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Sample records for acetylene inhibition technique

  1. Inhibition of alkylbenzene biodegradation under denitrifying conditions by using the acetylene block technique.

    PubMed Central

    Hutchins, S R

    1992-01-01

    Addition of acetylene to microcosms simultaneously amended with nitrate and alkylbenzenes resulted in inhibition of the rate of alkylbenzene biodegradation under denitrifying conditions. Toluene, xylenes, and 1,2,4-trimethylbenzene were recalcitrant, whereas ethylbenzene was degraded at a slower rate than usual. Benzene was not degraded in either case. Addition of acetylene to microcosms preexposed to nitrate and alkylbenzenes produced similar inhibition. These data indicate that the activities of microorganisms that degrade alkylbenzenes under denitrifying conditions may be suppressed if the standard acetylene block technique is used to verify denitrifying activity. PMID:1444371

  2. Theoretical and practical limitations of the acetylene inhibition technique to determine total denitrification losses

    NASA Astrophysics Data System (ADS)

    Felber, R.; Conen, F.; Flechard, C. R.; Neftel, A.

    2012-10-01

    The loss of N2 from intensively managed agro-ecosystems is an important part of the N budget. Flux monitoring of N2 emissions at the field scale, e.g., by eddy correlation or aerodynamic gradient method, is impossible due to the large atmospheric N2 background (78%). The acetylene (C2H2) inhibition technique (AIT) is a rather simple and frequently used, albeit imperfect, method to determine N2 losses from intact soil cores. In principle, AIT allows an estimation of total denitrification at high temporal resolution and on small spatial scales, with limited workload and costs involved. To investigate its potential and limitations, a laboratory system with two different detection systems (photoacoustic IR spectroscopy and gas chromatography) is presented, which allowed simultaneous measurements of up to 7 intact soil cores in air-tight glass tubes in a temperature controlled cabinet (adjusted to field conditions) with automated C2H2 injection. A survey of total denitrification losses (N2 + N2O) over 1.5 yr in soil cores from an intensively managed, cut grassland system in central Switzerland supports previous reports on severe limitations of the AIT, which precluded reliable estimates of total denitrification losses. Further, the unavoidable sampling and transfer of soil samples to the laboratory causes unpredictable deviations from the denitrification activity in the field.

  3. The acetylene inhibition technique to determine total denitrification (N2 + N2O) losses from soil samples: potentials and limitations

    NASA Astrophysics Data System (ADS)

    Felber, R.; Conen, F.; Flechard, C. R.; Neftel, A.

    2012-03-01

    The loss of N2 from intensively managed agro-ecosystems is an important part of the N budget. The monitoring of N2 emissions at the field scale is impossible due to the high atmospheric background of 78%, which precludes the measurement of fluxes. The acetylene (C2H2) inhibition technique is a rather simple, albeit imperfect, method to determine N2 losses from entire soil cores. Despites serious limitations it is one among very few methodological options to estimate total denitrification at high temporal resolution and on small spatial scale, with limited workload and costs involved. A laboratory system with two different detection systems (photoacoustic IR spectroscopy and gas chromatography) is presented, which allowed parallel measurements of up to 7 intact soil cores in air-tight glass tubes in a temperature controlled cabinet (adjusted to field conditions) with an automated C2H2 injection. A survey of total denitrification losses (N2 + N2O) over 1.5 yr in soil from an intensively managed, cut grassland system in central Switzerland showed a lower bound loss in the range of 6 to 25 kg N ha-1 yr-1 (3-13% of added N), roughly 3.4 times higher than the N2O loss. However, several drawbacks of the C2H2 inhibition technique preclude a more precise determination of the total denitrification loss.

  4. Inhibiting the combustion of air-acetylene mixtures

    NASA Astrophysics Data System (ADS)

    Kopylov, S. N.; Gubina, T. V.

    2016-01-01

    The effect propane, methane, and a mixture of 18 vol % C3H6-40 vol % C3H8-42 vol % C4H10 have on the combustion of air-acetylene mixtures is investigated experimentally. The upper concentration limit of flame propagation, maximum explosion pressure, and maximum rate of rise of explosion pressure are determined. It is found that propane and a mixture of 18 vol % C3H6-40 vol % C3H8-42 vol % C4H10 are strong inhibitors of combustion of acetylene in its concentration ranges of 2-8 vol %. The inhibition effect becomes weaker as the acetylene content in the mixture increases. It disappears completely at C2H2 concentrations exceeding 15 vol %. The above experimental findings are explained using the proposed scheme of acetylene oxidation.

  5. Aquatic acetylene-reduction techniques: solutions to several problems.

    PubMed

    Flett, R J; Hamilton, R D; Campbell, N E

    1976-01-01

    Previous methods of performing aquatic acetylene-reduction assays are described and several problems associated with them are discussed. A refinement of these older techniques is introduced and problems that it overcomes are also discussed. A depth profile of nitrogen fixation (C2H4 production), obtained by the refined technique, is shown for a fertilized Canadian Shield lake in the Experimental Lakes Area of northwestern Ontario. PMID:814983

  6. Application of the 15N gas-flux method for measuring in situ N2 and N2O fluxes due to denitrification in natural and semi-natural terrestrial ecosystems and comparison with the acetylene inhibition technique

    NASA Astrophysics Data System (ADS)

    Sgouridis, Fotis; Stott, Andrew; Ullah, Sami

    2016-03-01

    Soil denitrification is considered the most un-constrained process in the global N cycle due to uncertain in situ N2 flux measurements, particularly in natural and semi-natural terrestrial ecosystems. 15N tracer approaches can provide in situ measurements of both N2 and N2O simultaneously, but their use has been limited to fertilized agro-ecosystems due to the need for large 15N additions in order to detect 15N2 production against the high atmospheric N2. For 15N-N2 analyses, we have used an "in-house" laboratory designed and manufactured N2 preparation instrument which can be interfaced to any commercial continuous flow isotope ratio mass spectrometer (CF-IRMS). The N2 prep unit has gas purification steps and a copper-based reduction furnace, and allows the analysis of small gas injection volumes (4 µL) for 15N-N2 analysis. For the analysis of N2O, an automated Tracegas Preconcentrator (Isoprime Ltd) coupled to an IRMS was used to measure the 15N-N2O (4 mL gas injection volume). Consequently, the coefficient of variation for the determination of isotope ratios for N2 in air and in standard N2O (0.5 ppm) was better than 0.5 %. The 15N gas-flux method was adapted for application in natural and semi-natural land use types (peatlands, forests, and grasslands) by lowering the 15N tracer application rate to 0.04-0.5 kg 15N ha-1. The minimum detectable flux rates were 4 µg N m-2 h-1 and 0.2 ng N m-2 h-1 for the N2 and N2O fluxes respectively. Total denitrification rates measured by the acetylene inhibition technique in the same land use types correlated (r = 0.58) with the denitrification rates measured under the 15N gas-flux method, but were underestimated by a factor of 4, and this was partially attributed to the incomplete inhibition of N2O reduction to N2, under a relatively high soil moisture content, and/or the catalytic NO decomposition in the presence of acetylene. Even though relatively robust for in situ denitrification measurements, methodological

  7. Application of the 15N-Gas Flux method for measuring in situ N2 and N2O fluxes due to denitrification in natural and semi-natural terrestrial ecosystems and comparison with the acetylene inhibition technique

    NASA Astrophysics Data System (ADS)

    Sgouridis, F.; Ullah, S.; Stott, A.

    2015-08-01

    Soil denitrification is considered the most un-constrained process in the global N cycle due to uncertain in situ N2 flux measurements, particularly in natural and semi-natural terrestrial ecosystems. 15N tracer approaches can provide in situ measurements of both N2 and N2O simultaneously, but their use has been limited to fertilised agro-ecosystems due to the need for large 15N additions in order to detect 15N2 production against the high atmospheric N2. For 15N-N2 analyses, we have used an "in house" laboratory designed and manufactured N2 preparation instrument which can be interfaced to any commercial continuous flow isotope ratio mass spectrometer (CF-IRMS). The N2 prep unit has gas purification steps, a copper based reduction furnace, and allows the analysis of small gas injection volumes (4 μL) for 15N-N2 analysis. For the analysis of N2O, an automated Tracegas Pre-concentrator (Isoprime Ltd) coupled to an IRMS was used to measure the 15N-N2O (4 mL gas injection volume). Consequently, the coefficient of variation for the determination of isotope ratios for N2 in air and in standard N2O (0.5 ppm) was better than 0.5 %. The 15N Gas-Flux method was adapted for application in natural and semi-natural land use types (peatlands, forests and grasslands) by lowering the 15N tracer application rate to 0.04-0.5 kg 15N ha-1. For our chamber design (volume / surface = 8:1) and a 20 h incubation period, the minimum detectable flux rates were 4 μg N m-2 h-1 and 0.2 ng N m-2 h-1 for the N2 and N2O fluxes respectively. The N2 flux ranged between 2.4 and 416.6 μg N m-2 h-1, and the grassland soils showed on average 3 and 14 times higher denitrification rates than the woodland and organic soils respectively. The N2O flux was on average 20 to 200 times lower than the N2 flux, while the denitrification product ratio (N2O/N2 + N2O) was low, ranging between 0.03 and 13 %. Total denitrification rates measured by the acetylene inhibition technique under the same field conditions

  8. Effects of sulfide and low redox potential on the inhibition of nitrous oxide reduction by acetylene in Pseudomonas nautica.

    PubMed

    Jensen, K M; Cox, R P

    1992-09-01

    Membrane introduction mass spectrometry was used to investigate the inhibitory effect of acetylene on the nitrous oxide reductase activity of intact cells of Pseudomonas nautica. We studied the effects of the concentrations of nitrate and sulfide, and the redox potential, which have all been implicated in causing a decrease in the inhibitory effects of acetylene during measurements of denitrification in natural environments. There was no evidence that the concentration of nitrate influenced the effect of acetylene. Lowering the redox potential with the reductant Ti(III)-nitrilotriacetate caused a slight alleviation of acetylene inhibition. Much greater effects at the same redox potential were obtained with concentrations of sulfide in the range 1-10 microM. PMID:1526461

  9. Stereoselective inhibition of muscarinic receptor subtypes by the enantiomers of hexahydro-difenidol and acetylenic analogues.

    PubMed Central

    Feifel, R.; Wagner-Röder, M.; Strohmann, C.; Tacke, R.; Waelbroeck, M.; Christophe, J.; Mutschler, E.; Lambrecht, G.

    1990-01-01

    1. The affinities of the (R)- and (S)-enantiomers of hexahydro-difenidol (1) and its acetylenic analogues hexbutinol (2), hexbutinol methiodide (3) and p-fluoro-hexbutinol (4) (stereochemical purity greater than 99.8%) for muscarinic receptors in rabbit vas deferens (M1), guinea-pig atria (M2) and guinea-pig ileum (M3) were measured by dose-ratio experiments. 2. The (R)-enantiomers consistently showed higher affinities than the (S)-isomers. The stereoselectivity ratios [(R)/(S)] were greatest with the enantiomers of 1 (vas deferens: 550; ileum: 191; atria: 17) and least with those of the p-Fluoro-analogue 4 (vas deferens: 34; ileum: 8.5; atria: 1.7). 3. The enantiomeric potency ratios for compounds 1-4 were highest in rabbit vas deferens, intermediate in guinea-pig ileum and much less in guinea-pig atria. Thus, these ratios may serve as a predictor of muscarinic receptor subtype identity. 4. (S)-p-Fluoro-hexbutinol [(S)-4] showed a novel receptor selectivity profile with preference for M3 receptors: M3 greater than M2 greater than or equal to M1. 5. These results do not conform to Pfeiffer's rule that activity differences between enantiomers are greater with more potent compounds. PMID:2331578

  10. Hydrogenase activity in Azospirillum brasilense is inhibited by nitrite, nitric oxide, carbon monoxide, and acetylene

    SciTech Connect

    Tibelius, K.H.; Knowles, R.

    1984-10-01

    Nitrite, NO, CO, and C/sub 2/H/sub 2/ inhibited O/sub 2/-dependent H/sub 2/ uptake (H/sup 3/H oxidation) in denitrifying Azospirillum brasilense Sp7 grown anaerobically on N/sub 2/O or NO/sub 3//sup -/. The apparent K/sub i/ values for inhibition of O/sub 2/-dependent H/sub 2/ uptake were 20 ..mu..M for NO/sub 2//sup -/, 0.4 ..mu..M for NO, 28 ..mu..M for CO, and 88 ..mu..M for C/sub 2/H/sub 2/. These inhibitors also affected methylene blue-dependent H/sub 2/ uptake, presumably by acting directly on the hydrogenase. Nitrite and NO inhibited H/sub 2/ uptake irreversibly, whereas inhibition due to CO was easily reversed by repeatedly evacuating and backfilling with N/sub 2/. The C/sub 2/H/sub 2/ inhibition was not readily reversed, partly due to difficulty in removing the last traces of this gas from solution. The NO/sub 2//sup -/ inhibition of malate-dependent respiration was readily reversed by repeatedly washing the cells, in contrast to the effect of NO/sub 2//sup -/ on H/sub 2/-dependent respiration. These results suggest that the low hydrogenase activities observed in NO/sub 3//sup -/-grown cultures of A. brasilense may be due to the irreversible inhibition of hydrogenase by NO/sub 2//sup -/ and NO produced by NO/sub 3//sup -/ reduction.

  11. Acetylene inhibition of N2O reduction in laboratory soil and groundwater denitrification assays: evaluation by 15N tracer and 15N site preference of N2O

    NASA Astrophysics Data System (ADS)

    Weymann, Daniel; Well, Reinhard; Lewicka-Szczebak, Dominika; Lena, Rohe

    2013-04-01

    The measurement of denitrification in soils and aquifers is still challenging and often enough associated with considerable experimental effort and high costs. Against this background, the acetylene inhibition technique (AIT) applied in laboratory soil and groundwater denitrification assays is by far the most effective approach. However, this method has been largely criticized, as it is susceptible to underestimate denitrification rates and adds an additional carbon source to the substrates to be investigated. Here we provide evidence that the AIT is not necessarily an inappropriate approach to measure denitrification, that its reliability depends on the drivers governing the process, and that the 15N site preference of N2O (SP) may serve as a tool to assess this reliability. Two laboratory batch experiments were conducted, where sandy aquifer material and a peat soil were incubated as slurries. We established (i) a standard anaerobic treatment by adding KNO3 (10 mg N L-1), (ii) an oxygen treatment by adding KNO3 and O2 (5 mg L-1), and (iii) a glucose treatment by adding KNO3 supplemented with glucose (200 mg C L-1). Both experiments were run under 10 % (v/v) acetylene atmosphere and as 15N tracer treatments using labeled K15NO3 (60 atom % 15N). In the case of the standard anaerobic treatments, we found a very good agreement of denitrification potential obtained by the AIT and 15N tracer methods. SP of N2O of the AIT samples from this treatment ranged between -4.8 and 2.6 ‰ which is indicative for N2O production during bacterial denitrification but not for N2O reduction to N2. In contrast, we observed substantial underestimation of denitrification by AIT for the glucose treatments compared to the 15N method, i.e. denitrification was underestimated by 36 % (sandy aquifer material) and 47 % (peat soil). SP of N2O of the AIT samples from this treatment ranged between 4.5 and 9.6 ‰, which suggests occurrence of bacterial N2O reduction. In the case of the oxygen

  12. Effect of Acetylene on Root Respiration and Acetylene Reducing Activity in Nodulated Soya Bean

    PubMed Central

    Gerbaud, Alain

    1990-01-01

    Acetylene decreased root and nodule respiration, as measured by CO2 evolution of nodulated or non-nodulated Glycine max. An inhibition of 25 to 35% in 15 to 30 minutes occurred when 13% C2H2 was introduced in the gas flux which aerated the root nutrient solution. When the light intensity was doubled to 800 microeinsteins per square meter per second, the inhibition increased to 50% and nodule acetylene reduction activity was inhibited 50%. Images Figure 1 PMID:16667582

  13. Properties of acetylene

    SciTech Connect

    Pavlovcak, J.T.

    1994-12-31

    Acetylene continues to be the most widely used fuel in the oxyfuel cutting and welding industry. It displays properties that enhance its benefits to the industry, but at the same time, present potential hazards that have to be addressed. The presentation explores the main properties or characteristics of acetylene -- odor, toxicity, flammability, composition, and manufacture. it expands on those properties that are unique to acetylene and which account for its main value to the user or which constitute the chief concern for safe use of acetylene. The presentation explains characteristics such as anosmia, flammable or explosive range, ignition energy, autoignition temperature, and flame temperature, comparing these values for acetylene to other common gaseous fuels. it explains the unique property of acetylene to decompose explosively in the absence of air or oxygen. The toxicological aspects of acetylene is discussed, including anesthetic effect and simple asphyxiant, showing the increasing severity of symptoms to increasing levels of oxygen deficiency. The main value of this basic review of the properties of acetylene is to remind people of the benefits of acetylene due to its unique properties, and to realert them to the potential hazards that also have to be addressed to control the properties of acetylene.

  14. Acetylenic carbon allotrope

    SciTech Connect

    1999-11-16

    A fourth allotrope of carbon, an acetylenic carbon allotrope, is described. The acetylenic carbon allotropes of the present invention are more soluble than the other known carbon allotropes in many common organic solvents and possesses other desirable characteristics, e.g. high electron density, ability to burn cleanly, and electrical conductive properties. Many uses for this fourth allotrope are described herein.

  15. Acetylenic carbon allotrope

    DOEpatents

    Lagow, Richard J.

    1999-01-01

    A fourth allotrope of carbon, an acetylenic carbon allotrope, is described. The acetylenic carbon allotropes of the present invention are more soluble than the other known carbon allotropes in many common organic solvents and possesses other desirable characteristics, e.g. high electron density, ability to burn cleanly, and electrical conductive properties. Many uses for this fourth allotrope are described herein.

  16. Acetylenic carbon allotrope

    DOEpatents

    Lagow, Richard J.

    1998-01-01

    A fourth allotrope of carbon, an acetylenic carbon allotrope, is described. The acetylenic carbon allotropes of the present invention are more soluble than the other known carbon allotropes in many common organic solvents and possesses other desirable characteristics, e.g. high electron density, ability to burn cleanly, and electrical conductive properties. Many uses for this fourth allotrope are described herein.

  17. Acetylenic carbon allotrope

    DOEpatents

    Lagow, R.J.

    1998-02-10

    A fourth allotrope of carbon, an acetylenic carbon allotrope, is described. The acetylenic carbon allotropes of the present invention are more soluble than the other known carbon allotropes in many common organic solvents and possesses other desirable characteristics, e.g. high electron density, ability to burn cleanly, and electrical conductive properties. Many uses for this fourth allotrope are described herein. 17 figs.

  18. Acetylene is an active-site-directed, slow-binding, reversible inhibitor of Azotobacter vinelandii hydrogenase

    SciTech Connect

    Hyman, M.R.; Arp, D.J.

    1987-10-06

    The inhibition of purified and membrane-bound hydrogenase from Azotobacter vinelandii by dihydrogen-free acetylene was investigated. The inhibition was a time-dependent process which exhibited first-order kinetics. Both H/sub 2/ and CO protected against the inhibition by acetylene. K/sub protect(app)/ values of 0.41 and 24 ..mu..M were derived for these gases, respectively. Both H/sub 2/-oxidizing activity and the tritium exchange capacity of the purified enzyme were inhibited at the same rate by acetylene. Removal of acetylene reversed the inhibition for both the purified and the membrane-associated form of the enzyme. The purified hydrogenases from both Rhizobium japonicum and Alcaligenes eutrophus H16 were also inhibited by acetylene in a time-dependent fashion. These findings suggest that acetylene is an active-site-directed, slow-binding, reversible inhibitor of some membrane-bound hydrogenases from aerobic bacteria.

  19. Vapor pressures of acetylene at low temperatures

    NASA Technical Reports Server (NTRS)

    Masterson, C. M.; Allen, John E., Jr.; Kraus, G. F.; Khanna, R. K.

    1990-01-01

    The atmospheres of many of the outer planets and their satellites contain a large number of hydrocarbon species. In particular, acetylene (C2H2) has been identified at Jupiter, Saturn and its satellite Titan, Uranus and Neptune. In the lower atmospheres of these planets, where colder temperatures prevail, the condensation and/or freezing of acetylene is probable. In order to obtain accurate models of the acetylene in these atmospheres, it is necessary to have a complete understanding of its vapor pressures at low temperatures. Vapor pressures at low temperatures for acetylene are being determined. The vapor pressures are measured with two different techniques in order to cover a wide range of temperatures and pressures. In the first, the acetylene is placed in a sample tube which is immersed in a low temperature solvent/liquid nitrogen slush bath whose temperature is measured with a thermocouple. The vapor pressure is then measured directly with a capacitance manometer. For lower pressures, a second technique which was called the thin-film infrared method (TFIR) was developed. It involves measuring the disappearance rate of a thin film of acetylene at a particular temperature. The spectra are then analyzed using previously determined extinction coefficient values, to determine the disappearance rate R (where R = delta n/delta t, the number of molecules that disappear per unit time). This can be related to the vapor pressure directly. This technique facilitates measurement of the lower temperatures and pressures. Both techniques have been calibrated using CO2, and have shown good agreement with the existing literature data.

  20. Acylamidation of acetylenes

    SciTech Connect

    Gridnev, I.D.; Balenkova, E.S.

    1989-01-10

    The reactions of phenylacetylene, 1-heptyne, and diphenylacetylene with the complexes of acetylfluoroborate with acetonitrile and with chloroacetonitrile take place regiospecifically and stereospecifically as syn-addition of the acetyl group and nitrile at the triple bond of the acetylene and lead to previously unknown Z-N-acyl-/beta/-amino, /alpha/,/beta/-unsaturated ketones.

  1. Acetylene terminated matrix resins

    NASA Technical Reports Server (NTRS)

    Goldfarb, I. J.; Lee, Y. C.; Arnold, F. E.; Helminiak, T. E.

    1985-01-01

    The synthesis of resins with terminal acetylene groups has provided a promising technology to yield high performance structural materials. Because these resins cure through an addition reaction, no volatile by-products are produced during the processing. The cured products have high thermal stability and good properties retention after exposure to humidity. Resins with a wide variety of different chemical structures between the terminal acetylene groups are synthesized and their mechanical properties studied. The ability of the acetylene cured polymers to give good mechanical properties is demonstrated by the resins with quinoxaline structures. Processibility of these resins can be manipulated by varying the chain length between the acetylene groups or by blending in different amounts of reactive deluents. Processing conditions similar to the state-of-the-art epoxy can be attained by using backbone structures like ether-sulfone or bis-phenol-A. The wide range of mechanical properties and processing conditions attainable by this class of resins should allow them to be used in a wide variety of applications.

  2. Anaerobic oxidation of acetylene by estuarine sediments and enrichment cultures

    USGS Publications Warehouse

    Culbertson, Charles W.; Zehnder, Alexander J. B.; Oremland, Ronald S.

    1981-01-01

    Acetylene disappeared from the gas phase of anaerobically incubated estuarine sediment slurries, and loss was accompanied by increased levels of carbon dioxide. Acetylene loss was inhibited by chloramphenicol, air, and autoclaving. Addition of 14C2H2 to slurries resulted in the formation of 14CO2 and the transient appearance of 14C-soluble intermediates, of which acetate was a major component. Acetylene oxidation stimulated sulfate reduction; however, sulfate reduction was not required for the loss of C2H2 to occur. Enrichment cultures were obtained which grew anaerobically at the expense of C2H2.

  3. Acetylene-Terminated Polyimide Siloxanes

    NASA Technical Reports Server (NTRS)

    St. Clair, Terry L.; Maudgal, Shubba

    1987-01-01

    Siloxane-containing addition polyimides yield toughened high-temperature adhesives and matrix resins. Addition polyimide made by reaction of aromatic tetracarboxylic acid dianhydride with aromatic diamine in presence of ethynyl-substituted aromatic monoamine. Acetylene-terminated siloxane imide cured by heating to yield acetylene-terminated polyimide siloxane.

  4. Decreased alanine aminotransferase activity in serum of man during gamma-acetylenic-GABA treatment.

    PubMed

    Olsen, R; Hørder, M

    1980-06-01

    Decreasing concentrations of alanine aminotransferase were observed in nine patients receiving gamma-acetylenic-GABA, an inhibitor of GABA aminotransferase. In vitro studies showed that preincubation at 37 degrees C of serum with gamma-acetylenic-GABA and with urine from a patient receiving the drug led to inhibition of alanine aminotransferase. This inhibition of alanine aminotransferase by gamma-acetylenic-GABA was neutralized by 1-analine, the natural substrate for the enzyme. The mechanism of inhibition may be a competition between the drug and 1-alanine for the substrate binding site of the enzyme. PMID:7414257

  5. Pleomorphism and acetylene-reducing activity of free-living rhizobia.

    PubMed Central

    Kaneshiro, T; Baker, F L; Johnson, D E

    1983-01-01

    Cowpea-type Rhizobium sp. strain 32H1 and Rhizobium japonicum USDA 26 and 110 grown on a glutamate-mannitol-gluconate agar medium showed increases in the number of pleomorphic cells coincident with their acetylene-reducing activity. Pleomorphs appeared to be inhibited in growth nonuniformly, because acetylene-reducing cultures were mixtures of rod, branched (V, Y, and T), and other irregularly shaped cells. In contrast, strain USDA 10 consistently failed to reduce acetylene, even though it also could grow and yield pleomorphic cells under various conditions. With minimal inhibitory supplements (5 micrograms per ml of medium) of nalidixic acid and novobiocin as cell division inhibitors, an increase in pleomorphic cells was observed, but the inhibited cultures displayed lower acetylene-reducing activity. A study of pleomorphic cells derived in different ways indicated that not all pleomorphs reduce acetylene. Images PMID:6822472

  6. Research in acetylene containing monomers

    NASA Technical Reports Server (NTRS)

    Ogliaruso, M. A.

    1976-01-01

    The preparation of precursor bisbenzils with pendant acetylene linkages for use in the synthesis of new aromatic poly (phenyl quinoxalines) was investigated. Attempts to condense para, para prime-dibromo benzil and potassium acetylide in liquid ammonia and in toluene, to prepare 4-phenyl acetyl phenyl ether, 4-(paraacetylphenyl) acetyl phenyl ether, 4-phenyl acetyl-4 primeacetyl phenyl acetyl phenyl ether, the reaction of 4-phenyl acetyl phenyl ether with Villsmeier reagent to prepare 4-(beta-chloro cinnamaldehyde) phenyl ether, the reaction of 4-(para-acetyl phenyl) acetyl phenyl ether with Villsmeier reagent, and the oxidation of bibenzil to prepare benzil are described. The reactions of phenyl acetylene with oxidizing agent, of phenyl acetylene with bromine, of 1,1,2,2-tetrabromo ethyl benzene with zinc and with oxidizing agent are described.

  7. The adaptive control system of acetylene generator

    NASA Astrophysics Data System (ADS)

    Kovaliuk, D. O.; Kovaliuk, Oleg; Burlibay, Aron; Gromaszek, Konrad

    2015-12-01

    The method of acetylene production in acetylene generator was analyzed. It was found that impossible to provide the desired process characteristics by the PID-controller. The adaptive control system of acetylene generator was developed. The proposed system combines the classic controller and fuzzy subsystem for controller parameters tuning.

  8. Mechanism-based inactivation of benzo(a)pyrene hydroxylase by aryl acetylenes and aryl olefins

    SciTech Connect

    Gan, L.S.; Lu, J.Y.L.; Alworth, W.L.

    1986-05-01

    A series of aryl acetylenes and aryl olefins have been examined as substrates and inhibitors of cytochrome P-450 dependent monooxgenases in liver microsomes from 5,6-benzoflavone or phenobarbital pretreated rats. 1-Ethynylpyrene, 3-ethynylperylene, 2-ethynylfluorene, methyl 1-pyrenyl acetylene, cis- and trans-1-(2-bromovinyl)pyrene, and 1-allylpyrene serve as mechanism-based irreversible inactivators (suicide inhibitors) of benzo(a)pyrene hydroxylase, while 1-vinylpyrene and phenyl 1-pyrenyl acetylene do not cause a detectable suicide inhibition of benzo(a)pyrene hydroxylase. The mechanism-based loss of benzo(a)pyrene hydroxylase caused by the aryl acetylenes is not accompanied by a corresponding loss of the P-450 content of the microsomes (suicide destruction). The suicide inhibition by these aryl acetylenes therefore does not involve covalent binding to the heme moiety of the monooxygenase. Nevertheless, in the presence of NADPH, /sup 3/H-labeled 1-ethynylpyrene becomes covalently attached to the cytochrome P-450 protein; the measured stoichiometry of binding is one 1-ethynylpyrene per P-450 heme unit. The authors conclude that the inhibition of benzo(a)pyrene hydroxylase produced by 1-ethynylpyrene may be related to the mechanism of suicide inhibition of P-450 activity by chloramphenicol rather than the mechanism of suicide destruction of P-450 previously described for acetylene and propyne.

  9. Pressure-induced Polymerization in Substituted Acetylenes

    NASA Astrophysics Data System (ADS)

    Chellappa, Raja; Dattelbaum, Dana; Sheffield, Stephen; Robbins, David

    2011-06-01

    A fundamental understanding of shock-induced chemical reactions in organics is still lacking and there are limited studies devoted to determining reaction mechanisms, evolution of bonding, and effect of functional group substitutions. The fast timescale of reactions occurring during shock compression create significant experimental challenges (diagnostics) to fully quantify the mechanisms involved. Static compression provides a complementary route to investigate the equilibrium phase space and metastable intermediates during high pressure chemistry, although at a much slower timescale. In this study, we present our results from our ongoing high pressure in situ synchrotron x-ray diffraction and vibrational spectroscopy experiments on substituted acetylenes: tert-butyl acetylene [TBA: (CH3)3 -C ≡CH] and ethynyl trimethylsilane [ETMS: (CH3)3 -Si ≡CH]. We observed that the onset pressure of chemical reactions (at room temperature) in these compounds is significantly higher in static compression (TBA: 11 GPa and ETMS: 26 GPa) when compared to shock input pressures (TBA: 6.1 GPa and ETMS: 6.6 GPa). The products were polymeric in nature, recovered to ambient conditions with little degradation and fully characterized using spectroscopy, calorimetry, and other techniques to identify reaction mechanisms. LDRD-DR (PI: Dana Dattelbaum)

  10. Acetylene-terminated polyimide adhesives

    NASA Technical Reports Server (NTRS)

    Hanky, A. O.

    1983-01-01

    The nadic-encapped LARC-13 addition polyimide exhibits excellent flow, is easy to process, and can be utilized for short terms at temperatures up to 593 C. It retains good lap shear strength as an adhesive for titanium after aging in air up to 125 hours at 316 C; but lap shear strength degrades with longer exposures at that temperature. Thermid 600, an addition polyimide that is acetylene encapped, exhibits thermomechanical properties even after long term exposure in at air at 316 C. An inherent drawback of this system is that it has a narrow processing window. An acetylene encapped, addition polyimide which is a hybrid of these two systems was developed. It has good retention of strength after long term aging and is easily processed. The synthesis and characterization of various molecular weight oligomers of this system are discussed as well as the bonding, aging, and testing of lap shear adhesive samples.

  11. Acetylene-terminated polyimide adhesives

    NASA Technical Reports Server (NTRS)

    Hanky, A. O.; St. Clair, T. L.

    1983-01-01

    The nadic-encapped LARC-43 addition polyimide exhibits excellent flow, is easy to process, and can be utilized for short terms at temperatures up to 593 C. It retains good lap shear strength as an adhesive for titanium after aging in air up to 125 hours at 316 C; but lap shear strength degrades with longer exposures at that temperature. Thermid 600, an addition polyimide that is acetylene encapped, exhibits thermomechanical properties even after long term exposure in at air at 316 C. An inherent drawback of this system is that it has a narrow processing window. An acetylene encapped, addition polyimide which is a hybrid of these two systems was developed. It has good retention of strength after long term aging and is easily processed. The synthesis and characterization of various molecular weight oligomers of this system are discussed as well as the bonding, aging, and testing of lap shear adhesive samples. Previously announced in STAR as N83-18910

  12. Thermal Conversion of Methane to Acetylene

    SciTech Connect

    Fincke, James Russell; Anderson, Raymond Paul; Hyde, Timothy Allen; Wright, Randy Ben; Bewley, Randy Lee; Haggard, Delon C; Swank, William David

    2000-01-01

    This report describes the experimental demonstration of a process for the direct thermal conversion of methane to acetylene. The process utilizes a thermal plasma heat source to dissociation products react to form a mixture of acetylene and hydrogen. The use of a supersonic expansion of the hot gas is investigated as a method of rapidly cooling (quenching) the product stream to prevent further reaction or thermal decomposition of the acetylene which can lower the overall efficiency of the process.

  13. Acetylene terminated aspartimides and resins therefrom

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Connell, John W. (Inventor); Havens, Stephen J. (Inventor)

    1989-01-01

    Acetylene terminated aspartimides are prepared using two methods. In the first, an amino-substituted aromatic acetylene is reacted with an aromatic bismaleimide in a solvent of glacial acetic acid and/or m-cresol. In the second method, an aromatic diamine is reacted with an ethynyl containing maleimide, such an N-(3-ethynyl phenyl) maleimide, in a solvent of glacial acetic acid and/or m-cresol. In addition, acetylene terminated aspartimides are blended with various acetylene terminated oligomers and polymers to yield composite materials exhibiting improved mechanical properties.

  14. Nitrogen Fixation (Acetylene Reduction) Associated with Duckweed (Lemnaceae) Mats

    PubMed Central

    Zuberer, D. A.

    1982-01-01

    Duckweed (Lemnaceae) mats in Texas and Florida were investigated, using the acetylene reduction assay, to determine whether nitrogen fixation occurred in these floating aquatic macrophyte communities. N2-fixing microorganisms were enumerated by plating or most-probable-number techniques, using appropriate N-free media. Results of the investigations indicated that substantial N2-fixation (C2H2) was associated with duckweed mats in Texas and Florida. Acetylene reduction values ranged from 1 to 18 μmol of C2H4 g (dry weight)−1 day−1 for samples incubated aerobically in light. Dark N2 fixation was always two- to fivefold lower. 3-(3,4-Dichlorophenyl)-1,1-dimethylurea (7 to 10 μM) reduced acetylene reduction to levels intermediate between light and dark incubation. Acetylene reduction was generally greatest for samples incubated anaerobically in the light. It was estimated that 15 to 20% of the N requirement of the duckweed could be supplied through biological nitrogen fixation. N2-fixing heterotrophic bacteria (105 cells g [wet weight]−1 and cyanobacteria (105 propagules g [wet weight]−1 were associated with the duckweed mats. Azotobacter sp. was not detected in these investigations. One diazotrophic isolate was classified as Klebsiella. PMID:16345992

  15. Acetylene fuels reductive dechlorination of TCE by Dehalococcoides/Pelobacter-containing microbial consortia

    NASA Astrophysics Data System (ADS)

    Oremland, R. S.; Mao, X.; Mahandra, C.; Baesman, S. M.; Gushgari, S.; Alvarez-Cohen, L.; Liu, T.

    2015-12-01

    Groundwater contamination by trichloroethene (TCE) poses a threat to health and leads to the generation of vinyl chloride (VC), a carcinogen. Dehalococcoides mccartyi is the only bacterium that can completely dechlorinate TCE to ethene (C2H4). Acetylene (C2H2) occurs in TCE-contaminated sites as a consequence of chemical degradation of TCE. Yet acetylene inhibits a variety of microbial processes including methanogesis and reductive dechlorination. Pelobacter acetylenicus and related species can metabolize acetylene via acetylene hydratase and acetaldehyde dismutatse thereby generating acetate and H2 as endproducts, which could serve as electron donor and carbon source for growth of D. mccartyi. We found that 1mM acetylene (aqueous) inhibits growth of D. mccartyi strain 195 on 0.3 mM TCE, but that the inhibition was removed after 12 days with the addition of an acetylene-utilizing isolate from San Francisco Bay, Pelobacter strain SFB93. TCE did not inhibit the growth of this Pelobacter at the concentrations tested (0.1-0.5 mM) and TCE was not consumed by strain SFB93. Co-cultures of strain 195 with strain SFB93 at 5% inoculation were established in 120 mL serum bottles containing 40 mL defined medium. TCE was supplied at a liquid concentration of 0.1 mM, with 0.1 mM acetylene and N2/CO2 (90:10 v/v) headspace at 34 °C. Co-cultures were subsequently transferred (5% vol/vol inoculation) to generate subcultures after 20 μmol TCE was reduced to VC and 36 μmol acetylene was depleted. Aqueous H2 ranged from 114 to 217 nM during TCE-dechlorination, and the cell yield of strain 195 was 3.7 ±0.3 × 107 cells μmol-1 Cl- released. In a D. mccartyi-containing enrichment culture (ANAS) under the same conditions as above, it was found that inhibition of dechlorination by acetylene was reversed after 19 days by adding SFB93. Thus we showed that a co-culture of Pelobacter SFB93 and D. mccartyi 195 could be maintained with C2H2 as the electron donor and carbon source while TCE

  16. The effect of incomplete acetylene washout on cardiac output measurement using open circuit acetylene uptake.

    PubMed

    Balouch, Jamal; Olfert, I Mark; Wagner, Peter D; Hopkins, Susan R

    2007-02-15

    The open circuit acetylene uptake method is a useful non-invasive means of measuring cardiac output. However, because of accumulation of inhaled acetylene in tissues, the cardiac output uptake is underestimated, if residual acetylene is not allowed to wash out completely in between measurements. We determined the effect of applying a correction factor that estimates mixed venous acetylene concentration from endtidal values to the calculation of cardiac output. This accounts for mixed venous acetylene present during measurements made before complete washout. Six healthy subjects performed steady-state exercise at approximately 30% and 60% of V(O2 max). Cardiac output measurements were made at each exercise intensity using the open circuit acetylene uptake method (inspired [acetylene] approximately 1%), with the first and last measurements having no detectible levels of acetylene in expired gas (reference measurement). Data were also obtained with immediate pre-measurement endtidal concentrations ranging from 3% to 15% of the inspired [acetylene], in random order in between. Oxygen consumption, carbon dioxide production and heart rate did not change significantly during testing at each exercise intensity. Reference cardiac output also did not change significantly and averaged 11.1+/-0.8 L/min at 30% of V(O2 max) and 16.5+/-2.0 L/min at 60% of V(O2 max). Uncorrected cardiac output measurements progressively underestimated cardiac output by 15% at the 3% of inspired endtidal [acetylene] and by over 50% at 15% [acetylene] (p<0.0001). However, when corrected for residual endtidal [acetylene], cardiac outputs were not significantly different from the reference measurements. The results of this study suggest that by accounting for residual endtidal acetylene in mixed venous blood, cardiac output can be accurately measured even when washout of acetylene is incomplete, allowing measurements as often as every 10-15 s. PMID:16714151

  17. Estimation of nitrogenase activity in the presence of ethylene biosynthesis by use of deuterated acetylene as a substrate

    SciTech Connect

    Lin-Vien, D.; Fateley, W.G.; Davis, L.C. )

    1989-02-01

    Nitrogenase reduces deuterated acetylene primarily to cis dideuterated ethylene. This can be distinguished from undeuterated ethylene by the use of Fourier transform infrared spectroscopy. Characteristic bands in the region from 800 to 3,500 cm-1 can be used to identify and quantitate levels of these products. This technique is applicable to field studies of nitrogen fixation where ethylene biosynthesis by plants or bacteria is occurring. We have verified the reaction stoichiometry by using Klebsiella pneumoniae and Bradyrhizobium japonicum in soybeans. The most useful bands for quantitation of substrate purity and product distribution are as follows: acetylene-d0, 3,374 cm-1; acetylene-d1, 2,584 cm-1; acetylene-d2, 2,439 cm-1; cis-ethylene-d2, 843 cm-1; trans-ethylene-d2, 988 cm-1; ethylene-d1, 943 cm-1; ethylene-d0, 949 cm-1. (The various deuterated ethylenes and acetylenes are designated by a lowercase d and subscript to indicate the number, but not the position, of deuterium atoms in the molecule.) Mass spectrometry coupled to a gas chromatograph system has been used to assist in quantitation of the substrate and product distributions. Significant amounts of trans-ethylene-d2 were produced by both wild-type and nifV mutant K. pneumoniae. Less of this product was observed with the soybean system.

  18. Near-infrared spectra of liquid/solid acetylene under Titan relevant conditions and implications for Cassini/VIMS detections

    NASA Astrophysics Data System (ADS)

    Singh, S.; Cornet, T.; Chevrier, V. F.; Combe, J.-Ph.; McCord, T. B.; Roe, L. A.; Le Mouélic, S.; Le Menn, E.; Wasiak, F. C.

    2016-05-01

    Acetylene is thought to be abundant on Titan according to most photochemical models. While detected in the atmosphere, its likely presence at the surface still lacks physical evidence. It is thought that solid acetylene could be a major component of Titan's lakes shorelines and dry lakebed, detected as the 5 μm-bright deposits with the Cassini/VIMS instrument. Acetylene could also be present under its liquid form as dissolved solids in Titan's methane-ethane lakes, as emphasized by thermodynamics studies. This paper is devoted to the near-infrared spectroscopy study of acetylene under solid and liquid phases between 1 and 2.2 μm, synthesized in a Titan simulation chamber that is able to reproduce extreme temperature conditions. From experiments, we observed a ∼10% albedo increase between liquid acetylene at 193-188 K and solid acetylene at 93 K. Using the NIR spectroscopy technique we successfully calculated the reflectivity ratio of solid/liquid acetylene as 1.13. The second difference we observed between liquid and solid acetylene is a shift in the major absorption band detected at 1.54 μm, the shift of ∼0.01 μm occurring toward higher wavelength. In order to assess the detectability of acetylene on Titan using the Cassini/VIMS instrument, we adapted our spectra to the VIMS spectral resolution. The spectral band at 1.55 μm and a negative slope at 2.0 μm falls in the Cassini/VIMS atmospheric windows over several VIMS infrared spectels, thus Cassini/VIMS should be able to detect acetylene.

  19. Examining the impact of acetylene on N-fixation and the active sediment microbial community

    PubMed Central

    Fulweiler, Robinson W.; Heiss, Elise M.; Rogener, Mary Kate; Newell, Silvia E.; LeCleir, Gary R.; Kortebein, Sarah M.; Wilhelm, Steven W.

    2015-01-01

    Here we examined the impact of a commonly employed method used to measure nitrogen fixation, the acetylene reduction assay (ARA), on a marine sediment community. Historically, the ARA technique has been broadly employed for its ease of use, in spite of numerous known artifacts. To gauge the severity of these effects in a natural environment, we employed high-throughput 16S rRNA gene sequencing to detect differences in acetylene-treated sediments vs. non-treated control sediments after a 7 h incubation. Within this short time period, significant differences were seen across all activity of microbes identified in the sediment, implying that the changes induced by acetylene occur quickly. The results have important implications for our understanding of marine nitrogen budgets. Moreover, because the ARA technique has been widely used in terrestrial and freshwater habitats, these results may be applicable to other ecosystems. PMID:26029177

  20. Acetylene Fermentation: Relevance to Primordial Biogeochemistry and the Search for Life in the Outer Solar System

    NASA Astrophysics Data System (ADS)

    Oremland, R. S.; Baesman, S. M.; Miller, L. G.

    2013-12-01

    Acetylene is a highly reactive component of planet(oid)s with anoxic, methane-rich atmospheres, such as Jupiter, Saturn, Titan, and perhaps the primordial Earth. Included in this group is Enceladus, although it is not clear if the acetylene detected within its jets by Cassini was formed by photolysis of methane, from thermo-catalysis of organic matter in the orb's interior, or a fragmentation artifact of the mass spectrum of a larger hydrocarbon. Acetylene inhibits many microbial processes (e.g., methanogenesis, methane oxidation, hydrogen metabolism, denitrification) yet a number of anaerobes can use it as a carbon and energy source to support growth. The best studied is Pelobacter acetylenicus, which carries out a two-step reaction involving the enzymes acetylene hydratase and acetaldehyde dismutase. The former, a low potential W-containing enzyme, forms acetaldehyde while the latter produces ethanol and acetate. Metabolism of acetylene by mixed microbial communities (sediments and/or enrichment cultures) produces these intermediates, and when coupled with sulfate-reduction or methanogenesis respectively forms CO2 or an equal mixtures of CO2 plus CH4. It is not inconceivable that such an anaerobic, microbial food chain could exist in the waters beneath the ice cap of Enceladus, Titan, or even in the mesothermal atmospheric regions of the gas giants. Detection of the identified intermediate products of acetylene fermentation, namely acetaldehyde, ethanol, acetate and formate in the atmospheres of these planet(oid)s would constitute evidence for a microbial life signature. This evidence would be strongly reinforced if a stable carbon isotope fractionation was identified as well, whereby the products of acetylene fermentation were enriched in 12C relative to 13C (i.e., had a lighter δ13C signal) when compared to that of the starting acetylene. The most practical target to test this hypothesis would be Enceladus (if the detected acetylene is shown to be a real

  1. Microporous metal–organic framework with dual functionalities for highly efficient removal of acetylene from ethylene/acetylene mixtures

    PubMed Central

    Hu, Tong-Liang; Wang, Hailong; Li, Bin; Krishna, Rajamani; Wu, Hui; Zhou, Wei; Zhao, Yunfeng; Han, Yu; Wang, Xue; Zhu, Weidong; Yao, Zizhu; Xiang, Shengchang; Chen, Banglin

    2015-01-01

    The removal of acetylene from ethylene/acetylene mixtures containing 1% acetylene is a technologically very important, but highly challenging task. Current removal approaches include the partial hydrogenation over a noble metal catalyst and the solvent extraction of cracked olefins, both of which are cost and energy consumptive. Here we report a microporous metal–organic framework in which the suitable pore/cage spaces preferentially take up much more acetylene than ethylene while the functional amine groups on the pore/cage surfaces further enforce their interactions with acetylene molecules, leading to its superior performance for this separation. The single X-ray diffraction studies, temperature dependent gas sorption isotherms, simulated and experimental column breakthrough curves and molecular simulation studies collaboratively support the claim, underlying the potential of this material for the industrial usage of the removal of acetylene from ethylene/acetylene mixtures containing 1% acetylene at room temperature through the cost- and energy-efficient adsorption separation process. PMID:26041691

  2. Diffusion of acetylene inside the Cu-BTC metal organic framework

    NASA Astrophysics Data System (ADS)

    Prabhudesai, S. A.; Sharma, V. K.; Mitra, S.; Mukhopadhyay, R.

    2012-06-01

    Dynamic of acetylene molecule adsorbed in Copper 1, 3, 5-benzenetricarboxylate metal-organic framework as studied using molecular dynamics simulation technique is reported here. The results showed that the translational motion of the guest molecule exist in two different time scales; faster one behave as free particle and other one is found to follow jump diffusion. Rotational motion of acetylene is found to be an order of magnitude faster than translational motion. Intermediate scattering functions corresponding to rotational motion show an unusual dip, which is described by the m-diffusion model.

  3. Hydration of Acetylene: A 125th Anniversary

    ERIC Educational Resources Information Center

    Ponomarev, Dmitry A.; Shevchenko, Sergey M.

    2007-01-01

    The year 2006 is the 125th anniversary of a chemical reaction, the discovery of which by Mikhail Kucherov had a profound effect on the development of industrial chemistry in the 19-20th centuries. This was the hydration of alkynes catalyzed by mercury ions that made possible industrial production of acetaldehyde from acetylene. Historical…

  4. Living on acetylene. A primordial energy source.

    PubMed

    Ten Brink, Felix

    2014-01-01

    The tungsten iron-sulfur enzyme acetylene hydratase catalyzes the conversion of acetylene to acetaldehyde by addition of one water molecule to the C-C triple bond. For a member of the dimethylsulfoxide (DMSO) reductase family this is a rather unique reaction, since it does not involve a net electron transfer. The acetylene hydratase from the strictly anaerobic bacterium Pelobacter acetylenicus is so far the only known and characterized acetylene hydratase. With a crystal structure solved at 1.26 Å resolution and several amino acids around the active site exchanged by site-directed mutagenesis, many key features have been explored to understand the function of this novel tungsten enzyme. However, the exact reaction mechanism remains unsolved. Trapped in the reduced W(IV) state, the active site consists of an octahedrally coordinated tungsten ion with a tightly bound water molecule. An aspartate residue in close proximity, forming a short hydrogen bond to the water molecule, was shown to be essential for enzyme activity. The arrangement is completed by a small hydrophobic pocket at the end of an access funnel that is distinct from all other enzymes of the DMSO reductase family. PMID:25416389

  5. A mid-infrared absorption diagnostic for acetylene detection

    NASA Astrophysics Data System (ADS)

    KC, Utsav; Nasir, Ehson F.; Farooq, Aamir

    2015-08-01

    Acetylene is an important combustion intermediate and plays a critical role in soot formation. Accurate measurements of trace concentrations of acetylene can be very useful in validating hydrocarbon oxidation and soot formation mechanisms. Strongest vibrational band of acetylene near 13.7 μm is probed here to develop a highly sensitive absorption diagnostic. Experiments are carried out behind reflected shock waves to measure absorption cross sections of acetylene near 730 cm-1 over a wide range of temperatures (1000-2200 K) and pressures (1-5 bar). The diagnostic is demonstrated by measuring acetylene formation during the shock-heated pyrolysis and oxidation of propene.

  6. Acetylenes and fatty acids from Codonopsis pilosula

    PubMed Central

    Jiang, Yueping; Liu, Yufeng; Guo, Qinglan; Jiang, Zhibo; Xu, Chengbo; Zhu, Chenggen; Yang, Yongchun; Lin, Sheng; Shi, Jiangong

    2015-01-01

    Four new acetylenes (1–4) and one new unsaturated ω-hydroxy fatty acid (5), together with 5 known analogues, were isolated from an aqueous extract of Codonopsis pilosula roots. Their structures were determined by spectroscopic and chemical methods. The new acetylenes are categorized as an unusual cyclotetradecatrienynone (1), tetradecenynetriol (2), and rare octenynoic acids (3 and 4), respectively, and 3 and 4 are possibly derived from oxidative metabolic degradation of 1 and/or 2. The absolute configuration of 1 was assigned by comparison of the experimental circular dichroism (CD) spectrum with the calculated electronic circular dichroism (ECD) spectra of stereoisomers based on the quantum-mechanical time-dependent density functional theory, while the configuration of 2 was assigned by using modified Mosher׳s method based on the MPA determination rule of ΔδRS values for diols. PMID:26579449

  7. Two new acetylenic compounds from Asparagus officinalis.

    PubMed

    Li, Xue-Mei; Cai, Jin-Long; Wang, Wen-Xiang; Ai, Hong-Lian; Mao, Zi-Chao

    2016-01-01

    Two new acetylenic compounds, asparoffins A (1) and B (2), together with two known compounds, nyasol (3) and 3″-methoxynyasol (4), were isolated from stems of Asparagus officinalis. The structures of two new compounds were elucidated on the basis of detailed spectroscopic analyses (UV, IR, MS, 1D, and 2D NMR). All compounds were evaluated for their cytotoxicities against three human cancer cell lines. PMID:26558641

  8. Opposite influence of haloalkanes on combustion and pyrolysis of acetylene

    NASA Astrophysics Data System (ADS)

    Drakon, A. V.; Emelianov, A. V.; Eremin, A. V.; Mikheyeva, E. Yu

    2015-11-01

    An influence of haloalkanes CF3H and CCl4 (known as inflammation and explosion suppressors) on combustion and pyrolysis of acetylene behind shock waves was experimentally studied. While ignition delay times in stoihiometric acetylene-oxygen mixtures were expectedly increased by halogenoalkanes admixtures, the induction times of carbon particle formation at acetylene pyrolysis were dramatically reduced in presence of CCl4. A simplified kinetic model was suggested and characteristic rates of diacetylene C4H2 formation were estimated as a limiting stage of acetylene polymerization. An analysis of obtained data has indicated that promoting species is atomic chlorine forming in CCl4 pyrolysis, which interacts with acetylene and produces C2H radical, initiating a chain mechanism of acetylene decomposition. The results of kinetic modeling agree well with experimental data.

  9. Spectroscopic study of acetylene and hydrogen cyanide

    NASA Astrophysics Data System (ADS)

    Rozario, Hoimonti Immaculata

    High-resolution molecular spectroscopy has been used to study acetylene line parameters and emission spectra of hydrogen cyanide. All acetylene spectra were recorded in our laboratory at the University of Lethbridge using a 3-channel tuneable diode laser spectrometer. N2-broadened line widths and N2-pressure induced line shifts have been measured for transitions in the v1+v3 band of acetylene at seven temperatures in the range 213-333K to obtain the temperature dependences of broadening and shift coefficients. The Voigt and hard-collision line profile models were used to retrieve the line parameters. The line-broadening and line-shift coefficients as well as their temperature-dependent parameters have been also evaluated theoretically, in the frame work of a semi-classical approach based on an exponential representation of the scattering operator, an intermolecular potential composed of electrostatic quadrupole--quadrupole and pairwise atom--atom interactions as well as on exact trajectories driven by an effective isotropic potential. The experimental results for both N2-broadening and shifting show good agreement with the theoretical results. We have studied the line intensities of the 1vl 20←0v120 band system from the HCN emission spectrum. The infrared emission spectrum of H12C 14N was measured at the Justus-Liebig University, Giessen, Germany. The emission spectrum was analyzed with the spectrum analysis software Symath running using Mathematica as a platform. This approach allowed us to retrieve information on band intensity parameters.

  10. Bromotheoynic acid, a brominated acetylenic acid from the marine sponge Theonella swinhoei.

    PubMed

    Aoki, Nobuwa; Yamamoto, Kazuyuki; Ogawa, Takayuki; Ohta, Emi; Ikeuchi, Toshitaka; Kamemura, Kazuo; Ikegami, Susumu; Ohta, Shinji

    2013-01-01

    A new brominated C(17) acetylenic acid (1) designated as bromotheoynic acid has been isolated from the marine sponge Theonella swinhoei, collected off the coast of Tanegashima, Kagoshima Prefecture, Japan. The structure was determined on the basis of the analysis of its extensive 2D NMR spectroscopic data as well as HRMS. Bromotheoynic acid (1) inhibited maturation of starfish oocytes and cell division of fertilised starfish eggs. Bromotheoynic acid (1) also inhibited proliferation of human leukaemia U937 and HL60 cells, human lung cancer A549 and H1299 cells, and human embryonic kidney 293 (HEK293) cells. PMID:22324431

  11. RECRYSTALLIZATION OF PMDA AND SYNTHESIS OF AN ACETYLENIC DIAMINE

    SciTech Connect

    Sanner, R; Cook, R C

    2004-09-21

    This memo provides documentation for the method of recrystallization of pyromeletic dianhydride (PMDA), the dianhydride used in the vapor deposition of Kapton-like polyimide for ICF shell ablators and for the synthesis of bis(3-aminophenyl) acetylene, a unique acetylenic diamine developed for vapor deposition testing.

  12. 76 FR 75782 - Revising Standards Referenced in the Acetylene Standard

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-12-05

    ... standards that reference or include language from outdated standards published by standards developing organizations (``SDO standards'') (69 FR 68283). A SDO standard referenced in OSHA's Acetylene Standard (29 CFR... of the Compressed Gas Association standard, CGA G-1-2003, in the Acetylene Standard. See 74 FR...

  13. Proton exchange membrane fuel cell cathode contamination - Acetylene

    NASA Astrophysics Data System (ADS)

    Zhai, Y.; St-Pierre, Jean

    2015-04-01

    Acetylene adsorption on PEMFC electrodes and contamination in single cells are investigated with 300 ppm acetylene at a cathode held at 80 °C. The results of adsorption experiments suggest that acetylene adsorbs readily on electrodes and is reduced to ethylene and ethane under an open circuit potential of H2/N2, as the adsorbates can be electro-oxidized at high potentials. The cell voltage response shows that 300 ppm acetylene results in a cell performance loss of approximately 88%. The voltage degradation curve is divided into two stages by an inflection point, which suggests that potential-dependent processes are involved in acetylene poisoning. These potential-dependent processes may include acetylene oxidation and reduction as well as accumulation of intermediates on the electrode surface. Electrochemical impedance spectroscopy analysis suggests that acetylene affects the oxygen reduction reaction and may also affect mass transport processes. Acetylene also may be reduced in the steady poisoning state of the operating cell. After neat air operation, the cyclic voltammetry results imply that the cathode catalyst surface is almost completely restored, with no contaminant residues remaining in the MEA. Linear scanning voltammetry measurements show no change in hydrogen crossover caused by contamination, and polarization curves confirm complete recovery of cell performance.

  14. Acetylene-based chemicals from coal and other natural resources

    SciTech Connect

    Tedeschi, R.J.

    1982-01-01

    The economic and technological changes which have affected acetylene directly are examined. Commodity chemicals, which were manufactured from acetylene more than thirty years ago, are now made almost entirely from hydrocarbons such as ethylene, propylene, or butadiene. During this period, calcium carbide acetylene was displaced by petrochemical acetylene, the latter was gradually displaced by less expensive olefins and alkanes. The calcium carbide process viewed in terms of its abundant raw materials, might again become an attractive technology as petroleum-based feedstocks become scarcer and more expensive. With improved furnace design and solids handling, further economics in this process may be possible. The greatest growth area for acetylene is now in Reppe-type chemicals such as butyndiol, tetrahydrofuran, N-methyl-2-pyrrolidone, vinyl pyrrolidone, and polyvinyl pyrrolidone, and a variety of acetylenic alcohols and glycols. The technology and applications for large-volume acetylenic products and their derivatives are outlined. Acetylene production processes purification, stability and guidelines for its safe use in chemical operations are described. 327 references, 30 figures, 19 tables.

  15. Acetylene-Based Materials in Organic Photovoltaics

    PubMed Central

    Silvestri, Fabio; Marrocchi, Assunta

    2010-01-01

    Fossil fuel alternatives, such as solar energy, are moving to the forefront in a variety of research fields. Organic photovoltaic systems hold the promise of a lightweight, flexible, cost-effective solar energy conversion platform, which could benefit from simple solution-processing of the active layer. The discovery of semiconductive polyacetylene by Heeger et al. in the late 1970s was a milestone towards the use of organic materials in electronics; the development of efficient protocols for the palladium catalyzed alkynylation reactions and the new conception of steric and conformational advantages of acetylenes have been recently focused the attention on conjugated triple-bond containing systems as a promising class of semiconductors for OPVs applications. We review here the most important and representative (poly)arylacetylenes that have been used in the field. A general introduction to (poly)arylacetylenes, and the most common synthetic approaches directed toward making these materials will be firstly given. After a brief discussion on working principles and critical parameters of OPVs, we will focus on molecular arylacetylenes, (co)polymers containing triple bonds, and metallopolyyne polymers as p-type semiconductor materials. The last section will deal with hybrids in which oligomeric/polymeric structures incorporating acetylenic linkages such as phenylene ethynylenes have been attached onto C60, and their use as the active materials in photovoltaic devices. PMID:20480031

  16. Polymerization of ionized acetylene clusters into covalent bonded ions: evidence for the formation of benzene radical cation.

    PubMed

    Momoh, Paul O; Abrash, Samuel A; Mabrouki, Ridha; El-Shall, M Samy

    2006-09-27

    Since the discovery of acetylene and benzene in protoplanetary nebulae under powerful ultraviolet ionizing radiation, efforts have been made to investigate the polymerization of ionized acetylene. Here we report the efficient formation of benzene ions within gas-phase ionized acetylene clusters (C2H2)n+ with n = 3-60. The results from experiments, which use mass-selected ion mobility techniques, indicate that the (C2H2)3+ ion has unusual stability similar to that of the benzene cation; its primary fragment ions are similar to those reported from the benzene cation, and it has a collision cross section of 47.4 A2 in helium at 300 K, similar to the value of 47.9 A2 reported for the benzene cation. In other words, (C2H2)3+ structurally looks like benzene, it has stability similar to that of benzene, it fragments such as benzene, therefore, it must be benzene! PMID:16984178

  17. Interpenetrating polymer networks from acetylene terminated materials

    NASA Technical Reports Server (NTRS)

    Connell, J. W.; Hergenrother, P. M.

    1989-01-01

    As part of a program to develop high temperature/high performance structural resins for aerospace applications, the chemistry and properties of a novel class of interpenetrating polymer networks (IPNs) were investigated. These IPNs consist of a simple diacetylenic compound (aspartimide) blended with an acetylene terminated arylene ether oligomer. Various compositional blends were prepared and thermally cured to evaluate the effect of crosslink density on resin properties. The cured IPNs exhibited glass transition temperatures ranging from 197 to 254 C depending upon the composition and cure temperature. The solvent resistance, fracture toughness and coefficient of thermal expansion of the cured blends were related to the crosslink density. Isothermal aging of neat resin moldings, adhesive and composite specimens showed a postcure effect which resulted in improved elevated temperature properties. The chemistry, physical and mechanical properties of these materials will be discussed.

  18. Pyrethrum stabilization by inactivation of natural acetylenic impurities

    SciTech Connect

    Evans, A.J.

    1989-01-17

    This patent describes a mixture of naturally occurring pyrethroid substances and derivatives of naturally occurring polyacetylenic substances wherein the derivatives of polyacetylenic substances are formed by substantially inactivating the acetylenic functional groups to promote the stability of the pyrethroid substances.

  19. Electronic Spectroscopy and Dynamics of the Acetylene - Complex

    NASA Astrophysics Data System (ADS)

    Ju, Shan-Shan

    The structures, intermolecular forces and excited state dynamics of acetylene(A) cdot Ar complex are investigated by combination of laser induced fluorescence spectroscopy pairwise potential model calculations. Acetylene is linear in the X state while trans-bent in the (A) state. Although only one structure has been known to exist for the acetylene(X) cdot Ar complex, two isomeric structures are determined for the acetylene(A) cdot Ar complex from the rotational band shape analysis of the fluorescence excitation spectra. One of the isomers has the argon sitting in the molecular plane of C _2H_2 (A), 3.77 A away from the center-of-mass of acetylene, the other has the argon 3.71 A above the plane on the C_2 axis. Formulas useful for calculating axis switching angles in non-planar molecules have been derived and applied to the two isomeric structures. It was found that despite the acetylene geometry change from the (X) to the (A) state, the axis switching effect is negligible for the complex spectral calculation. A pair potential model with parameters directly extracted from the ones calculated for ethene (X) cdot Ar is able to produce the two structures. Based on the structures and the calculated potential surface, three of the vdW frequencies are assigned to be: upsilon_{rm stretch } = 28 cm^{-1} for the out-of-plane isomer, upsilon_ {rm bend1} = 11 cm^ {-1} (the in-plane bend) and upsilon_{rm bend2} = 8.5 cm^{-1} (the out -of-plane bend) for the in-plane isomer. The existence of the two isomers allowed the study of the orientation dependence in intersystem crossing (ISC) of acetylene(S _1) induced by interaction with argon. Similar ISC lifetimes (~100 ns) were observed for the two isomers, suggesting that the pi and pi^* orbitals are equally susceptible to spin-changing interactions with Ar.

  20. Mortality of workers at acetylene production plants.

    PubMed Central

    Newhouse, M L; Matthews, G; Sheikh, K; Knight, K L; Oakes, D; Sullivan, K R

    1988-01-01

    To reduce the risk of explosion oxyacetylene cylinders are filled with a spongy mass, acetone is added to saturate the mass, and acetylene is pumped into the cylinder. The first cylinders manufactured before 1936 used a kapok filling topped off with about 16 oz of crocidolite asbestos, with a metal gauze thimble inserted to reduce risk of flash back. Cylinders must be examined annually. The use of crocidolite ceased in 1972 and other fillings have been adopted since 1970; kapok cylinders now constitute less than 5% of the total stock. To assess possible hazards, a mortality study of workers first employed between 1935 and 1975 and followed up to December 1984 was undertaken. Simulation tests showed low concentrations of asbestos in the air even in the earliest period. The population studied consisted of 370 workers at the Bilston plant in the West Midlands, 611 at the 14 other plants in England and Wales, and 120 in Scotland. No deaths occurred from mesothelial tumours but there was an excess of deaths from cancer, particularly lung cancer, cancer of the stomach, and cancer of the pancreas, the latter accounting for eight deaths. Risks appeared to be concentrated at the Bilston plant. The importance of these findings is discussed. PMID:3342189

  1. Electron impact induced anion production in acetylene.

    PubMed

    Szymańska, Ewelina; Čadež, Iztok; Krishnakumar, E; Mason, Nigel J

    2014-02-28

    A detailed experimental investigation of electron induced anion production in acetylene, C2H2, in the energy range between 1 and 90 eV is presented. The anions are formed by two processes in this energy range: dissociative electron attachment (DEA) and dipolar dissociation (DD). DEA in C2H2 is found to lead to the formation of H(-) and C2(-)/C2H(-) through excitation of resonances in the electron energy range 1-15 eV. These anionic fragments are formed with super thermal kinetic energy and reveal no anisotropy in the angular distributions. DD in C2H2 leads to the formation of H(-), C(-)/CH(-) and C2(-)/C2H(-) with threshold energies of 15.7, 20.0 and 16.5 eV respectively. The measured anion yields have been used to calculate anion production rates for H(-), C(-)/CH(-) and C2(-)/C2H(-) in Titan's ionosphere. PMID:24343432

  2. Ion-induced dissociation dynamics of acetylene

    SciTech Connect

    De, Sankar; Rajput, Jyoti; Roy, A.; Safvan, C. P.; Ghosh, P. N.

    2008-02-15

    We report on the results of dissociation dynamics of multiple charged acetylene molecules formed in collision with 1.2 MeV Ar{sup 8+} projectiles. Using the coincidence map, we can separate out the different dissociation pathways between carbon and hydrogen ionic fragments as well as complete two-body breakup events. From the measured slopes of the coincidence islands for carbon atomic fragments and theoretical values determined from the charge and momentum distribution of the correlated particles, we observe a diatom like behavior of the C-C charged complex during dissociation of multiply charged C{sub 2}H{sub 2}. We conclude that this behavior in breakup dynamics is a signature of sequentiality in dissociation of this multiply charged molecular species. The shape and orientation of the islands give further information about the momentum balance in the fragmentation process of two- or many-body dissociation pathways. Kinetic energy release of different breakup channels are reported here and compared with values calculated from the pure Coulomb explosion model.

  3. Process hydrogenates unwanted diolefins and acetylenes

    SciTech Connect

    Vora, B.V. )

    1988-12-05

    Diolefins and actetylenes in C/sub 3//C/sub 4/ olefin streams can be selectively hydrogenated to produce high-purity mono-olefins for downstream polyolefin production. C/sub 3//C/sub 4/ olefin sources, fluid catalytic cracking (FCC), steam crackers, and dehydrogenation of C/sub 3//C/sub 4/ paraffins, all contain these undesirable polyunsaturated compounds. Hydrogenation of these compounds in alkylation unit feeds can also improve the economics of the alkylation process. Production of high-purity mono-olefins for downstream polyolefins production requires a feedstock that is essentially free of dienes and acetylenes to minimize undesirable side reactions. Although alkylation units can tolerate some diolefins in the feed, economics dictate that these diolefins should be minimized. The selective hydrogenation process (SHP) developed by others at its Marl, West Germany, plant, has undergone additional development work since commercialization of the process in 1980. The unit was designed to feed 160,000 metric tons/year of clean C/sub 4/ raffinate from a steam cracker, with a maximum polyunsaturated content of 0.8 wt%.

  4. Acetylene on Titan’s Surface

    NASA Astrophysics Data System (ADS)

    Singh, S.; McCord, T. B.; Combe, J.-Ph.; Rodriguez, S.; Cornet, T.; Le Mouélic, S.; Clark, R. N.; Maltagliati, L.; Chevrier, V. F.

    2016-09-01

    Titan’s atmosphere is opaque in the near-infrared due to gaseous absorptions, mainly by methane, and scattering by aerosols, except in a few “transparency windows.” Thus, the composition of Titan’s surface remains difficult to access from space and is still poorly constrained. Photochemical models suggest that most of the organic compounds formed in the atmosphere are heavy enough to condense and build up at the surface in liquid and solid states over geological timescales. Acetylene (C2H2) net production in the atmosphere is predicted to be larger than any other compound and C2H2 has been speculated to exist on the surface of Titan. C2H2 was detected as a trace gas sublimated/evaporated from the surface using the Gas Chromatograph Mass Spectrometer after the landing of the Huygens probe. Here we show evidence of C2H2 on the surface of Titan by detecting absorption bands at 1.55 and 4.93 μm using the Cassini Visual and Infrared Mapping Spectrometer at three different equatorial areas—Tui Regio, eastern Shangri La, and Fensal–Aztlan/Quivira. We found that C2H2 is preferentially detected in low-albedo areas, such as sand dunes and near the Huygens landing site. The specific location of the C2H2 detections suggests that C2H2 is mobilized by surface processes, such as surface weathering by liquids through dissolution/evaporation processes.

  5. Identification of Acetylene on Titan's Surface

    NASA Astrophysics Data System (ADS)

    Singh, S.; McCord, T. B.; Rodriguez, S.; Combe, J. P.; Cornet, T.; Le Mouelic, S.; Maltagliati, L.; Chevrier, V.; Clark, R. N.

    2015-12-01

    Titan's atmosphere is opaque in the near infrared due to gaseous absorptions, mainly by methane, and scattering by aerosols, except in a few "transparency windows" (e.g., Sotin et al., 2005). Thus, the composition of Titan surface remains difficult to access from space and is still poorly constrained, limited to ethane in the polar lakes (Brown et al., 2008) and a few possible organic molecules on the surface (Clark et al., 2010). Photochemical models suggest that most of the organic compounds formed in the atmosphere are heavy enough to condense and build up at the surface in liquid and solid states over geological timescale (Cordier et al., 2009, 2011). Acetylene (C2H2) is one of the most abundant organic molecules in the atmosphere and thus thought to present on the surface as well. Here we report direct evidence of solid C2H2 on Titan's surface using Cassini Visual and Infrared Mapping Spectrometer (VIMS) data. By comparing VIMS observations and laboratory measurements of solid and liquid C2H2, we identify a specific absorption at 1.55 µm that is widespread over Titan but is particularly strong in the brightest terrains. This surface variability suggests that C2H2 is mobilized by surface processes, such as surface weathering, topography, and dissolution/evaporation. The detection of C2H2 on the surface of Titan opens new paths to understand and constrain Titan's surface activity. Since C2H2 is highly soluble in Titan liquids (Singh et al. 2015), it can easily dissolve in methane/ethane and may play an important role in carving of fluvial channels and existence of karstic lakes at higher latitudes on Titan. These processes imply the existence of a dynamic surface with a continued history of erosion and deposition of C2H2 on Titan.

  6. Chemistry and properties of blends of acetylene terminated materials

    NASA Technical Reports Server (NTRS)

    Connell, John W.; Hergenrother, Paul M.

    1991-01-01

    As part of a NASA program to develop new high temperature/high performance structural materials, the chemistry and properties of acetylene-containing materials and their cured resins are under investigation. The objective of this work is to develop materials that are readily processable (i.e., 200-300 C and about 1.4 MPa or less) and possess usable mechanical properties at temperatures as high as 177 C. An acetylene-terminated aspartimide (ATA) was blended with an equal weight of an acetylene-terminated arylene ether (ATAE) oligomer. The blend was subsequently thermally cured to yield a resin which was evaluated in the form of neat resin moldings, adhesive specimens, and laminates. Adhesive specimens and laminates gave good mechanical properties to temperatures as high as 177 C. In addition, preliminary laminate work is presented on the resin from a blend of a new N-methyl substituted ATA and an ATAE.

  7. Effects of acido-basic support properties on the catalytic hydrogenation of acetylene on gold nano-particles

    NASA Astrophysics Data System (ADS)

    Manda, Abdullah Ahmed

    Metallic gold nanoparticles supported on gamma-Al2O 3 and magnesia-alumina mixed oxide, with different magnesia content have been prepared by sol-gel method and characterized by different techniques (inductive coupled plasma-mass spectroscopy (ICP-MS), XRD, BET surface area analysis, transmission electron microscopy (TEM), CO2 and NH 3 temperature programmed desorption (TPD), H2 temperature programmed reduction (TPR) and FTIR of adsorbed CO2). Such systems were found to produce catalysts with controllable acidity, varying from catalyst possessing large density of acidic and low density of basic sites, others with acidic and basic sites of equal strength and density, and others with large basic and low acid sites densities, respectively. The catalytic assessment of the generated acidity was carried out using 2-propanol decomposition as a test reaction. The results obtained indicate that the presence of magnesia and reduced gold nanopartilces has imparted the catalysts, 1%Au/4%Mg-Al 2O3 and 1%Au/8%Mg-Al2O3, with significant base-catalytic properties. Acetylene hydrogenation and formation of coke deposits were investigated on a gold catalyst supported on gamma-Al2O3 and gold supported on alumina-magnisia mixed oxide with different gold content; 1%Au/gamma-Al 2O3, 1%Au/15%Mg-Al2O3, 2%Au/15%Mg-Al 2O3 and 4%Au/15%Mg-Al2O3. The effect of the H2/C2H2 ratio was studied over a range of values. The catalytic activity and selectivity towards ethylene and other products were investigated at different reaction temperatures. Acetylene hydrogenation was investigated in the presence and absence of ethylene in stream. It is investigated that the adsorption of the triple bond is preferred over the double bond and during selective catalytic (SCR) of C2H2 the two hydrocarbons do not compete for the same adsorption sites. The deactivation of catalysts was studied by temperature programmed oxidation (TPO). Higher content of coke over 1%Au/Al2O3 catalyst was investigated in contrast to

  8. Effect of Varying Inert Gas and Acetylene Concentration on the Synthesis of Carbon Nanotubes.

    PubMed

    Afrin, Rahat; Abbas, Syed Mustansar; Shah, Nazar Abbas; Mustafa, Muhammad Farooq; Ali, Zulfiqar; Ahmad, Nisar

    2016-03-01

    The multiwalled carbon nanotubes (MWCNTs) with small diameter and high purity were achieved by chemical vapor deposition technique using silicon substrate. The introduction of specific concentration of inert gas with hydrocarbon played a key role in controlling morphology and diameter of MWCNTs. Nickel mixed ferrite nanoparticles were used as a catalyst for the growth of MWCNTs. Growth parameters like concentration of hydrocarbon source and inert gas flow, composition of catalyst particles and growth temperature were studied. In this work smaller diameter and twisted MWCNTs were formed by dilution of acetylene with argon gas. Electrical properties suggest a semimetallic behavior of synthesized MWCNTs. PMID:27455741

  9. Microgravity Superagglomerates Produced By Silane And Acetylene

    NASA Technical Reports Server (NTRS)

    Gokoglu, Suleyman (Technical Monitor); Bundy, Matthew; Mulholland, George W.; Manzello, Samuel; Yang, Jiann; Scott, John Henry; Sivathanu, Yudaya

    2003-01-01

    The size of the agglomerates produced in the upper portion of a flame is important for a variety of applications. Soot particle size and density effect the amount of radiative heat transfer from a fire to its surroundings. Particle size determines the lifetime of smoke in a building or in the atmosphere, and exposure hazard for smoke inhaled and deposited in the lungs. The visibility through a smoke layer and dectectability of the smoke are also greatly affected by agglomerate size. Currently there is limited understanding of soot growth with an overall dimension of 10 m and larger. In the case of polystyrene, smoke agglomerates in excess of 1 mm have been observed raining out from large fires. Unlike hydrocarbon fuels, silane has the advantage that silica particles are the major combustion product resulting in a particle volume fraction a factor of ten greater than that for a carbonaceous smoke. There are two very desirable properties of silica aero-gels that are important for both space and earth based applications. The first important property is its inertness to most oxidizing and reducing atmospheres. Therefore, silica aero-gels make excellent fire ablatives and can be used in very demanding applications. The second important property is that silica aero-gels are expected to have very high porosity (greater than 0.999), making them lightweight and ideal for aerospace applications. The added benefit of the high porosity is that they can be used as extremely efficient filters for many earth based applications as well. Evidence of the formation of superagglomerates in a laminar acetylene/air diffusion flame was found by Sorensen et al. [1]. An interconnecting web of super-agglomerates was observed to span the width of the soot plume in the region just above the flame tip and described as a gel state. It was observed that this gel state immediately breaks up into agglomerates as larges as 100 m due to buoyancy induced turbulence. Large soot agglomerates were

  10. Siloxane containing addition polyimides. II - Acetylene terminated polyimides

    NASA Technical Reports Server (NTRS)

    Maudgal, S.; St. Clair, T. L.

    1984-01-01

    Acetylene terminated polyimide oligomers having a range of molecular weights have been synthesized by reacting bis (gamma-aminopropyl) tetramethyldisiloxane, aminophenylacetylene and 3, 3', 4, 4' benzophenonetetracarboxylic dianhydride in different molar ratios. The prepolymers were isolated and characterized for melt flow and cure properties. They show promise as adhesives for bonding titanium to titanium and as matrix resins for graphite cloth reinforced composites. The most promising system has been blended in varying proportions with Thermid 600, a commercially available acetylene terminated polyimide oligomer, and the mixtures have been tested for application as composite matrix resins.

  11. Acetylene, a mammalian metabolite of 1,1,1-trichloroethane.

    PubMed

    Dürk, H; Poyer, J L; Klessen, C; Frank, H

    1992-09-01

    1,1,1-Trichloroethane (TCE) is a widely used industrial solvent of low acute toxicity. It is slowly oxidized to trichloroethanol and trichloroacetic acid by cytochrome P-450-dependent mono-oxygenases. Increased inhalative uptake by rats under hypoxia and spin-trapping experiments indicate that TCE is also reductively metabolized to a radical intermediate. Acetylene is formed as a metabolite, suggesting transfer of an additional electron to form the corresponding carbene. Hypoxia and induction of mixed-function mono-oxygenases accelerate the formation of acetylene. Experiments performed in vitro with rat liver microsomal fractions yield analogous results. PMID:1326938

  12. Synthesis of functional acetylene derivatives from calcium carbide.

    PubMed

    Lin, Zhewang; Yu, Dingyi; Sum, Yin Ngai; Zhang, Yugen

    2012-04-01

    AHA Erlebnis: CaC(2), used to produce acetylene until several decades ago, is re-emerging as a cheap, sustainable resource synthesized from coal and lignocellulosic biomass. We report efficient catalytic protocols for the synthesis of functional acetylene derivatives from CaC(2) through aldehyde, alkyne, and amine (AAA) as well as alkyne, haloalkane, and amine (AHA) couplings, and in addition demonstrate its use in click and Sonogashira chemistry, showing that calcium carbide is a sustainable and cost-efficient carbon source. PMID:22378645

  13. Channel-resolved above-threshold double ionization of acetylene.

    PubMed

    Gong, Xiaochun; Song, Qiying; Ji, Qinying; Lin, Kang; Pan, Haifeng; Ding, Jingxin; Zeng, Heping; Wu, Jian

    2015-04-24

    We experimentally investigate the channel-resolved above-threshold double ionization (ATDI) of acetylene in the multiphoton regime using an ultraviolet femtosecond laser pulse centered at 395 nm by measuring all the ejected electrons and ions in coincidence. As compared to the sequential process, diagonal lines in the electron-electron joint energy spectrum are observed for the nonsequential ATDI owing to the correlative sharing of the absorbed multiphoton energies. We demonstrate that the distinct channel-resolved sequential and nonsequential ATDI spectra can clearly reveal the photon-induced acetylene-vinylidene isomerization via proton migration on the cation or dication states. PMID:25955049

  14. Measurement of volume resistivity/conductivity of metallic alloy in inhibited seawater by optical interferometry techniques

    SciTech Connect

    Habib, K.

    2011-03-15

    Optical interferometry techniques were used for the first time to measure the volume resistivity/conductivity of carbon steel samples in seawater with different concentrations of a corrosion inhibitor. In this investigation, the real-time holographic interferometry was carried out to measure the thickness of anodic dissolved layer or the total thickness, U{sub total}, of formed oxide layer of carbon steel samples during the alternating current (ac) impedance of the samples in blank seawater and in 5-20 ppm TROS C-70 inhibited seawater, respectively. In addition, a mathematical model was derived in order to correlate between the ac impedance (resistance) and the surface (orthogonal) displacement of the surface of the samples in solutions. In other words, a proportionality constant [resistivity ({rho}) or conductivity ({sigma})= 1/{rho}] between the determined ac impedance [by electrochemical impedance spectroscopy (EIS) technique] and the orthogonal displacement (by the optical interferometry techniques) was obtained. The value of the resistivity of the carbon steel sample in the blank seawater was found similar to the value of the resistivity of the carbon steel sample air, around 1 x 10{sup -5}{Omega} cm. On the contrary, the measured values of the resistivity of the carbon steel samples were 1.85 x 10{sup 7}, 3.35 x 10{sup 7}, and 1.7 x 10{sup 7}{Omega} cm in 5, 10, and 20 ppm TROS C-70 inhibited seawater solutions, respectively. Furthermore, the determined value range of {rho} of the formed oxide layers, from 1.7 x 10{sup 7} to 3.35 x 10{sup 7}{Omega} cm, is found in a reasonable agreement with the one found in literature for the Fe oxide-hydroxides, i.e., goethite ({alpha}-FeOOH) and for the lepidocrocite ({gamma}-FeOOH), 1 x 10{sup 9}{Omega} cm. The {rho} value of the Fe oxide-hydroxides, 1 x 10{sup 9}{Omega} cm, was found slightly higher than the {rho} value range of the formed oxide layer of the present study. This is because the former value was determined

  15. 46 CFR 56.50-103 - Fixed oxygen-acetylene distribution piping.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 2 2013-10-01 2013-10-01 false Fixed oxygen-acetylene distribution piping. 56.50-103... oxygen-acetylene distribution piping. (a) This section applies to fixed piping installed for the distribution of oxygen and acetylene carried in cylinders as vessels stores. (b) The distribution piping...

  16. 46 CFR 56.50-103 - Fixed oxygen-acetylene distribution piping.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 2 2012-10-01 2012-10-01 false Fixed oxygen-acetylene distribution piping. 56.50-103... oxygen-acetylene distribution piping. (a) This section applies to fixed piping installed for the distribution of oxygen and acetylene carried in cylinders as vessels stores. (b) The distribution piping...

  17. 46 CFR 56.50-103 - Fixed oxygen-acetylene distribution piping.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 2 2011-10-01 2011-10-01 false Fixed oxygen-acetylene distribution piping. 56.50-103... oxygen-acetylene distribution piping. (a) This section applies to fixed piping installed for the distribution of oxygen and acetylene carried in cylinders as vessels stores. (b) The distribution piping...

  18. 46 CFR 56.50-103 - Fixed oxygen-acetylene distribution piping.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 2 2010-10-01 2010-10-01 false Fixed oxygen-acetylene distribution piping. 56.50-103... oxygen-acetylene distribution piping. (a) This section applies to fixed piping installed for the distribution of oxygen and acetylene carried in cylinders as vessels stores. (b) The distribution piping...

  19. 46 CFR 56.50-103 - Fixed oxygen-acetylene distribution piping.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 2 2014-10-01 2014-10-01 false Fixed oxygen-acetylene distribution piping. 56.50-103... oxygen-acetylene distribution piping. (a) This section applies to fixed piping installed for the distribution of oxygen and acetylene carried in cylinders as vessels stores. (b) The distribution piping...

  20. 46 CFR 154.1735 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... mixture must have a refrigeration system without vapor compression or have a refrigeration system with the... separate cargo piping, vent piping, and refrigeration equipment for methyl acetylene-propadiene that are segregated from other cargo piping, vent piping and refrigeration equipment on the vessel....

  1. 46 CFR 154.1735 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... mixture must have a refrigeration system without vapor compression or have a refrigeration system with the... separate cargo piping, vent piping, and refrigeration equipment for methyl acetylene-propadiene that are segregated from other cargo piping, vent piping and refrigeration equipment on the vessel....

  2. 46 CFR 154.1735 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... mixture must have a refrigeration system without vapor compression or have a refrigeration system with the... separate cargo piping, vent piping, and refrigeration equipment for methyl acetylene-propadiene that are segregated from other cargo piping, vent piping and refrigeration equipment on the vessel....

  3. Interstitial pneumonitis after acetylene welding: a case report.

    PubMed

    Brvar, Miran

    2014-01-01

    Acetylene is a colorless gas commonly used for welding. It acts mainly as a simple asphyxiant. In this paper, however, we present a patient who developed a severe interstitial pneumonitis after acetylene exposure during aluminum welding. A 44-year old man was welding with acetylene, argon and aluminum electrode sticks in a non-ventilated aluminum tank for 2 h. Four hours after welding dyspnea appeared and 22 h later he was admitted at the Emergency Department due to severe respiratory insufficiency with pO2 = 6.7 kPa. Chest X-ray showed diffuse interstitial infiltration. Pulmonary function and gas diffusion tests revealed a severe restriction (55% of predictive volume) and impaired diffusion capacity (47% of predicted capacity). Toxic interstitial pneumonitis was diagnosed and high-dose systemic corticosteroid methylprednisolone and inhalatory corticosteroid fluticasone therapy was started. Computed Tomography (CT) of the lungs showed a diffuse patchy ground-glass opacity with no signs of small airway disease associated with interstitial pneumonitis. Corticosteroid therapy was continued for the next 8 weeks gradually reducing the doses. The patient's follow-up did not show any deterioration of respiratory function. In conclusion, acetylene welding might result in severe toxic interstitial pneumonitis that improves after an early systemic and inhalatory corticosteroid therapy. PMID:24658888

  4. Fatal carbon monoxide intoxication after acetylene gas welding of pipes.

    PubMed

    Antonsson, Ann-Beth; Christensson, Bengt; Berge, Johan; Sjögren, Bengt

    2013-06-01

    Acetylene gas welding of district heating pipes can result in exposure to high concentrations of carbon monoxide. A fatal case due to intoxication is described. Measurements of carbon monoxide revealed high levels when gas welding a pipe with closed ends. This fatality and these measurements highlight a new hazard, which must be promptly prevented. PMID:23307861

  5. Low energy electron impact vibrational excitation of acetylene

    NASA Astrophysics Data System (ADS)

    Patra, Sigma; Hargreaves, Leigh; Khakoo, Murtadha

    2016-05-01

    Experimental differential cross sections for the vibration excitation of the four fundamental modes of acetylene at low incident electron energies from 1 eV to 20 eV and scattering angles of 10o to 130o will be presented. The results will be compared to results available in the literature. Funded by NSF-AMOP-RUI Grant.

  6. 77 FR 13969 - Revising Standards Referenced in the Acetylene Standard

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-08

    ... Association (GGA) acetylene standard (see 76 FR 75782). In the DFR, OSHA deleted reference to CGA G-1-2003 and... final rule published on December 5, 2011 (76 FR 75782), is effective on March 5, 2012. For the purposes....C. 553, Secretary of Labor's Order 1-2012 (77 FR 3912), and 29 CFR part 1911. Signed at...

  7. 76 FR 75840 - Revising Standards Referenced in the Acetylene Standard

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-12-05

    ... language from outdated standards published by standards developing organizations (``SDO standards'') (69 FR... Association standard, CGA G-1-2003, in the Acetylene Standard. See 74 FR 40442 and 74 FR 40450, respectively. OSHA received no adverse comments on the DFR, and it became effective on November 9, 2009. See 74...

  8. Near-threshold vibrational excitation of acetylene by positron impact

    SciTech Connect

    Oliveira, Eliane M. de; Lima, Marco A. P.; Sanchez, Sergio d'A.; Varella, Marcio T. do N.

    2010-01-15

    We report vibrational excitation cross sections for C-C and C-H symmetric stretch modes of acetylene by positron impact. The contribution of these infrared inactive modes to the annihilation parameter is also addressed. The Feshbach projection operator approach was employed to vibrationally resolve e{sup +}-acetylene scattering phase shifts obtained with the Schwinger multichannel method. The present results point out a virtual state pole at the equilibrium geometry of acetylene that becomes a bound state as either bond is stretched, in qualitative agreement with previous calculations for small hydrocarbons. The vibrational couplings are stronger for the C-C mode, giving rise to a bound state pole within the Franck-Condon region of the vibrational ground state. These bound and virtual states give rise to sharp threshold structures (vibrational resonances) in both the vibrational excitation cross sections and the annihilation parameter (Z{sub eff}). We found fair agreement between the present calculations and previously reported e{sup +}-acetylene vibrational excitation cross sections.

  9. Potent In Vitro Antifungal Activities of Naturally Occurring Acetylenic Acids▿

    PubMed Central

    Li, Xing-Cong; Jacob, Melissa R.; Khan, Shabana I.; Ashfaq, M. Khalid; Babu, K. Suresh; Agarwal, Ameeta K.; ElSohly, Hala N.; Manly, Susan P.; Clark, Alice M.

    2008-01-01

    Our continuing effort in antifungal natural product discovery has led to the identification of five 6-acetylenic acids with chain lengths from C16 to C20: 6-hexadecynoic acid (compound 1), 6-heptadecynoic acid (compound 2), 6-octadecynoic acid (compound 3), 6-nonadecynoic acid (compound 4), and 6-icosynoic acid (compound 5) from the plant Sommera sabiceoides. Compounds 2 and 5 represent newly isolated fatty acids. The five acetylenic acids were evaluated for their in vitro antifungal activities against Candida albicans, Candida glabrata, Candida krusei, Candida tropicalis, Candida parapsilosis, Cryptococcus neoformans, Aspergillus fumigatus, Aspergillus flavus, Aspergillus niger, Trichophyton mentagrophytes, and Trichophyton rubrum by comparison with the positive control drugs amphotericin B, fluconazole, ketoconazole, caspofungin, terbinafine, and undecylenic acid. The compounds showed various degrees of antifungal activity against the 21 tested strains. Compound 4 was the most active, in particular against the dermatophytes T. mentagrophytes and T. rubrum and the opportunistic pathogens C. albicans and A. fumigatus, with MICs comparable to several control drugs. Inclusion of two commercially available acetylenic acids, 9-octadecynoic acid (compound 6) and 5,8,11,14-eicosatetraynoic acid (compound 7), in the in vitro antifungal testing further demonstrated that the antifungal activities of the acetylenic acids were associated with their chain lengths and positional triple bonds. In vitro toxicity testing against mammalian cell lines indicated that compounds 1 to 5 were not toxic at concentrations up to 32 μM. Furthermore, compounds 3 and 4 did not produce obvious toxic effects in mice at a dose of 34 μmol/kg of body weight when administered intraperitoneally. Taking into account the low in vitro and in vivo toxicities and significant antifungal potencies, these 6-acetylenic acids may be excellent leads for further preclinical studies. PMID:18458131

  10. Inhibition of cultivable bacteria by chlorhexidine treatment of dentin lesions treated with the ART technique.

    PubMed

    Ersin, Nazan Kocatas; Uzel, Atac; Aykut, Arzu; Candan, Umit; Eronat, Cemal

    2006-01-01

    The aim of this study was to examine the changes in the cultivable microflora of carious dentin before and after atraumatic restorative treatment (ART) and investigate the inhibitory effect of chlorhexidine-gluconate-based cavity disinfectant in the microflora. Using a split mouth design, 35 primary molar pairs with class II carious lesions in 35 patients (mean age 7.31+/-0.47 years) were selected. The total viable counts (TVC), Streptococcus mutans and lactobacilli were first measured in the center of the infected demineralized lesion and then from the hard dentine after caries removal by the ART technique. Chlorhexidine-gluconate (2%)-based cavity disinfectant was applied to one of the molar pairs and the other molar received no disinfectant treatment. Thereafter, all of the teeth were restored with glass ionomer cement (GIC). Cavities were reassessed after 6 months and again dentine samples were microbiologically investigated. Removal of carious dentine by ART significantly reduced TVC, S. mutans and lactobacilli. After 6 months, application of chlorhexidine exhibited a greater significant reduction in TVC (p=0.013), and a significant reduction in S. mutans compared to the nondisinfected group (p<0.001). A significant reduction in lactobacilli counts was observed in both groups after 6 months, but the difference between the disinfected and nondisinfected groups was not significant (p=0.056). ART was found to be effective in reducing the cultivable microflora and chlorhexidine-gluconate-based cavity disinfectant might serve as a suitable additional agent in inhibiting the residual bacteria in the dentine. PMID:16508277

  11. Enhanced acetylene emission near the north pole of Jupiter

    NASA Technical Reports Server (NTRS)

    Drossart, Pierre; Bezard, Bruno; Encrenaz, Therese; Atreya, Sushil; Lacy, John; Serabyn, Eugene; Tokunaga, Alan

    1986-01-01

    The present paper is concerned with observations of acetylene fundamental and hot band vibrational emission lines from the planet Jupiter. It is pointed out that the observation of a polar bright spot in the atmosphere of Jupiter is characterized by an enhancement in the individual lines of C2H2 which can be interpreted as an enhancement in the acetylene abundance. However, a purely thermal effect, on non-LTE phenomena cannot be excluded. The intensity of the observed hot band lines is also consistent with either hypothesis. The reported observations were performed with a cooled Fabry-Perot Grating Spectrometer (FPGS). Observations and instrumentation are considered in detail along with the calculation of synthetic spectra on the basis of a line-by-line computation, and the interpretation of the obtained data.

  12. Enhanced acetylene emission near the north pole of Jupiter

    NASA Technical Reports Server (NTRS)

    Drossart, P.; Bezard, B.; Atreya, S.; Lacy, J.; Serabyn, E.

    1986-01-01

    The present paper is concerned with observations of acetylene fundamental and hot band vibrational emission lines from the planet Jupiter. It is pointed out that the observation of a polar bright spot in the atmosphere of Jupiter is characterized by an enhancement in the individual lines of C2H2 which can be interpreted as an enhancement in the acetylene abundance. However, a purely thermal effect, or non-LTE phenomena cannot be excluded. The intensity of the observed hot band lines is also consistent with either hypothesis. The reported observations were performed with a cooled Fabry-Perot Grating Spectrometer (FPGS). Observations and instrumentation are considered in detail along with the calculation of synthetic spectra on the basis of a line-by-line computation, and the interpretation of the obtained data.

  13. Detonation engine fed by acetylene-oxygen mixture

    NASA Astrophysics Data System (ADS)

    Smirnov, N. N.; Betelin, V. B.; Nikitin, V. F.; Phylippov, Yu. G.; Koo, Jaye

    2014-11-01

    The advantages of a constant volume combustion cycle as compared to constant pressure combustion in terms of thermodynamic efficiency has focused the search for advanced propulsion on detonation engines. Detonation of acetylene mixed with oxygen in various proportions is studied using mathematical modeling. Simplified kinetics of acetylene burning includes 11 reactions with 9 components. Deflagration to detonation transition (DDT) is obtained in a cylindrical tube with a section of obstacles modeling a Shchelkin spiral; the DDT takes place in this section for a wide range of initial mixture compositions. A modified ka-omega turbulence model is used to simulate flame acceleration in the Shchelkin spiral section of the system. The results of numerical simulations were compared with experiments, which had been performed in the same size detonation chamber and turbulent spiral ring section, and with theoretical data on the Chapman-Jouguet detonation parameters.

  14. Orbital-resolved strong-field single ionization of acetylene

    NASA Astrophysics Data System (ADS)

    Ji, Qinying; Cui, Sen; You, Xinyuan; Gong, Xiaochun; Song, Qiying; Lin, Kang; Pan, Haifeng; Ding, Jingxin; Zeng, Heping; He, Feng; Wu, Jian

    2015-10-01

    We resolve the strong-field single ionization of acetylene into different channels by differentially normalizing the lateral momenta of the directly escaped electrons from the aligned and antialigned molecules. Distinct electron momentum distributions for different channels are observed using both near-infrared and ultraviolet femtosecond laser pulses with Keldysh parameters close to 1. The results are interpreted as a signature of multiple ionization orbitals.

  15. Tuning the Electronic Properties of Acetylenic Fluorenes by Phosphaalkene Incorporation.

    PubMed

    Svyaschenko, Yurii V; Orthaber, Andreas; Ott, Sascha

    2016-03-14

    Versatile synthetic protocols for 2,7- and 3,6-diacetylenic fluorene-9-ylidene phosphanes (F9Ps) were developed. Protodesilylation of trimethylsilyl-protected acetylenic F9Ps affords terminal acetylenes that can be employed in Sonogashira and Glaser-type C-C coupling reactions to give thienyl-decorated and butadiyne-bridged fluorene-9-ylidene phosphanes, respectively. As evidenced by UV/Vis spectroscopy and cyclic voltammetry and corroborated by ab initio calculations, the presence of the P center in the F9Ps induces a significantly reduced HOMO-LUMO splitting that originates from stabilization of the LUMO levels. Variation of the acetylene substitution pattern is an additional tool to influence the optical and electronic properties. Whereas 3,6-disubstituted F9Ps have strong absorptions around 400 nm, mainly due to π-π* transitions, 2,7-diacetylenic F9Ps exhibit longest-wavelength absorptions that have significant charge-transfer character with an onset around 520 nm. PMID:26833389

  16. Kinetics and Structure of Superagglomerates Produced by Silane and Acetylene

    NASA Technical Reports Server (NTRS)

    Mulholland, G. W.; Hamins, A.; Sivathanu, Y.

    1999-01-01

    The evolution of smoke in a laminar diffusion flame involves several steps. The first step is particle inception/nucleation in the high-temperature fuel-rich region of the flame followed by surface growth and coagulation/coalescence of the small particles. As the primary spheres grow in size and lose hydrogen, the colliding particles no longer coalesce but retain their identity as a cluster of primary spheres, termed an agglomerate. Finally, in the upper portion of the flame, the particles enter an oxidizing environment which may lead to partial or complete burnout of the agglomerates. Currently there is no quantitative model for describing the growth of smoke agglomerates up to superagglomerates with an overall dimension of 10 microns and greater. Such particles are produced during the burning of acetylene and fuels containing benzene rings such as toluene and polystyrene. In the case of polystyrene, smoke agglomerates in excess of 1 mm have been observed "raining" out from large fires. Evidence of the formation of superagglomerates in a laminar acetylene/air diffusion flame has been recently reported. Acetylene was chosen as the fuel since the particulate loading in acetylene/air diffusion flames is very high. Photographs were obtained by Sorensen using a microsecond xenon lamp of the "stream" of soot just above the flame. For low flow rates of acetylene, only submicrometer soot clusters are produced and they give rise to the homogeneous appearance of the soot stream. When the flow rate is increased to 1.7 cu cm/s, soot clusters up to 10 microns are formed and they are responsible for the graininess and at a flow rate of 3.4 cu cm/s, a web of interconnected clusters as large as the width of the flame is seen. This interconnecting web of superagglomerates is described as a gel state by Sorensen et al (1998). This is the first observation of a gel for a gas phase system. It was observed that this gel state immediately breaks up into agglomerates due to buoyancy

  17. Acetylene-derived polymers and their applications in hair and skin care.

    PubMed

    Petter, P J

    1989-02-01

    Synopsis Since the introduction over 30 years ago of polyvinylpyrrolidone (PVP) as the first synthetic hairspray resin, acetylene-derived polymers have found wide and increasing applications in the cosmetics and toiletries industry. This review covers the two main classes of acetylenic polymers. In the first class, in which the chemistry may be traced back to reaction of acetylene with formaldehyde, are included PVP homopolymers and copolymers of VP with vinyl acetate, dimethylaminoethyl methacrylate, vinylcaprolactam and styrene. In the second class, stemming from reaction of acetylene with methanol, are the poly (vinyl methyl ether/maleic acid) monoester resins. PMID:19456933

  18. Synthesis, structure and cytotoxic activity of acetylenic derivatives of betulonic and betulinic acids

    NASA Astrophysics Data System (ADS)

    Bębenek, Ewa; Chrobak, Elwira; Wietrzyk, Joanna; Kadela, Monika; Chrobak, Artur; Kusz, Joachim; Książek, Maria; Jastrzębska, Maria; Boryczka, Stanisław

    2016-02-01

    A series of acetylenic derivatives of betulonic and betulinic acids has been synthesized and characterized by 1H and 13C NMR, IR and MS spectroscopy. The structure of propargyl betulonate 4 and propargyl betulinate-DMF solvate 8A was solved by X-ray diffraction. Thermal properties were examined using a DSC technique. The resulting alkynyl derivatives, as well as betulin 1 and betulinic acid 3, were evaluated in vitro for their cytotoxic activity against human T47D breast cancer, CCRF/CEM leukemia, SW707 colorectal, murine P388 leukemia and BALB3T3 normal fibroblasts cell lines. Several of the obtained compounds have a favorable cytotoxic profile than betulin 1. Propargyl betulinate 8 was the most active derivative, being up to 3-fold more potent than betulin 1 against the human leukemia (CCRF/CEM) cell line, with an IC50 value of 3.9 μg/mL.

  19. Inhibition of denitrification by ultraviolet radiation

    NASA Astrophysics Data System (ADS)

    Mancinelli, R. L.; White, M. R.

    It has been shown that UV-A (λ = 320- 400 nm) and UV-B (λ = 280 - 320 nm) inhibit photosynthesis, nitrogen fixation and nitrification. The purpose of this study was to determine the effects, if any, on denitrification in a microbial community inhabiting the intertidal. The community studied is the microbial mat consisting primarily of Lyngbya that inhabits the Pacific marine intertidal, Baja California, Mexico. Rates of denitrification were determined using the acetylene blockage technique. Pseudomonas fluorescens (ATCC # 17400) was used as a control organism, and treated similarly to the mat samples. Samples were incubated either beneath a PAR transparent, UV opaque screen (OP3), or a mylar screen to block UV-B, or a UV transparent screen (UVT) for 2 to 3 hours. Sets of samples were also treated with nitrapyrin to inhibit nitrification, or DCMU to inhibit photosynthesis and treated similarly. Denitrification rates were greater in the UV protected samples than in the UV exposed samples the mat samples as well as for the Ps. fluorescens cultures. Killed controls exhibited no activity. In the DCMU and nitrapyrin treated samples denitrification rates were the same as in the untreated samples. These data indicate that denitrification is directly inhibited by UV radiation.

  20. Inhibition of denitrification by ultraviolet radiation.

    PubMed

    Mancinelli, R L; White, M R

    2000-01-01

    It has been shown that UV-A (lambda=320-400 nm) and UV-B (lambda=280-320 nm) inhibit photosynthesis, nitrogen fixation and nitrification. The purpose of this study was to determine the effects, if any, on denitrification in a microbial community inhabiting the intertidal. The community studied is the microbial mat consisting primarily of Lyngbya that inhabits the Pacific marine intertidal, Baja California, Mexico. Rates of denitrification were determined using the acetylene blockage technique. Pseudomonas fluorescens (ATCC #17400) was used as a control organism, and treated similarly to the mat samples. Samples were incubated either beneath a PAR transparent, UV opaque screen (OP3), or a mylar screen to block UV-B, or a UV transparent screen (UVT) for 2 to 3 hours. Sets of samples were also treated with nitrapyrin to inhibit nitrification, or DCMU to inhibit photosynthesis and treated similarly. Denitrification rates were greater in the UV protected samples than in the UV exposed samples the mat samples as well as for the Ps fluorescens cultures. Killed controls exhibited no activity. In the DCMU and nitrapyrin treated samples denitrification rates were the same as in the untreated samples. These data indicate that denitrification is directly inhibited by UV radiation. PMID:12038490

  1. Autoxidation and acetylene-accelerated oxidation of NO in a 2-phase system; implications for the expression of denitrification in ex situ experiments

    NASA Astrophysics Data System (ADS)

    Nadeem, Shahid; Dörsch, Peter; Bakken, Lars

    2013-04-01

    flasks (with and without C2H2), and monitored for O2, NO, N2O and N2 production while depleting the oxygen and switching to anoxic respiration. Acetylene effectively scavenged NO from the cultures until oxygen concentration reached below ~0.19 mL L-1, and the estimated rate of acetylene-accelerated NO oxidation was more than sufficient to explain an observed reduction of the N2O production induced by acetylene. When [O2] reached below 0.19 mL L-1, the NO concentrations increased and stabilized at the same level as in the treatments without acetylene, but the rate of denitrification was much lower than without acetylene. The results indicate that the early accumulation of 10-20 nM NO during oxygen depletion has a significant effect on the expression of denitrification in soil communities. This warrants a greater interest in NO as a regulator of denitrification in soils and shows that the acetylene inhibition method may be problematic even for intentionally anoxic incubations, unless precautions are taken to secure initial O2-concentrations below 0.19 mL O2 L-1.

  2. Mechanism of cinnamic acid-induced trypsin inhibition: A multi-technique approach

    NASA Astrophysics Data System (ADS)

    Zhang, Hongmei; Zhou, Qiuhua; Cao, Jian; Wang, Yanqing

    2013-12-01

    In order to investigate the association of the protease trypsin with cinnamic acid, the interaction was characterized by using fluorescence, UV-vis absorption spectroscopy, molecular modeling and an enzymatic inhibition assay. The binding process may be outlined as follows: cinnamic acid can interact with trypsin with one binding site to form cinnamic acid-trypsin complex, resulting in inhibition of trypsin activity; the spectroscopic data show that the interaction is a spontaneous process with the estimated enthalpy and entropy changes being -8.95 kJ mol-1 and 50.70 J mol-1 K-1, respectively. Noncovalent interactions make the main contribution to stabilize the trypsin-cinnamic acid complex; cinnamic acid can enter into the primary substrate-binding pocket and alter the environment around Trp and Tyr residues.

  3. Acetylene Fermentation: Relevance to Primordial Biogeochemistry and the Search for Life in the Outer Solar System

    NASA Astrophysics Data System (ADS)

    Oremland, R. S.; Baesman, S. M.; Miller, L. G.

    2014-02-01

    Acetylene supports the growth of some terrestrial anaerobes. The reaction is highly exothermic. The abundance of acetylene in the methane-rich planet(oid)s of the outer solar system could represent a means of nourishment for resident alien microbes.

  4. Nitrogen fixation (Acetylene Reduction) by annual winter legumes on a coal surface mine

    SciTech Connect

    Gabrielson, F.C.

    1982-01-01

    The winter annuals, crimson clover, rose clover, subterranean clover and hairy vetch, were evaluated for nitrogen fixing capacity on coal surface mine substrates by measuring their ability to reduce acetylene to ethylene. The effects of fertilizer, Abruzzi rye, Kentucky 31 fescue grass and a phytotoxic plant Chenopodium album on nitrogen fixation were also assessed. Crimson clover was recommended as the best legume to use on topsoil and shale in the south. Hairy vetch gave good results on shale and subterranean clover did well on topsoil. The use of these species for revegetation is discussed. Overall, no correlation between substrate pH and ethylene levels was found and effects of substrate depended upon the legume species. Super phosphate fertilizer supported less nitrogen fixation than 13-13-13. Abruzzi rye in some unknown way inhibited plant density and nitrogen fixation by legumes but not by free living substrate micro-organisms. Shale from under dead Chenopodium plants in both field and greehouse experiments did not inhibit nitrogen fixation. 7 tables.

  5. Nitrogen fixation (acetylene reduction) by annual winter legumes on a coal surface mine

    SciTech Connect

    Gabrielson, F.C.

    1982-01-01

    The winter annuals, crimson clover, rose clover, subterranean clover and hairy vetch, were evaluated for their ability to fix nitrogen on coal surface mine substrates by measuring their ability to reduce acetylene to ethylene. The effects of fertilizer, Abruzzi ryegrass, Kentucky 31 fescue grass and a phytotoxic plant Chenopodium album on nitrogen fixation was also assessed. Crimson clover was recommended as the best legume to use on topsoil and shale in the South. Hairy vetch gave good results on shale and subterranean clover did well on topsoil. The use of these species for revegetation is discussed. Overall, no correlation between substrate pH and ethylene levels was found and effects of substrate depended upon the legume species. Super phosphate fertilizer supported less nitrogen fixation than 13-13-13. Abruzzi ryegrass in some unknown way inhibited plant density and nitrogen fixation by legumes but not by free living substrate micro-organisms. Shale from under dead Chenopodium plants in both field and greenhouse experiments did not inhibit nitrogen fixation. 11 references, 7 tables.

  6. Numerical study of ethylene and acetylene laminar flame speeds

    SciTech Connect

    Marinov, N.M.; Pitz, W.J.; Westbrook, C.K.

    1995-03-01

    Detailed chemical kinetic computations for ethylene-air and acetylene-air mixtures have been performed to simulate laminar flame speeds. Sensitivity analysis was applied to determine those reactions which strongly influence flame propagation. In ethylene-air mixtures, the C{sub 2}H{sub 3} + O{sub 2} = CH{sub 2}CHO + O reaction was one of the most sensitive reactions in the C{sub 2}H{sub 4}/C{sub 2}H{sub 3} submechanism and therefore this reaction was very important to ethylene flame propagation. This reaction was not considered in previously reported mechanisms used to model ethylene-air flame propagation. In acetylene-air mixtures, the C{sub 2}H{sub 2}+O {yields} Products, HCCO+H=CH{sub 2}(s)+CO, HCCO+O{sub 2}=CO{sub 2}+CO+H, H+C{sub 2}H{sub 2}(+M) = C{sub 2}H{sub 3}(+M) and CH{sub 2}(s)+C{sub 2}H{sub 2} = H{sub 2}CCCH+H were the most sensitive reactions in the C{sub 2}H{sub 2}/HCCO / CH{sub 2}(s) reaction set.

  7. Ultrafast hydrogen migration in acetylene cation driven by non-adiabatic effects.

    PubMed

    Madjet, Mohamed El-Amine; Li, Zheng; Vendrell, Oriol

    2013-03-01

    Non-adiabatic dynamics of the acetylene cation is investigated using mixed quantum-classical dynamics based on trajectory surface hopping. To describe the non-adiabatic effects, two surface hopping methods are used, namely, Tully's fewest switches and Landau-Zener surface hopping. Similarities and differences between the results based on those two methods are discussed. We find that the photoionization of acetylene into the first excited state A(2)Σg(+) drives the molecule from the linear structure to a trans-bent structure. Through a conical intersection the acetylene cation can relax back to either the ground state of acetylene or vinylidene. We conclude that hydrogen migration always takes place after non-radiative electronic relaxation to the ground state of the monocation. Based on the analysis of correlation functions we identify coherent oscillations between acetylene and vinylidene with a period of about 70 fs after the electronic relaxation. PMID:23485298

  8. Low optical insertion-loss and vacuum-pressure all-fiber acetylene cell based on hollow-core photonic crystal fiber.

    PubMed

    Light, P S; Couny, F; Benabid, F

    2006-09-01

    We report a novel and easy-to-implement hollow-core photonic crystal fiber cell fabrication technique based on helium diffusion through silica. The formed gas cells combine low optical insertion loss (1.8 dB) and vacuum acetylene pressure (microbar regime). The estimates of the final gas pressure, using both Voigt interpolation and electromagnetically induced transparency, show a good match with the initial fitting pressure. PMID:16902611

  9. Quantum Chemical Simulations Reveal Acetylene-Based Growth Mechanisms in the Chemical Vapor Deposition Synthesis of Carbon Nanotubes

    SciTech Connect

    Eres, Gyula; Wang, Ying; Gao, Xingfa; Qian, Hu-Jun; Ohta, Yasuhito; Wu, Xiaona; Morokuma, Keiji; Irle, Stephan

    2014-01-01

    Nonequilibrium quantum chemical molecular dynamics (QM/MD) simulation of early stages in the nucleation process of carbon nanotubes from acetylene feedstock on an Fe38 cluster was performed based on the density-functional tight-binding (DFTB) potential. Representative chemical reactions were studied by complimentary static DFTB and density functional theory (DFT) calculations. Oligomerization and cross-linking reactions between carbon chains were found as the main reaction pathways similar to that suggested in previous experimental work. The calculations highlight the inhibiting effect of hydrogen for the condensation of carbon ring networks, and a propensity for hydrogen disproportionation, thus enriching the hydrogen content in already hydrogen-rich species and abstracting hydrogen content in already hydrogen-deficient clusters. The ethynyl radical C2H was found as a reactive, yet continually regenerated species, facilitating hydrogen transfer reactions across the hydrocarbon clusters. The nonequilibrium QM/MD simulations show the prevalence of a pentagon-first nucleation mechanism where hydrogen may take the role of one arm of an sp2 carbon Y-junction. The results challenge the importance of the metal carbide formation for SWCNT cap nucleation in the VLS model and suggest possible alternative routes following hydrogen-abstraction acetylene addition (HACA)-like mechanisms commonly discussed in combustion synthesis.

  10. The Effect of Surface Finish on Low-Temperature Acetylene-Based Carburization of 316L Austenitic Stainless Steel

    NASA Astrophysics Data System (ADS)

    Ge, Yindong; Ernst, Frank; Kahn, Harold; Heuer, Arthur H.

    2014-12-01

    We observed a strong influence of surface finish on the efficacy of low-temperature acetylene-based carburization of AISI 316L austenitic stainless steel. Steel coupons were prepared with different surface finishes prior to carburization, from P400 SiC grit paper to 1- µm-diameter-diamond-paste. The samples with the finer surface finish developed a thicker "case" (a carbon-rich hardened surface layer) and a larger surface carbon concentration. Transmission electron microscopy revealed that the differences arose mainly from the nature of the deformation-induced disturbed layer on the steel surface. A thick (>400 nm) disturbed layer consisting of nano-crystalline grains (≈10 nm diameter) inhibits acetylene-based carburization. The experimental observations can be explained by assuming that during machining or coarse polishing, the surface oxide layer is broken up and becomes incorporated into the deformation-induced disturbed layer. The incorporated oxide-rich films retard or completely prevent the ingress of carbon into the stainless steel.

  11. A first principles study of the acetylene-water interaction

    SciTech Connect

    Tzeli, Demeter; Mavridis, Aristides; Xantheas, Sotiris S.

    2000-04-08

    We present an extensive study of the stationary points on the acetylene-water (AW) ground-state potential energy surface (PES) aimed in establishing accurate energetics for the two different bonding scenarios that are considered. Those include arrangements in which water acts either as a proton acceptor from one of the acetylene hydrogen atoms or a proton donor to the triple bond. We used a hierarchy of theoretical methods to account for electron correlation [MP2 (second-order Moller-Plesset), MP4 (fourth-order Moller-Plesset), and CCSD(T) (coupled-cluster single double triple)] coupled with a series of increasing size augmented correlation consistent basis sets (aug-cc-pVnZ, n=2,3,4). We furthermore examined the effect of corrections due to basis set superposition error (BSSE). We found that those have a large effect in altering the qualitative features of the PES of the complex. They are responsible for producing a structure of higher (C{sub 2v}) symmetry for the global minimum. Zero-point energy (ZPE) corrections were found to increase the stability of the C{sub 2v} arrangement. For the global (water acceptor) minimum of C{sub 2v} symmetry our best estimates are {delta}E{sub e}=-2.87 kcal/mol ({delta}E{sub 0}=-2.04 kcal/mol) and a van der Waals distance of R{sub e}=2.190 Aa. The water donor arrangement lies 0.3 kcal/mol (0.5 kcal/mol including ZPE corrections) above the global minimum. The barrier for its isomerization to the global minimum is E{sub e}=0.18 kcal/mol; however, inclusion of BSSE- and ZPE-corrections destabilize the water donor arrangement suggesting that it can readily convert to the global minimum. We therefore conclude that there exists only one minimum on the PES in accordance with previous experimental observations. To this end, vibrational averaging and to a lesser extend proper description of intermolecular interactions (BSSE) were found to have a large effect in altering the qualitative features of the ground-state PES of the acetylene

  12. Mechanism-based inactivation of cytochrome P-450 dependent benzo(a)pyrene hydroxylase activity by acetylenic and olefinic polycyclic arylhydrocarbons

    SciTech Connect

    Gan, L.S.

    1986-01-01

    A series of aryl acetylenes and aryl olefins have been examined as substrates and inhibitors of cytochrome P-450 dependent monooxygenases in liver microsomes from 5,6-benzoflavone or phenobarbital pretreated rats. 1-Ethynylpyrene (EP), 3-ethynylperylene (EPL), cis- and trans-1-(2-bromo-vinyl)pyrene (c-BVP and t-BVP), and 1-allylpyrene (AP) serve as mechanism-based irreversible inactivators (suicide inhibitors) of benzo(a)pyrene (BP) hydroxylase, while 1-vinyl-pyrene (VP) and phenyl 1-pyrenyl acetylene (PPA) do not cause a detectable suicide inhibition of the BP hydroxylase. The mechanism-based loss of BP hydroxylase activity caused by the aryl acetylenes is not accompanied by a corresponding loss of the P-450 content of the microsomes. In the presence of NADPH, /sup 3/H-labeled EP covalently attached to P-450 isozymes with a measured stoichiometry of one mole of EP per mole of the P-450 heme. The results of the effects of these aryl derivatives in the mammalian cell-mediated mutagenesis assay and toxicity assay show that none of the compounds examined nor any of the their metabolites produced in the incubation system are cytotoxic to V79 cells.

  13. Correlation between hydrogen bond basicity and acetylene solubility in room temperature ionic liquids.

    PubMed

    Palgunadi, Jelliarko; Hong, Sung Yun; Lee, Jin Kyu; Lee, Hyunjoo; Lee, Sang Deuk; Cheong, Minserk; Kim, Hoon Sik

    2011-02-10

    Room temperature ionic liquids (RTILs) are proposed as the alternative solvents for the acetylene separation in ethylene generated from the naphtha cracking process. The solubility behavior of acetylene in RTILs was examined using a linear solvation energy relationship based on Kamlet-Taft solvent parameters including the hydrogen-bond acidity or donor ability (α), the hydrogen-bond basicity or acceptor ability (β), and the polarity/polarizability (π*). It is found that the solubility of acetylene linearly correlates with β value and is almost independent of α or π*. The solubility of acetylene in RTILs increases with increasing hydrogen-bond acceptor (HBA) ability of the anion, but is little affected by the nature of the cation. Quantum mechanical calculations demonstrate that the acidic proton of acetylene specifically forms hydrogen bond with a basic oxygen atom on the anion of a RTIL. On the other hand, although C-H···π interaction is plausible, all optimized structures indicate that the acidic protons on the cation do not specifically associate with the π cloud of acetylene. Thermodynamic analysis agrees well with the proposed correlation: the higher the β value of a RTIL is, the more negative the enthalpy of acetylene absorption in the RTIL is. PMID:21218815

  14. Pattern Recognition Techniques Applied to the Study of Leishmanial Glyceraldehyde-3-Phosphate Dehydrogenase Inhibition

    PubMed Central

    Lozano, Norka B. H.; Oliveira, Rafael F.; Weber, Karen C.; Honorio, Kathia M.; Guido, Rafael V. C.; Andricopulo, Adriano D.; de Sousa, Alexsandro G.; da Silva, Albérico B. F.

    2014-01-01

    Chemometric pattern recognition techniques were employed in order to obtain Structure-Activity Relationship (SAR) models relating the structures of a series of adenosine compounds to the affinity for glyceraldehyde 3-phosphate dehydrogenase of Leishmania mexicana (LmGAPDH). A training set of 49 compounds was used to build the models and the best ones were obtained with one geometrical and four electronic descriptors. Classification models were externally validated by predictions for a test set of 14 compounds not used in the model building process. Results of good quality were obtained, as verified by the correct classifications achieved. Moreover, the results are in good agreement with previous SAR studies on these molecules, to such an extent that we can suggest that these findings may help in further investigations on ligands of LmGAPDH capable of improving treatment of leishmaniasis. PMID:24566143

  15. Organogermanium Chemistry: Germacyclobutanes and digermane Additions to Acetylenes

    SciTech Connect

    Andrew Michael Chubb

    2003-12-12

    This dissertation comprises two main research projects. The first project, presented in Chapter 1, involves the synthesis and thermochemistry of germacyclobutanes (germetanes). Four new germetanes (spirodigermetane, diallylgermetane, dichlorogermetane, and germacyclobutane) have been synthesized using a modified di-Grignard synthesis. Diallylgermetane is shown to be a useful starting material for obtaining other germetanes, particularly the parent germetane, germacyclobutane. The gas-phase thermochemistries of spirodigermetane, diallylgermetane and germacyclobutane have been explored via pulsed stirred-flow reactor (SFR) studies, showing remarkable differences in decomposition, depending on the substitution at the germanium atom. The second project investigates the thermochemical, photochemical, and catalytic additions of several digermanes to acetylenes. The first examples of thermo- and photochemical additions of Ge-Ge bonds to C{triple_bond}C are demonstrated. Mechanistic investigations are described and comparisons are made to analogous disilane addition reactions, previously studied in their group.

  16. Acetylene fuel from atmospheric CO2 on Mars

    NASA Technical Reports Server (NTRS)

    Landis, Geoffrey A.; Linne, Diane L.

    1992-01-01

    The Mars mission scenario proposed by Baker and Zubrin (1990) intended for an unmanned preliminary mission is extended to maximize the total impulse of fuel produced with a minimum mass of hydrogen from Earth. The hydrogen along with atmospheric carbon dioxide is processed into methane and oxygen by the exothermic reaction in an atmospheric processing module. Use of simple chemical reactions to produce acetylene/oxygen rocket fuel on Mars from hydrogen makes it possible to produce an amount of fuel that is nearly 100 times the mass of hydrogen brought from earth. If such a process produces the return propellant for a manned Mars mission, the required mission mass in LEO is significantly reduced over a system using all earth-derived propellants.

  17. Inclusion of 13C and D in protonated acetylene

    NASA Astrophysics Data System (ADS)

    Fortenberry, Ryan C.; Roueff, Evelyne; Lee, Timothy J.

    2016-04-01

    The rovibrational spectrum of cyclic, protonated acetylene has been established. The improvement in modern telescopes coupled with the different branching ratios in reaction models welcomes study of 13C-substitution for C2H3+. Quartic force fields (QFFs) have been previously utilized to predict the antisymmetric HCCH stretch in standard c-C2H3+ to within 0.1 cm-1 of experiment and are employed here to generate rovibrational insights for the 13C isotopologues. The zero-point energies are also given for the cyclic and 'Y'-shaped isomers for both 13C and D substitutions. Vibrational intensities and the dipole moments are provided in order to characterize more fully this simple cation.

  18. Ultrafast Extreme Ultraviolet Induced Isomerization of Acetylene Cations

    SciTech Connect

    Jiang, Y.; Rudenko, Artem; Herrwerth, O.; Foucar, L.; Kurka, M.; Kuhnel, K.; Lezius, M.; Kling, Matthias; van Tilborg, Jeroen; Belkacem, Ali; Ueda, K.; Dusterer, S.; Treusch, R.; Schroter, Claus-Dieter; Moshammer, Robbert; Ullrich, Joachim

    2011-06-17

    Ultrafast isomerization of acetylene cations ([HC = CH]{sup +}) in the low-lying excited A{sup 2}{Sigma}{sub g}{sup +} state, populated by the absorption of extreme ultraviolet (XUV) photons (38 eV), has been observed at the Free Electron Laser in Hamburg, (FLASH). Recording coincident fragments C{sup +} + CH{sub 2}{sup +} as a function of time between XUV-pump and -probe pulses, generated by a split-mirror device, we find an isomerization time of 52 {+-} 15 fs in a kinetic energy release (KER) window of 5.8 < KER < 8 eV, providing clear evidence for the existence of a fast, nonradiative decay channel.

  19. Adhesive and composite evaluation of acetylene-terminated phenylquinoxaline resins

    NASA Technical Reports Server (NTRS)

    Hergenrother, P. M.

    1981-01-01

    A series of acetylene-terminated phenylquinoxaline (ATPQ) oligomers of various molecular weights were prepared and subsequently chain extended by the thermally induced reaction of the ethynyl groups. The processability and thermal properties of these oligomers and their cured resins were compared with that of a relatively high molecular weight linear polyphenylquinoxaline (PPQ) with the same chemical backbone. The ATPQ oligomers exhibited significantly better processability than the linear PPQ but the PPQ displayed substantially better thermooxidative stability. Adhesive (Ti/Ti) and composite (graphite filament reinforcement) work was performed to evaluate the potential of these materials for structural applications. The PPQ exhibited better retention of adhesive and laminate properties than the ATPQ resins at 260 C after aging for 500 hr at 260 C in circulating air.

  20. Ultrafast Extreme Ultraviolet Induced Isomerization of Acetylene Cations

    SciTech Connect

    Jiang, Y. H.; Kurka, M.; Kuehnel, K. U.; Schroeter, C. D.; Moshammer, R.; Rudenko, A.; Foucar, L.; Herrwerth, O.; Lezius, M.; Kling, M. F.; Tilborg, J. van; Belkacem, A.; Ueda, K.; Duesterer, S.; Treusch, R.; Ullrich, J.

    2010-12-31

    Ultrafast isomerization of acetylene cations ([HC=CH]{sup +}) in the low-lying excited A{sup 2}{Sigma}{sub g}{sup +} state, populated by the absorption of extreme ultraviolet (XUV) photons (38 eV), has been observed at the Free Electron Laser in Hamburg, (FLASH). Recording coincident fragments C{sup +}+CH{sub 2}{sup +} as a function of time between XUV-pump and -probe pulses, generated by a split-mirror device, we find an isomerization time of 52{+-}15 fs in a kinetic energy release (KER) window of 5.8

  1. Acetylene as Fast Food: Implications for Development of Life on Anoxic Primordial Earth and in the Outer Solar System

    NASA Astrophysics Data System (ADS)

    Oremland, Ronald S.; Voytek, Mary A.

    2008-02-01

    Acetylene occurs, by photolysis of methane, in the atmospheres of jovian planets and Titan. In contrast, acetylene is only a trace component of Earth's current atmosphere. Nonetheless, a methane-rich atmosphere has been hypothesized for early Earth; this atmosphere would also have been rich in acetylene. This poses a paradox, because acetylene is a potent inhibitor of many key anaerobic microbial processes, including methanogenesis, anaerobic methane oxidation, nitrogen fixation, and hydrogen oxidation. Fermentation of acetylene was discovered 25 years ago, and Pelobacter acetylenicus was shown to grow on acetylene by virtue of acetylene hydratase, which results in the formation of acetaldehyde. Acetaldehyde subsequently dismutates to ethanol and acetate (plus some hydrogen). However, acetylene hydratase is specific for acetylene and does not react with any analogous compounds. We hypothesize that microbes with acetylene hydratase played a key role in the evolution of Earth's early biosphere by exploiting an available source of carbon from the atmosphere and in so doing formed protective niches that allowed for other microbial processes to flourish. Furthermore, the presence of acetylene in the atmosphere of a planet or planetoid could possibly represent evidence for an extraterrestrial anaerobic ecosystem.

  2. Acetylene as fast food: Implications for development of life on anoxic primordial earth and in the outer solar system

    USGS Publications Warehouse

    Oremland, R.S.; Voytek, M.A.

    2008-01-01

    Acetylene occurs, by photolysis of methane, in the atmospheres of jovian planets and Titan. In contrast, acetylene is only a trace component of Earth's current atmosphere. Nonetheless, a methane-rich atmosphere has been hypothesized for early Earth; this atmosphere would also have been rich in acetylene. This poses a paradox, because acetylene is a potent inhibitor of many key anaerobic microbial processes, including methanogenesis, anaerobic methane oxidation, nitrogen fixation, and hydrogen oxidation. Fermentation of acetylene was discovered 25 years ago, and Pelobacter acetylenicus was shown to grow on acetylene by virtue of acetylene hydratase, which results in the formation of acetaldehyde. Acetaldehyde subsequently dismutates to ethanol and acetate (plus some hydrogen). However, acetylene hydratase is specific for acetylene and does not react with any analogous compounds. We hypothesize that microbes with acetylene hydratase played a key role in the evolution of Earth's early biosphere by exploiting an available source of carbon from the atmosphere and in so doing formed protective niches that allowed for other microbial processes to flourish. Furthermore, the presence of acetylene in the atmosphere of a planet or planetoid could possibly represent evidence for an extraterrestrial anaerobic ecosystem. ?? Mary Ann Liebert, Inc.

  3. Acetylene as fast food: implications for development of life on anoxic primordial Earth and in the outer solar system.

    PubMed

    Oremland, Ronald S; Voytek, Mary A

    2008-02-01

    Acetylene occurs, by photolysis of methane, in the atmospheres of jovian planets and Titan. In contrast, acetylene is only a trace component of Earth's current atmosphere. Nonetheless, a methane-rich atmosphere has been hypothesized for early Earth; this atmosphere would also have been rich in acetylene. This poses a paradox, because acetylene is a potent inhibitor of many key anaerobic microbial processes, including methanogenesis, anaerobic methane oxidation, nitrogen fixation, and hydrogen oxidation. Fermentation of acetylene was discovered approximately 25 years ago, and Pelobacter acetylenicus was shown to grow on acetylene by virtue of acetylene hydratase, which results in the formation of acetaldehyde. Acetaldehyde subsequently dismutates to ethanol and acetate (plus some hydrogen). However, acetylene hydratase is specific for acetylene and does not react with any analogous compounds. We hypothesize that microbes with acetylene hydratase played a key role in the evolution of Earth's early biosphere by exploiting an available source of carbon from the atmosphere and in so doing formed protective niches that allowed for other microbial processes to flourish. Furthermore, the presence of acetylene in the atmosphere of a planet or planetoid could possibly represent evidence for an extraterrestrial anaerobic ecosystem. PMID:18199006

  4. Ionization of large homogeneous and heterogeneous clusters generated in acetylene-Ar expansions: cluster ion polymerization.

    PubMed

    Kočišek, J; Lengyel, J; Fárník, M

    2013-03-28

    Pure acetylene and mixed Ar-acetylene clusters are formed in supersonic expansions of acetylene/argon mixtures and analysed using reflectron time-of-flight mass spectrometer with variable electron energy ionization source. Acetylene clusters composed of more than a hundred acetylene molecules are generated at the acetylene concentration of ≈8%, while mixed species are produced at low concentrations (≈0.7%). The electron energy dependence of the mass spectra revealed the ionization process mechanisms in clusters. The ionization above the threshold for acetylene molecule of 11.5 eV results in the main ionic fragment progression (C2H2)n(+). At the electron energies ≥21.5 eV above the CH+CH(+) dissociative ionization limit of acetylene the fragment ions nominally labelled as (C2H2)nCH(+), n ≥ 2, are observed. For n ≤ 7 these fragments correspond to covalently bound ionic structures as suggested by the observed strong dehydrogenation [(C2H2)n - k × H](+) and [(C2H2)nCH - k × H](+). The dehydrogenation is significantly reduced in the mixed clusters where evaporation of Ar instead of hydrogen can stabilize the nascent molecular ion. The C3H3(+) ion was previously assigned to originate from the benzene molecular ion; however, the low appearance energy of ≈13.7 eV indicates that a less rigid covalently bound structure of C6H6(+) ion must also be formed upon the acetylene cluster electron ionization. The appearance energy of Arn(C2H2)(+) fragments above ≈15.1 eV indicates that the argon ionization is the first step in the fragment ion production, and the appearance energy of Arn≥2(C2H2)m≥2(+) at ≈13.7 eV is discussed in terms of an exciton transfer mechanism. PMID:23556722

  5. The vanadium nitrogenase of Azotobacter chroococcum. Reduction of acetylene and ethylene to ethane.

    PubMed Central

    Dilworth, M J; Eady, R R; Eldridge, M E

    1988-01-01

    1. The vanadium (V-) nitrogenase of Azobacter chroococcum transfers up to 7.4% of the electrons used in acetylene (C2H2) reduction for the formation of ethane (C2H6). The apparent Km for C2H2 (6 kPa) is the same for either ethylene (C2H4) or ethane (C2H6) formation and much higher than the reported Km values for C2H2 reduction to C2H4 by molybdenum (Mo-) nitrogenases. Reduction of C2H2 in 2H2O yields predominantly [cis-2H2]ethylene. 2. The ratio of electron flux yielding C2H6 to that yielding C2H4 (the C2H6/C2H4 ratio) is increased by raising the ratio of Fe protein to VFe protein and by increasing the assay temperature up to at least 40 degrees C. pH values above 7.5 decrease the C2H6/C2H4 ratio. 3. C2H4 and C2H6 formation from C2H2 by V-nitrogenase are not inhibited by H2. CO inhibits both processes much less strongly than it inhibits C2H4 formation from C2H2 with Mo-nitrogenase. 4. Although V-nitrogenase also catalyses the slow CO-sensitive reduction of C2H4 to C2H6, free C2H4 is not an intermediate in C2H6 formation from C2H2. 5. Propyne (CH3C identical to CH) is not reduced by the V-nitrogenase. 6. Some implications of these results for the mechanism of C2H6 formation by the V-nitrogenase are discussed. PMID:3162672

  6. Xe-bearing hydrocarbon ions: Observation of Xe.acetylene+rad and Xe.benzene+rad radical cations and calculations of their ground state structures

    NASA Astrophysics Data System (ADS)

    Cui, Zhong-hua; Attah, Isaac K.; Platt, Sean P.; Aziz, Saadullah G.; Kertesz, Miklos; El-Shall, M. S.

    2016-04-01

    This work reports evidence for novel types of Xe-bearing hydrocarbon radical cations. The Xe.acetylene+rad radical cation adduct is observed at nearly room temperature using the mass-selected drift cell technique. The irreversible addition of the Xe atom and the lack of back dissociation to HCCH+rad + Xe is consistent with the calculated binding energy of 0.85 eV to be contrasted with the metastable nature of the neutral Xe.acetylene adduct. The observed Xe.benzene+rad radical cation appears to be a weakly bound complex stabilized mainly by ion-induced dipole interaction consistent with a calculated binding energy in the range of 0.14-0.17 eV.

  7. Acetylene as a substrate in the development of primordial bacterial communities

    USGS Publications Warehouse

    Culbertson, C.W.; Strohmaier, F.E.; Oremland, R.S.

    1988-01-01

    The fermentation of atmospheric acetylene by anaerobic bacteria is proposed as the basis of a primordial heterotrophic food chain. The accumulation of fermentation products (acetaldehyde, ethanol, acetate and hydrogen) would create niches for sulfate-respiring bacteria as well as methanogens. Formation of acetylene-free environments in soils and sediments would also alter the function of nitrogenase from detoxification to nitrogen-fixation. The possibility of an acetylene-based anaerobic food chain in Jovian-type atmospheres is discussed. ?? 1988 Kluwer Academic Publishers.

  8. A systematic investigation of acetylene activation and hydracyanation of the activated acetylene on Aun (n = 3-10) clusters via density functional theory.

    PubMed

    Gautam, Seema; Sarkar, Abir De

    2016-05-18

    A systematic investigation of the selective catalytic conversion of poisonous HCN gas through hydracyanation of C2H2 activated on Au clusters, presented here for the first time, is of paramount importance from both scientific and technological perspectives. Hydracyanation of activated acetylene on an Au-cluster based catalyst leads to vinyl isocyanide (H2C[double bond, length as m-dash]CHNC) formation, a versatile chemical intermediate. Using density functional theory, bond activation of acetylene and selective catalytic hydracyanation of activated acetylene on small gold clusters Aun (n = 3-10) have been studied through a detailed analysis of the geometric and electronic structures. Different possible complexes of Aun-CHCH have been studied and two possible modes of adsorption of acetylene over the gold clusters, namely, the π- and di-σ modes, have been observed. The hydracyanation of the acetylene molecule is found to occur via the cleavage of one of acetylene triple bonds at the cost of formation of two Au-C bonds followed by the binding of HCN to the activated C[double bond, length as m-dash]C bond via nitrogen's lone pair. Preferential binding sites for HCN and C2H2 are analyzed through Fukui function calculations, frontier molecular orbital analysis and natural population charge distribution analysis. Based on adsorption energies, odd-sized Aun clusters are found to be significantly more favorable for C2H2 adsorption with the C-C bond stretching up to 1.31 Å with respect to the C-C triple bond length of 1.21 Å in the gas phase. The stretching frequency of adsorbed complexes, C2H2/Aun, (3460 cm(-1)), decreases notably relative to the frequency of the free acetylene molecule (7948 cm(-1)), which is a signature of the bond activation of the acetylene molecule over the Au clusters. The high adsorption energy of HCN on the Au9-C2H2 complex implies the considerable binding strength and activation of C2H2 and HCN on the Au9 clusters. Due to the importance of

  9. Designing supported palladium-on-gold bimetallic nano-catalysts for controlled hydrogenation of acetylene in large excess of ethylene

    NASA Astrophysics Data System (ADS)

    Malla, Pavani

    Ethylene is used as a starting point for many chemical intermediates in the petrochemical industry. It is predominantly produced through steam cracking of higher hydrocarbons (ethane, propane, butane, naphtha, and gas oil). During the cracking process, a small amount of acetylene is produced as a side product. However, acetylene must be removed since it acts as a poison for ethylene polymerization catalysts at even ppm concentrations (>5 ppm). Thus, the selective hydrogenation of acetylene to ethylene is an important process for the purification of ethylene. Conventional, low weight loading Pd catalysts are used for this selective reaction in high concentration ethylene streams. Gold was initially considered to be catalytically inactive for a long time. This changed when gold was seen in the context of the nanometric scale, which has indeed shown it to have excellent catalytic activity as a homogeneous or a heterogeneous catalyst. Gold is proved to have high selectivity to ethylene but poor at conversion. Bimetallic Au and Pd catalysts have exhibited superior activity as compared to Pd particles in semi-hydrogenation. Hydrogenation of acetylene was tested using this bimetallic combination. The Pd-on-Au bimetallic catalyst structure provides a new synthesis approach in improving the catalytic properties of monometallic Pd materials. TiO 2 as a support material and 0.05%Pd loading on 1%Au on titania support and used different treatment methods like washing plasma and reduction between the two metal loadings and was observed under 2:1 ratio. In my study there were two set of catalysts which were prepared by a modified incipient wetness impregnation technique. Out of all the reaction condition the catalyst which was reduced after impregnating gold and then impregnating palladium which was further treated in non-thermal hydrogen plasma and then pretreated in hydrogen till 250°C for 1 hour produced the best activity of 76% yield at 225°C. Stability tests were conducted

  10. Dissimilatory reduction of nitrate and nitrite in the bovine rumen: nitrous oxide production and effect of acetylene.

    PubMed Central

    Kaspar, H F; Tiedje, J M

    1981-01-01

    15N tracer methods and gas chromatography coupled to an electron capture detector were used to investigate dissimilatory reduction of nitrate and nitrite by the rumen microbiota of a fistulated cow. Ammonium was the only 15N-labeled end product of quantitative significance. Only traces of nitrous oxide were detected as a product of nitrate reduction; but in experiments with nitrite, up to 0.3% of the added nitrogen accumulated as nitrous oxide, but it was not further reduced. Furthermore, when 13NO3- was incubated with rumen microbiota virtually no [13N]N2 was produced. Acetylene partially inhibited the reduction of nitrite to ammonium as well as the formation of nitrous oxide. It is suggested that in the rumen ecosystem nitrous oxide is a byproduct of dissimilatory nitrite reduction to ammonium rather than a product of denitrification and that the latter process is absent from the rumen habitat. PMID:7224631

  11. Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene.

    PubMed

    Cui, Xili; Chen, Kaijie; Xing, Huabin; Yang, Qiwei; Krishna, Rajamani; Bao, Zongbi; Wu, Hui; Zhou, Wei; Dong, Xinglong; Han, Yu; Li, Bin; Ren, Qilong; Zaworotko, Michael J; Chen, Banglin

    2016-07-01

    The trade-off between physical adsorption capacity and selectivity of porous materials is a major barrier for efficient gas separation and purification through physisorption. We report control over pore chemistry and size in metal coordination networks with hexafluorosilicate and organic linkers for the purpose of preferential binding and orderly assembly of acetylene molecules through cooperative host-guest and/or guest-guest interactions. The specific binding sites for acetylene are validated by modeling and neutron powder diffraction studies. The energies associated with these binding interactions afford high adsorption capacity (2.1 millimoles per gram at 0.025 bar) and selectivity (39.7 to 44.8) for acetylene at ambient conditions. Their efficiency for the separation of acetylene/ethylene mixtures is demonstrated by experimental breakthrough curves (0.73 millimoles per gram from a 1/99 mixture). PMID:27198674

  12. Evaluation of Sorbents for Acetylene Separation in Atmosphere Revitalization Loop Closure

    NASA Technical Reports Server (NTRS)

    Abney, Morgan B.; Miller, Lee A.; Barton, Katherine

    2012-01-01

    State-of-the-art carbon dioxide reduction technology uses a Sabatier reactor to recover water from metabolic carbon dioxide. In order to maximize oxygen loop closure, a byproduct of the system, methane, must be reduced to recover hydrogen. NASA is currently exploring a microwave plasma methane pyrolysis system for this purpose. The resulting product stream of this technology includes unreacted methane, product hydrogen, and acetylene. The hydrogen and the small amount of unreacted methane resulting from the pyrolysis process can be returned to the Sabatier reactor thereby substantially improving the overall efficiency of the system. However, the acetylene is a waste product that must be removed from the pyrolysis product. Two materials have been identified as potential sorbents for acetylene removal: zeolite 4A, a commonly available commercial sorbent, and HKUST-1, a newly developed microporous metal. This paper provides an explanation of the rationale behind acetylene removal and the results of separation testing with both materials

  13. Evaluation of Sorbents for Acetylene Separation in Atmosphere Revitalization Loop Closure

    NASA Technical Reports Server (NTRS)

    Abney, Morgan B.; Miller, Lee A.; Barton, Katherine

    2011-01-01

    State-of-the-art carbon dioxide reduction technology uses a Sabatier reactor to recover water from metabolic carbon dioxide. In order to maximize oxygen loop closure, a byproduct of the system, methane, must be reduced to recover hydrogen. NASA is currently exploring a microwave plasma methane pyrolysis system for this purpose. The resulting product stream of this technology includes unreacted methane, product hydrogen, and acetylene. The hydrogen and the small amount of unreacted methane resulting from the pyrolysis process can be returned to the Sabatier reactor thereby substantially improving the overall efficiency of the system. However, the acetylene is a waste product that must be removed from the pyrolysis product. Two materials have been identified as potential sorbents for acetylene removal: zeolite 4A, a commonly available commercial sorbent, and HKUST-1, a newly developed microporous metal. This paper provides an explanation of the rationale behind acetylene removal and the results of separation testing with both materials.

  14. KISS: Kinetics and Structure of Superagglomerates Produced by Silane and Acetylene

    NASA Technical Reports Server (NTRS)

    Mulholland, G. W.; Yang, J. C.; Scott, J. H.; Sivithanu, Y.

    2001-01-01

    The objective of this study is to understand the process of gas phase agglomeration leading to superagglomerates and a gel-like structure for microgravity (0-g) silane and acetylene flames. Ultimately one would apply this understanding to predicting flame conditions that could lead to the gas phase production of an aero-gel. The approach is to burn acetylene and silane and to analyze the evolution of the soot and silica agglomerates. Acetylene is chosen because it has one of the highest soot volume fractions and there is evidence of super agglomerates being formed in laminar acetylene flames. Silane has the advantage that silica particles are the major combustion product resulting in a particle volume fraction a factor of ten greater than that for a carbonaceous smoke.

  15. Characterization of the Minimum Energy Paths and Energetics for the Reaction of Vinylidene with Acetylene

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.; Taylor, Peter R.

    1995-01-01

    The reaction of vinylidene (CH2C) with acetylene may be an initiating reaction in soot formation. We report minimum energy paths and accurate energetics for a pathway leading to vinyl-acetylene and for a number of isomers of C4H4. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contacted configuration interaction (ICCI) and/or coupled cluster singles and doubles with a perturbational estimate of triple excitations (CCSD(T)) to determine the energetics. We find an entrance channel barrier of about 5 kcal/mol for the addition of vinylidene to acetylene, but no barriers above reactants for the reaction pathway leading to vinyl-acetylene.

  16. Structure of the non-redox-active tungsten/[4Fe:4S] enzyme acetylene hydratase.

    PubMed

    Seiffert, Grazyna B; Ullmann, G Matthias; Messerschmidt, Albrecht; Schink, Bernhard; Kroneck, Peter M H; Einsle, Oliver

    2007-02-27

    The tungsten-iron-sulfur enzyme acetylene hydratase stands out from its class because it catalyzes a nonredox reaction, the hydration of acetylene to acetaldehyde. Sequence comparisons group the protein into the dimethyl sulfoxide reductase family, and it contains a bis-molybdopterin guanine dinucleotide-ligated tungsten atom and a cubane-type [4Fe:4S] cluster. The crystal structure of acetylene hydratase at 1.26 A now shows that the tungsten center binds a water molecule that is activated by an adjacent aspartate residue, enabling it to attack acetylene bound in a distinct, hydrophobic pocket. This mechanism requires a strong shift of pK(a) of the aspartate, caused by a nearby low-potential [4Fe:4S] cluster. To access this previously unrecognized W-Asp active site, the protein evolved a new substrate channel distant from where it is found in other molybdenum and tungsten enzymes. PMID:17360611

  17. Laboratory studies, analysis, and interpretation of the spectra of hydrocarbons present in planetary atmospheres including cyanoacetylene, acetylene, propane, and ethane

    NASA Technical Reports Server (NTRS)

    Blass, William E.; Daunt, Stephen J.; Peters, Antoni V.; Weber, Mark C.

    1990-01-01

    Combining broadband Fourier transform spectrometers (FTS) from the McMath facility at NSO and from NRC in Ottawa and narrow band TDL data from the laboratories with computational physics techniques has produced a broad range of results for the study of planetary atmospheres. Motivation for the effort flows from the Voyager/IRIS observations and the needs of Voyager analysis for laboratory results. In addition, anticipation of the Cassini mission adds incentive to pursue studies of observed and potentially observable constituents of planetary atmospheres. Current studies include cyanoacetylene, acetylene, propane, and ethane. Particular attention is devoted to cyanoacetylen (H3CN) which is observed in the atmosphere of Titan. The results of a high resolution infrared laboratory study of the line positions of the 663, 449, and 22.5/cm fundamental bands are presented. Line position, reproducible to better than 5 MHz for the first two bands, are available for infrared astrophysical searches. Intensity and broadening studies are in progress. Acetylene is a nearly ubiquitous atmospheric constituent of the outer planets and Titan due to the nature of methane photochemistry. Results of ambient temperature absolute intensity measurements are presented for the fundamental and two two-quantum hotband in the 730/cm region. Low temperature hotband intensity and linewidth measurements are planned.

  18. Negative ion density in magnetically confined low-pressure argon-acetylene plasmas using laser-induced photodetachment

    NASA Astrophysics Data System (ADS)

    Margot, Joelle; Al Makdessi, Georges; Hamdan, Ahmad; Clergereaux, Richard

    2015-09-01

    In plasmas generated in reactive gases such as silane and acetylene, dust particles can spontaneously form provided the residence time of the precursors is large enough for allowing volume interactions to dominate over surface interactions. In discharges at intermediate pressure (e.g. 100 mTorr), anions are considered to be the most likely precursors to dust particles formation. In the present work, we examine the negative ion density in very low pressure conditions, namely 1-10 mTorr. For this purpose, we investigate magnetized dusty plasmas produced in argon-acetylene mixtures in which dust particles have been observed. The negative ion density is measured using a laser photodetachment technique. It is is observed to increase with the magnetic field intensity and to slightly decrease with increasing C2H2 percentage in argon. In addition, it decreases with increasing gas pressure. The photodetachment cross section deduced from the photodetachment signal as a function of laser energy is found to be significantly higher than the value expected for the C2H- ion, which may be explained by the presence in the plasma of negatively charged dust particles.

  19. Adsorption of Acetylene on a Pd-Pb Bimetallic Surface — a Theoretical Study

    NASA Astrophysics Data System (ADS)

    Ferullo, R. M.; Touroude, R.; Castellani, N. J.

    A semiempirical molecular orbital study of acetylene adsorption over Pd(111) and Pd3Pb(111) has been performed. A strong negative effect of Pb atoms on Pd chemisorptive strength was observed in the alloy. This behavior is related to a lower hybridization between acetylene π* and Pd orbitals when this mental interacts with Pb. Moreover this negative effect of Pb is of a strong local character.

  20. Tunable thermal conductivity in carbon allotrope sheets: Role of acetylenic linkages

    NASA Astrophysics Data System (ADS)

    Wang, Jian; Zhang, Ai-Juan; Tang, Yuansheng

    2015-11-01

    The versatility of carbon in forming the hybridization states allows one to design more carbon allotropes with various fascinating properties by replacing some aromatic bonds with acetylenic linkages. We investigate thermal conductivities of carbon allotrope sheets with different configurations by nonequilibrium molecular dynamic simulations. It is found that the acetylenic linkages not only considerably reduce thermal conductivity but also can effectively tune thermal conductivity through the various bonding methods. We suggest that the structure of stripes of benzene rings transversely bonded with the acetylenic linkages can potentially be one of high thermoelectric materials. We find that the reason for the manipulation of thermal conductivity by the acetylenic linkage can be attributed to the strong localizations of phonon modes that result in the reduced phonon group velocity and the shortened lifetime of phonons. It is also observed that thermal conductivity of graphyne sheet shows a power-law divergence with respect to the length. We propose a new approach to manipulating thermal conductivities in the carbon allotropes through the assembling of acetylenic linkages. Our findings conclusively clarify the role of acetylenic linkages in thermal transport and offer some valuable insights into the exploration of new thermoelectric materials as well as the experimental control of heat flux.

  1. A porous metal-organic framework with ultrahigh acetylene uptake capacity under ambient conditions.

    PubMed

    Pang, Jiandong; Jiang, Feilong; Wu, Mingyan; Liu, Caiping; Su, Kongzhao; Lu, Weigang; Yuan, Daqiang; Hong, Maochun

    2015-01-01

    Acetylene, an important petrochemical raw material, is very difficult to store safely under compression because of its highly explosive nature. Here we present a porous metal-organic framework named FJI-H8, with both suitable pore space and rich open metal sites, for efficient storage of acetylene under ambient conditions. Compared with existing reports, FJI-H8 shows a record-high gravimetric acetylene uptake of 224 cm(3) (STP) g(-1) and the second-highest volumetric uptake of 196 cm(3) (STP) cm(-3) at 295 K and 1 atm. Increasing the storage temperature to 308 K has only a small effect on its acetylene storage capacity (∼200 cm(3) (STP) g(-1)). Furthermore, FJI-H8 exhibits an excellent repeatability with only 3.8% loss of its acetylene storage capacity after five cycles of adsorption-desorption tests. Grand canonical Monte Carlo simulation reveals that not only open metal sites but also the suitable pore space and geometry play key roles in its remarkable acetylene uptake. PMID:26123775

  2. A porous metal-organic framework with ultrahigh acetylene uptake capacity under ambient conditions

    PubMed Central

    Pang, Jiandong; Jiang, Feilong; Wu, Mingyan; Liu, Caiping; Su, Kongzhao; Lu, Weigang; Yuan, Daqiang; Hong, Maochun

    2015-01-01

    Acetylene, an important petrochemical raw material, is very difficult to store safely under compression because of its highly explosive nature. Here we present a porous metal-organic framework named FJI-H8, with both suitable pore space and rich open metal sites, for efficient storage of acetylene under ambient conditions. Compared with existing reports, FJI-H8 shows a record-high gravimetric acetylene uptake of 224 cm3 (STP) g−1 and the second-highest volumetric uptake of 196 cm3 (STP) cm−3 at 295 K and 1 atm. Increasing the storage temperature to 308 K has only a small effect on its acetylene storage capacity (∼200 cm3 (STP) g−1). Furthermore, FJI-H8 exhibits an excellent repeatability with only 3.8% loss of its acetylene storage capacity after five cycles of adsorption–desorption tests. Grand canonical Monte Carlo simulation reveals that not only open metal sites but also the suitable pore space and geometry play key roles in its remarkable acetylene uptake. PMID:26123775

  3. Acetylene-chromene terminated resins as high temperature thermosets

    NASA Technical Reports Server (NTRS)

    Godschalx, J. P.; Inbasekaran, M. N.; Bartos, B. R.; Scheck, D. M.; Laman, S. A.

    1990-01-01

    A novel phase transfer catalyzed process for the preparation of propargyl ethers has been developed. The propargyl ethers serve as precursors to a new class of thermosetting resins called acetylene-chromene terminated (ACT) resins. Heat treatment of a solution of propargyl ethers with various catalysts, followed by removal of solvent leads to the ACT resins via partial conversion of the propargyl ether groups to chromenes. This process reduces the energy content of the resin systems and reduces the amount of shrinkage found during cure. Due to the presence of the solvent the process is safe and gives rise to low viscosity products suitable for resin transfer molding and filament winding type applications. Due to the high glass transition temperature, high modulus, and low moisture uptake the cured resins display better than 232 C/wet performance. The thermal stability of the ACT resins in air at 204 C is superior to that of conventional bismaleimide resins. The resins also display excellent electrical properties.

  4. Discovery, Development, and Commercialization of Gold Catalysts for Acetylene Hydrochlorination.

    PubMed

    Johnston, Peter; Carthey, Nicholas; Hutchings, Graham J

    2015-11-25

    Vinyl chloride monomer (VCM) is a major chemical intermediate for the manufacture of polyvinyl chloride (PVC), which is the third most important polymer in use today. Hydrochlorination of acetylene is a major route for the production of vinyl chloride, since production of the monomer is based in regions of the world where coal is abundant. Until now, mercuric chloride supported on carbon is used as the catalyst in the commercial process, and this exhibits severe problems associated with catalyst lifetime and mercury loss. It has been known for over 30 years that gold is a superior catalyst, but it is only now that it is being commercialized. In this Perspective we discuss the use and disadvantages of the mercury catalyst and the advent of the gold catalysts for this important reaction. The nature of the active site and the possible reaction mechanism are discussed. Recent advances in the design and preparation of active gold catalysts containing ultralow levels of gold are described. In the final part, a view to the future of this chemistry will be discussed as well as the possible avenues for the commercial potential of gold catalysis. PMID:26529366

  5. An improved processible acetylene-terminated polyimide for composites

    NASA Technical Reports Server (NTRS)

    Landis, A. L.; Naselow, A. B.

    1985-01-01

    The newest member of a family of thermosetting acetylene-substituted polyimide oligomers is HR600P. This oligomer is the isoimide version of the oligomer known as HR600P and Thermid 600. Although both types of material yield the same heat resistant end products after cure, HR600P has much superior processing characteristics. This attributed to its lower melting temperature (160 + or - 10 C, 320 + or - 20 F) in contrast to 202 C (396 F) for Thermid MC-600, its longer gel time at its processing temperature (16 to 30 minutes bvs 3 minutes), and its excellent solubility in low boiling solvents such as tetrahydrofuran, glymes, or 4:1 methyl ethyl ketone/toluene mixtures. These advantages provide more acceptable coating and impregnation procedures, allow for more complete removal at lower temperatures, provide a longer pot life or working time, and allow composite structure fabrication in conventional autoclaves used for epoxy composite curing. The excellent processing characteristics of HR600P allow its use in large area laminated structures, structural composites, and molding compositions.

  6. Acetylene fermentation: An Earth-based analog of biological carbon cycling on Titan

    NASA Astrophysics Data System (ADS)

    Miller, L. G.; Baesman, S. M.; Hoeft, S. E.; Kirshtein, J.; Wolf, K.; Voytek, M. A.; Oremland, R. S.

    2009-12-01

    Acetylene (C2H2) is present in part per million quantities in the atmosphere of Titan; conceivably as an intermediate product of methane photolysis. Currently, Earth’s atmosphere contains only trace amounts of C2H2 (~40 pptv), however higher concentrations likely prevailed during the Hadean and early Archean eons (4.5 - 3.5 Ga). We isolated C2H2-fermenting microbes from various aquatic and sedimentary environments. Acetylene fermentation proceeds via acetylene hydratase (AH) through acetaldehyde, which dismutates to ethanol and acetate, and if oxidants are present (e.g., sulfate) eventually to CO2. Thus, the remnants of a C2H2 cycle exists today on Earth but may also occur on Titan and/or Enceladus, both being planetary bodies hypothesized to have liquid water underlying their frozen surfaces. We developed a molecular method for AH by designing PCR primers to target the functional gene in Pelobacter acetylenicus. We used this method to scan new environments for the presence of AH and we employed DNA sequencing of the 16S rRNA gene in order to positively identify pelobacters in environmental samples. Acetylene fermentation was documented in five diverse salt-, fresh-, and ground-water sites. Pelobacter was identified as the genus responsible for acetylene fermentation in some, but not all, of these sites. Successful probing for AH preceded the discovery of acetylene consumption in a contaminated groundwater site, demonstrating the utility of functional gene probing. A pure culture of a C2H2-fermenting pelobacter was obtained from an intertidal mudflat. We also obtained an enrichment culture (co-cultured with a sulfate reducer) from freshwater lake sediments, but neither was pelobacter nor AH detected in this sample, suggesting that an alternative pathway may be involved here. Slurry experiments using these lake sediments either with or without added C2H2 or sulfate showed that sulfate reduction and acetylene fermentation were independent processes. In general, the

  7. Inhibition of nitrogen fixation in alfalfa by arsenate, heavy metals, fluoride, and simulated acid rain

    SciTech Connect

    Porter, J.R.; Sheridan, R.P.

    1981-07-01

    The acute effects of aqueous solutions of As, Cd, Cu, Pb, F, and Zn ions at concentrations from 0.01 to 100 micrograms per milliliter and solutions adjusted to pH 2 to 6 with nitric or sulfuric acid were studied with respect to acetylene reduction, net photosynthesis, respiration rate, and chlorophyll content in Vernal alfalfa. The effects of the various treatments on acetylene reduction varied from no demonstrable effect by any concentration of F/sup -/ and 42% inhibition by 100 micrograms Pb/sup 2 +/ per milliliter, to 100% inhibition by 10 micrograms Cd/sup 2 +/ per milliliter and 100 micrograms per milliliter As, Cu/sup 2 +/, and Zn/sup 2 +/ showed statistically significant inhibition of activity at 0.1 micrograms per milliliter. Acid treatments were not inhibitory above pH 2, at which pH nitric acid inhibited acetylene reduction activity more than did sulfuric acid. The inhibition of acetylene reduction by these ions was Zn/sup 2 +/ > Cd/sup 2 +/ > Cu/sup 2 +/ > AsO/sub 3//sup -/ > F/sup -/. The sensitivity of acetylene reduction to the ions was roughly equal to the sensitivity of photosynthesis, respiration, and chlorophyll content when Pb/sup 2 +/ was applied, but was 1000 times more sensitive to Zn/sup 2 +/. The relationship of the data to field conditions and industrial pollution is discussed.

  8. Inhibition of Nitrogen Fixation in Alfalfa by Arsenate, Heavy Metals, Fluoride, and Simulated Acid Rain

    PubMed Central

    Porter, John R.; Sheridan, Richard P.

    1981-01-01

    The acute effects of aqueous solutions of As, Cd, Cu, Pb, F, and Zn ions at concentrations from 0.01 to 100 micrograms per milliliter and solutions adjusted to pH 2 to 6 with nitric or sulfuric acid were studied with respect to acetylene reduction, net photosynthesis, respiration rate, and chlorophyll content in Vernal alfalfa (Medicago sativa L. cv. Vernal). The effects of the various treatments on acetylene reduction varied from no demonstrable effect by any concentration of F− and 42% inhibition by 100 micrograms Pb2+ per milliliter, to 100% inhibition by 10 micrograms Cd2+ per milliliter and 100 micrograms per milliliter As, Cu2+, and Zn2+ ions. Zn2+ showed statistically significant inhibition of activity at 0.1 micrograms per milliliter. Acid treatments were not inhibitory above pH 2, at which pH nitric acid inhibited acetylene reduction activity more than did sulfuric acid. The inhibition of acetylene reduction by these ions was Zn2+ > Cd2+ > Cu2+ > AsO3− > Pb2+ > F−. The sensitivity of acetylene reduction to the ions was roughly equal to the sensitivity of photosynthesis, respiration, and chlorophyll content when Pb2+ was applied, but was 1,000 times more sensitive to Zn2+. The relationship of the data to field conditions and industrial pollution is discussed. PMID:16661858

  9. Inhibition of nitrogen fixation in alfalfa by arsenate, heavy metals, fluoride, and simulated Acid rain.

    PubMed

    Porter, J R; Sheridan, R P

    1981-07-01

    The acute effects of aqueous solutions of As, Cd, Cu, Pb, F, and Zn ions at concentrations from 0.01 to 100 micrograms per milliliter and solutions adjusted to pH 2 to 6 with nitric or sulfuric acid were studied with respect to acetylene reduction, net photosynthesis, respiration rate, and chlorophyll content in Vernal alfalfa (Medicago sativa L. cv. Vernal). The effects of the various treatments on acetylene reduction varied from no demonstrable effect by any concentration of F(-) and 42% inhibition by 100 micrograms Pb(2+) per milliliter, to 100% inhibition by 10 micrograms Cd(2+) per milliliter and 100 micrograms per milliliter As, Cu(2+), and Zn(2+) ions. Zn(2+) showed statistically significant inhibition of activity at 0.1 micrograms per milliliter. Acid treatments were not inhibitory above pH 2, at which pH nitric acid inhibited acetylene reduction activity more than did sulfuric acid. The inhibition of acetylene reduction by these ions was Zn(2+) > Cd(2+) > Cu(2+) > AsO(3) (-) > Pb(2+) > F(-). The sensitivity of acetylene reduction to the ions was roughly equal to the sensitivity of photosynthesis, respiration, and chlorophyll content when Pb(2+) was applied, but was 1,000 times more sensitive to Zn(2+). The relationship of the data to field conditions and industrial pollution is discussed. PMID:16661858

  10. Diameter control of carbon nanotubes using argon-acetylene mixture and their application as IR sensor

    NASA Astrophysics Data System (ADS)

    Afzal, Rana Arslan; Afrin, Rahat; Manzoor, Umair; Bhatti, Arshad Saleem; Islam, Mohammad; Amin, Muhammad T.; Alazba, Abdulrahman A.

    2015-08-01

    Multi-walled carbon nanotubes (CNTs) were grown via pyrolytic chemical vapor deposition technique and explored for their infrared sensing behavior. CNT synthesis was carried out over cobalt zinc ferrite (Co0.5Zn0.5Fe2O4) catalyst nanoparticles under different gas flow conditions to control outside diameter of the nanotubes. It was found that a progressive decrease in the carbon precursor gas (acetylene in this case) from 5:1 to 9:1 (v/v) causes reduction of average CNT diameter from 85 nm to 635 nm. Growth conditions involving higher temperatures yield nanotubes/nanofibers with outer diameter of >500 nm, presumably due to surface aggregation of nanoparticles or increased flux of carbonaceous species at the catalyst surface or both. Current-voltage characteristics of the nanotubes depending on the CNT diameter, revealed linear or nonlinear behavior. When incorporated as sensing layer, the sensitivity of ˜5.3 was noticed with response time of ˜4.1 s. It is believed that IR sensing characteristics of such CNT-based detectors can be further enhanced through post-synthesis purification and chemical functionalization treatments.

  11. Synthesis and characterization of graphenated carbon nanotubes on IONPs using acetylene by chemical vapor deposition method

    NASA Astrophysics Data System (ADS)

    Atchudan, Raji; Perumal, Suguna; Edison, Thomas Nesakumar Jebakumar Immanuel; Pandurangan, Arumugam; Lee, Yong Rok

    2015-11-01

    The graphenated carbon nanotubes (G-CNTs) were synthesized on monodisperse spherical iron oxide nanoparticles (IONPs) using acetylene as carbon precursor by simple chemical vapor deposition method. The reaction parameters such as temperature and flow of carbon source were optimized in order to achieve G-CNTs with excellent quality and quantity. Transmission electron microscopy (TEM) clearly illustrated that the graphene flakes are forming along the whole length on CNTs. The degree of graphitization was revealed by X-ray diffraction (XRD) analysis and Raman spectroscopic techniques. The intensity of D to G value was less than one which confirms the obtained G-CNTs have high degree of graphitization. The optimum reaction temperature for the IONPs to form metallic clusters which in turn lead to the formation of G-CNTs with high carbon deposition yield is at 900 °C. The TEM shows the CNTs diameter is 50 nm with foiled graphene flakes of diameter around 70 nm. Our results advocate for IONPs as a promising catalytic template for quantitative and qualitative productivity of nanohybrid G-CNTs. The produced G-CNTs with high degree of graphitization might be an ideal candidate for nanoelectronic application like super capacitors and so on.

  12. Rapid Diamond Deposition on Ni and Co Coatings by Using Twin Acetylene/Oxygen Gas Welding Torches

    NASA Astrophysics Data System (ADS)

    Ando, Yasutaka; Noda, Yoshimasa; Adachi, Shin-ichiro

    2015-12-01

    Cermet coatings have been widely used because of their high hardness and excellent wear resistance even under high-temperature conditions. However, since cermet coatings include expensive materials such as WC, TiC, TiN and so on, low-cost hard particles as a dispersing agent need to be developed. In this study, in order to develop a low-cost diamond dispersion system for the creation of diamond/thermal sprayed metal hybrid coatings, diamond deposition on thermal sprayed Ni and Co coatings and Mo and Ni metal substrates by the combustion flame method using twin acetylene/oxygen gas welding torches was carried out. Consequently, even in cases of thermal sprayed Ni and Co coatings, diamond particles could be deposited within only 5 min. From these results, this technique is proved to have a high potential for rapid diamond deposition in order to create diamond/thermal sprayed metal hybrid coatings.

  13. Infrared Spectra and Optical Constants of Acetylene and Ethane Ices

    NASA Astrophysics Data System (ADS)

    Moore, Marla H.; Ferrante, R. F.; Hudson, R. L.; Moore, W. J.

    2012-10-01

    Hydrocarbon-containing ices have characteristic absorption bands in both the mid- and near-infrared spectral regions, yet accurate optical constants are not available for most of these molecules. Ices with a hydrocarbon component have been identified on several TNOs (1) and the presence of volatiles, such as hydrocarbons, is inferred for intermediate or large TNOs based on sublimation models (2, 3). In our laboratory we recently have undertaken low-temperature spectroscopic studies of C2 hydrocarbons. We report IR spectra for acetylene (C2H2) and ethane (C2H6) ice in both the amorphous and crystalline phases at multiple temperatures. We include measurements of the refractive index at 670 nm for both the amorphous and crystalline phases of each ice. The optical constants, the real (n) and imaginary (k) components of the complex index of refraction, were determined from 7000 - 400 cm-1 (1.4 - 25 microns) at multiple temperatures using a Kramers-Kronig analysis. A goal of the present work is to provide a data base of optical constants of C2 molecules similar to that of Hudgins et al. (4) and Moore et al. (5). These values, as well as our calculated individual band strengths, will have great practical importance for the ongoing analysis of TNO spectra. (1) Brown, M.E. et al., Astron J., 133, 284, 2007. (2) Delsanti, A. et al., A&A, 52, A40, 2010. (3) Schaller, E. L. & Brown, M. E., ApJ, 659, L61, 2007. (4) Hudgins, D. M. et al., ApJS, 86, 713, 1993. (5) Moore, M. H. et al., ApJS, 191, 96, 2010. This work is supported by NASA’s Planetary Atmospheres, Outer Planets, and Cassini Data Analysis programs, and The Goddard Center for Astrobiology.

  14. Ionization of large homogeneous and heterogeneous clusters generated in acetylene-Ar expansions: Cluster ion polymerization

    SciTech Connect

    Kocisek, J.; Lengyel, J.; Farnik, M.

    2013-03-28

    Pure acetylene and mixed Ar-acetylene clusters are formed in supersonic expansions of acetylene/argon mixtures and analysed using reflectron time-of-flight mass spectrometer with variable electron energy ionization source. Acetylene clusters composed of more than a hundred acetylene molecules are generated at the acetylene concentration of Almost-Equal-To 8%, while mixed species are produced at low concentrations ( Almost-Equal-To 0.7%). The electron energy dependence of the mass spectra revealed the ionization process mechanisms in clusters. The ionization above the threshold for acetylene molecule of 11.5 eV results in the main ionic fragment progression (C{sub 2}H{sub 2}){sub n}{sup +}. At the electron energies Greater-Than-Or-Slanted-Equal-To 21.5 eV above the CH+CH{sup +} dissociative ionization limit of acetylene the fragment ions nominally labelled as (C{sub 2}H{sub 2}){sub n}CH{sup +}, n Greater-Than-Or-Slanted-Equal-To 2, are observed. For n Less-Than-Or-Slanted-Equal-To 7 these fragments correspond to covalently bound ionic structures as suggested by the observed strong dehydrogenation [(C{sub 2}H{sub 2}){sub n}-k Multiplication-Sign H]{sup +} and [(C{sub 2}H{sub 2}){sub n}CH -k Multiplication-Sign H]{sup +}. The dehydrogenation is significantly reduced in the mixed clusters where evaporation of Ar instead of hydrogen can stabilize the nascent molecular ion. The C{sub 3}H{sub 3}{sup +} ion was previously assigned to originate from the benzene molecular ion; however, the low appearance energy of Almost-Equal-To 13.7 eV indicates that a less rigid covalently bound structure of C{sub 6}H{sub 6}{sup +} ion must also be formed upon the acetylene cluster electron ionization. The appearance energy of Ar{sub n}(C{sub 2}H{sub 2}){sup +} fragments above Almost-Equal-To 15.1 eV indicates that the argon ionization is the first step in the fragment ion production, and the appearance energy of Ar{sub n{>=}2}(C{sub 2}H{sub 2}){sub m{>=}2}{sup +} at Almost-Equal-To 13

  15. Flexible band gap tuning of hexagonal boron nitride sheets interconnected by acetylenic bonds.

    PubMed

    Zhang, Hongyu; Luo, Youhua; Feng, Xiaojuan; Zhao, Lixia; Zhang, Meng

    2015-08-21

    The energetic and electronic properties of acetylenic-bond-interconnected hexagonal boron nitride sheets (BNyne), in which the number of rows of BN hexagonal rings (denoted as BN width) between neighboring arrays of acetylenic linkages increases consecutively, have been explored using first-principles calculations. Depending on the spatial position of B/N atoms with respect to the acetylenic linkages, there are two different types of configurations. The band structure features and band gap evolutions of BNyne structures as a function of the BN width can be categorized into two families, corresponding to two distinct types of configurations. In particular, for both types of BNyne structures, the band gap variations exhibit odd-even oscillating behavior depending on the BN width, which is related to the different symmetries of acetylenic chains in the unit cell. These results suggest that the embedded linear acetylenic chains can provide more flexibility for manipulation of the atomic and electronic properties of hexagonal boron nitride. These sp-sp(2) hybrid structures might promise importantly potential applications for developing nanoscale electronic and optoelectronic devices. PMID:26194068

  16. [Photodissociation of Acetylene and Acetone using Step-Scan Time-Resolved FTIR Emission Spectroscopy

    NASA Technical Reports Server (NTRS)

    McLaren, Ian A.; Wrobel, Jacek D.

    1997-01-01

    The photodissociation of acetylene and acetone was investigated as a function of added quenching gas pressures using step-scan time-resolved FTIR emission spectroscopy. Its main components consist of Bruker IFS88, step-scan Fourier Transform Infrared (FTIR) spectrometer coupled to a flow cell equipped with Welsh collection optics. Vibrationally excited C2H radicals were produced from the photodissociation of acetylene in the unfocused experiments. The infrared (IR) emission from these excited C2H radicals was investigated as a function of added argon pressure. Argon quenching rate constants for all C2H emission bands are of the order of 10(exp -13)cc/molecule.sec. Quenching of these radicals by acetylene is efficient, with a rate constant in the range of 10(exp -11) cc/molecule.sec. The relative intensity of the different C2H emission bands did not change with the increasing argon or acetylene pressure. However, the overall IR emission intensity decreased, for example, by more than 50% when the argon partial pressure was raised from 0.2 to 2 Torr at fixed precursor pressure of 160mTorr. These observations provide evidence for the formation of a metastable C2H2 species, which are collisionally quenched by argon or acetylene. Problems encountered in the course of the experimental work are also described.

  17. Measurement of cardiac output during exercise by open-circuit acetylene uptake.

    PubMed

    Barker, R C; Hopkins, S R; Kellogg, N; Olfert, I M; Brutsaert, T D; Gavin, T P; Entin, P L; Rice, A J; Wagner, P D

    1999-10-01

    Noninvasive measurement of cardiac output (QT) is problematic during heavy exercise. We report a new approach that avoids unpleasant rebreathing and resultant changes in alveolar PO(2) or PCO(2) by measuring short-term acetylene (C(2)H(2)) uptake by an open-circuit technique, with application of mass balance for the calculation of QT. The method assumes that alveolar and arterial C(2)H(2) pressures are the same, and we account for C(2)H(2) recirculation by extrapolating end-tidal C(2)H(2) back to breath 1 of the maneuver. We correct for incomplete gas mixing by using He in the inspired mixture. The maneuver involves switching the subject to air containing trace amounts of C(2)H(2) and He; ventilation and pressures of He, C(2)H(2), and CO(2) are measured continuously (the latter by mass spectrometer) for 20-25 breaths. Data from three subjects for whom multiple Fick O(2) measurements of QT were available showed that measurement of QT by the Fick method and by the C(2)H(2) technique was statistically similar from rest to 90% of maximal O(2) consumption (VO(2 max)). Data from 12 active women and 12 elite male athletes at rest and 90% of VO(2 max) fell on a single linear relationship, with O(2) consumption (VO(2)) predicting QT values of 9.13, 15.9, 22.6, and 29.4 l/min at VO(2) of 1, 2, 3, and 4 l/min. Mixed venous PO(2) predicted from C(2)H(2)-determined QT, measured VO(2), and arterial O(2) concentration was approximately 20-25 Torr at 90% of VO(2 max) during air breathing and 10-15 Torr during 13% O(2) breathing. This modification of previous gas uptake methods, to avoid rebreathing, produces reasonable data from rest to heavy exercise in normal subjects. PMID:10517785

  18. Highly enantioselective reductive cyclization of acetylenic aldehydes via rhodium catalyzed asymmetric hydrogenation.

    PubMed

    Rhee, Jong Uk; Krische, Michael J

    2006-08-23

    Catalytic hydrogenation of acetylenic aldehydes 1a-12a using chirally modified cationic rhodium catalysts enables highly enantioselective reductive cyclization to afford cyclic allylic alcohols 1b-12b. Using an achiral hydrogenation catalyst, the chiral racemic acetylenic aldehydes 13a-15a engage in highly syn-diastereoselective reductive cyclizations to afford cyclic allylic alcohols 13b-15b. Ozonolysis of cyclization products 7b and 9b allows access to optically enriched alpha-hydroxy ketones 7c and 9c. Reductive cyclization of enyne 7a under a deuterium atmosphere provides the monodeuterated product deuterio-7b, consistent with a catalytic mechanism involving alkyne-carbonyl oxidative coupling followed by hydrogenolytic cleavage of the resulting oxametallacycle. These hydrogen-mediated transformations represent the first examples of the enantioselective reductive cyclization of acetylenic aldehydes. PMID:16910650

  19. Deactivation mechanisms for Pd/Al{sub 2}O{sub 3} acetylene hydrogenation catalysts

    SciTech Connect

    Hall, J.B.; Huggins, B.J.; Meyers, B.L.; Kaminsky, M.P.

    1994-12-31

    The selective hydrogenation of acetylenic impurities to ethylene is a crucial purification step in the production of olefins by steam cracking. This hydrogenation is done catalytically using a Pd/Al{sub 2}O{sub 3} catalyst in a fixed bed reactor. The designed lifetime of the catalyst in a front end acetylene converter is about 4 years. Accelerated catalyst deactivation and thermal runaways caused by loss in catalyst selectivity are common problems which plague acetylene converters. Such problems result in unscheduled shutdowns and increased costs to replace deactivated catalyst. This presentation outlines several deactivation mechanisms of the catalyst and discusses how they affect catalyst lifetime and performance. Catalyst characterization using electron microscopy and CO chemisorption provides information on how poisons deteriorate the catalyst and Pd particle size changes produced by use and regeneration. Thermal gravimetric analysis was also used to determine the extent of coke burn-off using less severe regeneration procedures.

  20. Electronic properties and strain sensitivity of CVD-grown graphene with acetylene

    NASA Astrophysics Data System (ADS)

    Yang, Meng; Sasaki, Shinichirou; Ohnishi, Masato; Suzuki, Ken; Miura, Hideo

    2016-04-01

    Although many studies have shown that large-area monolayer graphene can be formed by chemical vapor deposition (CVD) using methane gas, the growth of monolayer graphene using highly reactive acetylene gas remains a big challenge. In this study, we synthesized a uniform monolayer graphene film by low-pressure CVD (LPCVD) with acetylene gas. On the base of Raman spectroscopy measurements, it was found that up to 95% of the as-grown graphene is monolayer. The electronic properties and strain sensitivity of the LPCVD-grown graphene with acetylene were also evaluated by testing the fabricated field-effect transistors (FETs) and strain sensors. The derived carrier mobility and gauge factor are 862-1150 cm2/(V·s) and 3.4, respectively, revealing the potential for high-speed FETs and strain sensor applications. We also investigated the relationship between the electronic properties and the graphene domain size.

  1. Biologically Active Acetylenic Amino Alcohol and N-Hydroxylated 1,2,3,4-Tetrahydro-β-carboline Constituents of the New Zealand Ascidian Pseudodistoma opacum.

    PubMed

    Wang, Jiayi; Pearce, A Norrie; Chan, Susanna T S; Taylor, Richard B; Page, Michael J; Valentin, Alexis; Bourguet-Kondracki, Marie-Lise; Dalton, James P; Wiles, Siouxsie; Copp, Brent R

    2016-03-25

    The first occurrence of an acetylenic 1-amino-2-alcohol, distaminolyne A (1), isolated from the New Zealand ascidian Pseudodistoma opacum, is reported. The isolation and structure elucidation of 1 and assignment of absolute configuration using the exciton coupled circular dichroism technique are described. In addition, a new N-9 hydroxy analogue (2) of the known P. opacum metabolite 7-bromohomotrypargine is also reported. Antimicrobial screening identified modest activity of 1 toward Escherichia coli, Staphylococcus aureus, and Mycobacterim tuberculosis, while 2 exhibited a moderate antimalarial activity (IC50 3.82 μM) toward a chloroquine-resistant strain (FcB1) of Plasmodium falciparum. PMID:26670413

  2. Effect of Protein Additives on Acetylene Reduction (Nitrogen Fixation) by Rhizobium in the Presence and Absence of Soybean Cells 1

    PubMed Central

    Anderson, Stephen J.; Phillips, Donald A.

    1976-01-01

    The effect of protein additives on acetylene reduction (N2 fixation) by Rhizobium associated with soybean cells (Glycine max [L.] Merr.) in vitro was studied. Acetylene reduction was promoted on the basal medium supplemented with 1.4 mg of N/ml supplied as aqueous extracts of hexane-extracted soybean, red kidney beans (Phaseolus vulgaris L.), or peas (Pisum sativum L.). Commercial samples of α-casein, or bovine serum albumin also promoted acetylene reduction at a concentration of 1.4 mg of N/ml of basal medium, but egg albumin supplying an equal amount of nitrogen to the basal medium completely suppressed acetylene reduction. Autoclaving the aqueous extract of hexane-extracted soybean meal had no effect on its ability to promote acetylene reduction. The presence of 40 mm succinate decreased acetylene reduction with leguminous proteins supplying 1.4 mg of N/ml but promoted acetylene reduction by Rhizobium 32H1-soybean cell associations on media containing α-casein, bovine serum albumin, or egg albumin suppling 1.4 mg of N/ml. Similar results were obtained with both cowpea Rhizobium 32H1 and Rhizobium japonicum 61A96. Pure cultures of Rhizobium 32H1 developed acetylene-reducing activity in the presence of soybean extract on basal agar medium and in vermiculite supplied with N-free mineral salts plus crude soybean meal. The results suggest that in certain situations, free living Rhizobium may reduce N2 under field conditions. PMID:16659592

  3. Heats of Formation of Triplet Ethylene, Ethylidene, and Acetylene

    SciTech Connect

    Nguyen, M.T.; Matus, M.H.; Lester Jr, W.A.; Dixon, David A.

    2007-06-28

    Heats of formation of the lowest triplet state of ethylene and the ground triplet state of ethylidene have been predicted by high level electronic structure calculations. Total atomization energies obtained from coupled-cluster CCSD(T) energies extrapolated to the complete basis set limit using correlation consistent basis sets (CBS), plus additional corrections predict the following heats of formation in kcal/mol: Delta H0f(C2H4,3A1) = 80.1 at 0 K and 78.5 at 298 K, and Delta H0f(CH3CH,3A") = 86.8 at 0 K and 85.1 at 298 K, with an error of less than +-1.0 kcal/mol. The vertical and adiabatic singlet-triplet separation energies of ethylene were calculated as Delta ES-T,vert = 104.1 and Delta ES-T,adia = 65.8 kcal/mol. These results are in excellent agreement with recent quantum Monte Carlo (DMC) values of 103.5 +- 0.3 and 66.4 +- 0.3 kcal/mol. Both sets of computational values differ from the experimental estimate of 58 +- 3 kcal/mol for the adiabatic splitting. The computed singlet-triplet gap at 0 K for acetylene is Delta ES-T,adia(C2H2) = 90.5 kcal/mol, which is in notable disagreement with the experimental value of 82.6 kcal/mol. The heat of formation of the triplet is Delta H0f(C2H2,3B2) = 145.3 kcal/mol. There is a systematic underestimation of the singlet-triplet gaps in recent photodecomposition experiments by ~;;7 to 8 kcal/mol. For vinylidene, we predict Delta H0f(H2CC,1A1) = 98.8 kcal/mol at 298 K (exptl. 100.3 +- 4.0), Delta H0f(H2CC,3B2) = 146.2 at 298 K, and an energy gap Delta ES-T-adia(H2CC) = 47.7 kcal/mol.

  4. Oxygen transport through polyethylene terephthalate (PET) coated with plasma-polymerized acetylene at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Wemlinger, Erik; Pedrow, Patrick; Garcia-Pérez, Manuel; Sablani, Shyam

    2011-10-01

    Moser et al. have shown that oxygen transport through polyethyleneterephthalate (PET) is reduced by a factor of up to 120 when, at reduced pressure, hydrogenated amorphous carbon film with thickness less than 100 nm is applied to the PET substrate. Our work includes using atmospheric pressure cold plasma to grow a plasma-polymerized acetylene film on PET substrate and measuring reductions in oxygen transport. The reactor utilizes corona discharges and is operated at 60 Hz with a maximum voltage of 10 kV RMS. Corona streamers emanate from an array of needles with an average radius of curvature of 50 μm. The reactor utilizes a cylindrical reaction chamber with a vertical orientation such that argon carrier gas and acetylene precursor gas are introduced at the top then pass through the cold plasma activation zone and then through a grounded stainless steel mesh. Acetylene radicals are incident on the PET substrate and form plasma-polymerized acetylene film. Moser et al. have shown that oxygen transport through polyethyleneterephthalate (PET) is reduced by a factor of up to 120 when, at reduced pressure, hydrogenated amorphous carbon film with thickness less than 100 nm is applied to the PET substrate. Our work includes using atmospheric pressure cold plasma to grow a plasma-polymerized acetylene film on PET substrate and measuring reductions in oxygen transport. The reactor utilizes corona discharges and is operated at 60 Hz with a maximum voltage of 10 kV RMS. Corona streamers emanate from an array of needles with an average radius of curvature of 50 μm. The reactor utilizes a cylindrical reaction chamber with a vertical orientation such that argon carrier gas and acetylene precursor gas are introduced at the top then pass through the cold plasma activation zone and then through a grounded stainless steel mesh. Acetylene radicals are incident on the PET substrate and form plasma-polymerized acetylene film. E.M. Moser, R. Urech, E. Hack, H. Künzli, E. Müller, Thin

  5. Simulations of shock-induced mixing& combustion of an acetylene cloud in a chamber

    SciTech Connect

    Bell, J B; Day, M S; Beckner, V E; Kuhl, A L; Neuwald, P; Reichenbach, H

    2001-02-06

    In this paper we present numerical simulations of the interaction of a blast wave with an acetylene bubble in a closed chamber. We model the system using the inviscid Euler equations for a mixture of ideal gases. The formulation specifies the thermodynamic behavior of the system using a Chemkin interface and includes the capability to model combustion as the ambient air mixes with the acetylene. The simulations are performed using a three-dimensional adaptive mesh refinement algorithm based on a second-order Godunov integration scheme. Simulations are compared with experimental measurements for the same configuration.

  6. Acetylene- and Phenylacetylene-Terminated Poly(Arylene Ether Benzimidazole)s (PAEBI's)

    NASA Technical Reports Server (NTRS)

    Connell, John W.; Hergenrother, Paul M.; Smith, Joseph G., Jr.

    1994-01-01

    Polymers prepared by first synthesizing polymers terminated with hydroxy groups, then reacting them with either 4-ethynylbenzoyl chloride or 4-fluoro-4'-phenylethynylbenzophenone. Endcapped polymers thermally cured to yield materials with attractive combination of properties. Cured acetylene-and phenylacetylene-terminated PAEBI's exhibit higher glass-transition temperatures and better retention of mechanical properties at high temperatures. Cured acetylene- and phenylacetylene-terminated polymers exhibit excellent adhesion to copper foil and polyimide film. Potentially useful as adhesives, coatings, composite matrices, fibers, films, membranes, and moldings.

  7. Mid-Infrared Pumped Laser-Induced Thermal Grating Spectroscopy for Detection of Acetylene in the Visible Spectral Range.

    PubMed

    Sahlberg, Anna-Lena; Kiefer, Johannes; Aldén, Marcus; Li, Zhongshan

    2016-06-01

    We present mid-infrared laser-induced thermal grating spectroscopy (IR-LITGS) using excitation radiation around 3 µm generated by a simple broadband optical parametric oscillator (OPO). Acetylene as a typical small hydrocarbon molecule is used as an example target species. A mid-infrared broadband OPO pumped by the fundamental output of a neodymium-doped yttrium aluminum garnet (Nd:YAG) laser was used to generate the pump beams, with pulse energies of 6-10 mJ depending on the wavelength. The line width of the OPO idler beam was ∼5 cm(-1), which is large enough to cover up to six adjacent acetylene lines. The probe beam was the radiation of a 532 nm cw solid state laser with 190 mW output power. Signals were generated in atmospheric pressure gas flows of N2, air, CO2 and Ar with small admixtures of C2H2 A detection limit of less than 300 ppm was found for a point measurement of C2H2 diluted in N2 As expected, the oscillation frequency of the IR-LITGS signal was found to have a large dependency on the buffer gas, which allows determination of the speed of sound. Moreover, the results reveal a very strong collisional energy exchange between C2H2 and CO2 compared to the other gases. This manifests as significant local heating. In summary, the MIR-LITGS technique enables spectroscopy of fundamental vibrational transitions in the infrared via detection in the visible spectral range. PMID:27091904

  8. 49 CFR 178.60 - Specification 8AL steel cylinders with porous fillings for acetylene.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 3 2012-10-01 2012-10-01 false Specification 8AL steel cylinders with porous...) SPECIFICATIONS FOR PACKAGINGS Specifications for Cylinders § 178.60 Specification 8AL steel cylinders with porous fillings for acetylene. (a) Type and service pressure. A DOT 8AL cylinder is a seamless steel cylinder...

  9. 49 CFR 178.60 - Specification 8AL steel cylinders with porous fillings for acetylene.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 3 2013-10-01 2013-10-01 false Specification 8AL steel cylinders with porous...) SPECIFICATIONS FOR PACKAGINGS Specifications for Cylinders § 178.60 Specification 8AL steel cylinders with porous fillings for acetylene. (a) Type and service pressure. A DOT 8AL cylinder is a seamless steel cylinder...

  10. 49 CFR 178.60 - Specification 8AL steel cylinders with porous fillings for acetylene.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 3 2014-10-01 2014-10-01 false Specification 8AL steel cylinders with porous...) SPECIFICATIONS FOR PACKAGINGS Specifications for Cylinders § 178.60 Specification 8AL steel cylinders with porous fillings for acetylene. (a) Type and service pressure. A DOT 8AL cylinder is a seamless steel cylinder...

  11. Association Mechanisms of Unsaturated C2 Hydrocarbons with Their Cations: Acetylene and Ethylene

    NASA Technical Reports Server (NTRS)

    Bera, Partha P.; Head-Gordon, Martin; Lee, Timothy J.

    2013-01-01

    The ion-molecule association mechanism of acetylene and ethylene with their cations is investigated by ab initio quantum chemical methods to understand the structures, association energies, and the vibrational and electronic spectra of the products. Stable puckered cyclic isomers are found as the result of first forming less stable linear and bridge isomers. The puckered cyclic complexes are calculated to be strongly bound, by 87, 35 and 56 kcal/mol for acetylene-acetylene cation, ethylene-ethylene cation and acetylene-ethylene cation, respectively. These stable complexes may be intermediates that participate in further association reactions. There are no association barriers, and no significant inter-conversion barriers, so the initial linear and bridge encounter complexes are unlikely to be observable. However, the energy gap between the bridged and cyclic puckered isomers greatly differs from complex to complex: it is 44 kcal/mol in C4H4 +, but only 6 kcal/mol in C4H8 +. The accurate CCSD(T) calculations summarized above are also compared against less computationally expensive MP2 and density functional theory (DFT) calculations for structures, relative energies, and vibrational spectra. Calculated vibrational spectra are compared against available experiments for cyclobutadiene cation. Electronic spectra are also calculated using time-dependent DFT.

  12. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... acetylene-propadiene mixture must have a refrigeration system that does not compress the cargo vapor or have a refrigeration system with the following features: (1) A vapor compressor that does not raise the... suction line. (c) The piping system, including the cargo refrigeration system, for tanks to be loaded...

  13. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... acetylene-propadiene mixture must have a refrigeration system that does not compress the cargo vapor or have a refrigeration system with the following features: (1) A vapor compressor that does not raise the... suction line. (c) The piping system, including the cargo refrigeration system, for tanks to be loaded...

  14. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... acetylene-propadiene mixture must have a refrigeration system that does not compress the cargo vapor or have a refrigeration system with the following features: (1) A vapor compressor that does not raise the... suction line. (c) The piping system, including the cargo refrigeration system, for tanks to be loaded...

  15. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... acetylene-propadiene mixture must have a refrigeration system that does not compress the cargo vapor or have a refrigeration system with the following features: (1) A vapor compressor that does not raise the... suction line. (c) The piping system, including the cargo refrigeration system, for tanks to be loaded...

  16. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... acetylene-propadiene mixture must have a refrigeration system that does not compress the cargo vapor or have a refrigeration system with the following features: (1) A vapor compressor that does not raise the... suction line. (c) The piping system, including the cargo refrigeration system, for tanks to be loaded...

  17. OZONE PRODUCTION FROM IRRADIATION OF ACETYLENE/CHLORINE MIXTURES IN AIR

    EPA Science Inventory

    The reaction of chlorine radicals with acetylene in air in the absence of oxides of nitrogen result In the formation of ozone. o ozone is observed when chlorine radicals react with methylacetylene or ethylacetylene under similar conditions. ormyl chloride is observed in all syste...

  18. Methane emissions measured at two California landfills by OTM-10 and an acetylene tracer method

    EPA Science Inventory

    Methane emissions were measured at two municipal solid waste landfills in California using static flux chambers, an optical remote sensing approach known as vertical radial plume mapping (VRPM) using a tunable diode laser (TDL) and a novel acetylene tracer method. The tracer meth...

  19. Conformational flexibility of fused tetracenedione propellers obtained from one-pot reductive dimerization of acetylenic quinones.

    PubMed

    Vasilevsky, Sergei F; Baranov, Denis S; Mamatyuk, Victor I; Fadeev, Dmitry S; Gatilov, Yurii V; Stepanov, Aleksandr A; Vasilieva, Nadezhda V; Alabugin, Igor V

    2015-02-01

    Reductive dimerization of acetylenic anthraquinones provides synthetic access to flexible nonplanar polyaromatics with a tetracenedione core. In solution, these nonplanar, contorted polycycles exist as equilibrating mixtures of two symmetric conformers. The fused tetracenediones are easily reduced and exhibit rich electrochemical behavior. PMID:25575160

  20. Selective hydrogenation of dienic and acetylenic compounds on metal-containing catalysts

    NASA Astrophysics Data System (ADS)

    Stytsenko, V. D.; Mel'nikov, D. P.

    2016-05-01

    Studies on selective hydrogenation of dienic and acetylenic hydrocarbons and their derivatives on metal-containing catalysts are reviewed. The review covers publications over a wide period of time and concentrates on the fundamental principles of catalyst operation. The catalysts modified in the surface layer were shown to be promising for selective hydrogenation.

  1. A Safe and Easy Classroom Demonstration of the Generation of Acetylene Gas.

    ERIC Educational Resources Information Center

    Cox, Marilyn Blagg; Krause, Paul

    1994-01-01

    In this demonstration of the generation and combustion of acetylene, calcium carbide and water are allowed to react in a latex examination glove. Two student volunteers perform the demonstration with instructor guidance. This safe, popular demonstration, originally intended to illustrate the alkyne family of compounds, can be used with a variety…

  2. Acetylene measurement in flames by chirp-based quantum cascade laser spectrometry.

    PubMed

    Quine, Zachary R; McNesby, Kevin L

    2009-06-01

    We have designed and characterized a mid-IR spectrometer built around a pulsed distributed-feedback quantum cascade laser using the characteristic frequency down-chirp to scan through the spectral region 6.5 cm(-1) spectral region. The behavior of this chirp is extensively measured. The accuracy and detection limits of the system as an absorption spectrometer are demonstrated first by measuring spectra of acetylene through a single pass 16 cm absorption cell in real time at low concentrations and atmospheric pressure. The smallest detectable peak is measured to be approximately 1.5 x 10(-4) absorbance units, yielding a minimum detectable concentration length product of 2.4 parts per million meter at standard temperature and pressure. This system is then used to detect acetylene within an ethylene-air opposed flow flame. Measurements of acetylene content as a function of height above the fuel source are presented, as well as measurements of acetylene produced in fuel breakdown as a function of preinjection fuel temperature. PMID:19488121

  3. Laboratory astrochemistry: catalytic conversion of acetylene to polycyclic aromatic hydrocarbons over SiC grains.

    PubMed

    Zhao, T Q; Li, Q; Liu, B S; Gover, R K E; Sarre, P J; Cheung, A S-C

    2016-02-01

    Catalytic conversion reactions of acetylene on a solid SiC grain surface lead to the formation of polycyclic aromatic hydrocarbons (PAHs) and are expected to mimic chemical processes in certain astrophysical environments. Gas-phase PAHs and intermediates were detected in situ using time-of-flight mass spectrometry, and their formation was confirmed using GC-MS in a separate experiment by flowing acetylene gas through a fixed-bed reactor. Activation of acetylene correlated closely with the dangling bonds on the SiC surface which interact with and break the C-C π bond. The addition of acetylene to the resulting radical site forms a surface ring structure which desorbs from the surface. The results of HRTEM and TG indicate that soot and graphene formation on the SiC surface depends strongly on reaction temperature. We propose that PAHs as seen through the 'UIR' emission bands can be formed through decomposition of a graphene-like material, formed on the surface of SiC grains in carbon-rich circumstellar envelopes. PMID:26752613

  4. TOXICITY OF ACETYLENIC ALCOHOLS TO THE FATHEAD MINNOW, PIMEPHALES PROMELAS: NARCOSIS AND PROELECTROPHILE ACTIVATION

    EPA Science Inventory

    The 96-h LC50 values for 16 acetylenic alcohols in the fathead minnow (Pimephales promelas) were determined using continuous-flow diluters. The measured LC50 values for seven tertiary propargylic alcohols agreed closely with the QSAR predictions based upon data for other organic ...

  5. Mechanism of tungsten-dependent acetylene hydratase from quantum chemical calculations.

    PubMed

    Liao, Rong-Zhen; Yu, Jian-Guo; Himo, Fahmi

    2010-12-28

    Acetylene hydratase is a tungsten-dependent enzyme that catalyzes the nonredox hydration of acetylene to acetaldehyde. Density functional theory calculations are used to elucidate the reaction mechanism of this enzyme with a large model of the active site devised on the basis of the native X-ray crystal structure. Based on the calculations, we propose a new mechanism in which the acetylene substrate first displaces the W-coordinated water molecule, and then undergoes a nucleophilic attack by the water molecule assisted by an ionized Asp13 residue at the active site. This is followed by proton transfer from Asp13 to the newly formed vinyl anion intermediate. In the subsequent isomerization, Asp13 shuttles a proton from the hydroxyl group of the vinyl alcohol to the α-carbon. Asp13 is thus a key player in the mechanism, but also W is directly involved in the reaction by binding and activating acetylene and providing electrostatic stabilization to the transition states and intermediates. Several other mechanisms are also considered but the energetic barriers are found to be very high, ruling out these possibilities. PMID:21149684

  6. Purification and characterization of acetylene hydratase of Pelobacter acetylenicus, a tungsten iron-sulfur protein.

    PubMed Central

    Rosner, B M; Schink, B

    1995-01-01

    Acetylene hydratase of the mesophilic fermenting bacterium Pelobacter acetylenicus catalyzes the hydration of acetylene to acetaldehyde. Growth of P. acetylenicus with acetylene and specific acetylene hydratase activity depended on tungstate or, to a lower degree, molybdate supply in the medium. The specific enzyme activity in cell extract was highest after growth in the presence of tungstate. Enzyme activity was stable even after prolonged storage of the cell extract or of the purified protein under air. However, enzyme activity could be measured only in the presence of a strong reducing agent such as titanium(III) citrate or dithionite. The enzyme was purified 240-fold by ammonium sulfate precipitation, anion-exchange chromatography, size exclusion chromatography, and a second anion-exchange chromatography step, with a yield of 36%. The protein was a monomer with an apparent molecular mass of 73 kDa, as determined by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The isoelectric point was at pH 4.2. Per mol of enzyme, 4.8 mol of iron, 3.9 mol of acid-labile sulfur, and 0.4 mol of tungsten, but no molybdenum, were detected. The Km for acetylene as assayed in a coupled photometric test with yeast alcohol dehydrogenase and NADH was 14 microM, and the Vmax was 69 mumol.min-1.mg of protein-1. The optimum temperature for activity was 50 degrees C, and the apparent pH optimum was 6.0 to 6.5. The N-terminal amino acid sequence gave no indication of resemblance to any enzyme protein described so far. PMID:7592321

  7. Seasonal Variations of Temperature, Acetylene and Ethane in Saturn's Stratosphere from 2005 to 2010

    NASA Astrophysics Data System (ADS)

    Sinclair, James; Irwin, P. G. J.; Fletcher, L. N.; Moses, J. I.; Greathouse, T. K.; Friedson, A. J.; Hesman, B.; Hurley, J.; Merlet, C.

    2012-10-01

    Acetylene (C2H2) and ethane (C2H6) exemplify by-products of complex photochemistry in Saturn’s stratosphere. Their relative stability together with their strong vertical gradients in concentration allow for their use as tracers of vertical motion in Saturn’s lower stratosphere. Earlier studies of Saturn's hydrocarbons have provided only a snapshot of their behaviour with temporal variations remaining to be determined. In this study, we investigate how the thermal structure and concentrations of acetylene and ethane have evolved on Saturn with the changing season. We use FIRMAP (15.5 cm-1 spectral resolution) Cassini-CIRS observations, initially retrieve temperature and subsequently retrieve the abundances of acetylene and ethane. In comparing 2005, 2009 and 2010 results, we observe the disappearance of Saturn's southern warm polar hood with cooling of up to 18.6 K ± 0.9 K at 1.1 mbar south of 75°S (planetographic). This suggests dissipation of Saturn's south polar vortex in addition to an autumnal cooling. We observe a 20% ± 9% enrichment of acetylene and a 30% ± 10% enrichment of ethane at 2.1 mbar at 25°N, together with a 14% ± 9% depletion of acetylene and an 18% ± 7% depletion of ethane at the same altitude at 15°S. This suggests the presence of localised downwelling and upwelling at these latitudes, respectively. These vertical motions are consistent with a recently-developed GCM (global circulation model) of Saturn's tropopause and stratosphere, which predicts this pattern of upwelling and downwelling as a result of seasonally-reversing Hadley circulation.

  8. High performance addition-type thermoplastics (ATTs) - Evidence for the formation of a Diels-Alder adduct in the reaction of an acetylene-terminated material and a bismaleimide

    NASA Technical Reports Server (NTRS)

    Pater, R. H.; Soucek, M. D.; Chang, A. C.; Partos, R. D.

    1991-01-01

    Recently, the concept and demonstration of a new versatile synthetic reaction for making a large number of high-performance addition-type thermoplastics (ATTs) were reported. The synthesis shows promise for providing polymers having an attractive combination of easy processability, good toughness, respectable high temperature mechanical performance, and excellent thermo-oxidative stability. The new chemistry involves the reaction of an acetylene-terminated material with a bismaleimide or benzoquinone. In order to clarify the reaction mechanism, model compound studies were undertaken in solutions as well as in the solid state. The reaction products were purified by flash chromatography and characterized by conventional analytical techniques including NMR, FT-IR, UV-visible, mass spectroscopy, and high pressure liquid chromatography. The results are presented of the model compound studies which strongly support the formation of a Diels-Alder adduct in the reaction of an acetylene-terminated compound and a bismaleimide or benzoquinone.

  9. Fine-tuning control on CNT diameter distribution, length and density using thermal CVD growth at atmospheric pressure: an in-depth analysis on the role of flow rate and flow duration of acetylene (C2H2) gas

    NASA Astrophysics Data System (ADS)

    Tripathi, Nishant; Mishra, Prabhash; Harsh, Harsh; Islam, S. S.

    2015-01-01

    An optimization control has been demonstrated to obtain carbon nanotubes having specific diameter distribution, length, homogeneity, and yield during its growth by thermal chemical vapor deposition technique under atmospheric pressure. Carbon nanotubes (CNTs) were grown on silicon wafer where a predeposition of iron catalyst of 2 nm thickness was made by sputtering. The growth was conducted under two variable parameters, i.e., flow rate and flow duration. Argon and hydrogen mixture was used for pretreatment of catalyst and as etching gas, and acetylene as a carbon precursor. In-depth analysis shows that increase in flow rate from 10 to 50 sccm resulted in increase in the concentration of amorphous carbon, CNTs diameter range and decrease in length, we found best result at 20 sccm flow rate of acetylene gas. On the other hand, as we varied flow duration from 6 to 14 min, with keeping flow rate of acetylene 20 sccm constant, dense homogeneous growth of horizontal CNTs network plus an increase in length and diameter range were observed. An optimization of flow rate and flow duration is presented here to obtain a selective diameter distribution and length as expected by this growth technique. Atomic force microscopy, field emission scanning electron microscopy and Raman spectroscopy were used to investigate the samples' morphologies in support of the observations made.

  10. Acetylene hydratase of Pelobacter acetylenicus. Molecular and spectroscopic properties of the tungsten iron-sulfur enzyme.

    PubMed

    Meckenstock, R U; Krieger, R; Ensign, S; Kroneck, P M; Schink, B

    1999-08-01

    Acetylene hydratase of Pelobacter acetylenicus is a tungsten iron-sulfur protein involved in the fermentation of acetylene to ethanol and acetate. Expression of the enzyme was increased 10-fold by feeding a 50-L batch culture continuously with 104 Pa acetylene at pH 6.8-7.0. Acetylene hydratase was purified to homogeneity by a three-step procedure in either the absence or presence of dioxygen. The enzyme was a monomer with a molecular mass of 73 kDa (SDS/PAGE) or 83 kDa (matrix-assisted laser-desorption ionization MS) and contained 0.5 +/- 0.1 W (inductively coupled plasma/MS) and 1.3 +/- 0.1 molybdopterin-guanine dinucleotide per mol. Selenium was absent. EPR spectra (enzyme as isolated, under air) showed a signal typical of a [3Fe-4S] cluster with gav = 2.01, at 10 K. In enzyme prepared under N2/H2, this signal was absent and reaction with dithionite led to a rhombic signal with gz = 2.048, gy = 1.939 and gx = 1.920 indicative of a low-potential ferredoxin-type [4Fe-4S] cluster. Upon oxidation with hexacyanoferrate(III), a new signal appeared with gx = 2.007, gy = 2.019 and gz = 2.048 (gav = 2.022), which disappeared after further oxidation. The signal was still visible at 150 K and was tentatively assigned to a W(V) center. The iron-sulfur center of acetylene hydratase (prepared under N2/H2) gave a midpoint redox potential of -410 +/- 20 mV in a spectrophotometric titration with dithionite. Enzyme activity depended on the redox potential of the solution, with 50% of maximum activity at -340 +/- 20 mV. The presence of a pterin-guanine dinucleotide cofactor differentiates acetylene hydratase from the aldehyde ferredoxin oxidoreductase-type enzymes which have a pterin mononucleotide cofactor. PMID:10447686

  11. Polycyclic propargylamine and acetylene derivatives as multifunctional neuroprotective agents.

    PubMed

    Zindo, Frank T; Barber, Quinton R; Joubert, Jacques; Bergh, Jacobus J; Petzer, Jacobus P; Malan, Sarel F

    2014-06-10

    The aim of this study was to design drug-like molecules with multiple neuroprotective mechanisms which would ultimately inhibit N-methyl-D-aspartate (NMDA) receptors, block L-type voltage gated calcium channels (VGCC) and inhibit apoptotic processes as well as the monoamine oxidase-B (MAO-B) enzyme in the central nervous system. These types of compounds may act as neuroprotective and symptomatic drugs for disorders such as Alzheimer's and Parkinson's disease. In designing the compounds we focused on the structures of rasagiline and selegiline, two well known MAO-B inhibitors and proposed neuroprotective agents. Based on this consideration, the compounds synthesised all contain the propargylamine functional group of rasagiline and selegiline or a derivative thereof, conjugated to various polycyclic cage moieties. Being non-polar, these polycyclic moieties have been shown to aid in the transport of conjugated compounds across the blood-brain barrier, as well as cell membranes and have secondary positive neuroprotective effects. All novel synthesised polycyclic derivatives proved to have significant anti-apoptotic activity (p < 0.05) which was comparable to the positive control, selegiline. Four compounds (12, 15 and 16) showed promising VGCC and NMDA receptor channel inhibitory activity ranging from 18% to 59% in micromolar concentrations and compared favourably to the reference compounds. In the MAO-B assay, 8-phenyl-ethynyl-8-hydroxypentacycloundecane (10), exhibited MAO-B inhibition of 73.32% at 300 μM. This compound also reduced the percentage of apoptotic cells by as much as 40% when compared to the control experiments. PMID:24769350

  12. A potential plant-derived antifungal acetylenic acid mediates its activity by interfering with fatty acid homeostasis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    6-Nonadecynoic acid (6-NDA), a plant-derived acetylenic acid, exhibits strong inhibitory activity against the human fungal pathogens Candida albicans, Aspergillus fumigatus, and Trichophyton mentagrophytes. In the present study, transcriptional profiling coupled with mutant and biochemical analyses...

  13. A detailed kinetic modeling study of aromatics formation in laminar premixed acetylene and ethylene flames

    SciTech Connect

    Wang, H.; Frenklach, M.

    1997-07-01

    A computational study was performed for the formation and growth of polycyclic aromatic hydrocarbons (PAHs) in laminar premixed acetylene and ethylene flames. A new detailed reaction mechanism describing fuel pyrolysis and oxidation, benzene formation, and PAH mass growth and oxidation is presented and critically tested. It is shown that the reaction model predicts reasonably well the concentration profiles of major and intermediate species and aromatic molecules in a number of acetylene and ethylene flames reported in the literature. It is demonstrated that reactions of n-C{sub 4}H{sub x} + C{sub 2}H{sub 2} leading to the formation of one-ring aromatics are as important as the propargyl recombination, and hence must be included in kinetic modeling of PAH formation in hydrocarbon flames. It is further demonstrated that the mass growth of PAHs can be accounted for by the previously proposed H-abstraction-C{sub 2}H{sub 2}-addiction mechanism.

  14. Isotope effect in normal-to-local transition of acetylene bending modes

    DOE PAGESBeta

    Ma, Jianyi; Xu, Dingguo; Guo, Hua; Tyng, Vivian; Kellman, Michael E.

    2012-01-01

    The normal-to-local transition for the bending modes of acetylene is considered a prelude to its isomerization to vinylidene. Here, such a transition in fully deuterated acetylene is investigated using a full-dimensional quantum model. It is found that the local benders emerge at much lower energies and bending quantum numbers than in the hydrogen isotopomer HCCH. This is accompanied by a transition to a second kind of bending mode called counter-rotator, again at lower energies and quantum numbers than in HCCH. These transitions are also investigated using bifurcation analysis of two empirical spectroscopic fitting Hamiltonians for pure bending modes, which helpsmore » to understand the origin of the transitions semiclassically as branchings or bifurcations out of the trans and normal bend modes when the latter become dynamically unstable. The results of the quantum model and the empirical bifurcation analysis are in very good agreement.« less

  15. Formation of Large Ag Clusters with Shells of Methane, Ethylene, and Acetylene in He Droplets.

    PubMed

    Loginov, Evgeny; Gomez, Luis F; Sartakov, Boris G; Vilesov, Andrey F

    2016-09-01

    Helium droplets were used to assemble composite metal-molecular clusters. Produced clusters have several hundreds of silver atoms in the core, immersed in a shell consisting of methane, ethylene, or acetylene molecules. The structure of the clusters was studied via infrared spectra of the C-H stretches of the hydrocarbon molecules. The spectra of the clusters containing methane and acetylene show two distinct features due to molecules on the interface with silver core and those in the volume of the neat molecular part of the clusters. The relative intensities of the peaks are in good agreement with the estimates based on the number of the captured particles. Experiments also suggest that selection rules for infrared transitions for molecules adsorbed on metal surfaces are also valid for silver clusters as small as 300 atoms. PMID:27500443

  16. Cold-atmospheric pressure plasma polymerization of acetylene on wood flour for improved wood plastics composites

    NASA Astrophysics Data System (ADS)

    Lekobou, William; Pedrow, Patrick; Englund, Karl; Laborie, Marie-Pierre

    2009-10-01

    Plastic composites have become a large class of construction material for exterior applications. One of the main disadvantages of wood plastic composites resides in the weak adhesion between the polar and hydrophilic surface of wood and the non-polar and hydrophobic polyolefin matrix, hindering the dispersion of the flour in the polymer matrix. To improve interfacial compatibility wood flour can be pretreated with environmentally friendly methods such as cold-atmospheric pressure plasma. The objective of this work is therefore to evaluate the potential of plasma polymerization of acetylene on wood flour to improve the compatibility with polyolefins. This presentation will describe the reactor design used to modify wood flour using acetylene plasma polymerization. The optimum conditions for plasma polymerization on wood particles will also be presented. Finally preliminary results on the wood flour surface properties and use in wood plastic composites will be discussed.

  17. Thermally and oxidatively stable carborane-siloxane-acetylenic-based thermosetting polymers

    SciTech Connect

    Henderson, L.J. Jr.; Keller, T.M.

    1993-12-31

    Inorganic-organic hybrid polymers that can be pyrolyzed to generate new ceramics are of current interest as a route to high temperature materials. Ceramics have desirable thermal stabilities, but are difficult to process. Inorganic-organic hybrid polymers as ceramic precursors combine organic`s ease of processability with inorganic`s desirable thermal and oxidative stability. Carborane-siloxane-acetylenic-based polymers are an application of this approach. The synthesis, characterization and thermooxidative properties of poly(butadiyne-1,7,bis(tetramethyldisiloxyl)-m-carborane) (polymer 2) is described. Polymer 2 is a viscous dark brown polymer that is soluble in most organic solvents making it was to process. Thermal crosslinking of acetylenic groups generates a thermoset which in turn can be pyrolyzed to ceramic material. Thermal and thermo-oxidative characterization is by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Cure studies of larger samples are also presented.

  18. The ozone acetylene reaction: concerted or non-concerted reaction mechanism? A quantum chemical investigation

    NASA Astrophysics Data System (ADS)

    Cremer, Dieter; Kraka, Elfi; Crehuet, Ramon; Anglada, Josep; Gräfenstein, Jürgen

    2001-10-01

    The ozone-acetylene reaction is found to proceed via an intermediate van der Waals complex (rather than a biradical), which is the precursor for a concerted symmetry-allowed [4+2] cycloaddition reaction leading to 1,2,3-trioxolene. CCSD(T)/6-311G+(2d, 2p) and CCSD(T)/CBS (complete basis set) calculations predict the ozone-acetylene van der Waals complex to be stable by 2.2 kcal mol -1, the calculated activation enthalpy for the cycloaddition reaction is 9.6 kcal mol -1 and the reaction enthalpy -55.5 kcal mol -1. Calculated kinetic data for the overall reaction ( k=0.8 l mol -1 s-1, A=1.71×10 6 l mol -1 s-1, E a=8.6 kcal mol -1) suggest that there is a need for refined kinetic measurements.

  19. Isotope effect in normal-to-local transition of acetylene bending modes

    SciTech Connect

    Ma, Jianyi; Xu, Dingguo; Guo, Hua; Tyng, Vivian; Kellman, Michael E.

    2012-01-01

    The normal-to-local transition for the bending modes of acetylene is considered a prelude to its isomerization to vinylidene. Here, such a transition in fully deuterated acetylene is investigated using a full-dimensional quantum model. It is found that the local benders emerge at much lower energies and bending quantum numbers than in the hydrogen isotopomer HCCH. This is accompanied by a transition to a second kind of bending mode called counter-rotator, again at lower energies and quantum numbers than in HCCH. These transitions are also investigated using bifurcation analysis of two empirical spectroscopic fitting Hamiltonians for pure bending modes, which helps to understand the origin of the transitions semiclassically as branchings or bifurcations out of the trans and normal bend modes when the latter become dynamically unstable. The results of the quantum model and the empirical bifurcation analysis are in very good agreement.

  20. Low pressure R.F. plasma reactions in light hydrocarbons. Ethylene and acetylene

    NASA Astrophysics Data System (ADS)

    Canepa, Pietro; Castello, Gianrico; Nicchia, Mario; Munari, Stelio

    The results obtained in the plasmolysis of ethylene and acetylene in an inductively coupled radiofrequency glow discharge are reported. A static system at a constant initial pressure of 0.5 torr and input power of 50 W was used; the gaseous and polymeric products were evaluated and compared with previous data on ethane plasmolysis and other available literature data. The decomposition products of ethylene were similar to those obtained during the plasmolysis of ethane, with a different distribution and a smaller initial increase of the total pressure. The total pressure of acetylene quickly decreased to near zero value at small specific energy, due to rapid polymerization. No gaseous products were detected, except hydrogen and traces of diacetylene.

  1. Application of the photoacoustic method to the measurement of acetylene reduction by nitrogenase enzyme

    NASA Astrophysics Data System (ADS)

    Schramm, D. U.; Sthel, M. S.; Carneiro, L. O.; Franco, A. A.; Campos, A. C.; Vargas, H.

    2005-06-01

    Nitrogenase is an enzyme responsible for the reduction of the atmospheric N2 into NH4^+, which represents the key entry point of the molecular nitrogen into the biogeochemical cycle of nitrogen. This enzyme is present in the rhizobial bacteroids, which are symbionts in a Leguminosae plant (Acacia Holosericea), and also reduces acetylene into ethylene at the same rate as the nitrogen reduction. Therefore, a CO2 Laser Photoacoustic system was used for detecting and monitoring the ethylene emission by the nitrogenase activity, in the rhizobial symbionts in Acacia Holosericea, when they are confined in test tubes with acetylene at two different volumes (0.1 and 0.5 ml). Ethylene concentrations are also determined in the ppm range.

  2. Characterization of the Minimum Energy Paths and Energetics for the reaction of Vinylidene with Acetylene

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.; Taylor, Peter R.

    1995-01-01

    The reaction of vinylidene (CH2C) with acetylene may be an initiating reaction in soot formation. We report minimum energy paths and accurate energetics for a pathway leading to vinylacetylene and for a number of isomers Of C4H4. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contacted configuration interaction (ICCI) and/or coupled cluster singles and doubles with a perturbational estimate of triple excitations (CCSD(T)) to determine the energetics. We find an entrance channel barrier of about 5 kcal/mol for the addition of vinylidene to acetylene, but no barriers above reactants for the reaction pathway leading to vinylacetylene.

  3. Probing Ionic Complexes of Ethylene and Acetylene with Vacuum-Ultraviolet Radiation.

    PubMed

    Bandyopadhyay, Biswajit; Stein, Tamar; Fang, Yigang; Kostko, Oleg; White, Alec; Head-Gordon, Martin; Ahmed, Musahid

    2016-07-14

    Mixed complexes of acetylene-ethylene are studied using vacuum-ultraviolet (VUV) photoionization mass spectrometry and theoretical calculations. These complexes are produced and ionized at different distances from the exit of a continuous nozzle followed by reflectron time-of-flight mass spectrometry detection. Acetylene, with a higher ionization energy (11.4 eV) than ethylene (10.6 eV), allows for tuning the VUV energy and initializing reactions either from a C2H2(+) or a C2H4(+) cation. Pure acetylene and ethylene expansions are separately carried out to compare, contrast, and hence identify products from the mixed expansion: these are C3H3(+) (m/z = 39), C4H5(+) (m/z = 53), and C5H5(+) (m/z = 65). Intensity distributions of C2H2, C2H4, their dimers and reactions products are plotted as a function of ionization distance. These distributions suggest that association mechanisms play a crucial role in product formation closer to the nozzle. Photoionization efficiency (PIE) curves of the mixed complexes demonstrate rising edges closer to both ethylene and acetylene ionization energies. We use density functional theory (ωB97X-V/aug-cc-pVTZ) to study the structures of the neutral and ionized dimers, calculate their adiabatic and vertical ionization energies, as well as the energetics of different isomers on the potential energy surface (PES). Upon ionization, vibrationally excited clusters can use the extra energy to access different isomers on the PES. At farther ionization distances from the nozzle, where the number densities are lower, unimolecular decay is expected to be the dominant mechanism. We discuss the possible decay pathways from the different isomers on the PES and examine the ones that are energetically accessible. PMID:26983013

  4. Deposition of Functional Coatings from an Acetylene-Containing Plasma at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Plevako, F. V.; Gorbatov, S. V.; Davidovich, P. A.; Prikhod‧ko, E. M.; Shushkov, S. V.; Krul‧, L. P.; Butovskaya, G. V.; Shakhno, O. V.; Gusakova, S. V.; Korolik, O. V.; Mazanik, A. V.

    2016-03-01

    Properties of thin coatings formed on polymer and glass substrates by plasma-enhanced chemical vapor deposition from a mixture of nitrogen with acetylene at atmospheric pressure were investigated. It was established that chemically stable transparent films with a mass ratio of fixed carbon and nitrogen C:N ~ 2:1 are formed on the surface of these substrates. When the deposition time was increased, arrays of dendrite-like structures were formed on the substrates.

  5. A new C-10 acetylene and A new triterpenoid from Conyza canadensis.

    PubMed

    Xie, Wei Dong; Gao, Xue; Jia, Zhong Jian

    2007-05-01

    From the whole plants of Conyza canadensis (Compositae), a new C-10 acetylene, namely 8R, 9R-dihydroxymatricarine methyl ester (1), and a new triterpenoid, namely 3beta, 16beta, 20beta-trihydroxytaraxast-3-O-palmitoxyl ester (4), were isolated along with eleven known compounds (2, 3, 5-13). The structures of all 13 compounds were elucidated on the basis of their spectral data. The antibacterial activities of compounds 1-3 were evaluated. PMID:17615671

  6. Theoretical study of the C-H bond dissociation energy of acetylene

    NASA Technical Reports Server (NTRS)

    Taylor, Peter R.; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1990-01-01

    The authors present a theoretical study of the convergence of the C-H bond dissociation energy (D sub o) of acetylene with respect to both the one- and n-particle spaces. Their best estimate for D sub o of 130.1 plus or minus 1.0 kcal/mole is slightly below previous theoretical estimates, but substantially above the value determined using Stark anticrossing spectroscopy that is asserted to be an upper bound.

  7. IUPAC-NIST Solubility Data Series. 97. Solubility of Higher Acetylenes and Triple Bonded Derivatives

    NASA Astrophysics Data System (ADS)

    Fogg, Peter G. T.

    2013-03-01

    Solubility of Ethyne in Liquids was published in 2001 as Vol. 76 of the IUPAC-NIST Solubility Data Series. The current work extends the coverage to the solubility in liquids of higher gaseous and liquid acetylenes and to derivatives that contain a triple carbon-carbon bond. Predictive methods for estimating solubilities in water are summarised and usually give values to within an order of magnitude. The literature has been surveyed to the end of 2010.

  8. Pulsed erbium fiber laser with an acetylene-filled photonic crystal fiber for saturable absorption.

    PubMed

    Marty, Patrick Thomas; Morel, Jacques; Feurer, Thomas

    2011-09-15

    We investigate the dynamics of an erbium-doped fiber ring laser that is equipped with an intracavity hollow core photonic crystal fiber gas cell. The cell is filled with acetylene as a saturable absorber. We observe cw operation at low pressures, Q switching at intermediate pressure levels, and mode locking at high pressures applied. Moreover, we show that the transition from the cw to the pulsed mode may be exploited for sensitive gas detection. PMID:21931393

  9. Infrared Absorption Spectroscopy of Acetylene in the Lecture

    ERIC Educational Resources Information Center

    Briggs, Thomas E.; Sanders, Scott T.

    2006-01-01

    Lecture-based experimental methods that include topics ranging from basic signal processing to the proper use of thermocouples to advanced optical techniques such as laser-induced fluorescence are described. The data obtained from this demonstration could be provided to the students in digital form to obtain useful engineering results such as an…

  10. Soluble fluorinated polyimides that contain curable acetylene units in the backbone

    SciTech Connect

    Takeichi, T.; Ogura, S.

    1993-12-31

    Soluble polyimides that contain internal acetylene groups in the backbone were prepared by reacting 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride with various ratio of bis(3-aminophenyl)acetylene and 4,4`-diaminodiphenyl ether. The polyimides were soluble in organic solvents such as N-methylpyrrolidone (NMP) and N,N-dimethylacetamide, and exhibited reduced viscosities in the range of 0.76-1.44 (in NMP at 30{degrees}C). The crosslinking behavior was examined by DSC. The onset of exotherm appeared at 321-345{degrees}C depending on the acetylene content. After thermal treatment at 350{degrees}C, the polyimides became insoluble in any organic solvents examined and in conc. sulfuric acid. The viscoelastic analyses showed the effect of crosslinking clearly. For example, Tg increased with thermal treatment, and was finally above 400{degrees}C. The drop of modulus at higher temperature also became very small. The TGA analyses also showed excellent thermal stability.

  11. Dehalogenative Homocoupling of Terminal Alkynyl Bromides on Au(111): Incorporation of Acetylenic Scaffolding into Surface Nanostructures.

    PubMed

    Sun, Qiang; Cai, Liangliang; Ma, Honghong; Yuan, Chunxue; Xu, Wei

    2016-07-26

    On-surface C-C coupling reactions of molecular precursors with alkynyl functional groups demonstrate great potential for the controllable fabrication of low-dimensional carbon nanostructures/nanomaterials, such as carbyne, graphyne, and graphdiyne, which demand the incorporation of highly active sp-hybridized carbons. Recently, through a dehydrogenative homocoupling reaction of alkynes, the possibility was presented to fabricate surface nanostructures involving acetylenic linkages, while problems lie in the fact that different byproducts are inevitably formed when triggering the reactions at elevated temperatures. In this work, by delicately designing the molecular precursors with terminal alkynyl bromide, we introduce the dehalogenative homocoupling reactions on the surface. As a result, we successfully achieve the formation of dimer structures, one-dimensional molecular wires and two-dimensional molecular networks with acetylenic scaffoldings on an inert Au(111) surface, where the unexpected C-Au-C organometallic intermediates are also observed. This study further supplements the database of on-surface dehalogenative C-C coupling reactions, and more importantly, it provides us an alternative efficient way for incorporating the acetylenic scaffolding into low-dimensional surface nanostructures. PMID:27326451

  12. Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

    SciTech Connect

    Han, Huixian; Li, Anyang; Guo, Hua

    2014-12-28

    A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S{sub 0}) electronic state has been constructed by fitting ∼37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm{sup −1}. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm{sup −1} above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.

  13. An autopsy case of suicide by acetylene explosion: a case report.

    PubMed

    Kashiwagi, Masayuki; Hara, Kenji; Takamoto, Mutsuo; Kageura, Mitsuyoshi; Matsusue, Aya; Sugimura, Tomoko; Kubo, Shin-ichi

    2009-04-01

    We report an autopsy case of a male welder in his thirties who was found dead in an exploded truck cabin. The roof, windows and doors of the cabin had been blown up to 50 metres away. An oxygen cylinder and an acetylene cylinder, both unexploded, were found in the back of the truck. The deceased was lying on the driver's seat. His entire body was burnt, carbonised and partially skeletonised. There was a small amount of soot in his oesophagus and stomach and a large volume of bloody fluid in the trachea and bronchi. There was an extensive haemorrhage in the posterior thoracic wall. No drugs were detected in the blood. Hardly any carbon monoxide and combustion-related gases were detected in the blood, therefore he was not considered to have died from the fire. Acetylene was detected in his blood (21.5 microg/ml in the femoral vein blood) and urine (7.49 microg/ml), with marked haemorrhaging in his back. We therefore concluded that the victim died because of an acetylene explosion in the cabin and also that this was a suicide. PMID:19537452

  14. Chemistry of polycyclic aromatic hydrocarbons formation from phenyl radical pyrolysis and reaction of phenyl and acetylene.

    PubMed

    Comandini, A; Malewicki, T; Brezinsky, K

    2012-03-15

    An experimental investigation of phenyl radical pyrolysis and the phenyl radical + acetylene reaction has been performed to clarify the role of different reaction mechanisms involved in the formation and growth of polycyclic aromatic hydrocarbons (PAHs) serving as precursors for soot formation. Experiments were conducted using GC/GC-MS diagnostics coupled to the high-pressure single-pulse shock tube present at the University of Illinois at Chicago. For the first time, comprehensive speciation of the major stable products, including small hydrocarbons and large PAH intermediates, was obtained over a wide range of pressures (25-60 atm) and temperatures (900-1800 K) which encompass the typical conditions in modern combustion devices. The experimental results were used to validate a comprehensive chemical kinetic model which provides relevant information on the chemistry associated with the formation of PAH compounds. In particular, the modeling results indicate that the o-benzyne chemistry is a key factor in the formation of multi-ring intermediates in phenyl radical pyrolysis. On the other hand, the PAHs from the phenyl + acetylene reaction are formed mainly through recombination between single-ring aromatics and through the hydrogen abstraction/acetylene addition mechanism. Polymerization is the common dominant process at high temperature conditions. PMID:22339468

  15. Discovery of acetylene hydratase activity of the iron–sulphur protein IspH

    PubMed Central

    Wang, Weixue; Zhang, Yonghui; Bacher, Adelbert; Eisenreich, Wolfgang; Li, Kai; Schulz, Charles; Oldfield, Eric; Groll, Michael

    2013-01-01

    The final step of the methylerythritol phosphate isoprenoid biosynthesis pathway is catalysed by the iron–sulphur enzyme IspH, producing the universal precursors of terpenes: isopentenyl diphosphate and dimethylallyl diphosphate. Here we report an unforeseen reaction discovered during the investigation of the interaction of IspH with acetylene inhibitors by X-ray crystallography, Mößbauer, and nuclear magnetic resonance spectroscopy. In addition to its role as a 2H+/2e− reductase, IspH can hydrate acetylenes to aldehydes and ketones via anti-Markovnikov/Markovnikov addition. The reactions only occur with the oxidised protein and proceed via η1-O-enolate intermediates. One of these is characterized crystallographically and contains a C4 ligand oxygen bound to the unique, fourth iron in the 4Fe-4S cluster: this intermediate subsequently hydrolyzes to produce an aldehyde product. This unexpected side to IspH reactivity is of interest in the context of the mechanism of action of other acetylene hydratases, as well as in the design of antiinfectives targeting IspH. PMID:22948824

  16. New insights into the anion formation mechanisms in dusty acetylene discharges

    NASA Astrophysics Data System (ADS)

    Mao, Ming; Benedikt, Jan; Consoli, Angelo; Bogaerts, Annemie

    2008-10-01

    Dust (or nanoparticle) formation is a well-known phenomenon occurring in reactive gas plasmas, such as silane or acetylene. Under some conditions, the dust formation is considered to be harmful, whereas for other applications, it turns out to be beneficial. In this presentation, the initial mechanisms of nanoparticle formation and growth in radiofrequency (RF) acetylene (C2H2) plasmas are investigated by means of a comprehensive self-consistent one-dimensional (1D) fluid model. Based on the comparison of our calculation results with available experimental data for acetylene plasmas in the literature, some new mechanisms for negative ion formation and growth are proposed. Possible routes are considered for the formation of larger (linear and branched) hydrocarbons C2nH2 (n=3-5), which contribute to the generation of C2nH^-anions (n=3-5) due to dissociative electron attachment. Moreover, beside the C2nH^- ions, also the vinylidene anion (H2CC^-) and higher C2nH2^- anions (n=2-4) are found to be important plasma species. This project was supported financially by the Fund for Scientific Research (FWO) Flanders (Project G. 0068.07), the Interuniversity Attraction Poles Programme of the Belgian State (Belgian Science Policy; Project P6/42) and the CALCUA computing facilities of the University of Antwerp.

  17. Acetylene from the co-pyrolysis of biomass and waste tires or coal in the H{sub 2}/Ar plasma

    SciTech Connect

    Bao, W.; Cao, Q.; Lv, Y.; Chang, L.

    2008-07-01

    Acetylene from carbon-containing materials via plasma pyrolysis is not only simple but also environmentally friendly. In this article, the acetylene produced from co-pyrolyzing biomass with waste tire or coal under the conditions of H{sub 2}/Ar DC arc plasma jet was investigated. The experimental results showed that the co-pyrolysis of mixture with biomass and waste tire or coal can improve largely the acetylene relative volume fraction (RVF) in gaseous products and the corresponding yield of acetylene. The change trends for the acetylene yield of plasma pyrolysis from mixture with raw sample properties were the same as relevant RVF. But the yield change trend with feeding rate is different from its RVF. The effects of the feeding rate of raw materials and the electric current of plasmatron on acetylene formation are also discussed.

  18. The anomalous behavior of the Zeeman anticrossing spectra of à 1Au acetylene: Theoretical considerations

    NASA Astrophysics Data System (ADS)

    Vacek, George; Sherrill, C. David; Yamaguchi, Yukio; Schaefer, Henry F., III

    1996-02-01

    P. Dupré, R. Jost, M. Lombardi, P. G. Green, E. Abramson, and R. W. Field have observed anomalous behavior of the anticrossing density in the Zeeman anticrossing (ZAC) spectra of gas phase à 1Au acetylene in the 42 200 to 45 300 cm-1 energy range. To best explain this result, they hypothesize a large singlet-triplet coupling due to the existence of a linear isomerization barrier connecting a triplet-excited cis- and trans-acetylene in the vicinity of the studied energy range (˜45 500 cm-1). Theoretically such a linear stationary point, however, must have two different degenerate bending vibrational frequencies which are either imaginary or exactly zero. Neither case has yet been experimentally detected. Here, we have studied the two lowest-lying linear triplet-excited-state stationary points of acetylene, 3Σ+u and 3Δu, to see if they fit Dupré et al.'s hypothesis. We have completed geometry optimization and harmonic vibrational frequency analysis using complete-active-space self-consistent field (CASSCF) wave functions as well as determined energy points at those geometries using the second-order configuration interaction (SOCI) method. Harmonic vibrational analyses of both stationary points reveal two different doubly degenerate vibrational modes with imaginary vibrational frequencies (or negative force constants) indicating that they are indeed saddle points with a Hessian index of four. At the DZP SOCI//CASSCF level of theory with zero-point vibrational energy (ZPVE) correction, the 3Σ+u stationary point lies 35 840 cm-1 above the ground state of acetylene. This is much too low in energy to contribute to the ZAC spectral anomaly. At the same level of theory with ZPVE correction, the 3Δu stationary point lies 44 940 cm-1 above the ground state consistent with Dupré et al.'s hypothesis. Several solutions to the anomalous ZAC spectra are discussed. We propose that the anomaly may also be due to coupling with a nearly linear structure on the T3 surface of

  19. Nitrogenase activity in cyanobacteria measured by the acetylene reduction assay: a comparison between batch incubation and on-line monitoring.

    PubMed

    Staal, M; Lintel-Hekkert, S T; Harren, F; Stal, L

    2001-05-01

    A new on-line method for measuring acetylene reduction is described. It consists of a gas-flow cell connected to an electronic gas-mixing system and an automatic sample loop in the gas chromatograph. Alternatively, ethylene can be determined by using laser-based trace gas detection. The laser-based trace gas detection technique achieves a detection limit that is three orders of magnitude better than gas chromatography. We have applied the on-line method to the measurement of nitrogen fixation in a culture of the heterocystous cyanobacterium Nodularia spumigena and compared it with conventional batch-type incubations. Incubation of N. spumigena in the gas-flow cell resulted in very short response times with a steady-state flux of ethylene obtained within 2 min. Nitrogenase was shown to respond immediately to changes in light and oxygen. Monitoring of nitrogenase activity could be continued for several hours without having a negative impact on nitrogen fixation rates in N. spumigena. This was not the case in batch incubations, in which changes in nitrogenase activities were recorded during incubations, probably as a result of varying oxygen concentrations. It was therefore concluded that the on-line method is superior to batch incubations when rates of nitrogenase activity are to be measured. The method is suitable for natural samples (water or sediment). PMID:11422321

  20. Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.; Nava, D. F.; Brobst, W. D.; Stief, L. J.

    1984-01-01

    The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.

  1. Structure and morphology of c-SiC films obtained by acetylene reaction with Si(111) surface

    NASA Astrophysics Data System (ADS)

    De Crescenzi, M.; Bernardini, R.; Gunnella, R.; Castrucci, P.

    2002-07-01

    In this work we investigated the structure and morphology of silicon carbide films grown under ultra-high-vacuum (UHV) conditions by acetylene (C 2H 2) carbonization of Si(111) surfaces kept at 650 °C. We used several UHV electron techniques to probe the local structural properties of the film and scanning tunneling microscopy (STM) to study its morphology. Our results indicated that C atoms occupy tetrahedral substitutional sites in the Si with a C-Si bond of 1.90±0.03 Å as in a bulk cubic SiC (c-SiC) crystal. X-ray diffraction data confirmed the formation of highly (111) oriented epitaxial crystallites characterized by the c-SiC lattice. STM images showed the formation of ordered, interconnected structures, rather flat at the atomic scale, triangular in shape, characterized by the same orientation and with an average area of 5000 nm 2 and an average height of 10-15 Å. Only a few holes can be detected which may be interpreted as empty spaces left by the patchwork growth of the silicon carbide triangular islands. Therefore, our growth procedure resulted to produce crystalline c-SiC films by using one of the most lowest temperature reported in literature.

  2. Interpretation of PAN, acetone and acetylene measurements from the MIPAS-E

    NASA Astrophysics Data System (ADS)

    Moore, D. P.; Remedios, J. J.; Parker, R. J.

    2009-04-01

    Emissions of anthropogenic pollution, from biomass burning events in particular, result in the injection of a wide range of carbon compounds into the atmosphere. Carbon monoxide (CO), methane (CH4) and volatile organic compounds (VOCs) are released in significant amounts, affecting both the oxidation capacity of the troposphere and ozone production. Upper troposphere (UT) measurements of PAN, acetone and acetylene have, in the past, been generally limited to sporadic in situ sampling during specialised campaign periods. The recent rapid progress in both the detection and retrieval of many VOC species from spaceborne instrumentation has been large. It has recently been established that the observation of the global distribution of VOCs in the UT can be made by measurements provided by instruments such as the Michelson Interferometer for Passive Atmospheric Sounding onboard ENVISAT (MIPAS-E) or the Atmospheric Chemistry Experiment (ACE) onboard SCISAT-1. In this work, we discuss the ability of MIPAS-E to provide new global measurements of acetone in the UT. We also describe both the distribution and seasonality observed in UT PAN volume mixing ratios (vmrs). From the MIPAS-E acetylene measurements, we analyse the extent and magnitude of the chemical isolation observed over the Middle East during August 2003. We show that this enhancement is due to fast westward transport from Asia via the Easterly Jet associated with the Asian monsoon anticyclone. A full error analysis is carried out for each of the three gases we analyse. Previous work has shown that characteristic infrared signatures of PAN, acetone and acetylene can be detected in MIPAS-E thermal emission spectra, with the 787-790 cm-1, 1216-1218 cm-1 and 776.0-776.15 cm-1 spectral ranges respectively being particularly sensitive to changes in each of the gases. We invert the measured MIPAS-E spectra into vmrs using an independent offline-retrieval scheme based on the optimal estimation approach which was

  3. Formation of Complex Organics by Gas Phase and Intracluster Ion-Molecule Reactions Involving Acetylene and Hydrogen Cyanide

    NASA Astrophysics Data System (ADS)

    El-Shall, S.; Hamed, A.; Soliman, A. R.; Momoh, P. O.

    2011-05-01

    Many complex organics including polycyclic aromatic hydrocarbons are present in flames and combustion processes as well as in interstellar clouds and solar nebulae. Here, we present evidence for the formation of complex covalent organics by gas phase and intracluster reactions of the benzene, phenylium, pyridine, pyrimidine, phenylacetylene and benzonitrile cations with acetylene and hydrogen cyanide molecules. These reactions are studied using mass-selected ion mobility, chemical reactivity, collisional dissociation, and ab initio calculations. Measurements of collision cross sections in helium provide structural information on the adducts and allow probing structural changes at different temperatures (isomerization). We observed multiple additions of five acetylene molecules on the pyridine cation at room temperature. This is a remarkable result considering that only two acetylene molecules were added to the phenyl cation and no addition was observed on the benzene cation at room temperature. The experimental results are in full agreement with the ab initio calculations which predict that the first and second acetylenes add to the pyridine ion in barrierless, highly exothermic reactions. Similar reactions have been observed for the pyrimidine radical cation although the extent of the addition reactions is limited to only two acetylene molecules at room temperature. The results provide the first evidence for the incorporation of nitrogen in the formation cyclic hydrocarbons via the gas phase reactions of pyridine and pyrimidine ions with acetylene molecules. In addition, the formation of covalent adducts in the ionized acetylene/HCN system will be reported for the first time. Sequential reactions leading to the formation of pyridine and pyrimidine radical cations and higher adducts are observed over a wide range of temperature and pressure. The formation of these covalent adducts may represent a general class of addition reactions that can form complex

  4. The comparison of the immediate effects of application of the suboccipital muscle inhibition and self-myofascial release techniques in the suboccipital region on short hamstring.

    PubMed

    Cho, Sung-Hak; Kim, Soo-Han; Park, Du-Jin

    2015-01-01

    [Purpose] The purpose of this study was to research the effect of performing the suboccipital muscle inhibition (SMI) and self-myofascial release (SMFR) techniques in the suboccipital area on the flexibility of the hamstring. [Subjects] Fifty persons with short hamstrings participated in this research. According to the results of the finger-floor distance (FFD) test, the subjects were allocated to SMI and SMFR groups of 25 subjects each. [Methods] The SMI and SMFR techniques were applied to the groups. For the analysis, we used the FFD test and the straight leg raise (SLR) test for the flexibility of hamstring. The evaluator was blindfolded. [Results] In the SMI group, FFD, SLR, and PA were significantly changed after the intervention, and in the SMFR group, there was a significant change in SLR after the intervention. In a comparison between the groups, FED was found to be significantly increased in the SMI group. [Conclusion] Application of the SMI and SMFR to persons with short hamstrings resulted in immediate increases in flexibility of the hamstring. However, we could see that the SMI technique was more effective. PMID:25642072

  5. ESI-MS, DFT, and synthetic studies on the H(2)-mediated coupling of acetylene: insertion of C=X bonds into rhodacyclopentadienes and Brønsted acid cocatalyzed hydrogenolysis of organorhodium intermediates.

    PubMed

    Williams, Vanessa M; Kong, Jong Rock; Ko, Byoung Joon; Mantri, Yogita; Brodbelt, Jennifer S; Baik, Mu-Hyun; Krische, Michael J

    2009-11-11

    The catalytic mechanism of the hydrogen-mediated coupling of acetylene to carbonyl compounds and imines has been examined using three techniques: (a) ESI-MS and ESI-CAD-MS analyses, (b) computational modeling, and (c) experiments wherein putative reactive intermediates are diverted to alternate reaction products. ESI-MS analysis of reaction mixtures from the hydrogen-mediated reductive coupling of acetylene to alpha-ketoesters or N-benzenesulfonyl aldimines corroborate a catalytic mechanism involving C horizontal lineX (X = O, NSO(2)Ph) insertion into a cationic rhodacyclopentadiene obtained by way of acetylene oxidative dimerization with subsequent Brønsted acid cocatalyzed hydrogenolysis of the resulting oxa- or azarhodacycloheptadiene. Hydrogenation of 1,6-diynes in the presence of alpha-ketoesters provides analogous coupling products. ESI mass spectrometric analysis again corroborates a catalytic mechanism involving carbonyl insertion into a cationic rhodacyclopentadiene. For all ESI-MS experiments, the structural assignments of ions are supported by multistage collisional activated dissociation (CAD) analyses. Further support for the proposed catalytic mechanism derives from experiments aimed at the interception of putative reactive intermediates and their diversion to alternate reaction products. For example, rhodium-catalyzed coupling of acetylene to an aldehyde in the absence of hydrogen or Brønsted acid cocatalyst provides the corresponding (Z)-butadienyl ketone, which arises from beta-hydride elimination of the proposed oxarhodacycloheptadiene intermediate, as corroborated by isotopic labeling. Additionally, the putative rhodacyclopentadiene intermediate obtained from the oxidative coupling of acetylene is diverted to the product of reductive [2 + 2 + 2] cycloaddition when N-p-toluenesulfonyl-dehydroalanine ethyl ester is used as the coupling partner. The mechanism of this transformation also is corroborated by isotopic labeling. Computer model studies

  6. High-resolution photoemission study of acetylene adsorption and reaction with the Si(100)-2x1 surface

    SciTech Connect

    Xu, S.H.; Yang, Y.; Keeffe, M.; Lapeyre, G.J.; Rotenberg, E.

    1999-02-09

    The adsorption and reaction of acetylene with the Si{approximately}100-231 surface has been studied using high-resolution photoemission by monitoring the Si 2p,C 1s, and valence-band (VB) spectra as a function of both acetylene coverage and post-adsorption annealing temperature. After the clean Si(100) surface is exposed to 0.5 monolayer (ML) acetylene, the surface state in the VB is absent. Meanwhile, the curve-fitting results show that there is only one interface component in the Si 2p core level. These results indicate that the asymmetric Si dimers may become symmetric dimers after acetylene adsorption, which can be explained well by the tetra-sigma model determined from our previous photoelectron holographic results. Significant changes in the electronic structure (Si 2p,C 1s, and VB) are found after subsequent annealing of the saturation overlayer. Annealing at lower temperature can induce some acetylene molecule desorption while most of the molecules decompose into C2Hx (x=1,0) and H species. After annealing above 660C, both of the reacted components of the Si 2p and C 1s lines show that the SiC species form clusterlike features. At the same time, the VB and Si 2p spectra indicate a restoration of a Si(100)-2x1 structure, and the asymmetric Si dimers reappear on the surface.

  7. Rotational spectroscopy and molecular structure of the 1-chloro-1-fluoroethylene-acetylene complex.

    PubMed

    Leung, Helen O; Marshall, Mark D; Grimes, David D

    2011-01-21

    Guided by ab initio calculations, Fourier transform microwave spectra in the 6-21 GHz region are obtained for seven isotopomers of the complex formed between 1-chloro-1-fluoroethylene and acetylene. These include the four possible combinations of (35)Cl- and (37)Cl-containing CH(2)CClF with the most abundant acetylene isotopic modification, HCCH, and its H(13)C(13)CH analogue, as well as three singly substituted deuterated isotopomers. Analysis of the spectra determines the rotational constants and additionally, the complete chlorine quadrupole hyperfine coupling tensors in both the inertial and principal electric field gradient axis systems, and where appropriate, the diagonal components of the deuterium quadrupole coupling tensors. The inertial information contained in the rotational constants provides the structure for CH(2)CClF-HCCH: a primary, hydrogen bonding interaction existing between the HCCH donor and the F atom acceptor on the 1-chloro-1-fluoroethylene moiety, while a secondary interaction occurs between the acetylenic bond on the HCCH molecule and the H atom cis to the hydrogen-bonded F atom on the substituted ethylene, which causes the hydrogen bond to deviate from linearity. This is similar to the structure obtained for 1,1-difluoroethylene-HCCH [H. O. Leung and M. D. Marshall, J. Chem. Phys. 126, 154301 (2006)], and indeed, to within experimental uncertainty, the intermolecular interactions in CH(2)CClF-HCCH and its 1,1-difluoroethylene counterpart are practically indistinguishable, even though ab initio calculations at the MP2∕6-311G++(2d, 2p) level suggest that the former complex is more strongly bound. PMID:21261349

  8. Soot Formation in Laminar Acetylene/Air Diffusion Flames at Atmospheric Pressure. Appendix C

    NASA Technical Reports Server (NTRS)

    Xu, F.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

    2000-01-01

    The flame structure and soot-formation (soot nucleation and growth) properties of axisymmetric laminar coflowing jet diffusion flames were studied experimentally. Test conditions involved acetylene-nitrogen jets burning in coflowing air at atmospheric pressure. Measurements were limited to the axes of the flames and included soot concentrations, soot temperatures, soot structure, major gas species concentrations, radical species (H, OH, and O) concentrations, and gas velocities. The results show that as distance increases along the axes of the flames, detectable soot formation begins when significant H concentrations are present, and ends when acetylene concentrations become small. Species potentially associated with soot oxidation-O2, CO2, H2O, O, and OH-are present throughout the soot-formation region so that soot formation and oxidation proceed at the same time. Strong rates of soot growth compared to soot nucleation early in the soot-formation process, combined with increased rates of soot nucleation and oxidation as soot formation proceeds, causes primary soot particle diameters to reach a maximum relatively early in the soot-formation process. Aggregation of primary soot particles proceeds, however, until the final stages of soot oxidation. Present measurements of soot growth (corrected for soot oxidation) in laminar diffusion flames were consistent with earlier measurements of soot growth in laminar premixed flames and exhibited encouraging agreement with existing hydrogen-abstraction/carbon-addition (HACA) soot growth mechanisms in the literature that were developed based on measurements within laminar premixed flames. Measured primary soot particle nucleation rates in the present laminar diffusion flames also were consistent with corresponding rates measured in laminar premixed flames and yielded a crude correlation in terms of acetylene and H concentrations and the temperature.

  9. Soot Formation in Laminar Acetylene/Air Diffusion Flames at Atmospheric Pressure. Appendix J

    NASA Technical Reports Server (NTRS)

    Xu, F.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

    2001-01-01

    The flame structure and soot-formation (soot nucleation and growth) properties of axisymmetric laminar coflowing jet diffusion flames were studied experimentally. Test conditions involved acetylene-nitrogen jets burning in coflowing air at atmospheric pressure. Measurements were limited to the axes of the flames and included soot concentrations, soot temperatures, soot structure, major gas species concentrations, radical species (H, OH, and O) concentrations, and gas velocities. The results show that as distance increases along the axes of the flames, detectable soot formation begins when significant H concentrations are present, and ends when acetylene concentrations become small. Species potentially associated with soot oxidation--O2, CO2, H2O, O, and OH-are present throughout the soot-formation region so that soot formation and oxidation proceed at the same time. Strong rates of soot growth compared to soot nucleation early in the soot-formation process, combined with increased rates of soot nucleation and oxidation as soot formation proceeds, causes primary soot particle diameters to reach a maximum relatively early in the soot-formation process. Aggregation of primary soot particles proceeds, however, until the final stages of soot oxidation. Present measurements of soot growth (corrected for soot oxidation) in laminar diffusion flames were consistent with earlier measurements of soot growth in laminar premixed flames and exhibited encouraging agreement with existing hydrogen-abstraction/carbon-addition (HACA) soot growth mechanisms in the literature that were developed based on measurements within laminar premixed flames. Measured primary soot particle nucleation rates in the present laminar diffusion flames also were consistent with corresponding rates measured in laminar premixed flames and yielded a crude correlation in terms of acetylene and H concentrations and the temperature.

  10. Soot Formation in Laminar Acetylene/Air Diffusion Flames at Atmospheric Pressure. Appendix H

    NASA Technical Reports Server (NTRS)

    Xu, F.; Faeth, G. M.; Yuan, Z.-G. (Technical Monitor); Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

    2001-01-01

    The flame structure and soot-formation (soot nucleation and growth) properties of axisymmetric laminar coflowing jet diffusion flames were studied experimentally. Test conditions involved acetylene-nitrogen jets burning in coflowing air at atmospheric pressure. Measurements were limited to the axes of the flames and included soot concentrations, soot temperatures, soot structure, major gas species concentrations, radical species (H, OH, and O) concentrations, and gas velocities. The results show that as distance increases along the axes of the flames, detectable soot formation begins when significant H concentrations are present, and ends when acetylene concentrations become small. Species potentially associated with soot oxidation-O2, CO2, H2O, O, and OH-are present throughout the soot-formation region so that soot formation and oxidation proceed at the same time. Strong rates of soot growth compared to soot nucleation early in the soot-formation process, combined with increased rates of soot nucleation and oxidation as soot formation proceeds, causes primary soot particle diameters to reach a maximum relatively early in the soot-formation process. Aggregation of primary soot particles proceeds, however, until the final stages of soot oxidation. Present measurements of soot growth (corrected for soot oxidation) in laminar diffusion flames were consistent with earlier measurements of soot growth in laminar premixed flames and exhibited encouraging agreement with existing hydrogen-abstraction/carbon-addition (HACA) soot growth mechanisms in the literature that were developed based on measurements within laminar premixed flames. Measured primary soot particle nucleation rates in the present laminar diffusion flames also were consistent with corresponding rates measured in laminar premixed flames and yielded a crude correlation in terms of acetylene and H concentrations and the temperature.

  11. A biogeochemical and genetic survey of acetylene fermentation by environmental samples and bacterial isolates

    USGS Publications Warehouse

    Miller, Laurence G.; Baesman, Shaun M.; Kirshtein, Julie; Voytek, Mary A.; Oremland, Ronald S.

    2013-01-01

    Anoxic samples (sediment and groundwater) from 13 chemically diverse field sites were assayed for their ability to consume acetylene (C2H2). Over incubation periods ranging from ˜ 10 to 80 days, selected samples from 7 of the 13 tested sites displayed significant C2H2 removal. No significant formation of ethylene was noted in these incubations; therefore, C2H2 consumption could be attributed to acetylene hydratase (AH) rather than nitrogenase activity. This putative AH (PAH) activity was observed in only 21% of the total of assayed samples, while amplification of AH genes from extracted DNA using degenerate primers derived from Pelobacter acetylenicus occurred in even fewer (9.8%) samples. Acetylene-fermenting bacteria were isolated as a pure culture from the sediments of a tidal mudflat in San Francisco Bay (SFB93) and as an enrichment culture from freshwater Searsville Lake (SV7). Comparison of 16S rDNA clone libraries revealed that SFB93 was closely related to P. carbolinicus, while SV7 consisted of several unrelated bacteria. AH gene was amplified from SFB93 but not SV7. The inability of the primers to generate amplicons in the SV7 enrichment, as well as from several of the environmental samples that displayed PAH activity, implied that either the primers were too highly constrained in their specificity or that there was a different type of AH gene in these environmental samples than occurs in P. acetylenicus. The significance of this work with regard to the search for life in the outer Solar System, where C2HL2 is abundant, is discussed.

  12. Electrochromic poly(acetylene)s with switchable visible/near-IR absorption characteristics.

    PubMed

    Pauly, Anja C; Varnado, C Daniel; Bielawski, Christopher W; Theato, Patrick

    2014-01-01

    Ferrocene is incorporated into a poly(acetylene) derivative via the postpolymerization amidation of a polymer precursor bearing pentafluorophenyl ester-leaving groups with aminoferrocene. While the neutral polymer exhibits a strong absorbance at 553 nm due to its conjugated backbone, oxidation of the ferrocene moieties with silver tetrafluoroborate causes the material to absorb in the near-IR (λ max ≈ 1215 nm). Subsequent reduction of the oxidized polymer with decamethylferrocene restores the initial absorbance profile, demonstrating that the material features switchable visible/near-IR absorption characteristics. PMID:23996218

  13. (-)-Duryne and its homologues, cytotoxic acetylenes from a marine Sponge Petrosia sp.

    PubMed

    Hitora, Yuki; Takada, Kentaro; Okada, Shigeru; Ise, Yuji; Matsunaga, Shigeki

    2011-05-27

    Six linear acetylenes, (-)-duryne (1) and (-)-durynes B-F (2-6), were isolated from the marine sponge Petrosia sp. Their structures were elucidated by NMR and tandem FABMS analyses. The positions of the olefinic bonds were confirmed by ozonolysis experiments, and the absolute configurations were determined by the modified Mosher's method. Compound 1 was found to be the enantiomer of duryne, a previously reported sponge metabolite. Compounds 1-6 show cytotoxicity against HeLa cells with IC50 values between 0.08 and 0.50 μM. PMID:21534590

  14. Adhesion of diamond coatings synthesized by oxygen-acetylene flame CVD on tungsten carbide

    SciTech Connect

    Marinkovic, S.; Stankovic, S.; Dekanski, A.

    1995-12-31

    The results of a study concerned with chemical vapor deposition of diamond on tungsten carbide cutting tools using an oxygen-acetylene flame in a normal ambient environment are presented. Effects of preparation conditions on the adhesion of the coating have been investigated, including different surface treatment, different position of the flame with respect to the coated surface, effect of an intermediate poorly crystalline diamond layer, etc. In particular, effect of polishing and ultrasonic lapping with diamond powder was compared with that of a corresponding treatment with SiC powder.

  15. Heat of Combustion of the Product Formed by the Reaction of Acetylene, Ethylene, and Diborane

    NASA Technical Reports Server (NTRS)

    Tannenbaum, Stanley

    1957-01-01

    The net heat of combustion of the product formed by the reaction of diborane with a mixture of acetylene and ethylene was found to be 20,440 +/- 150 Btu per pound for the reaction of liquid fuel to gaseous carbon dioxide, gaseous water, and solid boric oxide. The measurements were made in a Parr oxygen-bomb calorimeter, and the combustion was believed to be 98 percent complete. The estimated net-heat of combustion for complete combustion would therefore be 20,850 +/- 150 Btu per pound.

  16. Synthesis of (iso)quinoline, (iso)coumarin and (iso)chromene derivatives from acetylene compounds

    NASA Astrophysics Data System (ADS)

    Ryabukhin, D. S.; Vasilyev, A. V.

    2016-06-01

    Published data on the methods of synthesis of quinoline, isoquinoline, coumarin, isocoumarin, chromene and isochromene derivatives from acetylene compounds are summarized. The reactions catalyzed by metal complexes (Pd, Pt, Ru, Rh, Au, Ag, Ni, Cu, etc.) and transformations induced by various electrophilic reagents (Brynsted and Lewis acids) are considered. Moieties of the mentioned heterocyclic systems are present in many biologically active natural products and pharmaceutical agents. Besides, derivatives of these heterocycles are used in the manufacture of catalysts, dyes, perfumery and cosmetic products, corrosion inhibitors and so on. The bibliography includes 211 references.

  17. Second hyperpolarizability of delta shaped disubstituted acetylene complexes of beryllium, magnesium, and calcium.

    PubMed

    Hatua, Kaushik; Nandi, Prasanta K

    2015-10-01

    Present theoretical study involves the delta shape complexes of beryllium, magnesium, and calcium where the metal atom interacts perpendicularly with disubstituted acetylene. Most of the complexes are found to be fairly stable. The dependence of second-hyperpolarizability on the basis set with increasing polarization and diffuse functions has been examined which showed the importance of 'f-type' type polarization function for heavy metal (Mg, Ca) and 'd-type' polarization function for beryllium. Larger second hyperpolarizability has been predicted for complexes having significant ground state polarization and low lying excited states favoring strong electronic coupling. Transition energy plays the most significant role in modulating the second hyperpolarizability. PMID:26361770

  18. Mechanisms of. pi. -bond oxidation by cytochrome p-450: acetylenes as probes

    SciTech Connect

    Komives, E.A.

    1987-01-01

    Phenylacetylene and biphenylacetylene are oxidized by microsomal and purified P-450 to the corresponding arylacetic acids. During this transformation, the acetylenic hydrogen undergoes a 1,2 shift which causes a kinetic isotope effect of 1.8 on the overall enzymatic rate. The same products and kinetic isotope effects are observed when the arylacetylenes are oxidized by m-chloroperbenzoic acid. Suicide inactivation of P-450 by the arylacetylenes, which occurs simultaneously with metabolite formation, is insensitive to isotopic substitution so the partition ratio changes from 26 for phenylacetylene of 14 for (1-/sup 2/H) phenylacetylene.

  19. Single-molecule phenyl-acetylene-macrocycle-based optoelectronic switch functioning as a quantum-interference-effect transistor.

    PubMed

    Hsu, Liang-Yan; Rabitz, Herschel

    2012-11-01

    This work proposes a new type of optoelectronic switch, the phenyl-acetylene-macrocycle-based single-molecule transistor, which utilizes photon-assisted tunneling and destructive quantum interference. The analysis uses single-particle Green's functions along with Floquet theory. Without the optical field, phenyl-acetylene-macrocycle exhibits a wide range of strong antiresonance between its frontier orbitals. The simulations show large on-off ratios (over 10(4)) and measurable currents (~10(-11) A) enabled by photon-assisted tunneling in a weak optical field (~2 × 10(5) V/cm) and at a small source-drain voltage (~0.05 V). Field amplitude power scaling laws and a range of field intensities are given for operating one- and two-photon assisted tunneling in phenyl-acetylene-macrocycle-based single-molecule transistors. This development opens up a new direction for creating molecular switches. PMID:23215309

  20. Synthesis of complex pyridine bases in the reaction of. cap alpha. ,omega-nitrileacetylenes with acetylene, catalyzed by cobalt complexes

    SciTech Connect

    Dzhemilev, U.M.; Selimov, F.A.; Khafizov, V.R.

    1987-01-20

    It has been shown that ..cap alpha..,omega-nitrileacetylenes under the action of homogeneous cobalt-containing catalysts undergo transformations into pyridine derivatives. In order to expand the scope of this method for synthesis of complex pyridine bases, for investigation of the reactivity of nitrileacetylenes of various structure in the reaction of cooligomerization with acetylene, as well as for the introduction to these reactions of new types of ..cap alpha..,omega-nitrileacetylenes, containing in their molecules an oxygen atom, they studied the homo- and codimerization of ..cap alpha..,omega-nitrileacetylenes with acetylene under the action of a Co(2-ethyl hexanoate)/sub 2/-AIR/sub 3/ catalyst in a toluene solution. Cyclodimerization of acetylene with ..cap alpha..,omega-nitrileacetylenes, catalyzed by a Co(2-ethyl hexanoate)/sub 2/-AlEt/sub 3/ system gives new types of mono- and bicyclic pyridines.

  1. Acetylene trimerization on Ag, Pd and Rh atoms deposited on MgO thin films.

    PubMed

    Judai, Ken; Wörz, Anke S; Abbet, Stéphane; Antonietti, Jean-Marie; Heiz, Ueli; Del Vitto, Annalisa; Giordano, Livia; Pacchioni, Gianfranco

    2005-03-01

    The acetylene trimerization on the group VIII transition metal atoms, Rh and Pd, as well as on Ag atoms supported on MgO thin films has been studied experimentally and theoretically. The three metal atoms with the atomic configurations 4d(8)5s1 (Rh), 4d10s0 (Pd) and 4d(10)5s1 (Ag) behave distinctly differently. The coinage metal atom silver is basically inert for this reaction, whereas Pd is active at 220 and 320 K, and Rh produces benzene in a rather broad temperature range from 350 to ca. 430 K. The origins of these differences are not only the different electronic configurations, leading to a weak interaction of acetylene with silver due to strong Pauli repulsion with the 5s electron but also the different stability and dynamics of the three atoms on the MgO surface. In particular, Rh and Pd atoms interact differently with surface defects like the oxygen vacancies (F centers) and the step edges. Pd atoms migrate already at low temperature exclusively to F centers where the cyclotrimerization is efficiently promoted. The Rh atoms on the other hand are not only trapped on F centers but also at step edges up to about 300 K. Interestingly, only Rh atoms on F centers catalyze the trimerization reaction whereas they are turned inert on the step edges due to strong steric effects. PMID:19791385

  2. Nonoxidative methane conversion to acetylene over zeolite in a low temperature plasma

    SciTech Connect

    Liu, C.; Mallinson, R.; Lobban, L.

    1998-10-01

    Previous investigations have found that the plasma catalytic conversion of methane is a low-temperature process for the activation of methane, the major component of natural gas. In this paper, the production of acetylene via plasma catalytic conversion of methane over NaY zeolite is discussed. Hydrogen is produced as a by-product during this plasma catalytic methane conversion. A methane/hydrogen feed with oxygen as an additive and helium as a diluent has been studied in this investigation. The CH{sub 4}/H{sub 2}/O{sub 2} system is found to be more selective for the production of C{sub 2} hydrocarbons, compared to the CH{sub 4}/O{sub 2}, CH{sub 4}H{sub 2}O, and CH{sub 4}/CO{sub 2} systems reported previously. A higher hydrogen concentration feed is more favorable for acetylene formation. The selectivity and yield of C{sub 2} hydrocarbons are related to the hydrogen feed rate, gas temperature, concentration of oxygen additive, and flowrate. The highest yield of C{sub 2} hydrocarbons (32%) is obtained at the lowest flowrate used (10 cm{sup 3}/s; residence time {approximately}2.3 s). A reaction mechanism is also presented to explain the experimental results.

  3. Taple-top imaging of the non-adiabatically driven isomerization in the acetylene cation

    NASA Astrophysics Data System (ADS)

    Beaulieu, Samuel; Ibrahim, Heide; Wales, Benji; Schmidt, Bruno E.; Thiré, Nicolas; Bisson, Éric; Hebeisen, Christoph T.; Wanie, Vincent; Giguere, Mathieu; Kieffer, Jean-Claude; Sanderson, Joe; Schuurman, Michael S.; Légaré, François

    2014-05-01

    One of the primary goals of modern ultrafast science is to follow nuclear and electronic evolution of molecules as they undergo a photo-chemical reaction. Most of the interesting dynamics phenomena in molecules occur when an electronically excited state is populated. When the energy difference between electronic ground and excited states is large, Free Electron Laser (FEL) and HHG-based VUV sources were, up to date, the only light sources able to efficiently initiate those non-adiabatic dynamics. We have developed a simple table-top approach to initiate those rich dynamics via multiphoton absorption. As a proof of principle, we studied the ultrafast isomerization of the acetylene cation. We have chosen this model system for isomerization since the internal conversion mechanism which leads to proton migration is still under debate since decades. Using 266 nm multiphoton absorption as a pump and 800 nm induced Coulomb Explosion as a probe, we have shoot the first high-resolution molecular movie of the non-adiabatically driven proton migration in the acetylene cation. The experimental results are in excellent agreement with high level ab initio trajectory simulations.

  4. Selective Hydrogenation of Acetylene over Pd, Au, and PdAu Supported Nanoparticles

    NASA Astrophysics Data System (ADS)

    Walker, Michael P.

    The removal of trace amounts of acetylene in ethylene streams is a high-volume industrial process that must possess high selectivity of alkyne hydrogenation over hydrogenation of alkenes. Current technology uses metallic nanoparticles, typically palladium or platinum, for acetylene removal. However, problems arise due to the deactivation of the catalysts at high temperatures as well as low selectivities at high conversions. Pore expanded MCM-41 is synthesized via a two-step strategy in which MCM-41 was prepared via cetyltrimethylammonium bromide (CTMABr) followed by the hydrothermal treatment with N,N-dimethyldecylamine (DMDA). This material was washed with ethanol to remove DMDA, or calcined to remove both surfactants. PE-MCM-41 based materials were impregnated with palladium, gold, and palladium-gold nanoparticles. The removal of DMDA had an effect on both the conversion and selectivity, in which they were found to drop significantly. However, by using the bimetallic PdAu catalysts, higher selectivity could be achieved due to increased electron density.

  5. Transient responses of nitrogenase to acetylene and oxygen in actinorhizal nodules and cultured Frania

    SciTech Connect

    Silvester, W.B.; Winship, L.J. )

    1990-02-01

    Nitrogenase activity in root nodules of four species of actinorhizal plants showed varying declines in response to exposure to acetylene (10% v/v). Gymnostoma papuanum (S.Moore) L. Johnson. and Casuarina equisetifolia L. nodules showed a small decline (5-15%) with little or no recovery over 15 minutes. Myrica gale L. nodules showed a sharp decline followed by a rapid return to peak activity. Alnus incana ssp. rugosa (Du Roi) Clausen. nodules usually showed varying degrees of decline followed by a slower return to peak or near-peak activity. We call these effects acetylene-induced transients. Rapid increases in oxygen tension also caused dramatic transient decreases in nitrogenase activity in all species. The magnitude of the transient decrease was related to the size of the O{sub 2} partial pressure (pO{sub 2}) rise, to the proximity of the starting and ending oxygen tensions to the pO{sub 2} optimum, and to the time for which the plant was exposed to the lower pO{sub 2}. Oxygen-induced transients, induced both by step jumps in pO{sub 2} and by O{sub 2} pulses, were also observed in cultures of Frankia. The effects seen in nodules are purely a response by the bacterium and not a nodule effect per se. Oxygen-induced nitrogenase transients in actinorhizal nodules from the plant genera tested here do not appear to be a result of changes in nodule diffusion resistance.

  6. Formation of artificial pores in nano-TiO2 photo-electrode films using acetylene-black for high-efficiency, dye-sensitized solar cells.

    PubMed

    Cho, Tae-Yeon; Han, Chi-Whan; Jun, Yongseok; Yoon, Soon-Gil

    2013-01-01

    Acetylene-black paste without a light scattering layer was applied to meso-porous TiO2 photo-electrode films with a crystalline framework, a low residual carbon, and a tunable morphological pore size. The thermal-treated TiO2 photo-electrode films had an increased acetylene-black concentration with an increase in artificial pores and a decrease in residual carbon. The performance of dye-sensitized solar cells (DSSCs) was enhanced by the use of the TiO2 photo-anode pastes at various acetylene-black concentrations. The photo-conversion efficiency of the DSSCs using TiO2 photo-electrode films with 1.5 wt% acetylene-black was enhanced from 7.98 (no acetylene-black) to 9.75% without the integration of a light- scattering layer. PMID:23511122

  7. Aldehyde dehydrogenase inhibitors: alpha,beta-acetylenic N-substituted aminothiolesters are reversible growth inhibitors of normal epithelial but irreversible apoptogens for cancer epithelial cells from human prostate in culture.

    PubMed

    Quash, Gerard; Fournet, Guy; Courvoisier, Charlotte; Martinez, Rosa M; Chantepie, Jacqueline; Paret, Marie Julie; Pharaboz, Julie; Joly-Pharaboz, Marie Odile; Goré, Jacques; André, Jean; Reichert, Uwe

    2008-05-01

    The pharmacomodulation of the N atom of alpha,beta-acetylenic aminothiolesters or the replacement of the thiolester moiety by more electrophilic groups did not permit any clear rationale to be established for improving the selective growth-inhibitory activity of this family of compounds over that of the previously synthesized alpha,beta-acetylenic aminothiolesters DIMATE and MATE [G. Quash, G. Fournet, J. Chantepie, J. Goré, C. Ardiet, D. Ardail, Y. Michal, U. Reichert, Biochem Pharmacol 64 (2002) 1279-92]. Hence DIMATE and MATE were investigated more thoroughly for selectivity and growth-inhibitory activity using human prostate epithelial normal cells (HPENC) on the one hand and human prostate epithelial cancer cells (DU145) on the other. Unequivocal evidence was obtained showing that both compounds were reversible growth inhibitors of HPENC but irreversible growth inhibitors of DU145. Growth-inhibition of DU145 was due to the induction of early apoptosis as revealed by the flow cytometric analytical profile of inhibitor-treated cells, of the decrease in the redox potential and increase in superoxide anion content of their mitochondria. Of the two intracellular enzymes: aldehyde dehydrogenases 1 and 3 (ALDH1 and ALDH3) targeted by DIMATE and MATE, ALDH3 was inhibited to the same extent by both compounds whereas ALDH1 was less susceptible to inhibition by MATE. As the induction of ALDH3 by xenobiotics is hormone-dependent, MATE, the more selective of the two inhibitors, is a useful tool not only for examining the role of the ALDH3 isoform in hormone-sensitive and resistant prostate cancer cells in culture but also for investigating if it can inhibit the growth of xenografts of prostate cancer in immunodeficient mice. PMID:17692435

  8. Terahertz Spectroscopy of the Bending Vibrations of Acetylene 12C2H2 and 12C2D2

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Drouin, B.; Pearson, J.

    2009-12-01

    Several fundamental interstellar molecules, e.g., C2H2, CH4 and C3, are completely symmetric molecules and feature no permanent dipole moment and no pure rotation spectrum. As a result they have only previously been observed in the infrared. However, directly observing them with the rest of the molecular column especially when the source is spatially resolved would be very valuable in understanding chemical evolution. Vibrational difference bands provide a means to detect symmetric molecules with microwave precision using terahertz techniques. Herschel, SOFIA and ALMA have the potential to identify a number of vibrational difference bands of light symmetric species. This paper reports laboratory results on 12C2H2 and 12C2D2. Symmetric acetylene isotopologues have two bending modes, the trans bending and the cis bending. Their difference bands are allowed and occur in the microwave, terahertz, and far-infrared wavelengths, with band origins at 3500 GHz for 12C2H2 and 900 GHz for 12C2D2. Twenty 12C2H2 P branch high-J transitions and two hundred and fifty-one 12C2D2 P Q and R branch transitions have been measured in the 0.2 - 1.6 THz region with precision of 50 to 100 kHz. These lines were modeled together with prior data on the pure bending levels. Significantly improved molecular parameters were obtained for 12C2H2 and 12C2D2 with the combined data set, and new frequency and intensity predictions were made to support astrophysics applications. The research was performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract with the National Aeronautics and Space Administration. S. Y. was supported by an appointment to the NASA Postdoctoral Program, administrated by Oak Ridge Associated Universities through a contract with NASA.

  9. Acetylene-argon plasmas measured at a biased substrate electrode for diamond-like carbon deposition: I. Mass spectrometry

    NASA Astrophysics Data System (ADS)

    Baby, A.; Mahony, C. M. O.; Maguire, P. D.

    2011-02-01

    We report, for the first time, quadrupole mass spectrometry of neutral and positive ionic hydrocarbon species measured at the rf-biased substrate electrode of an inductively coupled plasma for acetylene rich C2H2 : Ar mixtures under various bias, frequency and pressure conditions. It has been observed that, irrespective of initial gas mixture, the resultant plasma is dominated by argon neutrals and ions. This is attributed to highly efficient conversion of acetylene to C2H due to the enhanced electron density compared with a standard capacitive plasma where the acetylene (neutral and ion) species remain dominant. This conversion may be crucial to film formation via inert rather than hydrocarbon ion bombardment. In addition, the transient formation of CH4 from acetylene has been discovered using IR absorption spectroscopy with time constants similar to observed pressure variations. Rate coefficients and rates for many of the reaction mechanisms, calculated using measured electron energy distribution functions and species densities, are given. These results have important application in plasma models and growth studies for hydrogenated amorphous or diamond-like carbon film deposition. Film growth under similar plasma conditions is reported in an associated paper along with ion energy distributions for important growth species. .

  10. Nonstationary coherent optical effects caused by pulse propagation through acetylene-filled hollow-core photonic-crystal fibers

    NASA Astrophysics Data System (ADS)

    Ocegueda, M.; Hernandez, E.; Stepanov, S.; Agruzov, P.; Shamray, A.

    2014-06-01

    Experimental observations of nonstationary coherent optical phenomena, i.e., optical nutation, free induction, and photon echo, in the acetylene (12C2H2) filled hollow-core photonic-crystal fiber (PCF) are reported. The presented results were obtained for the acetylene vibration-rotational transition P9 at wavelength 1530.37 nm at room temperature under a gas pressure of <0.5 Torr. An all-fiber pumped-through cell based on the commercial 2.6-m-long PCF with a 10-μm hollow-core diameter was used. The characteristic relaxation time T2 during which the optical coherent effects were typically observed in our experiments was estimated to be ≈8 ns. This time is governed by the limited time of the acetylene molecules' presence inside the effective PCF modal area and by intermolecule collisions. An accelerated attenuation of the optical nutation oscillations is explained by a random orientation of acetylene molecules.

  11. Rhodium(III)-catalyzed C-H activation/annulation with vinyl esters as an acetylene equivalent.

    PubMed

    Webb, Nicola J; Marsden, Stephen P; Raw, Steven A

    2014-09-19

    The behavior of electron-rich alkenes in rhodium-catalyzed C-H activation/annulation reactions is investigated. Vinyl acetate emerges as a convenient acetylene equivalent, facilitating the synthesis of sixteen 3,4-unsubstituted isoquinolones, as well as select heteroaryl-fused pyridones. The complementary regiochemical preferences of enol ethers versus enol esters/enamides is discussed. PMID:25165993

  12. Characterization of the Minimum Energy Paths for the Ring Closure Reactions of C4H3 with Acetylene

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1995-01-01

    The ring closure reaction of C4H3 with acetylene to give phenyl radical is one proposed mechanism for the formation of the first aromatic ring in hydrocarbon combustion. There are two low-lying isomers of C4H3; 1-dehydro-buta-l-ene-3-yne (n-C4H3) and 2-dehydro-buta-l-ene-3-yne (iso-C4H3). It has been proposed that only n-C4H3 reacts with acetylene to give phenyl radical, and since iso-C4H3 is more stable than n-C4H3, formation of phenyl radical by this mechanism is unlikely. We report restricted Hartree-Fock (RHF) plus singles and doubles configuration interaction calculations with a Davidson's correction (RHF+1+2+Q) using the Dunning correlation consistent polarized valence double zeta basis set (cc-pVDZ) for stationary point structures along the reaction pathway for the reactions of n-C4H3 and iso-C4H3 with acetylene. n-C4H3 plus acetylene (9.4) has a small entrance channel barrier (17.7) (all energetics in parentheses are in kcal/mol with respect to iso-C4H3 plus acetylene) and the subsequent closure steps leading to phenyl radical (-91.9) are downhill with respect to the entrance channel barrier. Iso-C4H3 Plus acetylene also has an entrance channel barrier (14.9) and there is a downhill pathway to 1-dehydro-fulvene (-55.0). 1-dehydro-fulvene can rearrange to 6-dehydro-fulvene (-60.3) by a 1,3-hydrogen shift over a barrier (4.0), which is still below the entrance channel barrier, from which rearrangement to phenyl radical can occur by a downhill pathway. Thus, both n-C4H3 and iso-C4H3 can react with acetylene to give phenyl radical with small barriers.

  13. High-resolution photoemission study of acetylene adsorption and reaction with the Si(100)-2{times}1 surface

    SciTech Connect

    Xu, S.H.; Yang, Y.; Keeffe, M.; Lapeyre, G.J.; Rotenberg, E.

    1999-10-01

    The adsorption and reaction of acetylene with the Si(100)-2{times}1 surface has been studied using high-resolution photoemission by monitoring the Si&hthinsp;2p, C&hthinsp;1s, and valence-band (VB) spectra as a function of both acetylene coverage and post-adsorption annealing temperature. After the clean Si(100) surface is exposed to 0.5 monolayer (ML) acetylene, the surface state in the VB is absent. Meanwhile, the curve-fitting results show that there is only one interface component in the Si&hthinsp;2p core level. These results indicate that the asymmetric Si dimers may become symmetric dimers after acetylene adsorption, which can be explained well by the tetra-{sigma} model determined from our previous photoelectron holographic results. Significant changes in the electronic structure (Si&hthinsp;2p, C&hthinsp;1s, and VB) are found after subsequent annealing of the saturation overlayer. Annealing at lower temperature can induce some acetylene molecule desorption while most of the molecules decompose into C{sub 2}H{sub x} (x=1,0) and H species. After annealing above 660&hthinsp;{degree}C, both of the reacted components of the Si&hthinsp;2p and C&hthinsp;1s lines show that the SiC species form clusterlike features. At the same time, the VB and Si&hthinsp;2p spectra indicate a restoration of a Si(100)-2{times}1 structure, and the asymmetric Si dimers reappear on the surface. {copyright} {ital 1999} {ital The American Physical Society}

  14. Carbon material formation on SBA-15 and Ni-SBA-15 and residue constituents during acetylene decomposition.

    PubMed

    Chiang, Hung-Lung; Wu, Trong-Neng; Ho, Yung-Shou; Zeng, Li-Xuan

    2014-07-15

    Carbon materials including carbon spheres and nanotubes were formed from acetylene decomposition on hydrogen-reduced SBA-15 and Ni-SBA-15 at 650-850°C. The physicochemical characteristics of SBA-15, Ni-SBA-15 and carbon materials were analyzed by field emission scanning electronic microscopy (FE-SEM), Raman spectrometry, and energy dispersive spectrometry (EDS). In addition, the contents of polyaromatic hydrocarbons (PAHs) in the tar and residue and volatile organic compounds (VOCs) in the exhaust were determined during acetylene decomposition on SBA-15 and Ni-SBA-15. Spherical carbon materials were observed on SBA-15 during acetylene decomposition at 750 and 850°C. Carbon filaments and ball spheres were formed on Ni-SBA-15 at 650-850°C. Raman spectroscopy revealed peaks at 1290 (D-band, disorder mode, amorphous carbon) and 1590 (G-band, graphite sp(2) structure)cm(-1). Naphthalene (2 rings), pyrene (4 rings), phenanthrene (3 rings), and fluoranthene (4 rings) were major PAHs in tar and residues. Exhaust constituents of hydrocarbon (as propane), H2, and C2H2 were 3.9-2.6/2.7-1.5, 1.4-2.8/2.6-4.3, 4.2-2.4/3.2-1.7% when acetylene was decomposed on SBA-15/Ni-SBA-15, respectively, corresponding to temperatures ranging from 650 to 850°C. The concentrations of 52 VOCs ranged from 9359 to 5658 and 2488 to 1104ppm for SBA-15 and Ni-SBA-15 respectively, at acetylene decomposition temperatures from 650 to 850°C, and the aromatics contributed more than 87% fraction of VOC concentrations. PMID:24858051

  15. Inhibition of ammonia monooxygenase in Nitrosomonas europaea by carbon disulfide.

    PubMed Central

    Hyman, M R; Kim, C Y; Arp, D J

    1990-01-01

    Carbon disulfide has long been recognized as a potent inhibitor of nitrification, and it is the likely active component in several nitrification inhibitors suitable for field use. The effects of this compound on Nitrosomonas europaea have been investigated, and the site of action has been determined. Low concentrations of CS2 (less than 400 microM) produced a time-dependent inhibition of ammonia-dependent O2 uptake but did not inhibit hydrazine-oxidizing activity. CS2 also produced distinct changes in difference spectra of whole cells. These results suggest that ammonia monooxygenase (AMO) is the site of action of CS2. Unlike the case for thiourea and acetylene, saturating concentrations of CS2 did not fully inhibit AMO, and the inhibition resulted in a low but significant rate of ammonia-dependent O2 uptake. The effects of CS2 were not competitive with respect to ammonia concentration, and the inhibition by CS2 did not require the turnover of AMO to take effect. The ability of CS2-treated cells to incorporate [14C]acetylene into the 28-kilodalton polypeptide of AMO was used to demonstrate that the effects of CS2 are compatible with a mode of action which involves a reduction of the rate of turnover of AMO without effects on the catalytic mechanism. It is proposed that CS2 may act on AMO by reversibly reacting with a suitable nucleophilic amino acid in close proximity to the active site copper. Images PMID:2118501

  16. Hydrothermal Synthesis and Acetylene Sensing Properties of Variety Low Dimensional Zinc Oxide Nanostructures

    PubMed Central

    Chen, Weigen; Peng, Shudi; Zeng, Wen

    2014-01-01

    Various morphologies of low dimensional ZnO nanostructures, including spheres, rods, sheets, and wires, were successfully synthesized using a simple and facile hydrothermal method assisted with different surfactants. Zinc acetate dihydrate was chosen as the precursors of ZnO nanostructures. We found that polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), glycine, and ethylene glycol (EG) play critical roles in the morphologies and microstructures of the synthesized nanostructures, and a series of possible growth processes were discussed in detail. Gas sensors were fabricated using screen-printing technology, and their sensing properties towards acetylene gas (C2H2), one of the most important arc discharge characteristic gases dissolved in oil-filled power equipments, were systematically measured. The ZnO nanowires based sensor exhibits excellent C2H2 sensing behaviors than those of ZnO nanosheets, nanorods, and nanospheres, indicating a feasible way to develop high-performance C2H2 gas sensor for practical application. PMID:24672324

  17. Shock-tube pyrolysis of acetylene - Sensitivity analysis of the reaction mechanism for soot formation

    NASA Technical Reports Server (NTRS)

    Frenklach, M.; Clary, D. W.; Gardiner, W. C., Jr.; Stein, S. E.

    1986-01-01

    The impact of thermodynamic parameters on the sensitivity of model predictions of soot formation by shock-tube pyrolysis of acetylene were assessed analytically. The pyrolysis process was treated as having three components: initiation, the initial pyrolysis stages; cyclization, formation of larger molecules and radicals and small aromatic molecules; and polymerization, further growth of aromatic rings. Rate equations are reviewed for each component. Thermodynamic effects were assessed by varying the C2H-H and C2H3-H bond energies and the Ct-(Ct) group additivity value. Any change in the C2H-H bond energy had a significant impact on the temperature and the maximum amount of the soot yield. The findings underscore the necessity of using accurate thermodynamic data for modeling high-temperature chemical kinetics.

  18. Interference in acetylene intersystem crossing acts as the molecular analog of Young's double-slit experiment

    PubMed Central

    de Groot, Mattijs; Field, Robert W.; Buma, Wybren J.

    2009-01-01

    We report on an experimental approach that reveals crucial details of the composition of singlet-triplet mixed eigenstates in acetylene. Intersystem crossing in this prototypical polyatomic molecule embodies the mixing of the lowest excited singlet state (S1) with 3 triplet states (T1, T2, and T3). Using high-energy (157-nm) photons from an F2 laser to record excited-state photoelectron spectra, we have decomposed the mixed eigenstates into their S1, T3, T2, and T1 constituent parts. One example of the interpretive power that ensues from the selective sensitivity of the experiment to the individual electronic state characters is the discovery and examination of destructive interference between two doorway-mediated intersystem crossing pathways. This observation of an interference effect in nonradiative decay opens up possibilities for rational coherent control over molecular excited state dynamics. PMID:19179288

  19. A novel metal-organic framework for high storage and separation of acetylene at room temperature

    NASA Astrophysics Data System (ADS)

    Duan, Xing; Wang, Huizhen; Ji, Zhenguo; Cui, Yuanjing; Yang, Yu; Qian, Guodong

    2016-09-01

    A novel 3D microporous metal-organic framework with NbO topology, [Cu2(L)(H2O)2]•(DMF)6·(H2O)2 (ZJU-10, ZJU = Zhejiang University; H4L =2‧-hydroxy-[1,1‧:4‧,1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid; DMF =N,N-dimethylformamide), has been synthesized and structurally characterized. With suitable pore sizes and open Cu2+ sites, ZJU-10a exhibits high BET surface area of 2392 m2/g, as well as moderately high C2H2 volumetric uptake capacity of 132 cm3/cm3. Meanwhile, ZJU-10a is a promising porous material for separation of acetylene from methane and carbon dioxide gas mixtures at room temperature.

  20. Infrared Spectra and Optical Constants of Astronomical Ices: I. Amorphous and Crystalline Acetylene

    NASA Technical Reports Server (NTRS)

    Hudson, R. L.; Ferrante, R. F.; Moore, M. H.

    2013-01-01

    Here we report recent measurements on acetylene (C2H2) ices at temperatures applicable to the outer Solar System and the interstellar medium. New near- and mid-infrared data, including optical constants (n, k), absorption coefficients (alpha), and absolute band strengths (A), are presented for both amorphous and crystalline phases of C2H2 that exist below 70 K. Comparisons are made to earlier work. Electronic versions of the data are made available, as is a computer routine to use our reported n and k values to simulate the observed IR spectra. Suggestions are given for the use of the data and a comparison to a spectrum of Makemake is made.

  1. Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes.

    PubMed

    Krause, Thilo; Baader, Sabrina; Erb, Benjamin; Gooßen, Lukas J

    2016-01-01

    Amide bond-forming reactions are of tremendous significance in synthetic chemistry. Methodological research has, in the past, focused on efficiency and selectivity, and these have reached impressive levels. However, the unacceptable amounts of waste produced have led the ACS GCI Roundtable to label 'amide bond formation avoiding poor atom economy' as the most pressing target for sustainable synthetic method development. In response to this acute demand, we herein disclose an efficient one-pot amide coupling protocol that is based on simple alkynes as coupling reagents: in the presence of a dichloro[(2,6,10-dodecatriene)-1,12-diyl]ruthenium catalyst, carboxylate salts of primary or secondary amines react with acetylene or ethoxyacetylene to vinyl ester intermediates, which undergo aminolysis to give the corresponding amides along only with volatile acetaldehyde or ethyl acetate, respectively. The new amide synthesis is broadly applicable to the synthesis of structurally diverse amides, including dipeptides. PMID:27282773

  2. Carbon dioxide reduction to methane and coupling with acetylene to form propylene catalyzed by remodeled nitrogenase

    PubMed Central

    Yang, Zhi-Yong; Moure, Vivian R.; Dean, Dennis R.; Seefeldt, Lance C.

    2012-01-01

    A doubly substituted form of the nitrogenase MoFe protein (α-70Val→Ala, α-195His→Gln) has the capacity to catalyze the reduction of carbon dioxide (CO2) to yield methane (CH4). Under optimized conditions, 1 nmol of the substituted MoFe protein catalyzes the formation of 21 nmol of CH4 within 20 min. The catalytic rate depends on the partial pressure of CO2 (or concentration of HCO3−) and the electron flux through nitrogenase. The doubly substituted MoFe protein also has the capacity to catalyze the unprecedented formation of propylene (H2C = CH-CH3) through the reductive coupling of CO2 and acetylene (HC≡CH). In light of these observations, we suggest that an emerging understanding of the mechanistic features of nitrogenase could be relevant to the design of synthetic catalysts for CO2 sequestration and formation of olefins. PMID:23150564

  3. Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation.

    PubMed

    Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel; Schmidt, Bruno E; Thiré, Nicolas; Fowe, Emmanuel P; Bisson, Éric; Hebeisen, Christoph T; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Spanner, Michael; Bandrauk, André D; Sanderson, Joseph; Schuurman, Michael S; Légaré, François

    2014-01-01

    The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging, we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using vacuum ultraviolet light from a free-electron laser. Here we show that 266 nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and quantitative ab initio trajectory simulations. PMID:25034613

  4. Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes

    PubMed Central

    Krause, Thilo; Baader, Sabrina; Erb, Benjamin; Gooßen, Lukas J.

    2016-01-01

    Amide bond-forming reactions are of tremendous significance in synthetic chemistry. Methodological research has, in the past, focused on efficiency and selectivity, and these have reached impressive levels. However, the unacceptable amounts of waste produced have led the ACS GCI Roundtable to label ‘amide bond formation avoiding poor atom economy' as the most pressing target for sustainable synthetic method development. In response to this acute demand, we herein disclose an efficient one-pot amide coupling protocol that is based on simple alkynes as coupling reagents: in the presence of a dichloro[(2,6,10-dodecatriene)-1,12-diyl]ruthenium catalyst, carboxylate salts of primary or secondary amines react with acetylene or ethoxyacetylene to vinyl ester intermediates, which undergo aminolysis to give the corresponding amides along only with volatile acetaldehyde or ethyl acetate, respectively. The new amide synthesis is broadly applicable to the synthesis of structurally diverse amides, including dipeptides. PMID:27282773

  5. Analysis for Mar Vel Black and acetylene soot low reflectivity surfaces for star tracker sunshade applications

    NASA Technical Reports Server (NTRS)

    Yung, E.

    1974-01-01

    Mar Vel Black is a revolutionary new extremely low reflectivity anodized coating developed by Martin Marietta of Denver. It is of great interest in optics in general, and in star trackers specifically because it can reduce extraneous light reflections. A sample of Mar Vel Black was evaluated. Mar Vel Black looks much like a super black surface with many small peaks and very steep sides so that any light incident upon the surface will tend to reflect many times before exiting that surface. Even a high reflectivity surface would thus appear to have a very low reflectivity under such conditions. Conversely, acetylene soot does not have the magnified surface appearance of a super black surface. Its performance is, however, predictable from the surface structure, considering the known configuration of virtually pure carbon.

  6. Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation

    NASA Astrophysics Data System (ADS)

    Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel; Schmidt, Bruno E.; Thiré, Nicolas; Fowe, Emmanuel P.; Bisson, Éric; Hebeisen, Christoph T.; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Spanner, Michael; Bandrauk, André D.; Sanderson, Joseph; Schuurman, Michael S.; Légaré, François

    2014-07-01

    The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging, we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using vacuum ultraviolet light from a free-electron laser. Here we show that 266 nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and quantitative ab initio trajectory simulations.

  7. Dubinin-Astakhov model for acetylene adsorption on metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Cheng, Peifu; Hu, Yun Hang

    2016-07-01

    Acetylene (C2H2) is explosive at a pressure above 29 psi, causing a safety issue for its storage and applications. C2H2 adsorption on metal-organic frameworks (MOFs) has been explored to solve the issue. However, a suitable isotherm equation for C2H2 adsorption on various MOFs has not been found. In this paper, it was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model to depict C2H2 adsorption on MOF-5, ZIF-8, HKUST-1, and MIL-53. In contrast, commonly used Langmuir and BET models exhibited their inapplicability for C2H2 adsorption on those MOFs.

  8. Analysis of Effluent Gases During the CCVD Growth of Multi Wall Carbon Nanotubes from Acetylene

    NASA Technical Reports Server (NTRS)

    Schmitt, T. C.; Biris, A. S.; Miller, D. W.; Biris, A. R.; Lupu, D.; Trigwell, S.; Rahman, Z. U.

    2005-01-01

    Catalytic chemical vapor deposition was used to grow multi-walled carbon nanotubes on a Fe:Co:CaCO3 catalyst from acetylene. The influent and effluent gases were analyzed by gas chromatography and mass spectrometry at different time intervals during the nanotubes growth process in order to better understand and optimize the overall reaction. A large number of byproducts were identified and it was found that the number and the level for some of the carbon byproducts significantly increased over time. The CaCO3 catalytic support thermally decomposed into CaO and CO2 resulting in a mixture of two catalysts for growing the nanotubes, which were found to have outer diameters belonging to two main groups 8 to 35 nm and 40 to 60 nm, respectively.

  9. HIV reverse transcriptase inhibiting antibodies detected by a new technique: relation to p24 and gp41 antibodies, HIV antigenemia and clinical variables.

    PubMed

    Neumüller, M; Karlsson, A; Lennerstrand, J; Källander, C F; Holmberg, V; Långström-Persson, U; Thorstensson, R; Sandström, E; Gronowitz, J S

    1991-05-01

    A new assay for HIV reverse transcriptase activity inhibiting antibodies (RTI-ab) was used for the analysis of a large collection of sera sampled before and after confirmation of HIV infection. In this assay HIV-RT was preincubated with diluted serum, after which residual RT activity was determined by a technique using a template coupled to macrobeads and 125I-lodo-deoxyuridine-triphosphate as the tracer-substrate. Of the 936 sera analysed, 818 were found positive for RTI-ab, and 824 were positive in Western blot (Wb). The prevalence of RTI-ab compared to Wb was therefore 99.3%. The corresponding figure for 930 sera analysed for envelope-ab, i.e., gp41-ab, was 823 positive, and of these 930 sera 815 were Wb positive, giving a comparative prevalence of 101%. In contrast, only 678 samples of 993 analyzed for core ab, i.e., p24, were positive, giving a prevalence of 77.0% as 880 of these samples were Wb positive. Thus, RTI-ab was as prevalent as gp41-ab, and although the analyses of RTI-ab amounts in different stages showed decreasing levels in stage IV compared to stages II or III, all of the sera except 1 were found positive in stages III and IV. Further, it was found that both the few RTI-ab negative samples in stage II and the few RTI-ab positive samples among Wb negative sera were sampled in connection with seroconversion. The specificity of the RTI-ab assay was 100% in a test of 200 serum samples from HIV negative blood donors. It was concluded that RTI-ab analyses can be made highly sensitive and specific and useful for studies of HIV infection. PMID:1715898

  10. Computational simulations of hydrogen circular migration in protonated acetylene induced by circularly polarized light.

    PubMed

    Shi, Xuetao; Li, Wen; Schlegel, H Bernhard

    2016-08-28

    The hydrogens in protonated acetylene are very mobile and can easily migrate around the C2 core by moving between classical and non-classical structures of the cation. The lowest energy structure is the T-shaped, non-classical cation with a hydrogen bridging the two carbons. Conversion to the classical H2CCH(+) ion requires only 4 kcal/mol. The effect of circularly polarized light on the migration of hydrogens in oriented C2H3 (+) has been simulated by Born-Oppenheimer molecular dynamics. Classical trajectory calculations were carried out with the M062X/6-311+G(3df,2pd) level of theory using linearly and circularly polarized 32 cycle 7 μm cosine squared pulses with peak intensity of 5.6 × 10(13) W/cm(2) and 3.15 × 10(13) W/cm(2), respectively. These linearly and circularly polarized pulses transfer similar amounts of energy and total angular momentum to C2H3 (+). The average angular momentum vectors of the three hydrogens show opposite directions of rotation for right and left circularly polarized light, but no directional preference for linearly polarized light. This difference results in an appreciable amount of angular displacement of the three hydrogens relative to the C2 core for circularly polarized light, but only an insignificant amount for linearly polarized light. Over the course of the simulation with circularly polarized light, this corresponds to a propeller-like motion of the three hydrogens around the C2 core of protonated acetylene. PMID:27586924

  11. Soot Volume Fraction Maps for Normal and Reduced Gravity Laminar Acetylene Jet Diffusion Flames

    NASA Technical Reports Server (NTRS)

    Greenberg, Paul S.; Ku, Jerry C.

    1997-01-01

    The study of soot particulate distribution inside gas jet diffusion flames is important to the understanding of fundamental soot particle and thermal radiative transport processes, as well as providing findings relevant to spacecraft fire safety, soot emissions, and radiant heat loads for combustors used in air-breathing propulsion systems. Compared to those under normal gravity (1-g) conditions, the elimination of buoyancy-induced flows is expected to significantly change the flow field in microgravity (O g) flames, resulting in taller and wider flames with longer particle residence times. Work by Bahadori and Edelman demonstrate many previously unreported qualitative and semi-quantitative results, including flame shape and radiation, for sooting laminar zas jet diffusion flames. Work by Ku et al. report soot aggregate size and morphology analyses and data and model predictions of soot volume fraction maps for various gas jet diffusion flames. In this study, we present the first 1-g and 0-g comparisons of soot volume fraction maps for laminar acetylene and nitrogen-diluted acetylene jet diffusion flames. Volume fraction is one of the most useful properties in the study of sooting diffusion flames. The amount of radiation heat transfer depends directly on the volume fraction and this parameter can be measured from line-of-sight extinction measurements. Although most Soot aggregates are submicron in size, the primary particles (20 to 50 nm in diameter) are in the Rayleigh limit, so the extinction absorption) cross section of aggregates can be accurately approximated by the Rayleigh solution as a function of incident wavelength, particles' complex refractive index, and particles' volume fraction.

  12. Rotational and vibrational energy transfer in vibrationally excited acetylene at energies near 6560 cm(-1).

    PubMed

    Han, Jiande; Freel, Keith; Heaven, Michael C

    2011-12-28

    Collisional energy transfer kinetics of vibrationally excited acetylene has been examined for states with internal energies near 6560 cm(-1). Total population removal rate constants were determined for selected rotational levels of the (1,0,1,0(0),0(0)) and (0,1,1,2(0),0(0)) states. Values in the range of (10-18) × 10(-10) cm(3) s(-1) were obtained. Measurements of state-to-state rotational energy transfer rate constants were also carried out for these states. The rotational energy transfer kinetics was found to be consistent with simple energy gap models for the transfer probabilities. Vibrational transfer out of the (0,1,1,2(0),0(0)) state accounted for no more than 16% of the total removal process. Transfer from (1,0,1,0(0),0(0)) to the u-symmetry (0,2,0,3(1),1(-1)), (0,1,1,2(0),0(0)), and (1,1,0,1(1),1(-1)) states was observed. Applying the principle of detailed balance to these data indicated that vibrational transfer to (1,0,1,0(0),0(0)) accounted for ~0.1% of the population loss from (0,2,0,3(1),1(-1)) or (0,1,1,2(0),0(0)), and 3% of the loss from (1,1,0,1(1),1(-1)). Relative rotational transfer probabilities were obtained for transfer to the g-symmetry (1,1,0,2(0),0(0))∕(0,0,2,0(0),0(0)) dyad. These results are related to recent studies of optically pumped acetylene lasers. PMID:22225153

  13. A DFT computational study of the bis-silylation reaction of acetylene catalyzed by palladium complexes.

    PubMed

    Bottoni, Andrea; Higueruelo, Alicia Perez; Miscione, Gian Pietro

    2002-05-15

    In this paper we have investigated at the DFT(B3LYP) level the catalytic cycle for the bis-silylation reaction of alkynes promoted by palladium complexes. A model-system formed by an acetylene molecule, a disilane molecule, and the Pd(PH(3))(2) complex has been used. The most relevant features of this catalytic cycle can be summarized as follows: (i) The first step of the cycle is an oxidative addition involving H(3)Si-SiH(3) and Pd(PH(3))(2). It occurs easily and leads to the cis (SiH(3))(2)Pd(PH(3))(2) complex that is 5.39 kcal mol(-1) lower in energy than reactants. (ii) The transfer of the two silyl groups to the C-C triple bond does not occur in a concerted way, but involves many steps. (iii) The cis (SiH(3))(2)Pd(PH(3))(2) complex, obtained from the oxidative addition, is involved in the formation of the first C-Si bond (activation barrier of 18.34 kcal mol(-1)). The two intermediates that form in this step cannot lead directly to the formation of the final bis(silyl)ethene product. However, they can isomerize rather easily (the two possible isomerizations have a barrier of 16.79 and 7.17 kcal mol(-1)) to new more stable species. In both these new intermediates the second silyl group is adjacent to the acetylene moiety and the formation of the second C-Si bond can occur rapidly leading to the (Z)-bis(silyl)ethene, as experimentally observed. (iv) The whole catalytic process is exothermic by 41.54 kcal mol(-1), in quite good agreement with the experimental estimate of this quantity (about 40 kcal mol(-1)). PMID:11996593

  14. A near-infrared acetylene detection system based on a 1.534 μm tunable diode laser and a miniature gas chamber

    NASA Astrophysics Data System (ADS)

    He, Qixin; Zheng, Chuantao; Liu, Huifang; Li, Bin; Wang, Yiding; Tittel, Frank K.

    2016-03-01

    A near-infrared (NIR) dual-channel differential acetylene (C2H2) detection system was experimentally demonstrated based on tunable diode laser absorption spectroscopy (TDLAS) technique and wavelength modulation spectroscopy (WMS) technique. A distributed feedback (DFB) laser modulated by a self-developed driver around 1.534 μm is used as light source. A miniature gas chamber with 15 cm path length is adopted as absorption pool, and an orthogonal lock-in amplifier is developed to extract the second harmonic (2f) signal. Sufficient standard C2H2 samples with different concentrations were prepared, and detailed measurements were carried out to study the detection performance. A good linear relationship is observed between the amplitude of the 2f signal and C2H2 concentration within the range of 200-10,000 ppm, and the relative measurement error is less than 5% within the whole range. A long-term monitoring lasting for 20 h on a 1000 ppm C2H2 sample was carried out, and the maximum concentration fluctuation is less than 2%. Due to the capability of using long-distance and low-loss optical fiber, the gas-cell can be placed in the filed for remote monitoring, which enables the system to have good prospects in industrial field.

  15. Inhibition of existing denitrification enzyme activity by chloramphenicol

    USGS Publications Warehouse

    Brooks, M.H.; Smith, R.L.; Macalady, D.L.

    1992-01-01

    Chloramphenicol completely inhibited the activity of existing denitrification enzymes in acetylene-block incubations with (i) sediments from a nitrate-contaminated aquifer and (ii) a continuous culture of denitrifying groundwater bacteria. Control flasks with no antibiotic produced significant amounts of nitrous oxide in the same time period. Amendment with chloramphenicol after nitrous oxide production had begun resulted in a significant decrease in the rate of nitrous oxide production. Chloramphenicol also decreased (>50%) the activity of existing denitrification enzymes in pure cultures of Pseudomonas denitrificans that were harvested during log- phase growth and maintained for 2 weeks in a starvation medium lacking electron donor. Short-term time courses of nitrate consumption and nitrous oxide production in the presence of acetylene with P. denitrificans undergoing carbon starvation were performed under optimal conditions designed to mimic denitrification enzyme activity assays used with soils. Time courses were linear for both chloramphenicol and control flasks, and rate estimates for the two treatments were significantly different at the 95% confidence level. Complete or partial inhibition of existing enzyme activity is not consistent with the current understanding of the mode of action of chloramphenicol or current practice, in which the compound is frequently employed to inhibit de novo protein synthesis during the course of microbial activity assays. The results of this study demonstrate that chloramphenicol amendment can inhibit the activity of existing denitrification enzymes and suggest that caution is needed in the design and interpretation of denitrification activity assays in which chloramphenicol is used to prevent new protein synthesis.

  16. Development of a spectrofluorimetry-based device for determining the acetylene content in the oils of power transformers.

    PubMed

    Quintella, Cristina M; Meira, Marilena; Silva, Weidson Leal; Filho, Rogério G D; Araújo, André L C; Júnior, Elias T S; Sales, Lindolfo J O

    2013-12-15

    Power transformers are essential for a functioning electrical system and therefore require special attention by maintenance programs because a fault can harm both the company and society. The temperature inside a power transformer and the dissolved gases, which are primarily composed of acetylene, are the two main parameters monitored when detecting faults. This paper describes the development of a device for analyzing the acetylene content in insulating oil using spectrofluorimetry. Using this device introduces a new methodology for the maintaining and operating power transformers. The prototype is currently operating in a substation. The results presented by this system were satisfactory; when compared to chromatographic data, the errors did not exceed 15%. This prototype may be used to confirm the quality of an insulating oil sample to detect faults in power transformers. PMID:24209339

  17. Ferrimagnetism in 2D networks of porphyrin-X and -XO (X=Sc,...,Zn) with acetylene bridges

    NASA Astrophysics Data System (ADS)

    Wierzbowska, Małgorzata; Sobolewski, Andrzej L.

    2016-03-01

    Magnetism in 2D networks of the acetylene-bridged transition metal porphyrins M(P)-2(C-C)-2 (denoted P-TM), and oxo-TM-porphyrins OM(P)-2(C-C)-2 (denoted P-TMO), is studied with the density functional theory (DFT) and the self-interaction corrected pseudopotential scheme (pSIC). Addition of oxygen lowers magnetism of P-TMO with respect to the corresponding P-TM for most of the first-half 3d-row TMs. In contrast, binding O with the second-half 3d-row TMs or Sc increases the magnetic moments. Ferrimagnetism is found for the porphyrin networks with the TMs from V to Co and also for these cases with oxygen. This is a long-range effect of the delocalized spin-polarization, extended even to the acetylene bridges.

  18. Three-dimensional carbon allotropes comprising phenyl rings and acetylenic chains in sp+sp2 hybrid networks

    DOE PAGESBeta

    Wang, Jian -Tao; Chen, Changfeng; Li, Han -Dong; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

    2016-04-18

    Here, we here identify by ab initio calculations a new type of three-dimensional (3D) carbon allotropes that consist of phenyl rings connected by linear acetylenic chains in sp+sp2 bonding networks. These structures are constructed by inserting acetylenic or diacetylenic bonds into an all sp2-hybridized rhombohedral polybenzene lattice, and the resulting 3D phenylacetylene and phenyldiacetylene nets comprise a 12-atom and 18-atom rhombohedral primitive unit cells R-3m symmetry, which are characterized as the 3D chiral crystalline modification of 2D graphyne and graphdiyne, respectively. Simulated phonon spectra reveal that these structures are dynamically stable. Electronic band calculations indicate that phenylacetylene is metallic, whilemore » phenyldiacetylene is a semiconductor with an indirect band gap of 0.58 eV. The present results establish a new type of carbon phases and offer insights into their outstanding structural and electronic properties.« less

  19. Three-Dimensional Carbon Allotropes Comprising Phenyl Rings and Acetylenic Chains in sp+sp(2) Hybrid Networks.

    PubMed

    Wang, Jian-Tao; Chen, Changfeng; Li, Han-Dong; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

    2016-01-01

    We here identify by ab initio calculations a new type of three-dimensional (3D) carbon allotropes that consist of phenyl rings connected by linear acetylenic chains in sp+sp(2) bonding networks. These structures are constructed by inserting acetylenic or diacetylenic bonds into an all sp(2)-hybridized rhombohedral polybenzene lattice, and the resulting 3D phenylacetylene and phenyldiacetylene nets comprise a 12-atom and 18-atom rhombohedral primitive unit cells in the symmetry, which are characterized as the 3D chiral crystalline modification of 2D graphyne and graphdiyne, respectively. Simulated phonon spectra reveal that these structures are dynamically stable. Electronic band calculations indicate that phenylacetylene is metallic, while phenyldiacetylene is a semiconductor with an indirect band gap of 0.58 eV. The present results establish a new type of carbon phases and offer insights into their outstanding structural and electronic properties. PMID:27087405

  20. Three-Dimensional Carbon Allotropes Comprising Phenyl Rings and Acetylenic Chains in sp+sp2 Hybrid Networks

    PubMed Central

    Wang, Jian-Tao; Chen, Changfeng; Li, Han-Dong; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

    2016-01-01

    We here identify by ab initio calculations a new type of three-dimensional (3D) carbon allotropes that consist of phenyl rings connected by linear acetylenic chains in sp+sp2 bonding networks. These structures are constructed by inserting acetylenic or diacetylenic bonds into an all sp2-hybridized rhombohedral polybenzene lattice, and the resulting 3D phenylacetylene and phenyldiacetylene nets comprise a 12-atom and 18-atom rhombohedral primitive unit cells in the symmetry, which are characterized as the 3D chiral crystalline modification of 2D graphyne and graphdiyne, respectively. Simulated phonon spectra reveal that these structures are dynamically stable. Electronic band calculations indicate that phenylacetylene is metallic, while phenyldiacetylene is a semiconductor with an indirect band gap of 0.58 eV. The present results establish a new type of carbon phases and offer insights into their outstanding structural and electronic properties. PMID:27087405

  1. Three-Dimensional Carbon Allotropes Comprising Phenyl Rings and Acetylenic Chains in sp+sp2 Hybrid Networks

    NASA Astrophysics Data System (ADS)

    Wang, Jian-Tao; Chen, Changfeng; Li, Han-Dong; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

    2016-04-01

    We here identify by ab initio calculations a new type of three-dimensional (3D) carbon allotropes that consist of phenyl rings connected by linear acetylenic chains in sp+sp2 bonding networks. These structures are constructed by inserting acetylenic or diacetylenic bonds into an all sp2-hybridized rhombohedral polybenzene lattice, and the resulting 3D phenylacetylene and phenyldiacetylene nets comprise a 12-atom and 18-atom rhombohedral primitive unit cells in the symmetry, which are characterized as the 3D chiral crystalline modification of 2D graphyne and graphdiyne, respectively. Simulated phonon spectra reveal that these structures are dynamically stable. Electronic band calculations indicate that phenylacetylene is metallic, while phenyldiacetylene is a semiconductor with an indirect band gap of 0.58 eV. The present results establish a new type of carbon phases and offer insights into their outstanding structural and electronic properties.

  2. Can Analysis of Acetylene and Its Biodegradation Products in Enceladus Plumes be Used to Detect the Presence of Sub-Surface Life?

    NASA Astrophysics Data System (ADS)

    Miller, L. G.; Baesman, S. M.; Oremland, R. S.

    2014-12-01

    The search for biosignatures of life on Earth includes measurement of the stable isotope fractionation of reactants and products attributed to enzymatic processes and comparison with the often smaller chemical (abiotic) fractionation. We propose that this approach might be applied to study the origin and fate of organic compounds contained in water vapor plumes emanating from Enceladus or other icy bodies, perhaps revealing information about the potential for biology occurring within a sub-surface "habitable" zone. Methanol and C2-hydrocarbons including ethylene, ethane and acetylene (C2H2) have been identified in the plumes of Enceladus. Biological degradation of acetylene proceeds by anaerobic fermentation via acetylene hydratase through acetaldehyde, with a second enzyme (acetaldehyde dismutase) forming acetate and ethanol. We found that incubation of cultures of acetylene-fermenting bacteria exhibit a kinetic isotope effect (KIE) associated with the net removal of C2H2. Consumption of acetylene by both growing and washed-cell cultures of bacteria closely related to Pelobacter acetylenicus (e.g, strain SFB93) was accompanied by a carbon isotopic fractionation of about 2 per mil (KIE = 1.8-2.7 ‰), a result we are examining with other cultures of acetylene fermenters. In addition, we are measuring the carbon isotopic composition of acetaldehyde, ethanol and acetate during fermentation to learn whether these products are fractionated sufficiently, relative to their substrate, to warrant measurement of their isotopic composition in Enceladus (or Europa) plumes to indicate enzymatic activity in liquid environments below the crust of these moons.

  3. Frequency Comb-Referenced Spectroscopy in the ν1 + ν3 Region of Acetylene

    NASA Astrophysics Data System (ADS)

    Cich, Matthew J.; Forthomme, Damien; Hall, Gregory E.; Mcraven, Christopher P.; Sears, Trevor J.; Twagirayezu, Sylvestre

    2014-06-01

    class="MsoNormal">By using saturation dip absorption spectroscopy with an extended cavity diode laser locked to a frequency comb, we have measured the rest frequencies of transitions in the ν4 = 1 and ν5 = 1 hot bands in the ν1 + ν3 combination band of acetylene. The measured line frequencies are accurate to approximately 20 kHz i.e. approximately one part in 1011. Positions of the hot-band lines quoted in the HITRAN database, which are derived from the analysis of high-resolution FTIR spectra, are of the order of 10's of MHz in error. These measurements were undertaken because pressure broadened lineshape measurements of rotational lines in the combination band indicated that weak underlying hot band features were not correctly accounted for on the basis of their previously reported positions. As a result, measured line profiles in the band could not be accurately fit leading to errors of up to 1% in acetylene concentrations derived from the measurements. In addition, the pressure broadened P(11) line in the ν1 + ν3 combination band has been studied as a function of varying concentration of the absorber in nitrogen. Mixture concentrations of 1, 5 and 10% at 296 K and pressures between a few Torr and one atmosphere were made and the measurements analyzed using two different speeddependent broadening models. These experiments are designed to test the additivity of contributions to pressure broadening and shift in speed-dependent line-shape modeling, i.e. whether the lineshape parameters follow partial pressure weighting in the binary mixtures. P(11) is relatively isolated with respect to underlying hot band transitions and neighboring transitions of the same band, but it was found that the accurate positions of underlying hot-band transitions were crucial to the successful modeling of the observed line shapes, even though these lines are typically 100-1000 times weaker than P(11) itself and are many Doppler line widths removed from the line center

  4. Quantum Chemical Evaluation of the Astrochemical Significance of Reactions between S Atom and Acetylene or Ethylene

    NASA Technical Reports Server (NTRS)

    Woon, David E.

    2007-01-01

    Addition-elimination reactions of S atom in its P-3 ground state with acetylene (C2H2) and ethylene (C2H4) were characterized with both molecular orbital and density functional theory calculations employing correlation consistent basis sets in order to assess the likelihood either reaction might play a general role in astrochemistry or a specific role in the formation of S2 (X (sup 3 SIGMA (sub g) (sup -)) via a mechanism proposed by Saxena and Misra (Mon. Not. R. Astron. Soc. 1995, 272, 89). The acetylene and ethylene reactions proceed through C2H2S ((sup 3)A")) and C2H4S ((sup 3)A")) intermediates, respectively, to yield HCCS ((sup 2)II)) and C2H3S ((sup 2)A')). Substantial barriers were found in the exit channels for every combination of method and basis set considered in this work, which effectively precludes hydrogen elimination pathways for both S + C2H2 and S + C2H4 in the ultracold interstellar medium where only very modest barriers can be surmounted and processes without barriers tend to predominate. However, if one or both intermediates is formed and stabilized efficiently under cometary or dense interstellar cloud conditions, they could serve as temporary reservoirs for S atom and participate in reactions such as S + C2H2S (right arrow) S2 = C2H2 or S + C2H4S (right arrow) S2 + C2H4. For formation and stabilization to be efficient, the reaction must possess a barrier height small enough to be surmountable at low temperatures yet large enough to prevent redissociation to reactants. Barrier heights computed with B3LYP and large basis sets are very low, but more rigorous QCISD(T) and RCCSD(T) results indicate that the barrier heights are closer to 3-4 kcal/mol. The calculations therefore indicate that S + C2H2 or S + C2H4 could contribute to the formation of S2 in comets and may serve as a means to gauge coma temperature. The energetics of the ethylene reaction are more favorable.

  5. A geochemical model of non-ideal solutions in the methane-ethane-propane-nitrogen-acetylene system on Titan

    NASA Astrophysics Data System (ADS)

    Glein, Christopher R.; Shock, Everett L.

    2013-08-01

    Saturn's largest moon, Titan, has an atmosphere and surface that are rich in organic compounds. Liquid hydrocarbons exist on the surface, most famously as lakes. Photochemical reactions produce solid organics in Titan's atmosphere, and these materials settle or snow onto the surface. At the surface, liquids can interact with solids, and geochemical processes can occur. The consequences of these processes can be explored using a thermodynamic model to calculate the solubilities of gases and solids in liquid hydrocarbons at cryogenic temperatures. The van Laar model developed in this study was parameterized using experimental phase equilibrium data, and accurately represents the data for the CH4-C2H6-C3H8-N2-C2H2 chemical system from 90 to 110 K. The model generally gives more accurate results than existing models. The model also features a suitable balance between accuracy and simplicity, and can serve as a foundation for studies of fluvial geochemistry on Titan because it can be extended to any number of components while maintaining thermodynamic consistency. Application of the model to Titan reveals that the equilibrium composition of surface liquids depends on the abundance of methane gas in the local atmosphere, consistent with prior studies. The concentration of molecular nitrogen in Titan's lakes varies inversely with the ethane content of the lakes. The model indicates that solid acetylene should be quite soluble in surface liquids, which implies that acetylene-rich sedimentary rocks would be susceptible to chemical erosion, and acetylene evaporites may form on Titan. The geochemical character of acetylene in liquid hydrocarbons on Titan appears to be intermediate to those of calcite and gypsum in surface waters on Earth. Specific recommendations are given of observational, experimental, and theoretical work that will lead to significant advancements in our knowledge of geochemical processes on Titan. This paper represents the beginning of a new kind of

  6. Silicon carbide-derived carbon nanocomposite as a substitute for mercury in the catalytic hydrochlorination of acetylene

    NASA Astrophysics Data System (ADS)

    Li, Xingyun; Pan, Xiulian; Yu, Liang; Ren, Pengju; Wu, Xing; Sun, Litao; Jiao, Feng; Bao, Xinhe

    2014-04-01

    Acetylene hydrochlorination is an important coal-based technology for the industrial production of vinyl chloride, however it is plagued by the toxicity of the mercury chloride catalyst. Therefore extensive efforts have been made to explore alternative catalysts with various metals. Here we report that a nanocomposite of nitrogen-doped carbon derived from silicon carbide activates acetylene directly for hydrochlorination in the absence of additional metal species. The catalyst delivers stable performance during a 150 hour test with acetylene conversion reaching 80% and vinyl chloride selectivity over 98% at 200 °C. Experimental studies and theoretical simulations reveal that the carbon atoms bonded with pyrrolic nitrogen atoms are the active sites. This proof-of-concept study demonstrates that such a nanocomposite is a potential substitute for mercury while further work is still necessary to bring this to the industrial stage. Furthermore, the finding also provides guidance for design of carbon-based catalysts for activation of other alkynes.

  7. Importance of surface carbide formation on the activity and selectivity of Pd surfaces in the selective hydrogenation of acetylene

    NASA Astrophysics Data System (ADS)

    Yang, Bo; Burch, Robbie; Hardacre, Christopher; Hu, P.; Hughes, Philip

    2016-04-01

    A recent experimental investigation (Kim et al. J. Catal. 306 (2013) 146-154) on the selective hydrogenation of acetylene over Pd nanoparticles with different shapes concluded that Pd(100) showed higher activity and selectivity than Pd(111) for acetylene hydrogenation. However, our recent density functional calculations (Yang et al. J. Catal. 305 (2013) 264-276) observed that the clean Pd(111) surface should result in higher activity and ethylene selectivity compared with the clean Pd(100) surface for acetylene hydrogenation. In the current work, using density functional theory calculations, we find that Pd(100) in the carbide form gives rise to higher activity and selectivity than Pd(111) carbide. These results indicate that the catalyst surface is most likely in the carbide form under the experimental reaction conditions. Furthermore, the adsorption energies of hydrogen atoms as a function of the hydrogen coverage at the surface and subsurface sites over Pd(100) are compared with those over Pd(111), and it is found that the adsorption of hydrogen atoms is always less favoured on Pd(100) over the whole coverage range. This suggests that the Pd(100) hydride surface will be less stable than the Pd(111) hydride surface, which is also in accordance with the experimental results reported.

  8. Study of acetylene poisoning of Pt cathode on proton exchange membrane fuel cell spatial performance using a segmented cell system

    NASA Astrophysics Data System (ADS)

    Reshetenko, Tatyana V.; St-Pierre, Jean

    2015-08-01

    Acetylene is a welding fuel and precursor for organic synthesis, which requires considering it to be a possible air pollutant. In this work, the spatial performance of a proton exchange membrane fuel cell exposed to 300 ppm C2H2 and different operating currents was studied with a segmented cell system. The injection of C2H2 resulted in a cell performance decrease and redistribution of segments' currents depending on the operating conditions. Performance loss was 20-50 mV at 0.1-0.2 A cm-2 and was accompanied by a rapid redistribution of localized currents. Acetylene exposure at 0.4-1.0 A cm-2 led to a sharp voltage decrease to 0.07-0.13 V and significant changes in current distribution during a transition period, when the cell reached a voltage of 0.55-0.6 V. A recovery of the cell voltage was observed after stopping the C2H2 injection. Spatial electrochemical impedance spectroscopy (EIS) data showed different segments' behavior at low and high currents. It was assumed that acetylene oxidation occurs at high cell voltage, while it reduces at low cell potential. A detailed analysis of the current density distribution, its correlation with EIS data and possible C2H2 oxidation/reduction mechanisms are presented and discussed.

  9. Structure and Function of the Unusual Tungsten Enzymes Acetylene Hydratase and Class II Benzoyl-Coenzyme A Reductase.

    PubMed

    Boll, Matthias; Einsle, Oliver; Ermler, Ulrich; Kroneck, Peter M H; Ullmann, G Matthias

    2016-01-01

    In biology, tungsten (W) is exclusively found in microbial enzymes bound to a bis-pyranopterin cofactor (bis-WPT). Previously known W enzymes catalyze redox oxo/hydroxyl transfer reactions by directly coordinating their substrates or products to the metal. They comprise the W-containing formate/formylmethanofuran dehydrogenases belonging to the dimethyl sulfoxide reductase (DMSOR) family and the aldehyde:ferredoxin oxidoreductase (AOR) families, which form a separate enzyme family within the Mo/W enzymes. In the last decade, initial insights into the structure and function of two unprecedented W enzymes were obtained: the acetaldehyde forming acetylene hydratase (ACH) belongs to the DMSOR and the class II benzoyl-coenzyme A (CoA) reductase (BCR) to the AOR family. The latter catalyzes the reductive dearomatization of benzoyl-CoA to a cyclic diene. Both are key enzymes in the degradation of acetylene (ACH) or aromatic compounds (BCR) in strictly anaerobic bacteria. They are unusual in either catalyzing a nonredox reaction (ACH) or a redox reaction without coordinating the substrate or product to the metal (BCR). In organic chemical synthesis, analogous reactions require totally nonphysiological conditions depending on Hg2+ (acetylene hydration) or alkali metals (benzene ring reduction). The structural insights obtained pave the way for biological or biomimetic approaches to basic reactions in organic chemistry. PMID:26959374

  10. Product toxicity and cometabolic competitive inhibition modeling of chloroform and trichloroethylene transformation by methanotrophic resting cells.

    PubMed Central

    Alvarez-Cohen, L; McCarty, P L

    1991-01-01

    The rate and capacity for chloroform (CF) and trichloroethylene (TCE) transformation by a mixed methanotrophic culture of resting cells (no exogenous energy source) and formate-fed cells were measured. As reported previously for TCE, formate addition resulted in an increased CF transformation rate (0.35 day-1 for resting cells and 1.5 day-1 for formate-fed cells) and transformation capacity (0.0065 mg of CF per mg of cells for resting cells and 0.015 mg of CF per mg of cells for formate-fed cells), suggesting that depletion of energy stores affects transformation behavior. The observed finite transformation capacity, even with an exogenous energy source, suggests that toxicity was also a factor. CF transformation capacity was significantly lower than that for TCE, suggesting a greater toxicity from CF transformation. The toxicity of CF, TCE, and their transformation products to whole cells was evaluated by comparing the formate oxidation activity of acetylene-treated cells to that of non-acetylene-treated cells with and without prior exposure to CF or TCE. Acetylene arrests the activity of methane monooxygenase in CF and TCE oxidation without halting cell activity toward formate. Significantly diminished formate oxidation by cells exposed to either CR or TCE without acetylene compared with that with acetylene suggests that the solvents themselves were not toxic under the experimental conditions but their transformation products were. The concurrent transformation of CF and TCE by resting cells was measured, and results were compared with predictions from a competitive-inhibition cometabolic transformation model. The reasonable fit between model predictions and experimental observations was supportive of model assumptions. PMID:1905516

  11. Infrared spectroscopy and Mie scattering of acetylene aerosols formed in a low temperature diffusion cell

    NASA Technical Reports Server (NTRS)

    Dunder, T.; Miller, R. E.

    1990-01-01

    A method is described for forming and spectroscopically characterizing cryogenic aerosols formed in a low temperature gas cell. By adjusting the cell pressure, gas composition and flow rate, the size distribution of aerosol particles can be varied over a wide range. The combination of pressure and flow rate determine the residence time of the aerosols in the cell and hence the time available for the particles to grow. FTIR spectroscopy, over the range from 600/cm to 6000/cm, is used to characterize the aerosols. The particle size distribution can be varied so that, at one extreme, the spectra show only absorption features associated with the infrared active vibrational bands and, at the other, they display both absorption and Mie scattering. In the latter case, Mie scattering theory is used to obtain semiquantitative aerosol size distributions, which can be understood in terms of the interplay between nucleation and condensation. In the case of acetylene aerosols, the infrared spectra suggest that the particles exist in the high temperature cubic phase of the solid.

  12. The Fourier transform absorption spectrum of acetylene between 8280 and 8700 cm-1

    NASA Astrophysics Data System (ADS)

    Lyulin, O. M.; Vander Auwera, J.; Campargue, A.

    2016-07-01

    High resolution (0.011 cm-1) room temperature (295 K) Fourier transform absorption spectra (FTS) of acetylene have been analyzed in the 8280-8700 cm-1 range dominated by the ν1+ν2+ν3 band at 8512 cm-1. Line positions and intensities were retrieved from FTS spectra recorded at 3.84 and 56.6 hPa. As a result, a list of 1001 lines was constructed with intensities ranging between about 2×10-26 and 10-22 cm/molecule. Comparison with accurate predictions provided by a global effective operator model led to the assignment of 629 12C2H2 lines. In addition, 114 lines of the 13C12CH2 isotopologue were assigned using information available in the literature. The 12C2H2 lines belong to thirteen bands, nine of which being newly reported. The 13C12CH2 lines belong to three bands, the intensities of which being reported for the first time. Spectroscopic parameters of the 12C2H2 upper vibrational levels were derived from band-by-band analyses of the line positions (typical rms are on the order of 0.002 cm-1). Three of the analyzed bands were found to be affected by rovibrational perturbations, which are discussed in the frame of a global effective Hamiltonian. The obtained line parameters are compared with those of the two bands included in the HITRAN 2012 database.

  13. Chromophores from photolyzed ammonia reacting with acetylene: Application to Jupiter's Great Red Spot

    NASA Astrophysics Data System (ADS)

    Carlson, R. W.; Baines, K. H.; Anderson, M. S.; Filacchione, G.; Simon, A. A.

    2016-08-01

    The high altitude of Jupiter's Great Red Spot (GRS) may enhance the upward flux of gaseous ammonia (NH3) into the high troposphere, where NH3 molecules can be photodissociated and initiate a chain of chemical reactions with downwelling acetylene molecules (C2H2). These reactions, experimentally studied earlier by (Ferris and Ishikawa [1987] Nature 326, 777-778) and (Ferris and Ishikawa [1988] J. Amer. Chem. Soc. 110, 4306-4312), produce chromophores that absorb in the visible and ultraviolet regions. In this work we photolyzed mixtures of NH3 and C2H2 using ultraviolet radiation with a wavelength of 214 nm and measured the spectral transmission of the deposited films in the visible region (400-740 nm). From these transmission data we estimated the imaginary indices of refraction. Assuming that ammonia grains at the top of the GRS clouds are coated with this material, we performed layered sphere and radiative transfer calculations to predict GRS reflection spectra. Comparison of those results with observed and previously unreported Cassini visible spectra and with true-color images of the GRS show that the unknown GRS chromophore is spectrally consistent with the coupled NH3-C2H2 photochemical products produced in our laboratory experiments. Using high-resolution mass spectrometry and infrared spectroscopy we infer that the chromophore-containing residue is composed of aliphatic azine, azo, and diazo compounds.

  14. Influence of nanoparticle formation on discharge properties in argon-acetylene capacitively coupled radio frequency plasmas

    NASA Astrophysics Data System (ADS)

    Wegner, Th.; Hinz, A. M.; Faupel, F.; Strunskus, T.; Kersten, H.; Meichsner, J.

    2016-02-01

    This contribution presents experimental results regarding the influence of nanoparticle formation in capacitively coupled radio frequency (13.56 MHz) argon-acetylene plasmas. The discharge is studied using non-invasive 160 GHz Gaussian beam microwave interferometry and optical emission spectroscopy. Particularly, the temporal behavior of the electron density from microwave interferometry is analyzed and compared with the changing plasma emission and self-bias voltage caused by nanoparticle formation. The periodic particle formation with a cycle duration between 30 s and 140 s starts with an electron density drop over more than one order of magnitude below the detection limit (8 × 1014 m-3). The electron density reduction is the result of electron attachment processes due to negative ions and nanoparticle formation. The onset time constant of nanoparticle formation is five times faster compared to the expulsion of the particles from the plasma due to multi-disperse size distribution. Moreover, the intensity of the argon transition lines increases and implies a rising effective electron temperature. The cycle duration of the particle formation is affected by the total gas flow rate and exhibits an inverse proportionality to the square of the total gas flow rate. The variation in the total gas flow rate influences the force balance, which determines the confinement time of the nanoparticles. As a further result, the cycle duration is dependent on the axial position of the powered electrode, which also corresponds to different distances relative to the fixed optical axis of the microwave interferometer.

  15. Nitrogen fixation (acetylene reduction) associated with roots of winter wheat and sorghum in Nebraska.

    PubMed Central

    Pedersen, W L; Chakrabarty, K; Klucas, R V; Vidaver, A K

    1978-01-01

    Root segments and root-soil cores (6.5-cm diameter) from fields and nurseries of winter wheat and sorghum were tested for N2 fixation by using the acetylene reduction assay. Wheat samples (approximately 1,200) from 109 sites generally had low or no activity (0 to 3.1 nmol of C2H4 produced per h per g [dry weight] of root segments), even after 24 h of incubation. However, a commercial field of Scout 66, located in western Nebraska, exhibited appreciable activity (290 nmol of C2H4 produced per h per g [dry weight] of root segments). Of 400 sorghum lines and crosses, grain sorghums (i.e., CK-60A, Wheatland A, B517, and NP-16) generally exhibited higher nitrogenase activity than forage sorghums or winter wheats. CK-60A, a male sterile grain sorghum, was sampled at four locations and had the most consistent activity of 24 to 1,100 nmol of C2H4 produced per h per core. The maximum rate extrapolated to 2.5 g of N per hectare per day. Numerous N2-fixing bacterial isolates were obtained from wheat and sorghum roots that exhibited high nitrogenase activity. Most isolates were members of the Enterobacteriacae, i.e., Klebsiella pneumoniae, Enterobacter cloacae, and Erwinia herbicola. PMID:623458

  16. Dipolar Bent and Linear Acetylenes Substituted by Cationic Quinolinium and Anionic Benzoates. Formation of Mesomeric Betaines.

    PubMed

    Schmidt, Andreas; Batsyts, Sviatoslav; Smeyanov, Alexey; Freese, Tyll; Hübner, Eike G; Nieger, Martin

    2016-05-20

    3-Ethynylquinoline was subjected to a Sonogashira-Hagihara reaction with methyl 2-, 3-, and 4-bromobenzoates, respectively, and then N-methylated to give 3-[((methoxycarbonyl)phenyl)ethynyl]-1-methylquinolinium salts (two X-ray analyses). On saponification of the 3- and 4-substituted benzoates, the mesomeric betaines 3- and 4-[(1-methylquinolinium-3-yl)ethynyl]benzoates were formed. By contrast, the 2-benzoate derivative gave either the corresponding (1-oxo-1H-isochromen-3-yl)quinolinium derivative or the mesomeric betaine 2-(1-methylquinolinium-3-yl)-1,3-dioxo-2,3-dihydro-1H-inden-2-ide depending on the reaction conditions. A DFT calculation predicts a transoid conformation of the acetylene bond in the intermediate 2-[(1-methylquinolinium-3-yl)ethynyl]benzoate which is due to a strong hydrogen bond between the carboxylate group and 2H of the quinolinium ring, in addition to a 1,5-interaction between the carboxylate group and the CC triple bond. The bond angles of the transoid CC triple bond were calculated to be 211.6° and -175.1° in vacuo. The corresponding linear triple bond is 50.4 kJ/mol less stable in vacuo according to the calculation, and the N-heterocyclic carbene quinoline-2-ylidene is not formed as a tautomer. PMID:27088664

  17. Chromophores from photolyzed ammonia reacting with acetylene: Application to Jupiters Great Red Spot

    NASA Technical Reports Server (NTRS)

    Carlson, Robert W.; Baines, Kevin H.; Anderson, M. S.; Filacchione, G.; Simon, A. A.

    2016-01-01

    The high altitude of Jupiter's Great Red Spot (GRS) may enhance the upward flux of gaseous ammonia (NH3 ) into the high troposphere, where NH3 molecules can be photodissociated and initiate a chain of chemical reactions with downwelling acetylene molecules (C2H2 ). These reactions, experimentally studied earlier by (Ferris and Ishikawa [1987] Nature 326, 777-778) and (Ferris and Ishikawa [1988] J. Amer. Chem. Soc. 110, 4306-4312), produce chromophores that absorb in the visible and ultraviolet regions. In this work we photolyzed mixtures of NH3 and C2H2 using ultraviolet radiation with a wavelength of 214 nm and measured the spectral transmission of the deposited films in the visible region (400-740 nm). From these transmission data we estimated the imaginary indices of refraction. Assuming that ammonia grains at the top of the GRS clouds are coated with this material, we performed layered sphere and radiative transfer calculations to predict GRS reflection spectra. Comparison of those results with observed and previously unreported Cassini visible spectra and with true-color images of the GRS show that the unknown GRS chromophore is spectrally consistent with the coupled NH3-C2H2 photochemical products produced in our laboratory experiments. Using high-resolution mass spectrometry and infrared spectroscopy we infer that the chromophore-containing residue is composed of aliphatic azine, azo, and diazo compounds.

  18. Time- and Isomer-Resolved Measurements of Sequential Addition of Acetylene to the Propargyl Radical.

    PubMed

    Savee, John D; Selby, Talitha M; Welz, Oliver; Taatjes, Craig A; Osborn, David L

    2015-10-15

    Soot formation in combustion is a complex process in which polycyclic aromatic hydrocarbons (PAHs) are believed to play a critical role. Recent works concluded that three consecutive additions of acetylene (C2H2) to propargyl (C3H3) create a facile route to the PAH indene (C9H8). However, the isomeric forms of C5H5 and C7H7 intermediates in this reaction sequence are not known. We directly investigate these intermediates using time- and isomer-resolved experiments. Both the resonance stabilized vinylpropargyl (vp-C5H5) and 2,4-cyclopentadienyl (c-C5H5) radical isomers of C5H5 are produced, with substantially different intensities at 800 K vs 1000 K. In agreement with literature master equation calculations, we find that c-C5H5 + C2H2 produces only the tropyl isomer of C7H7 (tp-C7H7) below 1000 K, and that tp-C7H7 + C2H2 terminates the reaction sequence yielding C9H8 (indene) + H. This work demonstrates a pathway for PAH formation that does not proceed through benzene. PMID:26722791

  19. Ion enhanced deposition by dual titanium and acetylene plasma immersion ion implantation

    NASA Astrophysics Data System (ADS)

    Zeng, Z. M.; Tian, X. B.; Chu, P. K.

    2003-01-01

    Plasma immersion ion implantation and deposition (PIII-D) offers a non-line-of-sight fabrication method for various types of thin films on steels to improve the surface properties. In this work, titanium films were first deposited on 9Cr18 (AISI440) stainless bearing steel by metal plasma immersion ion implantation and deposition (MePIII-D) using a titanium vacuum arc plasma source. Afterwards, carbon implantation and carbon film deposition were performed by acetylene (C2H2) plasma immersion ion implantation. Multiple-layered structures with superior properties were produced by conducting Ti MePIII-D + C2H2 PIII successively. The composition and structure of the films were investigated employing Auger electron spectroscopy and Raman spectroscopy. It is shown that the mixing for Ti and C atoms is much better when the target bias is higher during Ti MePIII-D. A top diamond-like carbon layer and a titanium oxycarbide layer are formed on the 9Cr18 steel surface. The wear test results indicate that this dual PIII-D method can significantly enhance the wear properties and decrease the surface friction coefficient of 9Cr18 steel.

  20. Global modeling of vibration-rotation spectra of the acetylene molecule

    NASA Astrophysics Data System (ADS)

    Lyulin, O. M.; Perevalov, V. I.

    2016-07-01

    The global modeling of both line positions and intensities of the acetylene molecule in the 50-9900 cm-1 region has been performed using the effective operators approach. The parameters of the polyad model of effective Hamiltonian have been fitted to the line positions collected from the literature. The used polyad model of effective Hamiltonian takes into account the centrifugal distortion, rotational and vibrational ℓ-doubling terms and both anharmonic and Coriolis resonance interaction operators arising due to the approximate relations between the harmonic frequencies: ω1≈ω3≈5ω4≈5ω5 and ω2≈3ω4≈3ω5. The dimensionless weighted standard deviation of the fit is 2.8. The fitted set of 237 effective Hamiltonian parameters allowed reproducing 24,991 measured line positions of 494 bands with a root mean squares deviation 0.0037 cm-1. The eigenfunctions of the effective Hamiltonian corresponding to the fitted set of parameters were used to fit the observed line intensities collected from the literature for 15 series of transitions: ΔP = 0-13,15, where P=5V1+5V3 +3V2+V4+V5 is the polyad number (Vi are the principal vibrational quantum numbers). The fitted sets of the effective dipole moment parameters reproduce the observed line intensities within their experimental uncertainties 2-20%.

  1. Theoretical investigation of alignment-dependent intense-field fragmentation of acetylene

    NASA Astrophysics Data System (ADS)

    Doblhoff-Dier, Katharina; Kitzler, Markus; Gräfe, Stefanie

    2016-07-01

    We analyze the alignment-dependent dissociative and nondissociative ionization of acetylene, C2H2 . Numerical models describing the yield of the singly and doubly charged ions (C2H2+,C2H22 +) and several fragmentation and isomerization channels (C2H++H+ ,CH++CH+ ,CH2++C+ ) as a function of the relative alignment angle between the laser polarization axis and the molecular axis are presented. We apply and compare two different approaches. The first is based on time-dependent density functional theory. The second is a quasi-single-particle approach using the Dyson orbitals. We find good agreement between the results of both methods. A comparison of our theoretical predictions with experimental data allows us to show that the alignment-dependent yield of most reaction channels is described to high accuracy assuming sequential ionization. However, for some of the fragmentation channels, namely, CH++CH+ and C2H++H+ , we find non-negligible influence of recollisional ionization.

  2. Seasonal variations of temperature, acetylene and ethane in Saturn's atmosphere from 2005 to 2010, as observed by Cassini-CIRS

    NASA Astrophysics Data System (ADS)

    Sinclair, J. A.; Irwin, P. G. J.; Fletcher, L. N.; Moses, J. I.; Greathouse, T. K.; Friedson, A. J.; Hesman, B.; Hurley, J.; Merlet, C.

    2013-07-01

    Acetylene (C2H2) and ethane (C2H6) are by-products of complex photochemistry in the stratosphere of Saturn. Both hydrocarbons are important to the thermal balance of Saturn's stratosphere and serve as tracers of vertical motion in the lower stratosphere. Earlier studies of Saturn's hydrocarbons using Cassini-CIRS observations have provided only a snapshot of their behaviour. Following the vernal equinox in August 2009, Saturn's northern and southern hemispheres have entered spring and autumn, respectively, however the response of Saturn's hydrocarbons to this seasonal shift remains to be determined. In this paper, we investigate how the thermal structure and concentrations of acetylene and ethane have evolved with the changing season on Saturn. We retrieve the vertical temperature profiles and acetylene and ethane volume mixing ratios from Δν˜=15.5cm-1 Cassini-CIRS observations. In comparing 2005 (solar longitude, Ls ˜ 308°), 2009 (Ls ˜ 3°) and 2010 (Ls ˜ 15°) results, we observe the disappearance of Saturn's warm southern polar hood with cooling of up to 17.1 K ± 0.8 K at 1.1 mbar at high-southern latitudes. Comparison of the derived temperature trend in this region with a radiative climate model (Section 4 of Fletcher et al., 2010 and Greathouse et al. (2013, in preparation)) indicates that this cooling is radiative although dynamical changes in this region cannot be ruled out. We observe a 21 ± 12% enrichment of acetylene and a 29 ± 11% enrichment of ethane at 25°N from 2005 to 2009, suggesting downwelling at this latitude. At 15°S, both acetylene and ethane exhibit a decrease in concentration of 6 ± 11% and 17 ± 9% from 2005 to 2010, respectively, which suggests upwelling at this latitude (though a statistically significant change is only exhibited by ethane). These implied vertical motions at 15°S and 25°N are consistent with a recently-developed global circulation model of Saturn's tropopause and stratosphere(Friedson and Moses, 2012), which

  3. Intramolecular competition between n-pair and π-pair hydrogen bonding: Microwave spectrum and internal dynamics of the pyridine-acetylene hydrogen-bonded complex.

    PubMed

    Mackenzie, Rebecca B; Dewberry, Christopher T; Coulston, Emma; Cole, George C; Legon, Anthony C; Tew, David P; Leopold, Kenneth R

    2015-09-14

    a-type rotational spectra of the hydrogen-bonded complex formed from pyridine and acetylene are reported. Rotational and (14)N hyperfine constants indicate that the complex is planar with an acetylenic hydrogen directed toward the nitrogen. However, unlike the complexes of pyridine with HCl and HBr, the acetylene moiety in HCCH-NC5H5 does not lie along the symmetry axis of the nitrogen lone pair, but rather, forms an average angle of 46° with the C2 axis of the pyridine. The a-type spectra of HCCH-NC5H5 and DCCD-NC5H5 are doubled, suggesting the existence of a low lying pair of tunneling states. This doubling persists in the spectra of HCCD-NC5H5, DCCH-NC5H5, indicating that the underlying motion does not involve interchange of the two hydrogens of the acetylene. Single (13)C substitution in either the ortho- or meta-position of the pyridine eliminates the doubling and gives rise to separate sets of spectra that are well predicted by a bent geometry with the (13)C on either the same side ("inner") or the opposite side ("outer") as the acetylene. High level ab initio calculations are presented which indicate a binding energy of 1.2 kcal/mol and a potential energy barrier of 44 cm(-1) in the C2v configuration. Taken together, these results reveal a complex with a bent hydrogen bond and large amplitude rocking of the acetylene moiety. It is likely that the bent equilibrium structure arises from a competition between a weak hydrogen bond to the nitrogen (an n-pair hydrogen bond) and a secondary interaction between the ortho-hydrogens of the pyridine and the π electron density of the acetylene. PMID:26374037

  4. Acetylene-derived strong organic acceptors for planar and nonplanar push-pull chromophores.

    PubMed

    Kivala, Milan; Diederich, François

    2009-02-17

    Though investigated for decades, interest in push-pull chromophores (D-pi-A), strong electron donors (D) connected by pi-conjugating spacers to strong electron acceptors (A), continues to grow. Such chromophores are of substantial interest for optoelectronic devices such as waveguides. Also, strong donors and acceptors form bimolecular charge-transfer (CT) complexes and salts, some of which exhibit electrical conductivity and magnetic behavior. Furthermore, strong organic acceptors are increasingly explored as dopants in the fabrication of organic light-emitting diodes (OLEDs) and solar cells. This Account describes systematic efforts pursued over the past decade in our laboratory to generate new families of organic electron acceptors (A) and conjugate them via pi-spacers to electron donors (D) under formation of push-pull systems with intense intramolecular CT interactions and high third-order optical nonlinearities. First, we describe donor-acceptor-substituted tetraethynylethenes (TEEs). In these chromophores, the peripherally attached p-nitrophenyl acceptors and N,N-dimethylanilino donors behave as nearly independent redox centers. Acetylenic scaffolding using TEE building blocks produces large all-carbon sheets, such as perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes with potent electron-acceptor properties. Arylated TEEs act as molecular switches allowing two-way photochemical interconversion that is not perturbed by thermal isomerization pathways. Upon sequential substitution of the acetylene moieties in TEEs, we formed another family of potent acceptors, the cyanoethynylethenes (CEEs). Donor-substituted CEEs are planar CT chromophores with very high third-order optical nonlinearities. Their high environmental stability allows for the formation of thin films by vapor-phase deposition. Through careful analysis of the physicochemical properties of CEEs, we established useful guidelines for evaluating and tuning the optical gap in

  5. Uptake of acetylene on cosmic dust and production of benzene in Titan's atmosphere

    NASA Astrophysics Data System (ADS)

    Frankland, Victoria L.; James, Alexander D.; Sánchez, Juan Diego Carrillo; Mangan, Thomas P.; Willacy, Karen; Poppe, Andrew R.; Plane, John M. C.

    2016-11-01

    A low-temperature flow tube and ultra-high vacuum apparatus were used to explore the uptake and heterogeneous chemistry of acetylene (C2H2) on cosmic dust analogues over the temperature range encountered in Titan's atmosphere below 600 km. The uptake coefficient, γ, was measured at 181 K to be (1.6 ± 0.4) × 10-4, (1.9 ± 0.4) × 10-4 and (1.5 ± 0.4) × 10-4 for the uptake of C2H2 on Mg2SiO4, MgFeSiO4 and Fe2SiO4, respectively, indicating that γ is independent of Mg or Fe active sites. The uptake of C2H2 was also measured on SiO2 and SiC as analogues for meteoric smoke particles in Titan's atmosphere, but was found to be below the detection limit (γ < 6 × 10-8 and < 4 × 10-7, respectively). The rate of cyclo-trimerization of C2H2 to C6H6 was found to be 2.6 × 10-5 exp(-741/T) s-1, with an uncertainty ranging from ± 27 % at 115 K to ± 49 % at 181 K. A chemical ablation model was used to show that the bulk of cosmic dust particles (radius 0.02-10 μm) entering Titan's atmosphere do not ablate (< 1% mass loss through sputtering), thereby providing a significant surface for heterogeneous chemistry. A 1D model of dust sedimentation shows that the production of C6H6via uptake of C2H2 on cosmic dust, followed by cyclo-trimerization and desorption, is probably competitive with gas-phase production of C6H6 between 80 and 120 km.

  6. An Experimental and Theoretical Study of Nitrogen-Broadened Acetylene Lines

    NASA Technical Reports Server (NTRS)

    Thibault, Franck; Martinez, Raul Z.; Bermejo, Dionisio; Ivanov, Sergey V.; Buzykin, Oleg G.; Ma, Qiancheng

    2014-01-01

    We present experimental nitrogen-broadening coefficients derived from Voigt profiles of isotropic Raman Q-lines measured in the 2 band of acetylene (C2H2) at 150 K and 298 K, and compare them to theoretical values obtained through calculations that were carried out specifically for this work. Namely, full classical calculations based on Gordon's approach, two kinds of semi-classical calculations based on Robert Bonamy method as well as full quantum dynamical calculations were performed. All the computations employed exactly the same ab initio potential energy surface for the C2H2N2 system which is, to our knowledge, the most realistic, accurate and up-to-date one. The resulting calculated collisional half-widths are in good agreement with the experimental ones only for the full classical and quantum dynamical methods. In addition, we have performed similar calculations for IR absorption lines and compared the results to bibliographic values. Results obtained with the full classical method are again in good agreement with the available room temperature experimental data. The quantum dynamical close-coupling calculations are too time consuming to provide a complete set of values and therefore have been performed only for the R(0) line of C2H2. The broadening coefficient obtained for this line at 173 K and 297 K also compares quite well with the available experimental data. The traditional Robert Bonamy semi-classical formalism, however, strongly overestimates the values of half-width for both Qand R-lines. The refined semi-classical Robert Bonamy method, first proposed for the calculations of pressure broadening coefficients of isotropic Raman lines, is also used for IR lines. By using this improved model that takes into account effects from line coupling, the calculated semi-classical widths are significantly reduced and closer to the measured ones.

  7. Oxy-acetylene driven laboratory scale shock tubes for studying blast wave effects.

    PubMed

    Courtney, Amy C; Andrusiv, Lubov P; Courtney, Michael W

    2012-04-01

    This paper describes the development and characterization of modular, oxy-acetylene driven laboratory scale shock tubes. Such tools are needed to produce realistic blast waves in a laboratory setting. The pressure-time profiles measured at 1 MHz using high-speed piezoelectric pressure sensors have relevant durations and show a true shock front and exponential decay characteristic of free-field blast waves. Descriptions are included for shock tube diameters of 27-79 mm. A range of peak pressures from 204 kPa to 1187 kPa (with 0.5-5.6% standard error of the mean) were produced by selection of the driver section diameter and distance from the shock tube opening. The peak pressures varied predictably with distance from the shock tube opening while maintaining both a true blast wave profile and relevant pulse duration for distances up to about one diameter from the shock tube opening. This shock tube design provides a more realistic blast profile than current compression-driven shock tubes, and it does not have a large jet effect. In addition, operation does not require specialized personnel or facilities like most blast-driven shock tubes, which reduces operating costs and effort and permits greater throughput and accessibility. It is expected to be useful in assessing the response of various sensors to shock wave loading; assessing the reflection, transmission, and absorption properties of candidate armor materials; assessing material properties at high rates of loading; assessing the response of biological materials to shock wave exposure; and providing a means to validate numerical models of the interaction of shock waves with structures. All of these activities have been difficult to pursue in a laboratory setting due in part to lack of appropriate means to produce a realistic blast loading profile. PMID:22559580

  8. Concentration Dependence of Line Shapes in the ν_1 + ν_3 Band of Acetylene

    NASA Astrophysics Data System (ADS)

    Cich, Matthew; Forthomme, Damien; Hall, Gregory; McRaven, C.; Sears, Trevor

    2014-06-01

    Using an extended cavity diode laser locked to a frequency comb, the line shape of the P(11) line in the ν_1 + ν_3 combination band of acetylene has been studied as a function of varying concentration of the absorber in nitrogen. Mixture concentrations of 1, 5 and 10% at 296 K and pressures between a few Torr and one atmosphere were made and the measurements analyzed using two different speed-dependent broadening models. These experiments are designed to test the additivity of contributions to pressure broadening and shift in speed-dependent line shape modeling, i.e. whether the lineshape parameters follow partial pressure weighting in the binary mixtures. P(11) is relatively isolated with respect to underlying hot band transitions and neighboring transitions of the same band, but it was found that the accurate positions of underlying hot band transitions were crucial to the successful modeling of the observed line shapes, even though these lines are typically 100-1000 times weaker than P(11) itself and are many Doppler line widths removed from the line center. Positions of the hot band lines quoted in the HITRAN database, which are derived from the analysis of high resolution FTIR spectra, are of the order of 10's of MHz in error. In parallel work, we have measured the positions of many of these lines by saturation dip spectroscopy. Progress in the analysis of the data and the new saturation dip line center measurements will be reported. [1] C. P. McRaven, et al. Paper RI05, 68th International Symposium on Molecular Spectroscopy, 2013 Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences.

  9. Chromophores from Photolyzed Ammonia Reacting with Acetylene: Application to Jupiter’s Great Red Spot

    NASA Astrophysics Data System (ADS)

    Carlson, Robert W.; Baines, K. H.; Anderson, M. S.; Filacchione, G.

    2012-10-01

    The production mechanisms of chromophores at Jupiter, and notably at the Great Red Spot (GRS), have been long-standing puzzles. A clue to the formation of the GRS coloring agent may be the great height of this storm, which can upwell ammonia to pressure levels of a few hundred mbar where solar photons capable of dissociating NH3 penetrate. Acetylene formed at higher altitudes can diffuse down and react with the NH3 photodissociation products, forming a deposit that absorbs in the ultraviolet and visible region (Ferris and Ishikawa, J. Amer. Chem. Soc. 110, 4306-4312, 1988). We have investigated the system NH3 + C2H2 + CH4 using a Zn lamp emitting at 214 nm to produce NH2 + H and subsequent reaction products. The deposits produced in these reactions were analyzed by optical and infrared spectroscopy and soft-ionization (He*) time-of-flight mass spectroscopy. The combination of NH3 + CH4 produced no visibly absorbing material, but NH3 + C2H2 and NH3 + C2H2 + CH4 mixtures both produced a yellow-orange film whose transmission spectra are similar to that of the GRS obtained by Cassini VIMS. Infrared spectra show a strong band at 2056 wavenumbers which may arise from nitrile (-CN), isonitrile (-NC), or diazide (-CNN) functional groups. The high-resolution mass spectra are consistent with compounds of the form CnH2n+1Nm, similar to the products formed in NH3 + CH4 spark discharges (Molton and Ponnamperuma, Icarus 21, 166-174, 1974). We thank NASA's Planetary Atmospheres Program for support.

  10. Double resonant absorption measurement of acetylene symmetric vibrational states probed with cavity ring down spectroscopy

    NASA Astrophysics Data System (ADS)

    Karhu, J.; Nauta, J.; Vainio, M.; Metsälä, M.; Hoekstra, S.; Halonen, L.

    2016-06-01

    A novel mid-infrared/near-infrared double resonant absorption setup for studying infrared-inactive vibrational states is presented. A strong vibrational transition in the mid-infrared region is excited using an idler beam from a singly resonant continuous-wave optical parametric oscillator, to populate an intermediate vibrational state. High output power of the optical parametric oscillator and the strength of the mid-infrared transition result in efficient population transfer to the intermediate state, which allows measuring secondary transitions from this state with a high signal-to-noise ratio. A secondary, near-infrared transition from the intermediate state is probed using cavity ring-down spectroscopy, which provides high sensitivity in this wavelength region. Due to the narrow linewidths of the excitation sources, the rovibrational lines of the secondary transition are measured with sub-Doppler resolution. The setup is used to access a previously unreported symmetric vibrational state of acetylene, ν 1 + ν 2 + ν 3 + ν4 1 + ν5 - 1 in the normal mode notation. Single-photon transitions to this state from the vibrational ground state are forbidden. Ten lines of the newly measured state are observed and fitted with the linear least-squares method to extract the band parameters. The vibrational term value was measured to be at 9775.0018(45) cm-1, the rotational parameter B was 1.162 222(37) cm-1, and the quartic centrifugal distortion parameter D was 3.998(62) × 10-6 cm-1, where the numbers in the parenthesis are one-standard errors in the least significant digits.

  11. Double resonant absorption measurement of acetylene symmetric vibrational states probed with cavity ring down spectroscopy.

    PubMed

    Karhu, J; Nauta, J; Vainio, M; Metsälä, M; Hoekstra, S; Halonen, L

    2016-06-28

    A novel mid-infrared/near-infrared double resonant absorption setup for studying infrared-inactive vibrational states is presented. A strong vibrational transition in the mid-infrared region is excited using an idler beam from a singly resonant continuous-wave optical parametric oscillator, to populate an intermediate vibrational state. High output power of the optical parametric oscillator and the strength of the mid-infrared transition result in efficient population transfer to the intermediate state, which allows measuring secondary transitions from this state with a high signal-to-noise ratio. A secondary, near-infrared transition from the intermediate state is probed using cavity ring-down spectroscopy, which provides high sensitivity in this wavelength region. Due to the narrow linewidths of the excitation sources, the rovibrational lines of the secondary transition are measured with sub-Doppler resolution. The setup is used to access a previously unreported symmetric vibrational state of acetylene, ν1+ν2+ν3+ν4 (1)+ν5 (-1) in the normal mode notation. Single-photon transitions to this state from the vibrational ground state are forbidden. Ten lines of the newly measured state are observed and fitted with the linear least-squares method to extract the band parameters. The vibrational term value was measured to be at 9775.0018(45) cm(-1), the rotational parameter B was 1.162 222(37) cm(-1), and the quartic centrifugal distortion parameter D was 3.998(62) × 10(-6) cm(-1), where the numbers in the parenthesis are one-standard errors in the least significant digits. PMID:27369508

  12. Acetylene as an essential building block for prebiotic formation of pyrimidine bases on Titan.

    PubMed

    Jeilani, Yassin A; Fearce, Chelesa; Nguyen, Minh Tho

    2015-10-01

    Prebiotic building blocks for the formation of biomolecules are important in understanding the abiotic origin of biomolecules. However, there is a limited choice of the building blocks as precursors for the biomolecules. Acetylene (HCCH) is found in Titan's atmosphere and is an abiotic-precursor of pyrimidine bases. HCCH reacts with urea to form both cytosine and uracil. The mechanisms for the formation of both cytosine and uracil were studied by density functional theory at B3LYP/6-311G(d,p) level. Ethynyl radicals (˙CCH) are relevant for the chemistry of Titan's atmosphere therefore both HCCH and ˙CCH were evaluated as carbon sources. The pathways, for both HCCH and ˙CCH, lead to intermediates with an unsaturated-group that facilitate the formation of the six-membered ring of the pyrimidine bases. The predicted structures for cytosine and uracil were compared with labeled cytosine and uracil that were formed from the reaction of DCCD with urea. The results suggest that cytosine is formed from HCCH while uracil is formed from ˙CCH. The mechanisms are energetically feasible and there is no conclusive evidence for the preferred pathway (HCCH or ˙CCH). The pathways were further extended for the formation of both uric acid and 8-oxoguanine from HCCH and urea, and demonstrate the utility of HCCH as a carbon source for diverse biomolecules. Biuret is identified as a precursor for the pyridimine bases, and it unifies the free radical pathways for the pyrimidine bases with those of triazines. The pathways are appropriate for the reducing atmosphere that creates both radicals and electrons due to ionizing radiation on Titan. The mechanisms are feasible for the extraterrestrial formation of the pyrimidine bases. PMID:26325173

  13. Oxy-acetylene driven laboratory scale shock tubes for studying blast wave effects

    NASA Astrophysics Data System (ADS)

    Courtney, Amy C.; Andrusiv, Lubov P.; Courtney, Michael W.

    2012-04-01

    This paper describes the development and characterization of modular, oxy-acetylene driven laboratory scale shock tubes. Such tools are needed to produce realistic blast waves in a laboratory setting. The pressure-time profiles measured at 1 MHz using high-speed piezoelectric pressure sensors have relevant durations and show a true shock front and exponential decay characteristic of free-field blast waves. Descriptions are included for shock tube diameters of 27-79 mm. A range of peak pressures from 204 kPa to 1187 kPa (with 0.5-5.6% standard error of the mean) were produced by selection of the driver section diameter and distance from the shock tube opening. The peak pressures varied predictably with distance from the shock tube opening while maintaining both a true blast wave profile and relevant pulse duration for distances up to about one diameter from the shock tube opening. This shock tube design provides a more realistic blast profile than current compression-driven shock tubes, and it does not have a large jet effect. In addition, operation does not require specialized personnel or facilities like most blast-driven shock tubes, which reduces operating costs and effort and permits greater throughput and accessibility. It is expected to be useful in assessing the response of various sensors to shock wave loading; assessing the reflection, transmission, and absorption properties of candidate armor materials; assessing material properties at high rates of loading; assessing the response of biological materials to shock wave exposure; and providing a means to validate numerical models of the interaction of shock waves with structures. All of these activities have been difficult to pursue in a laboratory setting due in part to lack of appropriate means to produce a realistic blast loading profile.

  14. Clickable Photoaffinity Ligands for Metabotropic Glutamate Receptor 5 Based on Select Acetylenic Negative Allosteric Modulators.

    PubMed

    Gregory, Karen J; Velagaleti, Ranganadh; Thal, David M; Brady, Ryan M; Christopoulos, Arthur; Conn, P Jeffrey; Lapinsky, David J

    2016-07-15

    G protein-coupled receptors (GPCRs) represent the largest class of current drug targets. In particular, small-molecule allosteric modulators offer substantial potential for selectively "tuning" GPCR activity. However, there remains a critical need for experimental strategies that unambiguously determine direct allosteric ligand-GPCR interactions, to facilitate both chemical biology studies and rational structure-based drug design. We now report the development and use of first-in-class clickable allosteric photoprobes for a GPCR based on metabotropic glutamate receptor 5 (mGlu5) negative allosteric modulator (NAM) chemotypes. Select acetylenic mGlu5 NAM lead compounds were rationally modified to contain either a benzophenone or an aryl azide as a photoreactive functional group, enabling irreversible covalent attachment to mGlu5 via photoactivation. Additionally, a terminal alkyne or an aliphatic azide was incorporated as a click chemistry handle, allowing chemoselective attachment of fluorescent moieties to the irreversibly mGlu5-bound probe via tandem photoaffinity labeling-bioorthogonal conjugation. These clickable photoprobes retained submicromolar affinity for mGlu5 and negative cooperativity with glutamate, interacted with the "common allosteric-binding site," displayed slow binding kinetics, and could irreversibly label mGlu5 following UV exposure. We depleted the number of functional mGlu5 receptors using an irreversibly bound NAM to elucidate and delineate orthosteric agonist affinity and efficacy. Finally, successful conjugation of fluorescent dyes via click chemistry was demonstrated for each photoprobe. In the future, these clickable photoprobes are expected to aid our understanding of the structural basis of mGlu5 allosteric modulation. Furthermore, tandem photoaffinity labeling-bioorthogonal conjugation is expected to be a broadly applicable experimental strategy across the entire GPCR superfamily. PMID:27115427

  15. Inactivation of the particulate methane monooxygenase (pMMO) in Methylococcus capsulatus (Bath) by acetylene.

    PubMed

    Pham, Minh D; Lin, Ya-Ping; Van Vuong, Quan; Nagababu, Penumaka; Chang, Brian T-A; Ng, Kok Yaoh; Chen, Chein-Hung; Han, Chau-Chung; Chen, Chung-Hsuan; Li, Mai Suan; Yu, Steve S-F; Chan, Sunney I

    2015-12-01

    Acetylene (HCCH) has a long history as a mechanism-based enzyme inhibitor and is considered an active-site probe of the particulate methane monooxygenase (pMMO). Here, we report how HCCH inactivates pMMO in Methylococcus capsulatus (Bath) by using high-resolution mass spectrometry and computational simulation. High-resolution MALDI-TOF MS of intact pMMO complexes has allowed us to confirm that the enzyme oxidizes HCCH to the ketene (C2H2O) intermediate, which then forms an acetylation adduct with the transmembrane PmoC subunit. LC-MS/MS analysis of the peptides derived from in-gel proteolytic digestion of the protein subunit identifies K196 of PmoC as the site of acetylation. No evidence is obtained for chemical modification of the PmoA or PmoB subunit. The inactivation of pMMO by a single adduct in the transmembrane PmoC domain is intriguing given the complexity of the structural fold of this large membrane-protein complex as well as the complicated roles played by the various metal cofactors in the enzyme catalysis. Computational studies suggest that the entry of hydrophobic substrates to, and migration of products from, the catalytic site of pMMO are controlled tightly within the transmembrane domain. Support of these conclusions is provided by parallel experiments with two related alkynes: propyne (CH3CCH) and trifluoropropyne (CF3CCH). Finally, we discuss the implication of these findings to the location of the catalytic site in pMMO. PMID:26275807

  16. A comparison of tabun-inhibited rat brain acetylcholinesterase reactivation by three oximes (HI-6, obidoxime, and K048) in vivo detected by biochemical and histochemical techniques.

    PubMed

    Bajgar, Jiri; Hajek, Petr; Zdarova, Jana Karasova; Kassa, Jiri; Paseka, Antonin; Slizova, Dasa; Krs, Otakar; Kuca, Kamil; Jun, Daniel; Fusek, Josef; Capek, Lukas

    2010-12-01

    Tabun belongs to the most toxic nerve agents. Its mechanism of action is based on acetylcholinesterase (AChE) inhibition at the peripheral and central nervous systems. Therapeutic countermeasures comprise administration of atropine with cholinesterase reactivators able to reactivate the inhibited enzyme. Reactivation of AChE is determined mostly biochemically without specification of different brain structures. Histochemical determination allows a fine search for different structures but is performed mostly without quantitative evaluation. In rats intoxicated with tabun and treated with a combination of atropine and HI-6, obidoxime, or new oxime K048, AChE activities in different brain structures were determined using biochemical and quantitative histochemical methods. Inhibition of AChE following untreated tabun intoxication was different in the various brain structures, having the highest degree in the frontal cortex and reticular formation and lowest in the basal ganglia and substantia nigra. Treatment resulted in an increase of AChE activity detected by both methods. The highest increase was observed in the frontal cortex. This reactivation was increased in the order HI-6 < K048 < obidoxime; however, this order was not uniform for all brain parts studied. A correlation between AChE activity detected by histochemical and biochemical methods was demonstrated. The results suggest that for the mechanism of action of the nerve agent tabun, reactivation in various parts of the brain is not of the same physiological importance. AChE activity in the pontomedullar area and frontal cortex seems to be the most important for the therapeutic effect of the reactivators. HI-6 was not a good reactivator for the treatment of tabun intoxication. PMID:21054236

  17. Acetylene hydratase: a non-redox enzyme with tungsten and iron-sulfur centers at the active site.

    PubMed

    Kroneck, Peter M H

    2016-03-01

    In living systems, tungsten is exclusively found in microbial enzymes coordinated by the pyranopterin cofactor, with additional metal coordination provided by oxygen and/or sulfur, and/or selenium atoms in diverse arrangements. Prominent examples are formate dehydrogenase, formylmethanofuran dehydrogenase, and aldehyde oxidoreductase all of which catalyze redox reactions. The bacterial enzyme acetylene hydratase (AH) stands out of its class as it catalyzes the conversion of acetylene to acetaldehyde, clearly a non-redox reaction and a reaction distinct from the reduction of acetylene to ethylene by nitrogenase. AH harbors two pyranopterins bound to W, and a [4Fe-4S] cluster. W is coordinated by four dithiolene sulfur atoms, one cysteine sulfur, and one oxygen ligand. AH activity requires a strong reductant suggesting W(IV) as the active oxidation state. Two different types of reaction pathways have been proposed. The 1.26 Å structure reveals a water molecule coordinated to W which could gain a partially positive net charge by the adjacent protonated Asp-13, enabling a direct attack of C2H2. To access the W-Asp site, a substrate channel was evolved distant from where it is found in other members of the DMSOR family. Computational studies of this second shell mechanism led to unrealistically high energy barriers, and alternative pathways were proposed where C2H2 binds directly to W. The architecture of the catalytic cavity, the specificity for C2H2 and the results from site-directed mutagenesis do not support this first shell mechanism. More investigations including structural information on the binding of C2H2 are needed to present a conclusive answer. PMID:26790879

  18. Fabrication of a Selective and Sensitive Sensor Based on Molecularly Imprinted Polymer/Acetylene Black for the Determination of Azithromycin in Pharmaceuticals and Biological Samples

    PubMed Central

    Zhou, Tingting; Tao, Yun; Jin, Hua; Song, Bin; Jing, Tao; Luo, Dan; Zhou, Yusun; Zhou, Yikai; Lee, Yong-Ill; Mei, Surong

    2016-01-01

    A new selective and sensitive sensor based on molecularly imprinted polymer/acetylene black (MIP/AB) was developed for the determination of azithromycin (AZM) in pharmaceuticals and biological samples. The MIP of AZM was synthesized by precipitation polymerization. MIP and AB were then respectively introduced as selective and sensitive elements for the preparation of MIP/AB-modified carbon paste (MIP/ABP) electrode. The performance of the obtained sensor was estimated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. Compared with non-molecularly imprinted polymer (NIP) electrodes, NIP/ABP electrodes, and MIP-modified carbon paste electrodes, MIP/ABP electrode exhibited excellent current response toward AZM. The prepared sensor also exhibited good selectivity for AZM in comparison with structurally similar compounds. The effect of electrode composition, extraction parameters, and electrolyte conditions on the current response of the sensor was investigated. Under the optimized conditions, the prepared sensor showed two dynamic linear ranges of 1.0 × 10−7 mol L−1 to 2.0 × 10−6 mol L−1 and 2.0 × 10−6 mol L−1 to 2.0 × 10−5 mol L−1, with a limit of detection of 1.1 × 10−8 mol L−1. These predominant properties ensured that the sensor exhibits excellent reliability for detecting AZM in pharmaceuticals and biological fluids without the assistance of any separation techniques. The results were validated by the high-performance liquid chromatography–tandem mass spectrometry method. PMID:26820753

  19. Heat of Combustion of the Product Formed by the Reaction of Acetylene and Diborane (LFPL-CZ-3)

    NASA Technical Reports Server (NTRS)

    Allen, Harrison, Jr.; Tannenbaum, Stanley

    1957-01-01

    The heat of combustion of the product formed by the reaction acetylene and diborane was found to be 20,100 +/- 100 Btu per pound for the reaction of liquid fuel to gaseous carbon dioxide, gaseous water, and solid boric oxide. The measurements were made in a Parr oxygen-bomb calorimeter, and chemical analyses both of the sample and of the combustion products indicated combustion in the bomb calorimeter to have been 97 percent complete. The estimated net heat of combustion for complete combustion would therefore be 20,700 +/- 100 Btu per pound.

  20. Configurations of stereoisomers of 1-(3-phenylprop-2-ynyl)-2-methyldecahydroquinol-4-one and the corresponding acetylenic alcohols

    SciTech Connect

    Klepikova, S.G.; Tarakov, S.A.; Krasnomolova, L.P.; Praliev, K.D.; Agashkin, O.V.; Sokolov, D.V.

    1987-08-01

    IR and PMR spectroscopy and chemical methods have been used to establish the structures of stereoisomeric 1-(3-phenylprop-2-ynyl)-2-methyldecahydroquinol-4-ones and the corresponding acetylenic alcohols. In the PMR spectrum two quartets of protons are seen for C(/sub 3/) with /sup 3/JHH constants characteristic of the axial 2-H proton. Consequently, the methyl group is axially disposed. The signals for protons 9-H and 10-H fall within the resonance region of the C(/sub 3/) protons. Deuteration under keto-enol tautomeric conditions enabled the chemical shifts and the coupling constants of these protons to be measured.

  1. The electronic structure and second-order nonlinear optical properties of donor-acceptor acetylenes - A detailed investigation of structure-property relationships

    NASA Technical Reports Server (NTRS)

    Stiegman, A. E.; Graham, Eva; Khundkar, Lutfur R.; Perry, Joseph W.; Cheng, L.-T.; Perry, Kelly J.

    1991-01-01

    A series of donor-acceptor acetylene compounds was synthesized in which systematic changes in both the conjugation length and the donor-acceptor strength were made. The effect of these structural changes on the spectroscopic and electronic properties of the molecules and, ultimately, on the measured second-order molecular hyperpolarizabilities (beta) was investigated. It was found that increases in the donor-acceptor strength resulted in increases in the magnitude of beta. For this class of molecules, the increase is dominated by the energy of the intramolecular charge-transfer transition, while factors such as the ground to excited-state dipole moment change and the transition-moment integral are much less important. Increasing the conjugation length from one to two acetylene linkers did not result in an increase in the value of beta; however, beta increased sharply in going from two acetylenes to three. This increase is attributed to the superposition of several nearly isoenergetic excited states.

  2. Untangling the reaction dynamics of the silylidyne radical (SiH; X2Π) with acetylene (C2H2; X1Σg+)

    NASA Astrophysics Data System (ADS)

    Yang, Tao; Dangi, Beni B.; Thomas, Aaron M.; Kaiser, Ralf I.

    2016-06-01

    The chemical reaction dynamics of silylidyne (SiH; X2Π) with acetylene (C2H2; X1Σg+) were studied exploiting the crossed molecular beam approach, and compared with previous studies on D1-silylidyne with acetylene. The reaction is initiated by a barrierless addition of silylidyne to one or both carbons of acetylene leading to 1-sila-1-propene-1,3-diylidene and/or the cyclic 1-silacyclopropenyl with the former isomerizing to the latter. 1-Silacyclopropenyl eventually loses atomic hydrogen yielding silacyclopropenylidene (c-SiC2H2) in an overall exoergic reaction (experiment: -14.7 ± 8.5 kJ mol-1; theory: -13 ± 3 kJ mol-1). The enthalpy of formation for silacyclopropenylidene is determined to be 421.4 ± 9.3 kJ mol-1.

  3. Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymers

    NASA Technical Reports Server (NTRS)

    Clarke, D. W.; Ferris, J. P.

    1997-01-01

    The structure and morphological properties of polymers produced photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been examined to evaluate their possible contribution to the haze layers found on Titan. A structural analysis of these polymers may contribute to our understanding of the data returned from the Huygens probe of the Cassini mission that will pass through the atmosphere of Titan in the year 2004. Infrared analysis, elemental analysis, and thermal methods (thermogravimetric analysis, thermolysis, pyrolysis) were used to examine structures of polycyanoacetylenes produced by irradiation of the gas phase HC3N at 185 and 254 nm. The resulting brown to black polymer, which exists as small particles, is believed to be a branched chain of conjugated carbon-carbon double bonds, which, on exposure to heat, cyclizes to form a graphitic structure. Similar methods of analysis were used to show that when HC3N is photolyzed in the presence of Titan's other atmospheric constituents (CH4, C2H6, C2H2, and CO), a copolymer is formed in which the added gases are incorporated as substituents on the polymer chain. Of special significance is the copolymer of HC3N and acetylene (C2H2). Even in experiments where C2H2 was absorbing nearly all of the incident photons, the ratio of C2H2 to HC3N found in the resulting polymer was only 2:1. Scanning electron microscopy was used to visually examine the polymer particles. While pure polyacetylene particles are amorphous spheres roughly 1 micrometer in diameter, polycyanoacetylenes appear to be strands of rough, solid particles slightly smaller in size. The copolymer of HC3N and C2H2 exhibits characteristics of both pure polymers. This is particularly important as pure polyacetylenes do not match the optical constants measured for Titan's atmospheric hazes. The copolymers produced by the incorporation of other minor atmospheric constituents, like HC3N, into the polyacetylenes are expected to have

  4. Differential solubility of ethylene and acetylene in room-temperature ionic liquids: a theoretical study.

    PubMed

    Zhao, Xu; Xing, Huabin; Yang, Qiwei; Li, Rulong; Su, Baogen; Bao, Zongbi; Yang, Yiwen; Ren, Qilong

    2012-04-01

    The room-temperature ionic liquids (RTILs) have potential in realizing the ethylene (C(2)H(4)) and acetylene (C(2)H(2)) separation and avoiding solvent loss and environmental pollution compared with traditional solvents. The interaction mechanisms between gases and RTILs are important for the exploration of new RTILs for gas separation; thus, they were studied by quantum chemical calculation and molecular dynamics simulation in this work. The optimized geometries were obtained for the complexes of C(2)H(4)/C(2)H(2) with anions (Tf(2)N(-), BF(4)(-), and OAc(-)), cation (bmim(+)), and their ion pairs, and the analysis for geometry, interaction energy, natural bond orbital (NBO), and atoms in molecules (AIM) was performed. The quantum chemical calculation results show that the hydrogen-bonding interaction between the gas molecule and anion is the dominant factor in determining the solubility of C(2)H(2) in RTILs. However, the hydrogen-bonding interaction, the p-π interaction in C(2)H(4)-anion, and the π-π interaction in C(2)H(4)-cation are weak and comparable, which all affect the solubility of C(2)H(4) in RTILs with comparable contribution. The calculated results for the distance of H(gas)···X (X = O or F in anions), the BSSE-corrected interaction energy, the electron density of H(gas)···X at the bond critical point (ρ(BCP)), and the relative second-order perturbation stabilization energy (E(2)) are consistent with the experimental data that C(2)H(2) is more soluble than C(2)H(4) in the same RTILs and the solubility of C(2)H(4) in RTILs has the following order: [bmim][Tf(2)N] > [bmim][OAc] > [bmim][BF(4)]. The calculated results also agree with the order of C(2)H(2) solubility in different RTILs that [bmim][OAc] > [bmim][BF(4)] > [bmim][Tf(2)N]. Furthermore, the calculation results indicate that there is strong C(2)H(2)-RTIL interaction, which cannot be negligible compared to the RTIL-RTIL interaction; thus, the regular solution theory is probably not

  5. Adsorption and reaction of acetylene on clean and oxygen-precovered Pd(100) studied with high-resolution X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Höfert, O.; Lorenz, M. P. A.; Streber, R.; Zhao, W.; Bayer, A.; Steinrück, H.-P.; Papp, C.

    2013-10-01

    We investigated the adsorption and thermal evolution of acetylene on clean Pd(100) and Pd(100) precovered with 0.25 ML oxygen. The measurements were performed in situ by fast XPS at the synchrotron radiation facility BESSY II. On Pd(100) acetylene molecularly adsorbs at 130 K. Upon heating transformation to a CCH species occurs around 390 K along with the formation of a completely dehydrogenated carbon species. On the oxygen-precovered surface partial CCH formation already occurs upon adsorption at 130 K, and the dehydrogenation temperature and the stability range of CCH are shifted to lower temperatures by ˜200 K.

  6. Adsorption and reaction of acetylene on clean and oxygen-precovered Pd(100) studied with high-resolution X-ray photoelectron spectroscopy.

    PubMed

    Höfert, O; Lorenz, M P A; Streber, R; Zhao, W; Bayer, A; Steinrück, H-P; Papp, C

    2013-10-28

    We investigated the adsorption and thermal evolution of acetylene on clean Pd(100) and Pd(100) precovered with 0.25 ML oxygen. The measurements were performed in situ by fast XPS at the synchrotron radiation facility BESSY II. On Pd(100) acetylene molecularly adsorbs at 130 K. Upon heating transformation to a CCH species occurs around 390 K along with the formation of a completely dehydrogenated carbon species. On the oxygen-precovered surface partial CCH formation already occurs upon adsorption at 130 K, and the dehydrogenation temperature and the stability range of CCH are shifted to lower temperatures by ∼200 K. PMID:24182063

  7. Relative rates of coke formation from hydrocarbons in steam cracking of naphtha. 2. Paraffins, naphthenes, mono-, di-, and cycloolefins, and acetylenes

    SciTech Connect

    Kopinke, F.D. ); Zimmermann, G. ); Reyniers, G.C.; Froment, G.F. )

    1993-01-01

    Relative rate constants of coke formation from saturated hydrocarbons, olefins, and acetylenes during steam cracking of naphtha at 810 C were determined by application of [sup 14]C-labeled compounds. The range of hydrocarbons investigated comprises 20 representatives of paraffins, from methane to hexadecane, and of naphthenes, from cyclopentane to hydroanthracene, and 20 olefins from ethene to styrene, including cyclo- and diolefins, and five acetylenes. Carbonaceous deposits in pyrolysis reactors from steel and quartz as well as in the transfer line exchange (TLE) section were determined separately.

  8. Stimulation and inhibition of bacterial growth by caffeine dependent on chloramphenicol and a phenolic uncoupler--a ternary toxicity study using microfluid segment technique.

    PubMed

    Cao, Jialan; Kürsten, Dana; Schneider, Steffen; Köhler, J Michael

    2012-10-01

    A droplet-based microfluidic technique for the fast generation of three dimensional concentration spaces within nanoliter segments was introduced. The technique was applied for the evaluation of the effect of two selected antibiotic substances on the toxicity and activation of bacterial growth by caffeine. Therefore a three-dimensional concentration space was completely addressed by generating large sequences with about 1150 well separated microdroplets containing 216 different combinations of concentrations. To evaluate the toxicity of the ternary mixtures a time-resolved miniaturized optical double endpoint detection unit using a microflow-through fluorimeter and a two channel microflow-through photometer was used for the simultaneous analysis of changes on the endogenous cellular fluorescence signal and on the cell density of E. coli cultivated inside 500 nL microfluid segments. Both endpoints supplied similar results for the dose related cellular response. Strong non-linear combination effects, concentration dependent stimulation and the formation of activity summits on bolographic maps were determined. The results reflect a complex response of growing bacterial cultures in dependence on the combined effectors. A strong caffeine induced enhancement of bacterial growth was found at sublethal chloramphenicol and sublethal 2,4-dinitrophenol concentrations. The reliability of the method was proved by a high redundancy of fluidic experiments. The results indicate the importance of multi-parameter investigations for toxicological studies and prove the potential of the microsegmented flow technique for such requirements. PMID:22888747

  9. Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene

    SciTech Connect

    Xiang, Sheng-Chang; Zhang, Zhangjing; Zhao, Cong-Gui; Hong, Kunlun; Zhao, Xuebo; Ding, De-Rong; Xie, Ming-Hua; Wu, Chuan-De; Madhab, Das; Gill, Rachel; Thomas, K Mark; Chen, Banglin

    2011-01-01

    Separation of acetylene and ethylene is an important industrial process because both compounds are essential reagents for a range of chemical products and materials. Current separation approaches include the partial hydrogenation of acetylene into ethylene over a supported Pd catalyst, and the extraction of cracked olefins using an organic solvent; both routes are costly and energy consuming. Adsorption technologies may allow separation, but microporous materials exhibiting highly selective adsorption of C{sub 2}H{sub 2}/C{sub 2}H{sub 4} have not been realized to date. Here, we report the development of tunable microporous enantiopure mixed-metal-organic framework (M'MOF) materials for highly selective separation of C{sub 2}H{sub 2} and C{sub 2}H{sub 4}. The high selectivities achieved suggest the potential application of microporous M'MOFs for practical adsorption-based separation of C{sub 2}H{sub 2}/C{sub 2}H{sub 4}.

  10. Forming a Two-Ring Polycyclic Aromatic Hydrocarbon without a Benzene Intermediate: the Reaction of Propargyl with Acetylene

    NASA Astrophysics Data System (ADS)

    Osborn, David; Savee, John; Selby, Talitha; Welz, Oliver; Taatjes, Craig

    The reaction of acetylene (HCCH) with a resonance-stabilized free radical is a commonly invoked mechanism for the generation of polycyclic aromatic hydrocarbons (PAH), which are likely precursors of soot particles in combustion. In this work, we examine the sequential addition of acetylene to the propargyl radical (H2CCCH) at temperatures of 800 and 1000 K. Using time-resolved multiplexed photoionization mass spectrometry with tunable ionizing radiation, we identified the isomeric forms of the C5H5 and C7H7 intermediates in this reaction sequence, and confirmed that the final C9H8 product is the two-ring aromatic compound indene. We identified two different resonance-stabilized C5H5 intermediates, with different temperature dependencies. Furthermore, the C7H7 intermediate is the tropyl radical (c-C7H7) , not the benzyl radical (C6H5CH2) , as is usually assumed in combustion environments. These experimental results are in general agreement with the latest electronic structure / master equation results of da Silva et al. This work shows a pathway for PAH formation that bypasses benzene / benzyl intermediates.

  11. In situ TDLAS measurement of absolute acetylene concentration profiles in a non-premixed laminar counter-flow flame

    NASA Astrophysics Data System (ADS)

    Wagner, S.; Klein, M.; Kathrotia, T.; Riedel, U.; Kissel, T.; Dreizler, A.; Ebert, V.

    2012-06-01

    Acetylene (C2H2), as an important precursor for chemiluminescence species, is a key to understand, simulate and model the chemiluminescence and the related reaction paths. Hence we developed a high resolution spectrometer based on direct Tunable Diode Laser Absorption Spectroscopy (TDLAS) allowing the first quantitative, calibration-free and spatially resolved in situ C2H2 measurement in an atmospheric non-premixed counter-flow flame supported on a Tsuji burner. A fiber-coupled distributed feedback diode laser near 1535 nm was used to measure several absolute C2H2 concentration profiles (peak concentrations up to 9700 ppm) in a laminar non-premixed CH4/air flame ( T up to 1950 K) supported on a modified Tsuji counter-flow burner with N2 purge slots to minimize end flames. We achieve a fractional optical resolution of up to 5×10-5 OD (1 σ) in the flame, resulting in temperature-dependent acetylene detection limits for the P17e line at 6513 cm-1 of up to 2.1 ppmṡm. Absolute C2H2 concentration profiles were obtained by translating the burner through the laser beam using a DC motor with 100 μm step widths. Intercomparisons of the experimental C2H2 profiles with simulations using our new hydrocarbon oxidation mechanisms show excellent agreement in position, shape and in the absolute C2H2 values.

  12. Infrared spectra reveal box-like structures for a pentamer and hexamer of mixed carbon dioxide-acetylene clusters.

    PubMed

    Rezaei, Mojtaba; Norooz Oliaee, J; Moazzen-Ahmadi, N; McKellar, A R W

    2016-01-21

    Except for a few cases like water and carbon dioxide, identification and structural characterization of clusters with more than four monomers is rare. Here, we provide experimental and theoretical evidence for existence of box-like structures for a pentamer and a hexamer of mixed carbon dioxide-acetylene clusters. Two mid-infrared cluster absorption bands are observed in the CO2ν3 band region using a tunable diode laser to probe a pulsed supersonic jet. Each requires the presence of both carbon dioxide and acetylene in the jet, and (from observed rotational spacings) involves clusters containing about 4 to 7 molecules. Structures are predicted for mixed CO2 + C2H2 clusters using a distributed multipole model, and the bands are assigned to a specific pentamer, (CO2)3-(C2H2)2, and hexamer, (CO2)4-(C2H2)2. The hexamer has a box-like structure whose D2d symmetry is supported by observed intensity alternation in the spectrum. The pentamer has a closely related structure which is obtained by removing one CO2 molecule from the hexamer. These are among the largest mixed molecular clusters to be assigned by high-resolution spectroscopy. PMID:26315679

  13. Chemical inhibition of potato ABA-8'-hydroxylase activity alters in vitro and in vivo ABA metabolism and endogenous ABA levels but does not affect potato microtuber dormancy duration.

    PubMed

    Suttle, Jeffrey C; Abrams, Suzanne R; De Stefano-Beltrán, Luis; Huckle, Linda L

    2012-09-01

    The effects of azole-type P450 inhibitors and two metabolism-resistant abscisic acid (ABA) analogues on in vitro ABA-8'-hydroxylase activity, in planta ABA metabolism, endogenous ABA content, and tuber meristem dormancy duration were examined in potato (Solanum tuberosum L. cv. Russet Burbank). When functionally expressed in yeast, three potato CYP707A genes were demonstrated to encode enzymatically active ABA-8'-hydroxylases with micromolar affinities for (+)-ABA. The in vitro activity of the three enzymes was inhibited by the P450 azole-type inhibitors ancymidol, paclobutrazol, diniconazole, and tetcyclasis, and by the 8'-acetylene- and 8'-methylene-ABA analogues, with diniconazole and tetcyclasis being the most potent inhibitors. The in planta metabolism of [(3)H](±)-ABA to phaseic acid and dihydrophaseic acid in tuber meristems was inhibited by diniconazole, tetcyclasis, and to a lesser extent by 8'-acetylene- and 8'-methylene-ABA. Continuous exposure of in vitro generated microtubers to diniconazole resulted in a 2-fold increase in endogenous ABA content and a decline in dihydrophaseic acid content after 9 weeks of development. Similar treatment with 8'-acetylene-ABA had no effects on the endogenous contents of ABA or phaseic acid but reduced the content of dihydrophaseic acid. Tuber meristem dormancy progression was determined ex vitro in control, diniconazole-, and 8'-acetylene-ABA-treated microtubers following harvest. Continuous exposure to diniconazole during microtuber development had no effects on subsequent sprouting at any time point. Continuous exposure to 8'-acetylene-ABA significantly increased the rate of microtuber sprouting. The results indicate that, although a decrease in ABA content is a hallmark of tuber dormancy progression, the decline in ABA levels is not a prerequisite for dormancy exit and the onset of tuber sprouting. PMID:22664582

  14. The small-scale production of [U-14C]acetylene from Ba14CO3: application to labeling of ammonia monooxygenase in autotrophic nitrifying bacteria.

    PubMed

    Hyman, M R; Arp, D J

    1990-11-01

    A small-scale method has been adapted from an established procedure for the generation of [U-14C]acetylene from inexpensive and commonly available precursors. The method involves the fusing of Ba14CO3 with excess barium metal to produce Ba14C2. The BaC2 is reacted with water to generate acetylene which is then selectively dissolved into dimethyl sulfoxide (DMSO). The results presented demonstrate the effect of Ba:BaCO3 ratio on the concentrations of various gases released during the hydrolysis reaction and quantify the selectivity of the DMSO-trapping process for each gas. [U-14C]Acetylene generated by this method has been used to inactivate ammonia monooxygenase in three species of autotrophic nitrifying bacteria: Nitrosomonas europaea, Nitrosococcus oceanus, and Nitrosolobus multiformis. Our results demonstrate that acetylene inactivation of this enzyme in all three species results in the covalent incorporation of radioactive label into a polypeptide of apparent Mr of 25,000-27,000, as determined by sodium dodecylsulfate-polyacrylamide gel electrophoresis and fluorography. PMID:2291478

  15. Indole synthesis by conjugate addition of anilines to activated acetylenes and an unusual ligand-free copper(II)-mediated intramolecular cross-coupling.

    PubMed

    Gao, Detian; Back, Thomas G

    2012-11-12

    A versatile new synthesis of indoles was achieved by the conjugate addition of N-formyl-2-haloanilines to acetylenic sulfones, ketones, and esters followed by a copper-catalyzed intramolecular C-arylation. The conjugate addition step was conducted under exceptionally mild conditions at room temperature in basic, aqueous DMF. Surprisingly, the C-arylation was performed most effectively by employing copper(II) acetate as the catalyst in the absence of external ligands, without the need for protection from air or water. An unusual feature of this process, for the case of acetylenic ketones, is the ability of the initial conjugate-addition product to serve as a ligand for the catalyst, which enables it to participate in the catalysis of its further transformation to the final indole product. Mechanistic studies, including EPR experiments, indicated that copper(II) is reduced to the active copper(I) species by the formate ion that is produced by the base-catalyzed hydrolysis of DMF. This process also served to recycle any copper(II) that was produced by the adventitious oxidation of copper(I), thereby preventing deactivation of the catalyst. Several examples of reactions involving acetylenic sulfones attached to a modified Merrifield resin demonstrated the feasibility of solid-phase synthesis of indoles by using this protocol, and tricyclic products were obtained in one pot by employing acetylenic sulfones that contain chloroalkyl substituents. PMID:23019064

  16. Just Click It: Undergraduate Procedures for the Copper(I)-Catalyzed Formation of 1,2,3-Triazoles from Azides and Terminal Acetylenes

    ERIC Educational Resources Information Center

    Sharpless, William D.; Peng Wu; Hansen, Trond Vidar; Lindberg, James G.

    2005-01-01

    The click chemistry uses only the most reliable reactions to build complex molecules from olefins, electrophiles and heteroatom linkers. A variation on Huisgen's azide-alkyne 1,2,3-triazole synthesis, the addition of the copper (I), the premium example of the click reaction, catalyst strongly activates terminal acetylenes towards the 1,3-dipole in…

  17. A Model for Self-Assembly of Carbon Nanotubes from Acetylene Based on Real-Time Studies of Vertically Aligned Growth Kinetics

    SciTech Connect

    Eres, Gyula

    2009-01-01

    Time-resolved optical reflectivity was used to study the kinetics in the early stages of vertically aligned carbon nanotube array growth from a molecular beam of acetylene. The molecular beam environment was used to suppress gas phase reaction pathways and limit the growth to surface reactions specific to the molecular structure of acetylene. The observed acetylene flux dependent induction delay and the threshold for vertically aligned growth are characteristic features of heterogeneous chain reactions. Propagation of chain reactions requires regeneration of the active sites that can occur only if catalytic activity is transferred from the metal catalyst film to surface carbon species. After the active site transformation, acetylene self-assembles into carbon structures of progressively increasing size such as chains, graphene fragments, and nanotubes. In this paper we show that a conceptual framework supported by ab initio density functional theory calculations in which active carbon species facilitate incorporation of new carbon readily explains recent results in vertically aligned nanotube growth that are puzzling in the context of the diffusion/precipitation model.

  18. Intramolecular competition between n-pair and π-pair hydrogen bonding: Microwave spectrum and internal dynamics of the pyridine–acetylene hydrogen-bonded complex

    SciTech Connect

    Mackenzie, Rebecca B.; Dewberry, Christopher T.; Leopold, Kenneth R. E-mail: david.tew@bristol.ac.uk; Coulston, Emma; Cole, George C.; Legon, Anthony C. E-mail: david.tew@bristol.ac.uk Tew, David P. E-mail: david.tew@bristol.ac.uk

    2015-09-14

    a-type rotational spectra of the hydrogen-bonded complex formed from pyridine and acetylene are reported. Rotational and {sup 14}N hyperfine constants indicate that the complex is planar with an acetylenic hydrogen directed toward the nitrogen. However, unlike the complexes of pyridine with HCl and HBr, the acetylene moiety in HCCH—NC{sub 5}H{sub 5} does not lie along the symmetry axis of the nitrogen lone pair, but rather, forms an average angle of 46° with the C{sub 2} axis of the pyridine. The a-type spectra of HCCH—NC{sub 5}H{sub 5} and DCCD—NC{sub 5}H{sub 5} are doubled, suggesting the existence of a low lying pair of tunneling states. This doubling persists in the spectra of HCCD—NC{sub 5}H{sub 5}, DCCH—NC{sub 5}H{sub 5}, indicating that the underlying motion does not involve interchange of the two hydrogens of the acetylene. Single {sup 13}C substitution in either the ortho- or meta-position of the pyridine eliminates the doubling and gives rise to separate sets of spectra that are well predicted by a bent geometry with the {sup 13}C on either the same side (“inner”) or the opposite side (“outer”) as the acetylene. High level ab initio calculations are presented which indicate a binding energy of 1.2 kcal/mol and a potential energy barrier of 44 cm{sup −1} in the C{sub 2v} configuration. Taken together, these results reveal a complex with a bent hydrogen bond and large amplitude rocking of the acetylene moiety. It is likely that the bent equilibrium structure arises from a competition between a weak hydrogen bond to the nitrogen (an n-pair hydrogen bond) and a secondary interaction between the ortho-hydrogens of the pyridine and the π electron density of the acetylene.

  19. Direct measurements of collisional Raman line broadening in the S-branch transitions of acetylene (C2H2)

    NASA Astrophysics Data System (ADS)

    Hsu, Paul S.; Stauffer, Hans U.; Jiang, Naibo; Gord, James R.; Roy, Sukesh

    2013-10-01

    We report direct measurements of the self- and N2-broadened Raman S-branch linewidths of acetylene (C2H2), obtained by employing time-resolved picosecond rotational coherent anti-Stokes Raman scattering spectroscopy. Using broadband 115-ps pump and Stokes pulses (˜135 cm-1 bandwidth) and a spectrally narrowed 90-ps probe pulse (˜0.2 cm-1 bandwidth), Raman-coherence lifetimes are measured at room temperature for the S-branch (ΔJ = +2) transitions associated with rotational quantum number J = 3-25. These directly measured Raman-coherence lifetimes, when converted to collisional linewidth broadening coefficients, differ from the previously reported broadening coefficients extracted from theoretical calculations by 6%-35% for self-broadening for C2H2 and by up to 60% for N2-broadened C2H2.

  20. Two-wavelength interferometer based on sinusoidal phase modulation with an acetylene stabilized laser and a second harmonic generation.

    PubMed

    Kawata, Yoshiyuki; Hyashi, Kyohei; Aoto, Tomohiro

    2015-06-15

    A two-wavelength interferometer (TWI) based on a sinusoidal-phase-modulation method with an acetylene stabilized laser and a second harmonic generation (SHG) was developed. The periodic non-linearity error for the TWI was estimated to be ± 0.1 µm at a dead path of 0.32 m. A long-term measurement showed that the TWI stability was ± 3 × 10(-7) at a dead path of 1.00 m for 12 hours with an ambient pressure variation of 3 hPa under controlled conditions of ambient temperature and humidity. Finally, we confirmed that the TWI has substantially better stability than a single-wavelength interferometer by comparing both interferometers with large temporal and spatial temperature variations. PMID:26193576

  1. Vibration-rotation spectroscopic database on acetylene, X ˜ 1 Σg + (12C2H2)

    NASA Astrophysics Data System (ADS)

    Amyay, B.; Fayt, A.; Herman, M.; Vander Auwera, J.

    2016-06-01

    A complete set of calculated vibration-rotation energies of 12C2H2 ( X ˜ 1 Σg + ) is provided for all vibrational states up to 13 000 cm-1 and some at higher energies, with rotational (J) and vibrational angular momentum (l) quantum numbers such that 0 ≤ J ≤ 100 and 0 ≤ |l| ≤ 20, respectively. The calculation is performed using a global effective Hamiltonian and related spectroscopic constants from the literature [B. Amyay et al., J. Mol. Spectrosc. 267, 80 (2011)], based on the polyad model. The numerical values of all related polyad matrix elements are also provided. The model and equations for the Hamiltonian matrix elements are gathered. The experimental acetylene database used for determining the parameters is listed.

  2. The discovery of the [2{sub s}+2{sub a}] reaction of dislanes and acetylenes and their applications

    SciTech Connect

    Za, Zhongxin; Barton, T.J.; Lin, Jibing; Gordon, M. |

    1997-12-31

    A concerted [2{sub s}+2{sub a}] intramolecular addition reaction was discovered between disilanes and acetylenes in unimolecular process. The reaction was performed with the 5,5,6,6-tetramethyl-3,3,8,8-tetraphenyl-4,7-dioxa-5,6-disilyl-cyclooctyne (1) under an argon flow at 600{degrees}C to give product 1,1,4,4-tetramethyl-3,3,6,6-tetraphenyl-2,5-dioxa-1,4-disilyl-dicyclo[3,3,0]octa-7-ene (2). Ab initio calculations were performed at the MP4/6-31G** level. The transition state structure was found and the activation energy was calculated to be 34 kcal/mol. The first example of a 3,3{prime}-disilyl-indeno[2,1-a]indene (4) was synthesized from dibenzo-5,6-disilylcyclooctyne (3) in the same manner.

  3. Indenyl effect due to metal slippage? Computational exploration of rhodium-catalyzed acetylene [2+2+2] cyclotrimerization.

    PubMed

    Orian, Laura; Swart, Marcel; Bickelhaupt, F Matthias

    2014-01-13

    The mechanism of CpRh (Cp=cyclopentadienyl) and IndRh (Ind=indenyl)-catalyzed acetylene [2+2+2] cyclotrimerization has been revisited aiming at finding an explanation for the better performance of the latter catalyst found experimentally. The hypothesis that an ancillary ligand of the precatalyst remains bonded to the metal center throughout the whole catalytic cycle, based on the experimental evidence that the nature of this ligand can exert some control in cocyclotrimerization of different alkynes, is considered. Strong hapticity variations occur in both the CpRh- and IndRh-catalyzed processes. As the Ind ligand undergoes a more facile slippage than Cp, the energy profile is far smoother in the IndRh-catalyzed cyclotrimerization. This difference in the energetics of the process translates into an enhanced activity of the IndRh catalyst, in nice agreement with experiment. PMID:24273097

  4. The Breathing Orbital Valence Bond Method in Diffusion Monte Carlo: C-H Bond Dissociation ofAcetylene

    SciTech Connect

    Domin, D.; Braida, Benoit; Lester Jr., William A.

    2008-05-30

    This study explores the use of breathing orbital valence bond (BOVB) trial wave functions for diffusion Monte Carlo (DMC). The approach is applied to the computation of the carbon-hydrogen (C-H) bond dissociation energy (BDE) of acetylene. DMC with BOVB trial wave functions yields a C-H BDE of 132.4 {+-} 0.9 kcal/mol, which is in excellent accord with the recommended experimental value of 132.8 {+-} 0.7 kcal/mol. These values are to be compared with DMC results obtained with single determinant trial wave functions, using Hartree-Fock orbitals (137.5 {+-} 0.5 kcal/mol) and local spin density (LDA) Kohn-Sham orbitals (135.6 {+-} 0.5 kcal/mol).

  5. Wavelength modulation spectroscopy at 1530.32 nm for measurements of acetylene based on Fabry-Perot tunable filter

    NASA Astrophysics Data System (ADS)

    Yun-Long, Li; Bing-Chu, Yang; Xue-Mei, Xu

    2016-02-01

    Sensitive detection of acetylene (C2H2) is performed by absorption spectroscopy and wavelength modulation spectroscopy (WMS) based on Fiber Fabry-Perot tunable filter (FFP-TF) at 1530.32 nm. After being calibrated by Fiber Bragg Grating (FBG), FFP-TF is frequency-multiplexed and modulated at 20 Hz and 2.5 kHz respectively to achieve wavelength modulation. The linearity with 0.9907 fitting coefficient is obtained by measuring different concentrations in a 100 ppmv-400 ppmv range. Furthermore, the stability of the system is analyzed by detecting 50 ppmv and 100 ppmv standard gases for 2 h under room temperature and ambient pressure conditions respectively. The precision of 11 ppmv is achieved by calculating the standard deviation. Therefore, the measuring system of C2H2 detection can be applied in practical applications. Project supported by the National Natural Science Foundation of China (Grant Nos. 61172047 and 61071025).

  6. Trapping aryl radicals with acetylene: Evidence for C{sub 2}-accretion as a mechanism for polycyclic aromatic hydrocarbon growth

    SciTech Connect

    Necula, A.; Scott, L.T.

    2000-02-23

    The formation of polycyclic aromatic hydrocarbons (PAH), fullerenes, soot, and other carbonaceous materials during the combustion or pyrolysis of low-molecular weight hydrocarbons requires, at a minimum, that small molecules and/or reactive intermediates somehow become joined to make larger ones. Most likely, more than one type of intermolecular C-C bond-forming reaction plays a role. The accretion of C{sub 2}-units has long been considered a probable pathway for the stepwise growth of PAH in flames, but evidence also points to the operation of bimolecular processes in which both partners can be relatively large. The experiments reported here address the former paradigm and provide clear support for a specific C{sub 2}-accretion pathway in which the key C-C bond-forming step involves the simple trapping of aryl radicals by acetylene (C{sub 2}H{sub 2}), both of which are abundant species in flames.

  7. Full-dimensional quantum dynamics study of vinylidene-acetylene isomerization: a scheme using the normal mode Hamiltonian.

    PubMed

    Ren, Yinghui; Li, Bin; Bian, Wensheng

    2011-02-14

    Full-dimensional quantum dynamics calculations of vinylidene-acetylene isomerization are performed and the state-specific resonance decay lifetimes of vinylidene(-d(2)) are computed. The theoretical scheme is a combination of several methods: normal coordinates are chosen to describe the nuclear motion of vinylidene, with both the parity and permutation symmetry exploited; phase space optimization in combination with physical considerations is used to generate an efficient discrete variable representation; the reaction coordinate is defined by us according to the three most relevant normal coordinates, along which a kind of optimal complex absorbing potential is imposed; the preconditioned inexact spectral transform method combined with an efficient preconditioner is employed to extract the energies and lifetimes of vinylidene. The overall computation is efficient. The computed energy levels generally agree with experiment well, and several state-specific lifetimes are reported for the first time. PMID:21186383

  8. ABSORPTION CROSS SECTION OF GASEOUS ACETYLENE AT 85 K IN THE WAVELENGTH RANGE 110-155 nm

    SciTech Connect

    Cheng, Bing-Ming; Chen, Hui-Fen; Lu, Hsiao-Chi; Chen, Hong-Kai; Alam, M. S.; Chou, Sheng-Lung; Lin, Meng-Yeh

    2011-09-01

    Absorption spectra and absorption cross sections of gaseous acetylene, C{sub 2}H{sub 2}, at 298 and 85 K were measured in the wavelength range 110-155 nm with a slit-jet system coupled to a synchrotron as a source of vacuum ultraviolet light. Using published spectral parameters of C{sub 2}H{sub 2}, we simulated the absorption profile for the Rydberg transition to state 4R{sub 0} in the range 124.6-125.1 nm, according to which the temperature of the jet-expanded sample at stagnation pressure 200 Torr is 85 {+-} 5 K. Our cross sections of C{sub 2}H{sub 2} are applicable for determining properties sensitive to temperature for diagnostic work on Saturn and Titan.

  9. Fabrication and Characterization of Nanocarbon-Based Nanofluids by Using an Oxygen-Acetylene Flame Synthesis System.

    PubMed

    Teng, Tun-Ping; Wang, Wei-Ping; Hsu, Yu-Chun

    2016-12-01

    In this study, an oxygen-acetylene flame synthesis system was developed to fabricate nanocarbon-based nanofluids (NCBNFs) through a one-step synthesis method. Measured in liters per minute (LPM), the flame's fuel flows combined oxygen and acetylene at four ratios: 1.5/2.5 (P1), 1.0/2.5 (P2), 0.5/2.5 (P3), and 0/2.5 (P4). The flow rate of cooling water (base fluid) was fixed at 1.2 LPM to produce different nanocarbon-based materials (NCBMs) and various concentrations of NCBNFs. Tests and analyses were conducted for determining the morphology of NCBMs, NCBM material, optical characteristics, the production rate, suspension performance, average particle size, zeta potential, and other relevant basic characteristics of NCBNFs to understand the characteristics and materials of NCBNFs produced through different process parameters (P1-P4). The results revealed that the NCBMs mainly had flaky and spherical morphologies and the diameters of the spherical NCBMs measured approximately 20-30 nm. X-ray diffraction and Raman spectroscopy revealed that the NCBMs contained graphene oxide (GO) and amorphous carbon (AC) when the oxygen flow rate was lower than 1.0 LPM. In addition, the NCBMs contained reduced GO, crystalline graphite (graphite-2H), and AC when the oxygen flow rate was higher than 1.0 LPM. The process parameters of P1, P2, P3, and P4 resulted in NCBMs produced at concentrations of 0.010, 0.013, 0.040, and 0.023 wt%, respectively, in NCBNFs. All the NCBNFs exhibited non-Newtonian and shear-thinning rheological properties. The P4 ratio showed the highest enhancement rate of thermal conductivity for NCBNFs, at a rate 4.85 % higher than that of water. PMID:27295256

  10. Fabrication and Characterization of Nanocarbon-Based Nanofluids by Using an Oxygen-Acetylene Flame Synthesis System

    NASA Astrophysics Data System (ADS)

    Teng, Tun-Ping; Wang, Wei-Ping; Hsu, Yu-Chun

    2016-06-01

    In this study, an oxygen-acetylene flame synthesis system was developed to fabricate nanocarbon-based nanofluids (NCBNFs) through a one-step synthesis method. Measured in liters per minute (LPM), the flame's fuel flows combined oxygen and acetylene at four ratios: 1.5/2.5 (P1), 1.0/2.5 (P2), 0.5/2.5 (P3), and 0/2.5 (P4). The flow rate of cooling water (base fluid) was fixed at 1.2 LPM to produce different nanocarbon-based materials (NCBMs) and various concentrations of NCBNFs. Tests and analyses were conducted for determining the morphology of NCBMs, NCBM material, optical characteristics, the production rate, suspension performance, average particle size, zeta potential, and other relevant basic characteristics of NCBNFs to understand the characteristics and materials of NCBNFs produced through different process parameters (P1-P4). The results revealed that the NCBMs mainly had flaky and spherical morphologies and the diameters of the spherical NCBMs measured approximately 20-30 nm. X-ray diffraction and Raman spectroscopy revealed that the NCBMs contained graphene oxide (GO) and amorphous carbon (AC) when the oxygen flow rate was lower than 1.0 LPM. In addition, the NCBMs contained reduced GO, crystalline graphite (graphite-2H), and AC when the oxygen flow rate was higher than 1.0 LPM. The process parameters of P1, P2, P3, and P4 resulted in NCBMs produced at concentrations of 0.010, 0.013, 0.040, and 0.023 wt%, respectively, in NCBNFs. All the NCBNFs exhibited non-Newtonian and shear-thinning rheological properties. The P4 ratio showed the highest enhancement rate of thermal conductivity for NCBNFs, at a rate 4.85 % higher than that of water.

  11. Nitrate inhibition of legume nodule growth and activity. I. Long term studies with a continuous supply of nitrate

    SciTech Connect

    Streeter, J.G.

    1985-02-01

    The synthesis and accumulation of nitrite has been suggested as a causative factor in the inhibition of legume nodules supplied with nitrate. Plants were grown in sand culture with a moderate level of nitrate (2.1 to 6.4 millimolar) supplied continuously from seed germination to 30 to 50 days after planting. In a comparison of nitrate treatments, a highly significant negative correlation between nitrite concentration in soybean (Glycine max (L.) Merr.) nodules and nodule fresh weight per shoot dry weight was found even when bacteroids lacked nitrate reductase (NR). However, in a comparison of two Rhizobium japonicum strains, there was only 12% as much nitrite in nodules formed by NR/sup -/ R. japonicum as in nodules formed by NR/sup +/ R. japonicum, and growth and acetylene reduction activity of both types of nodules was about equally inhibited. The very small concentration of nitrite found in P. vulgaris nodules was probably below that required for the inhibition of nitrogenase based on published in vitro experiments, and yet the specific acetylene reduction activity was inhibited 83% by nitrate. The overall results do not support the idea that nitrite plays a role in the inhibition of nodule growth and nitrogenase activity by nitrate.

  12. [Optimization on slow-release inhibition of biomethane and the kinetics model of diffusion].

    PubMed

    Zhang, Li-jie; Zhao, Tian-tao; Zhao, You-cai; Deng, Yu-ping

    2010-07-01

    The diffusion mechanism of acetylene,which can inhibit the activity of methanogens, was studied. Paraffin wax and rosin were used as matrix of slow-release and calcium carbide was used as inhibition material. Based on the T. Higuchi equation and the characteristics of slow-release inhibitors, a mechanism model was derived. Moreover, the effective diffusion coefficients (De) can be acquired by this model. During the diffusion process, the reaction heat of calcium carbide and water could make acetylene gas expansion and caused the slow-release inhibitors expansion if the hardness of the slow-release inhibitors is inadequate. The hardness and compactness were enhanced and the effective diffusion coefficients reached 2.2849 x 10(-8) cm2/min (R2 = 0.9901) when the mass faction of rosin was 20% and the mass ratio of matrix to calcium carbide was 1/1. Hence,the mitigation the methane generation with municipal solid waste (MSW) can be achieved by the technology of slow-release inhibition. PMID:20825047

  13. Bioassay-directed isolation and identification of phytotoxic and fungitoxic acetylenes from Conyza canadensis.

    PubMed

    Queiroz, Sonia C N; Cantrell, Charles L; Duke, Stephen O; Wedge, David E; Nandula, Vijay K; Moraes, Rita M; Cerdeira, Antonio L

    2012-06-13

    Conyza canadensis (L.) Cronquist syn. (horseweed) is a problematic and invasive weed with reported allelopathic properties. To identify the phytotoxic constituents of the aerial parts, a systematic bioactivity-guided fractionation of the dichloromethane extract was performed. Three active enyne derivatives, (2Z,8Z)-matricaria acid methyl ester, (4Z,8Z)-matricaria lactone, and (4Z)-lachnophyllum lactone, were identified. The lactones inhibited growth of the monocot Agrostis stolonifera (bentgrass) and the dicot Lactuca sativa (lettuce) at 1 mg mL(-1), while the (2Z,8Z)-matricaria acid methyl ester was less active. In a dose-response screening of the lactones for growth inhibitory activity against Lemna paucicostata , (4Z)-lachnophyllum lactone was the most active with an IC50 of 104 μM, while the (4Z,8Z)-matricaria lactone was less active (IC50 of 220 μM). In a fungal direct bioautography assay, the two lactones at 10 and 100 μg/spot inhibited growth of the plant pathogenic fungi Colletotrichum acutatum , Colletotrichum fragariae , and Colletotrichum gloeosporioides . In a dose-response screening of the lactones against six different plant pathogenic fungi, (4Z,8Z)-matricaria lactone was more active than the commercial fungicide azoxystrobin on Col. acutatum , Col. fragariae , and Col. gloeosporioides at 30 μM and about as active as the commercial fungicide captan against Col. gloeosporioides , while (4Z)-lachnophyllum lactone was less active. PMID:22612410

  14. Effect of Au nano-particle aggregation on the deactivation of the AuCl3/AC catalyst for acetylene hydrochlorination.

    PubMed

    Dai, Bin; Wang, Qinqin; Yu, Feng; Zhu, Mingyuan

    2015-01-01

    A detailed study of the valence state and distribution of the AuCl3/AC catalyst during the acetylene hydrochlorination deactivation process is described and discussed. Temperature-programmed reduction and X-ray photoelectron spectral analysis indicate that the active Au(3+) reduction to metallic Au(0) is one reason for the deactivation of AuCl3/AC catalyst. Transmission electron microscopy characterization demonstrated that the particle size of Au nano-particles increases with increasing reaction time. The results indicated that metallic Au(0) exhibits considerable catalytic activity and that Au nano-particle aggregation may be another reason for the AuCl3/AC catalytic activity in acetylene hydrochlorination. PMID:25994222

  15. Effect of Au nano-particle aggregation on the deactivation of the AuCl3/AC catalyst for acetylene hydrochlorination

    PubMed Central

    Dai, Bin; Wang, Qinqin; Yu, Feng; Zhu, Mingyuan

    2015-01-01

    A detailed study of the valence state and distribution of the AuCl3/AC catalyst during the acetylene hydrochlorination deactivation process is described and discussed. Temperature-programmed reduction and X-ray photoelectron spectral analysis indicate that the active Au3+ reduction to metallic Au0 is one reason for the deactivation of AuCl3/AC catalyst. Transmission electron microscopy characterization demonstrated that the particle size of Au nano-particles increases with increasing reaction time. The results indicated that metallic Au0 exhibits considerable catalytic activity and that Au nano-particle aggregation may be another reason for the AuCl3/AC catalytic activity in acetylene hydrochlorination. PMID:25994222

  16. Detection of acetylene impurities in ethylene and polyethylene manufacturing processes using tunable diode laser spectroscopy in the 3-μm range

    NASA Astrophysics Data System (ADS)

    Kluczynski, P.; Jahjah, M.; Nähle, L.; Axner, O.; Belahsene, S.; Fischer, M.; Koeth, J.; Rouillard, Y.; Westberg, J.; Vicet, A.; Lundqvist, S.

    2011-11-01

    Using recently developed GaInAsSb/AlGaInAsSb DFB lasers, tunable diode laser spectroscopy (TDLS) has been extended into the 3-μm wavelength region for the detection of acetylene impurities in hydrocarbon compounds encountered in ethylene manufacturing. Measurements of acetylene in pure polymer grade ethylene and in a gas mixture of ethylene and ethane typical of the process stream around a hydrogenation reactor have been performed. Using a procedure incorporating subtraction of a hydrocarbon background spectrum a detection limit of 5 ppb m was achieved under ordinary laboratory conditions. Under forced temperature cycling conditions, the detection limit deteriorated to 180 ppb m, due to temperature drift caused by optical interferences generated by reflections in the laser TO8 can.

  17. Synthesis of 3-iodoindoles by the Pd/Cu-catalyzed coupling of N,N-dialkyl-2-iodoanilines and terminal acetylenes, followed by electrophilic cyclization.

    PubMed

    Yue, Dawei; Yao, Tuanli; Larock, Richard C

    2006-01-01

    [reaction: see text] 3-Iodoindoles have been prepared in excellent yields by coupling terminal acetylenes with N,N-dialkyl-o-iodoanilines in the presence of a Pd/Cu catalyst, followed by an electrophilic cyclization of the resulting N,N-dialkyl-o-(1-alkynyl)anilines using I2 in CH2Cl2. Aryl-, vinylic-, alkyl-, and silyl-substituted terminal acetylenes undergo this process to produce excellent yields of 3-iodoindoles. The reactivity of the carbon-nitrogen bond cleavage during cyclization follows the following order: Me > n-Bu, Me > Ph, and cyclohexyl > Me. Subsequent palladium-catalyzed Sonogashira, Suzuki, and Heck reactions of the resulting 3-iodoindoles proceed smoothly in good yields. PMID:16388618

  18. Acetylene dithiolate linking up the [Tp'W(CO)(CN)] moiety with Ru(II) or Pd(II.).

    PubMed

    Seidel, Wolfram W; Dachtler, Woldemar; Semmler, Julia; Tänzler, Marco; Folk, Manuel; Villinger, Alexander

    2013-10-18

    A series of heterodinuclear complexes with acetylene dithiolate (acdt(2-) ) as the bridging moiety were synthesised by a facile one-pot procedure that avoided use of the highly elusive acetylene dithiol. Generation of the W-Ru complex [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] (Tp'=hydrotris(3,5-dimethylpyrazolyl)borate) and the W-Pd complexes [Tp'W(CN)(CO)(C2 S2 )Pd(dppe)] and [Tp'W(CO)2 (C2 S2 )Pd(dppe)][PF6 ] (dppe=1,2-bis(diphenylphoshino)ethane), which exhibit a [W(η(2) -κ(2) -C2 S2 )M] core (M=Ru, Pd), was accomplished by using a transition-metal-assisted solvolytical removal of the Me3 Si-ethyl thiol protecting groups. All intermediate species of the reaction have been fully characterised. The highly coloured W-Ru complex [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] shows reversible redox chemistry, as does the prototype complex [Tp'W(CO)2 (C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )][PF6 ]. Single crystal X-ray diffraction and IR, EPR and UV/Vis spectroscopic studies in conjunction with DFT calculations prove the high electronic delocalisation of states over the acdt(2-) linker. Comparative studies revealed a higher donor strength and more pronounced dithiolate character of acdt(2-) in [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] relative to [Tp'W(CO)2 (C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )](+) . In addition, the influence of the overall complex charge on the metric parameters was investigated by single-crystal X-ray diffraction studies with the W-Pd complexes [Tp'WL2 (C2 S2 )Pd(dppe)] (L=(CN(-) )(CO) or (CO)2 ). The central [W(C2 S2 )Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals. PMID:24026953

  19. The adsorption of small hydrocarbons on Cu(111): A combined He-atom scattering and x-ray absorption study for ethane, ethylene, and acetylene

    NASA Astrophysics Data System (ADS)

    Fuhrmann, D.; Wacker, D.; Weiss, K.; Hermann, K.; Witko, M.; Wöll, Ch.

    1998-02-01

    Ethane (C2H6), ethylene (C2H4), and acetylene (C2H2) adsorbed on Cu (111) are investigated using high-resolution helium atom scattering and x-ray absorption spectroscopy (NEXAFS). For C2H6/Cu(111) and C2H4/Cu(111) the excitation energies of the frustrated molecular translation normal to the surface (FTz) amount to 6.7 meV, suggesting the presence of a physisorbed species which is consistent with the NEXAFS data for ethylene. In contrast, for C2H2/Cu(111) the NEXAFS data indicate strong intramolecular distortions of the acetylene adsorbate compatible with a tilt of both CH ends away from the molecular axis. While the latter finding is in agreement with recent theoretical studies the theoretically predicted chemisorbed ethylene species could not be observed by the experiment. However, more detailed theoretical studies of the ethylene-Cu(111) interaction potential reveal two minima separated by an activation barrier. The minimum closer to the surface refers to strongly distorted chemisorbed C2H4 whereas the outer minimum is characterized by a free molecule-like physisorbed species. Thus the results from the present measurements are explained by the theoretically confirmed physisorbed species while chemisorbed C2H4 has to be excluded. Complementary results for ethylene and acetylene adsorbed on Pb(111) reveal a FTz-mode energy of 6.5 and 6.7 meV, respectively, thus revealing a much weaker acetylene-substrate binding than seen for Cu(111). Also in case of Pb(111) the FTz-mode showed an Einstein-like behavior with a flat dispersion curve, as for corresponding modes on the Cu(111)-substrate, see above.

  20. Numerical analysis of the effect of acetylene and benzene addition to low-pressure benzene-rich flat flames on polycyclic aromatic hydrocarbon formation

    SciTech Connect

    Kunioshi, Nilson; Komori, Seisaku; Fukutani, Seishiro

    2006-10-15

    A modification of the CHEMKIN II package has been proposed for modeling addition of an arbitrary species at an arbitrary temperature to an arbitrary distance from the burner along a flat flame. The modified program was applied to the problem of addition of acetylene or benzene to different positions of a 40-Torr, {phi}=2.4 benzene/O{sub 2}/40%-N{sub 2} premixed flame to reach final equivalence ratios of {phi}=2.5 and 2.681. The results obtained showed that acetylene addition to early positions of the flame led to significant increase in pyrene production rates, but pyrene concentrations were lower in the flames with acetylene addition in both the {phi}=2.5 and 2.681 cases. Addition of benzene to the flame did not alter pyrene production rates in either the {phi}=2.5 or 2.681 cases; however, for {phi}=2.5, pyrene concentrations increased with benzene addition, while for {phi}=2.681, pyrene contents decreased in comparison to the correspondent flames with no addition. Acetylene addition led to a significant increase in pyrene production rates, but the pyrene levels dropped due to increase in the flow velocity. Pyrene production rates were not sensitive to benzene addition, but pyrene contents increased with benzene addition when the flow velocity decreased. These results show that PAH concentration changes accompanying species addition to flames should be interpreted carefully, because an increase or decrease in the content of a PAH species does not necessarily reflect an effect on its formation rate or mechanism. (author)

  1. High rate of N2 fixation by East Siberian cryophilic soil bacteria as determined by measuring acetylene reduction in nitrogen-poor medium solidified with gellan gum.

    PubMed

    Hara, Shintaro; Hashidoko, Yasuyuki; Desyatkin, Roman V; Hatano, Ryusuke; Tahara, Satoshi

    2009-05-01

    For evaluating N(2) fixation of diazotrophic bacteria, nitrogen-poor liquid media supplemented with at least 0.5% sugar and 0.2% agar are widely used for acetylene reduction assays. In such a soft gel medium, however, many N(2)-fixing soil bacteria generally show only trace acetylene reduction activity. Here, we report that use of a N(2) fixation medium solidified with gellan gum instead of agar promoted growth of some gellan-preferring soil bacteria. In a soft gel medium solidified with 0.3% gellan gum under appropriate culture conditions, bacterial microbiota from boreal forest bed soils and some free-living N(2)-fixing soil bacteria isolated from the microbiota exhibited 10- to 200-fold-higher acetylene reduction than those cultured in 0.2% agar medium. To determine the N(2) fixation-activating mechanism of gellan gum medium, qualitative differences in the colony-forming bacterial components from tested soil microbiota were investigated in plate cultures solidified with either agar or gellan gum for use with modified Winogradsky's medium. On 1.5% agar plates, apparently cryophilic bacterial microbiota showed strictly distinguishable microbiota according to the depth of soil in samples from an eastern Siberian Taiga forest bed. Some pure cultures of proteobacteria, such as Pseudomonas fluorescens and Burkholderia xenovorans, showed remarkable acetylene reduction. On plates solidified with 1.0% gellan gum, some soil bacteria, including Luteibacter sp., Janthinobacterium sp., Paenibacillus sp., and Arthrobacter sp., uniquely grew that had not grown in the presence of the same inoculants on agar plates. In contrast, Pseudomonas spp. and Burkholderia spp. were apparent only as minor colonies on the gellan gum plates. Moreover, only gellan gum plates allowed some bacteria, particularly those isolated from the shallow organic soil layer, to actively swarm. In consequence, gellan gum is a useful gel matrix to bring out growth potential capabilities of many soil

  2. Effect of Nitrate and Acetylene on nirS, cnorB, and nosZ Expression and Denitrification Activity in Pseudomonas mandelii▿

    PubMed Central

    Saleh-Lakha, Saleema; Shannon, Kelly E.; Henderson, Sherri L.; Zebarth, Bernie J.; Burton, David L.; Goyer, Claudia; Trevors, Jack T.

    2009-01-01

    Nitrate acts as an electron acceptor in the denitrification process. The effect of nitrate in the range of 0 to 1,000 mg/liter on Pseudomonas mandelii nirS, cnorB, and nosZ gene expression was studied, using quantitative reverse transcription-quantitative PCR. Denitrification activity was measured by using the acetylene blockage method and gas chromatography. The effect of acetylene on gene expression was assessed by comparing denitrification gene expression in P. mandelii culture grown in the presence or absence of acetylene. The higher the amount of NO3− present, the greater the induction and the longer the denitrification genes remained expressed. nirS gene expression reached a maximum at 2, 4, 4, and 6 h in cultures grown in the presence of 0, 10, 100, and 1,000 mg of KNO3/liter, respectively, while induction of nirS gene ranged from 12- to 225-fold compared to time zero. cnorB gene expression also followed a similar trend. nosZ gene expression did not respond to NO3− treatment under the conditions tested. Acetylene decreased nosZ gene expression but did not affect nirS or cnorB gene expression. These results showed that nirS and cnorB responded to nitrate concentrations; however, significant denitrification activity was only observed in culture with 1,000 mg of KNO3/liter, indicating that there was no relationship between gene expression and denitrification activity under the conditions tested. PMID:19525277

  3. A fragment method for systematic improvement of anharmonic adsorbate vibrational frequencies: Acetylene on Cu(001)

    SciTech Connect

    Chulkov, Sergey K. Benoit, David M.

    2013-12-07

    We suggest a novel method for systematic improvement of anharmonic adsorbate frequencies based on a fragment approach. The calculations are carried out by considering the adsorbed molecule separately and computing an energy correction using high-level ab initio method in addition to a standard calculation of the whole adsorbed system using quantum mechanical techniques with periodic boundary conditions. We demonstrate its reliability for a C{sub 2}H{sub 2} molecule chemisorbed on a Cu(001) surface. We also show that the accuracy of the presented approach with a suitable description of the periodic surface depends mainly on the accuracy of the high-level ab initio method used to describe the adsorbate molecule. Moreover, our technique potentially allows to predict adsorbate vibrational spectra with spectroscopic accuracy.

  4. Direct Observation of Cascade of Photoinduced Ultrafast Intramolecular Charge Transfer Dynamics in Diphenyl Acetylene Derivatives: Via Solvation and Intramolecular Relaxation.

    PubMed

    Karunakaran, Venugopal; Das, Suresh

    2016-07-21

    Interaction of light with electron donor-acceptor π-conjugated systems leading to intramolecular charge transfer (ICT) plays an essential role in transformation of light energy. Here the cascade of photoinduced ICT processes is directly observed by investigating the excited state relaxation dynamics of cyano and mono/di methoxy substituted diphenyl acetylene derivatives using femtosecond pump-probe spectroscopy and nanosecond laser flash photolysis. The femtosecond transient absorption spectra of the chromophores upon ultrafast excitation reveal the dynamics of intermediates involved in transition from initially populated Frank-Condon state to local excited state (LE). It also provides the dynamic details of the transition from the LE to the charge transfer state yielding the formation of the radical ions. Finally, the charge transfer state decays to the triplet state by geminate charge recombination. The latter dynamics are observed in the nanosecond transient absorption spectra. It is found that excited state relaxation pathways are controlled by different stages of solvation and intramolecular relaxation depending on the solvent polarity. The twisted ICT state is more stabilized (978 ps) in acetonitrile than cyclohexane where major components of transient absorption originate from the S1 state. PMID:27347705

  5. Synthesis of Highly Stable Silver-Loaded Vertical ZnO Nanowires Array and its Acetylene Sensing Properties

    NASA Astrophysics Data System (ADS)

    Uddin, Abu Sadat Mohammad Iftekhar; Chung, Gwiy-Sang

    2016-09-01

    A silver-loaded one-dimensional (1D) vertical ZnO nanowires (NWs) array synthesized by a facile seed mediated hydrothermal-RF magnetron sputtering method has been investigated for the fabrication of a highly stable and reproducible acetylene (C2H2) gas sensor. Successful immobilization of silver nanoparticles (NPs) as a sensitizer on the ZnO NWs array significantly enhanced the C2H2 sensing properties and showed a stable sensing performance. The grown structure exhibited high response magnitude (30.8 at 1000ppm), short response time (43s) and excellent selectivity at 220∘C. The enhanced performance can probably be accounted for the effect of combining the highly orientated ZnO NWs and catalytically active silver-based network. The superior sensing features toward C2H2 along with broad detection range (1-1000ppm), outstanding stability and excellent reproducibility indicate that the sensor is a promising candidate for practical applications.

  6. Rotationally Resolved Vacuum Ultraviolet Resonance-Enhanced Multiphoton Ionization (VUV REMPI) of Acetylene via the G̃ Rydberg State.

    PubMed

    Schmidt-May, Alice F; Grütter, Monika; Neugebohren, Jannis; Kitsopoulos, T N; Wodtke, Alec M; Harding, Dan J

    2016-07-14

    We present a 1 + 1' resonance-enhanced multiphoton ionization (REMPI) scheme for acetylene via the linear G̃ 4sσ (1)Πu Rydberg state, offering partial rotational resolution and the possibility to detect excitation in both the cis- and trans-bending modes. The resonant transition to the G̃ state is driven by a vacuum ultraviolet (VUV) photon, generated by resonant four-wave mixing (FWM) in krypton. Ionization from the short-lived G̃ state then occurs quickly, driven by the high intensity of the residual light from the FWM process. We have observed nine bands in the region between 79 200 cm(-1) and 80 500 cm(-1) in C2H2 and C2D2. We compare our results with published spectra in this region and suggest alternative assignments for some of the Renner-Teller split bands. Similar REMPI schemes should be applicable to other small molecules with picosecond lifetime Rydberg states. PMID:27073931

  7. Optimization of Acetylene Black Conductive Additive andPolyvinylidene Difluoride Composition for High Power RechargeableLithium-Ion Cells

    SciTech Connect

    Liu, G.; Zheng, H.; Battaglia, V.S.; Simens, A.S.; Minor, A.M.; Song, X.

    2007-07-01

    Fundamental electrochemical methods were applied to study the effect of the acetylene black (AB) and the polyvinylidene difluoride (PVDF) polymer binder on the performance of high-power designed rechargeable lithium ion cells. A systematic study of the AB/PVDF long-range electronic conductivity at different weight ratios is performed using four-probe direct current tests and the results reported. There is a wide range of AB/PVDF ratios that satisfy the long-range electronic conductivity requirement of the lithium-ion cathode electrode; however, a significant cell power performance improvement is observed at small AB/PVDF composition ratios that are far from the long-range conductivity optimum of 1 to 1.25. Electrochemical impedance spectroscopy (EIS) tests indicate that the interfacial impedance decreases significantly with increase in binder content. The hybrid power pulse characterization results agree with the EIS tests and also show improvement for cells with a high PVDF content. The AB to PVDF composition plays a significant role in the interfacial resistance. We believe the higher binder contents lead to a more cohesive conductive carbon particle network that results in better overall all local electronic conductivity on the active material surface and hence reduced charge transfer impedance.

  8. Short-term influence of nitrate on acetylene reduction, photosynthesis and nodule respiration of black alder seedlings

    SciTech Connect

    Cazell, B.H.; Samuelson, L.J.; Seiler, J.R. )

    1990-05-01

    Black alder (Alnus glutinosa L. Gaernt.) has shown significant benefits in several silvicultural applications such as nurse-trees. However, little is known concerning the nitrate/N-fixing interactions. Our objections were to examine the effects of three nitrate levels on acetylene reduction (AR), net photosynthesis (Ps) and nodule respiration (NR). Fifteen month-old black alder rooted cuttings were inoculated with one strain of Frankia inoculum (ARgN22D) at six months, maintained under 16h photoperiod at ambient greenhouse conditions, and fertilized for two months prior to study with a modified Crone's N-free solution. At study initiation seedlings were fertilized for six days with 0, 7.5 or 15 mM NO{sub 3}{sup {minus}}. Measurements of AR, Ps and NR were collected on the second, fourth and sixth day of NO{sub 3}{sup {minus}} application. By day four AR was significantly lowered by 75% for the 15 mM NO{sub 3}{sup {minus}} treatment when compared with the controls. On day six, Ps and NR were lowered significantly by 29% and 59%, respectively, for the 15 mM NO{sub 3}{sup {minus}} treatments when compared to control values. Results suggest any benefit from black alder N-fixation might be negated by nitrate fertilization.

  9. Evidence of Perturbations on the S_1 Surface of Acetylene from Patterns in Stimulated Emission Pumping Spectra

    NASA Astrophysics Data System (ADS)

    Park, G. Barratt; Baraban, Joshua H.; Steeves, Adamh.; Field, Robert W.

    2011-06-01

    Stimulated Emission Pumping (SEP) spectra from the 3^4 level of S_1 acetylene to the N_B=10 polyad of S_0 contain evidence of an unexpected interference effect. S_0 intrapolyad intensity distributions are as a rule governed solely by the fractionation of the (single) bright state. However, the intensity distribution in the SEP spectrum observed from 3^4 deviates from the expected pattern. Reduced dimension DVR calculations on the S_1 surface predict a three-state interaction involving one of the S_1 interloper bands. According to the calculation, this cis interloper state engenders an indirect coupling between the trans 2^13^16^2 and 3^4 zero order states, causing the eigenstates to lie substantially farther apart than one might expect, and lending intensity to the cis 3^16^1 interloper band that appears between them. These predictions agree quite well with the experimental observations. The intensity distribution in the SEP spectrum observed from 3^4 seems to contain an interfering combination of the bright state patterns seen in the 2^13^2 and the 3^2B^2 spectra. This type of indirect effect can yield much information about state mixing, and is particularly interesting in this case since its effects on the level structure cannot reasonably be accounted for by effective Hamiltonian models that rely solely on polyads.

  10. [Application of near-infrared absorption spectrum scanning techniques in gas quantitative measurement].

    PubMed

    Ding, Hui; Liang, Jian-Qi; Cui, Jun-Hong; Wu, Xiang-Nan; Li, Xian-Li

    2010-03-01

    A practical gas sensing system utilizing absorption spectrum scanning techniques was developed. Using the narrow-band transmission of a fiber tunable filter (TOF) and wavelength modulation technique, the so-called cross-sensing effects of the traditional spectrum absorption based gas sensor were reduced effectively and thus the target gas was detected sensitively and selectively. In order to reduce the effects of nonlinearity of TOF on the measurement results and improve the system stability in operation, the reflection spectrum of a reference FBG was monitored and employed to control the modulation region and center of TOF wavelength precisely. Moreover, a kind of weak signal detecting circuits was developed to detect the weak response signal of the system with high sensitivity. The properties of the proposed system were demonstrated experimentally by detection of acetylene. Approximate linear relationships between the system responses and the input acetylene concentrations were demonstrated by experiments. The minimum detectable acetylene of 5 x 10(-6), with signal-noise ratio of 3, was also achieved by experiments. PMID:20496683

  11. Current issues in arthrogenous inhibition.

    PubMed Central

    Young, A

    1993-01-01

    Joint disease commonly results in severe weakness of associated muscles. Efforts to restore strength are often unsuccessful, even in the absence of pain. This is because of the underlying inhibition of motoneurones by afferent signals from in and around the affected joint, 'arthrogenous inhibition'. This phenomenon has received scant scientific attention, but several experimental techniques are now available with which it can be studied in man. Animal studies suggest possible neurophysiological mechanisms. Selective atrophy of different muscle fibre types, perhaps implying selective inhibition of different types of motor unit, remains unexplained, however. The severity of arthrogenous inhibition can be temporarily reduced by silencing afferent traffic but none of the techniques is yet generally applicable in practice. An alternative therapeutic approach is to produce involuntary muscle contractions by electrical stimulation. The effectiveness of therapeutic electrical stimulation may depend on the frequency and other characteristics of the stimulus. PMID:8250616

  12. Description of toluene inhibition of methyl bromide biodegradation in seawater and isolation of a marine toluene oxidizer that degrades methyl bromide.

    PubMed

    Goodwin, Kelly D; Tokarczyk, Ryszard; Stephens, F Carol; Saltzman, Eric S

    2005-07-01

    Methyl bromide (CH3Br) and methyl chloride (CH3Cl) are important precursors for destruction of stratospheric ozone, and oceanic uptake is an important component of the biogeochemical cycle of these methyl halides. In an effort to identify and characterize the organisms mediating halocarbon biodegradation, we surveyed the effect of potential cometabolic substrates on CH3Br biodegradation using a 13CH3Br incubation technique. Toluene (160 to 200 nM) clearly inhibited CH3Br and CH3Cl degradation in seawater samples from the North Atlantic, North Pacific, and Southern Oceans. Furthermore, a marine bacterium able to co-oxidize CH3Br while growing on toluene was isolated from subtropical Western Atlantic seawater. The bacterium, Oxy6, was also able to oxidize o-xylene and the xylene monooxygenase (XMO) pathway intermediate 3-methylcatechol. Patterns of substrate oxidation, lack of acetylene inhibition, and the inability of the toluene 4-monooxygenase (T4MO)-containing bacterium Pseudomonas mendocina KR1 to degrade CH3Br ruled out participation of the T4MO pathway in Oxy6. Oxy6 also oxidized a variety of toluene (TOL) pathway intermediates such as benzyl alcohol, benzylaldehyde, benzoate, and catechol, but the inability of Pseudomonas putida mt-2 to degrade CH3Br suggested that the TOL pathway might not be responsible for CH3Br biodegradation. Molecular phylogenetic analysis identified Oxy6 to be a member of the family Sphingomonadaceae related to species within the Porphyrobacter genus. Although some Sphingomonadaceae can degrade a variety of xenobiotic compounds, this appears to be the first report of CH3Br degradation for this class of organism. The widespread inhibitory effect of toluene on natural seawater samples and the metabolic capabilities of Oxy6 indicate a possible link between aromatic hydrocarbon utilization and the biogeochemical cycle of methyl halides. PMID:16000753

  13. A DFT study on the mechanisms for the cycloaddition reactions between 1-aza-2-azoniaallene cations and acetylenes.

    PubMed

    Wang, Jing-mei; Li, Zhi-ming; Wang, Quan-rui; Tao, Feng-gang

    2013-01-01

    The mechanisms of cycloaddition reactions between 1-aza-2-azoniaallene cations 1 and acetylenes 2 have been investigated using the global electrophilicity and nucleophilicity of the corresponding reactants as global reactivity indexes defined within the conceptual density functional theory. The reactivity and regioselectivity of these reactions were predicted by analysis of the energies, geometries, and electronic nature of the transition state structures. The theoretical results revealed that the reaction features a tandem process: an ionic 1,3-dipolar cycloaddition to produce the cycloadducts 3 H-pyrazolium salts 3 followed by a [1,2]-shift affording the thermodynamically more stable adducts 4 or 5. The mechanism of the cycloaddition reactions can be described as an asynchronous concerted pathway with reverse electron demand. The model reaction has also been investigated at the QCISD/6-31++G(d,p) and CCSD(T)/6-31++G(d,p)//B3LYP/6-31++G(d,p) levels as well as by the DFT. The polarizable continuum model, at the B3LYP/6-31++G(d,p) level of theory, was used to study solvent effects on all the studied reactions. In solvent dichloromethane, all the initial cycloadducts 3 were obtained via direct ionic process as the result of the solvent effect. The consecutive [1,2]-shift reaction, in which intermediates 3 are rearranged to the five-membered heterocycles 4/5, is proved to be a kinetically controlled reaction, and the regioselectivity can be modulated by varying the migrant. The LOL function and RDG function based on localized electron analysis were used to analysis the covalent bond and noncovalent interactions in order to unravel the mechanism of the title reactions. PMID:22810049

  14. Synthesis, characterization, and stability of Fe-MCM-41 for production of carbon nanotubes by acetylene pyrolysis.

    PubMed

    Amama, Placidus B; Lim, Sangyun; Ciuparu, Dragos; Yang, Yanhui; Pfefferle, Lisa; Haller, Gary L

    2005-02-24

    Fe-substituted MCM-41 molecular sieves with ca. 1, 2, and 3 wt % Fe were synthesized hydrothermally using different sources of colloidal silica (HiSil and Cab-O-Sil) and characterized by ICP, XRD, N2 physisorption, UV-vis, EPR, TPR, and X-ray absorption. Catalysts synthesized from Cab-O-Sil showed higher structural order and stability than those from HiSil. The local environment of Fe in the mesoporous material as studied by UV-vis reveals the dominance of framework Fe in all the as-synthesized Fe-MCM-41 samples. Dislodgement of some Fe species to extraframework location occurs upon calcination, and this effect is more severe for Fe-MCM-41 (2 wt %) and Fe-MCM-41 (3 wt %), as confirmed by EPR and X-ray absorption. These materials have been used as catalytic templates for the production of carbon nanotubes (CNTs) by acetylene pyrolysis at atmospheric pressure. A relationship between the Fe loading in MCM-41 and the carbon species produced during this reaction has been established. Using our optimized conditions for this system, Fe-MCM-41 with ca. 2 wt % Fe showed the best results with particularly high selectivity for single-wall carbon nanotube (SWNT) production. This catalyst was selective for carbon nanotubes with a low amount of amorphous carbon for a narrow range of temperatures from 1073 to 1123 K. To account for the different selectivity of these catalysts for CNTs production, the local environment and chemical state of Fe in the used catalyst was further probed by X-band EPR. PMID:16851270

  15. Diel Interactions of Oxygenic Photosynthesis and N2 Fixation (Acetylene Reduction) in a Marine Microbial Mat Community

    PubMed Central

    Bebout, Brad M.; Paerl, Hans W.; Crocker, Kenneth M.; Prufert, Leslie E.

    1987-01-01

    Diel variations in N2 fixation (acetylene reduction), CO2 fixation, and oxygen concentrations were measured, on three separate occasions, in a marine microbial mat located on Shackleford Banks, North Carolina. Nitrogenase activity (NA) was found to be inversely correlated with CO2 fixation and, in two of the three diel periods studied, was higher at night than during the day. Oxygen concentrations within the top 3 mm of the mat ranged from 0 to 400 μM on a diel cycle; anaerobic conditions generally persisted below 4 mm. NA in the mat was profoundly affected by naturally occurring oxygen concentrations. Experimentally elevated oxygen concentrations resulted in a significant depression of NA, whereas the addition of the Photosystem II inhibitor 3(3,4-dichlorophenyl)-1,1-dimethylurea decreased oxygen concentrations within the mat and resulted in a significant short-term enhancement of NA. Mat N2-fixing microorganisms include cyanobacteria and heterotrophic, photoautotrophic, and chemolithotrophic eubacteria. Measured (whole-mat) NA is probably due to a combination of the NA of each of these groups of organisms. The relative contributions of each group to whole-mat NA probably varied during diel and seasonal (successional) cycles. Reduced compounds derived from photosynthetic CO2 fixation appeared to be an important source of energy for NA during the day, whereas heterotrophic or chemolithotrophic utilization of reduced compounds appeared to be an important source of energy for NA at night, under reduced ambient oxygen concentrations. Previous estimates of N2 fixation calculated on the basis of daytime measurements may have seriously underestimated diel and seasonal nitrogen inputs in mat systems. PMID:16347456

  16. BMAA Inhibits Nitrogen Fixation in the Cyanobacterium Nostoc sp. PCC 7120

    PubMed Central

    Berntzon, Lotta; Erasmie, Sven; Celepli, Narin; Eriksson, Johan; Rasmussen, Ulla; Bergman, Birgitta

    2013-01-01

    Cyanobacteria produce a range of secondary metabolites, one being the neurotoxic non-protein amino acid β-N-methylamino-L-alanine (BMAA), proposed to be a causative agent of human neurodegeneration. As for most cyanotoxins, the function of BMAA in cyanobacteria is unknown. Here, we examined the effects of BMAA on the physiology of the filamentous nitrogen-fixing cyanobacterium Nostoc sp. PCC 7120. Our data show that exogenously applied BMAA rapidly inhibits nitrogenase activity (acetylene reduction assay), even at micromolar concentrations, and that the inhibition was considerably more severe than that induced by combined nitrogen sources and most other amino acids. BMAA also caused growth arrest and massive cellular glycogen accumulation, as observed by electron microscopy. With nitrogen fixation being a process highly sensitive to oxygen species we propose that the BMAA effects found here may be related to the production of reactive oxygen species, as reported for other organisms. PMID:23966039

  17. BMAA inhibits nitrogen fixation in the cyanobacterium Nostoc sp. PCC 7120.

    PubMed

    Berntzon, Lotta; Erasmie, Sven; Celepli, Narin; Eriksson, Johan; Rasmussen, Ulla; Bergman, Birgitta

    2013-08-01

    Cyanobacteria produce a range of secondary metabolites, one being the neurotoxic non-protein amino acid β-N-methylamino-L-alanine (BMAA), proposed to be a causative agent of human neurodegeneration. As for most cyanotoxins, the function of BMAA in cyanobacteria is unknown. Here, we examined the effects of BMAA on the physiology of the filamentous nitrogen-fixing cyanobacterium Nostoc sp. PCC 7120. Our data show that exogenously applied BMAA rapidly inhibits nitrogenase activity (acetylene reduction assay), even at micromolar concentrations, and that the inhibition was considerably more severe than that induced by combined nitrogen sources and most other amino acids. BMAA also caused growth arrest and massive cellular glycogen accumulation, as observed by electron microscopy. With nitrogen fixation being a process highly sensitive to oxygen species we propose that the BMAA effects found here may be related to the production of reactive oxygen species, as reported for other organisms. PMID:23966039

  18. Reactions of organoaluminum compounds with acetylene as a method for the synthesis of aliphatic derivatives with a z-disubstituted double bond

    SciTech Connect

    Andreeva, N.I.; Kuchin, A.V.; Tolstikov, G.A.

    1985-11-01

    This paper develops a method for the synthesis of aliphatic compounds with a Z-disubstituted double bond, which are important synthons for the preparation of such natural products as insect pheromones, aromatic principles, etc. In the carbalumination reaction of acetylene Z-alkenyldialkylaluminums are formed selectively. A-Alkenyldialkylaluminums are highly reactive and can readily be converted into Z-allyl alcohols and their ethers, and into Z-iodovinyl derivatives. By the reactions of vinyl organoaluminum compounds with the complex CH/sub 3/COClhaAlCl/sub 3/ E-conjugated ketones were obtained.

  19. Cycloisomerization of acetylenic acids to γ-alkylidene lactones using a palladium(II) catalyst supported on amino-functionalized siliceous mesocellular foam.

    PubMed

    Nagendiran, Anuja; Verho, Oscar; Haller, Clémence; Johnston, Eric V; Bäckvall, Jan-E

    2014-02-01

    Cycloisomerization of various γ-acetylenic acids to their corresponding γ-alkylidene lactones by the use of a heterogeneous Pd(II) catalyst supported on amino-functionalized siliceous mesocellular foam is described. Substrates containing terminal as well as internal alkynes were cyclized in high to excellent yields within 2–24 h under mild reaction conditions. The protocol exhibited high regio- and stereoselectivity, favoring the exo-dig product with high Z selectivity. Moreover, the catalyst displayed excellent stability under the employed reaction conditions, as demonstrated by its good recyclability and low leaching. PMID:24467515

  20. Catalyst-Directed Diastereoselectivity in Hydrogenative Couplings of Acetylene to α-Chiral Aldehydes: Formal Synthesis of All Eight L-Hexoses

    PubMed Central

    Han, Soo Bong; Kong, Jong Rock; Krische, Michael J.

    2011-01-01

    Hydrogenative coupling of acetylene to α-chiral aldehydes 1a–4a using enantiomeric rhodium catalysts ligated by (S)-MeO-BIPHEP and (R)-MeO-BIPHEP delivers the diastereomeric products of carbonyl-(Z)-butadienylation 1b–4b and 1c–4c, respectively, with good to excellent levels of catalyst directed diastereofacial selectivity. Diastereomeric L-glyceraldehyde acetonide adducts 1b and 1c were converted to the four isomeric enoates 6b, 8b, 6c, and 8c, representing a formal synthesis of all eight L-hexoses. PMID:18729371

  1. Infrared inhibition of embryonic hearts

    NASA Astrophysics Data System (ADS)

    Wang, Yves T.; Rollins, Andrew M.; Jenkins, Michael W.

    2016-06-01

    Infrared control is a new technique that uses pulsed infrared lasers to thermally alter electrical activity. Originally developed for nerves, we have applied this technology to embryonic hearts using a quail model, previously demonstrating infrared stimulation and, here, infrared inhibition. Infrared inhibition enables repeatable and reversible block, stopping cardiac contractions for several seconds. Normal beating resumes after the laser is turned off. The block can be spatially specific, affecting propagation on the ventricle or initiation on the atrium. Optical mapping showed that the block affects action potentials and not just calcium or contraction. Increased resting intracellular calcium was observed after a 30-s exposure to the inhibition laser, which likely resulted in reduced mechanical function. Further optimization of the laser illumination should reduce potential damage. Stopping cardiac contractions by disrupting electrical activity with infrared inhibition has the potential to be a powerful tool for studying the developing heart.

  2. Reactions between chlorine atom and acetylene in solid para-hydrogen: Infrared spectrum of the 1-chloroethyl radical

    SciTech Connect

    Golec, Barbara; Lee, Yuan-Pern

    2011-10-28

    We applied infrared matrix isolation spectroscopy to investigate the reactions between Cl atom and acetylene (C{sub 2}H{sub 2}) in a para-hydrogen (p-H{sub 2}) matrix at 3.2 K; Cl was produced via photodissociation at 365 nm of matrix-isolated Cl{sub 2} in situ. The 1-chloroethyl radical ({center_dot}CHClCH{sub 3}) and chloroethene (C{sub 2}H{sub 3}Cl) are identified as the main products of the reaction Cl + C{sub 2}H{sub 2} in solid p-H{sub 2}. IR absorption lines at 738.2, 1027.6, 1283.4, 1377.1, 1426.6, 1442.6, and 2861.2 cm{sup -1} are assigned to the 1-chloroethyl radical. For the reaction of Cl + C{sub 2}D{sub 2}, lines due to the {center_dot}CDClCH{sub 2}D radical and trans-CHDCDCl are observed; the former likely has a syn-conformation. These assignments are based on comparison of observed vibrational wavenumbers and {sup 13}C- and D-isotopic shifts with those predicted with the B3LYP/aug-cc-pVDZ and MP2/aug-cc-pVDZ methods. Our observation indicates that the primary addition product of Cl + C{sub 2}H{sub 2}, 2-chlorovinyl ({center_dot}CHCHCl) reacts readily with a neighboring p-H{sub 2} molecule to form {center_dot}CHClCH{sub 3} and C{sub 2}H{sub 3}Cl. Observation of {center_dot}CDClCH{sub 2}D and trans-CHDCDCl from Cl + C{sub 2}D{sub 2} further supports this conclusion. Although the reactivity of p-H{sub 2} appears to be a disadvantage for making highly reactive free radicals in solid p-H{sub 2}, the formation of 1-chloroethyl radical indicates that this secondary reaction might be advantageous in producing radicals that are difficult to prepare from simple photolysis or bimolecular reactions in situ.

  3. Reactions between chlorine atom and acetylene in solid para-hydrogen: Infrared spectrum of the 1-chloroethyl radical

    SciTech Connect

    Golec, Barbara; Lee, Yuan-Pern

    2011-11-07

    We applied infrared matrix isolation spectroscopy to investigate the reactions between Cl atom and acetylene (C{sub 2}H{sub 2}) in a para-hydrogen (p-H{sub 2}) matrix at 3.2 K; Cl was produced via photodissociation at 365 nm of matrix-isolated Cl{sub 2} in situ. The 1-chloroethyl radical ({center_dot}CHClCH{sub 3}) and chloroethene (C{sub 2}H{sub 3}Cl) are identified as the main products of the reaction Cl + C{sub 2}H{sub 2} in solid p-H{sub 2}. IR absorption lines at 738.2, 1027.6, 1283.4, 1377.1, 1426.6, 1442.6, and 2861.2 cm{sup -1} are assigned to the 1-chloroethyl radical. For the reaction of Cl + C{sub 2}D{sub 2}, lines due to the {center_dot}CDClCH{sub 2}D radical and trans-CHDCDCl are observed; the former likely has a syn-conformation. These assignments are based on comparison of observed vibrational wavenumbers and {sup 13}C- and D-isotopic shifts with those predicted with the B3LYP/aug-cc-pVDZ and MP2/aug-cc-pVDZ methods. Our observation indicates that the primary addition product of Cl + C{sub 2}H{sub 2}, 2-chlorovinyl ({center_dot}CHCHCl) reacts readily with a neighboring p-H{sub 2} molecule to form {center_dot}CHClCH{sub 3} and C{sub 2}H{sub 3}Cl. Observation of {center_dot}CDClCH{sub 2}D and trans-CHDCDCl from Cl + C{sub 2}D{sub 2} further supports this conclusion. Although the reactivity of p-H{sub 2} appears to be a disadvantage for making highly reactive free radicals in solid p-H{sub 2}, the formation of 1-chloroethyl radical indicates that this secondary reaction might be advantageous in producing radicals that are difficult to prepare from simple photolysis or bimolecular reactions in situ.

  4. High resolution absorption spectroscopy of the ν1=2-6 acetylenic overtone bands of propyne: Spectroscopy and dynamics

    NASA Astrophysics Data System (ADS)

    Campargue, A.; Biennier, L.; Garnache, A.; Kachanov, A.; Romanini, D.; Herman, M.

    1999-11-01

    The rotationally resolved nν1 (n=2-6) overtone transitions of the CH acetylenic stretching of propyne (CH3-C≡C-H) have been recorded by using Fourier transform spectroscopy (n=2), various intracavity laser absorption spectrometers (n=3, 4, and 6) and cavity ring down spectroscopy (CRDS) (n=5). The 2ν1, 3ν1, and 6ν1 bands exhibit a well-resolved and mostly unperturbed J-rotational structure, whose analysis is reported. The 5ν1 band recorded by pulsed CRDS shows an unresolved rotational envelope. In the region of 12 700 cm-1, an anharmonic interaction is confirmed between 4ν1 and 3ν1+ν3+ν5. The band at a higher wave number in this dyad exhibits a partly resolved K-structure, whose analysis is reported. The mixing coefficient of the two interacting states is determined consistently using different procedures. The 1/35 anharmonic resonance evidenced in the 4ν1 manifold induces weaker intensity borrowing from the 2ν1 and 3ν1 levels to the ν1+ν3+ν5 and 2ν1+ν3+ν5 level, respectively, which have been predicted and identified. Several hot bands around the 2ν1, 3ν1, and 3ν1+ν3+ν5 bands arising from the ν9=1 and ν10=1 and 2 bending levels are identified and rotationally analyzed, also leading to determine x1,9 [-20.3(3) cm-1], x1,10 [-1.7975(75) cm-1], and x3,10 [-6.56 cm-1]. The J-clumps of the P and R branches in the 6ν1 band at 18 499 cm-1 show a Lorentzian homogeneous profile mostly J-independent with an average full width at half maximum (FWHM) of 0.17 cm-1, attributed to arising from the intramolecular vibrational energy redistribution towards the bath of vibrational states. A detailed comparative examination of the fine structure in all investigated nν1 (n=2 to 7) overtone bands and the similar behavior of the cold and hot bands arising from ν10=1 definitively suggests that a highly specific low-order anharmonic coupling, still unidentified, dominates the hierarchy of interaction mechanisms connecting the nν1 levels to the background

  5. New assignments and a rare peculiarity in the high sensitivity CRDS spectrum of acetylene near 8000 cm-1

    NASA Astrophysics Data System (ADS)

    Kassi, S.; Lyulin, O. M.; Béguier, S.; Campargue, A.

    2016-08-01

    The absorption spectrum of acetylene has been recorded at room temperature (296 K) using high sensitivity Cavity Ring Down Spectroscopy in the 7914 and 8252 cm-1 interval. The noise equivalent absorption of the spectra is αmin ∼ 5×10-11 cm-1. A list of about 5600 absorption features was constructed. The smallest intensities are on the order of 10-29 cm/molecule. A total of 1325 rovibrational lines of 12C2H2 were assigned by comparison with accurate predictions provided by a global effective operator model. In addition, 132 rovibrational lines of 12C13CH2 present in natural isotopic abundance were assigned on the basis of their published positions. The assigned 12C2H2 lines belong to 12 new and 6 already known bands, for which additional J-lines were assigned. The line intensities of the three cold bands of 12C13CH2 are reported for the first time. The new data will be valuable to refine the parameters of the global effective Hamiltonian and dipole moments of 12C2H2 in the region. Spectroscopic parameters of the 12C2H2 and 12C13CH2 upper vibrational levels were derived from a band-by-band fit of the line positions (typical rms values are on the order of 0.001 cm-1). A few of the analyzed bands were found to be affected by rovibrational perturbations, which are discussed. In particular, the rotational structure of the 2ν1 + (ν4 + ν5)0 Σu+-Σg+ band near 7994 cm-1 exhibits a particularly surprising intensity distribution: while the P(19) and R(17) transitions share the same J = 18 upper level, the R(17) line has an intensity about 4 orders of magnitude smaller than the P(19) line. This unusual situation is quantitatively interpreted as resulting from a Coriolis interaction between the ν1 + 2ν2 + ν51 and 2ν1 + (ν4 + ν5)0 bands with a energy crossing at J = 18. The accidental nearly perfect cancelation of the two terms contributing to the line strength of the R(17) line leads to the near disappearance of this line.

  6. Synthesis, characterization and reactivity of group 4 metallocene bis(diphenylphosphino)acetylene complexes-a reactivity and bonding study.

    PubMed

    Haehnel, Martin; Hansen, Sven; Schubert, Kathleen; Arndt, Perdita; Spannenberg, Anke; Jiao, Haijun; Rosenthal, Uwe

    2013-11-20

    A study of the coordination chemistry of bis(diphenylphosphino)acetylene, Ph2P-C≡C-PPh2, with selected group 4 metallocenes is presented. By substitution of the alkyne in complexes of the type Cp'2M(L)(η(2)-Me3SiC2SiMe3) (M = Ti, no L; M = Zr, L = pyridine; Cp' = substituted or unsubstituted bridged or unbridged η(5)-cyclopentadienyl), the expected mononuclear complexes Cp*2Ti(η(2)-Ph2PC2PPh2) (4Ti), (rac-ebthi)Ti(η(2)-Ph2PC2PPh2) (5Ti), and (rac-ebthi)Zr(η(2)-Ph2PC2PPh2) (5Zr) [ebthi = ethylenebis(tetrahydroindenyl)] were obtained. When [Cp2Zr] was used in the reaction of Cp2Zr(py)(η(2)-Me3SiC2SiMe3) with Ph2P-C≡C-PPh2, the dinuclear complex [Cp2Zr(η(2)-Ph2PC2PPh2)]2 (6) was formed and isolated in the solid state. In solution, this complex is in equilibrium with the very spectacular structure of complex 7b as the first example of such a highly strained four-membered heterometallacycle of a group 4 metal, involving the rare R2PCCR' fragment in the cyclic unit. Both the stability and reactivity of heterodisubstituted alkynes X-C≡C-X (X = NR2, PR2, SR, SiR3, etc.) themselves and also of their complexes are of general interest. Complex 6 did not react with a second [Cp2Zr] fragment to form a homobimetallic complex. In contrast, for (rac-ebthi)Zr(η(2)-Ph2PC2PPh2) (5Zr) this reaction occurs. In the reaction of complex 4Ti with the Ni(0) complex (Cy3P)2Ni(η(2)-C2H4) (Cy = cyclohexyl), C-P bond cleavage of the alkyne ligand resulted in the formation of the isolated complex [(Cy3P)Ni(μ-PPh2)]2 (11). The structure and bonding of the complexes were investigated by DFT analysis to compare the different possible coordination modes of the R2P-C≡C-PR2 ligand. For compound 7b, a flip-flop coordination of the phosphorus atoms was proposed. Complexes 4Ti, 5Ti, 5Zr, 6, and 11 were characterized by X-ray crystallography. PMID:24156561

  7. [A Detection Technique for Gas Concentration Based on the Spectral Line Shape Function].

    PubMed

    Zhou, Mo; Yang, Bing-chu; Tao, Shao-hua

    2015-04-01

    The methods that can rapidly and precisely measure concentrations of various gases have extensive applications in the fields such as air quality analysis, environmental pollution detection, and so on. The gas detection method based on the tunable laser absorption spectroscopy is considered a promising technique. For the infrared spectrum detection techniques, the line shape function of an absorption spectrum of a gas is an important parameter in qualitative and quantitative analysis of a gas. Specifically, how to obtain the line shape function of an absorption spectrum of a gas quickly and accurately is a key problem in the gas detection fields. In this paper we analyzed several existing line shape functions and proposed a method to calculate precisely the line shape function of a gas, and investigated the relation between the gas concentration and the peak value of a line shape function. Then we experimentally measured the absorption spectra of an acetylene gas in the wavelength range of 1,515-1,545 nm with a tunable laser source and a built-in spectrometer. With Lambert-Beer law we calculated the peak values of the line shape function of the gas at the given frequencies, and obtained a fitting curve for the line shape function in the whole waveband by using a computer program. Comparing the measured results with the calculated results of the Voigt function, we found that there was a deviation-between the experimental results and the calculated results. And we found that the measured concentration of the acetylene gas by using the fitting curve of the line shape function was more accurate and compatible with the actual situation. Hence, the empirical formula for the line shape function obtained from the experimental results would be more suitable for the concentration measurement of a gas. As the fitting curve for the line shape function of the acetylene gas has been deduced from the experiment, the corresponding peak values of the spectral lines can be

  8. A theoretical study on the reaction pathways and the mechanism of 1,3- dipolar cycloaddition of vinyl acetylene and methyl azide.

    PubMed

    Siadati, Seyyed Amir; Mahboobifar, Ali; Nasiri, Ramin

    2014-01-01

    1,3-dipolar cycloaddition procedure is one of the most widely practiced methods in order to synthesize heterocyclic compounds. Although, it seems very simple, but, there are numerous precursors of heterocyclic molecules who have more than one positions to react with a 1,3-dipole species. As a result, while using a precursor with more than one position for reaction, it is probable to synthesize several products with different structures. This paper studies all possible interactions of vinyl acetylene, which has two positions for reaction, with methyl azide. This reaction could lead to the emergence of any 1,3-dipolar cycloaddition products. Our ultimate goal is to help researchers to find out how precursors containing both carbon-carbon double, and the triple bonds interact with 1,3- dipolar species. The present study used the DFT calculations at B3LYP/6-311++G(3df,pd) level to check all probable interactions between vinyl acetylene and methyl azide, and determined Potential Energy Surface, and optimized all species. PMID:24852164

  9. Reactions of glutamate semialdehyde aminotransferase (glutamate-1-semialdehyde 2,1 aminomutase) with vinyl and acetylenic substrate analogues analysed by rapid scanning spectrophotometry.

    PubMed Central

    Tyacke, R J; Contestabile, R; Grimm, B; Harwood, J L; John, R A

    1995-01-01

    The reactions occurring when glutamate-1-semialdehyde amino-transferase (glutamate-1-semialdehyde 2,1 aminomutase, EC 5.4.3.8) was treated with two potential mechanism-based inactivators, namely 4-aminohex-5-enoate and 4-aminohex-5-ynoate, have been investigated by monitoring rapid transient changes in the absorption spectrum of the enzyme's prosthetic group, pyridoxal 5'-phosphate. In both cases a short-lived chromophore absorbing maximally at about 500 nm was formed in a few milliseconds. In the case of the vinyl analogue (4-aminohex-5-enoate) this chromophore, considered to be a quinonoid intermediate, converted rapidly into the pyridoxamine phosphate form of the co-enzyme in a single turnover which was accompanied by negligible inactivation. However, slow inactivation of the enzyme by this compound was observed when the enzyme was made to undergo multiple turnovers by including the efficient aldehyde substrate, succinic semialdehyde. The acetylenic compound, aminohexynoate, produced more complex spectral changes with the consecutive formation of compounds absorbing maximally at 496 nm, 450 nm, 564 nm and 330 nm. The enzyme was 90% inactivated by aminohexynoate within 10 s and thereafter lost no further activity unless aldehyde substrate was added. Mechanisms and kinetic constants consistent with the observations are proposed for each compound. The observation that the acetylenic compound is a much more potent inactivator than its vinyl analogue is attributed to the occurrence of a conjugated allene as intermediate. PMID:7619072

  10. A new route for the prebiotic synthesis of nucleobases and hydantoins in water/ice solutions involving the photochemistry of acetylene.

    PubMed

    Menor-Salván, César; Marín-Yaseli, Margarita R

    2013-05-10

    The origin of nucleobases and other heterocycles is a classic question in the chemistry of the origins of life. The construction of laboratory models for the abiotic synthesis of nitrogen heterocycles in plausible natural conditions also aids the understanding and prediction of chemical species in the Solar System. Here, we report a new explanation for the origin of hydantoins, purines, and pyrimidines in eutectic water/ice/urea solutions driven by ultraviolet irradiation (in the 185-254 nm range, UVC) of acetylene under anoxic conditions. An analysis of the products indicates the synthesis of hydantoin and 5-hydroxyhydantoin, the purines uric acid, xanthine, and guanine, and the pyrimidines uracil and cytosine. The synthesis occurred together with the photo-oxidation of bases in a complex process for which possible pathways are proposed. In conclusion, an acetylene-containing atmosphere could contribute to the origin of nucleobases in the presence of a urea/water system by an HCN-independent mechanism. The presence of ice has a dual role as a favorable medium for the synthesis of nucleobases and protection against degradation and as a source of free radicals for the synthesis of highly oxidized heterocycles. A mechanism for the origin of hydantoins and uracil from urea in plausible conditions for prebiotic chemistry is also proposed. PMID:23536286

  11. Investigtion of the metabolic inhibition observed in solid-substrate cultivation of Clostidium thermocellum on avicel

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Clostridium thermocellum exhibits premature metabolic inhibition during solid-substrate cultivation on Avicel, but the reason for the inhibition is not well understood. Inhibition was investigated by comparing three different cultivation techniques; submerged fermentation (SmF), solid substrate cult...

  12. 'Clicking' on the nanoscale: 1,3-dipolar cycloaddition of terminal acetylenes on azide functionalized, nanometric surface templates with nanometer resolution

    NASA Astrophysics Data System (ADS)

    Haensch, Claudia; Hoeppener, Stephanie; Schubert, Ulrich S.

    2009-04-01

    Electro-oxidative lithography is used as a tool to create chemical nanostructures on an n-octadecyltrichlorosilane (OTS) monolayer self-assembled on silicon. The use of a bromine precursor molecule, which is exclusively assembled on these chemical templates, can be used to further functionalize the nanostructures by the site-selective generation of azide functions and performing the highly effective 1,3-dipolar cycloaddition reaction with acetylene functionalized molecules. The versatility of this reaction scheme provides the potential to integrate a large variety of functional molecules, to tailor the surface properties of the nanostructures or to anchor molecular building blocks or particles in confined, pre-defined surface areas. The results demonstrated in the present study introduce a conceivable route towards the functionalization of chemically active surface templates with high fidelity and reliability. It is demonstrated that surface features with a lateral resolution of 50 nm functionalized with propargyl alcohol can be fabricated.

  13. Hydrogenation of Acetylene-Ethylene Mixtures over Pd and Pd-Ag Alloys: First-Principles Based Kinetic Monte Carlo Simulations

    SciTech Connect

    Mei, Donghai; Neurock, Matthew; Smith, C Michael

    2009-10-22

    The kinetics for the selective hydrogenation of acetylene-ethylene mixtures over model Pd(111) and bimetallic Pd-Ag alloy surfaces were examined using first principles based kinetic Monte Carlo (KMC) simulations to elucidate the effects of alloying as well as process conditions (temperature and hydrogen partial pressure). The mechanisms that control the selective and unselective routes which included hydrogenation, dehydrogenation and C-C bond breaking pathways were analyzed using first-principle density functional theory (DFT) calculations. The results were used to construct an intrinsic kinetic database that was used in a variable time step kinetic Monte Carlo simulation to follow the kinetics and the molecular transformations in the selective hydrogenation of acetylene-ethylene feeds over Pd and Pd-Ag surfaces. The lateral interactions between coadsorbates that occur through-surface and through-space were estimated using DFT-parameterized bond order conservation and van der Waal interaction models respectively. The simulation results show that the rate of acetylene hydrogenation as well as the ethylene selectivity increase with temperature over both the Pd(111) and the Pd-Ag/Pd(111) alloy surfaces. The selective hydrogenation of acetylene to ethylene proceeds via the formation of a vinyl intermediate. The unselective formation of ethane is the result of the over-hydrogenation of ethylene as well as over-hydrogenation of vinyl to form ethylidene. Ethylidene further hydrogenates to form ethane and dehydrogenates to form ethylidyne. While ethylidyne is not reactive, it can block adsorption sites which limit the availability of hydrogen on the surface and thus act to enhance the selectivity. Alloying Ag into the Pd surface decreases the overall rated but increases the ethylene selectivity significantly by promoting the selective hydrogenation of vinyl to ethylene and concomitantly suppressing the unselective path involving the hydrogenation of vinyl to ethylidene

  14. Nitrogen Fixation (Acetylene Reduction) Associated with Decaying Leaves of Pond Cypress (Taxodium distichum var. nutans) in a Natural and a Sewage-Enriched Cypress Dome

    PubMed Central

    Dierberg, Forrest E.; Brezonik, Patrick L.

    1981-01-01

    Surface litter from a natural and a sewage-enriched cypress dome in north-central Florida showed a pronounced seasonal pattern of nitrogenase (acetylene reduction) activity associated with seasonal leaf fall from deciduous trees in the domes. Samples of peat from cores indicated negligible nitrogenase activity below the surface layer. Integrating the monthly rates of nitrogen fixation (based on the theoretical molar ratio of 3:2 for C2H4/NH3) yielded 0.39 and 0.12 g of N/m2 per year fixed in the litter of the natural and sewage-enriched domes, respectively. The nitrogen fixed in the first 3 months after leaf fall in the natural dome represented about 14% of the nitrogen increment in the decomposing cypress leaves, but fixation contributed a negligible amount of nitrogen (<1%) to decomposing litter in the sewage-enriched dome. PMID:16345796

  15. Direct determination of total sulfur in wine using a continuum-source atomic-absorption spectrometer and an air-acetylene flame.

    PubMed

    Huang, Mao Dong; Becker-Ross, Helmut; Florek, Stefan; Heitmann, Uwe; Okruss, Michael

    2005-08-01

    Determination of sulfur in wine is an important analytical task, particularly with regard to food safety legislation, wine trade, and oenology. Hitherto existing methods for sulfur determination all have specific drawbacks, for example high cost and time consumption, poor precision or selectivity, or matrix effects. In this paper a new method, with low running costs, is introduced for direct, reliable, rapid, and accurate determination of the total sulfur content of wine samples. The method is based on measurement of the molecular absorption of carbon monosulfide (CS) in an ordinary air-acetylene flame by using a high-resolution continuum-source atomic-absorption spectrometer including a novel high-intensity short-arc xenon lamp. First results for total sulfur concentrations in different wine samples were compared with data from comparative ICP-MS measurements. Very good agreement within a few percent was obtained. PMID:15999269

  16. The energy separation between the classical and nonclassical isomers of protonated acetylene - An extensive study in one- and n-particle space saturation

    NASA Technical Reports Server (NTRS)

    Lindh, Roland; Rice, Julia E.; Lee, Timothy J.

    1991-01-01

    The energy separation between the classical and nonclassical forms of protonated acetylene has been reinvestigated in light of the recent experimentally deduced lower bound to this value of 6.0 kcal/mol. The objective of the present study is to use state-of-the-art ab initio quantum mechanical methods to establish this energy difference to within chemical accuracy (i.e., about 1 kcal/mol). The one-particle basis sets include up to g-type functions and the electron correlation methods include single and double excitation coupled-cluster (CCSD), the CCSD(T) extension, multireference configuration interaction, and the averaged coupled-pair functional methods. A correction for zero-point vibrational energies has also been included, yielding a best estimate for the energy difference between the classical and nonclassical forms of 3.7 + or - 1.3 kcal/mol.

  17. In situ spectroscopic characterization of Ni1-xZnx/ZnO catalysts and their selectivity for acetylene semihydrogenation in excess ethylene

    SciTech Connect

    Spanjers, Charles S.; Sim, Richard S.; Sturgis, Nicholas P.; Kabius, Bernd; Rioux, Robert M.

    2015-10-30

    The structures of ZnO-supported Ni catalysts were explored with in situ X-ray absorption spectroscopy, temperature-programmed reduction, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy, and electron energy loss spectroscopy. Calcination of nickel nitrate on a nanoparticulate ZnO support at 450 °C results in the formation of Zn-doped NiO (ca. N₀̣̣₈₅ Zn₀̣̣₁₅O) nanoparticles with the rock salt crystal structure. Subsequent in situ reduction monitored by X-ray absorption near-edge structure (XANES) at the Ni K edge reveals a direct transformation of the Zn-doped NiO nanoparticles to a face-centered cubic alloy, Ni1-xZnx, at ~400 °C with x increasing with increasing temperature. Both in situ XANES and ex situ HRTEM provide evidence for intermetallic β₁-NiZn formation at ~550 °C. In comparison to a Ni/SiO₂ catalyst, Ni/ZnO necessitates a higher temperature for the reduction of NiII to Ni⁰, which highlights the strong interaction between Ni and the ZnO support. The catalytic activity for acetylene removal from an ethylene feed stream is decreased by a factor of 20 on Ni/ZnO in comparison to Ni/SiO₂. The decrease in catalytic activity of Ni/ZnO is accompanied by a reduced absolute selectivity to ethylene. H–D exchange measurements demonstrate a reduced ability of Ni/ZnO to dissociate hydrogen in comparison to Ni/SiO₂.These results of the catalytic experiments suggest that the catalytic properties are controlled, in part, by the zinc oxide support and stress the importance of reporting absolute ethylene selectivity for the catalytic semihydrogenation of acetylene in excess ethylene.

  18. Corrosion inhibiting organic coatings

    SciTech Connect

    Sasson, E.

    1984-10-16

    A corrosion inhibiting coating comprises a mixture of waxes, petroleum jelly, a hardener and a solvent. In particular, a corrosion inhibiting coating comprises candelilla wax, carnauba wax, microcrystalline waxes, white petrolatum, an oleoresin, lanolin and a solvent.

  19. The acetylenic tricyclic bis(cyano enone), TBE-31, targets microtubule dynamics and cell polarity in migrating cells.

    PubMed

    Chan, Eddie; Saito, Akira; Honda, Tadashi; Di Guglielmo, Gianni M

    2016-04-01

    Cell migration is dependent on the microtubule network for structural support as well as for the proper delivery and positioning of polarity proteins at the leading edge of migrating cells. Identification of drugs that target cytoskeletal-dependent cell migration and protein transport in polarized migrating cells is important in understanding the cell biology of normal and tumor cells and can lead to new therapeutic targets in disease processes. Here, we show that the tricyclic compound TBE-31 directly binds to tubulin and interferes with microtubule dynamics, as assessed by end binding 1 (EB1) live cell imaging. Interestingly, this interference is independent of in vitro tubulin polymerization. Using immunofluorescence microscopy, we also observed that TBE-31 interferes with the polarity of migratory cells. The polarity proteins Rac1, IQGAP and Tiam1 were localized at the leading edge of DMSO-treated migrating cell, but were observed to be in multiple protrusions around the cell periphery of TBE-31-treated cells. Finally, we observed that TBE-31 inhibits the migration of Rat2 fibroblasts with an IC50 of 0.75 μM. Taken together, our results suggest that the inhibition of cell migration by TBE-31 may result from the improper maintenance of cell polarity of migrating cells. PMID:26775215

  20. Full dimensional Franck-Condon factors for the acetylene A{sup ~} {sup 1}A{sub u}—X{sup ~1}Σ{sup +}{sub g}  transition. I. Method for calculating polyatomic linear—bent vibrational intensity factors and evaluation of calculated intensities for the gerade vibrational modes in acetylene

    SciTech Connect

    Park, G. Barratt

    2014-10-07

    Franck-Condon vibrational overlap integrals for the A{sup ~1}A{sub u}—X{sup ~1}Σ{sup +}{sub g} transition in acetylene have been calculated in full dimension in the harmonic normal mode basis. The calculation uses the method of generating functions first developed for polyatomic Franck-Condon factors by Sharp and Rosenstock [J. Chem. Phys. 41(11), 3453–3463 (1964)], and previously applied to acetylene by Watson [J. Mol. Spectrosc. 207(2), 276–284 (2001)] in a reduced-dimension calculation. Because the transition involves a large change in the equilibrium geometry of the electronic states, two different types of corrections to the coordinate transformation are considered to first order: corrections for axis-switching between the Cartesian molecular frames and corrections for the curvilinear nature of the normal modes at large amplitude. The angular factor in the wave function for the out-of-plane component of the trans bending mode, ν{sub 4}{sup ″}, is treated as a rotation, which results in an Eckart constraint on the polar coordinates of the bending modes. To simplify the calculation, the other degenerate bending mode, ν{sub 5}{sup ″}, is integrated in the Cartesian basis and later transformed to the constrained polar coordinate basis, restoring the conventional v and l quantum numbers. An updated A{sup ~}-state harmonic force field obtained recently in the R. W. Field research group is evaluated. The results for transitions involving the gerade vibrational modes are in qualitative agreement with experiment. Calculated results for transitions involving ungerade modes are presented in Paper II of this series [G. B. Park, J. H. Baraban, and R. W. Field, “Full dimensional Franck–Condon factors for the acetylene A{sup ~1}A{sub u}—X{sup ~1}Σ{sup +}{sub g} transition. II. Vibrational overlap factors for levels involving excitation in ungerade modes,” J. Chem. Phys. 141, 134305 (2014)].

  1. Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units.

    PubMed

    Yao, Zizhu; Zhang, Zhangjing; Liu, Lizhen; Li, Ziyin; Zhou, Wei; Zhao, Yunfeng; Han, Yu; Chen, Banglin; Krishna, Rajamani; Xiang, Shengchang

    2016-04-11

    Acetylene separation is a very important but challenging industrial separation task. Here, through the solvothermal reaction of CuI and 5-triazole isophthalic acid in different solvents, two metal-organic frameworks (MOFs, FJU-21 and FJU-22) with open O donor sites and controllable robustness have been obtained for acetylene separation. They contain the same paddle-wheel {Cu2 (COO2 )4 } nodes and metal-ligand connection modes, but with different helical chains as secondary building units (SBUs), leading to different structural robustness for the MOFs. FJU-21 and FJU-22 are the first examples in which the MOFs' robustness is controlled by adjusting the helical chain SBUs. Good robustness gives the activated FJU-22 a, which has higher surface area and gas uptakes than the flexible FJU-21 a. Importantly, FJU-22 a shows extraordinary separation of acetylene mixtures under ambient conditions. The separation capacity of FJU-22 a for 50:50 C2 H2 /CO2 mixtures is about twice that of the high-capacity HOF-3, and its actual separation selectivity for C2 H2 /C2 H4 mixtures containing 1 % acetylene is the highest among reported porous materials. Based on first-principles calculations, the extraordinary separation performance of C2 H2 for FJU-22 a was attributed to hydrogen-bonding interactions between the C2 H2 molecules with the open O donors on the wall, which provide better recognition ability for C2 H2 than other functional sites, including open metal sites and amino groups. PMID:26934040

  2. Dismantling techniques

    SciTech Connect

    Wiese, E.

    1998-03-13

    Most of the dismantling techniques used in a Decontamination and Dismantlement (D and D) project are taken from conventional demolition practices. Some modifications to the techniques are made to limit exposure to the workers or to lessen the spread of contamination to the work area. When working on a D and D project, it is best to keep the dismantling techniques and tools as simple as possible. The workers will be more efficient and safer using techniques that are familiar to them. Prior experience with the technique or use of mock-ups is the best way to keep workers safe and to keep the project on schedule.

  3. The formation of cyclo-addition adducts in the reaction of an acetylene-terminated material with a bismaleimide: A model compound study for addition-type thermoplastics (ATTs) using metal catalysts

    SciTech Connect

    Soucek, M.D., Pater, R.H.; Ritenour, S.L.

    1993-12-31

    A model compound study using an acetylene-terminated material and a bismaleimide has provided evidence that a diruthenium complex Ru{sub 2}(CO){sub 6}[1,2-({mu}-PPh){sub 2}C{sub 6}H{sub 4}] and a rhodium complex Rh(PPh{sub 3}){sub 3}Cl can catalyze a Diels-Alder type cycloaddition in which acetylene-terminated material acts as a diene and the bismaleimide is a dieneophile. The molten state reaction of N-(3-ethynylphenyl) phthalimide and N-(4-phenoxyphenyl) maleimide with Ru{sub 2}(CO){sub 6}[{mu}-(PhP){sub 2}C{sub 6}H{sub 4}] or Rh(PPh{sub 3}){sub 3}Cl heated to 170{degrees}C led to two major products. The spectral data for the first major product is consistent with a 2:1 Diels-Alder adduct formed from two molecules of the acetylene compound and one molecule of the maleimide. The spectral data for the second major product is consistent with a 2:2 Diels-Alder adduct formed from two molecules of each reactant.

  4. Substrate inhibition kinetics of phenol biodegradation

    SciTech Connect

    Goudar, C.T.; Ganji, S.H.; Pujar, B.G.; Strevett, K.A.

    2000-02-01

    Phenol biodegradation was studied in batch experiments using an acclimated inoculum and initial phenol concentrations ranging from 0.1 to 1.3 g/L. Phenol depletion an associated microbial growth were monitored over time to provide information that was used to estimate the kinetics of phenol biodegradation. Phenol inhibited biodegradation at high concentrations, and a generalized substrate inhibition model based on statistical thermodynamics was used to describe the dynamics of microbial growth in phenol. For experimental data obtained in this study, the generalized substrate inhibition model reduced to a form that is analogous to the Andrews equation, and the biokinetic parameters {micro}{sub max}, maximum specific growth; K{sub s}, saturation constant; and K{sub i}, inhibition constant were estimated as 0.251 h{sup {minus}1}, 0.011 g/L, and 0.348 g/L, respectively, using a nonlinear least squares technique. Given the wide variability in substrate inhibition models used to describe phenol biodegradation, an attempt was made to justify selection of particular model based on theoretical considerations. Phenol biodegradation data from nine previously published studies were used in the generalized substrate inhibition model to determine the appropriate form of the substrate inhibition model. In all nine cases, the generalized substrate inhibition model reduced to a form analogous to the Andrews equation suggesting the suitability of the Andrews equation to describe phenol biodegradation data.

  5. Application of saturation spectroscopy to the measurement of C(2), (3)II(u) concentrations in oxy-acetylene flames.

    PubMed

    Baronavski, A P; McDonald, J R

    1977-07-01

    The technique of saturation spectroscopy is applied to measure the concentration of C(2) in the (3)II(u) state in oxyacetylene flames. The two level model is further developed and extended for use in intensity regions slightly lower than that required to saturate the resonances completely. As a result, it has proved feasible to measure both the C(2) number density in the (3)II(u) state of ~10(16)/cm(3) and an excited electronic state lifetime of ~10(-12) sec, both of which depend only on the Einstein A coefficient. The experimental setup is described in detail, and possible extensions of the technique to other atomic and molecular systems are discussed. PMID:20168830

  6. Stable carbon isotope fractionation during bacterial acetylene fermentation: Potential for life detection in hydrocarbon-rich volatiles of icy planet(oid)s

    USGS Publications Warehouse

    Miller, Laurence; Baesman, Shaun; Oremland, Ron

    2015-01-01

    We report the first study of stable carbon isotope fractionation during microbial fermentation of acetylene (C2H2) in sediments, sediment enrichments, and bacterial cultures. Kinetic isotope effects (KIEs) averaged 3.7 ± 0.5‰ for slurries prepared with sediment collected at an intertidal mudflat in San Francisco Bay and 2.7 ± 0.2‰ for a pure culture of Pelobacter sp. isolated from these sediments. A similar KIE of 1.8 ± 0.7‰ was obtained for methanogenic enrichments derived from sediment collected at freshwater Searsville Lake, California. However, C2H2 uptake by a highly enriched mixed culture (strain SV7) obtained from Searsville Lake sediments resulted in a larger KIE of 9.0 ± 0.7‰. These are modest KIEs when compared with fractionation observed during oxidation of C1 compounds such as methane and methyl halides but are comparable to results obtained with other C2compounds. These observations may be useful in distinguishing biologically active processes operating at distant locales in the Solar System where C2H2 is present. These locales include the surface of Saturn's largest moon Titan and the vaporous water- and hydrocarbon-rich jets emanating from Enceladus.

  7. Optical absorption of carbon and hydrocarbon species from shock heated acetylene and methane in the 135-220 nm wavelength range

    NASA Technical Reports Server (NTRS)

    Shinn, J. L.

    1981-01-01

    Absorption spectroscopy of carbon and hydrocarbon species has been performed in a shock tube at an incident shock condition for a wavelength range of 135-220 nm, in order to obtain information needed for calculating radiation blockage ahead of a planetary probe. Instrumentation consisted of high frequency response pressure transducers, thin-film heat transfer gages, or photomultipliers coupled by light pipes. Two test-gas mixtures, one with acetylene and the other with methane, both diluted with argon, were used to provide a reliable variation of C3 and C2H concentration ratio. Comparison of tests results of the two mixtures, in the temperature range of 3750 + or - 100 K, showed the main absorbing species to be C3. The wavelength for maximum absorption agrees well with the theoretical values of 7.68 eV and 8.03 eV for the vertical excitation energy, and a value of 0.90 for the electronic oscillator strength, obtained from the measured absorption band, is also in good agreement with the predicted value of 0.92.

  8. Improvements of anti-corrosion and mechanical properties of NiTi orthopedic materials by acetylene, nitrogen and oxygen plasma immersion ion implantation

    NASA Astrophysics Data System (ADS)

    Poon, Ray W. Y.; Ho, Joan P. Y.; Liu, Xuanyong; Chung, C. Y.; Chu, Paul K.; Yeung, Kelvin W. K.; Lu, William W.; Cheung, Kenneth M. C.

    2005-08-01

    Nickel-titanium shape memory alloys (NiTi) are useful materials in orthopedics and orthodontics due to their unique super-elasticity and shape memory effects. However, the problem associated with the release of harmful Ni ions to human tissues and fluids has been raising safety concern. Hence, it is necessary to produce a surface barrier to impede the out-diffusion of Ni ions from the materials. We have conducted acetylene, nitrogen and oxygen plasma immersion ion implantation (PIII) into NiTi alloys in an attempt to improve the surface properties. All the implanted and annealed samples surfaces exhibit outstanding corrosion and Ni out-diffusion resistance. Besides, the implanted layers are mechanically stronger than the substrate underneath. XPS analyses disclose that the layer formed by C2H2 PIII is composed of mainly TiCx with increasing Ti to C concentration ratios towards the bulk. The nitrogen PIII layer is observed to be TiN, whereas the oxygen PIII layer is composed of oxides of Ti4+, Ti3+ and Ti2+.

  9. Performance of practical-sized membrane-electrode assemblies using titanium nitride-supported platinum catalysts mixed with acetylene black as the cathode catalyst layer

    NASA Astrophysics Data System (ADS)

    Shintani, Haruhiko; Kakinuma, Katsuyoshi; Uchida, Hiroyuki; Watanabe, Masahiro; Uchida, Makoto

    2015-04-01

    The performance of practical-sized membrane-electrode assemblies (MEAs) using titanium nitride-supported platinum (Pt/TiN) as the cathode catalysts was evaluated with the use of a practical single cell designed for microscale combined heat and power (CHP) applications. The performance can be controlled by adding acetylene black (AB), with the behavior being dominated by the percolation law. The electrical resistance of the MEAs drastically decreased for AB contents greater than 37 vol%. The Pt utilization percentage was close to 100% for Pt/TiN with percolated AB networks. It was also found that the percolated AB networks supplied effective gas transport pathways, which were not flooded by generated water, thus enhancing the oxygen mass transport. The practical-sized MEA using Pt/TiN + 47 vol% AB showed 1.5 times greater mass activity and a comparable performance under a practical operating condition for micro-CHP applications, compared with the MEA using a commercial graphitized carbon black-supported platinum catalyst.

  10. XPS and STM study of SiC synthesized by acetylene and disilane reaction with the Si(1 0 0)2 × 1 surface

    NASA Astrophysics Data System (ADS)

    Santoni, A.; Frycek, R.; Castrucci, P.; Scarselli, M.; De Crescenzi, M.

    2005-05-01

    The SiC formation on a ordered Si(1 0 0) substrate at low temperatures (980-1180 K) and low total pressures (10 -6 mbar) has been investigated by in situ X-ray photoemission spectroscopy (XPS) and ex situ scanning tunneling microscopy (STM). SiC was grown by chemical vapor deposition (CVD) from C 2H 2 and Si 2H 6 as the precursor gases. At all the temperatures and in presence of both C 2H 2 and Si 2H 6 XPS data showed the formation of sub-stoichiometric Si 1- xC x alloys characterized by excess silicon. By exposing to C 2H 2 only, stoichiometric SiC could be synthesized up to 1080 K. At 1180 K the formation of a Si 1- xC x alloy was observed. STM analysis has pointed out the role of silicon from the gas phase in the growth mechanisms and it has shown that uniform films with low roughness and small nanostructures can be obtained by tuning the acetylene/disilane ratios independently from the temperature selected in the investigated range.

  11. Acetylene Black Induced Heterogeneous Growth of Macroporous CoV2O6 Nanosheet for High-Rate Pseudocapacitive Lithium-Ion Battery Anode.

    PubMed

    Zhang, Lei; Zhao, Kangning; Luo, Yanzhu; Dong, Yifan; Xu, Wangwang; Yan, Mengyu; Ren, Wenhao; Zhou, Liang; Qu, Longbing; Mai, Liqiang

    2016-03-23

    Metal vanadates suffer from fast capacity fading in lithium-ion batteries especially at a high rate. Pseudocapacitance, which is associated with surface or near-surface redox reactions, can provide fast charge/discharge capacity free from diffusion-controlled intercalation processes and is able to address the above issue. In this work, we report the synthesis of macroporous CoV2O6 nanosheets through a facile one-pot method via acetylene black induced heterogeneous growth. When applied as lithium-ion battery anode, the macroporous CoV2O6 nanosheets show typical features of pseudocapacitive behavior: (1) currents that are mostly linearly dependent on sweep rate and (2) redox peaks whose potentials do not shift significantly with sweep rate. The macroporous CoV2O6 nanosheets display a high reversible capacity of 702 mAh g(-1) at 200 mA g(-1), excellent cyclability with a capacity retention of 89% (against the second cycle) after 500 cycles at 500 mA g(-1), and high rate capability of 453 mAh g(-1) at 5000 mA g(-1). We believe that the introduction of pseudocapacitive properties in lithium battery is a promising direction for developing electrode materials with high-rate capability. PMID:26938306

  12. Stable Carbon Isotope Fractionation during Bacterial Acetylene Fermentation: Potential for Life Detection in Hydrocarbon-Rich Volatiles of Icy Planet(oid)s

    PubMed Central

    Baesman, Shaun M.; Oremland, Ronald S.

    2015-01-01

    Abstract We report the first study of stable carbon isotope fractionation during microbial fermentation of acetylene (C2H2) in sediments, sediment enrichments, and bacterial cultures. Kinetic isotope effects (KIEs) averaged 3.7 ± 0.5‰ for slurries prepared with sediment collected at an intertidal mudflat in San Francisco Bay and 2.7 ± 0.2‰ for a pure culture of Pelobacter sp. isolated from these sediments. A similar KIE of 1.8 ± 0.7‰ was obtained for methanogenic enrichments derived from sediment collected at freshwater Searsville Lake, California. However, C2H2 uptake by a highly enriched mixed culture (strain SV7) obtained from Searsville Lake sediments resulted in a larger KIE of 9.0 ± 0.7‰. These are modest KIEs when compared with fractionation observed during oxidation of C1 compounds such as methane and methyl halides but are comparable to results obtained with other C2 compounds. These observations may be useful in distinguishing biologically active processes operating at distant locales in the Solar System where C2H2 is present. These locales include the surface of Saturn's largest moon Titan and the vaporous water- and hydrocarbon-rich jets emanating from Enceladus. Key Words: Acetylene—Fermentation—Isotope fractionation—Enceladus—Life detection. Astrobiology 15, 977–986. PMID:26539733

  13. Mitigating Nitrous Oxide Emissions from Agricultural Landscape: The Role of Isotopic Techniques

    NASA Astrophysics Data System (ADS)

    Zaman, Mohammad; Nguyen, Minh Long

    2014-05-01

    A review of studies from agricultural landscapes indicate that intensification of agricultural activities, inefficient use of reactive nitrogen (N) fertilizers and irrigation water, increasing human population and changes in their diet (more protein demand), high stocking rate (number of grazing livestock per hectare) and intensive cultivation are the major influencing factors for nitrous oxide (N2O) emissions into the atmosphere. Nitrification (both autotrophic and heterotrophic), denitrification and dissimilatory nitrate reduction to ammonium (DNRA) are the three major microbial processes that produce greenhouse N2O and non-greenhouse gas (N2) and can sometimes occur concurrently in a given soil system. The contribution of N2O production from each of these microbial processes is inconclusive because of the complex interactions between various microbial processes and the physical and chemical conditions in soil microsite (s). Nitrous oxide emissions across an agricultural landscape from different N inputs (chemical fertilizers and animal manure) and soil types are also extremely variable both temporally and spatially and range from 1-20% of the applied N and could therefore represent agronomic loss. The available conventional methods such as acetylene (C2H2) inhibition and helium (He) cannot accurately measure both N2O and N2 and their ratio in a given soil. The use of 15N stable isotopic technique offers the best option to measure both N2O and N2 and to identify their source (nitrification and denitrification) with a greater accuracy. Manipulating soil and fertilizer management practices can minimise these gaseous N losses. For example the combined use of urease inhibitor like (N-(n-butyl) thiophosphoric triamide (nBTPT) (trade name Agrotain®) and nitrification inhibitor dicyandiamide (DCD) with urea (100 kg N ha-1) or animal urine (600 kg N ha-1) was shown to reduce N losses by 39-53 % via denitrification-nitrification-DNRA processes. Other farm management

  14. Inhibition of urinary calculi -- a spectroscopic study

    NASA Astrophysics Data System (ADS)

    Manciu, Felicia; Govani, Jayesh; Durrer, William; Reza, Layra; Pinales, Luis

    2008-10-01

    Although a considerable number of investigations have already been undertaken and many causes such as life habits, metabolic disorders, and genetic factors have been noted as sources that accelerate calculi depositions and aggregations, there are still plenty of unanswered questions regarding efficient inhibition and treatment mechanisms. Thus, in an attempt to acquire more insights, we propose here a detailed scientific study of kidney stone formation and growth inhibition based on a traditional medicine approach with Rotula Aquatica Lour (RAL) herbal extracts. A simplified single diffusion gel growth technique was used for synthesizing the samples for the present study. The unexpected Zn presence in the sample with RAL inhibitor, as revealed by XPS measurements, explains the inhibition process and the dramatic reflectance of the incident light observed in the infrared transmission studies. Raman data demonstrate potential binding of the inhibitor with the oxygen of the kidney stone. Photoluminescence results corroborate to provide additional evidence of Zn-related inhibition.

  15. Development and applications of laser spectroscopic techniques related to combustion diagnostics

    NASA Astrophysics Data System (ADS)

    Aldén, Marcus

    2006-07-01

    Thanks to features as non-intrusiveness combined with high spatial and temporal resolution, various laser diagnostic techniques have during the last decades become of utmost importance for characterization of combustion related phenomena. In the following presentation some further development of the techniques will be highlighted aiming at a) surface temperatures using Thermographic Phosphors, TP, b) species specific, spatially and temporally resolved detection of species absorbing in the IR spectral region using polarization spectroscopy and Laser-induced fluorescence, and finally c) high speed visualization using a special designed laser system in combination with a framing camera. In terms of surface thermometry, Thermographic Phosphors have been used for many years for temperature measurements on solid surfaces. We have during the last years further developed and applied this technique for temperature measurements on burning surfaces and on materials going through phase shifts, e.g. pyrolysis and droplets. The basic principle behind this technique is to apply micron size particles to the surface of interest. By exciting the TP with a short pulse UV laser (ns), the phosphorescence will exhibit a behaviour where the spectral emission as well as the temporal decay are dependent on the temperature. It is thus possible to measure the temperature both in one and two dimensions. The presentation will include basic description of the technique as well as various applications, e.g in fire science, IC engines and gasturbines. Several of the species of interest for combustion/flow diagnostics exhibit a molecular structure which inhibits the use of conventional laser-induced fluorescence for spatially and spectrally resolved measurements. We have during the last years investigated the use of excitation and detection in the infrared region of the spectrum. Here, it is possible to detect both carbonmono/dioxide, water as well as species specific hydrocarbons. The techniques

  16. Saccadic Inhibition in Reading

    ERIC Educational Resources Information Center

    Reingold, Eyal M.; Stampe, Dave M.

    2004-01-01

    In 5 experiments, participants read text that was briefly replaced by a transient image for 33 ms at random intervals. A decrease in saccadic frequency, referred to as saccadic inhibition, occurred as early as 60-70 ms following the onset of abrupt changes in visual input. It was demonstrated that the saccadic inhibition was influenced by the…

  17. Strategies Targeting Telomerase Inhibition

    PubMed Central

    Chen, Huaping; Li, Yuanyuan; Tollefsbol, Trygve O.

    2008-01-01

    Telomerase plays a pivotal role in cellular immortality and tumorigenesis. Its activity is normally not detectable in most somatic cells while it is reactivated in the vast majority of cancer cells. Therefore, inhibition of telomerase has been viewed as a promising anticancer approach due to its specificity for cancer cells. Studies so far have shown that telomerase inhibition can inhibit the proliferation of cancer cells or cause apoptosis while it has no effect on most normal cells. Strategies currently being applied to induce telomerase inhibition target virtually all of the major components of the ribonucleoprotein holoenzyme and related cell signal pathways that regulate its activity. These strategies include inhibition of telomerase through targeting at the telomerase reverse transcriptase (TERT) catalytic subunit, the telomerase RNA (TR) component, and associated proteins. Other strategies have been developed to target the proteins associated with telomerase at the telomeric ends of chromosomes such as tankyrase. The specific mechanisms that mediate those inhibition effects include small molecules, antisense RNA, and ribozymes. Although the beneficial evidence of telomerase inhibition is obvious, limitations of strategies remain to be resolved to increase the feasibility of clinical application. This analysis will summarize recent developments of strategies in telomerase inhibition. PMID:18956258

  18. Stapedectomy technique.

    PubMed

    House, J W

    1993-06-01

    This article reviews the evolution of the author's stapedectomy technique from total footplate removal with single loop wire prosthesis and Gelfoam seal to small fenestra stapedectomy with platinum ribbon piston prosthesis and blood seal. The author concludes that the microdrill is effective, safe, and cost effective for performing this procedure. Since using this technique, the author has had no cases of sensorineural hearing loss and few complaints of dizziness or vertigo. PMID:8341570

  19. Spatial Techniques

    NASA Astrophysics Data System (ADS)

    Jabeur, Nafaa; Sahli, Nabil

    The environment, including the Earth and the immense space, is recognized to be the main source of useful information for human beings. During several decades, the acquisition of data from this environment was constrained by tools and techniques with limited capabilities. However, thanks to continuous technological advances,spatial data are available in huge quantities for different applications. The technological advances have been achieved in terms of hardware and software as well. They are allowing for better accuracy and availability, which in turn improves the quality and quantity of useful knowledge that can be extracted from the environment. They have been applied to geography, resulting in geospatial techniques. Applied to both science and technology, geospatial techniques resulted in areas of expertise, such as land surveying, cartography, navigation, remote sensing, Geographic Infor-mation Systems (GISs), and Global Positioning Systems (GPSs). They had evolved quickly with advances in computing, satellite technology and a growing demand to understand our global environment. In this chapter, we will discuss three important techniques that are widely used in spatial data acquisition and analysis: GPS and remote sensing techniques that are used to collect spatial data and a GIS that is used to store, manipulate, analyze, and visualize spatial data. Later in this book, we will discuss the techniques that are currently available for spatial knowledge discovery.

  20. Vibration-rotation alchemy in acetylene (12C2H2), ? at low vibrational excitation: from high resolution spectroscopy to fast intramolecular dynamics

    NASA Astrophysics Data System (ADS)

    Perry, David S.; Miller, Anthony; Amyay, Badr; Fayt, André; Herman, Michel

    2010-04-01

    The link between energy-resolved spectra and time-resolved dynamics is explored quantitatively for acetylene (12C2H2), ? with up to 8600 cm-1 of vibrational energy. This comparison is based on the extensive and reliable knowledge of the vibration-rotation energy levels and on the model Hamiltonian used to fit them to high precision [B. Amyay, S. Robert, M. Herman, A. Fayt, B. Raghavendra, A. Moudens, J. Thiévin, B. Rowe, and R. Georges, J. Chem. Phys. 131, 114301 (2009)]. Simulated intensity borrowing features in high resolution absorption spectra and predicted survival probabilities in intramolecular vibrational redistribution (IVR) are first investigated for the v 4 + v 5 and v 3 bright states, for J = 2, 30 and 100. The dependence of the results on the rotational quantum number and on the choice of vibrational bright state reflects the interplay of three kinds of off-diagonal resonances: anharmonic, rotational l-type, and Coriolis. The dynamical quantities used to characterize the calculated time-dependent dynamics are the dilution factor φ d, the IVR lifetime τ IVR , and the recurrence time τ rec. For the two bright states v 3 + 2v 4 and 7v 4, the collisionless dynamics for thermally averaged rotational distributions at T = 27, 270 and 500 K were calculated from the available spectroscopic data. For the 7v 4 bright state, an apparent irreversible decay of is found. In all cases, the model Hamiltonian allows a detailed calculation of the energy flow among all of the coupled zeroth-order vibration-rotation states.

  1. New adsorbents based on principles of chemical complexation: Monolayer-dispersed nickel(II) for acetylene separation by {pi}-complexation

    SciTech Connect

    Yang, R.T.; Foldes, R.

    1996-04-01

    A sorbent was prepared by dispersing a monolayer of Ni{sup 2+} ions (by spreading a monolayer of NiCl{sub 2} {center_dot} 6H{sub 2}O) on a high-surface-area {gamma}-Al{sub 2}O{sub 3}. This sorbent showed high selectivities for acetylene (C{sub 2}H{sub 2}) over other hydrocarbons, by forming a weak {pi}-complexation bond between Ni{sup 2+} and C{sub 2}H{sub 2}. For example, at 60 C, the equilibrium amounts of hydrocarbons adsorbed at 1 atm were (in mmol/g) C{sub 2}H{sub 2} = 1.56, C{sub 2}H{sub 6} = 0.043, C{sub 2}H{sub 4} = 0.061, C{sub 3}H{sub 6} = 0.42, and C{sub 3}H{sub 8} = 0.30. The bond energy for the Ni{sup 2+}-C{sub 2}H{sub 2} complex was approximately 9.3 kcal/mol, and the adsorption was reversible. The stoichiometry of the complex was Ni{sup 2+}(C{sub 2}H{sub 2}){sub n} where n = 1--3 at 25 C and subatmospheric pressure. The {pi}-complexation bond was formed by the donation of the C{sub 2}H{sub 2} {pi}-electrons to the vacant hybridized dsp{sup 2} orbitals of Ni{sup 2+} and the back-donation of electrons from the filled d (or dp-hybrid) orbitals of Ni{sup 2+} into the antibonding orbitals of C{sub 2}H{sub 2}. This work demonstrates that new sorbents can be designed and prepared by exploiting the weak, reversible {pi}-complexation bonds, and, consequently, conventional separation/purification processes can be replaced by more efficient adsorption processes.

  2. A All-Vacuum High Resolution Fourier Transform Spectrometer with Absorption Pathlengths up to 352 M: Acetylene Spectrum at 1.4-1.7 Microns.

    NASA Astrophysics Data System (ADS)

    Keppler, Karen Ann

    1995-01-01

    The spectra of acetylene (C_2H _2) and of water vapor have been recorded at room temperature with Doppler- or pressure -broadening-limited resolution at pathlengths up to 352m. The spectra were obtained with the combination of a FTIR (Fourier Transform Infrared) spectrometer, evacuated transfer optics, and a multipass cell of 4m base length. The measurements were performed at the Justus-Liebig-Universitat in Giessen, Germany, using the FTIR spectrometer at that university, the multipass cell assembled at The Ohio State University, and the vacuum transfer optics designed by the author. The regions in which the spectra were recorded are 5900-7150 cm^{-1} and 1850-6600 cm^{-1}. Calibration difficulties pertaining to the determination of the absolute accuracy of the data have been resolved, and molecular parameters have been extracted for the HCCH data. These calibration problems were not documented in earlier studies using high resolution Fourier transform spectrometers. For this reason, the dissertation addresses this matter in somewhat greater detail. This work contains a description of the technology used to obtain the data, and a description of the calibration of the spectra to make them suitable for future use as secondary wavenumber calibration standards. The bands detected for the first time in this study have been reported, and updated energy level diagrams for HCCH and H^{13}CCH have been included. The molecular parameters obtained from the HCCH spectra have been presented. The appendices include, among others, the basic observational data, a spectral map and associated wavenumber lists of HCCH, and a description of the weighting scheme developed by the author for Fourier Transform spectra.

  3. Non-covalent C-Cl…π interaction in acetylene-carbon tetrachloride adducts: Matrix isolation infrared and ab initio computational studies.

    PubMed

    Ramanathan, N; Sundararajan, K; Vidya, K; Jemmis, Eluvathingal D

    2016-03-15

    Non-covalent halogen-bonding interactions between π cloud of acetylene (C2H2) and chlorine atom of carbon tetrachloride (CCl4) have been investigated using matrix isolation infrared spectroscopy and quantum chemical computations. The structure and the energies of the 1:1 C2H2-CCl4 adducts were computed at the B3LYP, MP2 and M05-2X levels of theory using 6-311++G(d,p) basis set. The computations indicated two minima for the 1:1 C2H2-CCl4 adducts; with the C-Cl…π adduct being the global minimum, where π cloud of C2H2 is the electron donor. The second minimum corresponded to a C-H…Cl adduct, in which C2H2 is the proton donor. The interaction energies for the adducts A and B were found to be nearly identical. Experimentally, both C-Cl…π and C-H…Cl adducts were generated in Ar and N2 matrixes and characterized using infrared spectroscopy. This is the first report on halogen bonded adduct, stabilized through C-Cl…π interaction being identified at low temperatures using matrix isolation infrared spectroscopy. Atoms in Molecules (AIM) and Natural Bond Orbital (NBO) analyses were performed to support the experimental results. The structures of 2:1 ((C2H2)2-CCl4) and 1:2 (C2H2-(CCl4)2) multimers and their identification in the low temperature matrixes were also discussed. PMID:26722673

  4. Non-covalent C-Cl…π interaction in acetylene-carbon tetrachloride adducts: Matrix isolation infrared and ab initio computational studies

    NASA Astrophysics Data System (ADS)

    Ramanathan, N.; Sundararajan, K.; Vidya, K.; Jemmis, Eluvathingal D.

    2016-03-01

    Non-covalent halogen-bonding interactions between π cloud of acetylene (C2H2) and chlorine atom of carbon tetrachloride (CCl4) have been investigated using matrix isolation infrared spectroscopy and quantum chemical computations. The structure and the energies of the 1:1 C2H2-CCl4 adducts were computed at the B3LYP, MP2 and M05-2X levels of theory using 6-311 ++G(d,p) basis set. The computations indicated two minima for the 1:1 C2H2-CCl4 adducts; with the C-Cl…π adduct being the global minimum, where π cloud of C2H2 is the electron donor. The second minimum corresponded to a C-H…Cl adduct, in which C2H2 is the proton donor. The interaction energies for the adducts A and B were found to be nearly identical. Experimentally, both C-Cl…π and C-H…Cl adducts were generated in Ar and N2 matrixes and characterized using infrared spectroscopy. This is the first report on halogen bonded adduct, stabilized through C-Cl…π interaction being identified at low temperatures using matrix isolation infrared spectroscopy. Atoms in Molecules (AIM) and Natural Bond Orbital (NBO) analyses were performed to support the experimental results. The structures of 2:1 ((C2H2)2-CCl4) and 1:2 (C2H2-(CCl4)2) multimers and their identification in the low temperature matrixes were also discussed.

  5. Pharmacokinetics and pharmacodynamics of orally administered acetylenic tricyclic bis(cyanoenone), a highly potent Nrf2 activator with a reversible covalent mode of action

    PubMed Central

    Kostov, Rumen V.; Knatko, Elena V.; McLaughlin, Lesley A.; Henderson, Colin J.; Zheng, Suqing; Huang, Jeffrey T.-J.; Honda, Tadashi; Dinkova-Kostova, Albena T.

    2015-01-01

    The acetylenic tricyclic bis(cyanoenone) TBE-31 is a highly potent cysteine targeting compound with a reversible covalent mode of action; its best-characterized target being Kelch-like ECH-associated protein-1 (Keap1), the cellular sensor for oxidants and electrophiles. TBE-31 reacts with cysteines of Keap1, impairing its ability to target nuclear factor-erythroid 2 p45-related factor 2 (Nrf2) for degradation. Consequently, Nrf2 accumulates and orchestrates cytoprotective gene expression. In this study we investigated the pharmacokinetic and pharmacodynamic properties of TBE-31 in C57BL/6 mice. After a single oral dose of 10 μmol/kg (∼200 nmol/animal), the concentration of TBE-31 in blood exhibited two peaks, at 22.3 nM and at 15.5 nM, 40 min and 4 h after dosing, respectively, as determined by a quantitative stable isotope dilution LC-MS/MS method. The AUC0–24h was 195.5 h/nmol/l, the terminal elimination half-life was 10.2 h, and the kel was 0.068 h−1. To assess the pharmacodynamics of Nrf2 activation by TBE-31, we determined the enzyme activity of its prototypic target, NAD(P)H:quinone oxidoreductase 1 (NQO1) and found it elevated by 2.4- and 1.5-fold in liver and heart, respectively. Continuous feeding for 18 days with diet delivering the same daily doses of TBE-31 under conditions of concurrent treatment with the immunosuppressive agent azathioprine had a similar effect on Nrf2 activation without any indications of toxicity. Together with previous reports showing the cytoprotective effects of TBE-31 in animal models of carcinogenesis, our results demonstrate the high potency, efficacy and suitability for chronic administration of cysteine targeting reversible covalent drugs. PMID:26265043

  6. Determination of sulfur forms in wine including free and total sulfur dioxide based on molecular absorption of carbon monosulfide in the air-acetylene flame.

    PubMed

    Huang, Mao Dong; Becker-Ross, Helmut; Florek, Stefan; Heitmann, Uwe; Okruss, Michael; Patz, Claus-Dieter

    2008-01-01

    A new method for the determination of sulfur forms in wine, i.e., free SO(2), total SO(2), bound SO(2), total S, and sulfate, is presented. The method is based on the measurement of the carbon monosulfide (CS) molecular absorption produced in a conventional air-acetylene flame using high-resolution continuum source absorption spectrometry. Individual sulfur forms can be distinguished because of the different sensitivities of the corresponding CS molecular absorption. The sensitivity of free SO(2) is about three times higher than the value for bound SO(2) and sulfate. The method makes use of procedures similar to those used in classic reference methods. Its performance is verified by analyzing six wine samples. Relative standard deviations are between 5 and 13% for free SO(2) and between 1 and 3% for total SO(2). For the validation of the accuracy of the new method, the results are compared with those of reference methods. The agreement of the values for total SO(2) with values of the classic method is satisfactory: five out of six samples show deviations less than 16%. Due to the instability of free SO(2) in wine and the known problems of the used reference method, serious deviations of the free SO(2) results are found for three samples. The evaluation of the limits of detection focuses on the value for free SO(2), which is the sulfur form having by far the lowest concentration in wine. Here, the achievable limit of detection is 1.8 mg L(-1). [figure: see text] Detection of non-metal elements using continuum source flame absorption spectrometry. PMID:17972067

  7. Optogenetic and chemogenetic strategies for sustained inhibition of pain

    PubMed Central

    Iyer, Shrivats M.; Vesuna, Sam; Ramakrishnan, Charu; Huynh, Karen; Young, Stephanie; Berndt, Andre; Lee, Soo Yeun; Gorini, Christopher J.; Deisseroth, Karl; Delp, Scott L.

    2016-01-01

    Spatially targeted, genetically-specific strategies for sustained inhibition of nociceptors may help transform pain science and clinical management. Previous optogenetic strategies to inhibit pain have required constant illumination, and chemogenetic approaches in the periphery have not been shown to inhibit pain. Here, we show that the step-function inhibitory channelrhodopsin, SwiChR, can be used to persistently inhibit pain for long periods of time through infrequent transdermally delivered light pulses, reducing required light exposure by >98% and resolving a long-standing limitation in optogenetic inhibition. We demonstrate that the viral expression of the hM4D receptor in small-diameter primary afferent nociceptor enables chemogenetic inhibition of mechanical and thermal nociception thresholds. Finally, we develop optoPAIN, an optogenetic platform to non-invasively assess changes in pain sensitivity, and use this technique to examine pharmacological and chemogenetic inhibition of pain. PMID:27484850

  8. Inhibition of selectin binding

    DOEpatents

    Nagy, Jon O.; Spevak, Wayne R.; Dasgupta, Falguni; Bertozzi, Caroline

    1999-01-01

    This invention provides compositions for inhibiting the binding between two cells, one expressing P- or L-selectin on the surface and the other expressing the corresponding ligand. A covalently crosslinked lipid composition is prepared having saccharides and acidic group on separate lipids. The composition is then interposed between the cells so as to inhibit binding. Inhibition can be achieved at an effective oligosaccharide concentration as low as 10.sup.6 fold below that of the free saccharide. Since selectins are involved in recruiting cells to sites of injury, these composition scan be used to palliate certain inflammatory and immunological conditions.

  9. Inhibition of selectin binding

    DOEpatents

    Nagy, Jon O.; Spevak, Wayne R.; Dasgupta, Falguni; Bertozzi, Carolyn

    1999-10-05

    This invention provides a system for inhibiting the binding between two cells, one expressing P- or L-selectin on the surface and the other expressing the corresponding ligand. A covalently crosslinked lipid composition is prepared having saccharides and acidic group on separate lipids. The composition is then interposed between the cells so as to inhibit binding. Inhibition can be achieved at an effective oligosaccharide concentration as low as 10.sup.6 fold below that of the free saccharide. Since selectins are involved in recruiting cells to sites of injury, this system can be used to palliate certain inflammatory and immunological conditions.

  10. Inhibition of selectin binding

    DOEpatents

    Nagy, Jon O.; Spevak, Wayne R.; Dasgupta, Falguni; Bertozzi, Caroline

    2001-10-09

    This invention provides compositions for inhibiting the binding between two cells, one expressing P- or L-selectin on the surface and the other expressing the corresponding ligand. A covalently crosslinked lipid composition is prepared having saccharides and acidic group on separate lipids. The composition is then interposed between the cells so as to inhibit binding. Inhibition can be achieved at an effective oligosaccharide concentration as low as 10.sup.6 fold below that of the free saccharide. Since selectins are involved in recruiting cells to sites of injury, these composition scan be used to palliate certain inflammatory and immunological conditions.

  11. Methods of Telomerase Inhibition

    PubMed Central

    Andrews, Lucy G.; Tollefsbol, Trygve O.

    2008-01-01

    Summary Telomerase is central to cellular immortality and is a key component of most cancer cells although this enzyme is rarely expressed to significant levels in normal cells. Therefore, the inhibition of telomerase has garnered considerable attention as a possible anticancer approach. Many of the methods applied to telomerase inhibition focus on either of the two major components of the ribonucleoprotein holoenzyme, that is, the telomerase reverse transcriptase (TERT) catalytic subunit or the telomerase RNA (TR) component. Other protocols have been developed to target the proteins, such as tankyrase, that are associated with telomerase at the ends of chromosomes. This chapter summarizes some of these recent advances in telomerase inhibition. PMID:18369812

  12. Decomposition techniques

    USGS Publications Warehouse

    Chao, T.T.; Sanzolone, R.F.

    1992-01-01

    Sample decomposition is a fundamental and integral step in the procedure of geochemical analysis. It is often the limiting factor to sample throughput, especially with the recent application of the fast and modern multi-element measurement instrumentation. The complexity of geological materials makes it necessary to choose the sample decomposition technique that is compatible with the specific objective of the analysis. When selecting a decomposition technique, consideration should be given to the chemical and mineralogical characteristics of the sample, elements to be determined, precision and accuracy requirements, sample throughput, technical capability of personnel, and time constraints. This paper addresses these concerns and discusses the attributes and limitations of many techniques of sample decomposition along with examples of their application to geochemical analysis. The chemical properties of reagents as to their function as decomposition agents are also reviewed. The section on acid dissolution techniques addresses the various inorganic acids that are used individually or in combination in both open and closed systems. Fluxes used in sample fusion are discussed. The promising microwave-oven technology and the emerging field of automation are also examined. A section on applications highlights the use of decomposition techniques for the determination of Au, platinum group elements (PGEs), Hg, U, hydride-forming elements, rare earth elements (REEs), and multi-elements in geological materials. Partial dissolution techniques used for geochemical exploration which have been treated in detail elsewhere are not discussed here; nor are fire-assaying for noble metals and decomposition techniques for X-ray fluorescence or nuclear methods be discussed. ?? 1992.

  13. Tracer Technique

    NASA Astrophysics Data System (ADS)

    Haba, H.; Motomura, S.; Kamino, S.; Enomoto, S.

    In radioactive tracer technique, radioactive nuclides are used to follow the behavior of elements or chemical species in chemical and other processes. This is realized by means of radioactivity measurement. In 1913, Hevesy and Paneth succeeded in determining the extremely low solubility of lead salts by using naturally occurring 210Pb as a radioactive tracer. As various radioactive nuclides became artificially available, this technique has been widely employed in studies of chemical equilibrium and reactions as well as in chemical analysis. It is also an essential technique in biochemical, biological, medical, geological, and environmental studies. Medical diagnosis and industrial process control are the fields of its most important practical application. In this chapter, fundamental ideas concerning radioactive tracers will be described followed by their application with typical examples. Detailed description on their application to life sciences and medicine is given in Vol. 4.

  14. AOP description: Acetylcholinesterase inhibition

    EPA Science Inventory

    This adverse outcome pathway (AOP) leverages existing knowledge in the open literature to describe the linkage between inhibition of acetylcholinesterase (AChE) and the subsequent mortality resulting from impacts at cholinergic receptors. The AOP takes a chemical category approa...

  15. Miscellaneous Techniques

    NASA Astrophysics Data System (ADS)

    Jha, Shyam N.

    Nondestructive way of determining the food quality is the need of the hour. Till now major methods such as colour measurements and their modeling; machine vision systems; X-ray, CT and MRI; NIR spectroscopy; electronic nose and tongue; and ultrasonic technology have been discussed in detail. These techniques, in general, are considered to be sophisticated and costly, and therefore probably are not being adopted as fast as it should be. I am however of the reverse opinion. While going through these techniques, it has been seen that majority of quality parameters have been measured and correlated with the signals obtained using different equipment.

  16. Method for inhibiting corrosion

    SciTech Connect

    Wu, Y.; Stapp, P. R.

    1985-12-03

    A composition comprising the reaction adduct or neutralized product resulting from the reaction of a maleic anhydride and an oil containing a polynuclear aromatic compound is provided which, when applied to a metal surface, forms a corrosion-inhibiting film thereon. The composition is particularly useful in the treatment of down-hole metal surfaces in oil and gas wells to inhibit the corrosion of the metal.

  17. Impact of The Seasonal Variations of Ethane and Acetylene Distributions On The Temperature Field of Titan's Stratosphere

    NASA Astrophysics Data System (ADS)

    Lebonnois, S.; Hourdin, F.; Rannou, P.; Luz, D.

    An enrichment has been observed for several compounds in Titan's stratosphere by IRIS/Voyager 1, for high latitudes coming out of winter (Coustenis and Bézard, Icarus 115, 1995). Bézard et al. (Icarus 113, 1995) showed that this enrichment sould be capable of affecting the temperature field in Titan's stratosphere by inducing a relative cooling at those latitudes. The impact of meridional dynamics on the composition of Titan's atmosphere has been studied recently with a 2-dimensional photochemical model (Lebonnois et al., Icarus 152, 2001).To go further into the study of the coupling between photochemistry and dynamics, a photochemical module has been directly introduced into the general cir- culation model of the Laboratoire de Météorologie Dynamique (described in Hourdin et al., Icarus 117, 1995). A simplified module has also been implemented, that uses for a limited number of species a simple linear relaxation toward a prescribed vertical profile, instead of the complex photochemical calculations. This technique, presented in Lebonnois et al. (2001), allows to reproduce the latitudinal variations observed in the stratosphere of Titan for some species. We consider here the case of C2H2 and C2H6, because the distributions of these compounds are taken into account in the ra- diative calculations of the GCM. The contributions of other trace compounds have been neglected until now, based on their equatorial mole fractions. Using this simplified coupled model, we have studied the impact on the temperature field of the variations of the distributions of C2H2 and C2H6 induced by meridional dynamics. The enrichment obtained in the descending branch of the Hadley cell is associated with a relative cooling for pressures under approximately 1 mbar (altitudes above 200 km). For lower altitudes, the effect is a slight heating. We will present these effects and their interpretation, and will discuss their signifi- cance, especially when compared to the thermal effects of

  18. Infrared and microwave spectra of the acetylene-ammonia and carbonyl sulfide-ammonia complexes: a comparative study of a weak C-H···N hydrogen bond and an S···N bond.

    PubMed

    Liu, Xunchen; Xu, Yunjie

    2011-08-21

    We report a combined high resolution infrared and microwave spectroscopic investigation of the acetylene-ammonia and carbonyl sulfide-ammonia complexes using a pulsed slit-nozzle multipass absorption spectrometer based on a quantum cascade laser and a pulsed nozzle beam Fourier transform microwave spectrometer, respectively. The ro-vibrational transitions of the acetylene-ammonia complex have been measured at 6 μm in the vicinity of the ν(4) band of ammonia for the first time. The previously reported pure rotational transitions have been extended to higher J and K values with (14)N nuclear quadrupole hyperfine components detected and analyzed. The spectral analysis reveals that acetylene binds to ammonia through a C-H···N weak hydrogen bond to form a C(3v) symmetric top, consistent with the previous microwave [Fraser et al., J. Chem. Phys., 1984, 80, 1423] and infrared spectroscopic study at 3 μm [Hilpert et al., J. Chem. Phys., 1996, 105, 6183]. A parallel study has also been carried out for the carbonyl sulfide-ammonia complex whose pure rotational and ro-vibrational spectra at 6 μm have been detected and analyzed for the first time. The spectral and the subsequent structural analyses, in conjunction with the corresponding ab initio calculation, indicate that the OCS-NH(3) complex assumes C(3v) symmetry with S pointing to N of NH(3), in contrast to the T-shaped geometries obtained for the isoelectronic N(2)O-NH(3) and CO(2)-NH(3) complexes. PMID:21776482

  19. Leukocyte migration inhibition in nickel dermatitis.

    PubMed

    Mirza, A M; Perera, M G; Maccia, C A; Dziubynskyj, O G; Bernstein, I L

    1975-01-01

    Leukocyte migration inhibitory factor assay was employed as an in vitro diagnostic aid in nickel dermatitis, the second most common contact dermatitis in North America. 15 patch test-positive and 5 patch test-negative patients, all giving a past history suggestive of nickel dermatitis, were investigated. Significant inhibition of leukocyte migration in both groups of patients was obtained only with nickel sulfate-albumin conjugate and not with unconjugated nickel sulfate. Specificity of this system was tested by utilizing an unrelated metallic albumin complex, and no inhibition was found. When patch testing is equivocal or contraindicated, this in vitro technique may be a practical alternative. PMID:1102460

  20. A photochemical study of the kinetics of the reactions of NH2 with phosphine, ethylene, and acetylene using flash photolysis-laser induced fluorescence. Ph.D. Thesis Catholic Univ. of America; [ammonia in the atmosphere of Jupiter

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.

    1982-01-01

    The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.

  1. Preparation of 1,7- and 3,9-dideazapurines from 2-amino-3-iodo- and 3-amino-4-iodopyridines and activated acetylenes by conjugate addition and copper-catalyzed intramolecular arylation.

    PubMed

    Zhu, Ying; Back, Thomas G

    2014-11-21

    The conjugate addition of N-formyl derivatives of 2-amino-3-iodo- and 3-amino-4-iodopyridines to acetylenes activated by sulfone, ester, or ketone groups, followed by intramolecular arylation, affords variously substituted 1,7- and 3,9-dideazapurines. The method employs DMF-water as the solvent and copper(II) acetate as the catalyst for the cyclization step. Neither added ligands nor the exclusion of oxygen is necessary. The process therefore provides a simple, convenient, and inexpensive route to this biologically interesting class of products. PMID:25333726

  2. Novel mode of 2-fold interpenetration observed in a primitive cubic network of formula [Ni(1,2-bis(4-pyridyl)acetylene)2(Cr2O7)]n.

    PubMed

    Scott, Hayley S; Bajpai, Alankriti; Chen, Kai-Jie; Pham, Tony; Space, Brian; Perry, John J; Zaworotko, Michael J

    2015-10-14

    A primitive cubic (pcu) network of formula [Ni(1,2-bis(4-pyridyl)acetylene)2(Cr2O7)]n, , has been synthesised and found to exhibit a novel type of inclined 2-fold interpenetration and an isosteric heat of adsorption (Q(st)) of 30.5 kJ mol(-1) towards CO2 at zero loading. Q(st) is relatively high in the broad context but less than that observed in related hybrid ultramicroporous materials, a feature that can be understood after studying pore structure and molecular simulations of CO2 adsorption. PMID:26307270

  3. Nitrate inhibition of legume nodule growth and activity. II. Short term studies with high nitrate supply

    SciTech Connect

    Streeter, J.G.

    1985-02-01

    Soybean plants (Glycine max (L.) Merr) were grown in sand culture with 2 millimolar nitrate for 37 days and then supplied with 15 millimolar nitrate for 7 days. Control plants received 2 millimolar nitrate and 13 millimolar chloride and, after the 7-day treatment period, all plants were supplied with nil nitrate. The temporary treatment with high nitrate inhibited nitrogenase (acetylene reduction) activity by 80% whether or not Rhizobium japonicum bacteroids had nitrate reductase (NR) activity. The pattern of nitrite accumulation in nodules formed by NR/sup +/ rhizobia was inversely related to the decrease and recovery of nitrogenase activity. However, nitrite concentration in nodules formed by NR/sup -/ rhizobia appeared to be too low to explain the inhibition of nitrogenase. Nodules on plants treated with 15 millimolar nitrate contained higher concentrations of amino N and, especially, ureide N than control nodules and, after withdrawal of nitrate, reduced N content of treated and control nodules returned to similar levels. The accumulation of N/sub 2/ fixation products in nodules in response to high nitrate treatment was observed with three R. japonicum strains, two NR/sup +/ and one NR/sup -/.

  4. Titration Techniques

    NASA Astrophysics Data System (ADS)

    Jacobsen, Jerrold J.; Houston Jetzer, Kelly; Patani, Néha; Zimmerman, John; Zweerink, Gerald

    1995-07-01

    Significant attention is paid to the proper technique for reading a meniscus. Video shows meniscus-viewing techniques for colorless and dark liquids and the consequences of not reading a meniscus at eye level. Lessons are provided on approaching the end point, focusing on end point colors produced via different commonly used indicators. The concept of a titration curve is illustrated by means of a pH meter. Carefully recorded images of the entire range of meniscus values in a buret, pipet, and graduated cylinder are included so that you can show your students, in lecture or pre-lab discussion, any meniscus and discuss how to read the buret properly. These buret meniscus values are very carefully recorded at the rate of one video frame per hundredth of a milliliter, so that an image showing any given meniscus value can be obtained. These images can be easily incorporated into a computer-based multimedia environment for testing or meniscus-reading exercises. Two of the authors have used this technique and found the exercise to be very well received by their students. Video on side two shows nearly 100 "bloopers", demonstrating both the right way and wrong ways to do tasks associated with titration. This material can be used in a variety of situations: to show students the correct way to do something; to test students by asking them "What is this person doing wrong?"; or to develop multimedia, computer-based lessons. The contents of Titration Techniques are listed below: Side 1 Titration: what it is. A simple titration; Acid-base titration animation; A brief redox titration; Redox titration animation; A complete acid-base titration. Titration techniques. Hand technique variations; Stopcock; Using a buret to measure liquid volumes; Wait before reading meniscus; Dirty and clean burets; Read meniscus at eye level (see Fig. 1); Meniscus viewing techniques--light colored liquids; Meniscus viewing techniques--dark liquids; Using a magnetic stirrer; Rough titration

  5. Pharmacology of cortical inhibition

    PubMed Central

    Krnjević, K.; Randić, Mirjana; Straughan, D. W.

    1966-01-01

    1. We have studied the effects of various pharmacological agents on the cortical inhibitory process described in the previous two papers (Krnjević, Randić & Straughan, 1966a, b); the drugs were mostly administered directly by iontophoresis from micropipettes and by systemic injection (I.V.). 2. Strychnine given by iontophoresis or by the application of a strong solution to the cortical surface potentiated excitatory effects, but very large iontophoretic doses also depressed neuronal firing. Subconvulsive and even convulsive systemic doses had little or no effect at the cortical level. There was no evidence, with any method of application, that strychnine directly interferes with the inhibitory process. 3. Tetanus toxin, obtained from two different sources and injected into the cortex 12-48 hr previously, also failed to block cortical inhibition selectively. As with strychnine, there was some evidence of increased responses to excitatory inputs. 4. Other convulsant drugs which failed to block cortical inhibition included picrotoxin, pentamethylene tetrazole, thiosemicarbazide, longchain ω-amino acids and morphine. 5. The inhibition was not obviously affected by cholinomimetic agents or by antagonists of ACh. 6. α- and β-antagonists of adrenergic transmission were also ineffective. 7. Cortical inhibition was fully developed in the presence of several general anaesthetics, including ether, Dial, pentobarbitone, Mg and chloralose. A temporary reduction in inhibition which is sometimes observed after systemic doses of pentobarbitone, is probably secondary to a fall in blood pressure. 8. Several central excitants such as amphetamine, caffeine and lobeline also failed to show any specific antagonistic action on cortical inhibition. 9. In view of the possibility that GABA is the chemical agent mediating cortical inhibition, an attempt was made to find a selective antagonist of its depressant action on cortical neurones. None of the agents listed above, nor any other

  6. Electrochemical Techniques

    SciTech Connect

    Chen, Gang; Lin, Yuehe

    2008-07-20

    Sensitive and selective detection techniques are of crucial importance for capillary electrophoresis (CE), microfluidic chips, and other microfluidic systems. Electrochemical detectors have attracted considerable interest for microfluidic systems with features that include high sensitivity, inherent miniaturization of both the detection and control instrumentation, low cost and power demands, and high compatibility with microfabrication technology. The commonly used electrochemical detectors can be classified into three general modes: conductimetry, potentiometry, and amperometry.

  7. Pharmacokinetics and pharmacodynamics of orally administered acetylenic tricyclic bis(cyanoenone), a highly potent Nrf2 activator with a reversible covalent mode of action

    SciTech Connect

    Kostov, Rumen V.; Knatko, Elena V.; McLaughlin, Lesley A.; Henderson, Colin J.; Zheng, Suqing; Huang, Jeffrey T.-J.; Honda, Tadashi; Dinkova-Kostova, Albena T.

    2015-09-25

    The acetylenic tricyclic bis(cyanoenone) TBE-31 is a highly potent cysteine targeting compound with a reversible covalent mode of action; its best-characterized target being Kelch-like ECH-associated protein-1 (Keap1), the cellular sensor for oxidants and electrophiles. TBE-31 reacts with cysteines of Keap1, impairing its ability to target nuclear factor-erythroid 2 p45-related factor 2 (Nrf2) for degradation. Consequently, Nrf2 accumulates and orchestrates cytoprotective gene expression. In this study we investigated the pharmacokinetic and pharmacodynamic properties of TBE-31 in C57BL/6 mice. After a single oral dose of 10 μmol/kg (∼200 nmol/animal), the concentration of TBE-31 in blood exhibited two peaks, at 22.3 nM and at 15.5 nM, 40 min and 4 h after dosing, respectively, as determined by a quantitative stable isotope dilution LC-MS/MS method. The AUC{sub 0–24h} was 195.5 h/nmol/l, the terminal elimination half-life was 10.2 h, and the k{sub el} was 0.068 h{sup −1}. To assess the pharmacodynamics of Nrf2 activation by TBE-31, we determined the enzyme activity of its prototypic target, NAD(P)H:quinone oxidoreductase 1 (NQO1) and found it elevated by 2.4- and 1.5-fold in liver and heart, respectively. Continuous feeding for 18 days with diet delivering the same daily doses of TBE-31 under conditions of concurrent treatment with the immunosuppressive agent azathioprine had a similar effect on Nrf2 activation without any indications of toxicity. Together with previous reports showing the cytoprotective effects of TBE-31 in animal models of carcinogenesis, our results demonstrate the high potency, efficacy and suitability for chronic administration of cysteine targeting reversible covalent drugs. - Highlights: • TBE-31 is a cysteine targeting compound with a reversible covalent mode of action. • After a single oral dose, the blood concentration of TBE-31 exhibits two peaks. • Oral TBE-31 is a potent activator of Nrf2-dependent enzymes in

  8. Right dorsolateral prefrontal cortical activity and behavioral inhibition.

    PubMed

    Shackman, Alexander J; McMenamin, Brenton W; Maxwell, Jeffrey S; Greischar, Lawrence L; Davidson, Richard J

    2009-12-01

    Individuals show marked variation in their responses to threat. Such individual differences in behavioral inhibition play a profound role in mental and physical well-being. Behavioral inhibition is thought to reflect variation in the sensitivity of a distributed neural system responsible for generating anxiety and organizing defensive responses to threat and punishment. Although progress has been made in identifying the key constituents of this behavioral inhibition system in humans, the involvement of dorsolateral prefrontal cortex (DLPFC) remains unclear. Here, we acquired self-reported Behavioral Inhibition System Sensitivity scores and high-resolution electroencephalography from a large sample (n= 51). Using the enhanced spatial resolution afforded by source modeling techniques, we show that individuals with greater tonic (resting) activity in right-posterior DLPFC rate themselves as more behaviorally inhibited. This observation provides novel support for recent conceptualizations of behavioral inhibition and clues to the mechanisms that might underlie variation in threat-induced negative affect. PMID:19906125

  9. Reactions of vanadium dioxide molecules with acetylene: infrared spectra of VO2(η(2)-C2H2)(x) (x = 1, 2) and OV(OH)CCH in solid neon.

    PubMed

    Zhou, Xiaojie; Chen, Mohua; Zhou, Mingfei

    2013-07-01

    Reactions of vanadium dioxide molecules with acetylene have been studied by matrix isolation infrared spectroscopy. Reaction intermediates and products are identified on the basis of isotopic substitutions as well as density functional frequency calculations. Ground state vanadium dioxide molecule reacts with acetylene in forming the side-on-bonded VO2(η(2)-C2H2) and VO2(η(2)-C2H2)2 complexes spontaneously on annealing in solid neon. The VO2(η(2)-C2H2) complex is characterized to have a (2)B2 ground state with C2v symmetry, whereas the VO2(η(2)-C2H2)2 complex has a (2)A ground state with C2 symmetry. The VO2(η(2)-C2H2) and VO2(η(2)-C2H2)2 complexes are photosensitive. The VO2(η(2)-C2H2) complex rearranges to the OV(OH)CCH molecule upon UV-vis light excitation. PMID:23718542

  10. Characterization of a spontaneous mutant of Azotobacter vinelandii in which vanadium-dependent nitrogen fixation is not inhibited by molybdenum.

    PubMed

    Bageshwar, U K; Raina, R; Das, H K

    1998-05-01

    A spontaneous mutant derivative of Azotobacter vinelandii CA12 (delta nif HDK), which vanadium-dependent nitrogen fixation is not inhibited by molybdenum (A. vinelandii CARR), grows profusely on BNF-agar containing 1 microM Na2MoO4, alone or supplemented with 1 microM V2O5. The expression of A. vinelandii vnfH::lacZ and vnfA::lacZ fusions in A. vinelandii CARR was not inhibited by 1 mM Na2MoO4, whereas molybdenum at much lower concentration inhibited the expression of vnfH::lacZ and vnfA::lacZ fusions in A. vinlandii CA12. The mutant also exhibited normal acetylene reduction activity in the presence of 1 microM Na2MoO4. The expression of A. vinelandii nifH::lacZ fusion in A. vinelandii CARR was low even though the cells were cultured under non-repressing conditions with urea as nitrogen source in the presence of Na2MoO4. The molybdenum content of A. vinelandii CARR cells was found to be about one-fourth that of A. vinelandii CA12. No nitrate reductase activity could be detected in A. vinelandii CARR when the cells were cultured in the presence of 10 microM Na2MoO4, whereas A. vinelandii CA12 exhibited some activity even with 100 pM Na2MoO4. PMID:9595678

  11. [Tracheostomy techniques].

    PubMed

    Mieth, M; Schellhaaß, A; Hüttner, F J; Larmann, J; Weigand, M A; Büchler, M W

    2016-01-01

    Due to the comprehensive establishment of modern techniques, tracheostomy has become a routine procedure in intensive care units (ICU). The negative effects of prolonged translaryngeal intubation on the laryngeal and tracheal mucosa up to tracheal stenosis can be reduced by tracheostomy. Furthermore, long-term ventilation is facilitated; however, there is no clear evidence on the optimal timing of tracheostomy in critically ill patients. The specific indications and contraindications of surgical as well as percutaneous tracheostomy must be strictly observed for a safe and successful intervention. Exchanging the tracheostomy tube may lead to potentially dangerous situations especially after percutaneous tracheostomy. A standardized and structured approach is therefore recommended. PMID:26643155

  12. Separation techniques.

    PubMed

    Duke, T

    1998-10-01

    The past two years have seen continued development of capillary electrophoresis methods. The separation performance of flowable sieving media now equals, and in some respects exceeds, that provided by gels. The application of microfabrication techniques to separation science is gaining pace. There is a continuing trend towards miniaturization and integration of separation with preparative or analytical steps. Innovative separation methods based on microfabrication technology include electrophoresis in purpose-designed molecular sieves, dielectric, trapping using microelectrodes, and force-free motion in Brownian ratchets. PMID:9818184

  13. Inhibition of nitrosation.

    PubMed

    Bartsch, H; Pignatelli, B; Calmels, S; Ohshima, H

    1993-01-01

    Humans are exposed through ingestion or inhalation to preformed N-nitroso compounds (NOC) in the environment and through the endogenous nitrosation of amino precursors in the body. Activated macrophages and bacterial strains isolated from human infections can enzymatically produce nitrosating agents and NOC from precursors at neutral pH. As a consequence, endogenous nitrosation may occur at various sites of the body, such as the oral cavity, stomach, urinary bladder, and at other sites of infection or inflammation. Numerous substances to which humans are exposed have been identified and shown to inhibit formation of NOC. Such inhibitors include vitamins C and E, certain phenolic compounds, and complex mixtures such as fruit and vegetable juices or other plant extracts. Nitrosation inhibitors normally destroy the nitrosating agents and, thus, act as competitors for the amino compound that serves as substrate for the nitrosating species. Independently, epidemiological studies have already established that fresh fruits and vegetables that are sources of vitamin C, other vitamins, and polyphenols have a protective effect against cancers at various sites and in particular gastric cancer. This article briefly reviews (a) the chemistry of NOC formation and inhibition; (b) the studies in experimental animals that showed that inhibition of endogenous NOC synthesis leads to a reduction of toxic, mutagenic, and carcinogenic effects; (c) recent studies in humans where the degree of inhibition of endogenous NOC synthesis was directly quantified; and (d) the possible contribution of nitrosation inhibitors to human cancer prevention. PMID:8304939

  14. Nitric oxide inhibition strategies

    PubMed Central

    Wong, Vivian (Wai Chong); Lerner, Ethan

    2015-01-01

    Nitric oxide is involved in many physiologic processes. There are efforts, described elsewhere in this volume, to deliver nitric oxide to tissues as a therapy. Nitric oxide also contributes to pathophysiologic processes. Inhibiting nitric oxide or its production can thus also be of therapeutic benefit. This article addresses such inhibitory strategies. PMID:26634146

  15. Zinc Inhibits Hedgehog Autoprocessing

    PubMed Central

    Xie, Jian; Owen, Timothy; Xia, Ke; Singh, Ajay Vikram; Tou, Emiley; Li, Lingyun; Arduini, Brigitte; Li, Hongmin; Wan, Leo Q.; Callahan, Brian; Wang, Chunyu

    2015-01-01

    Zinc is an essential trace element with wide-ranging biological functions, whereas the Hedgehog (Hh) signaling pathway plays crucial roles in both development and disease. Here we show that there is a mechanistic link between zinc and Hh signaling. The upstream activator of Hh signaling, the Hh ligand, originates from Hh autoprocessing, which converts the Hh precursor protein to the Hh ligand. In an in vitro Hh autoprocessing assay we show that zinc inhibits Hh autoprocessing with a Ki of 2 μm. We then demonstrate that zinc inhibits Hh autoprocessing in a cellular environment with experiments in primary rat astrocyte culture. Solution NMR reveals that zinc binds the active site residues of the Hh autoprocessing domain to inhibit autoprocessing, and isothermal titration calorimetry provided the thermodynamics of the binding. In normal physiology, zinc likely acts as a negative regulator of Hh autoprocessing and inhibits the generation of Hh ligand and Hh signaling. In many diseases, zinc deficiency and elevated level of Hh ligand co-exist, including prostate cancer, lung cancer, ovarian cancer, and autism. Our data suggest a causal relationship between zinc deficiency and the overproduction of Hh ligand. PMID:25787080

  16. Novel technique for coal pyrolysis and hydrogenation product analysis

    SciTech Connect

    Pfefferle, L.D.; Boyle, J.

    1993-03-15

    A microjet reactor coupled to a VUV photoionization time-of-flight mass spectrometer has been used to obtain species measurements during high temperature pyrolysis and oxidation of a wide range of hydrocarbon compounds ranging from allene and acetylene to cyclohexane, benzene and toluene. Initial work focused on calibration of the technique, optimization of ion collection and detection and characterization of limitations. Using the optimized technique with 118 nm photoionization, intermediate species profiles were obtained for analysis of the hydrocarbon pyrolysis and oxidation mechanisms. The soft'' ionization, yielding predominantly molecular ions, allowed the study of reaction pathways in these high temperature systems where both sampling and detection challenges are severe. Work has focused on the pyrolysis and oxidative pyrolysis of aliphatic and aromatic hydrocarbon mixtures representative of coal pyrolysis and hydropyrolysis products. The detailed mass spectra obtained during pyrolysis and oxidation of hydrocarbon mixtures is especially important because of the complex nature of the product mixture even at short residence times and low primary reactant conversions. The combustion community has advanced detailed modeling of pyrolysis and oxidation to the C4 hydrocarbon level but in general above that size uncertainties in rate constant and thermodynamic data do not allow us to a priori predict products from mixed hydrocarbon pyrolyses using a detailed chemistry model. For pyrolysis of mixtures of coal-derived liquid fractions with a large range of compound structures and molecular weights in the hundreds of amu the modeling challenge is severe. Lumped models are possible from stable product data.

  17. Photorespiration and Oxygen Inhibition of Photosynthesis in Chlorella pyrenoidosa.

    PubMed

    Shelp, B J; Canvin, D T

    1980-05-01

    The inhibition of photosynthesis by O(2) in air-grown Chlorella pyrenoidosa was investigated using three experimental techniques (artificial leaf, aqueous method, and O(2) electrode) to measure carbon assimilation. CO(2) response curves were determined under different O(2), pH, and temperature conditions. Regardless of the experimental technique and condition, O(2) inhibition was not evident until a concentration of 50% was reached; V(max) values were reduced whereas K(m) (CO(2)) values were unaffected by the increasing O(2) concentration. The response of photosynthesis to O(2) was independent of CO(2) and HCO(3) (-) concentrations as well as temperature. Relative rates of photosynthesis showed a 4 to 5% stimulation in 2% O(2), a 12% inhibition in 50% O(2), and a 24% inhibition in 100% O(2). The inhibition by 50% O(2) was still reversible after 20 minutes exposure whereas 100% O(2) caused irreversible inhibition after only 4 minutes.The O(2) inhibition is discussed in terms of the oxygenase reaction and a Mehler reaction supporting pseudocyclic electron flow. The results are inconsistent with the proposals that photorespiration exists in these algae and that a CO(2)-concentrating mechanism suppresses the O(2) inhibition of photosynthesis. PMID:16661282

  18. New techniques

    NASA Astrophysics Data System (ADS)

    Pisacane, V. L.

    1983-04-01

    Equipment, operations, calibration, and accuracy of existing positioning, geodetic, and gravimetric equipment are explored. Radio navigation and positioning systems now include OMEGA, LORAN, VOR, DME, TACAN, and LONAR. Dedicated positioning satellites comprise the Transit and Navstar systems, with positioning accuracies of 8 m available with the GPS. Missile tracking, particularly for submarine launched rockets, is accomplished with the Satrack satellite, which furnishes position and velocity accuracy to within 40 ft and 0.08 ft/sec, respectively. VLBI techniques permit sighting of astronomical objects to obtain 20 cm accuracy for pole positioning and 1 m/sec for earth rotation speeds. Methods have been devised to use portable equipment which compensates for refraction when using lasers and masers in ranging trials. NASA has established a fixed and mobile global laser tracking network to provide a ranging accuracy of 100 cm when employed with satellite and lunar reflectors. Lasers are also used for terrain contouring, aircraft ranging, and satellite altimetry. A free-fall gravimeter has been developed which involves dropping one reflector of a two-beam Michelson interferometer, yielding an accuracy of 10 microgal. It is noted that new standards are needed for the NASA Deep Space Network.

  19. Drugs that inhibit complement.

    PubMed

    Schrezenmeier, Hubert; Höchsmann, Britta

    2012-02-01

    The complement system is an important part of the innate immune system. Complement plays a crucial role in the pathophysiology of many disorders. Despite the pivotal role of the complement system, an approved targeted inhibitor of a complement factor became available only recently. Eculizumab is a humanized monoclonal antibody that inhibits complement factor C5. It is a targeted, disease modifying, treatment of paroxysmal nocturnal hemoglobinuria (PNH). It was approved be the US FDA and the European Commission in 2007. In this review we will update the experience with eculizumab in PNH and discuss potential use of eculizumab in other disorders (e.g. cold agglutinin disease; atypical HUS) and new approaches to complement inhibition with drugs other than eculizumab. PMID:22169380

  20. Substrate inhibition of transketolase.

    PubMed

    Solovjeva, Olga N; Kovina, Marina V; Kochetov, German A

    2016-03-01

    We studied the influence of the acceptor substrate of transketolase on the activity of the enzyme in the presence of reductants. Ribose-5-phosphate in the presence of cyanoborohydride decreased the transketolase catalytic activity. The inhibition is caused by the loss of catalytic function of the coenzyme-thiamine diphosphate. Similar inhibitory effect was observed in the presence of NADPH. This could indicate its possible regulatory role not only towards transketolase, but also towards the pentose phosphate pathway of carbohydrate metabolism overall, taking into account the fact that it inhibits not only transketolase but also another enzyme of the pentose phosphate pathway--glucose 6-phosphate dehydrogenase [Eggleston L.V., Krebs H.A. Regulation of the pentose phosphate cycle, Biochem. J. 138 (1974) 425-435]. PMID:26708478

  1. Simvastatin Inhibits Airway Hyperreactivity

    PubMed Central

    Zeki, Amir A.; Franzi, Lisa; Last, Jerold; Kenyon, Nicholas J.

    2009-01-01

    Rationale: Statin use has been linked to improved lung health in asthma and chronic obstructive pulmonary disease. We hypothesize that statins inhibit allergic airway inflammation and reduce airway hyperreactivity via a mevalonate-dependent mechanism. Objectives: To determine whether simvastatin attenuates airway inflammation and improves lung physiology by mevalonate pathway inhibition. Methods: BALB/c mice were sensitized to ovalbumin over 4 weeks and exposed to 1% ovalbumin aerosol over 2 weeks. Simvastatin (40 mg/kg) or simvastatin plus mevalonate (20 mg/kg) was injected intraperitoneally before each ovalbumin exposure. Measurements and Main Results: Simvastatin reduced total lung lavage leukocytes, eosinophils, and macrophages (P < 0.05) in the ovalbumin-exposed mice. Cotreatment with mevalonate, in addition to simvastatin, reversed the antiinflammatory effects seen with simvastatin alone (P < 0.05). Lung lavage IL-4, IL-13, and tumor necrosis factor-α levels were all reduced by treatment with simvastatin (P < 0.05). Simvastatin treatment before methacholine bronchial challenge increased lung compliance and reduced airway hyperreactivity (P = 0.0001). Conclusions: Simvastatin attenuates allergic airway inflammation, inhibits key helper T cell type 1 and 2 chemokines, and improves lung physiology in a mouse model of asthma. The mevalonate pathway appears to modulate allergic airway inflammation, while the beneficial effects of simvastatin on lung compliance and airway hyperreactivity may be independent of the mevalonate pathway. Simvastatin and similar agents that modulate the mevalonate pathway may prove to be treatments for inflammatory airway diseases, such as asthma. PMID:19608720

  2. Element-selective trace detection of toxic species in environmental samples using chromatographic techniques and derivative diode laser absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Koch, J.; Zybin, A.; Niemax, K.

    1998-10-01

    Very sensitive laser absorption techniques based on a double-beam scheme with logarithmic processing of the detector signals and wavelength modulation of laser diodes are presented. Detection limits equivalent to 10-7 absorption per square root of detection bandwidth are obtained if sufficient laser power is available and if the absorption is also subject to additional modulation. The analytical versatility of these techniques is demonstrated by quantitative analysis of very low concentrations of (i) Cr(VI) species in tap water and (ii) chlorinated poly-aromatics (chlorophenols) in plant extracts, both after chromatographic separation. The atomic absorption measurements were performed in an air-acetylene flame (Cr) and in a low-pressure microwave-induced plasma (chlorophenols).

  3. Facile, soot free approach toward synthesis of carbon nanoropes via chemical vapor deposition of acetylene in the presence of MnFe2O4 coated on stainless steel

    NASA Astrophysics Data System (ADS)

    Dhand, Vivek; Bharadwaj, S.; Amareshwari, K.; Himabindu, V.; Rhee, Kyong Yop; Park, Soo-Jin; Hui, David

    2015-12-01

    High density, soot free, novel and a facile approach toward synthesis of carbon nanoropes (CNRs) were successfully carried out in a chemical vapor deposition (CVD) process. Manganese ferrite (MnFe2O4) coated on stainless steel foil (SS 316 grade) was used as a catalyst to initiate the growth of CNR. The coated catalyst was introduced into the CVD and the chamber temperature was set at 700 °C later followed with the release of acetylene (50 sccm) and nitrogen (500 sccm) gas, respectively. Total reaction continued until 30 min. No purification or oxidation process of the soot was involved. Analysis reveals the presence of intermingled CNRs with semi crystalline nature of the sample. The elemental analysis confirms the presence of manganese and iron whereas Raman spectrum shows the characteristic narrow G and D bands. The sample displays a super-paramagnetic behavior and is thermally stable up to 500-550 °C presenting a strong exothermic reaction.

  4. Beneficial bacteria inhibit cachexia

    PubMed Central

    Varian, Bernard J.; Goureshetti, Sravya; Poutahidis, Theofilos; Lakritz, Jessica R.; Levkovich, Tatiana; Kwok, Caitlin; Teliousis, Konstantinos; Ibrahim, Yassin M.; Mirabal, Sheyla; Erdman, Susan E.

    2016-01-01

    Muscle wasting, known as cachexia, is a debilitating condition associated with chronic inflammation such as during cancer. Beneficial microbes have been shown to optimize systemic inflammatory tone during good health; however, interactions between microbes and host immunity in the context of cachexia are incompletely understood. Here we use mouse models to test roles for bacteria in muscle wasting syndromes. We find that feeding of a human commensal microbe, Lactobacillus reuteri, to mice is sufficient to lower systemic indices of inflammation and inhibit cachexia. Further, the microbial muscle-building phenomenon extends to normal aging as wild type animals exhibited increased growth hormone levels and up-regulation of transcription factor Forkhead Box N1 [FoxN1] associated with thymus gland retention and longevity. Interestingly, mice with a defective FoxN1 gene (athymic nude) fail to inhibit sarcopenia after L. reuteri therapy, indicating a FoxN1-mediated mechanism. In conclusion, symbiotic bacteria may serve to stimulate FoxN1 and thymic functions that regulate inflammation, offering possible alternatives for cachexia prevention and novel insights into roles for microbiota in mammalian ontogeny and phylogeny. PMID:26933816

  5. Pharmacological inhibition of FTO.

    PubMed

    McMurray, Fiona; Demetriades, Marina; Aik, WeiShen; Merkestein, Myrte; Kramer, Holger; Andrew, Daniel S; Scudamore, Cheryl L; Hough, Tertius A; Wells, Sara; Ashcroft, Frances M; McDonough, Michael A; Schofield, Christopher J; Cox, Roger D

    2015-01-01

    In 2007, a genome wide association study identified a SNP in intron one of the gene encoding human FTO that was associated with increased body mass index. Homozygous risk allele carriers are on average three kg heavier than those homozygous for the protective allele. FTO is a DNA/RNA demethylase, however, how this function affects body weight, if at all, is unknown. Here we aimed to pharmacologically inhibit FTO to examine the effect of its demethylase function in vitro and in vivo as a first step in evaluating the therapeutic potential of FTO. We showed that IOX3, a known inhibitor of the HIF prolyl hydroxylases, decreased protein expression of FTO (in C2C12 cells) and reduced maximal respiration rate in vitro. However, FTO protein levels were not significantly altered by treatment of mice with IOX3 at 60 mg/kg every two days. This treatment did not affect body weight, or RER, but did significantly reduce bone mineral density and content and alter adipose tissue distribution. Future compounds designed to selectively inhibit FTO's demethylase activity could be therapeutically useful for the treatment of obesity. PMID:25830347

  6. Beneficial bacteria inhibit cachexia.

    PubMed

    Varian, Bernard J; Goureshetti, Sravya; Poutahidis, Theofilos; Lakritz, Jessica R; Levkovich, Tatiana; Kwok, Caitlin; Teliousis, Konstantinos; Ibrahim, Yassin M; Mirabal, Sheyla; Erdman, Susan E

    2016-03-15

    Muscle wasting, known as cachexia, is a debilitating condition associated with chronic inflammation such as during cancer. Beneficial microbes have been shown to optimize systemic inflammatory tone during good health; however, interactions between microbes and host immunity in the context of cachexia are incompletely understood. Here we use mouse models to test roles for bacteria in muscle wasting syndromes. We find that feeding of a human commensal microbe, Lactobacillus reuteri, to mice is sufficient to lower systemic indices of inflammation and inhibit cachexia. Further, the microbial muscle-building phenomenon extends to normal aging as wild type animals exhibited increased growth hormone levels and up-regulation of transcription factor Forkhead Box N1 [FoxN1] associated with thymus gland retention and longevity. Interestingly, mice with a defective FoxN1 gene (athymic nude) fail to inhibit sarcopenia after L. reuteri therapy, indicating a FoxN1-mediated mechanism. In conclusion, symbiotic bacteria may serve to stimulate FoxN1 and thymic functions that regulate inflammation, offering possible alternatives for cachexia prevention and novel insights into roles for microbiota in mammalian ontogeny and phylogeny. PMID:26933816

  7. Pharmacological Inhibition of FTO

    PubMed Central

    McMurray, Fiona; Demetriades, Marina; Aik, WeiShen; Merkestein, Myrte; Kramer, Holger; Andrew, Daniel S.; Scudamore, Cheryl L.; Hough, Tertius A.; Wells, Sara; Ashcroft, Frances M.; McDonough, Michael A.; Schofield, Christopher J.; Cox, Roger D.

    2015-01-01

    In 2007, a genome wide association study identified a SNP in intron one of the gene encoding human FTO that was associated with increased body mass index. Homozygous risk allele carriers are on average three kg heavier than those homozygous for the protective allele. FTO is a DNA/RNA demethylase, however, how this function affects body weight, if at all, is unknown. Here we aimed to pharmacologically inhibit FTO to examine the effect of its demethylase function in vitro and in vivo as a first step in evaluating the therapeutic potential of FTO. We showed that IOX3, a known inhibitor of the HIF prolyl hydroxylases, decreased protein expression of FTO (in C2C12 cells) and reduced maximal respiration rate in vitro. However, FTO protein levels were not significantly altered by treatment of mice with IOX3 at 60 mg/kg every two days. This treatment did not affect body weight, or RER, but did significantly reduce bone mineral density and content and alter adipose tissue distribution. Future compounds designed to selectively inhibit FTO’s demethylase activity could be therapeutically useful for the treatment of obesity. PMID:25830347

  8. Laser Pyrolysis Techniques: Application To Catalysis, Combustion Diagnostics, And Kinetics

    NASA Astrophysics Data System (ADS)

    Smith, Gregory P.

    1984-05-01

    A pulsed laser pyrolysis method has been developed to study kinetic processes at high temperatures. A CO2 laser is used to irradiate a 100 torr mixture of an infrared absorber (SF6), bath gas (N2), and reactants. Rapid heating to 700-1400 K occurs, followed by two-stage cooling. Unimolecular reactions are studied by competitive kinetics with a known standard, using mass-spectrometric or gas-chromatographic analysis. Bimolecular processes are examined using laser-induced fluorescence (LIF). The technique offers great advantages in reaching reactive temperatures in a fast and time-resolved manner, without the complications of hot surfaces. It is thus an ideal tool for analyzing and measuring some of the basic processes occurring in more complicated, real, hot systems. Our recent applications of the laser pyrolysis method in the areas of catalysis and combustion are summarized here. Several transition metal-carbonyl bond dissociation energies have been measured, and catalysis by the hot metal particulate products was observed. Since the use of LIF as a flame diagnotic requires some knowledge of the fluorescence quenching rates at high temperatures, the laser pyrolysis method was used to measure these rates for the important OH radical. Its reaction rate with acetylene was also measured, with implications for flame modeling and the mechanism of soot formation. Finally, this method can be used to ignite low concentrations of fuel and oxidant, and then study the time-resolved evolution of the flame chemistry by LIF and chemiluminescence observations.

  9. Inhibition of food intake.

    PubMed

    Young, Andrew

    2005-01-01

    Over 100 publications, principally from five groups, describe an effect of amylin and amylin analogs in inhibition of food intake in animals and humans. The major groups contributing to this area are those of the following: Chance and Balasubramaniam (Balasubramaniam et al., 1991a,b; Chance et al., 1991a,b, 1992a,b, 1993). Morley, Flood, and Edwards (Edwards and Morley, 1992; Flood and Morley, 1992; Macintosh et al., 2000; Morley and Flood, 1991, 1994; Morley et al., 1992, 1993, 1994, 1995, 1996, 1997). Lutz, Geary, and others (Barth et al., 2003; Del Prete et al., 2002; Lutz et al., 1994, 1995a,b, 1996a,b, 1997a,b, 1998a,b,c, 2000a,b, 2001a,b,c, 2003; Mollet et al., 2001, 2003a,b, 2004; Riediger et al., 2002, 2004; Rushing et al., 2000a,b, 2001, 2002). Workers at Amylin Pharmaceuticals Inc., or their collaborators (Bhavsar et al., 1995, 1996, 1997a, 1998; Birkemo et al., 1995; Chapman et al., 2004a,b; Edwards et al., 1998; Feinle et al., 2002; Mack et al., 2003; Riediger et al., 1999; Roth et al., 2004; Watkins et al., 1996; Weyer et al., 2004; Young, 1997; Young and Bhavsar, 1996). Arnelo, Reidelberger, and others (Arnelo et al., 1996a,b, 1997a,b, 1998, 2000; Fruin et al., 1997; Granqvist et al., 1997; Reidelberger et al., 2001, 2002, 2004). The magnitude of amylin inhibition of food intake, and its potency for this effect when delivered peripherally, suggests a physiological role in satiogenesis. Increases in food intake following disruption of amylin signal-signaling (e.g., with amylin receptor blockade, or with amylin gene knock-out mice) further support a role of endogenous amylin to tonically restrict nutrient intake. In addition, synergies with other endogenous satiety agents may be present, and convey greater physiological importance than is conveyed by single signals. The anorectic effect of amylin is consistent with a classic amylin pharmacology. The anorectic effect of peripheral amylin appears principally due to a direct action at the area postrema

  10. Checkpoint inhibition in meningiomas.

    PubMed

    Bi, Wenya Linda; Wu, Winona W; Santagata, Sandro; Reardon, David A; Dunn, Ian F

    2016-06-01

    Meningiomas are increasingly appreciated to share similar features with other intra-axial central nervous system neoplasms as well as systemic cancers. Immune checkpoint inhibition has emerged as a promising therapy in a number of cancers, with durable responses of years in a subset of patients. Several lines of evidence support a role for immune-based therapeutic strategies in the management of meningiomas, especially high-grade subtypes. Meningiomas frequently originate juxtaposed to venous sinuses, where an anatomic conduit for lymphatic drainage resides. Multiple populations of immune cells have been observed in meningiomas. PD-1/PD-L1 mediated immunosuppression has been implicated in high-grade meningiomas, with association between PD-L1 expression with negative prognostic outcome. These data point to the promise of future combinatorial therapeutic strategies in meningioma. PMID:27197540

  11. Analytical techniques: A compilation

    NASA Technical Reports Server (NTRS)

    1975-01-01

    A compilation, containing articles on a number of analytical techniques for quality control engineers and laboratory workers, is presented. Data cover techniques for testing electronic, mechanical, and optical systems, nondestructive testing techniques, and gas analysis techniques.

  12. Laser Frequency Stabilization for Coherent Lidar Applications using Novel All-Fiber Gas Reference Cell Fabrication Technique

    NASA Technical Reports Server (NTRS)

    Meras, Patrick, Jr.; Poberezhskiy, Ilya Y.; Chang, Daniel H.; Levin, Jason; Spiers, Gary D.

    2008-01-01

    Compact hollow-core photonic crystal fiber (HC-PCF)gas frequency reference cell was constructed using a novel packaging technique that relies on torch-sealing a quartz filling tube connected to a mechanical splice between regular and hollow-core fibers. The use of this gas cell for laser frequency stabilization was demonstrated by locking a tunable diode laser to the center of the P9 line from the (nu)1+(nu)3 band of acetylene with RMS frequency error of 2.06 MHz over 2 hours. This effort was performed in support of a task to miniaturize the laser frequency stabilization subsystem of JPL/LMCT Laser Absorption Spectrometer (LAS) instrument.

  13. Inhibition of anaerobic digestion process: a review.

    PubMed

    Chen, Ye; Cheng, Jay J; Creamer, Kurt S

    2008-07-01

    Anaerobic digestion is an attractive waste treatment practice in which both pollution control and energy recovery can be achieved. Many agricultural and industrial wastes are ideal candidates for anaerobic digestion because they contain high levels of easily biodegradable materials. Problems such as low methane yield and process instability are often encountered in anaerobic digestion, preventing this technique from being widely applied. A wide variety of inhibitory substances are the primary cause of anaerobic digester upset or failure since they are present in substantial concentrations in wastes. Considerable research efforts have been made to identify the mechanism and the controlling factors of inhibition. This review provides a detailed summary of the research conducted on the inhibition of anaerobic processes. The inhibitors commonly present in anaerobic digesters include ammonia, sulfide, light metal ions, heavy metals, and organics. Due to the difference in anaerobic inocula, waste composition, and experimental methods and conditions, literature results on inhibition caused by specific toxicants vary widely. Co-digestion with other waste, adaptation of microorganisms to inhibitory substances, and incorporation of methods to remove or counteract toxicants before anaerobic digestion can significantly improve the waste treatment efficiency. PMID:17399981

  14. Spectroscopic analysis of urinary calculi and inhibition of their growth

    NASA Astrophysics Data System (ADS)

    Manciu, Felicia; Durrer, William; Govani, Jayesh; Reza, Layra; Pinales, Luis

    2009-10-01

    We present here a study of kidney stone formation and growth inhibition based on a traditional medicine approach with Aquatica Lour (RAL) herbal extracts. Kidney stone material systems were synthesized in vitro using a simplified single diffusion gel growth technique. With the objective of revealing the mechanism of inhibition of calculi formation by RAL extracts, samples prepared without the presence of extract, and with the presence of extract, were analyzed using Raman, photoluminescence, and XPS. The unexpected presence of Zn revealed by XPS in a sample prepared with RAL provides an explanation for the inhibition process, and also explains the dramatic reflectance of incident light observed in attempts to obtain infrared transmission data. Raman data are consistent with the binding of the inhibitor to the oxygen of the kidney stone. Photoluminescence data corroborate with the other results to provide additional evidence of Zn-related inhibition.

  15. Can Arousal Modulate Response Inhibition?

    ERIC Educational Resources Information Center

    Weinbach, Noam; Kalanthroff, Eyal; Avnit, Amir; Henik, Avishai

    2015-01-01

    The goal of the present study was to examine if and how arousal can modulate response inhibition. Two competing hypotheses can be drawn from previous literature. One holds that alerting cues that elevate arousal should result in an impulsive response and therefore impair response inhibition. The other suggests that alerting enhances processing of…

  16. Inhibition of cellulases by phenols

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The inhibition of enzymes by the end products that they make is a well-known phenomenon. Another form of inhibition is manifested by the decrease in hydrolysis of pretreated cellulosic material as the concentration of solid biomass material increases, even though the ratio of enzyme to cellulose is...

  17. Protoporphyrinogen Oxidase-Inhibiting Herbicides

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Protoporphyrinogen oxidase-inhibiting herbicides (also referred to as Protox- or PPO-inhibiting herbicides) were commercialized in the 1960s and their market share reached approximately 10% (total herbicide active ingredient output) in the late 1990’s. The wide-spread adoption of glyphosate-resista...

  18. Balanced feedforward inhibition and dominant recurrent inhibition in olfactory cortex.

    PubMed

    Large, Adam M; Vogler, Nathan W; Mielo, Samantha; Oswald, Anne-Marie M

    2016-02-23

    Throughout the brain, the recruitment of feedforward and recurrent inhibition shapes neural responses. However, disentangling the relative contributions of these often-overlapping cortical circuits is challenging. The piriform cortex provides an ideal system to address this issue because the interneurons responsible for feedforward and recurrent inhibition are anatomically segregated in layer (L) 1 and L2/3 respectively. Here we use a combination of optical and electrical activation of interneurons to profile the inhibitory input received by three classes of principal excitatory neuron in the anterior piriform cortex. In all classes, we find that L1 interneurons provide weaker inhibition than L2/3 interneurons. Nonetheless, feedforward inhibitory strength covaries with the amount of afferent excitation received by each class of principal neuron. In contrast, intracortical stimulation of L2/3 evokes strong inhibition that dominates recurrent excitation in all classes. Finally, we find that the relative contributions of feedforward and recurrent pathways differ between principal neuron classes. Specifically, L2 neurons receive more reliable afferent drive and less overall inhibition than L3 neurons. Alternatively, L3 neurons receive substantially more intracortical inhibition. These three features--balanced afferent drive, dominant recurrent inhibition, and differential recruitment by afferent vs. intracortical circuits, dependent on cell class--suggest mechanisms for olfactory processing that may extend to other sensory cortices. PMID:26858458

  19. Reaction Mechanism of the Symmetry-Forbidden [2+2] Addition of Ethylene and Acetylene to Amido-Substituted Digermynes and Distannynes Ph2N-EE-NPh2, (E = Ge, Sn): A Theoretical Study.

    PubMed

    Zhao, Lili; Jones, Cameron; Frenking, Gernot

    2015-08-24

    Quantum chemical calculations of reaction mechanisms for the formal [2+2] addition of ethylene and acetylene to the amido-substituted digermyne and distannyne Ph2N-EE-NPh2 (E = Ge, Sn) have been carried out by using density functional theory at the BP86/def2-TZVPP level. The nature and bonding situations were studied with the NBO method and with the charge and energy decomposition analysis EDA-NOCV. The addition of ethylene to Ph2N-EE-NPh2 takes place through an initial [2+1] addition to one metal atom and consecutive rearrangement to four-membered cyclic species, which feature a weak E-E bond. Rotation about the C-C bond with concomitant rupture of the E-E bond leads to the 1,2-disubstituted ethanes, which have terminal E(NPh2) groups. The overall reaction Ph2N-EE-NPh2+C2H4→(Ph2N)E-C2H4-E(NPh2) has very low activation barriers and is slightly exergonic for E = Ge but slightly endergonic for E = Sn. The analysis of the electronic structure shows that there is charge donation of nearly one electron to the ethylene moiety already in the first part of the reaction. The energy partitioning analysis suggests that the HOMO(Ph2N-EE-NPh2)→LUMO(C2H4) interaction has a similar strength as the HOMO(C2H4)→LUMO(Ph2N-EE-NPh2) interaction. The [2+2] addition of acetylene to Ph2N-EE-NPh2 also takes place through an initial [2+1] approach, which eventually leads to 1,2-disubstituted olefins (Ph2N)E-C2H2-E(NPh2). The formation of the energetically lowest lying conformations of cis-(Ph2N)E-C2H2-E(NPh2), which occurs with very low activation barriers, is clearly exergonic for the germanium and the tin compound. The trans-coordinated isomers of (Ph2N)E-C2H2-E(NPh2) are slightly lower in energy than the cis form but they are separated by a substantial energy barrier for the rotation about the C-C bond. The energy decomposition analysis indicates that the initial reaction takes place under formation of electron-sharing bonds between triplet fragments rather than HOMO

  20. Catalase is inhibited by flavonoids.

    PubMed

    Krych, Justyna; Gebicka, Lidia

    2013-07-01

    Catalases, heme enzymes, which catalyze decomposition of hydrogen peroxide to water and molecular oxygen, belong to the antioxidant defense system of the cell. In this work we have shown that catalase from bovine liver is inhibited by flavonoids. The inhibition is, at least partially, due to the formation of hydrogen bonds between catalase and flavonoids. In the presence of some flavonoids the formation of unreactive catalase compound II has been detected. The most potent catalase inhibitors among the tested flavonoids have appeared myricetin, epicatechin gallate and epigallocatechin gallate. The relationship between the degree of enzyme inhibition and molecular structure of flavonoids has been analyzed. PMID:23567286

  1. The role of isovalency in the reactions of the cyano (CN), boron monoxide (BO), silicon nitride (SiN), and ethynyl (C2H) radicals with unsaturated hydrocarbons acetylene (C2H2) and ethylene (C2H4).

    PubMed

    Parker, D S N; Mebel, A M; Kaiser, R I

    2014-04-21

    The classification of chemical reactions based on shared characteristics is at the heart of the chemical sciences, and is well exemplified by Langmuir's concept of isovalency, in which 'two molecular entities with the same number of valence electrons have similar chemistries'. Within this account we further investigate the ramifications of the isovalency of four radicals with the same X(2)Σ(+) electronic structure - cyano (CN), boron monoxide (BO), silicon nitride (SiN), and ethynyl (C2H), and their reactions with simple prototype hydrocarbons acetylene (C2H2) and ethylene (C2H4). The fact that these four reactants own the same X(2)Σ(+) electronic ground state should dictate the outcome of their reactions with prototypical hydrocarbons holding a carbon-carbon triple and double bond. However, we find that other factors come into play, namely, atomic radii, bonding orbital overlaps, and preferential location of the radical site. These doublet radical reactions with simple hydrocarbons play significant roles in extreme environments such as the interstellar medium and planetary atmospheres (CN, SiN and C2H), and combustion flames (C2H, BO). PMID:24418936

  2. Aerodynamic measurement techniques. [laser based diagnostic techniques

    NASA Technical Reports Server (NTRS)

    Hunter, W. W., Jr.

    1976-01-01

    Laser characteristics of intensity, monochromatic, spatial coherence, and temporal coherence were developed to advance laser based diagnostic techniques for aerodynamic related research. Two broad categories of visualization and optical measurements were considered, and three techniques received significant attention. These are holography, laser velocimetry, and Raman scattering. Examples of the quantitative laser velocimeter and Raman scattering measurements of velocity, temperature, and density indicated the potential of these nonintrusive techniques.

  3. Inhibition of MMPs by alcohols

    PubMed Central

    Tezvergil-Mutluay, Arzu; Agee, Kelli A.; Hoshika, Tomohiro; Uchiyama, Toshikazu; Tjäderhane, Leo; Breschi, Lorenzo; Mazzoni, Annalisa; Thompson, Jeremy M.; McCracken, Courtney E.; Looney, Stephen W.; Tay, Franklin R.; Pashley, David H.

    2011-01-01

    Objectives While screening the activity of potential inhibitors of matrix metalloproteinases (MMPs), due to the limited water solubility of some of the compounds, they had to be solubilized in ethanol. When ethanol solvent controls were run, they were found to partially inhibit MMPs. Thus, the purpose of this study was to compare the MMP-inhibitory activity of a series of alcohols. Methods The possible inhibitory activity of a series of alcohols was measured against soluble rhMMP-9 and insoluble matrix-bound endogenous MMPs of dentin in completely demineralized dentin. Increasing concentrations (0.17, 0.86, 1.71 and 4.28 moles/L) of a homologous series of alcohols (i.e. methanol, ethanol, propanols, butanols, pentanols, hexanols, the ethanol ester of methacrylic acid, heptanols and octanol) were compared to ethanediol, and propanediol by regression analysis to calculate the molar concentration required to inhibit MMPs by 50% (i.e. the IC50). Results Using two different MMP models, alcohols were shown to inhibit rhMMP-9 and the endogenous proteases of dentin matrix in a dose-dependent manner. The degree of MMP inhibition by alcohols increased with chain length up to 4 methylene groups. Based on the molar concentration required to inhibit rhMMP-9 fifty percent, 2-hydroxyethylmethacrylate (HEMA), 3-hexanol, 3-heptanol and 1-octanol gave the strongest inhibition. Significance The results indicate that alcohols with 4 methylene groups inhibit MMPs more effectively than methanol or ethanol. MMP inhibition was inversely related to the Hoy's solubility parameter for hydrogen bonding forces of the alcohols (i.e. to their hydrophilicity). PMID:21676453

  4. Inhibition of anaerobic digestion by organic priority pollutants

    SciTech Connect

    Johnson, L.D.

    1981-01-01

    Process instability caused by toxic inhibition is a major problem with anaerobic waste treatment systems. A batch bioassay technique was used to determine inhibitory effects from the twenty-four representative organic pollutants selected for testing. Only seven produced significant inhibition of gas production at concentrations of 100 mg/l or less. These seven were (a) nitrobenzene, (b) 4-nitrophenol, (c) 2-nitrophenol, (d) hexachloroethane, (e) hexachlorocyclopentadiene, (f) 2,4-dichlorophenol, and (g) hexachloro-1,3-butadiene. Reversible inhibition was observed for all of these except (f) and (g). The recovery of methane production inhibited by the nitro organics was due to biological reduction of the nitro group to a relatively nontoxic amine group. Recovery of gas production in cultures inhibited by (d) was due to acclimation of the microorganisms to the low concentrations of this compound remaining in solution after removal by adsorption onto the solids in the cultures. A combination of adsorption and anaerobic dechlorination of (e) caused the removal of this compound from solution and thus the recovery of gas production. The concentration of (g) was significantly reduced by adsorption, but gas production did not recover in cultures inhibited by this compound.

  5. Isotope fractionations factors of N2O production and reduction by denitrification: a. Laboratory incubation studies using N2O reductase inhibition

    NASA Astrophysics Data System (ADS)

    Well, Reinhard; Weymann, Daniel; Lewicka-Szczebak, Dominika; Rohe, Lena; Flessa, Heinz

    2013-04-01

    Isotopologue signatures of N2O such as δ18O, average δ15N (δ15Nbulk) and 15N site preference (SP = difference in δ15N between the central and peripheral N positions of the asymmetric N2O molecule) can be used to constrain the atmospheric N2O budget and to characterize N2O turnover processes. However, the use of this approach to study N2O dynamics in soils requires knowledge of isotopologue fractionation factors (?) for the various partial processes involved, e.g. N2O production by nitrification or denitrification, and N2O reduction by denitrification. Here we present results from laboratory incubations of soils and aquifer material to determine ?gf N2O production (?prod) and N2O reduction to N2 (?red) during denitrification. ?prod for δ18O, δ15Nbulk and SP was obtained by anaerobic incubation of NO3- amended soils when N2O reduction was inhibited by 10 kPa acetylene. ?red of the respective signatures was derived by comparing treatments with and without inhibition of N2O reduction. We investigated samples from 4 mineral soils, one organic soil and from a sandy aquifer. The mineral soils were incubated under unsaturated conditions in closed or open systems, the organic and aquifer samples as homogenized slurries in a closed system. Results of fractionation factors, process rates and incubation conditions will be presented and discussed in view of previous studies and theoretical considerations.

  6. Behavioral inhibition and childhood stuttering

    PubMed Central

    Choi, Dahye; Conture, Edward G.; Walden, Tedra A.; Lambert, Warren E.; Tumanova, Victoria

    2013-01-01

    Purpose The purpose of this study was to assess the relation of behavioral inhibition to stuttering and speech/language output in preschool-age children who do (CWS) and do not stutter (CWNS). Method Participants were preschool-age (ages 36 to 68 months), including 26 CWS (22 males) and 28 CWNS (13 males). Participants’ behavioral inhibition (BI) was assessed by measuring the latency to their sixth spontaneous comment during conversation with an unfamiliar experimenter, using methodology developed by Kagan, Reznick, and Gibbons (1989). In addition to these measures of BI, each participant’s stuttered and non-stuttered disfluencies and mean length of utterance (in morphemes) were assessed. Results Among the more salient findings, it was found that (1) there was no significant difference in BI between preschool-age CWS and CWNS as a group, (2) when extremely high versus low inhibited children were selected, there were more CWS with higher BI and fewer CWS with lower BI when compared to their CWNS peers, and (3) more behaviorally inhibited CWS, when compared to less behaviorally inhibited CWS, exhibited more stuttering. Conclusions Findings are taken to suggest that one aspect of temperament (i.e., behavioral inhibition) is exhibited by some preschool-age CWS and that these children stutter more than CWS with lower behavioral inhibition. The present results seem to support continued study of the association between young children’s temperamental characteristics and stuttering, the diagnostic entity (i.e., CWS versus CWNS), as well as stuttering, the behavior (e.g., frequency of stuttered disfluencies). PMID:23773669

  7. Heme oxygenase/carbon monoxide pathway inhibition plays a role in ameliorating fibrosis following splenectomy.

    PubMed

    Wang, Qiu-Ming; Duan, Zhi-Jun; Du, Jian-Ling; Guo, Shi-Bin; Sun, Xiao-Yu; Liu, Zhen

    2013-05-01

    Splenectomy is a recognized therapy for liver cirrhosis with splenomegaly, since it decreases free iron concentration that accompanies the destruction of red blood cells. Heme oxygenase (HO)-1 and its by-products, iron and carbon monoxide (CO), play crucial roles in hepatic fibrosis. The aim of the present study was to determine whether splenectomy in cirrhotic rats induced by bile duct ligation (BDL), through the HO/CO pathway, could slow down the development of liver fibrosis. Male Sprague-Dawley rats were divided randomly into the sham, BDL, splenectomy, Fe, zinc protoporphyrin (Znpp) and cobalt protoporphyrin (Copp) treatment groups, for inhibiting and inducing HO-1 expression. The level of HO-1 was detected by western blot analysis and reverse transcription-polymerase chain reaction. Serum carboxyhemoglobin (COHb), iron and portal vein pressure (PVP) were also quantified. Liver iron was measured by atomic absorption spectrometry with acetylene-air flame atomization. HO-1 and α-smooth muscle actin (α-SMA) were localized by immunohistochemistry. Liver and spleen iron were visualized by Perls' Prussian blue staining. Hepatic fibrosis was assessed using hematoxylin and eosin (H&E) staining. Enzyme-linked immunosorbent assay (ELISA) was used to detect serum transforming growth factor-β1 (TGF-β1). The results showed that liver, spleen and serum levels of HO-1, COHb and iron were greatly enhanced in the BDL group compared with the sham group; they were reduced following splenectomy and Znpp treatment, but were elevated in the Copp and Fe groups. Hydroxyproline, TGF-β1, α-SMA, PVP and malonaldehyde levels were lower in the splenectomy and Znpp groups compared to BDL, while higher levels were observed in the Copp and Fe-treated groups. Our study shows that splenectomy reduces iron and CO levels in part by reducing HO-1 expression, and it decreases portal pressure and slightly decreases hepatic fibroproliferation. PMID:23525258

  8. Remote inhibition of polymer degradation.

    SciTech Connect

    Clough, Roger Lee; Celina, Mathias Christopher

    2005-08-01

    Polymer degradation has been explored on the basis of synergistic infectious and inhibitive interaction between separate materials. A dual stage chemiluminescence detection system with individually controlled hot stages was applied to probe for interaction effects during polymer degradation in an oxidizing environment. Experimental confirmation was obtained that volatile antioxidants can be transferred over a relatively large distance. The thermal degradation of a polypropylene (PP) sample receiving traces of inhibitive antioxidants from a remote source is delayed. Similarly, volatiles from two stabilized elastomers were also capable of retarding a degradation process remotely. This observation demonstrates inhibitive cross-talk as a novel interactive phenomenon between different polymers and is consequential for understanding general polymer interactions, fundamental degradation processes and long-term aging effects of multiple materials in a single environment.

  9. Novel technique for coal pyrolysis and hydrogenation product analysis. Final technical report

    SciTech Connect

    Pfefferle, L.D.; Boyle, J.

    1993-03-15

    A microjet reactor coupled to a VUV photoionization time-of-flight mass spectrometer has been used to obtain species measurements during high temperature pyrolysis and oxidation of a wide range of hydrocarbon compounds ranging from allene and acetylene to cyclohexane, benzene and toluene. Initial work focused on calibration of the technique, optimization of ion collection and detection and characterization of limitations. Using the optimized technique with 118 nm photoionization, intermediate species profiles were obtained for analysis of the hydrocarbon pyrolysis and oxidation mechanisms. The ``soft`` ionization, yielding predominantly molecular ions, allowed the study of reaction pathways in these high temperature systems where both sampling and detection challenges are severe. Work has focused on the pyrolysis and oxidative pyrolysis of aliphatic and aromatic hydrocarbon mixtures representative of coal pyrolysis and hydropyrolysis products. The detailed mass spectra obtained during pyrolysis and oxidation of hydrocarbon mixtures is especially important because of the complex nature of the product mixture even at short residence times and low primary reactant conversions. The combustion community has advanced detailed modeling of pyrolysis and oxidation to the C4 hydrocarbon level but in general above that size uncertainties in rate constant and thermodynamic data do not allow us to a priori predict products from mixed hydrocarbon pyrolyses using a detailed chemistry model. For pyrolysis of mixtures of coal-derived liquid fractions with a large range of compound structures and molecular weights in the hundreds of amu the modeling challenge is severe. Lumped models are possible from stable product data.

  10. Post-Stop-Signal Adjustments: Inhibition Improves Subsequent Inhibition

    ERIC Educational Resources Information Center

    Bissett, Patrick G.; Logan, Gordon D.

    2012-01-01

    Performance in the stop-signal paradigm involves a balance between going and stopping, and one way that this balance is struck is through shifting priority away from the go task, slowing responses after a stop signal, and improving the probability of inhibition. In 6 experiments, the authors tested whether there is a corresponding shift in…

  11. Homo economicus belief inhibits trust.

    PubMed

    Xin, Ziqiang; Liu, Guofang

    2013-01-01

    As a foundational concept in economics, the homo economicus assumption regards humans as rational and self-interested actors. In contrast, trust requires individuals to believe partners' benevolence and unselfishness. Thus, the homo economicus belief may inhibit trust. The present three experiments demonstrated that the direct exposure to homo economicus belief can weaken trust. And economic situations like profit calculation can also activate individuals' homo economicus belief and inhibit their trust. It seems that people's increasing homo economicus belief may serve as one cause of the worldwide decline of trust. PMID:24146907

  12. Homo Economicus Belief Inhibits Trust

    PubMed Central

    Xin, Ziqiang; Liu, Guofang

    2013-01-01

    As a foundational concept in economics, the homo economicus assumption regards humans as rational and self-interested actors. In contrast, trust requires individuals to believe partners’ benevolence and unselfishness. Thus, the homo economicus belief may inhibit trust. The present three experiments demonstrated that the direct exposure to homo economicus belief can weaken trust. And economic situations like profit calculation can also activate individuals’ homo economicus belief and inhibit their trust. It seems that people’s increasing homo economicus belief may serve as one cause of the worldwide decline of trust. PMID:24146907

  13. Action spectra for photosynthetic inhibition

    NASA Technical Reports Server (NTRS)

    Caldwell, M. M.; Flint, S.; Camp, L. B.

    1981-01-01

    The ultraviolet action spectrum for photosynthesis inhibition was determined to fall between that of the general DNA action spectrum and the generalized plant action spectrum. The characteristics of this action spectrum suggest that a combination of pronounced increase in effectiveness with decreasing wavelength, substantial specificity for the UV-B waveband, and very diminished response in the UV-A waveband result in large radiation amplification factors when the action spectra are used as weighting functions. Attempted determination of dose/response relationships for leaf disc inhibition provided inconclusive data from which to deconvolute an action spectrum.

  14. Role of substrate inhibition kinetics in enzymatic chemical oscillations.

    PubMed Central

    Shen, P; Larter, R

    1994-01-01

    Two chemical kinetic models are investigated using standard nonlinear dynamics techniques to determine the conditions under which substrate inhibition kinetics can lead to oscillations. The first model is a classical substrate inhibition scheme based on Michaelis-Menten kinetics and involves a single substrate. Only when this reaction takes place in a flow reactor (i.e., both substrate and product are taken to follow reversible flow terms) are oscillations observed; however, the range of parameter values over which such oscillations occur is so narrow it is experimentally unobservable. A second model based on a general mechanism applied to the kinetics of many pH-dependent enzymes is also studied. This second model includes both substrate inhibition kinetics as well as autocatalysis through the activation of the enzyme by hydrogen ion. We find that it is the autocatalysis that is always responsible for oscillatory behavior in this scheme. The substrate inhibition terms affect the steady-state behavior but do not lead to oscillations unless product inhibition or multiple substrates are present; this is a general conclusion we can draw from our studies of both the classical substrate inhibition scheme and the pH-dependent enzyme mechanism. Finally, an analysis of the nullclines for these two models allows us to prove that the nullcline slopes must have a negative value for oscillatory behavior to exist; this proof can explain our results. From our analysis, we conclude with a brief discussion of other enzymes that might be expected to produce oscillatory behavior based on a pH-dependent substrate inhibition mechanism. Images FIGURE 8 FIGURE 10 PMID:7819481

  15. Menthol Binding and Inhibition of α7-Nicotinic Acetylcholine Receptors

    PubMed Central

    Ashoor, Abrar; Nordman, Jacob C.; Veltri, Daniel; Yang, Keun-Hang Susan; Al Kury, Lina; Shuba, Yaroslav; Mahgoub, Mohamed; Howarth, Frank C.; Sadek, Bassem; Shehu, Amarda; Kabbani, Nadine; Oz, Murat

    2013-01-01

    Menthol is a common compound in pharmaceutical and commercial products and a popular additive to cigarettes. The molecular targets of menthol remain poorly defined. In this study we show an effect of menthol on the α7 subunit of the nicotinic acetylcholine (nACh) receptor function. Using a two-electrode voltage-clamp technique, menthol was found to reversibly inhibit α7-nACh receptors heterologously expressed in Xenopus oocytes. Inhibition by menthol was not dependent on the membrane potential and did not involve endogenous Ca2+-dependent Cl− channels, since menthol inhibition remained unchanged by intracellular injection of the Ca2+ chelator BAPTA and perfusion with Ca2+-free bathing solution containing Ba2+. Furthermore, increasing ACh concentrations did not reverse menthol inhibition and the specific binding of [125I] α-bungarotoxin was not attenuated by menthol. Studies of α7- nACh receptors endogenously expressed in neural cells demonstrate that menthol attenuates α7 mediated Ca2+ transients in the cell body and neurite. In conclusion, our results suggest that menthol inhibits α7-nACh receptors in a noncompetitive manner. PMID:23935840

  16. Nondestructive evaluation technique guide

    NASA Technical Reports Server (NTRS)

    Vary, A.

    1973-01-01

    A total of 70 individual nondestructive evaluation (NDE) techniques are described. Information is presented that permits ease of comparison of the merits and limitations of each technique with respect to various NDE problems. An NDE technique classification system is presented. It is based on the system that was adopted by the National Materials Advisory Board (NMAB). The classification system presented follows the NMAB system closely with the exception of additional categories that have been added to cover more advanced techniques presently in use. The rationale of the technique is explained. The format provides for a concise description of each technique, the physical principles involved, objectives of interrogation, example applications, limitations of each technique, a schematic illustration, and key reference material. Cross-index tabulations are also provided so that particular NDE problems can be referred to appropriate techniques.

  17. The radiocarbon hydroxyl technique

    NASA Technical Reports Server (NTRS)

    Campbell, Malcolm J.; Sheppard, John C.

    1994-01-01

    The Radiocarbon Technique depends upon measuring the rate of oxidation of CO in an essentially unperturbed sample of air. The airborne technique is slightly different. Hydroxyl concentrations can be calculated directly; peroxyl concentrations can be obtained by NO doping.

  18. Seals and Sealing Techniques

    NASA Technical Reports Server (NTRS)

    1972-01-01

    Developments by the aerospace industry in seals and sealing techniques are announced for possible use in other areas. The announcements presented are grouped as: sealing techniques for cryogenic fluids, high pressure applications, and modification for improved performance.

  19. Islam Does Not Inhibit Science.

    ERIC Educational Resources Information Center

    Shanavas, T. O.

    1999-01-01

    Compares the science/religion relationship in both Christian and Islamic countries. Presents Muslim scholars' ideas about the presence of humans on earth. Presents ideas on active nature, Noah's curse, and the age of the universe. Refutes the notion that Islam inhibited science and advocates the belief that Islam promoted science. (YDS)

  20. Infant Predictors of Behavioural Inhibition

    ERIC Educational Resources Information Center

    Moehler, Eva; Kagan, Jerome; Oelkers-Ax, Rieke; Brunner, Romuald; Poustka, Luise; Haffner, Johann; Resch, Franz

    2008-01-01

    Behavioural inhibition in the second year of life is a hypothesized predictor for shyness, social anxiety and depression in later childhood, adolescence and even adulthood. To search for the earliest indicators of this fundamental temperamental trait, this study examined whether behavioural characteristics in early infancy can predict behavioural…