2014-01-01

    The synthesis of diesel or jet fuels intermediates from furfural or 5-hydroxymethylfurfural (HMF) via aqueous aldol-condensation with cyclopentanone was studied. Cyclopentanone is the product of furfural rearrangement in an aqueous system. Since the aldol-condensation reaction is conducted in an aqueous solution all these biomass-derived reactants can be applied as water solutions formed in the processes of their preparation. The aldol condensation of furfural with cyclopentanone is at low concentration of base and molar ratio of reactants 2:1 highly selective and after 40–80 min of reaction at a temperature of 40–100 °C more than 95 mol% yield of 2,5-bis (2-furylmethylidene) cyclopentan-1-one (F 2 C) was obtained. When instead of furfural as a reactant HMF was used higher than 98 mol% yield of 2,5-bis (5-hydroxymethyl-2-furylmethylidene) cyclopentan-1-one was achieved. The final products of aldol condensation of furfural and HMF are exclusively corresponding dimers, what enables to obtain after subsequent hydrogenation/hydrodeoxygenation step dialkylcyclopentane type of diesel or jet fuels having C 15 or C 17 molecules. - Highlights: • The aldol condensation of biomass derived cyclopentanone with furfural and HMF. • More than 95 mol % yields of products are achieved. • The products are compounds having exclusively 15 or 17 carbon atoms in molecule. • Reactants can be used as diluted aqueous solutions. • The products are separated as solids insoluble in water

  10. Efficiency analysis of alternative refrigerants for ejector cooling cycles

    International Nuclear Information System (INIS)

    Gil, Bartosz; Kasperski, Jacek

    2015-01-01

    Highlights: • Advantages of using alternative refrigerants as ejector refrigerants were presumed. • Computer software basing on theoretical model of Huang et al. (1999) was prepared. • Optimal temperature range of primary vapor for each working fluid was calculated. - Abstract: Computer software, basing on the theoretical model of Huang et al. with thermodynamic properties of selected refrigerants, was prepared. Investigation was focused on alternative refrigerants that belong to two groups of substances: common solvents (acetone, benzene, cyclopentane, cyclohexane and toluene) and non-flammable synthetic refrigerants applied in Organic Rankine Cycle (ORC) (R236ea, R236fa, R245ca, R245fa, R365mfc and RC318). Refrigerants were selected to detect a possibility to use them in ejector cooling system powered by a high-temperature heat source. A series of calculations were carried out for the generator temperature between 70 and 200 °C, with assumed temperatures of evaporation 10 °C and condensation 40 °C. Investigation revealed that there is no single refrigerant that ensures efficient operation of the system in the investigated temperature range of primary vapor. Each substance has its own maximum entrainment ratio and COP at its individual temperature of the optimum. The use of non-flammable synthetic refrigerants allows obtaining higher COP in the low primary vapor temperature range. R236fa was the most beneficial among the non-flammable synthetic refrigerants tested. The use of organic solvents can be justified only for high values of motive steam temperature. Among the solvents, the highest values of entrainment ratio and COP throughout the range of motive temperature were noted for cyclopentane. Toluene was found to be an unattractive refrigerant from the ejector cooling point of view

  11. Contribution to the study of catalytic hydrogen-deuterium exchange between hydrogen and hydrocarbons; Contribution a l'etude de l'echange catalytique hydrogene-deuterium entre l'hydrogene et les hydrocarbures

    Energy Technology Data Exchange (ETDEWEB)

    Ravoire, J

    1958-12-20

    The hydrogen-deuterium exchange between molecular hydrogen and hydrocarbons over a platinum and charcoal catalyst was studied in a static system. The change in isotopic composition of molecular hydrogen was followed by a thermal conductivity method. Cyclo-pentane and cyclohexane were chosen because of their stability. A reversible inactivation of the catalyst was observed with both hydrocarbons. The reasons for this inactivation are unknown but it was shown that reactivation led to satisfactory reproducibility. A kinetic study was done with cyclohexane in the range 30 to 160 deg. C, and 40 to 360 mm for the pressure of hydrogen, and 10 to 70 mm for the pressure of cyclohexane. The order of the reaction with respect to cyclohexane pressure is always close to zero; the order with respect to that of hydrogen is 0.5 above 100 deg. C. It decreases with increasing temperature and becomes negative (-0.5 at 30 deg. C), characterizing an inhibition by hydrogen. At the same time, the apparent activation energy goes from 6 to 13 kcal/mole. (author) [French] L'echange hydrogene-deuterium entre l'hydrogene moleculaire et les hydrocarbures sur un catalyseur au platine depose sur charbon a ete etudie a l'aide d'un appareil statique. La teneur en deuterium de L'hydrogene moleculaire a ete suivie par conductibilite thermique. Le cyclopentane et le cyclohexane ont ete choisis en raison de leur stabilite. Une desactivation reversible du catalyseur pendant son utilisation a ete observee pour les deux hydrocarbures. Les causes de la desactivation n'ont pas ete determinees, mais il a ete montre qu'une reactivation conduisait une reproductibilite satisfaisante. Une etude cinetique a ete conduite avec le cyclohexane dans le domaine: 30 deg C - 160 deg C, 40 mm - 360 mm comme pression d'hydrogene, 10 mm - 70 mm comme pression de cyclohexane. L'ordre par rapport a la pression de cyclohexane est toujours voisin de zero; l'ordre par rapport a la pression d'hydrogene est de 0,5 au-dessus de

  12. A novel cascade organic Rankine cycle (ORC) system for waste heat recovery of truck diesel engines

    International Nuclear Information System (INIS)

    Chen, Tao; Zhuge, Weilin; Zhang, Yangjun; Zhang, Lei

    2017-01-01

    Highlights: • A confluent cascade expansion ORC (CCE-ORC) system is proposed. • Cyclopentane is considered as the most suitable fluid for this system. • The CCE-ORC system performance under full operating conditions is analyzed. • The BSFC of diesel engine can be reduced by 9.2% with the CCE-ORC system. • Performance comparison of CCE-ORC and dual-loop ORC is conducted. - Abstract: Waste heat recovery (WHR) of engines has attracted increasingly more concerns recently, as it can improve engine thermal efficiency and help truck manufacturers meet the restrictions of CO_2 emission. The organic Rankine cycle (ORC) has been considered as the most potential technology of WHR. To take full advantage of waste heat energy, the waste heat in both exhaust gases and the coolant need to be recovered; however, conventional multi-source ORC systems are too complex for vehicle applications. This paper proposed a confluent cascade expansion ORC (CCE-ORC) system for engine waste heat recovery, which has simpler architecture, a smaller volume and higher efficiency compared with conventional dual-loop ORC systems. Cyclopentane is analyzed to be regarded as the most suitable working fluid for this novel system. A thermodynamic simulation method is established for this system, and off-design performance of main components and the working fluid side pressure drop in the condenser have been taken into consideration. System performance simulations under full engine operating conditions are conducted for the application of this system on a heavy-duty truck diesel engine. Results show that the engine peak thermal efficiency can be improved from 45.3% to 49.5% where the brake specific fuel consumption (BSFC) decreases from 185.6 g/(kW h) to 169.9 g/(kW h). The average BSFC in the frequently operating region can decrease by 9.2% from 187.9 g/(kW h) to 172.2 g/(kW h). Compared with the conventional dual-loop ORC system, the CCE-ORC system can generate 8% more net power, while the

  13. Dynamic viscosities of binary mixtures of cycloalkanes with primary alcohols at T = (293.15, 298.15, and 303.15) K: New UNIFAC-VISCO interaction parameters

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez, Begona [Chemical Engineering Department, Vigo University, 36200 Vigo (Spain); Calvar, Noelia [Chemical Engineering Department, Vigo University, 36200 Vigo (Spain); Dominguez, Angeles [Chemical Engineering Department, Vigo University, 36200 Vigo (Spain)]. E-mail: admguez@uvigo.es; Tojo, Jose [Chemical Engineering Department, Vigo University, 36200 Vigo (Spain)

    2007-02-15

    In this work, dynamic viscosities, densities, and speed of sound have been measured over the whole composition range and 0.1 MPa for the binary mixtures (cyclopentane and cyclohexane with ethanol, 1-propanol, and 1-butanol) at several temperatures (293.15, 298.15, 303.15) K along with the properties of the pure components. Excess molar volumes, molar isentropic compression, excess molar isentropic compression, and excess free energy of activation for the binary systems at the above mentioned temperatures, were calculated and fitted to the Redlich-Kister equation to determine the fitting parameters and the root-mean-square deviations. The UNIQUAC equation was used to correlate the experimental viscosity data. The UNIFAC-VISCO method and ASOG-VISCO method, based on contribution groups, were used to predict the dynamic viscosities of the binary mixtures. The interaction parameters of cycloalkanes with primary alcohol (CH{sub cy}/-OH) have been determined for their application in the predictive UNIFAC-VISCO method.

  14. Picot-Benoit Effect in Polymer Solutions

    Science.gov (United States)

    Beaucage, Gregory; Sukumaran, Sathish; Ilavsky, Jan

    2003-03-01

    SAXS from polymers in solution is well described at intermediate (q = 0.01-0.1 Å-1) scattering vectors by scaling theory which predicts three regimes in concentration: dilute, semi-dilute and concentrated [1-3]. A persistent problem is the appearance of excess scattering at low-q, q molecular weight dependence for these fluctuations in the dilute and semi-dilute regimes. The later is unexpected since above c* scaling theory predicts no M dependencies due to screening [1-3]. The literature associates PB features with semi-dilute and concentrated solutions, yet we have observed excess scattering even in dilute solutions of polystyrene in cyclopentane. 1) de Gennes P-G, Scaling Concepts in Polymer Physics, 1979. 2) Strobl G, The Physics of Polymers, Berlin 1997. 3) Doi M, Introduction to Polymer Physics, Oxford 1997. 4) Benoit H, Picot C Pure Appl. Chem. 12 545 (1966). 5) Benoit H, Picot C Pure Appl. Chem. 12 1271 (1966). 6) Xie Y, et al. Physica A 232 94 (1996). 7) Korberstein JT, et al. Polymer 26 673 (1985). 8) Morfin I, et al. Macromolecules 32 7208 (1999). 9) Blanco CM, et al. Langmuir 16 8585 (2000).

  15. Substitution of carcinogenic solvent dichloromethane for the extraction of volatile compounds in a fat-free model food system.

    Science.gov (United States)

    Cayot, Nathalie; Lafarge, Céline; Bou-Maroun, Elias; Cayot, Philippe

    2016-07-22

    Dichloromethane is known as a very efficient solvent, but, as other halogenated solvents, is recognized as a hazardous product (CMR substance). The objective of the present work is to propose substitution solvent for the extraction of volatile compounds. The most important physico-chemical parameters in the choice of an appropriate extraction solvent of volatile compounds are reviewed. Various solvents are selected on this basis and on their hazard characteristics. The selected solvents, safer than dichloromethane, are compared using the extraction efficiency of volatile compounds from a model food product able to interact with volatile compounds. Volatile compounds with different hydrophobicity are used. High extraction yields were positively correlated with high boiling points and high Log Kow values of volatile compounds. Mixtures of solvents such as azeotrope propan-2-one/cyclopentane, azeotrope ethyl acetate/ethanol, and mixture ethyl acetate/ethanol (3:1, v/v) gave higher extraction yields than those obtained with dichloromethane. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Synthesis and photophysical properties of a series of cyclopenta[b]naphthalene solvatochromic fluorophores.

    Science.gov (United States)

    Benedetti, Erica; Kocsis, Laura S; Brummond, Kay M

    2012-08-01

    The synthesis and photophysical properties of a series of naphthalene-containing solvatochromic fluorophores are described within. These novel fluorophores are prepared using a microwave-assisted dehydrogenative Diels-Alder reaction of styrene, followed by a palladium-catalyzed cross coupling reaction to install an electron donating amine group. The new fluorophores are structurally related to Prodan. Photophysical properties of the new fluorophores were studied and intriguing solvatochromic behavior was observed. For most of these fluorophores, high quantum yields (60-99%) were observed in methylene chloride in addition to large Stokes shifts (95-226 nm) in this same solvent. As the solvent polarity increased, so did the observed Stokes shift with one derivative displaying a Stokes shift of ~300 nm in ethanol. All fluorophore emission maxima, and nearly all absorption maxima were significantly red-shifted when compared to Prodan. Shifting the absorption and emission maxima of a fluorophore into the visible region increases its utility in biological applications. Moreover, the cyclopentane portion of the fluorophore structure provides an attachment point for biomolecules that will minimize disruptions of the photophysical properties.

  17. Preparation of Peleted Ni-Pt/Zeolite for Conversion of Amyl and Isoamyl Alcohol to Hydrocarbon

    Directory of Open Access Journals (Sweden)

    Abdullah Abdullah

    2010-06-01

    Full Text Available Catalysts with Ni and Pt as active metals in peleted zeolite were used for conversion of amyl alcohol, isoamyl alcohol and their mixture to hydrocarbon compounds. The catalysts were prepared by impregnation the peleted zeolite in NiCl2.6H2O and PtCI4 solution, while stirring for 24 hours then followed by oxidation with 02 gas at 350 °C for 2 hours and reduced by hydrogen gas at 400 °C for 1 hour. Ni and Pt in catalysts were determined by MS, specific surface area, total pore volume and gas sorption analyzer NOVA-1000 determined pore radius average. Determination of catalysts acidity was carried out by absorption of ammonia method. The activity of catalysts was evaluated in a micro reactor by flow system. Experimental temperature by varied between 300 and 400 °C with the increment of 25 °C. Products were analyzed by gas chromatographic and mass spectrometric method. The result shows that Ni-Pt/zeolite is more active than Ni/zeolite can be used for converting all of the alcohol. Products for conversion are 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, cyclopentane, 3-methyl-1-butanaldehide and acetone. The highest conversion was observed on isoamyl alcohol (31.37% at 400 °C.

  18. Isotopic exchange of cyclic ethers with deuterium over metal catalysts

    International Nuclear Information System (INIS)

    Duchet, J.C.; Cornet, D.

    1976-01-01

    The exchange reaction between deuterium and cyclic ethers (oxolane and α-methyl derivatives) has been investigated using rhodium and palladium catalysts. The first hydrogen undergoing exchange has been found to be located on a β-carbon. This fact, and the poisoning of the exchange of cyclopentane in the presence of ether, suggest that the O atom participates in the exchange mechanism of ethers. It appears, however, that the oxygen--metal bonding occurs only during this simple exchange process; simultaneous adsorption of oxygen and a vicinal carbon causes hydrogenolysis of the O--C bond. In each case multiple exchange is important. In the oxolane molecule two sets of exchangeable hydrogens are distinguished according to their reactivities, as could be expected by analogy with cycloalkanes. However, this distinction is not so clear in the exchange patterns of substituted oxolanes, since intermediate maxima are observed in these cases. It is suggested that the conformational properties of the substituted rings cause a constraint in the formation of 3,4-diadsorbed oxolanes. Thus, multiple exchange, based on α,β-process, and epimerization via the ''roll-over'' mechanism occur preferentially in certain parts of the molecules

  19. Emission of VOC's from modified rendering process

    International Nuclear Information System (INIS)

    Bhatti, Z.A.; Raja, I.A.; Saddique, M.; Langenhove, H.V.

    2005-01-01

    Rendering technique for processing of dead animal and slaughterhouse wastes into valuable products. It involves cooking of raw material and later Sterilization was added to reduce the Bovine Spongiform Encephalopathy (BSE). Studies have been carried out on rendering emission, with the normal cooking process. Our study shows, that the sterilization step in rendering process increases the emission of volatile organic compounds (VOC's). Gas samples, containing VOC's, were analyzed by the GC/MS (Gas Chromatograph and Mass Spectrometry). The most important groups of compounds- alcohols and cyclic hydrocarbons were identified. In the group of alcohol; 1-butanol, l-pentanol and l-hexanol compounds were found while in the group of cyclic hydrocarbon; methyl cyclopentane and cyclohexane compounds were detected. Other groups like aldehyde, sulphur containing compounds, ketone and furan were also found. Some compounds, like l-pentanol, 2-methyl propanal, dimethyl disulfide and dimethyl trisulfide, which belong to these groups, cause malodor. It is important to know these compounds to treat odorous gasses. (author)

  20. Development of the ReaxFFCBN reactive force field for the improved design of liquid CBN hydrogen storage materials.

    Science.gov (United States)

    Pai, Sung Jin; Yeo, Byung Chul; Han, Sang Soo

    2016-01-21

    Liquid CBN (carbon-boron-nitrogen) hydrogen-storage materials such as 3-methyl-1,2-BN-cyclopentane have the advantage of being easily accessible for use in current liquid-fuel infrastructure. To develop practical liquid CBN hydrogen-storage materials, it is of great importance to understand the reaction pathways of hydrogenation/dehydrogenation in the liquid phase, which are difficult to discover by experimental methods. Herein, we developed a reactive force field (ReaxFFCBN) from quantum mechanical (QM) calculations based on density functional theory for the storage of hydrogen in BN-substituted cyclic hydrocarbon materials. The developed ReaxFFCBN provides similar dehydrogenation pathways and energetics to those predicted by QM calculations. Moreover, molecular dynamics (MD) simulations with the developed ReaxFFCBN can predict the stability and dehydrogenation behavior of various liquid CBN hydrogen-storage materials. Our simulations reveal that a unimolecular dehydrogenation mechanism is preferred in liquid CBN hydrogen-storage materials. However, as the temperature in the simulation increases, the contribution of a bimolecular dehydrogenation mechanism also increases. Moreover, our ReaxFF MD simulations show that in terms of thermal stability and dehydrogenation kinetics, liquid CBN materials with a hexagonal structure are more suitable materials than those with a pentagonal structure. We expect that the developed ReaxFFCBN could be a useful protocol in developing novel liquid CBN hydrogen-storage materials.

  1. Screening of hydrocarbons as supercritical ORCs working fluids by thermal stability

    International Nuclear Information System (INIS)

    Dai, Xiaoye; Shi, Lin; An, Qingsong; Qian, Weizhong

    2016-01-01

    Highlights: • A rapid evaluation method for thermal stability of hydrocarbons for ORCs. • Methane and hydrogen are confirmed to be decomposition indicators. • The decomposition temperatures for some hydrocarbons using the rapid method. • Long carbon chain hydrocarbons are not suitable for supercritical ORCs. - Abstract: Organic Rankine Cycle (ORC) systems are widely used for industrial waste heat recovery and renewable energy utilization. The supercritical ORC is currently one of the main development directions due to its low exergy loss, high thermal efficiency and high work output. The thermal stability is the major limitation of organic working fluid selection with high temperature heat sources. This paper presents a rapid experimental method for assessing the thermal stability of hydrocarbons for ORCs. The fluids were tested in a high temperature reactor with methane and hydrogen theoretically and experimentally confirmed to be the indicators of thermal decomposition. The thermal decomposition temperatures were obtained for n-hexane, n-pentane, isopentane, cyclopentane, n-butane and isobutane using the rapid experimental method. The results show that cycloalkanes are not the good choices by thermal stability and long carbon chain hydrocarbons (longer than C6) are not suitable for supercritical ORCs due to the thermal stability limitation.

  2. Organic Rankine cycle - review and research directions in engine applications

    Science.gov (United States)

    Panesar, Angad

    2017-11-01

    Waste heat to power conversion using Organic Rankine Cycles (ORC) is expected to play an important role in CO2 reductions from diesel engines. Firstly, a review of automotive ORCs is presented focusing on the pure working fluids, thermal architectures and expanders. The discussion includes, but is not limited to: R245fa, ethanol and water as fluids; series, parallel and cascade as architectures; dry saturated, superheated and supercritical as expansion conditions; and scroll, radial turbine and piston as expansion machines. Secondly, research direction in versatile expander and holistic architecture (NOx + CO2) are proposed. Benefits of using the proposed unconventional approaches are quantified using Ricardo Wave and Aspen HYSYS for diesel engine and ORC modelling. Results indicate that, the implementation of versatile piston expander tolerant to two-phase and using cyclopentane can potentially increase the highway drive cycle power by 8%. Furthermore, holistic architecture offering complete utilisation of charge air and exhaust recirculation heat increased the performance noticeably to 5% of engine power at the design point condition.

  3. Organic Rankine cycle – review and research directions in engine applications

    Directory of Open Access Journals (Sweden)

    Panesar Angad

    2017-01-01

    Full Text Available Waste heat to power conversion using Organic Rankine Cycles (ORC is expected to play an important role in CO2 reductions from diesel engines. Firstly, a review of automotive ORCs is presented focusing on the pure working fluids, thermal architectures and expanders. The discussion includes, but is not limited to: R245fa, ethanol and water as fluids; series, parallel and cascade as architectures; dry saturated, superheated and supercritical as expansion conditions; and scroll, radial turbine and piston as expansion machines. Secondly, research direction in versatile expander and holistic architecture (NOx + CO2 are proposed. Benefits of using the proposed unconventional approaches are quantified using Ricardo Wave and Aspen HYSYS for diesel engine and ORC modelling. Results indicate that, the implementation of versatile piston expander tolerant to two-phase and using cyclopentane can potentially increase the highway drive cycle power by 8%. Furthermore, holistic architecture offering complete utilisation of charge air and exhaust recirculation heat increased the performance noticeably to 5% of engine power at the design point condition.

  4. Carbasugars: Synthesis and Functions

    Science.gov (United States)

    Kobayashi, Yoshiyuki

    It is well recognized that glycosidase inhibitors are not only tools to elucidate the mechanism of a living system manipulated by glycoconjugates but also potential clinical drugs and insecticides by inducing the failure of glycoconjugates to perform their function. In this chapter, the syntheses and functions of natural glycosidase inhibitors (cyclophelitol , allosamidine , and trehazoilin ), which possess highly oxygenated and functionalized cyclohexanes or cyclopentanes in their structures and are defined as carbasugars , and the structure and activity relationships (SAR) of their derivatives are described. Also, recently much attention has been focused on neuraminidase inhibitors as anti-influenza drugs since relenza , which was derived from sialic acid, and also, tamiflu , which is the artificial carbasugar designed as a transition state analogue in the hydrolysis pathway of substrates by neuraminidase, were launched in the market. Herein, the medicinal chemistry efforts to discover tamiflu and some efficient syntheses applicable to process chemistry are described. Finally, useful synthetic methodologies for carbasugar formation from sugars are also introduced in this chapter.

  5. Contribution to the study of catalytic hydrogen-deuterium exchange between hydrogen and hydrocarbons

    International Nuclear Information System (INIS)

    Ravoire, J.

    1958-01-01

    The hydrogen-deuterium exchange between molecular hydrogen and hydrocarbons over a platinum and charcoal catalyst was studied in a static system. The change in isotopic composition of molecular hydrogen was followed by a thermal conductivity method. Cyclo-pentane and cyclohexane were chosen because of their stability. A reversible inactivation of the catalyst was observed with both hydrocarbons. The reasons for this inactivation are unknown but it was shown that reactivation led to satisfactory reproducibility. A kinetic study was done with cyclohexane in the range 30 to 160 deg. C, and 40 to 360 mm for the pressure of hydrogen, and 10 to 70 mm for the pressure of cyclohexane. The order of the reaction with respect to cyclohexane pressure is always close to zero; the order with respect to that of hydrogen is 0.5 above 100 deg. C. It decreases with increasing temperature and becomes negative (-0.5 at 30 deg. C), characterizing an inhibition by hydrogen. At the same time, the apparent activation energy goes from 6 to 13 kcal/mole. (author) [fr

  6. Optimized Jasmonic Acid Production by Lasiodiplodia theobromae Reveals Formation of Valuable Plant Secondary Metabolites.

    Directory of Open Access Journals (Sweden)

    Felipe Eng

    Full Text Available Jasmonic acid is a plant hormone that can be produced by the fungus Lasiodiplodia theobromae via submerged fermentation. From a biotechnological perspective jasmonic acid is a valuable feedstock as its derivatives serve as important ingredients in different cosmetic products and in the future it may be used for pharmaceutical applications. The objective of this work was to improve the production of jasmonic acid by L. theobromae strain 2334. We observed that jasmonic acid formation is dependent on the culture volume. Moreover, cultures grown in medium containing potassium nitrate as nitrogen source produced higher amounts of jasmonic acid than analogous cultures supplemented with ammonium nitrate. When cultivated under optimal conditions for jasmonic acid production, L. theobromae secreted several secondary metabolites known from plants into the medium. Among those we found 3-oxo-2-(pent-2-enyl-cyclopentane-1-butanoic acid (OPC-4 and hydroxy-jasmonic acid derivatives, respectively, suggesting that fungal jasmonate metabolism may involve similar reaction steps as that of plants. To characterize fungal growth and jasmonic acid-formation, we established a mathematical model describing both processes. This model may form the basis of industrial upscaling attempts. Importantly, it showed that jasmonic acid-formation is not associated to fungal growth. Therefore, this finding suggests that jasmonic acid, despite its enormous amount being produced upon fungal development, serves merely as secondary metabolite.

  7. Thermal Characterisation of Micro Flat Aluminium Heat Pipe Arrays by Varying Working Fluid and Inclination Angle

    Directory of Open Access Journals (Sweden)

    Guanghan Huang

    2018-06-01

    Full Text Available A micro heat pipe array is desirable owing to its high heat transfer capacity, compact size, and high surface–volume ratio compared with conventional heat pipes. In this study, micro flat aluminium heat pipe arrays (MF-AHPA were developed and systematically characterised by varying working fluid and inclination angle. Three MF-AHPAs with different working fluids, i.e., acetone, cyclopentane, and n-hexane, were fabricated. The acetone MF-AHPA achieved the best thermal performance. The underlying mechanism is the small flow viscous friction and small shearing force of liquid vapour. Additionally, the experimental results show a strong dependence of MF-AHPAs’ thermal resistance on the orientation due to the gravitational effect on axial liquid distribution. Finally, a criterion is proposed to determine the optimal inclination angle of the MF-AHPA. In the present study, a volumetric fraction (αa,c of 74 ± 7% has been shown to well predict an optimal inclination angle of the MF-AHPAs with various working fluids and heat loads.

  8. Milestone Report #2: Direct Evaporator Leak and Flammability Analysis Modifications and Optimization of the Organic Rankine Cycle to Improve the Recovery of Waste Heat

    Energy Technology Data Exchange (ETDEWEB)

    Guillen, Donna Post [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2013-09-01

    The direct evaporator is a simplified heat exchange system for an Organic Rankine Cycle (ORC) that generates electricity from a gas turbine exhaust stream. Typically, the heat of the exhaust stream is transferred indirectly to the ORC by means of an intermediate thermal oil loop. In this project, the goal is to design a direct evaporator where the working fluid is evaporated in the exhaust gas heat exchanger. By eliminating one of the heat exchangers and the intermediate oil loop, the overall ORC system cost can be reduced by approximately 15%. However, placing a heat exchanger operating with a flammable hydrocarbon working fluid directly in the hot exhaust gas stream presents potential safety risks. The purpose of the analyses presented in this report is to assess the flammability of the selected working fluid in the hot exhaust gas stream stemming from a potential leak in the evaporator. Ignition delay time for cyclopentane at temperatures and pressure corresponding to direct evaporator operation was obtained for several equivalence ratios. Results of a computational fluid dynamic analysis of a pinhole leak scenario are given.

  9. Polyurethane Foams for Thermal Insulation Uses Produced from Castor Oil and Crude Glycerol Biopolyols.

    Science.gov (United States)

    Carriço, Camila S; Fraga, Thaís; Carvalho, Vagner E; Pasa, Vânya M D

    2017-07-02

    Rigid polyurethane foams were synthesized using a renewable polyol from the simple physical mixture of castor oil and crude glycerol. The effect of the catalyst (DBTDL) content and blowing agents in the foams' properties were evaluated. The use of physical blowing agents (cyclopentane and n-pentane) allowed foams with smaller cells to be obtained in comparison with the foams produced with a chemical blowing agent (water). The increase of the water content caused a decrease in density, thermal conductivity, compressive strength, and Young's modulus, which indicates that the increment of CO₂ production contributes to the formation of larger cells. Higher amounts of catalyst in the foam formulations caused a slight density decrease and a small increase of thermal conductivity, compressive strength, and Young's modulus values. These green foams presented properties that indicate a great potential to be used as thermal insulation: density (23-41 kg·m -3 ), thermal conductivity (0.0128-0.0207 W·m -1 ·K -1 ), compressive strength (45-188 kPa), and Young's modulus (3-28 kPa). These biofoams are also environmentally friendly polymers and can aggregate revenue to the biodiesel industry, contributing to a reduction in fuel prices.

  10. Rhodium (II) cycle alkanecarboxylate: synthesis, spectroscopic and thermo analytic studies and evaluation of the antitumor potential

    International Nuclear Information System (INIS)

    Souza, Aparecido Ribeiro de

    1995-01-01

    Four new rhodium(II) carboxylates (cyclopropane, cyclobutane, cyclopentane, and cyclohexanecarboxylate), and other already known rhodium (II) carboxylates (acetate, propionate, butyrate, metoxyacetate, dichloroacetate, and trifluoroacetate), have been prepared for study in this work. The compounds were characterized by elementary and thermogravimetric analysis, magnetic susceptibility, and electronic, Raman, and infrared spectroscopy. The reaction of Rh CL 3 .aq with the sodium carboxylates was studied aiming to improve the understanding of the redox process involved. Spectroscopy studies (Raman and electronic) were made to examine the transition involved in the Rh-Rh and Rh-O bonds. The results have shown a direct relation between the force of the carboxylic acid and the Rh-O force, but show a inverse relation with the Rh-Rh bond force. Thermal analysis studies were undertaken and the obtained date show a resemblance of the TG/DTG curves with that found in literature. In the other hand, the DSC curves show a different results: in open crucible, the peaks associated with the cage breakdown are exothermic and, in closed crucible this peaks are endothermic. The thermodecomposition products were analyzed. The evolved gases were identified by GC?MS and 1 H and 13 C NMR spectra. The residues were analyzed by X-ray diffraction. Antitumor activity of rhodium cyclopropanecarboxylate was evaluated in vitro (cell cultures K562 and Ehrlich) and in vivo (Balb-c mice with ascite Ehrlich tumor), indicating an increased life span (87.5%) of the treated animals. (author)

  11. Novel nanotechnology for efficient production of binary clathrate hydrates of hydrogen and other compounds

    Energy Technology Data Exchange (ETDEWEB)

    Di Profio, P.; Arca, S.; Germani, R.; Savelli, G. [Perugia Univ., Perugia (Italy). Dept. of Chemistry, Center of Excellence on Innovative Nanostructured Materials

    2008-07-01

    The development of a hydrogen-based economy depends on finding ways to store hydrogen, but current hydrogen storage methods have significant disadvantages. One main challenge in storing sufficient amounts of hydrogen (up to 4 weight per cent) into a clathrate matrix is that of a kinetic origin, in that the mass transfer of hydrogen gas into clathrate structures is significantly limited by the macroscopic scale of the gas-liquid or gas-ice interfaces involved. This paper discussed the possibility of storing hydrogen in clathrate hydrates. It presented a newly developed method for preparing binary hydrogen hydrates that is based on the formation of amphiphile-aided nanoemulsions. Nanotechnology is used to reduce the size of hydrate particles to a few nanometers, thereby minimizing the kinetic hindrance to hydrate formation. This process has potential for increasing the amount of hydrogen stored, as it has provided ca. 1 weight per cent of hydrogen. Two new co-formers were also successfully tested, namely cyclopentane and tetrahydrothiophene. 23 refs., 10 figs.

  12. Metabolism of the carbocyclic analogue of (E)-5-(2-iodovinyl)-2'-deoxyuridine in herpes simplex virus-infected cells. Incorporation of C-IVDU into DNA

    International Nuclear Information System (INIS)

    De Clercq, E.; Bernaerts, R.; Balzarini, J.; Herdewijn, P.; Verbruggen, A.

    1985-01-01

    The carbocyclic analogues of (E)-5-(2-bromovinyl)-2'-deoxyuridine (BVDU) and (E)-5-(2-iodovinyl)-2'-deoxyuridine (IVDU), in which the sugar moiety is replaced by a cyclopentane ring and which have been designated as C-BVDU and C-IVDU, respectively, are, like their parent compounds BVDU and IVDU, potent and selective inhibitors of herpes simplex virus type 1 (HSV-1) and, to a lesser extent, herpes simplex virus type 2 (HSV-2) replication. The authors have now synthesized the radiolabeled C-IVDU analogue, C-[ 125 I]IVDU, and determined its metabolism by HSV-infected and mock-infected Vero cells. C-[ 125 I]IVDU was effectively phosphorylated by HSV-1-infected cells and, to a lesser extent, HSV-2-infected cells. C-[ 125 I]IVDU was not phosphorylated to an appreciable extent by either mock-infected cells or cells that had been infected with a thymidine kinase-deficient mutant of HSV-1. Furthermore, C-[ 125 I]IVDU was incorporated into both viral and cellular DNA of HSV-1-infected Vero cells. This finding represents the first demonstration of the incorporation of a cyclopentylpyrimidine into DNA

  13. Rhodium (II) cycle alkanecarboxylate: synthesis, spectroscopic and thermo analytic studies and evaluation of the antitumor potential; Cicloalcanocarboxilatos de rodio(II). Sintese, estudos espectroscopicos, termoanaliticos e avaliacao do potencial antitumor

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Aparecido Ribeiro de

    1995-07-01

    Four new rhodium(II) carboxylates (cyclopropane, cyclobutane, cyclopentane, and cyclohexanecarboxylate), and other already known rhodium (II) carboxylates (acetate, propionate, butyrate, metoxyacetate, dichloroacetate, and trifluoroacetate), have been prepared for study in this work. The compounds were characterized by elementary and thermogravimetric analysis, magnetic susceptibility, and electronic, Raman, and infrared spectroscopy. The reaction of Rh CL{sub 3}.aq with the sodium carboxylates was studied aiming to improve the understanding of the redox process involved. Spectroscopy studies (Raman and electronic) were made to examine the transition involved in the Rh-Rh and Rh-O bonds. The results have shown a direct relation between the force of the carboxylic acid and the Rh-O force, but show a inverse relation with the Rh-Rh bond force. Thermal analysis studies were undertaken and the obtained date show a resemblance of the TG/DTG curves with that found in literature. In the other hand, the DSC curves show a different results: in open crucible, the peaks associated with the cage breakdown are exothermic and, in closed crucible this peaks are endothermic. The thermodecomposition products were analyzed. The evolved gases were identified by GC?MS and {sup 1}H and {sup 13} C NMR spectra. The residues were analyzed by X-ray diffraction. Antitumor activity of rhodium cyclopropanecarboxylate was evaluated in vitro (cell cultures K562 and Ehrlich) and in vivo (Balb-c mice with ascite Ehrlich tumor), indicating an increased life span (87.5%) of the treated animals. (author)

  14. Exergetic Analysis of an Integrated Tri-Generation Organic Rankine Cycle

    Directory of Open Access Journals (Sweden)

    Ratha Z. Mathkor

    2015-08-01

    Full Text Available This paper reports on a study of the modelling, validation and analysis of an integrated 1 MW (electrical output tri-generation system energized by solar energy. The impact of local climatic conditions in the Mediterranean region on the system performance was considered. The output of the system that comprised a parabolic trough collector (PTC, an organic Rankine cycle (ORC, single-effect desalination (SED, and single effect LiBr-H2O absorption chiller (ACH was electrical power, distilled water, and refrigerant load. The electrical power was produced by the ORC which used cyclopentane as working fluid and Therminol VP-1 was specified as the heat transfer oil (HTO in the collectors with thermal storage. The absorption chiller and the desalination unit were utilize the waste heat exiting from the steam turbine in the ORC to provide the necessary cooling energy and drinking water respectively. The modelling, which includes an exergetic analysis, focuses on the performance of the solar tri-generation system. The simulation results of the tri-generation system and its subsystems were produced using IPSEpro software and were validated against experimental data which showed good agreement. The tri-generation system was able to produce about 194 Ton of refrigeration, and 234 t/day distilled water.

  15. Macroscopic investigation of water volume effects on interfacial dynamic behaviors between clathrate hydrate and water.

    Science.gov (United States)

    Cha, Minjun; Couzis, Alexander; Lee, Jae W

    2013-05-14

    This study investigated the effects of the water volume on the interfacial dynamics between cyclopentane (CP) hydrate and water droplet in a CP/n-decane oil mixture. The adhesion force between CP hydrate and various water droplets was determined using the z-directional microbalance. Through repetition of precise measurements over several cycles from contact to detachment, we observed abnormal wetting behaviors in the capillary bridge during the retraction process when the water drop volume is larger than 100 μL. With the increase in water droplet volumes, the contact force between CP hydrate and water also increases up to 300 μL. However, there is a dramatic reduction of increasing rate in the contact forces over 300 μL of water droplet. With the addition of the surfactants of sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) to the water droplet, the contact force between CP hydrate and solution droplet exhibits a lower value and a transition volume of the contact force comes with a smaller solution volume of 200 μL. The water volume effects on the liquid wetting of the probe and the size of capillary bridges provide important insight into hydrate growth and aggregation/agglomeration in the presence of free water phase inside gas/oil pipelines.

  16. Novel archaeal tetraether lipids with a cyclohexyl ring identified in Fayetteville Green Lake, NY, and other sulfidic lacustrine settings.

    Science.gov (United States)

    Liu, Xiao-Lei; De Santiago Torio, Ana; Bosak, Tanja; Summons, Roger Everett

    2016-05-30

    The meromictic Fayetteville Green Lake (FGL) is of significant geobiological interest because of microbial cycling of sulfur within and below the permanent chemocline and in the euxinic deep waters. Studies of glycerol dibiphytanyl glycerol tetraethers (GDGTs) may help shed light on understanding the activity of archaeal communities in these habitats. Normal-phase and reversed-phase liquid chromatography/mass spectrometry (LC/MS) analysis on total lipid extracts of environmental samples revealed series of GDGTs with different biphytane structures. Comparison of the mass spectrum of biphytane obtained from separated novel GDGTs with that of a synthetic C 40 biphytane confirms our structural assignments. A unique cyclohexyl ring configured in the middle of a C 40 biphytane chain was identified in these novel GDGTs. We suggest the trivial name S-GDGTs for these compounds, where 'S' stands for 'sulfidic' and 'six-membered ring'. S-GDGT derivatives composed of biphytanes modified with double bonds and cyclopentane rings were also detected in the samples we analyzed. Intact polar lipid precursors of S-GDGT include compounds with mono- and diglycosyl head groups. The carbon isotopic composition of S-GDGTs and their occurrence in FGL, Messel Shale as well as Salt Pond and salt marshes on Cape Cod suggest that S-GDGTs may be produced by chemoautotrophic archaea that prefer sulfidic conditions. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  17. How strained are carbomeric-cycloalkanes?

    Science.gov (United States)

    Wodrich, Matthew D; Gonthier, Jérôme F; Steinmann, Stephan N; Corminboeuf, Clémence

    2010-06-24

    The ring strain energies of carbomeric-cycloalkanes (molecules with one or more acetylene spacer units placed into carbon single bonds) are assessed using a series of isodesmic, homodesmotic, and hyperhomodesmotic chemical equations. Isodesmic bond separation reactions and other equations derived from the explicitly defined hierarchy of homodesmotic equations are insufficient for accurately determining these values, since not all perturbing effects (i.e., conjugation and hyperconjugation) are fully balanced. A set of homodesmotic reactions is proposed, which succeeds in balancing all stereoelectronic effects present within the carbomeric rings, allowing for a direct assessment of the strain energies. Values calculated from chemical equations are validated using an increment/additivity approach. The ring strain energy decreases as acetylene units are added, manifesting from the net stabilization gained by opening the C-CH(2)-C angle around the methylene groups and the destabilization arising from bending the C-C identical withC angles of the spacer groups. This destabilization vanishes with increasing parent ring size (i.e., the angle distortion is less in the carbomeric-cyclobutanes than in the carbomeric-cyclopropanes), leading to strain energies near zero for carbo(n)-cyclopentanes and carbo(n)-cyclohexanes.

  18. A bonding study of c-C5H8 adsorption on Pt(111)

    International Nuclear Information System (INIS)

    Simonetti, S.; Jasen, P.; Gonzalez, E.; Juan, A.; Brizuela, G.

    2006-01-01

    The chemisorption of cyclopentane (c-C 5 H 8 ) on Pt(111) has been studied using a qualitative band-structure calculations in the framework of tight-binding implementation with the YAeHMOP package. We modeled the metal surface by a two-dimensional slab of finite thickness with an overlayer of c-C 5 H 8 , in a (3x3) di-σ geometry. The c-C 5 H 8 molecule is attached to the surface with its C?C atoms bonded mainly with two Pt atoms while the opposite CH 2 bends towards the surface. The Pt?Pt bonds in the underlying surface and the C?C bonds of c-C 5 H 8 are weakened upon the chemisorption. A noticeable Pt-H and Pt-C interactions has been observed. We found that of Pt 5d z 2 band plays an important role in the bonding between c-C 5 H 8 and the surface, as do the Pt 6s and 6p z bands. The HOMO-LUMO bands of c-C 5 H 8 are very dispersed, indicative of a strong interaction with the metal surface

  19. Metabolism of monoterpanes: metabolic fate of (+)-camphor in sage (Salvia officinalis)

    International Nuclear Information System (INIS)

    Croteau, R.; El-Bialy, H.; Dehal, S.S.

    1987-01-01

    The bicyclic monoterpene ketone (+)-camphor undergoes lactonization to 1,2-campholide in mature sage (Salvia officinalis L.) leaves followed by conversion to the β-D-glucoside-6-O-glucose ester of the corresponding hydroxy acid (1-carboxymethyl-3-hydroxy-2,2,3-trimethyl cyclopentane). Analysis of the disposition of (+)-[G- 3 H]camphor applied to midstem leaves of intact flowering plants allowed the kinetics of synthesis of the bis-glucose derivative and its transport from leaf to root to be determined, and gave strong indication that the transport derivative was subsequently metabolized in the root. Root extracts were shown to possess β-glucosidase and acyl glucose esterase activities, and studies with (+)-1,2[U- 14 C]campholide as substrate, using excised root segments, revealed that the terpenoid was converted to lipid materials. Localization studies confirmed the radiolabeled lipids to reside in the membranous fractions of root extracts, and analysis of this material indicated the presence of labeled phytosterols and labeled fatty acids (C 14 to C 20 ) of acyl lipids. Although it was not possible to detail the metabolic steps between 1,2-campholide and the acyl lipids and phytosterols derived therefrom because of the lack of readily detectable intermediates, it seemed likely that the monoterpene lactone was degraded to acetyl CoA which was reincorporated into root membrane components via standard acyl lipid and isoprenoid biosynthetic pathways. Monoterpene catabolism thus appears to represent a salvage mechanism for recycling mobile carbon from senescing oil glands on the leaves to the roots

  20. Factors controlling the distribution of archaeal tetraethers in terrestrial hot springs.

    Science.gov (United States)

    Pearson, Ann; Pi, Yundan; Zhao, Weidong; Li, WenJun; Li, Yiliang; Inskeep, William; Perevalova, Anna; Romanek, Christopher; Li, Shuguang; Zhang, Chuanlun L

    2008-06-01

    Glycerol dialkyl glycerol tetraethers (GDGTs) found in hot springs reflect the abundance and community structure of Archaea in these extreme environments. The relationships between GDGTs, archaeal communities, and physical or geochemical variables are underexamined to date and when reported often result in conflicting interpretations. Here, we examined profiles of GDGTs from pure cultures of Crenarchaeota and from terrestrial geothermal springs representing a wide distribution of locations, including Yellowstone National Park (United States), the Great Basin of Nevada and California (United States), Kamchatka (Russia), Tengchong thermal field (China), and Thailand. These samples had temperatures of 36.5 to 87 degrees C and pH values of 3.0 to 9.2. GDGT abundances also were determined for three soil samples adjacent to some of the hot springs. Principal component analysis identified four factors that accounted for most of the variance among nine individual GDGTs, temperature, and pH. Significant correlations were observed between pH and the GDGTs crenarchaeol and GDGT-4 (four cyclopentane rings, m/z 1,294); pH correlated positively with crenarchaeol and inversely with GDGT-4. Weaker correlations were observed between temperature and the four factors. Three of the four GDGTs used in the marine TEX(86) paleotemperature index (GDGT-1 to -3, but not crenarchaeol isomer) were associated with a single factor. No correlation was observed for GDGT-0 (acyclic caldarchaeol): it is effectively its own variable. The biosynthetic mechanisms and exact archaeal community structures leading to these relationships remain unknown. However, the data in general show promise for the continued development of GDGT lipid-based physiochemical proxies for archaeal evolution and for paleo-ecology or paleoclimate studies.

  1. Factors Controlling the Distribution of Archaeal Tetraethers in Terrestrial Hot Springs▿

    Science.gov (United States)

    Pearson, Ann; Pi, Yundan; Zhao, Weidong; Li, WenJun; Li, Yiliang; Inskeep, William; Perevalova, Anna; Romanek, Christopher; Li, Shuguang; Zhang, Chuanlun L.

    2008-01-01

    Glycerol dialkyl glycerol tetraethers (GDGTs) found in hot springs reflect the abundance and community structure of Archaea in these extreme environments. The relationships between GDGTs, archaeal communities, and physical or geochemical variables are underexamined to date and when reported often result in conflicting interpretations. Here, we examined profiles of GDGTs from pure cultures of Crenarchaeota and from terrestrial geothermal springs representing a wide distribution of locations, including Yellowstone National Park (United States), the Great Basin of Nevada and California (United States), Kamchatka (Russia), Tengchong thermal field (China), and Thailand. These samples had temperatures of 36.5 to 87°C and pH values of 3.0 to 9.2. GDGT abundances also were determined for three soil samples adjacent to some of the hot springs. Principal component analysis identified four factors that accounted for most of the variance among nine individual GDGTs, temperature, and pH. Significant correlations were observed between pH and the GDGTs crenarchaeol and GDGT-4 (four cyclopentane rings, m/z 1,294); pH correlated positively with crenarchaeol and inversely with GDGT-4. Weaker correlations were observed between temperature and the four factors. Three of the four GDGTs used in the marine TEX86 paleotemperature index (GDGT-1 to -3, but not crenarchaeol isomer) were associated with a single factor. No correlation was observed for GDGT-0 (acyclic caldarchaeol): it is effectively its own variable. The biosynthetic mechanisms and exact archaeal community structures leading to these relationships remain unknown. However, the data in general show promise for the continued development of GDGT lipid-based physiochemical proxies for archaeal evolution and for paleo-ecology or paleoclimate studies. PMID:18390673

  2. Volatile-organic molecular characterization of shale-oil produced water from the Permian Basin.

    Science.gov (United States)

    Khan, Naima A; Engle, Mark; Dungan, Barry; Holguin, F Omar; Xu, Pei; Carroll, Kenneth C

    2016-04-01

    Growth in unconventional oil and gas has spurred concerns on environmental impact and interest in beneficial uses of produced water (PW), especially in arid regions such as the Permian Basin, the largest U.S. tight-oil producer. To evaluate environmental impact, treatment, and reuse potential, there is a need to characterize the compositional variability of PW. Although hydraulic fracturing has caused a significant increase in shale-oil production, there are no high-resolution organic composition data for the shale-oil PW from the Permian Basin or other shale-oil plays (Eagle Ford, Bakken, etc.). PW was collected from shale-oil wells in the Midland sub-basin of the Permian Basin. Molecular characterization was conducted using high-resolution solid phase micro extraction gas chromatography time-of-flight mass spectrometry. Approximately 1400 compounds were identified, and 327 compounds had a >70% library match. PW contained alkane, cyclohexane, cyclopentane, BTEX (benzene, toluene, ethylbenzene, and xylene), alkyl benzenes, propyl-benzene, and naphthalene. PW also contained heteroatomic compounds containing nitrogen, oxygen, and sulfur. 3D van Krevelen and double bond equivalence versus carbon number analyses were used to evaluate molecular variability. Source composition, as well as solubility, controlled the distribution of volatile compounds found in shale-oil PW. The salinity also increased with depth, ranging from 105 to 162 g/L total dissolved solids. These data fill a gap for shale-oil PW composition, the associated petroleomics plots provide a fingerprinting framework, and the results for the Permian shale-oil PW suggest that partial treatment of suspended solids and organics would support some beneficial uses such as onsite reuse and bio-energy production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. CO_2 capture from flue gas using clathrate formation in the presence of thermodynamic promoters

    International Nuclear Information System (INIS)

    Kim, Soyoung; Choi, Sung-Deuk; Seo, Yongwon

    2017-01-01

    Tetrahydrofuran (THF) as a water-soluble sII clathrate former, cyclopentane (CP) as a water-insoluble sII clathrate former, and tetra n-butyl ammonium chloride (TBAC) as a water-soluble semiclathrate former were used to investigate their thermodynamic promotion effects on clathrate-based CO_2 capture from simulated flue gas. The phase equilibria of CO_2 (20%) + N_2 (80%) + promoter clathrates at different promoter concentrations revealed that the presence of THF, CP, and TBAC could significantly reduce the clathrate formation pressure. THF solutions provided the highest gas uptake and steepest CO_2 concentration changes in the vapor phase, whereas TBAC solutions showed the highest CO_2 selectivity (∼61%) in the clathrate phase. CP solutions exhibited a slower formation rate, but their final gas uptake and CO_2 selectivity in the clathrate phase were comparable to the THF solutions. Raman spectroscopy confirmed the enclathration of both CO_2 and N_2 in the clathrate cages and a structural transition due to the inclusion of promoters in the clathrate phase. The overall experimental results indicate that TBAC is a viable thermodynamic promoter for clathrate-based CO_2 capture from simulated flue gas, considering the lower pressure requirement for clathrate formation, higher CO_2 enrichment in the clathrate phase, non-toxicity, and non-volatility. - Highlights: • Clathrate-based CO_2 capture was investigated in the presence of thermodynamic promoters. • THF, CP, and TBAC demonstrated a significant thermodynamic promotion for CO_2 (20%) + N_2 (80%) clathrates. • The highest gas uptake was observed for the THF (5.6 mol%) solution. • TBAC solutions showed the highest CO_2 selectivity in the clathrate phase (∼61%). • Raman spectroscopy confirmed the guest gas enclathration and clathrate structure.

  4. Optimization of the octane response of gasoline/ethanol blends

    KAUST Repository

    Badra, Jihad

    2017-07-04

    The octane responses of gasoline/ethanol mixtures are not well understood because of the unidentified intermolecular interactions in such blends. In general, when ethanol is blended with gasoline, the Research Octane Number (RON) and the Motor Octane Number (MON) non-linearly increase or decrease, and the non-linearity is determined by the composition of the base gasoline and the amount of added ethanol. The complexity of commercial gasolines, comprising of hundreds of different components, makes it challenging to understand ethanol-gasoline synergistic/antagonistic blending effects. Understanding ethanol blending effects with simpler gasoline surrogates is critical to acquire knowledge about ethanol blending with complex multi-component gasoline fuels. In this study, the octane numbers (ON) of ethanol blends with five relevant gasoline surrogate molecules were measured. The molecules investigated in this study include: n-pentane, iso-pentane, 1,2,4-trimethylbenzene, cyclopentane and 1-hexene. These new measurements along with the available data of n-heptane, iso-octane, toluene, various primary reference fuels (PRF) and toluene primary reference fuels (TPRF) with ethanol are used to develop a blending rule for the octane response (RON and MON) of multi-component blends with ethanol. In addition, new ON data are collected for six Fuels for Advanced Combustion Engine (FACE) with ethanol. The relatively simple volume based model successfully predicts the octane numbers (ON) of the various ethanol/PRF and ethanol/TPRF blends with the majority of predictions being within the ASTM D2699 (RON) and D2700 (MON) reproducibility limits. The model is also successfully validated against the ON of the FACE gasolines blended with ethanol with the majority of predictions being within the reproducibility limits. Finally, insights into the possible causes of the synergistic and antagonistic effects of different molecules with ethanol are provided.

  5. Hybrid gas turbine–organic Rankine cycle for seawater desalination by reverse osmosis in a hydrocarbon production facility

    International Nuclear Information System (INIS)

    Eveloy, Valérie; Rodgers, Peter; Qiu, Linyue

    2015-01-01

    Highlights: • Seawater reverse osmosis driven by hybrid gas turbine–organic Rankine power cycle. • High ambient air and seawater temperatures, and high seawater salinity. • Energy–exergy analysis of power and desalination systems for six organic fluids. • Economic viability of waste heat recovery in subsidized utility pricing context. - Abstract: Despite water scarcity, the use of industrial waste heat for seawater desalination has been limited in the Middle East to date. This study evaluates the technical and economic feasibility of integrating on-site gas turbine power generation and reverse osmosis equipment for the production of both electricity and fresh water in a coastal hydrocarbon production facility. Gas turbine exhaust gas waste heat is recovered using an intermediate heat transfer fluid and fed to an organic Rankine cycle evaporator, to generate mechanical power to drive the reverse osmosis high pressure pump. Six candidate organic working fluids are evaluated, namely toluene, benzene, cyclohexane, cyclopentane, n-pentane and R245fa. Thermodynamic and desalination performance are assessed in the harsh climatic and salinity conditions of the Arabian Gulf. The performance metrics considered incorporate electric power and permeate production, thermal and exergy efficiency, specific energy consumption, system size, and permeate quality. Using toluene in the bottoming power cycle, a gain in power generation efficiency of approximately 12% is achieved relative to the existing gas turbine cycle, with an annual average of 2260 m"3/h of fresh water produced. Depending upon the projected evolution of local water prices, the investment becomes profitable after two to four years, with an end-of-life net present value of 220–380 million USD, and internal rate of return of 26–48%.

  6. Optimization of the octane response of gasoline/ethanol blends

    KAUST Repository

    Badra, Jihad; AlRamadan, Abdullah S.; Sarathy, Mani

    2017-01-01

    The octane responses of gasoline/ethanol mixtures are not well understood because of the unidentified intermolecular interactions in such blends. In general, when ethanol is blended with gasoline, the Research Octane Number (RON) and the Motor Octane Number (MON) non-linearly increase or decrease, and the non-linearity is determined by the composition of the base gasoline and the amount of added ethanol. The complexity of commercial gasolines, comprising of hundreds of different components, makes it challenging to understand ethanol-gasoline synergistic/antagonistic blending effects. Understanding ethanol blending effects with simpler gasoline surrogates is critical to acquire knowledge about ethanol blending with complex multi-component gasoline fuels. In this study, the octane numbers (ON) of ethanol blends with five relevant gasoline surrogate molecules were measured. The molecules investigated in this study include: n-pentane, iso-pentane, 1,2,4-trimethylbenzene, cyclopentane and 1-hexene. These new measurements along with the available data of n-heptane, iso-octane, toluene, various primary reference fuels (PRF) and toluene primary reference fuels (TPRF) with ethanol are used to develop a blending rule for the octane response (RON and MON) of multi-component blends with ethanol. In addition, new ON data are collected for six Fuels for Advanced Combustion Engine (FACE) with ethanol. The relatively simple volume based model successfully predicts the octane numbers (ON) of the various ethanol/PRF and ethanol/TPRF blends with the majority of predictions being within the ASTM D2699 (RON) and D2700 (MON) reproducibility limits. The model is also successfully validated against the ON of the FACE gasolines blended with ethanol with the majority of predictions being within the reproducibility limits. Finally, insights into the possible causes of the synergistic and antagonistic effects of different molecules with ethanol are provided.

  7. Virtual Screening for Potential Inhibitors of NS3 Protein of Zika Virus

    Directory of Open Access Journals (Sweden)

    Maheswata Sahoo

    2016-09-01

    Full Text Available Zika virus (ZIKV is a mosquito borne pathogen, belongs to Flaviviridae family having a positive-sense single-stranded RNA genome, currently known for causing large epidemics in Brazil. Its infection can cause microcephaly, a serious birth defect during pregnancy. The recent outbreak of ZIKV in February 2016 in Brazil realized it as a major health risk, demands an enhanced surveillance and a need to develop novel drugs against ZIKV. Amodiaquine, prochlorperazine, quinacrine, and berberine are few promising drugs approved by Food and Drug Administration against dengue virus which also belong to Flaviviridae family. In this study, we performed molecular docking analysis of these drugs against nonstructural 3 (NS3 protein of ZIKV. The protease activity of NS3 is necessary for viral replication and its prohibition could be considered as a strategy for treatment of ZIKV infection. Amongst these four drugs, berberine has shown highest binding affinity of –5.8 kcal/mol and it is binding around the active site region of the receptor. Based on the properties of berberine, more similar compounds were retrieved from ZINC database and a structure-based virtual screening was carried out by AutoDock Vina in PyRx 0.8. Best 10 novel drug-like compounds were identified and amongst them ZINC53047591 (2-(benzylsulfanyl-3-cyclohexyl-3H-spiro[benzo[h]quinazoline-5,1'-cyclopentan]-4(6H-one was found to interact with NS3 protein with binding energy of –7.1 kcal/mol and formed H-bonds with Ser135 and Asn152 amino acid residues. Observations made in this study may extend an assuring platform for developing anti-viral competitive inhibitors against ZIKV infection.

  8. Study of mixtures based on hydrocarbons used in ORC (Organic Rankine Cycle) for engine waste heat recovery

    International Nuclear Information System (INIS)

    Shu, Gequn; Gao, Yuanyuan; Tian, Hua; Wei, Haiqiao; Liang, Xingyu

    2014-01-01

    For high temperature ORC (Organic Rankine Cycle) used in engine waste heat recovery, it's very critical to select a high temperature working fluid. HCs (Hydrocarbons) usually have excellent cycle performance, but the flammability limits their practical application. Considering that some retardants can be used to suppress flammability, the paper presents an application of mixtures based on hydrocarbons blending with refrigerant retardants to engine waste heat ORC. Three pure hydrocarbons (cyclopentane, cyclohexane, benzene) and two retardants (R11, R123) are selected for combination. Thermal efficiency and exergy loss are selected as the main objective functions. Based on thermodynamic model, the effects of retardants mass fraction, evaporation temperature and IHE (internal heat exchanger) are investigated. Results show that zeotropic mixtures do have higher thermal efficiency and lower exergy loss than pure fluids, at a certain mixture ratio. There exists the OMR (optimal mixture ratio) for different mixtures, and it changes with the evaporation temperature. When adding IHE to system, cycle performance could be obviously improved, and for benzene/R11 (0.7/0.3), the efficiency growth is about 7.12%∼9.72%. Using it, the maximum thermal efficiency of the system can achieve 16.7%, and minimum exergy loss is only 30.76 kW. - Highlights: • A theoretical analysis of Organic Rankine Cycle for engine exhaust heat recovery is proposed. • Mixtures based on hydrocarbons as working fluids have been suggested. • Effects of the IHE (internal heat exchanger) on ORC system are investigated. • OMR (Optimal mixture ratio) changes with the evaporation temperature. • Using the system, maximum thermal efficiency can achieve 16.7%

  9. Comparative study of the essential oil and hydrolate composition of Lythrum salicaria L. obtained by hydro-distillation and microwave distillation methods

    Directory of Open Access Journals (Sweden)

    A. Manayi

    2014-04-01

    Full Text Available Essential oils are considered as very complex natural mixtures containing numerous components at quite various concentrations. Lythrum salicaria has not been previously subjected to examination of its volatile oil. The present study was carried out to evaluate the essential oil composition of the flowering aerial parts of the plant by using conventionally hydro-distillation (HD and microwave assisted hydro-distillation (MAH methods along with the aromatic water obtained by hydro-distillation. Components of these three samples were recognized by GC/MS. Identification of components resulted in recognition of 14 (98% oil, 32 (98.4%, and 10 (95.5% compounds for HD, its hydrolate, and MAH samples, respectively. The predominant constituents in the HD oil were bis (2-ethylhexyl phthalate (29.2%, n-hexadecanoic acid (22%, and pentacosane (9.5%. The major constituents of the hydrolate were elucidated as 2(4H-benzofuranone-5,6,7,7a-tetrahydro-4,4,7a-trimethyl (6.4%, neryl acetone (6%, pentanoic acid (5.7%, nonanoic acid (5.6%, and octanoic acid (5.5%. Accordingly, bis (2-ethylhexyl phthalate (43.2%, methyl-cyclopentane (36.5%, and pentacosane (4.7% were assessed as the main components of MAH oil. Comparing the three samples compositions, it was concluded that the extraction procedure led to variations in quality and quantity of volatiles. Besides, bis (2-ethylhexyl phthalate, the common plasticizer, was identified as the main pollutant in both HD and MAH oils. The presence of this substance in the oils provided the evidence of contaminations that was absorbed from water into the plant suggesting GC/MS as a suitable method for its detection in plant materials.

  10. GC/MS Analysis of Oil Extractives from Wood and Bark of Pinus sylvestris, Abies alba, Picea abies, and Larix decidua

    Directory of Open Access Journals (Sweden)

    Mohamed Zidan Mohamed Salem

    2015-09-01

    Full Text Available Wood and bark oil extractives components (OECs of Pinus sylvestris, Abies alba, Picea abies, and Larix decidua grown in the Czech Republic were analyzed using gas chromatography/ mass spectrometry (GC/MS. The analysis showed the presence of monoterpene, sesquiterpene, diterpenoids, and resin acids. The highest percentages of OECs in the wood of P. sylvestris were α-fenchyl alcohol (26.04%, D-fenchyl alcohol (12.39%, and L-borneol (8.81%; the OECs in the bark included α-methyl-γ-butyrolactone (31.88% and isodecyl octyl phthalate (15.85%. The most frequently occurring OEC in A. alba wood were 4-hydroxy-4-methyl-2-pentanone (73.36%, α-cedrol (10.08%, and 2,6-dimethyl-1,3,6-heptatriene (7.35%; the most OECs in the bark were di(2-ethylhexylphthalate (59.83%, methyl cyclopentane (16.63%, and 13-epimanool (6.31%. P. abies wood OECs included 4-hydroxy-4-methyl-2-pentanone (29.42%, α-cedrol (26.98%, ∆3-carene (6.08%, and terpinen-4-ol (5.42%; the most OECs in the bark were di(2-ethylhexylphthalate (30.91%, cyclohexane (12.89%, caryophyllene oxide (8.90%, and α-pinene (4.59%. OECs of L. decidua wood were α-terpineol (26.06%, isoborneol (14.12%, camphene (11.78%, D-fenchyl alcohol (10.39%, and larixol (4.85%; OECs in the bark were larixol (33.29%, phthalic acid mono-2-ethylhexyl ester (16.96%, 13-epimanool (15.40%, and cyclohexane (8.44%.

  11. A Chemical Alphabet for Macromolecular Communications.

    Science.gov (United States)

    Giannoukos, Stamatios; McGuiness, Daniel Tunç; Marshall, Alan; Smith, Jeremy; Taylor, Stephen

    2018-06-08

    Molecular communications in macroscale environments is an emerging field of study driven by the intriguing prospect of sending coded information over olfactory networks. For the first time, this article reports two signal modulation techniques (on-off keying-OOK, and concentration shift keying-CSK) which have been used to encode and transmit digital information using odors over distances of 1-4 m. Molecular transmission of digital data was experimentally investigated for the letter "r" with a binary value of 01110010 (ASCII) for a gas stream network channel (up to 4 m) using mass spectrometry (MS) as the main detection-decoding system. The generation and modulation of the chemical signals was achieved using an automated odor emitter (OE) which is based on the controlled evaporation of a chemical analyte and its diffusion into a carrier gas stream. The chemical signals produced propagate within a confined channel to reach the demodulator-MS. Experiments were undertaken for a range of volatile organic compounds (VOCs) with different diffusion coefficient values in air at ambient conditions. Representative compounds investigated include acetone, cyclopentane, and n-hexane. For the first time, the binary code ASCII (American Standard Code for Information Interchange) is combined with chemical signaling to generate a molecular representation of the English alphabet. Transmission experiments of fixed-width molecular signals corresponding to letters of the alphabet over varying distances are shown. A binary message corresponding to the word "ion" was synthesized using chemical signals and transmitted within a physical channel over a distance of 2 m.

  12. A Micro and Mesocosm Approach to Understanding the Response of Branched GDGTs to Environmental Perturbation

    Science.gov (United States)

    Martínez-Sosa, P.; Tierney, J. E.; Castañeda, I. S.

    2017-12-01

    Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane lipids with 15 known structures. Thought to be synthesized by bacteria, they are found in peatlands, soils, near-shore marine sediments and lakes. Previous studies have reported a correlation between the number and position of methyl groups and cyclopentane moieties in these lipids with environmental factors such as pH and temperature, leading to the creation of the methylation and cyclisation indices (MBT and CBT respectively). Although an empirical relationship between these structural modifications and environmental conditions has been described, the source organism for these molecules remains unknown. Lacking pure cultures of brGDGT producing bacteria, a different approach is necessary to study their response to environmental perturbations under controlled conditions. To this end, we studied the production of brGDGTs in water from two fishing lakes in Arizona using a series of microcosms, comprised by 1L flasks filled with environmental water; and mesocosm experiments, where two 20L tanks were filled with either lake water or lake water and synthetic sediments. This experimental design allowed us to modify environmental factors while preserving the natural conditions of the sample. Our experiments point to a production of brGDGTs on the suspended particulate matter in the water column, which appears to contribute to some extent to the presence of this molecules on lake sediments. Furthermore, we observed a shift in the ratio between 5' and 6' isomers related to both the presence of a carbon source and temperature. Limited oxygen availability appears to correlate with higher brGDGT concentration. Notably, we find that methylation decreases with increasing temperature in our experiments at a rate that is roughly in agreement with empirical observations. To our knowledge, these experiments provide the first evidence of growth and alteration of brGDGTs under laboratory conditions, which could be

  13. Volatile-organic molecular characterization of shale-oil produced water from the Permian Basin

    Science.gov (United States)

    Khan, Naima A.; Engle, Mark A.; Dungan, Barry; Holguin, F. Omar; Xu, Pei; Carroll, Kenneth C.

    2016-01-01

    Growth in unconventional oil and gas has spurred concerns on environmental impact and interest in beneficial uses of produced water (PW), especially in arid regions such as the Permian Basin, the largest U.S. tight-oil producer. To evaluate environmental impact, treatment, and reuse potential, there is a need to characterize the compositional variability of PW. Although hydraulic fracturing has caused a significant increase in shale-oil production, there are no high-resolution organic composition data for the shale-oil PW from the Permian Basin or other shale-oil plays (Eagle Ford, Bakken, etc.). PW was collected from shale-oil wells in the Midland sub-basin of the Permian Basin. Molecular characterization was conducted using high-resolution solid phase micro extraction gas chromatography time-of-flight mass spectrometry. Approximately 1400 compounds were identified, and 327 compounds had a >70% library match. PW contained alkane, cyclohexane, cyclopentane, BTEX (benzene, toluene, ethylbenzene, and xylene), alkyl benzenes, propyl-benzene, and naphthalene. PW also contained heteroatomic compounds containing nitrogen, oxygen, and sulfur. 3D van Krevelen and double bond equivalence versus carbon number analyses were used to evaluate molecular variability. Source composition, as well as solubility, controlled the distribution of volatile compounds found in shale-oil PW. The salinity also increased with depth, ranging from 105 to 162 g/L total dissolved solids. These data fill a gap for shale-oil PW composition, the associated petroleomics plots provide a fingerprinting framework, and the results for the Permian shale-oil PW suggest that partial treatment of suspended solids and organics would support some beneficial uses such as onsite reuse and bio-energy production.

  14. Comparative Analysis of Fruit Metabolites and Pungency Candidate Genes Expression between Bhut Jolokia and Other Capsicum Species.

    Directory of Open Access Journals (Sweden)

    Sarpras M

    Full Text Available Bhut jolokia, commonly known as Ghost chili, a native Capsicum species found in North East India was recorded as the naturally occurring hottest chili in the world by the Guinness Book of World Records in 2006. Although few studies have reported variation in pungency content of this particular species, no study till date has reported detailed expression analysis of candidate genes involved in capsaicinoids (pungency biosynthesis pathway and other fruit metabolites. Therefore, the present study was designed to evaluate the diversity of fruit morphology, fruiting habit, capsaicinoids and other metabolite contents in 136 different genotypes mainly collected from North East India. Significant intra and inter-specific variations for fruit morphological traits, fruiting habits and 65 fruit metabolites were observed in the collected Capsicum germplasm belonging to three Capsicum species i.e., Capsicum chinense (Bhut jolokia, 63 accessions, C. frutescens (17 accessions and C. annuum (56 accessions. The pungency level, measured in Scoville Heat Unit (SHU and antioxidant activity measured by 2, 2-diphenyl-1-picrylhydrazyl (DPPH free radical scavenging assay showed maximum levels in C. chinense accessions followed by C. frutescens accessions, while C. annuum accessions showed the lowest value for both the traits. The number of different fruit metabolites detected did not vary significantly among the different species but the metabolite such as benzoic acid hydroxyl esters identified in large percentage in majority of C. annuum genotypes was totally absent in the C. chinense genotypes and sparingly present in few genotypes of C. frutescens. Significant correlations were observed between fruit metabolites capsaicin, dihydrocapsaicin, hexadecanoic acid, cyclopentane, α-tocopherol and antioxidant activity. Furthermore, comparative expression analysis (through qRT-PCR of candidate genes involved in capsaicinoid biosynthesis pathway revealed many fold higher

  15. On the density scaling of pVT data and transport properties for molecular and ionic liquids.

    Science.gov (United States)

    López, Enriqueta R; Pensado, Alfonso S; Fernández, Josefa; Harris, Kenneth R

    2012-06-07

    In this work, a general equation of state (EOS) recently derived by Grzybowski et al. [Phys. Rev. E 83, 041505 (2011)] is applied to 51 molecular and ionic liquids in order to perform density scaling of pVT data employing the scaling exponent γ(EOS). It is found that the scaling is excellent in most cases examined. γ(EOS) values range from 6.1 for ammonia to 13.3 for the ionic liquid [C(4)C(1)im][BF(4)]. These γ(EOS) values are compared with results recently reported by us [E. R. López, A. S. Pensado, M. J. P. Comuñas, A. A. H. Pádua, J. Fernández, and K. R. Harris, J. Chem. Phys. 134, 144507 (2011)] for the scaling exponent γ obtained for several different transport properties, namely, the viscosity, self-diffusion coefficient, and electrical conductivity. For the majority of the compounds examined, γ(EOS) > γ, but for hexane, heptane, octane, cyclopentane, cyclohexane, CCl(4), dimethyl carbonate, m-xylene, and decalin, γ(EOS) liquids. For viscosities and the self-diffusion coefficient-temperature ratio, we have tested the relation linking EOS and dynamic scaling parameters, proposed by Paluch et al. [J. Phys. Chem. Lett. 1, 987-992 (2010)] and Grzybowski et al. [J. Chem. Phys. 133, 161101 (2010); Phys. Rev. E 82, 013501 (2010)], that is, γ = (γ(EOS)/φ) + γ(G), where φ is the stretching parameter of the modified Avramov relation for the density scaling of a transport property, and γ(G) is the Grüneisen constant. This relationship is based on data for structural relaxation times near the glass transition temperature for seven molecular liquids, including glass formers, and a single ionic liquid. For all the compounds examined in our much larger database the ratio (γ(EOS)/φ) is actually higher than γ, with the only exceptions of propylene carbonate and 1-methylnaphthalene. Therefore, it seems the relation proposed by Paluch et al. applies only in certain cases, and is really not generally applicable to liquid transport properties such as

  16. The experimental and theoretical landscape of a new antiplatelet drug ticagrelor: Insight into supramolecular architecture directed by Csbnd H⋯F, π⋯π and Csbnd H⋯π interactions

    Science.gov (United States)

    Bojarska, Joanna; Remko, Milan; Fruziński, Andrzej; Maniukiewicz, Waldemar

    2018-02-01

    The crystal and molecular structure landscape of a new drug ticagrelor has been investigated by using experimental and theoretical approach. The structures of this cyclopentyl-triazolo-pyrimidine derivative, (1) and its DMSO solvate (2), were determined by SC-XRD at 100 K. (1) crystallizes in the orthorhombic space group P21212 with four independent molecules, while (2) belongs to the monoclinic system with the space group C2, including two ticagrelor and 0.5 DMSO molecules in the asymmetric unit. Both crystals present diverse interactions, such as: Osbnd H⋯O, Nsbnd H⋯O and Csbnd H⋯X (X = O, N, F, S). H-bonds between Ntriazolopyrimidine and sbnd OH groups of cyclopentane-1,2-diol ring connect ticagrelor molecules into dimers forming three fused rings, encoded as R22(9) and R22(10) graph-set motifs, which are further linked by Chydroxyethoxy-H⋯Fsbnd C3,4difluorophenyl into a supramolecular chain. A comparative insight into the studies of all contacts in the crystal lattices of ticagrelors and other related adenosine derivatives from the CSD was provided using Hirshfeld surface analysis. It highlights a significant difference in terms of various substituents. Notably, F⋯H/H⋯F are more meaningful than O⋯H/H⋯O and N⋯H/H⋯N H-bonds. The π⋯π stacking and Csbnd H⋯π interactions participate in a cooperative way to stabilize the supramolecular architecture. The geometry of both ticagrelor forms was optimized in the gas-phase and solvated state, using the DFT method, at the Becke 3LYP/B97D level. The theoretical results show a good agreement with those obtained from the X-ray study. Moreover, structural elucidation of a new drug was extended by 1D 1H, 13C NMR, 2D 1H, 13C HSQC NMR, FT-IR and TG/DTG techniques.

  17. Methane recovery from coal mine gas using hydrate formation in water-in-oil emulsions

    International Nuclear Information System (INIS)

    Zhong, Dong-Liang; Ding, Kun; Lu, Yi-Yu; Yan, Jin; Zhao, Wei-Long

    2016-01-01

    Highlights: • A water-in-oil emulsion was developed for CH_4 separation from coal mine methane gas. • Stable W/O emulsions were obtained with water cut in the range of (10–70%). • Gas hydrates nucleated faster with the reduction of water–oil volume ratio. • Gas uptake increased with the decrease of water–oil volume ratio. • CH_4 recovery was greatly enhanced by hydrate formation in W/O emulsions. - Abstract: In this work, a water-in-oil (W/O) emulsion was developed using liquid water, mineral oil, Sorbitan monooleate (Span 80), and cyclopentane. It was employed to enhance gas hydrate formation for CH_4 separation from a simulated coal mine methane (CMM) gas (30 mol% CH_4, 60 mol% N_2, and 10 mol% O_2). The stability test at atmospheric pressure and at a high pressure of 3.5 MPa showed that stable W/O emulsions were obtained when the water–oil volume ratio (WOR) was below 80%. The emulsified droplets size was measured with WOR ranging from 10% to 70%. Then kinetic experiments of CH_4 separation by hydrate formation in W/O emulsions were carried out at 273.6 K and (3.5–5.0) MPa in batch operation. The results indicated that water–oil volume ratio is a key factor that affects the kinetics of gas hydrate formation from the CMM gas mixture. Hydrate nucleation was observed to occur faster while WOR was decreased, and gas uptake increased significantly with the decrease of WOR. CH_4 concentration in the recovered gas mixture was increased to 52 mol% as compared to 30 mol% in the original gas mixture through one-stage hydrate formation in the W/O emulsions. It was found that the experimental conditions of 273.6 K, 3.5 MPa and WOR = 30% were favorable for CH_4 recovery from the CMM gas. The CH_4 recovery obtained under these conditions was 43%. It was higher than those obtained at WOR = 10% and 70%, and was greatly increased as compared with those obtained in the same reactor with the presence of TBAB (26%) and CP (33%).

  18. Comparative Analysis of Fruit Metabolites and Pungency Candidate Genes Expression between Bhut Jolokia and Other Capsicum Species.

    Science.gov (United States)

    M, Sarpras; Gaur, Rashmi; Sharma, Vineet; Chhapekar, Sushil Satish; Das, Jharna; Kumar, Ajay; Yadava, Satish Kumar; Nitin, Mukesh; Brahma, Vijaya; Abraham, Suresh K; Ramchiary, Nirala

    2016-01-01

    Bhut jolokia, commonly known as Ghost chili, a native Capsicum species found in North East India was recorded as the naturally occurring hottest chili in the world by the Guinness Book of World Records in 2006. Although few studies have reported variation in pungency content of this particular species, no study till date has reported detailed expression analysis of candidate genes involved in capsaicinoids (pungency) biosynthesis pathway and other fruit metabolites. Therefore, the present study was designed to evaluate the diversity of fruit morphology, fruiting habit, capsaicinoids and other metabolite contents in 136 different genotypes mainly collected from North East India. Significant intra and inter-specific variations for fruit morphological traits, fruiting habits and 65 fruit metabolites were observed in the collected Capsicum germplasm belonging to three Capsicum species i.e., Capsicum chinense (Bhut jolokia, 63 accessions), C. frutescens (17 accessions) and C. annuum (56 accessions). The pungency level, measured in Scoville Heat Unit (SHU) and antioxidant activity measured by 2, 2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging assay showed maximum levels in C. chinense accessions followed by C. frutescens accessions, while C. annuum accessions showed the lowest value for both the traits. The number of different fruit metabolites detected did not vary significantly among the different species but the metabolite such as benzoic acid hydroxyl esters identified in large percentage in majority of C. annuum genotypes was totally absent in the C. chinense genotypes and sparingly present in few genotypes of C. frutescens. Significant correlations were observed between fruit metabolites capsaicin, dihydrocapsaicin, hexadecanoic acid, cyclopentane, α-tocopherol and antioxidant activity. Furthermore, comparative expression analysis (through qRT-PCR) of candidate genes involved in capsaicinoid biosynthesis pathway revealed many fold higher expression of

  19. Public aquaria as long-term enrichments for investigating planktonic Archaea

    Science.gov (United States)

    Goldenstein, Nadine I.; Warren, Courtney E.; Lipp, Julius S.; Pagani, Mark; Hinrichs, Kai-Uwe

    2016-04-01

    archaeal intact polar and core membrane lipid composition. We detected a set of more than 90 different lipid structures comprised of diverse glyco- as well as phospho- based head groups combined with di- and tetraether cores containing up to 5 cyclopentane rings or unsaturations. The correlation of the variability within the lipid portfolio with the 30 different environmental variables, measured in the individual tanks, like e.g., water chemistry, light availability and temperature will lead to a better understanding of the factors controlling planktonic archaeal distribution in the marine environment and the derived lipid-based proxies. References: Karner et al. (2001). Nature 409, p507-510. Könneke et al. (2014). Proc Natl Acad Sci U S A 111, p8239-44. Schouten et al. (2002). Earth Planet Sci Lett 204, p265-274. Wuchter et al. (2006). Proc Natl Acad Sci U S A 103, p12317-12322. Bale et al. (2013), Biogeosciences Discuss 10, p12593-12624. Elling et al. (2014). Geochim Cosmochim Acta 141, p579-597. Elling et al. (2015). Geochim Cosmochim Acta 171, p238-255.

  20. Development of novel cycloaliphatic siloxanes for thermal and UV-curable applications

    Science.gov (United States)

    Chakraborty, Ruby

    Siloxanes have been extensively used as additives to modulate surface properties such as surface tension, hydrophobicity/hydrophobicity, and adhesion, etc. Although, polydimethyl -siloxane and polydiphenylsiloxane are the most commonly used siloxanes, the properties are at extremes in terms of glass transition temperature and flexibility. It is proposed that the ability to control the properties in between the these extremes can be provided by cycloaliphatic substitutions at the siloxane backbone. It is expected that this substitution might work due to the intermediate backbone rigidity. In order to achieve the above objectives, a synthetic route was developed to prepare cycloaliphatic (cyclopentane and cyclohexane) silane monomers followed by subsequent polymerization and functionalizations to obtain glycidyl epoxy, aliphatic amine and methacrylate telechelic siloxanes. The siloxanes were either thermally or UV-cured depending on end functionalizations. Chemical characterization of monomers, oligomers and polymers were performed using 1H, 13C, 29Si-NMR, FT-IR and GPC. The curing kinetics of photo-induced reactions were investigated through photo-differential scanning calorimetry (PDSC). The oxygen permeability, mechanical, coatings, and release properties of siloxanes were studied as a function of the backbone substitutions. The mechanical, coatings and released properties of cycloaliphatic siloxanes improved with respect to polydimethylsiloxanes. The thermal analysis of the cured films were carried out using differential scanning calorimetry (DSC). Viscoelastic properties of the cured siloxanes due to the variation of substitution at the siloxane backbone were measured using dynamic mechanical thermal analysis (DMTA). The cycloaliphatic substituted siloxanes showed an increased glass transition temperature and permeability but reduced crosslink density, conversion, and rate of curing with respect to polydimethylsiloxanes. Hybrids of siloxanes were prepared with

  1. Etude de la formation de resonances electroniques et de leur role dans la fragmentation neutre de molecules d'interet biologique

    Science.gov (United States)

    Lepage, Martin

    1998-12-01

    Cette these est presentee a la Faculte de medecine de l'Universite de Sherbrooke en vue de l'obtention du grade de Ph.D. en Radiobiologie. Elle contient des resultats experimentaux enregistres avec un spectrometre d'electrons a haute resolution. Ces resultats portent sur la formation de resonances electroniques en phase condensee et de differents canaux pour leur decroissance. En premier lieu, nous presentons des mesures d'excitations vibrationnelles de l'oxygene dilue en matrice d'argon pour des energies des electrons incidents de 1 a 20 eV. Les resultats suggerent que le temps de vie des resonances de l'oxygene est modifie par la densite d'etats d'electrons dans la bande de conduction de l'argon. Nous presentons aussi des spectres de pertes d'energie d'electrons des molecules de tetrahydrofuranne (THF) et d'acetone. Dans les deux cas, la position en energie des pertes associees aux excitations vibrationnelles est en excellent accord avec les resultats trouves dans la litterature. Les fonctions d'excitation de ces modes revelent la presence de plusieurs nouvelles resonances electroniques. Nous comparons les resonances du THF et celles de la molecule de cyclopentane en phase gazeuse. Nous proposons une origine commune aux resonances ce qui implique qu'elles ne sont pas necessairement attribuees a l'excitation des electrons non-apparies de l'oxygene du THF. Nous proposons une nouvelle methode basee sur la spectroscopie par pertes d'energie des electrons pour detecter la production de fragments neutres qui demeurent a l'interieur d'un film mince condense a basse temperature. Cette methode se base sur la detection des excitations electroniques du produit neutre. Nous presentons des resultats de la production de CO dans un film de methanol. Le taux de production de CO en fonction de l'energie incidente des electrons est calibre en termes d'une section efficace totale de diffusion des electrons. Les resultats indiquent une augmentation lineaire du taux de production de

  2. Long Island Sound Water Temperatures During the Last Two Thousand Years

    Science.gov (United States)

    Warren, C. E.; Varekamp, J. C.; Thomas, E.

    2010-12-01

    influenced by the carbonate saturation state of the water. The tetraether index (TEX86) temperature proxy is based on the number of cyclopentane rings in the glycerol dialkyl glycerol tetraethers (GDGTs) from the membrane lipids of marine Crenarchaeota, which changes in response to temperature. Crenarcheota are one of the three major groups of non-thermophilic Archaea, a widely distributed, abundant and ecologically diverse group. This proxy can be used in organic-rich sediments deposited in many different settings. We analyzed samples for TEX86 in LIS cores in order to generate a 2,000 year temperature record. We compare the TEX86 paleotemperature record data (dominantly reflecting surface water temperatures) with a Mg/Ca record based on benthic foraminifera (reflecting bottom water temperatures), and an oxygen isotope record based on benthic foraminifera and corrected for salinity changes by using the Mg/Ca record. The Mg/Ca record appears to show evidence for the Little Ice Age and Medieval Warm Period. Preliminary TEX86 data indicate that temperatures of LIS waters, as averaged over the part of the year that the proxy organisms are biologically active, generally fluctuated between 12-14°C.

  3. Branched tetraether membrane lipids: A versatile group of molecular fossils as testimony of past climate change (Outstanding Young Scientist Lecture)

    Science.gov (United States)

    Weijers, J. W. H.

    2009-04-01

    Studying fossils of any kind provides a small window into past times and could learn us why the world around us is as it is today (and might become in the near future). Like paleontologists studying bone remains and palaeobotanists studying fossil plant remains, many organic geochemists study fossil molecules to learn about geochemical cycles, evolution, ecology and climate. Branched Glycerol Dialkyl Glycerol Tetraether (GDGT) membrane lipids are an example of such molecular fossils and have been the core subject of my research. These molecules were initially detected a decade ago in near coastal marine sediments and structurally resemble isoprenoid GDGTs, a group of membrane lipids synthesised by Archaea, a Domain of life separate from Bacteria and Eukarya. With nuclear magnetic resonance techniques we showed, however, that branched GDGTs are of bacterial rather than archaeal origin and analysis of soils, peat bogs and marine surface sediments pointed to a terrestrial origin. As isoprenoid GDGTs are mainly produced by marine archaea the ratio between the two groups, the Branched vs. Isoprenoid Tetraether (BIT) index, could be used to trace the input of soil organic matter into marine sediments. In this lecture I will provide examples of applications of this BIT index in the Channel River during the last Glacial Maximum and the Congo deep sea fan over the last deglaciation. Meanwhile, it appeared that in soils the distribution of individual branched GDGTs, which differ in their content of methyl branches and cyclopentane rings, was different from place to place. Analysis of over 100 soils at different locations revealed that the distribution of the branched GDGTs is most strongly related to both soil pH and annual mean air temperature. This is explained by the fact that bacteria have to adapt the composition of their cell membrane to ambient conditions in order to keep it properly functioning. This empirical relation opened opportunities to reconstruct past annual

  4. Conversion of medium and low temperature heat to power

    Science.gov (United States)

    Fischer, Johann; Wendland, Martin; Lai, Ngoc Anh

    2013-04-01

    improvement. Presently, the best feasible systems seem to be ORC cycles using WF with a nearly vertical dew line in the T,s-diagram as HFO-1234yf, n-butane or cyclopentane and upper pressures close below or above (sORC) the critical pressure. Finally, we will consider the above cycles also with mixtures as WF including the Kalina cycle and coupled processes like cascade or multistage processes. [1] B Saleh, G Koglbauer, M Wendland, J Fischer, Working fluids for low temperature ORC-processes, Energy 32, 1210-21 (2007). [2] N A Lai, J Fischer, Efficiencies of Power Flash Cycles, Energy 44, 1017-27 (2012). [3] T Ho, S S Mao, R Greif, Comparison of the Organic Flash Cycle (OFC) to other advanced vapor cycles for intermediate and high temperature waste heat reclamation and solar thermal energy, Energy 42, 213-23 (2012).

  5. Novel Carbon (C)-Boron (B)-Nitrogen (N)-Containing H2 Storage Materials

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shih-Yuan [Boston College, Chestnut Hill, MA (United States); Giustra, Zachary X. [Boston College, Chestnut Hill, MA (United States); Autrey, Tom [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Univ. of Alabama, Tuscaloosa, AL (United States); Osenar, Paul [Protonex Technology Corporation, Southborough, MA (United States)

    2017-09-20

    The following summarizes the research conducted for DOE project DE-EE0005658 “Novel Carbon(C)-Boron(B)-Nitrogen(N)-Containing H2 Storage Materials”. This work focused in part on the continued study of two materials identified from the preceding project DE-FG360GO18143 (“Hydrogen Storage by Novel CBN Heterocycle Materials”) as lead candidates to meet the DOE technical targets for either vehicular or non-automotive hydrogen storage applications. Specifically, a room-temperature liquid, 3-methyl-1,2-cyclopentane (B), and a high H2 capacity solid, 1,2-BN-cyclohexane (J), were selected for further characterization and performance optimization. In addition to these compounds, the current project also aimed to prepare several new materials predicted to be disposed towards direct reversibility of H2 release and uptake, a feature deemed critical to achieving efficient recycling of spent fuel end products. To assist in the rational design of these and other next-generation materials, this project undertook to investigate the mechanism of hydrogen release from established compounds (mainly B and J) using a combined experimental/computational approach. Among this project’s signature accomplishments, the preliminary synthetic route to B was optimized for production on decagram scale. With such quantities of material available, its performance in powering an actual 30 W proton exchange membrane (PEM) fuel cell stack was tested and found to be identical to that of facility H2. Despite this positive proof-of-concept achievement, however, further consideration of neat B as a potential hydrogen storage material was abandoned due to evidence of thermal instability. Specifically, mass spectrometry-coupled thermogravimetric analysis (TGA-MS) revealed significant H2 release from B to initiate at 50 °C, well below the 60 °C minimum threshold set by the DOE. This result prompted a more extensive investigation in the decomposition mechanism of B vis-à-vis that of J, which