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Sample records for acetylene reduction activity

  1. The Relationship between H2 Evolution and Acetylene Reduction in Pisum sativum-Rhizobium leguminosarum Symbioses Differing in Uptake Hydrogenase Activity 1

    PubMed Central

    Mahon, John D.; Nelson, Louise M.

    1986-01-01

    Peas (Pisum sativum L.) were inoculated with strains of Rhizobium leguminosarum having different levels of uptake hydrogenase (Hup) activity and were grown in sterile Leonard jars under controlled conditions. Rates of H2 evolution and acetylene reduction were determined for intact nodulated roots at intervals after the onset of darkness or after removal of the shoots. Hup activity was estimated using treatment plants or equivalent plants from the growth chamber, by measuring the uptake of H2 or 3H2 in the presence of acetylene. In all cases, the rate of H2 evolution was a continuous function of the rate of acetylene reduction. In symbioses with no demonstrable Hup activity, H2 evolution increased in direct proportion to acetylene reduction and the slopes were similar with the Hup− strains NA502 and 128C79. Hup activity was similar in strains 128C30 and 128C52 but significantly lower in strain 128C54. With these strains, the slopes of the H2 evolution versus acetylene reduction curves initially increased with acetylene reduction, but became constant and similar to those for the Hup− strains at high rates of acetylene reduction. On these parallel portions of the curves, the decreases in H2 evolution by Hup+ strains were similar in magnitude to their H2-saturated rates of Hup activity. The curvilinear relationship between H2 evolution and acetylene reduction for a representative Hup+ strain (128C52) was the same, regardless of the experimental conditions used to vary the nitrogenase activity. PMID:16664984

  2. Nitrogen fixation (acetylene reduction) by epiphytes of freshwater macrophytes.

    PubMed

    Finke, L R; Seeley, H W

    1978-07-01

    The involvement of epiphytic microorganisms in nitrogen fixation was investigated in a shallow freshwater pond near Ithaca, N.Y. The acetylene reduction technique was used to follow diel and seasonal cycles of nitrogen fixation by epiphytes of Myriophyllum spicatum. Acetylene-reducing activity was maximal between noon and 6 p.m., but substantial levels of activity relative to daytime rates continued through the night. Experiments with the seasonal course of activity showed a gradual decline during the autumn months and no activity in January or February. Activity commenced in May, with an abrupt increase to levels between 0.45 and 0.95 nmol of ethylene formed per mg (dry weight) of plant per h. Through most of the summer months, mean rates of acetylene reduction remained between 0.15 and 0.60 nmol/mg (dry weight) per h. It was calculated from diel and seasonal cycles that, in the pond areas studied, epiphytes were capable of adding from 7.5 to 12.5 mug of N per mg of plant per year to the pond. This amount is significant relative to the total amount of nitrogen incorporated into the plant. Blue-green algae (cyanobacteria), particularly Gloeotrichia, appeared to bear prime responsibility for nitrogen fixation, but photosynthetic bacteria of the genus Rhodopseudomonas were isolated from M. spicatum and shown to support high rates of acetylene reduction.

  3. Interactions between Lugol's fixative and ethylene in the acetylene-reduction assay for nitrogenase activity in lake water.

    PubMed

    Leonardson, L

    1980-05-01

    Lugol's solution is a practical and efficient fixative for the acetylene-reduction assay of nitrogenase activity in aquatic organisms. Correction must be made, however, for the solubility of ethylene in the liquid phase and reactions between Lugol's solution and ethylene. With a vapor phase-liquid phase volume ratio of 1.9:1, the mean solubility of ethylene in mixtures of lake water and Lugol's solution was 7.2%. No correlation was found between ethylene solubility and the concentration of Lugol's solution. Storage of fixed samples for more than 1 day before gas chromatographic analysis resulted in increased loss of ethylene from the vapor phase; the loss amounted to ca. 18% after 3 days. Higher losses were noted at higher concentrations of Lugol's solution. Most probably these effects were caused by iodine addition to ethylene, as indicated by the consumption of ethylene by iodine-potassium iodide solutions. The reaction was catalyzed by the rubber septa of the incubaton vessels when the septa were in contact with the liquid phase. Loss of ethylene decreased with increased concentration of phytoplankton because the organisms absorbed iodine. By using a standardized technique and determining ethylene solubility and reaction patterns between ethylene and the mixture of water and Lugol's solution, it is possible to correct for the loss of ethylene.

  4. 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

  5. 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.

  6. Simultaneous Measurement of Acetylene Reduction and Respiratory Gas Exchange of Attached Root Nodules 1

    PubMed Central

    Winship, Lawrence J.; Tjepkema, John D.

    1982-01-01

    A method was developed for the simultaneous measurement of acetylene reduction, carbon dioxide evolution and oxygen uptake by individual root nodules of intact nitrogen-fixing plants (Alnus rubra Bong.). The nodules were enclosed in a temperature-controlled leak-tight cuvette. Assay gas mixtures were passed through the cuvette at a constant, known flow rate and gas exchange was measured by the difference between inlet and outlet gas compositions. Gas concentrations were assayed by a combination of an automated gas chromatograph and a programmable electronic integrator. Carbon dioxide and ethylene evolution were determined with a coefficient of variation which was less than 2%, whereas the coefficient of variation for oxygen uptake measurements was less than 5%. Nodules subjected to repeated removal from and reinsertion into the cuvette and to long exposures of 10% v/v acetylene showed no irreversible decline in respiration or acetylene reduction. This system offers long-term stability and freedom from disturbance artifacts plus the ability to monitor continuously, rapidly and specifically the changes in root nodule activity caused by environmental perturbation. PMID:16662496

  7. Acetylene fuels TCE reductive dechlorination by defined Dehalococcoides/Pelobacter consortia

    USGS Publications Warehouse

    Mao, Xinwei; Oremland, Ronald S.; Liu, Tong; Landers, Abigail A; Baesman, Shaun; Alvarez-Cohen, Lisa

    2017-01-01

    Acetylene (C2H2) can be generated in contaminated groundwater sites as a consequence of chemical degradation of trichloroethene (TCE) by in situ minerals, and C2H2 is known to inhibit bacterial dechlorination. In this study, we show that while high C2H2 (1.3 mM) concentrations reversibly inhibit reductive dechlorination of TCE by Dehalococcoides mccartyi isolates as well as enrichment cultures containing D. mccartyi sp., low C2H2 (0.4 mM) concentrations do not inhibit growth or metabolism of D. mccartyi. Cocultures of Pelobacter SFB93, a C2H2-fermenting bacterium, with D. mccartyi strain 195 or with D. mccartyi strain BAV1 were actively sustained by providing acetylene as the electron donor and carbon source while TCE or cis-DCE served as the electron acceptor. Inhibition by acetylene of reductive dechlorination and methanogenesis in the enrichment culture ANAS was observed, and the inhibition was removed by adding Pelobacter SFB93 into the consortium. Transcriptomic analysis of D. mccartyi strain 195 showed genes encoding for reductive dehalogenases (e.g., tceA) were not affected during the C2H2-inhibition, while genes encoding for ATP synthase, biosynthesis, and Hym hydrogenase were down-regulated during C2H2 inhibition, consistent with the physiological observation of lower cell yields and reduced dechlorination rates in strain 195. These results will help facilitate the optimization of TCE-bioremediation at contaminated sites containing both TCE and C2H2.

  8. 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

  9. 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

  10. Towards Structural-Functional Mimics of Acetylene Hydratase: Reversible Activation of Acetylene using a Biomimetic Tungsten Complex.

    PubMed

    Peschel, Lydia M; Belaj, Ferdinand; Mösch-Zanetti, Nadia C

    2015-10-26

    The synthesis and characterization of a biomimetic system that can reversibly bind acetylene (ethyne) is reported. The system has been designed to mimic catalytic intermediates of the tungstoenzyme acetylene hydratase. The thiophenyloxazoline ligand S-Phoz (2-(4',4'-dimethyloxazolin-2'-yl)thiophenolate) is used to generate a bioinspired donor environment around the W center, facilitating the stabilization of W-acetylene adducts. The featured complexes [W(C2 H2 )(CO)(S-Phoz)2 ] (2) and [WO(C2 H2 )(S-Phoz)2 ] (3) are extremely rare from a synthetic and structural point of view as very little is known about W-C2 H2 adducts. Upon exposure to visible light, 3 can release C2 H2 from its coordination sphere to yield the 14-electron species [WO(S-Phoz)2 ] (4). Under light-exclusion 4 re-activates C2 H2 making this the first fully characterized system for the reversible activation of acetylene.

  11. Root-Associated N2 Fixation (Acetylene Reduction) by Enterobacteriaceae and Azospirillum Strains in Cold-Climate Spodosols

    PubMed Central

    Haahtela, Kielo; Wartiovaara, Tuula; Sundman, Veronica; Skujiņš, J.

    1981-01-01

    N2 fixation by bacteria in associative symbiosis with washed roots of 13 Poaceae and 8 other noncultivated plant species in Finland was demonstrated by the acetylene reduction method. The roots most active in C2H2 reduction were those of Agrostis stolonifera, Calamagrostis lanceolata, Elytrigia repens, and Phalaris arundinacea, which produced 538 to 1,510 nmol of C2H4·g−1 (dry weight)· h−1 when incubated at pO2 0.04 with sucrose (pH 6.5), and 70 to 269 nmol of C2H4· g−1 (dry weight)·h−1 without an added energy source and unbuffered. Azospirillum lipferum, Enterobacter agglomerans, Klebsiella pneumoniae, and a Pseudomonas sp. were the acetylene-reducing organisms isolated. The results demonstrate the presence of N2-fixing organisms in associative symbiosis with plant roots found in a northern climatic region in acidic soils ranging down to pH 4.0. PMID:16345687

  12. 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

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

    PubMed

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

    2012-11-27

    A doubly substituted form of the nitrogenase MoFe protein (α-70(Val)(→Ala), α-195(His→Gln)) has the capacity to catalyze the reduction of carbon dioxide (CO(2)) to yield methane (CH(4)). Under optimized conditions, 1 nmol of the substituted MoFe protein catalyzes the formation of 21 nmol of CH(4) within 20 min. The catalytic rate depends on the partial pressure of CO(2) (or concentration of HCO(3)(-)) and the electron flux through nitrogenase. The doubly substituted MoFe protein also has the capacity to catalyze the unprecedented formation of propylene (H(2)C = CH-CH(3)) through the reductive coupling of CO(2) 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 CO(2) sequestration and formation of olefins.

  14. La-Activated Bicyclo-oligomerization of Acetylene to Naphthalene.

    PubMed

    Hewage, Dilrukshi; Silva, W Ruchira; Cao, Wenjin; Yang, Dong-Sheng

    2016-03-02

    We report the first example of metal-mediated acetylene bicyclopentamerization to form naphthalene in the gas phase. The bicyclic aromatic compound was observed in a complex with La. The La(naphthalene) complex was formed by the reaction of laser-ablated La atoms with acetylene molecules in a molecular beam source and was characterized by mass-analyzed threshold ionization spectroscopy. The bicyclo-oligomerization reaction occurs through sequential acetylene additions coupled with dehydrogenation. Three intermediates in the reaction have been identified: lanthanacyclopropene [La(C2H2)], La(cyclobut-1-en-3-yne) [La(C4H2)], and La(benzyne) [(La(C6H4)]. The metal-ligand bonding in the three intermediates is considerably different from that in the La(naphthalene) complex, as suggested by accurately measured adiabatic ionization energies.

  15. Adsorption of binary mixtures of ethane and acetylene on activated carbon

    SciTech Connect

    Lee, T.V.; Huang, J.C.; Rothstein, D.; Madey, R.

    1984-01-01

    Dynamic measurement of the adsorption of binary mixtures of ethane and acetylene (and also of each gas alone) in a helium carrier gas were made on an (Columbia 4LXC 12/28) activated carbon adsorber bed at 25/sup 0/C. The adsorption capacities of the activated carbon for the pure gases and for each component in the mixtures are extracted from the transmission curves by the use of a mass balance equation. Transmission is the ratio of the concentration at the outlet of the adsorber bed to that at the inlet. The adsorption isotherms for pure ethane and acetylene can be presented by a modified Langmuir isotherm known as the Chakravarti-Dhar isotherm at gas concentrations up to at least 4.2 X 19/sup -7/ mol/cm/sup 3/ (viz., 7.8 mmHg). The gas-adsorbate equilibrium composition and the adsorption capacity of each component in the binary mixture of ethane and acetylene are estimated from the corresponding single-component isotherms by applying ideal adsorbed solution theory (IAST). The fact that the estimated values of the adsorption capacities and the gas-adsorbate equilibrium compositions are in good agreement with those extracted from the measurements for the binary mixtures of ethane and acetylene confirms that the ethane-acetylene system forms an ideal adsorbed phase on activated carbon at a pressure of about 7.3 mmHg and a temperature of 25/sup 0/C. 20 references, 4 figures, 4 tables.

  16. 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.

  17. The cytochrome P-450 active site. Regiospecificity of prosthetic heme alkylation by olefins and acetylenes.

    PubMed

    Kunze, K L; Mangold, B L; Wheeler, C; Beilan, H S; Ortiz de Montellano, P R

    1983-04-10

    Hepatic microsomal cytochrome P-450 from phenobarbital-pretreated rats is inactivated during the metabolism of linear olefins (ethylene, propene, and octene) and acetylenes (acetylene, propyne, and octyne). As expected from previous work, the inactivation is due to N-alkylation of the prosthetic heme group by the substrate. The N-alkyl group in each adduct is formally obtained by addition of a porphyrin nitrogen to the terminal carbon and of an oxygen atom (as a hydroxyl function) to the internal carbon of the pi-bond. The oxygen is shown here by 18O studies to be catalytically introduced by the enzyme. The olefins exclusively alkylate the nitrogen of pyrrole ring D, but the acetylenes alkylate that of pyrrole ring A. Acetylene is an exception in that it reacts with more than one nitrogen. Circular dichroism studies of the ethylene adduct and of the ring D regioisomer of N-ethylprotoporphyrin IX obtained by alkylation of the prosthetic heme of hemoglobin have been used to determine which face of cytochrome P-450 heme is alkylated by the unsaturated substrates. These results implicate an active site that is sterically encumbered in the region over pyrrole ring B and has a lipophilic binding site that accommodates chains of at least six carbon atoms over pyrrole ring C.

  18. 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...

  19. 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

  20. ANTIPROLIFERATIVE ACTIVITY OF NOVEL ACETYLENIC DERIVATIVES OF BETULIN AGAINST G-361 HUMAN MELANOMA CELLS.

    PubMed

    Bębenek, Ewa; Chodurek, Ewa; Orchel, Arkadiusz; Dzierżewicz, Zofia; Boryczka, Stanisław

    2015-01-01

    Acetylenic derivatives of betulin were tested in vitro for their antiproliferative activity against G-361 human melanoma cells. Two types of betulin derivatives were studied: monoesters, obtained by modification of the hydroxyl group at C-28 position, and diesters modified at both C-28 and C-3 positions. To assess cell proliferation, a colorimetric sulforhodamine B based method was used. All the tested monoesters inhibited cellular growth and 28-O-propynoylbetulin showed the strongest cytotoxic effect. Esterification of the C-3 hydroxyl group of the molecule abolished its growth inhibitory activity.

  1. 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.

  2. 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.

  3. Acetylene-sourced CVD-synthesised catalytically active graphene for electrochemical biosensing.

    PubMed

    Osikoya, Adeniyi Olugbenga; Parlak, Onur; Murugan, N Arul; Dikio, Ezekiel Dixon; Moloto, Harry; Uzun, Lokman; Turner, Anthony Pf; Tiwari, Ashutosh

    2017-03-15

    In this study, we have demonstrated the use of chemical vapour deposition (CVD) grown-graphene to develop a highly-ordered graphene-enzyme electrode for electrochemical biosensing. The graphene sheets were deposited on 1.00mm thick copper sheet at 850°C using acetylene (C2H2) as carbon source in an argon (Ar) and nitrogen (N2) atmosphere. An anionic surfactant was used to increase wettability and hydrophilicity of graphene; thereby facilitating the assembly of biomolecules on the electrode surface. Meanwhile, the theoretical calculations confirmed the successful modification of hydrophobic nature of graphene through the anionic surface assembly, which allowed high-ordered immobilisation of glucose oxidase (GOx) on the graphene. The electrochemical sensing activities of the graphene-electrode was explored as a model for bioelectrocatalysis. The bioelectrode exhibited a linear response to glucose concentration ranging from 0.2 to 9.8mM, with sensitivity of 0.087µA/µM/cm(2) and a detection limit of 0.12µM (S/N=3). This work sets the stage for the use of acetylene-sourced CVD-grown graphene as a fundamental building block in the fabrication of electrochemical biosensors and other bioelectronic devices.

  4. 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.

  5. 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.

  6. 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.

  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. On-demand electrochemical activation of the click reaction on self-assembled monolayers on gold presenting masked acetylene groups.

    PubMed

    Choi, Inseong; Kim, Young-Kwan; Min, Dal-Hee; Lee, SangWook; Yeo, Woon-Seok

    2011-10-26

    We report on a new surface modification method for grafting a "dynamic" property for on-demand activation of the click reaction. Our approach utilizes the acetylene group masked with dicobalt hexacarbonyl, Co(2)(CO)(6), which is not reactive toward the click reaction. Electrochemical treatment reveals the acetylene group on the selected region, which is then used as a chemical handle for surface functionalization via the click reaction with an azide-containing molecule. Electrochemical and chemical conversions on the surface were verified by cyclic voltammetry, X-ray photoelectron spectroscopy, and fluorescence spectroscopy. We have demonstrated immobilization of an azide-modified RGD peptide and promotion of cell adhesion/migration to the region of electrochemical induction.

  9. Synthesis, structure and cytotoxic activity of new acetylenic derivatives of betulin.

    PubMed

    Boryczka, Stanisław; Bębenek, Ewa; Wietrzyk, Joanna; Kempińska, Katarzyna; Jastrzębska, Maria; Kusz, Joachim; Nowak, Maria

    2013-04-17

    A new series of betulin derivatives containing one or two pharmacophores bearing an acetylenic and carbonyl function at the C-3 and/or C-28 positions has been synthesized and characterized by ¹H- and ¹³C-NMR, IR, MS and elemental analyses. The crystal structure of 28-O-propynoylbetulin was determined by X-ray structural analysis. All new compounds, as well as betulin, were tested in vitro for their antiproliferative activity against human SW707 colorectal, CCRF/CEM leukemia, T47D breast cancer, and against murine P388 leukemia and Balb3T3 normal fibroblasts cell lines. Most of the compounds showed better cytotoxicity than betulin and cisplatin used as reference agent. 28-O-Propynoylbetulin was the most potent derivative, being over 500 times more potent than betulin and about 100 times more cytotoxic than cisplatin against the human leukemia (CCRF/CEM) cell line, with an ID₅₀ value of 0.02 μg/mL.

  10. Comparison of N(2) Fixation and Yields in Cajanus cajan between Hydrogenase-Positive and Hydrogenase-Negative Rhizobia by In Situ Acetylene Reduction Assays and Direct N Partitioning.

    PubMed

    La Favre, J S; Focht, D D

    1983-08-01

    Pigeon peas [Cajanus cajan (L.) Millsp.] were grown in soil columns containing (15)N-enriched organic matter. Seasonal N(2) fixation activity was determined by periodically assaying plants for reduction of C(2)H(2). N(2) fixation rose sharply from the first assay period at 51 days after planting to a peak of activity between floral initiation and fruit set. N(2) fixation (acetylene reduction) activity dropped concomitantly with pod maturation but recovered after pod harvests. Analysis of (15)N content of plant shoots revealed that approximately 91 to 94% of plant N was derived from N(2) fixation. The effect of inoculation with hydrogenase-positive and hydrogenase-negative rhizobia was examined. Pigeon peas inoculated with strain P132 (hydrogenase-positive) yielded significantly more total shoot N than other inoculated or uninoculated treatments. However, two other hydrogenase-positive strains did not yield significantly more total shoot N than a hydrogenase-negative strain. The extent of nodulation by inoculum strains compared to indigenous rhizobia was determined by typing nodules according to intrinsic antibiotic resistance of the inoculum strains. The inoculum strains were detected in almost all typed nodules of inoculated plants.Gas samples were taken from soil columns several times during the growth cycle of the plants. H(2) was never detected, even in columns containing pigeon peas inoculated with hydrogenase-negative rhizobia. This was attributed to H(2) consumption by soil bacteria. Estimation of N(2) fixation by acetylene reduction activity was closest to the direct (15)N method when ethylene concentrations in the gas headspace (between the column lid and soil surface) were extrapolated to include the soil pore space as opposed solely to measurement in the headspace. There was an 8-fold difference between the two acetylene reduction assay methods of estimation. Based on a planting density of 15,000 plants per hectare, the direct (15)N fixation rates ranged

  11. Nitrogenase of Klebsiella pneumoniae. Inhibition of acetylene reduction by magnesium ion explained by the formation of an inactive dimagnesium–adenosine triphosphate complex

    PubMed Central

    Thorneley, Roger N. F.; Willison, Keith R.

    1974-01-01

    Acetylene-reducing activity of purified nitrogenase from Klebsiella pneumoniae was studied over a range of ATP and Mg2+ concentrations at 15°C, pH7.8. Inhibition at Mg2+ concentrations of 2.5–30mm was due to the formation of the inactive complex, Mg2ATP. At higher Mg2+ concentrations an additional inhibitory effect was observed. The results were consistent with a MgATP complex being the active substrate with an apparent Km(MgATP)=0.4mm. PMID:4618775

  12. Chemically activated reactions on the C7H5 energy surface: propargyl + diacetylene, i-C5H3 + acetylene, and n-C5H3 + acetylene.

    PubMed

    da Silva, Gabriel; Trevitt, Adam J

    2011-05-21

    This study uses computational chemistry and statistical reaction rate theory to investigate the chemically activated reaction of diacetylene (butadiyne, C(4)H(2)) with the propargyl radical (C˙H(2)CCH) and the reaction of acetylene (C(2)H(2)) with the i-C(5)H(3) (CH(2)CCCC˙H) and n-C(5)H(3) (CHCC˙HCCH) radicals. A detailed G3SX-level C(7)H(5) energy surface demonstrates that the C(3)H(3) + C(4)H(2) and C(5)H(3) + C(2)H(2) addition reactions proceed with moderate barriers, on the order of 10 to 15 kcal mol(-1), and form activated open-chain C(7)H(5) species that can isomerize to the fulvenallenyl radical with the highest barrier still significantly below the entrance channel energy. Higher-energy pathways are available leading to other C(7)H(5) isomers and to a number of C(7)H(4) species + H. Rate constants in the large multiple-well (15) multiple-channel (30) chemically activated system are obtained from a stochastic solution of the one-dimensional master equation, with RRKM theory for microcanonical rate constants. The dominant products of the C(4)H(2) + C(3)H(3) reaction at combustion-relevant temperatures and pressures are i-C(5)H(3) + C(2)H(2) and CH(2)CCHCCCCH + H, along with several quenched C(7)H(5) intermediate species below 1500 K. The major products in the n-C(5)H(3) + C(2)H(2) reaction are i-C(5)H(3) + C(2)H(2) and a number of C(7)H(4) species + H, with C(7)H(5) radical stabilization at lower temperatures. The i-C(5)H(3) + C(2)H(2) reaction predominantly leads to C(7)H(4) + H and to stabilized C(7)H(5) products. The title reactions may play an important role in polycyclic aromatic hydrocarbon (PAH) formation in combustion systems. The C(7)H(5) potential energy surface developed here also provides insight into several other important reacting gas-phase systems relevant to combustion and astrochemistry, including C(2)H + the C(3)H(4) isomers propyne and allene, benzyne + CH, benzene + C((3)P), and C(7)H(5) radical decomposition, for which some

  13. Discovery of acetylene hydratase activity of the iron-sulphur protein IspH.

    PubMed

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

    2012-01-01

    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 η(1)-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.

  14. Design, synthesis, and structure-activity relationships of acetylene-based histamine H3 receptor antagonists.

    PubMed

    Ali, S M; Tedford, C E; Gregory, R; Handley, M K; Yates, S L; Hirth, W W; Phillips, J G

    1999-03-11

    New, potent, and selective histamine H3 receptor antagonists have been synthesized by employing the use of (1) an appropriately positioned nonpolar acetylene spacer group, (2) either a two-carbon straight chain linker or a conformationally restricting trans-cyclopropane ring between the C-4 position of an imidazole headgroup and the acetylene spacer, and (3) a Topliss operational scheme for side-chain substitution for optimizing the hydrophobic domain. Compounds 9-18 are examples synthesized with the two-carbon straight chain linker, whereas 26-31 are analogues prepared by incorporation of the trans-(+/-)-cyclopropane at the C-4 position of an imidazole headgroup. Synthesis of both the (1R,2R)- and (1S, 2S)-cyclopropyl enantiomers of the most potent racemic compound 31 (Ki = 0.33 +/- 0.13 nM) demonstrated a stereopreference in H3 receptor binding affinity for the (1R,2R) enantiomer 32 (Ki = 0.18 +/- 0.04 nM) versus the (1S,2S) enantiomer 33 (Ki = 5.3 +/- 0.5 nM). (1R,2R)-4-(2-(5,5-Dimethylhex-1-ynyl)cyclopropyl)imidazole (32) is one of the most potent histamine H3 receptor antagonists reported to date.

  15. 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

  16. 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.

  17. Effect of nitrate and acetylene on nirS, cnorB, and nosZ expression and denitrification activity in Pseudomonas mandelii.

    PubMed

    Saleh-Lakha, Saleema; Shannon, Kelly E; Henderson, Sherri L; Zebarth, Bernie J; Burton, David L; Goyer, Claudia; Trevors, Jack T

    2009-08-01

    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 NO(3)(-) 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 KNO(3)/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 NO(3)(-) 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 KNO(3)/liter, indicating that there was no relationship between gene expression and denitrification activity under the conditions tested.

  18. Dihydrogen and Acetylene Activation by a Gold(I)/Platinum(0) Transition Metal Only Frustrated Lewis Pair.

    PubMed

    Campos, Jesús

    2017-03-01

    The first example of a frustrated Lewis pair (FLP) solely constructed around transition metal centers is described in this work. We have focused on the established capacity of Au(I) and Pt(0) complexes to act as Lewis acidic and basic fragments, respectively, while employing sufficiently bulky P(t)Bu3 and terphenyl phosphine ligands. This avoids formation of metallic Lewis adducts and confers the Au(I)/Pt(0) pair a remarkable capacity to activate dihydrogen and acetylene molecules in a fashion that closely resembles that of traditional main group FLP systems. As a consequence, unusual heterobimetallic Au(I)/Pt(II) complexes containing hydride (-H), acetylide (-C≡CH), and vinylene (-HC═CH-) bridges have been isolated.

  19. The Effect of NaCl on growth, N2 fixation (acetylene reduction), and percentage total nitrogen in Leucaena leucocephala (Leguminosae) var. K-8.

    PubMed

    Anthraper, Annie; Dubois, John D

    2003-05-01

    Leucaena leucocephala var. K-8 is a fast-growing, tropical leguminous tree that has multiple economic uses. This study was conducted to evaluate the effect(s) of varying NaCl concentrations on growth, N(2) fixation, and percentage of total tissue nitrogen in different organs in L. leucocephala. Seeds were germinated and grown for 10 wk with a nitrogen-free fertilizer applied every 2 wk. At 10 wk, plants were treated for either 0, 7, 14, 21, or 28 wk with either deionized water (control), 0.00625 mol/L, 0.0125 mol/L, 0.025 mol/L, 0.05 mol/L, or 0.1 mol/L NaCl in addition to the fertilizer every 2 wk. Growth was measured as plant height, nodule number and mass, and dry tissue mass. N(2) fixation was measured by the acetylene reduction assay. Percentage of tissue nitrogen was determined using Kjeldahl analysis. In younger plants (7-wk treatment), major fluctuations in NaCl tolerance were observed in the different plant organs. As plants matured (14- and 21-wk treatment) NaCl concentrations of 0.025 mol/L and higher caused the greatest reduction in growth and tissue nitrogen. We conclude that NaCl concentrations of 0.025 mol/L and greater caused a major decrease in growth, N(2) fixation, and percentage of tissue nitrogen in L. leucocephala plants that were less than 1 yr old.

  20. Selective Reductions. 46. Effect of the Steric Requirement at the 2- Position of Apopinene on Chiral Reductions. B-Iso-2-n-Propylapopinocampheyl-9- Borabicyclo(3.3.1)Nonane as Improved Reagents for the Chiral Reduction of Alpha, Beta-Acetylenic Ketones and Alpha-Keto Esters

    DTIC Science & Technology

    1991-01-17

    prepared in situ from methyllithium and cuprous iodide. (+)-2-n-Propylapopinene was synthesized by Schlosser metallation of (+)-ac- pinene followed by...into its components, ac- pinene and 9-BBN with the less reactive ketones resultingo iuAchiral reduction.8 The dehydroboration is suppressed by...cc- pinene . 10 A comparison-of the enantiomeric e cesses of the product alcohols obtained from the reduction of prochiral’acetylenic ketones showsthat 2

  1. Synthesis of indoles, benzofurans, and related heterocycles via an acetylene-activated SNAr/intramolecular cyclization cascade sequence in water or DMSO.

    PubMed

    Hudson, R; Bizier, N P; Esdale, K N; Katz, J L

    2015-02-28

    The synthesis of 2-substituted indoles and benzofurans was achieved by nucleophilic aromatic substitution, followed by subsequent 5-endo-dig cyclization between the nucleophile and an ortho acetylene. The acetylene serves the dual role of the electron withdrawing group to activate the substrate for SNAr, and the C1-C2 carbon scaffold for the newly formed 5-membered heteroaromatic ring. This method allows for the bond forming sequence of Ar-X-N/O-C1 to proceed in a single synthetic step, furnishing indoles and benzofurans in moderate to high yields. Since the method is not transition metal mediated, brominated and chlorinated substrates are tolerated, and benzofuran formation can be conducted using water or water-DMSO mixtures as solvent.

  2. 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.

  3. 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.

  4. 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.

  5. Measuring Substantial Reductions in Activity

    PubMed Central

    Schafer, Charles; Evans, Meredyth; Jason, Leonard A.; So, Suzanna; Brown, Abigail

    2015-01-01

    The case definitions for Myalgic Encephalomyelitis/chronic fatigue syndrome (ME/CFS), Myalgic Encephalomyelitis (ME), and chronic fatigue syndrome (CFS) each include a disability criterion requiring substantial reductions in activity in order to meet diagnostic criteria. Difficulties have been encountered in defining and operationalizing the substantial reduction disability criterion within these various illness definitions. The present study sought to relate measures of past and current activities in several domains including the SF-36, an objective measure of activity (e.g. actigraphy), a self-reported quality of life scale, and measures of symptom severity. Results of the study revealed that current work activities had the highest number of significant associations with domains such as the SF-36 subscales, actigraphy, and symptom scores. As an example, higher self-reported levels of current work activity were associated with better health. This suggests that current work related activities may provide a useful domain for helping operationalize the construct of substantial reductions in activity. PMID:25584524

  6. A Potent Plant-Derived Antifungal Acetylenic Acid Mediates Its Activity by Interfering with Fatty Acid Homeostasis

    PubMed Central

    Xu, Tao; Tripathi, Siddharth K.; Feng, Qin; Lorenz, Michael C.; Wright, Marsha A.; Jacob, Melissa R.; Mask, Melanie M.; Baerson, Scott R.; Li, Xing-Cong; Clark, Alice M.

    2012-01-01

    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 were conducted using the model yeast Saccharomyces cerevisiae to investigate its mechanism of action. 6-NDA elicited a transcriptome response indicative of fatty acid stress, altering the expression of genes that are required for yeast growth in the presence of oleate. Mutants of S. cerevisiae lacking transcription factors that regulate fatty acid β-oxidation showed increased sensitivity to 6-NDA. Fatty acid profile analysis indicated that 6-NDA inhibited the formation of fatty acids longer than 14 carbons in length. In addition, the growth inhibitory effect of 6-NDA was rescued in the presence of exogenously supplied oleate. To investigate the response of a pathogenic fungal species to 6-NDA, transcriptional profiling and biochemical analyses were also conducted in C. albicans. The transcriptional response and fatty acid profile of C. albicans were comparable to those obtained in S. cerevisiae, and the rescue of growth inhibition with exogenous oleate was also observed in C. albicans. In a fluconazole-resistant clinical isolate of C. albicans, a fungicidal effect was produced when fluconazole was combined with 6-NDA. In hyphal growth assays, 6-NDA inhibited the formation of long hyphal filaments in C. albicans. Collectively, our results indicate that the antifungal activity of 6-NDA is mediated by a disruption in fatty acid homeostasis and that 6-NDA has potential utility in the treatment of superficial Candida infections. PMID:22430960

  7. New acetylenic derivatives of betulin and betulone, synthesis and cytotoxic activity.

    PubMed

    Bębenek, Ewa; Kadela-Tomanek, Monika; Chrobak, Elwira; Wietrzyk, Joanna; Sadowska, Joanna; Boryczka, Stanisław

    2017-01-01

    Betulin 1 and its semisynthetic derivatives exhibit a cytotoxic activity toward various cancer cell lines. These compounds are a promising and potential anticancer candidates. A series of betulin derivatives was prepared and tested for the antiproliferative activity in vitro against T47D breast cancer, CCRF/CEM leukemia, HL-60 promyelocytic leukemia, SW707 colorectal, murine P388 leukemia, as well as BALB3T3 normal fibroblasts cell lines. Cisplatin and betulin 1 were used as a reference compounds. Some derivatives of betulin showed a higher cytotoxic activity than the parent compound 1. Two derivatives (5 and 17) were 24-fold potent than betulin 1 against the human promyelocytic leukemia cell line (HL-60), with an IC50 value of 0.3 µg/mL.

  8. Flavin reduction activates Drosophila cryptochrome.

    PubMed

    Vaidya, Anand T; Top, Deniz; Manahan, Craig C; Tokuda, Joshua M; Zhang, Sheng; Pollack, Lois; Young, Michael W; Crane, Brian R

    2013-12-17

    Entrainment of circadian rhythms in higher organisms relies on light-sensing proteins that communicate to cellular oscillators composed of delayed transcriptional feedback loops. The principal photoreceptor of the fly circadian clock, Drosophila cryptochrome (dCRY), contains a C-terminal tail (CTT) helix that binds beside a FAD cofactor and is essential for light signaling. Light reduces the dCRY FAD to an anionic semiquinone (ASQ) radical and increases CTT proteolytic susceptibility but does not lead to CTT chemical modification. Additional changes in proteolytic sensitivity and small-angle X-ray scattering define a conformational response of the protein to light that centers at the CTT but also involves regions remote from the flavin center. Reduction of the flavin is kinetically coupled to CTT rearrangement. Chemical reduction to either the ASQ or the fully reduced hydroquinone state produces the same conformational response as does light. The oscillator protein Timeless (TIM) contains a sequence similar to the CTT; the corresponding peptide binds dCRY in light and protects the flavin from oxidation. However, TIM mutants therein still undergo dCRY-mediated degradation. Thus, photoreduction to the ASQ releases the dCRY CTT and promotes binding to at least one region of TIM. Flavin reduction by either light or cellular reductants may be a general mechanism of CRY activation.

  9. Flavin reduction activates Drosophila cryptochrome

    PubMed Central

    Vaidya, Anand T.; Top, Deniz; Manahan, Craig C.; Tokuda, Joshua M.; Zhang, Sheng; Pollack, Lois; Young, Michael W.; Crane, Brian R.

    2013-01-01

    Entrainment of circadian rhythms in higher organisms relies on light-sensing proteins that communicate to cellular oscillators composed of delayed transcriptional feedback loops. The principal photoreceptor of the fly circadian clock, Drosophila cryptochrome (dCRY), contains a C-terminal tail (CTT) helix that binds beside a FAD cofactor and is essential for light signaling. Light reduces the dCRY FAD to an anionic semiquinone (ASQ) radical and increases CTT proteolytic susceptibility but does not lead to CTT chemical modification. Additional changes in proteolytic sensitivity and small-angle X-ray scattering define a conformational response of the protein to light that centers at the CTT but also involves regions remote from the flavin center. Reduction of the flavin is kinetically coupled to CTT rearrangement. Chemical reduction to either the ASQ or the fully reduced hydroquinone state produces the same conformational response as does light. The oscillator protein Timeless (TIM) contains a sequence similar to the CTT; the corresponding peptide binds dCRY in light and protects the flavin from oxidation. However, TIM mutants therein still undergo dCRY-mediated degradation. Thus, photoreduction to the ASQ releases the dCRY CTT and promotes binding to at least one region of TIM. Flavin reduction by either light or cellular reductants may be a general mechanism of CRY activation. PMID:24297896

  10. 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.

  11. 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.

  12. Anaerobic Oxidation of Acetylene by Estuarine Sediments and Enrichment Cultures

    PubMed Central

    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. PMID:16345714

  13. 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

  14. Design, synthesis, anticancer, antimicrobial activities and molecular docking studies of theophylline containing acetylenes and theophylline containing 1,2,3-triazoles with variant nucleoside derivatives.

    PubMed

    Ruddarraju, Radhakrishnam Raju; Murugulla, Adharvana Chari; Kotla, Ravindar; Chandra Babu Tirumalasetty, Muni; Wudayagiri, Rajendra; Donthabakthuni, Shobha; Maroju, Ravichandar; Baburao, K; Parasa, Lakshmana Swamy

    2016-11-10

    A new series of theophylline containing acetylene derivatives (6a-6b and 7-13) and theophylline containing 1,2,3-triazoles with variant nucleoside derivatives (20-32) have been designed and synthesized. These compounds were screened for anticancer and antimicrobial activity. Further the computational docking and 2D QSAR were performed using MOE software to identify novel scaffolds. The results showed that compound 29 and 30 exhibit significant cytotoxic effect on all four cancer cells such as lung (A549), colon (HT-29), breast (MCF-7) and melanoma (A375) with IC50 values of 2.56, 2.19, 1.89, 4.89 μM and 3.57, 2.90, 2.10, 5.81 μM respectively. Whereas quite different results were observed for these compounds in antimicrobial studies. Compounds 11, 21 and 26 have exhibited significant minimum inhibitory concentrations (MIC) against Staphylococcus aureus, Bacillus cereus, Escherichia coli and Pseudomonas aeruginosa. The docking studies demonstrate that compound 27, 28, 29 and 30 have good dock score and binding affinities with various therapeutic targets in cancer cell proliferation. In addition these compounds have shown acceptable correlation with bioassay results in the regression plots generated in 2D QSAR models. This is the first report to demonstrate the theophylline containing acetylene derivatives and theophylline containing 1,2,3-triazole nucleoside hybrids as potential anticancer and antimicrobial agents with comprehensive in silico analysis.

  15. 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.

  16. 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.

  17. Induction of Olefin Metathesis by Acetylenes.

    DTIC Science & Technology

    1980-11-20

    essentially that of 2. The acetylene is thus an activator, but unlike the organometallic co- catalysts like C2 H5A1C1 2 , which it replaces, it is unique in...J.C.; Moulijn, J.A. Adv. Catal. 1975, 24, 131. (4) Some of the results were discussed at the 3rd NSF Workshop on Organo - metallic Chemistry, Pingree

  18. Quantification and Removal of Some Contaminating Gases from Acetylene Used to Study Gas-Utilizing Enzymes and Microorganisms

    PubMed Central

    Hyman, Michael R.; Arp, Daniel J.

    1987-01-01

    Acetylene generated from various grades of calcium carbide and obtained from commercial- and purified-grade acetylene cylinders was shown to contain high concentrations of various contaminants. Dependent on the source of acetylene, these included, at maximal values, H2 (0.023%), O2 (0.779%), N2 (3.78%), PH3 (0.06%), CH4 (0.073%), and acetone (1 to 10%). The concentration of the contaminants in cylinder acetylene was highly dependent on the extent of cylinder discharge. Several conventional methods used to partially purify cylinder acetylene were compared. A small-scale method for extensively purifying acetylene is described. An effect of acetylene quality on acetylene reduction assays conducted with purified nitrogenase from Azotobacter vinelandii was demonstrated. PMID:16347278

  19. 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.

  20. Synthesis of functional poly(disubstituted acetylene)s through the post-polymerization modification route.

    PubMed

    Gao, Yuan; Wang, Xiao; Sun, Jing Zhi; Tang, Ben Zhong

    2015-04-01

    We report the recent progress in the preparation of functional poly(disubstituted acetylene)s (PDSAs) through post-polymerization modification routes. The metathesis polymerization of disubstituted acetylene monomers activated by Mo/W-Sn complex catalysts, which do not tolerate highly polar functionalities, was assumed to be a key step in the polymer synthetic procedures. We and other groups have explored several approaches to prepare PDSAs with latent reactive functionalities, which are inactive to Mo/W-Sn complex catalysts but can be used as highly reactive sites for post-polymerization modification. Click chemistry, Michael-type addition reactions, the use of activated esters and other strategies are demonstrated by recently published examples. These works indicate that post-polymerization modification is an efficient route to the synthesis of various functional PDSAs.

  1. Vertical activity distribution of dissimilatory nitrate reduction in coastal marine sediments

    NASA Astrophysics Data System (ADS)

    Behrendt, A.; de Beer, D.; Stief, P.

    2013-05-01

    The relative importance of two dissimilatory nitrate reduction pathways, denitrification (DEN) and dissimilatory nitrate reduction to ammonium (DNRA), was investigated in intact sediment cores from five different coastal marine field sites. The vertical distribution of DEN activity was examined using the acetylene inhibition technique combined with N2O microsensor measurements, whereas NH4+ production via DNRA was measured with a recently developed gel probe-stable isotope technique. At all field sites, dissimilatory nitrate reduction was clearly dominated by DEN (> 59% of the total NO3- reduced) rather than by DNRA, irrespective of the sedimentary inventories of electron donors such as organic carbon, sulfide, and iron. Ammonium production via DNRA (8.9% of the total NO3- reduced) was exclusively found at one site with very high concentrations of total sulfide and NH4+ in the layer of NO3- reduction and below. Sediment from two field sites, one with and one without DNRA activity in the core incubations, was also used for slurry incubations. Now, in both sediments high DNRA activity was detected accounting for 37-77% of the total NO3- reduced. These contradictory results can be explained by enhanced NO3- availability for DNRA bacteria in the sediment slurries compared to the core-incubated sediments. It can be argued that the gel probe technique gives more realistic estimates of DNRA activity in diffusion-dominated sediments, while slurry incubations are more suitable for advection-dominated sediments.

  2. Improving the Working Efficiency of a Triboelectric Nanogenerator by the Semimetallic PEDOT:PSS Hole Transport Layer and Its Application in Self-Powered Active Acetylene Gas Sensing.

    PubMed

    Uddin, A S M Iftekhar; Yaqoob, Usman; Chung, Gwiy-Sang

    2016-11-09

    Herein we report an enhanced triboelectric nanogenerator (TENG) based on the contact-separation mode between a patterned film of polydimethylsiloxane (PDMS) with a semimetallic elastomer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and a nylon fiber film. The addition of ethylene glycol to the PEDOT:PSS film improves the functionality of the TENG significantly, yielding promising applicability in both indoor and outdoor (i.e., under sunlight) environments, with the maximum instantaneous power of 0.09 mW (indoors) and 0.2 mW (outdoors) for the load resistance of 3.8 MΩ. The device can also generate 11.2 V and 0.08 μA cm(-2) in response to the forearm movement of a human. Additionally, by replacing the bare nylon fiber in the TENG design with a Ag@ZnO/nylon fiber film, a self-powered active sensor (triboelectric nanogenerator-based sensor; TENS) has been realized to detect acetylene (C2H2) gas. The TENS exhibits excellent sensitivity of 70.9% (indoors) and 89% (outdoors) to C2H2 gas of 1000 ppm concentration. The proposed approach for harvesting energy and sensing can be advantageous in practical applications and may stimulate new research that will enhance nanogenerators as well as wearable, self-powered active sensors.

  3. Acetylene on Titan

    NASA Astrophysics Data System (ADS)

    Singh, Sandeep; McCord, Thomas B.; Combe, Jean-Philippe; Rodriguez, Sebastien; Cornet, Thomas; Le Mouélic, Stéphane; Clark, Roger Nelson; Maltagliati, Luca; Chevrier, Vincent

    2016-10-01

    Saturn's moon Titan possesses a thick atmosphere that is mainly composed of N2 (98%), CH4 (2 % overall, but 4.9% close to the surface) and less than 1% of minor species, mostly hydrocarbons [1]. A dissociation of N2 and CH4 forms complex hydrocarbons in the atmsophere and acetylene (C2H2) and ethane (C2H6) are produced most abundently. Since years, C2H2 has been speculated to exist on the surface of Titan based on its high production rate in the stratosphere predicted by photochemical models [2,3] and from its detection as trace gas sublimated/evaporated from the surface after the landing of the Huygens probe by the Gas Chromatograph Mass Spectrometer (GCMS) [1]. Here we show evidence of acetylene (C2H2) on the surface of Titan by detecting absorption bands at 1.55 µm and 4.93 µm using Cassini Visual and Infrared Mapping Spectrometer (VIMS) [4] at equatorial areas of eastern Shangri-La, and Fensal-Aztlan/Quivira.An anti-correlation of absorption band strength with albedo indicates greater concentrations of C2H2 in the dark terrains, 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.References:[1]Niemann et al., Nature 438, 779-784 (2005).[2]Lavvas et al., Planetary and Space Science 56, 67 - 99 (2008).[3]Lavvas et al., Planetary and Space Science 56, 27 - 66 (2008).[4] Brown et al., The Cassini-Huygens Mission 111-168 (Springer, 2004).

  4. 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

  5. Analog VLSI system for active drag reduction

    SciTech Connect

    Gupta, B.; Goodman, R.; Jiang, F.; Tai, Y.C.; Tung, S.; Ho, C.M.

    1996-10-01

    In today`s cost-conscious air transportation industry, fuel costs are a substantial economic concern. Drag reduction is an important way to reduce costs. Even a 5% reduction in drag translates into estimated savings of millions of dollars in fuel costs. Drawing inspiration from the structure of shark skin, the authors are building a system to reduce drag along a surface. Our analog VLSI system interfaces with microfabricated, constant-temperature shear stress sensors. It detects regions of high shear stress and outputs a control signal to activate a microactuator. We are in the process of verifying the actual drag reduction by controlling microactuators in wind tunnel experiments. We are encouraged that an approach similar to one that biology employs provides a very useful contribution to the problem of drag reduction. 9 refs., 21 figs.

  6. Interaction of the mechanism-based inactivator acetylene with ammonia monooxygenase of Nitrosomonas europaea.

    PubMed

    Gilch, Stefan; Vogel, Manja; Lorenz, Matthias W; Meyer, Ortwin; Schmidt, Ingo

    2009-01-01

    The ammonia monooxygenase (AMO) of Nitrosomonas europaea is a metalloenzyme that catalyses the oxidation of ammonia to hydroxylamine. We have identified histidine 191 of AmoA as the binding site for the oxidized mechanism-based inactivator acetylene. Binding of acetylene changed the molecular mass of His-191 from 155.15 to 197.2 Da (+42.05), providing evidence that acetylene was oxidized to ketene (CH2CO; 42.04 Da) which binds specifically to His-191. It must be assumed that His-191 is part of the acetylene-activating site in AMO or at least directly neighbours this site.

  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. Acetylene soot reaction with NO in the presence of CO.

    PubMed

    Mendiara, T; Alzueta, M U; Millera, A; Bilbao, R

    2009-07-30

    The heterogeneous reaction of soot with NO can be considered as a means of reduction of the emissions of both pollutants from combustion systems. In this paper, the influence of the presence of CO in the soot-NO reaction is studied. Soot was obtained by pyrolysis at 1373 K of 5000 ppmv acetylene in nitrogen. The study of the influence of CO on the soot-NO reaction was performed in experiments fixing NO concentration at 900 ppmv and introducing different CO concentrations among 0 and 9900 ppmv. An increase in both the carbon consumption rate and NO reduction by acetylene soot was observed as the concentration of CO increases. These results can be explained by the oxide-stripping reaction, CO+C(f)(O)-->CO(2)+C(f). The direct reaction of CO with NO catalyzed by the carbon surface, CO+NO-->CO(2)+1/2N(2) may not be considered in this case the dominant process due to the absence of mineral impurities in the acetylene soot. The influence of CO in the acetylene soot-NO reaction was also tested in the presence of oxygen (250-5000 ppmv). In these conditions and for relatively high CO/O(2) ratios, CO seems to also contribute to NO reduction by the previous oxide-stripping reaction.

  9. Vertical activity distribution of dissimilatory nitrate reduction in coastal marine sediments

    NASA Astrophysics Data System (ADS)

    Behrendt, A.; de Beer, D.; Stief, P.

    2013-11-01

    The relative importance of two dissimilatory nitrate reduction pathways, denitrification (DEN) and dissimilatory nitrate reduction to ammonium (DNRA), was investigated in intact sediment cores from five different coastal marine field sites (Dorum, Aarhus Bight, Mississippi Delta, Limfjord and Janssand). The vertical distribution of DEN activity was examined using the acetylene inhibition technique combined with N2O microsensor measurements, whereas NH4+ production via DNRA was measured with a recently developed gel probe-stable isotope technique. At all field sites, dissimilatory nitrate reduction was clearly dominated by DEN (59-131% of the total NO3- reduced) rather than by DNRA, irrespective of the sedimentary inventories of electron donors such as organic carbon, sulfide, and iron. Highest ammonium production via DNRA, accounting for up to 8.9% of the total NO3- reduced, was found at a site with very high concentrations of total sulfide and NH4+ within and below the layer in which NO3- reduction occurred. Sediment from two field sites, one with low and one with high DNRA activity in the core incubations, was also used for slurry incubations. Now, in both sediments high DNRA activity was detected accounting for 37-77% of the total NO3- reduced. These contradictory results might be explained by enhanced NO3- availability for DNRA bacteria in the sediment slurries compared to the core-incubated sediments in which diffusion of NO3- from the water column may only reach DEN bacteria, but not DNRA bacteria. The true partitioning of dissimilatory nitrate reduction between DNRA and DEN may thus lie in between the values found in whole core (underestimation of DNRA) and slurry incubations (overestimation of DNRA).

  10. 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

  11. Effect of Au nano-particle aggregation on the deactivation of the AuCl3/AC catalyst for acetylene hydrochlorination

    NASA Astrophysics Data System (ADS)

    Dai, Bin; Wang, Qinqin; Yu, Feng; Zhu, Mingyuan

    2015-05-01

    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.

  12. 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.

  13. 41 CFR 50-204.66 - Acetylene.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 41 Public Contracts and Property Management 1 2010-07-01 2010-07-01 true Acetylene. 50-204.66..., Vapors, Fumes, Dusts, and Mists § 50-204.66 Acetylene. (a) The in-plant transfer, handling, storage, and utilization of acetylene in cylinders shall be in accordance with Compressed Gas Association Pamphlet...

  14. 29 CFR 1910.102 - Acetylene.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 5 2010-07-01 2010-07-01 false Acetylene. 1910.102 Section 1910.102 Labor Regulations... OCCUPATIONAL SAFETY AND HEALTH STANDARDS Hazardous Materials § 1910.102 Acetylene. (a) Cylinders. Employers must ensure that the in-plant transfer, handling, storage, and use of acetylene in cylinders...

  15. 29 CFR 1910.102 - Acetylene.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... may comply with the provisions of Chapter 7 (“Acetylene Piping”) of NFPA 51A-2001 (“Standard for... comply with the provisions of NFPA 51A-2006 (“Standard for Acetylene Charging Plants”) (National Fire... OCCUPATIONAL SAFETY AND HEALTH STANDARDS Hazardous Materials § 1910.102 Acetylene. (a) Cylinders....

  16. 29 CFR 1910.102 - Acetylene.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... may comply with the provisions of Chapter 7 (“Acetylene Piping”) of NFPA 51A-2001 (“Standard for... comply with the provisions of NFPA 51A-2006 (“Standard for Acetylene Charging Plants”) (National Fire... OCCUPATIONAL SAFETY AND HEALTH STANDARDS Hazardous Materials § 1910.102 Acetylene. (a) Cylinders....

  17. 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.

  18. Reduction of bromate by granular activated carbon

    SciTech Connect

    Kirisits, M.J.; Snoeyink, V.L.; Kruithof, J.C.

    1998-07-01

    Ozonation of waters containing bromide can lead to the formation of bromate, a probable human carcinogen. Since bromate will be regulated at 10 {micro}g/L by the Stage 1 Disinfectants/Disinfection By-Products Rule, there is considerable interest in finding a suitable method of bromate reduction. Granular activated carbon (GAC) can be used to chemically reduce bromate to bromide, but interference from organic matter and anions present in natural water render this process inefficient. In an effort to improve bromate reduction by GAC, several modifications were made to the GAC filtration process. The use of a biologically active carbon (BAC) filter ahead of a fresh GAC filter with and without preozonation, to remove the biodegradable organic matter, did not substantially improve the bromate removal of the GAC filter. The use of the BAC filter for biological bromate reduction proved to be the most encouraging experiment. By lowering the dissolved oxygen in the influent to the BAC from 8.0 mg/L to 2.0 mg/L, the percent bromate removal increased from 42% to 61%.

  19. Electron ionization of acetylene.

    PubMed

    King, Simon J; Price, Stephen D

    2007-11-07

    Relative partial ionization cross sections and precursor specific relative partial ionization cross sections for fragment ions formed by electron ionization of C2H2 have been measured using time-of-flight mass spectrometry coupled with a 2D ion-ion coincidence technique. We report data for the formation of H+, H+2, C2+, C+/C2+ 2, CH+/C2H+2, CH+2, C+2, and C2H+ relative to the formation of C2H+2, as a function of ionizing electron energy from 30-200 eV. While excellent agreement is found between our data and one set of previously published absolute partial ionization cross sections, some discrepancies exist between the results presented here and two other recent determinations of these absolute partial ionization cross sections. We attribute these differences to the loss of some translationally energetic fragment ions in these earlier studies. Our relative precursor-specific partial ionization cross sections enable us, for the first time, to quantify the contribution to the yield of each fragment ion from single, double, and triple ionization. Analysis shows that at 50 eV double ionization contributes 2% to the total ion yield, increasing to over 10% at an ionizing energy of 100 eV. From our ion-ion coincidence data, we have derived branching ratios for charge separating dissociations of the acetylene dication. Comparison of our data to recent ab initio/RRKM calculations suggest that close to the double ionization potential C2H2+2 dissociates predominantly on the ground triplet potential energy surface (3Sigma*g) with a much smaller contribution from dissociation via the lowest singlet potential energy surface (1Delta g). Measurements of the kinetic energy released in the fragmentation reactions of C2H2+2 have been used to obtain precursor state energies for the formation of product ion pairs, and are shown to be in good agreement with available experimental data and with theory.

  20. Suicidal inactivation and labelling of ammonia mono-oxygenase by acetylene.

    PubMed Central

    Hyman, M R; Wood, P M

    1985-01-01

    Acetylene brings about a progressive inactivation of ammonia mono-oxygenase, the ammonia-oxidizing enzyme in Nitrosomonas europaea. High NH4+ ion concentrations were protective. The inactivation followed first-order kinetics, with a rate constant of 1.5 min-1 at saturating concentrations of acetylene. If acetylene was added in the absence of O2, the cells remained active until O2 was re-introduced. A protective effect was also demonstrated with thiourea, a reversible non-competitive inhibitor of ammonia oxidation. Incubation of cells with [14C]acetylene was found to cause labelling of a single membrane polypeptide. This ran on dodecyl sulphate/polyacrylamide-gel electrophoresis with an Mr value of 28 000. It is concluded that acetylene is a suicide substrate for the mono-oxygenase. The labelling experiment provides the first identification of a constituent polypeptide of ammonia mono-oxygenase. Images Fig. 4. PMID:4004794

  1. Regulatory effect of hydrogen on nitrogenase activity of the blue-green alga (cyanobacterium) Nostoc muscorum.

    PubMed

    Scherer, S; Kerfin, W; Böger, P

    1980-03-01

    Preincubation of the blue-green alga (cyanobacterium) Nostoc muscorum under an atmosphere of argon plus acetylene in the light led to a greater than fourfold increase of light-induced hydrogen evolution and to a 50% increase of acetylene reduction, as compared to cells that had not been preconditioned. The basic and the increased hydrogen evolution were both due to nitrogenase activity. Furthermore, after preincubation the hydrogen uptake, usually observed with unconditional cells, was abolished. Nostoc preincubated under acetylene evolved hydrogen in the light even in the presence of nitrogen for at least 2 h, with a 15-fold increase as compared to the unconditioned cells. These acetylene effects could be completely abolished by the presence of hydrogen during acetylene preincubation. These findings indicate that the hydrogen concentration in N. muscorum cells plays a role in regulation of nitrogenase activity.

  2. 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

  3. Acetylene-based materials in organic photovoltaics.

    PubMed

    Silvestri, Fabio; Marrocchi, Assunta

    2010-04-08

    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 C(60), and their use as the active materials in photovoltaic devices.

  4. International Space Station (ISS) Risk Reduction Activities

    NASA Technical Reports Server (NTRS)

    Fodroci, Michael

    2011-01-01

    As the assembly of the ISS nears completion, it is worthwhile to step back and review some of the actions pursued by the Program in recent years to reduce risk and enhance the safety and health of ISS crewmembers, visitors, and space flight participants. While the ISS requirements and initial design were intended to provide the best practicable levels of safety, it is always possible to reduce risk -- given the determination and commitment to do so. The following is a summary of some of the steps taken by the ISS Program Manager, by our International Partners, by hardware and software designers, by operational specialists, and by safety personnel to continuously enhance the safety of the ISS. While decades of work went into developing the ISS requirements, there are many things in a Program like the ISS that can only be learned through actual operational experience. These risk reduction activities can be divided into roughly three categories: (1) Areas that were initially noncompliant which have subsequently been brought into compliance or near compliance (i.e., Micrometeoroid and Orbital Debris [MMOD] protection, acoustics) (2) Areas where initial design requirements were eventually considered inadequate and were subsequently augmented (i.e., Toxicity Level 4 materials, emergency hardware and procedures) (3) Areas where risks were initially underestimated, and have subsequently been addressed through additional mitigation (i.e., Extravehicular Activity [EVA] sharp edges, plasma shock hazards) Due to the hard work and cooperation of many parties working together across the span of nearly a decade, the ISS is now a safer and healthier environment for our crew, in many cases exceeding the risk reduction targets inherent in the intent of the original design. It will provide a safe and stable platform for utilization and discovery.

  5. 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.

  6. High yield of pure multiwalled carbon nanotubes from the catalytic decomposition of acetylene on in-situ formed cobalt nanoparticles.

    PubMed

    Delpeux, Sandrine; Szostak, Katarzyna; Frackowiak, Elzbieta; Bonnamy, Sylvie; Béguin, François

    2002-10-01

    For the first time, multiwalled carbon nanotubes (MWNTs) could be formed selectively in a high yield, free of any disordered carbon by-product, from the catalytic decomposition of acetylene at 600 degrees C on a CoxMg(1-x)O solid solution. Starting from 1 g of catalytic substrate, 4 g of pure MWNTs were obtained after its dissolution in boiling concentrated HCl, without any additional purification in strongly oxidizing medium, as is required for other methods of nanotube production. In situ reduction of CoO by dihydrogen liberated from acetylene decomposition allows highly divided metal particles to be continuously produced as synthesis proceeds. This is undoubtedly the reason for the good performance of the catalyst and for the ability to produce nanotubes in a narrow diameter range, namely from 10 to 15 nm. With the use of acetylene instead of methane, the synthesis proceeds at low temperature, which prevents the growth of carbon shells, in which the metal particles are generally embedded, decreasing their activity. Because of the very low specific surface area of the catalyst support, the amount of disordered carbon by-product formed is negligible.

  7. 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.

  8. 76 FR 75782 - Revising Standards Referenced in the Acetylene Standard

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-12-05

    ... the Acetylene Standard AGENCY: Occupational Safety and Health Administration (OSHA), Department of... is revising its Acetylene Standard for general industry by updating a reference to a standard... and Explanation of Revisions to the Acetylene Standard IV. Procedural Determinations A....

  9. 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.

  10. 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

  11. 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.

  12. 41 CFR 50-204.66 - Acetylene.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 41 Public Contracts and Property Management 1 2014-07-01 2014-07-01 false Acetylene. 50-204.66 Section 50-204.66 Public Contracts and Property Management Other Provisions Relating to Public Contracts.... (b) The piped systems for the in-plant transfer and distribution of acetylene shall be...

  13. 41 CFR 50-204.66 - Acetylene.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 41 Public Contracts and Property Management 1 2012-07-01 2009-07-01 true Acetylene. 50-204.66 Section 50-204.66 Public Contracts and Property Management Other Provisions Relating to Public Contracts.... (b) The piped systems for the in-plant transfer and distribution of acetylene shall be...

  14. 46 CFR 147.70 - Acetylene.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Acetylene. 147.70 Section 147.70 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) DANGEROUS CARGOES HAZARDOUS SHIPS' STORES Stowage and Other Special Requirements for Particular Materials § 147.70 Acetylene. (a) Seventeen cubic meters (600...

  15. 29 CFR 1910.102 - Acetylene.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... with the provisions of CGA Pamphlet G-1-2003 (“Acetylene”) (Compressed Gas Association, Inc., 11th ed..., 2006, these employers may comply with the provisions of Chapter 7 (“Acetylene Piping”) of NFPA 51A-2001 (“Standard for Acetylene Charging Plants”) (National Fire Protection Association, 2001 ed., 2001). (3)...

  16. Reactions of Acetylene in Superbasic Media

    NASA Astrophysics Data System (ADS)

    Trofimov, Boris A.

    1981-02-01

    The results of studies of fundamentally new reactions of acetylene and its substituted derivatives in media of very high basicity are surveyed. They lead to hitherto unknown or relatively inaccessible monomers, reagents, and intermediates: 2-vinyloxybuta-1,3-diene, pyrroles, and N-vinylpyrroles, divinyl sulphide, divinyl telluride, 4-methylene-1,3-oxathiolan, di(buta-1,3-dienyl)sulphide, dihydrothiophen, 1-vinyl-2-thiabicyclo[3,2,0]hept-3-ene, etc. The most important properties of superbasic media consisting of an alkali metal hydroxide and a dipolar aprotic solvent as well as the probable mechanisms of their activating effect on anions and the triple bond are examined. An attempt is made to analyse these reactions in terms of coordination catalysis by alkali metal cations. The bibliography includes 199 references.

  17. [The gas chromatographic detection of acetylene in cadaveric material].

    PubMed

    Iablochkin, V D

    1999-01-01

    Acetylene traces were detected by gas chromatography in the cadaveric right crural muscle of a 30-year-old man dead from an explosion of an acetylene reservoir at a plant. Acetylene was identified using the absolute calibration method on 3 standard gas chromatographic columns, reaction gas chromatography, and acetylene "deduction" by silver sulfate on silicagel.

  18. Tunable mid-infrared emission from acetylene-filled hollow-core fiber

    NASA Astrophysics Data System (ADS)

    Wang, Zefeng; Zhou, Zhiyue; Li, Zhixian; Zhang, Naiqian; Chen, Yubin

    2016-11-01

    We report here a step tunable mid-infrared laser emission from acetylene-filled hollow-core fiber. Two kinds of anti-resonant hollow-core fibers are filled with mbar level of acetylene gas, and pumped with a modulated, amplified, narrow linewidth, fine tunable, 1.5 μm diode laser, then 3 μm laser emissions are generated by the intrinsic absorption of acetylene molecules. The laser wavelength is step-tunable in the range of 3.1 3.2 μm when the pump laser is precisely tuned to different absorption lines of P-branch of acetylene. By properly designing the fiber's transmission bands, and carefully selecting active gases and pump lasers, this paper provides a novel method for efficient, compact and tunable mid-infrared fiber lasers over a broad spectrum range.

  19. 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.

  20. Analog VLSI for active drag reduction

    NASA Astrophysics Data System (ADS)

    Gupta, Vidyabhusan

    In today's cost-conscious air transportation industry, fuel costs are a substantial economic concern. Drag reduction is an important way to increase fuel efficiency which reduces these costs. Even a 1% reduction in drag can translate into estimated savings of tens of millions of dollars in annual fuel costs. Fluid mechanicists believe that microscopic vortex pairs impinging on the surface play an important role in turbulent transport that may cause large skin friction drag. The microscopic nature and unpredictable appearance of these structures has limited practical approaches to their control. With the advent of micromachining technology providing the ability to build mechanical structures with microscopic dimensions, the tools finally exist with which to detect and control the vortex structures. These sensors and actuators require control circuitry between them in order to build a complete system. We propose an analog VLSI system that can process information along a surface in a moving fluid with the goal of controlling actuators to minimize the surface shear stress. We obtain the information from the surface by using microsensors which measure the surface shear stress. The actuators interact with the fluid by moving up and down in an attempt to diminish the impact of the drag-inducing structures in the fluid. We have designed the fabricated an analog control system. We have tested the system in several different experiments to verify its effectiveness in providing a control signal that energizes an actuator. We also have studied the methodology for a completely integrated wafer-scale system.

  1. Dropout Prevention/Reduction Programs and Activities.

    ERIC Educational Resources Information Center

    Dade County Public Schools, Miami, FL.

    Seventeen activities or programs conducted in the Dade County (Florida) public elementary and secondary schools in order to reduce or prevent dropout are described in this resource guide. The programs activities include: (1) workshops to develop school-based dropout prevention programs; (2) "Students Working Intelligently to Combat High…

  2. 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.

  3. 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

  4. Oligomers Terminated By Maleimide And Acetylene

    NASA Technical Reports Server (NTRS)

    St. Clair, Terry L.; Pater, Ruth H.; Gerber, Margaret K.

    1994-01-01

    Oligomeric molecules terminated with maleimide and acetylene groups synthesized and thermally treated to form cross-linked polymers exhibiting high or undetectable glass-transition temperatures and high thermo-oxidative stabilities. Compounds used to make thermally stable, glassy polymers.

  5. Initial stages of soot formation in thermal pyrolysis of acetylene. I. Mechanism for homogeneous pyrolysis of acetylene

    SciTech Connect

    Merkulov, A.A.; Ovsyannikov, A.A.; Polak, L.S.; Popov, V.T.; Pustilnikov, V.Yu. )

    1989-03-01

    A probable mechanism for the homogeneous pyrolysis of acetylene, using carbene reactions, is considered. Analysis of the energetics for the probable mechanism of the initiation reactions shows the rearrangement C{sub 2}H{sub 2} {yields}:CCH{sub 2} to be the most probable. Using the energetic barriers for simple carbene reactions and formation enthalpies for more complicated carbenes, the authors evaluated the activation energies for the reactions mechanism. The vibrational excitation of the products of carbene reactions is taken into account. Calculations of the acetylene conversion kinetics and yields of the main gas-phase pyrolysis products, based on the carbene molecular mechanism, show significantly better agreement with available experimental data as compared to those based on traditional radical mechanisms. The calculated time for the appearance of aromatic products is close to the measured induction times for the appearance of soot particles.

  6. Annual waste reduction activities report. Issue 1

    SciTech Connect

    1991-03-18

    This report discusses the waste minimization activities for the Pinellas Plant. The Pinellas Plant deals with low-level radioactive wastes, solvents, scrap metals and various other hazardous materials. This program has realized cost savings through recycling and reuse of materials.

  7. Growth of Nocardia rhodochrous on acetylene gas.

    PubMed Central

    Kanner, D; Bartha, R

    1979-01-01

    Soil sediment enrichment cultures yielded a coryneform bacterium capable of growing in a mineral salts solution with acetylene gas as its only source of carbon and energy. Based on morphological and physiological traits as well as on cell wall analysis, the bacterium was characterized as a strain of Nocardia rhodochrous. Maximal growth rates (generation time 2.7 to 3.0 h) on acetylene were obtained at 5 to 20% acetylene, 25 to 40% oxygen, pH 7.0 and 26 to 28 degrees C. Yields (grams of dry cells produced per gram of acetylene consumed) ranged between 90 and 110%. N. rhodochrous exhibits a growth factor requirement for the pyrimidine moiety of thiamine. Acetylene utilization is not an obligate trait, and a wide range of alternate carbon sources is utilized. Ethylene is neither produced nor consumed. The only previous report on acetylene utilization appeared in 1932. The Mycobacterium lacticola strain described in that report strongly resembles N. rhodochrous. PMID:37235

  8. REPEATED REDUCTIVE AND OXIDATIVE TREATMENTS ON GRANULAR ACTIVATED CARBON

    EPA Science Inventory

    Fenton oxidation and Fenton oxidation preceded by reduction solutions were applied to granular activated carbon (GAC) to chemically regenerate the adsorbent. No adsorbate was present on the GAC so physicochemical effects from chemically aggressive regeneration of the carbon coul...

  9. 29 CFR 4043.23 - Active participant reduction.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... EVENTS AND CERTAIN OTHER NOTIFICATION REQUIREMENTS Post-Event Notice of Reportable Events § 4043.23 Active participant reduction. (a) Reportable event. A reportable event occurs when the number of active...., facility shutdown or sale); and (2) The number of active participants at the date the reportable...

  10. 29 CFR 4043.23 - Active participant reduction.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... EVENTS AND CERTAIN OTHER NOTIFICATION REQUIREMENTS Post-Event Notice of Reportable Events § 4043.23 Active participant reduction. (a) Reportable event. A reportable event occurs when the number of active...., facility shutdown or sale); and (2) The number of active participants at the date the reportable...

  11. 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

  12. 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

  13. Chromium Isotope Behaviour During Aerobic Microbial Reduction Activities

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Amor, K.; Porcelli, D.; Thompson, I.

    2014-12-01

    Microbial activity is a very important, and possibly even the dominant, reduction mechanism for many metals in natural water systems. Isotope fractionations during microbial metal reduction can reflect one major mechanism in metal cycling in the environment, and isotopic signatures can be used to identify and quantify reduction processes during biogeochemical cycling in the present environment as well as in the past. There are many Cr (VI)-reducing bacteria that have been discovered and isolated from the environment, and Cr isotopes were found to be fractionated during microbial reduction processes. In this study, Cr reduction experiments have been undertaken to determine the conditions under which Cr is reduced and the corresponding isotope signals that are generated. The experiments have been done with a facultative bacteria Pseudomonas fluorescens LB 300, and several parameters that have potential impact on reduction mechanisms have been investigated. Electron donors are important for bacteria growth and metabolism. One factor that can control the rate of Cr reduction is the nature of the electron donor. The results show that using citrate as an electron donor can stimulate bacteria reduction activity to a large extent; the reduction rate is much higher (15.10 mgˑL-1hour-1) compared with experiments using glucose (6.65 mgˑL-1ˑhour-1), acetate (4.88 mgˑL-1hour-1) or propionate (4.85 mgˑL-1hour-1) as electron donors. Groups with higher electron donor concentrations have higher reduction rates. Chromium is toxic, and when increasing Cr concentrations in the medium, the bacteria reduction rate is also higher, which reflects bacteria adapting to the toxic environment. In the natural environment, under different pH conditions, bacteria may metabolise in different ways. In our experiments with pH, bacteria performed better in reducing Cr (VI) when pH = 8, and there are no significant differences between groups with pH = 4 or pH = 6. To investigate this further, Cr

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

    NASA Astrophysics Data System (ADS)

    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

    2015-06-01

    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.

  15. 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

  16. 75 FR 5707 - Revising Standards Referenced in the Acetylene Standard

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-04

    ... in the Acetylene Standard AGENCY: Occupational Safety and Health Administration (OSHA), Labor. ACTION... accompanied its direct-final rule revising the Acetylene Standard for general industry. DATES: As of February...- final rule to update the incorporated references in its Acetylene Standard for general industry at...

  17. 77 FR 13969 - Revising Standards Referenced in the Acetylene Standard

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-08

    ... the Acetylene Standard AGENCY: Occupational Safety and Health Administration (OSHA), Department of... date of its direct final rule that revises the Acetylene Standard for general industry by updating the... that revised the Acetylene Standard for general industry by updating a reference to the Compressed...

  18. 77 FR 13997 - Revising Standards Referenced in the Acetylene Standard

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-08

    ... in the Acetylene Standard AGENCY: Occupational Safety and Health Administration (OSHA), Labor. ACTION... accompanied its direct-final rule revising the Acetylene Standard for general industry. DATES: Effective March...-final rule to update the incorporated references in its Acetylene Standard for general industry at...

  19. 46 CFR 154.1735 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Methyl acetylene-propadiene mixture. 154.1735 Section... Operating Requirements § 154.1735 Methyl acetylene-propadiene mixture. (a) The composition of the methyl acetylene-propadiene mixture at loading must be within the following limits or specially approved by...

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

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Methyl acetylene-propadiene mixture. 154.1735 Section... Operating Requirements § 154.1735 Methyl acetylene-propadiene mixture. (a) The composition of the methyl acetylene-propadiene mixture at loading must be within the following limits or specially approved by...

  1. 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.

  2. Thermodynamics of acetylene van der Waals dimerization

    NASA Technical Reports Server (NTRS)

    Colussi, A. J.; Sander, S. P.; Friedl, R. R.

    1991-01-01

    Integrated band intensities of the 620/cm absorption in (C2H2)2 are measured by FTIR spectroscopy at constant acetylene pressure between 198 and 273 K. These data, in conjunction with ab initio results for (C2H2)2, are used for the statistical evaluation of the equilibrium constant Kp(T) for acetylene-cluster dimerization. The present results are used to clarify the role of molecular clusters in chemical systems at or near equilibrium, in particular in Titan's stratosphere.

  3. Low Cost Aromatic Acetylene and Oligomeric Benzils and Their Conversion to Acetylene Terminated Quinoxalines

    DTIC Science & Technology

    1982-07-01

    methyl-3-butyn-2-ol by warming with methylbutynol in the presence of cuprous iodide in triethylamine was very rapid, indicating that the acetylene can...8.6/1 actually caused a significant rate increase in Runs 75, 114, and 115. The presence of cuprous iodide shows little effect in the reaction of...bromoarenes with olefins.(9) The effect in the acetylene reaction, how- ever, is very significant. Cuprous iodide probably is involved in two modes

  4. Influence of and additives on acetylene detonation

    NASA Astrophysics Data System (ADS)

    Drakon, A.; Emelianov, A.; Eremin, A.

    2014-03-01

    The influence of and admixtures (known as detonation suppressors for combustible mixtures) on the development of acetylene detonation was experimentally investigated in a shock tube. The time-resolved images of detonation wave development and propagation were registered using a high-speed streak camera. Shock wave velocity and pressure profiles were measured by five calibrated piezoelectric gauges and the formation of condensed particles was detected by laser light extinction. The induction time of detonation development was determined as the moment of a pressure rise at the end plate of the shock tube. It was shown that additive had no influence on the induction time. For , a significant promoting effect was observed. A simplified kinetic model was suggested and characteristic rates of diacetylene formation were estimated as the limiting stage of acetylene polymerisation. An analysis of the obtained data indicated that the promoting species is atomic chlorine formed by pyrolysis, which interacts with acetylene and produces radical, initiating a chain mechanism of acetylene decomposition. The results of kinetic modelling agree well with the experimental data.

  5. 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…

  6. Unconventional ionic hydrogen bonds: CH +⋯π (C tbnd C) binding energies and structures of benzene + rad (acetylene) 1-4 clusters

    NASA Astrophysics Data System (ADS)

    Soliman, Abdel-Rahman; Hamid, Ahmed M.; Abrash, Samuel A.; El-Shall, M. Samy

    2012-01-01

    Rapid condensation of acetylene onto the benzene cation with the addition of up to eight acetylene molecules is observed in the gas phase at 120-140 K forming the C6D6rad +(C2H2)n clusters. The binding energies and entropy changes of the stepwise condensation of the first four acetylene molecules onto the benzene cation have been measured and correlated with the calculated lowest energy isomers. The measured binding energies (3-4 kcal/mol) reflect weak charge-induced dipole and (benzene) Csbnd Hδ+⋯π Ctbnd C (acetylene) hydrogen bonding interactions. Associative charge transfer is suggested to activate the cyclization of three acetylene molecules to form a benzene molecule (C6H6).

  7. Tuning the C-H···π Interaction by Different Substitutions in Benzene-Acetylene Complexes.

    PubMed

    Mishra, Brijesh Kumar; Karthikeyan, S; Ramanathan, V

    2012-06-12

    The influence of substitutions in aromatic moieties on the binding strength of their complexes is a subject of broad importance. Using a set of various substituted benzenes, Sherrill and co-workers ( J. Am. Chem. Soc. 2011 , 133 , 13244 ; J. Phys. Chem. A 2003 , 107 , 8377 ) recently showed that the strength of a stacking interaction (π···π interaction) is enhanced by adding substituents regardless of their nature. Although the binding strength of an activated C-H···π interaction is comparable to that of a stacking interaction, a similar systematic study is hitherto unknown in the literature. We have computed the stabilization energies of the C-H···π complex of acetylene and multiple fluoro-/methyl-substituted benzenes at the coupled-cluster single and double (triple) excitation [CCSD(T)]/complete basis set (CBS) limit. The trend for interaction energies was found to be hexafluorobenzene-acetylene < sym-tetrafluorobenzene-acetylene < sym-trifluorobenzene-acetylene < sym-difluorobenzene-acetylene < benzene-acetylene < sym-dimethylbenzene-acetylene < sym-trimethylbenzene-acetylene < sym-tetramethylbenzene-acetylene < hexamethylbenzene-acetylene. Therefore, contrary to the case of stacking interaction ( Hohenstein et al. J. Am. Chem. Soc. 2011 , 133 , 13244 ), we show here that electron-withdrawing groups weaken the dimer while electron-donating groups strengthen the interaction energy of the dimer. Various recently developed density functional theoretic (DFT) methods were assessed for their performance and the M05-2X, M06-2X, and ωB97X-D methods were found to be the best performers. These best DFT performers were employed in determining the influence of other representative substituents (-NO2, -CN, -COOH, -Br, -Cl, -OH, and -NH2) as an extension to the above work. The results for the complex of acetylene and various para-disubstituted benzenes revealed a trend in binding energies that is in accordance with the ring-activating/deactivating capacity of

  8. 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.

  9. Active viscoelastic matter: from bacterial drag reduction to turbulent solids.

    PubMed

    Hemingway, E J; Maitra, A; Banerjee, S; Marchetti, M C; Ramaswamy, S; Fielding, S M; Cates, M E

    2015-03-06

    A paradigm for internally driven matter is the active nematic liquid crystal, whereby the equations of a conventional nematic are supplemented by a minimal active stress that violates time-reversal symmetry. In practice, active fluids may have not only liquid-crystalline but also viscoelastic polymer degrees of freedom. Here we explore the resulting interplay by coupling an active nematic to a minimal model of polymer rheology. We find that adding a polymer can greatly increase the complexity of spontaneous flow, but can also have calming effects, thereby increasing the net throughput of spontaneous flow along a pipe (a "drag-reduction" effect). Remarkably, active turbulence can also arise after switching on activity in a sufficiently soft elastomeric solid.

  10. Electromagnetic films as lightweight actuators for active noise reduction

    NASA Astrophysics Data System (ADS)

    Sachau, Delf; Kletschkowski, Thomas

    2006-03-01

    The increasing industrialization and markets across the globe do result in noise pollution that affects humans. In order to reduce the sound pressure level (SPL) of disturbing noise active noise control (also known as noise cancellation, active noise reduction (ANR) or anti-noise) is a good option. Herewith unwanted noise from a primary sound source can be reduced significantly by anti-noise generated from a secondary source: At present commercial active noise reduction systems are using moving-coil loudspeakers as actuators. These actuators need a quite large built-in volume and they are not lightweight. Therefore the industrial application of ANR in vehicles is limited. To reduce these difficulties the use of flat loudspeakers made of electromagnetic films seems to be a promising approach. It is a precondition for the use of such new technologies within an ANR- system to have a basic understanding of the dynamic systems behaviour and the sound transmission behaviour of such a lightweight active component: This paper describes the investigation of a flat panel speaker which is based on electrostatic loudspeaker technology. First of all the passive transmission properties have been measured in a test bed. The passive acoustic insulation has been analyzed and weak spots in the frequency response were discovered. Afterwards the flat panel speaker has been used as actuator in an ANR-System to support insulation at those frequencies. An adaptive filter (FxLMS) was adjusted to the panel and the reduction capabilities of a single-output system have been determined.

  11. Reduction of polygalacturonase activity in tomato fruit by antisense RNA.

    PubMed

    Sheehy, R E; Kramer, M; Hiatt, W R

    1988-12-01

    Polygalacturonase [PG; poly(1,4-alpha-D-galacturonide) glycanhydrolase; EC 3.2.1.15] is expressed in tomato only during the ripening stage of fruit development. PG becomes abundant during ripening and has a major role in cell wall degradation and fruit softening. Tomato plants were transformed to produce antisense RNA from a gene construct containing the cauliflower mosaic virus 35S promoter and a full-length PG cDNA in reverse orientation. The construct was integrated into the tomato genome by Agrobacterium-mediated transformation. The constitutive synthesis of PG antisense RNA in transgenic plants resulted in a substantial reduction in the levels of PG mRNA and enzymatic activity in ripening fruit. The steady-state levels of PG antisense RNA in green fruit of transgenic plants were lower than the levels of PG mRNA normally attained during ripening. However, analysis of transcription in isolated nuclei demonstrated that the antisense RNA construct was transcribed at a higher rate than the tomato PG gene(s). Analysis of fruit from transgenic plants demonstrated a reduction in PG mRNA and enzymatic activity of 70-90%. The reduction in PG activity did not prevent the accumulation of the red pigment lycopene.

  12. Blood pressure reduction following accumulated physical activity in prehypertensive

    PubMed Central

    Saxena, Yogesh; Gupta, Rani; Moinuddin, Arsalan; Narwal, Ravinder

    2016-01-01

    Context: Accumulated moderate physical activity (PA) for 30 min in a day is the only recommended treatment of prehypertension. Objective: We investigated autonomic modulation as a possible mechanism for the decrease in blood pressure (BP) during the rest periods in each 10 min session of PA. Design, Setting, and Participants: We conducted a single-blind randomized multi-arm control trial on 40 prehypertensive (pre-HT) young male adults. Methods: Participants were randomly divided by using random number table into four groups. Control (no intervention); Group 1 (walking at 50% of predicted VO2 peak); Group 2 (walking at 60% of predicted VO2 peak); Group 3 (walking at 70% of predicted VO2 peak). BP, heart rate variability (HRV), and heart rate recovery 1 min (HRR 1 min) were measured at baseline and during the rest period after each session of 10 min over 30 min of accumulated physical activity (PAcumm). Results: Significant diastolic BP (DBP) reduction (P < 0.001) was observed during the rest period after each session of PAcumm in intervention groups. An average reduction in DBP was more in pre-HT undertaking PAcumm at 70% of predicted VO2 Peak. Decrease in the mean value of low-frequency (LF) and LF/high-frequency ratio was observed following PAcumm in all intervention groups irrespective of the intensity of PA. No significant association of reduction of BP with HRV and HRR 1 s was observed. Conclusion: Reduction in BP was observed during the rest period after each 10 min session of PAcumm irrespective of the intensity of PA. Autonomic modulation does not seem to be the possible mechanism for the reduction in BP during the sessions. PMID:27843840

  13. 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.

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

    PubMed Central

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

    2010-01-01

    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

  15. Coal pyrolysis to acetylene using dc hydrogen plasma torch: effects of system variables on acetylene concentration

    NASA Astrophysics Data System (ADS)

    Chen, Longwei; Meng, Yuedong; Shen, Jie; Shu, Xingsheng; Fang, Shidong; Xiong, Xinyang

    2009-03-01

    In order to unveil the inner mechanisms that determine acetylene concentration, experimental studies on the effect of several parameters such as plasma torch power, hydrogen flux and coal flux were carried out from coal pyrolysis in a dc plasma torch. Xinjiang long flame coals including volatile constituents at a level of about 42% were used in the experiment. Under the following experimental conditions, namely plasma torch power, hydrogen flow rate and pulverized coal feed speed of 2.12 MW, 32 kg h-1 and 900 kg h-1, respectively, acetylene volume concentration of about 9.4% was achieved. The experimental results indicate that parameters such as plasma torch power and coal flux play important roles in the formation of acetylene. Acetylene concentration increases inconspicuously with hydrogen flux. A chemical thermodynamic equilibrium model using the free energy method is introduced in this paper to numerically simulate each experimental condition. The numerical results are qualitatively consistent with the experimental results. Two parameters, i.e. the gas temperature and the ratio of hydrogen/carbon, are considered to be the dominant and independent factors that determine acetylene concentration.

  16. Sulfate Reduction at a Lignite Seam: Microbial Abundance and Activity.

    PubMed

    Detmers, J.; Schulte, U.; Strauss, H.; Kuever, J.

    2001-10-01

    In a combined isotope geochemical and microbiological investigation, a setting of multiple aquifers was characterized. Biologically mediated redox processes were observed in the aquifers situated in marine sands of Tertiary age and overlying Quaternary gravel deposits. Intercalated lignite seams define the aquitards, which separate the aquifers. Bacterial oxidation of organic matter is evident from dissolved inorganic carbon characterized by average carbon isotope values between ?18.4 per thousand and ?15.7 per thousand (PDB). Strongly positive sulfur isotope values of up to +50 per thousand (CTD) for residual sulfate indicate sulfate reduction under closed system conditions with respect to sulfate availability. Both, hydrochemical and isotope data are thus consistent with the recent activity of sulfate-reducing bacteria (SRB). Microbiological investigations revealed the presence of an anaerobic food chain in the aquifers. Most-probable-number (MPN) determinations for SRB and fermenting microorganisms reached highest values at the interface between aquifer and lignite seam (1.5 x 103 cells/g sediment dry mass). Five strains of SRB were isolated from highest MPN dilutions. Spore-forming bacteria appeared to dominate the SRB population. Sulfate reduction rates were determined by the 35S-radiotracer method. A detailed assessment indicates an increase in the reduction rate in proximity to the lignite seam, with a maximum turnover of 8.4 mM sulfate/a, suggesting that lignite-drived compounds represent the substrate for sulfate reduction.

  17. Reductive activation of mitomycins A and C by vitamin C.

    PubMed

    Paz, Manuel M

    2013-06-01

    The anticancer drug mitomycin C produces cytotoxic effects after being converted to a highly reactive bis-electrophile by a reductive activation, a reaction that a number of 1-electron or 2-electron oxidoreductase enzymes can perform in cells. Several reports in the literature indicate that ascorbic acid can modulate the cytotoxic effects of mitomycin C, either potentiating or inhibiting its effects. As ascorbic acid is a reducing agent that is known to be able to reduce quinones, it could be possible that the observed modulatory effects are a consequence of a direct redox reduction between mitomycin C and ascorbate. To determine if this is the case, the reaction between mitomycin C and ascorbate was studied using UV/Vis spectroscopy and LC/MS. We also studied the reaction of ascorbate with mitomycin A, a highly toxic member of the mitomycin family with a higher redox potential than mitomycin C. We found that ascorbate is capable to reduce mitomycin A efficiently, but it reduces mitomycin C rather inefficiently. The mechanisms of activation have been elucidated based on the kinetics of the reduction and on the analysis of the mitosene derivatives formed after the reaction. We found that the activation occurs by the interplay of three different mechanisms that contribute differently, depending on the pH of the reaction. As the reduction of mitomycin C by ascorbate is rather inefficiently at physiologically relevant pH values we conclude that the modulatory effect of ascorbate on the cytotoxicity of mitomycin C is not the result of a direct redox reaction and therefore this modulation must be the consequence of other biochemical mechanisms.

  18. 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

  19. 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.

  20. 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.

  1. Aromatic Radicals-Acetylene Particulate Matter Chemistry

    DTIC Science & Technology

    2011-12-01

    atmosphere1. In addition to acute respiratory problems, long-term effects include lung cancer and cardiopulmonary diseases , as studied by Pope at al...problems such as ischemic heart disease , fatal arrhythmia, and congestive heart failure4,5. Strategies to reduce fine particulate matter (PM...acetylene reaction have been made by Fahr and Stein15, who deduced an Arrhenius expression in a 4 temperature range between 1000 and 1330 K in

  2. Cross Sections for Electron Collisions with Acetylene

    NASA Astrophysics Data System (ADS)

    Song, Mi-Young; Yoon, Jung-Sik; Cho, Hyuck; Karwasz, Grzegorz P.; Kokoouline, Viatcheslav; Nakamura, Yoshiharu; Tennyson, Jonathan

    2017-03-01

    Cross section data are compiled from the literature for electron collisions with the acetylene (HCCH) molecule. Cross sections are collected and reviewed for total scattering, elastic scattering, momentum transfer, excitations of rotational and vibrational states, dissociation, ionization, and dissociative attachment. The data derived from swarm experiments are also considered. For each of these processes, the recommended values of the cross sections are presented. The literature has been surveyed through early 2016.

  3. High temperature polymer from maleimide-acetylene terminated monomers

    NASA Technical Reports Server (NTRS)

    Gerber, Margaret K. (Inventor); St.clair, Terry L. (Inventor)

    1993-01-01

    Thermally stable, glassy polymeric materials were prepared from maleimide-acetylene terminated monomeric materials by several methods. The monomers were heated to self-polymerize. The A-B structure of the monomer allowed it to polymerize with either bismaleimide monomers/oligomers or bis-acetylene monomers/oligomers. Copolymerization can also take place by mixing bismaleimide and bisacetylene monomers/oligomers with the maleimide-acetylene terminated monomers to yield homogenous glassy polymers.

  4. Reductive activation of Cr(Vi) by nitric oxide synthase.

    PubMed

    Porter, Ryan; Jáchymová, Marie; Martásek, Pavel; Kalyanaraman, B; Vásquez-Vivar, Jeannette

    2005-05-01

    Chromium(VI) is a recognized toxicant whose effects have been linked to its reduction to lower oxidation states. Although Cr(VI) is reduced by several systems, it is anticipated that its reduction by nitric oxide synthase (NOS) could have significant effects in endothelial and brain cells that express high constitutive levels of the enzyme. This possibility was examined by electron paramagnetic resonance that showed the formation of a stable Cr(V) species from NOS/Cr(VI). The formation of Cr(V) was calcium/calmodulin-independent indicating that Cr(VI) to Cr(V) reduction occurs at the flavin-containing domain of NOS. Accordingly, Cr(VI) reduction by the reductase domain of NOS and the chimera protein cytochrome-P450-reductase+tail-nNOS also generated Cr(V). Activation of tetrahydrobiopterin (BH(4))-free NOS with calcium/calmodulin diminished Cr(V) steady-state levels while increasing superoxide formation. Since SOD restored Cr(V) to control levels, this result was taken as evidence for a reaction between Cr(V) and superoxide. Supplementation of NOS with BH(4) cofactor not only failed to increase Cr(V) yields but generated superoxide and hydroxyl radical. Since the holoenzyme does not generate superoxide, this reaction indicated that Cr(V) mediates the oxidation of BH(4)-bound to the enzyme. In the presence of L-arginine, however, Cr(VI) neither enhances superoxide release nor inhibits NO formation from fully active NOS. This suggests that L-arginine protects BH(4) from Cr(V)-mediated oxidation. While Cr(V) was inactive toward NO, spin trapping experiments with 5-tert-butoxycarbonyl 5-methyl-1-pyrroline N-oxide and oxygen consumption measurements showed that Cr(V) reacts with superoxide by a one-electron-transfer mechanism to generate oxygen and Cr(IV). Thus, reduction of Cr(VI) to Cr(V) by NOS occurs in resting and fully active states. It is likely that the reaction between Cr(V) and superoxide influences the cytotoxic mechanisms of Cr(VI) in cells.

  5. High-resolution FTIR spectroscopy of the ν3 band of methyl acetylene-d

    NASA Astrophysics Data System (ADS)

    Pal, Ayan Kumar; Kshirsagar, R. J.

    2014-04-01

    The high-resolution Fourier transform spectrum of methyl acetylene-d1 (CH3CCD) at room temperature has been recorded in the region of the ν3 band (1980-2035 cm-1) at an apodized resolution of 0.004 cm-1. About 600 vibration-rotation transitions have been assigned, with J upto 36 and K upto 6. The spectrum shows the presence of several perturbations. The observed minus calculated deviation of the fit for K = 4 subband is much more than the expected, shows the presence of Fermi resonance with the nearby vibrational state.

  6. Reduction of propeller noise by active noise control

    NASA Astrophysics Data System (ADS)

    Bschorr, O.; Kubanke, D.

    1992-04-01

    Active noise control, a method of cancelling noise by means of interference with a secondary anti-noise source, is now in full development. The first commercial application of this technique is in the case of active electronically controlled head sets. The next step will be the active noise cancellation in air ducts and in passenger cabins. The aim of this paper is to assess the possibilities of the anti-noise technique for reducing propeller noise. First, by a mathematical simulation the theoretical noise reduction on the ground was calculated and found to be promising for further investigations. In the case of the periodic engine and propeller noise, for example, with only a single anti-noise source, the noise foot prints of the lower propeller harmonics can be reduced by up to 10 dB. In laboratory tests the theoretical values will be confirmed experimentally. For cancellation of the periodic noise one can use synchronous anti-noise generators. Compared with the engine and propeller noise the reduction of jet noise by the anti-noise technique is much more difficult. Therefore a sensor and controlling unit are necessary because of the stochastic nature of jet noise. Since aircraft noise is a severe problem, all methods are to be considered.

  7. Active Clustering with Model-Based Uncertainty Reduction.

    PubMed

    Xiong, Caiming; Johnson, David M; Corso, Jason J

    2017-01-01

    Semi-supervised clustering seeks to augment traditional clustering methods by incorporating side information provided via human expertise in order to increase the semantic meaningfulness of the resulting clusters. However, most current methods are passive in the sense that the side information is provided beforehand and selected randomly. This may require a large number of constraints, some of which could be redundant, unnecessary, or even detrimental to the clustering results. Thus in order to scale such semi-supervised algorithms to larger problems it is desirable to pursue an active clustering method-i.e., an algorithm that maximizes the effectiveness of the available human labor by only requesting human input where it will have the greatest impact. Here, we propose a novel online framework for active semi-supervised spectral clustering that selects pairwise constraints as clustering proceeds, based on the principle of uncertainty reduction. Using a first-order Taylor expansion, we decompose the expected uncertainty reduction problem into a gradient and a step-scale, computed via an application of matrix perturbation theory and cluster-assignment entropy, respectively. The resulting model is used to estimate the uncertainty reduction potential of each sample in the dataset. We then present the human user with pairwise queries with respect to only the best candidate sample. We evaluate our method using three different image datasets (faces, leaves and dogs), a set of common UCI machine learning datasets and a gene dataset. The results validate our decomposition formulation and show that our method is consistently superior to existing state-of-the-art techniques, as well as being robust to noise and to unknown numbers of clusters.

  8. Active Clustering with Model-Based Uncertainty Reduction.

    PubMed

    Xiong, Caiming; Johnson, David M; Corso, Jason J

    2016-03-09

    Semi-supervised clustering seeks to augment traditional clustering methods by incorporating side information provided via human expertise in order to increase the semantic meaningfulness of the resulting clusters. However, most current methods are passive in the sense that the side information is provided beforehand and selected randomly. This may require a large number of constraints, some of which could be redundant, unnecessary, or even detrimental to the clustering results. Thus in order to scale such semi-supervised algorithms to larger problems it is desirable to pursue an active clustering method- i.e. an algorithm that maximizes the effectiveness of the available human labor by only requesting human input where it will have the greatest impact. Here, we propose a novel online framework for active semi-supervised spectral clustering that selects pairwise constraints as clustering proceeds, based on the principle of uncertainty reduction. Using a first-order Taylor expansion, we decompose the expected uncertainty reduction problem into a gradient and a step-scale, computed via an application of matrix perturbation theory and cluster-assignment entropy, respectively. The resulting model is used to estimate the uncertainty reduction potential of each sample in the dataset. We then present the human user with pairwise queries with respect to only the best candidate sample. We evaluate our method using three different image datasets (faces, leaves and dogs), a set of common UCI machine learning datasets and a gene dataset. The results validate our decomposition formulation and show that our method is consistently superior to existing state-of-the-art techniques, as well as being robust to noise and to unknown numbers of clusters.

  9. Long-Term International Space Station (ISS) Risk Reduction Activities

    NASA Technical Reports Server (NTRS)

    Forroci, Michael P.; Gafka, George K.; Lutomski, Michael G.; Maher, Jacilyn S.

    2011-01-01

    As the assembly of the ISS nears completion, it is worthwhile to step back and review some of the actions pursued by the Program in recent years to reduce risk and enhance the safety and health of ISS crewmembers, visitors, and space flight participants. While the initial ISS requirements and design were intended to provide the best practicable levels of safety, it is always possible to further reduce risk given the determination, commitment, and resources to do so. The following is a summary of some of the steps taken by the ISS Program Manager, by our International Partners, by hardware and software designers, by operational specialists, and by safety personnel to continuously enhance the safety of the ISS, and to reduce risk to all crewmembers. While years of work went into the development of ISS requirements, there are many things associated with risk reduction in a Program like the ISS that can only be learned through actual operational experience. These risk reduction activities can be divided into roughly three categories: Areas that were initially noncompliant which have subsequently been brought into compliance or near compliance (i.e., Micrometeoroid and Orbital Debris [MMOD] protection, acoustics) Areas where initial design requirements were eventually considered inadequate and were subsequently augmented (i.e., Toxicity hazard level-4 materials, emergency procedures, emergency equipment, control of drag-throughs) Areas where risks were initially underestimated, and have subsequently been addressed through additional mitigation (i.e., Extravehicular Activity [EVA] sharp edges, plasma shock hazards). Due to the hard work and cooperation of many parties working together across the span of more than a decade, the ISS is now a safer and healthier environment for our crew, in many cases exceeding the risk reduction targets inherent in the intent of the original design. It will provide a safe and stable platform for utilization and discovery for years to come.

  10. Propulsion Risk Reduction Activities for Nontoxic Cryogenic Propulsion

    NASA Technical Reports Server (NTRS)

    Smith, Timothy D.; Klem, Mark D.; Fisher, Kenneth L.

    2010-01-01

    The Propulsion and Cryogenics Advanced Development (PCAD) Project s primary objective is to develop propulsion system technologies for nontoxic or "green" propellants. The PCAD project focuses on the development of nontoxic propulsion technologies needed to provide necessary data and relevant experience to support informed decisions on implementation of nontoxic propellants for space missions. Implementation of nontoxic propellants in high performance propulsion systems offers NASA an opportunity to consider other options than current hypergolic propellants. The PCAD Project is emphasizing technology efforts in reaction control system (RCS) thruster designs, ascent main engines (AME), and descent main engines (DME). PCAD has a series of tasks and contracts to conduct risk reduction and/or retirement activities to demonstrate that nontoxic cryogenic propellants can be a feasible option for space missions. Work has focused on 1) reducing the risk of liquid oxygen/liquid methane ignition, demonstrating the key enabling technologies, and validating performance levels for reaction control engines for use on descent and ascent stages; 2) demonstrating the key enabling technologies and validating performance levels for liquid oxygen/liquid methane ascent engines; and 3) demonstrating the key enabling technologies and validating performance levels for deep throttling liquid oxygen/liquid hydrogen descent engines. The progress of these risk reduction and/or retirement activities will be presented.

  11. Propulsion Risk Reduction Activities for Non-Toxic Cryogenic Propulsion

    NASA Technical Reports Server (NTRS)

    Smith, Timothy D.; Klem, Mark D.; Fisher, Kenneth

    2010-01-01

    The Propulsion and Cryogenics Advanced Development (PCAD) Project s primary objective is to develop propulsion system technologies for non-toxic or "green" propellants. The PCAD project focuses on the development of non-toxic propulsion technologies needed to provide necessary data and relevant experience to support informed decisions on implementation of non-toxic propellants for space missions. Implementation of non-toxic propellants in high performance propulsion systems offers NASA an opportunity to consider other options than current hypergolic propellants. The PCAD Project is emphasizing technology efforts in reaction control system (RCS) thruster designs, ascent main engines (AME), and descent main engines (DME). PCAD has a series of tasks and contracts to conduct risk reduction and/or retirement activities to demonstrate that non-toxic cryogenic propellants can be a feasible option for space missions. Work has focused on 1) reducing the risk of liquid oxygen/liquid methane ignition, demonstrating the key enabling technologies, and validating performance levels for reaction control engines for use on descent and ascent stages; 2) demonstrating the key enabling technologies and validating performance levels for liquid oxygen/liquid methane ascent engines; and 3) demonstrating the key enabling technologies and validating performance levels for deep throttling liquid oxygen/liquid hydrogen descent engines. The progress of these risk reduction and/or retirement activities will be presented.

  12. Guided cobalamin biosynthesis supports Dehalococcoides mccartyi reductive dechlorination activity.

    PubMed

    Yan, Jun; Im, Jeongdae; Yang, Yi; Löffler, Frank E

    2013-04-19

    Dehalococcoides mccartyi strains are corrinoid-auxotrophic Bacteria and axenic cultures that require vitamin B12 (CN-Cbl) to conserve energy via organohalide respiration. Cultures of D. mccartyi strains BAV1, GT and FL2 grown with limiting amounts of 1 µg l(-1) CN-Cbl quickly depleted CN-Cbl, and reductive dechlorination of polychlorinated ethenes was incomplete leading to vinyl chloride (VC) accumulation. In contrast, the same cultures amended with 25 µg l(-1) CN-Cbl exhibited up to 2.3-fold higher dechlorination rates, 2.8-9.1-fold increased growth yields, and completely consumed growth-supporting chlorinated ethenes. To explore whether known cobamide-producing microbes supply Dehalococcoides with the required corrinoid cofactor, co-culture experiments were performed with the methanogen Methanosarcina barkeri strain Fusaro and two acetogens, Sporomusa ovata and Sporomusa sp. strain KB-1, as Dehalococcoides partner populations. During growth with H2/CO2, M. barkeri axenic cultures produced 4.2 ± 0.1 µg l(-1) extracellular cobamide (factor III), whereas the Sporomusa cultures produced phenolyl- and p-cresolyl-cobamides. Neither factor III nor the phenolic cobamides supported Dehalococcoides reductive dechlorination activity suggesting that M. barkeri and the Sporomusa sp. cannot fulfil Dehalococcoides' nutritional requirements. Dehalococcoides dechlorination activity and growth occurred in M. barkeri and Sporomusa sp. co-cultures amended with 10 µM 5',6'-dimethylbenzimidazole (DMB), indicating that a cobalamin is a preferred corrinoid cofactor of strains BAV1, GT and FL2 when grown with chlorinated ethenes as electron acceptors. Even though the methanogen and acetogen populations tested did not produce cobalamin, the addition of DMB enabled guided biosynthesis and generated a cobalamin that supported Dehalococcoides' activity and growth. Guided cobalamin biosynthesis may offer opportunities to sustain and enhance Dehalococcoides activity in contaminated

  13. Theoretical investigation of the first-shell mechanism of acetylene hydration catalyzed by a biomimetic tungsten complex.

    PubMed

    Liu, Yan-Fang; Liao, Rong-Zhen; Ding, Wan-Jian; Yu, Jian-Guo; Liu, Ruo-Zhuang

    2011-06-01

    The reaction mechanism of the hydration of acetylene to acetaldehyde catalyzed by [W(IV)O(mnt)(2)](2-) (where mnt(2-) is 1,2-dicyanoethylenedithiolate) is studied using density functional theory. Both the uncatalyzed and the catalyzed reaction are considered to find out the origin of the catalysis. Three different models are investigated, in which an aquo, a hydroxo, or an oxo coordinates to the tungsten center. A first-shell mechanism is suggested, similarly to recent calculations on tungsten-dependent acetylene hydratase. The acetylene substrate first coordinates to the tungsten center in an η(2) fashion. Then, the tungsten-bound hydroxide activates a water molecule to perform a nucleophilic attack on the acetylene, resulting in the formation of a vinyl anion and a tungsten-bound water molecule. This is followed by proton transfer from the tungsten-bound water molecule to the newly formed vinyl anion intermediate. Tungsten is directly involved in the reaction by binding and activating acetylene and providing electrostatic stabilization to the transition states and intermediates. Three other mechanisms are also considered, but the associated energetic barriers were found to be very high, ruling out those possibilities.

  14. 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

  15. 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.

  16. 76 FR 75840 - Revising Standards Referenced in the Acetylene Standard

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-12-05

    ... the Acetylene Standard AGENCY: Occupational Safety and Health Administration (OSHA), Department of... rulemaking, the Agency is proposing to revise its Acetylene Standard for general industry by updating a... Companion Proposed Rule C. Request for Comment III. Summary and Explanation of Revisions to the...

  17. 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.

  18. Low Cost Routes to Acetylenic Intermediates

    DTIC Science & Technology

    1979-12-01

    palladium as catalyst, diethyl amine as solvent and cuprous iodide as cocatalyst (Equation 1). Cl 2Pd (PPh 3)2 ArX + H-CE-C-R Ar-C-C-R (1) Et 2 NH...an acetylene and cuprous iodide was not brought to a conclusion because this work was interrupted by work on the ATS system. We synthesized a variety...triethyl amine and cuprous iodide. At 940, the production of the substituted phenylacetylene and the disappearance of bromobenzene were examined by GC

  19. Reduction of selenite to elemental selenium nanoparticles by activated sludge.

    PubMed

    Jain, Rohan; Matassa, Silvio; Singh, Satyendra; van Hullebusch, Eric D; Esposito, Giovanni; Lens, Piet N L

    2016-01-01

    Total selenium removal by the activated sludge process, where selenite is reduced to colloidal elemental selenium nanoparticles (BioSeNPs) that remain entrapped in the activated sludge flocs, was studied. Total selenium removal efficiencies with glucose as electron donor (2.0 g chemical oxygen demand (COD) L(-1)) at neutral pH and 30 °C gave 2.9 and 6.8 times higher removal efficiencies as compared to the electron donors lactate and acetate, respectively. Total selenium removal efficiencies of 79 (±3) and 86 (±1) % were achieved in shake flasks and fed batch reactors, respectively, at dissolved oxygen (DO) concentrations above 4.0 mg L(-1) and 30 °C when fed with 172 mg L(-1) (1 mM) Na2SeO3 and 2.0 g L(-1) COD of glucose. Continuously operated reactors operating at neutral pH, 30 °C and a DO >3 mg L(-1) removed 33.98 and 36.65 mg of total selenium per gram of total suspended solids (TSS) at TSS concentrations of 1.3 and 3.0 g L(-1), respectively. However, selenite toxicity to the activated sludge led to failure of a continuously operating activated sludge reactor at the applied loading rates. This suggests that a higher hydraulic retention time (HRT) or different reactor configurations need to be applied for selenium-removing activated sludge processes. Graphical Abstract Scheme representing the possible mechanisms of selenite reduction at high and low DO levels in the activated sludge process.

  20. Physical activity, stress reduction, and mood: insight into immunological mechanisms.

    PubMed

    Hamer, Mark; Endrighi, Romano; Poole, Lydia

    2012-01-01

    Psychosocial factors, such as chronic mental stress and mood, are recognized as an important predictor of longevity and wellbeing. In particular, depression is independently associated with cardiovascular disease and all-cause mortality, and is often comorbid with chronic diseases that can worsen their associated health outcomes. Regular exercise is thought to be associated with stress reduction and better mood, which may partly mediate associations between depression, stress, and health outcomes. The underlying mechanisms for the positive effects of exercise on wellbeing remain poorly understood. In this overview we examine epidemiological evidence for an association between physical activity and mental health. We then describe the exercise withdrawal paradigm as an experimental protocol to study mechanisms linking exercise, mood, and stress. In particular we will discuss the potential role of the inflammatory response as a central mechanism.

  1. Highly active oxide photocathode for photoelectrochemical water reduction.

    PubMed

    Paracchino, Adriana; Laporte, Vincent; Sivula, Kevin; Grätzel, Michael; Thimsen, Elijah

    2011-06-01

    A clean and efficient way to overcome the limited supply of fossil fuels and the greenhouse effect is the production of hydrogen fuel from sunlight and water through the semiconductor/water junction of a photoelectrochemical cell, where energy collection and water electrolysis are combined into a single semiconductor electrode. We present a highly active photocathode for solar H(2) production, consisting of electrodeposited cuprous oxide, which was protected against photocathodic decomposition in water by nanolayers of Al-doped zinc oxide and titanium oxide and activated for hydrogen evolution with electrodeposited Pt nanoparticles. The roles of the different surface protection components were investigated, and in the best case electrodes showed photocurrents of up to -7.6 mA cm(-2) at a potential of 0 V versus the reversible hydrogen electrode at mild pH. The electrodes remained active after 1 h of testing, cuprous oxide was found to be stable during the water reduction reaction and the Faradaic efficiency was estimated to be close to 100%.

  2. Highly active oxide photocathode for photoelectrochemical water reduction

    NASA Astrophysics Data System (ADS)

    Paracchino, Adriana; Laporte, Vincent; Sivula, Kevin; Grätzel, Michael; Thimsen, Elijah

    2011-06-01

    A clean and efficient way to overcome the limited supply of fossil fuels and the greenhouse effect is the production of hydrogen fuel from sunlight and water through the semiconductor/water junction of a photoelectrochemical cell, where energy collection and water electrolysis are combined into a single semiconductor electrode. We present a highly active photocathode for solar H2 production, consisting of electrodeposited cuprous oxide, which was protected against photocathodic decomposition in water by nanolayers of Al-doped zinc oxide and titanium oxide and activated for hydrogen evolution with electrodeposited Pt nanoparticles. The roles of the different surface protection components were investigated, and in the best case electrodes showed photocurrents of up to -7.6 mA cm-2 at a potential of 0 V versus the reversible hydrogen electrode at mild pH. The electrodes remained active after 1 h of testing, cuprous oxide was found to be stable during the water reduction reaction and the Faradaic efficiency was estimated to be close to 100%.

  3. Antibacterial activity of silver bionanocomposites synthesized by chemical reduction route

    PubMed Central

    2012-01-01

    Background The aim of this study is to investigate the functions of polymers and size of nanoparticles on the antibacterial activity of silver bionanocomposites (Ag BNCs). In this research, silver nanoparticles (Ag NPs) were incorporated into biodegradable polymers that are chitosan, gelatin and both polymers via chemical reduction method in solvent in order to produce Ag BNCs. Silver nitrate and sodium borohydride were employed as a metal precursor and reducing agent respectively. On the other hand, chitosan and gelatin were added as a polymeric matrix and stabilizer. The antibacterial activity of different sizes of silver nanoparticles was investigated against Gram-positive and Gram-negative bacteria by the disk diffusion method using Mueller-Hinton Agar. Results The properties of Ag BNCs were studied as a function of the polymer weight ratio in relation to the use of chitosan and gelatin. The morphology of the Ag BNCs films and the distribution of the Ag NPs were also characterized. The diameters of the Ag NPs were measured and their size is less than 20 nm. The antibacterial trait of silver/chitosan/gelatin bionanocomposites was investigated. The silver ions released from the Ag BNCs and their antibacterial activities were scrutinized. The antibacterial activities of the Ag BNC films were examined against Gram-negative bacteria (E. coli and P. aeruginosa) and Gram-positive (S. aureus and M. luteus) by diffusion method using Muller-Hinton agar. Conclusions The antibacterial activity of Ag NPs with size less than 20 nm was demonstrated and showed positive results against Gram-negative and Gram-positive bacteria. The Ag NPs stabilized well in the polymers matrix. PMID:22967920

  4. Nanocomposite vacuum-Arc TiC/a-C:H coatings prepared using an additional ionization of acetylene

    NASA Astrophysics Data System (ADS)

    Trakhtenberg, I. Sh.; Gavrilov, N. V.; Emlin, D. R.; Plotnikov, S. A.; Vladimirov, A. B.; Volkova, E. G.; Rubshtein, A. P.

    2014-07-01

    The composition, structure, and properties of TiC/a-C:H coatings obtained by simultaneous vacuum-arc deposition of titanium and carbon in a low-pressure argon-acetylene medium additionally activated by a low-energy (a few hundreds of electron-volts) electron beam. The creation of conditions under which the decomposition of acetylene is provided by the ionization and dissociation of molecules due to electron impacts and by the recharging of molecules through titanium and argon ions with subsequent dissociation should favor the most complete decomposition of acetylene in a wide range of pressures. With increasing acetylene pressure, the structure of the nanocomposite coating changes: the size of TiC crystallites decreases, and the fraction of interfaces (or the fraction of regions with a disordered (amorphous) structure) increases. The application of a bias voltage leads to an increase in the sizes of TiC nanocrystallites. The coatings with a maximum microhardness (˜40 GPa) have been obtained without the action of an electron beam under an acetylene pressure of ˜0.05-0.08 Pa and the atomic ratio Ti: C ˜ 0.9: 1.1 in the coating.

  5. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Methyl acetylene-propadiene mixture. 151.50-79 Section... acetylene-propadiene mixture. (a) The composition of the methyl acetylene-propadiene mixture at loading must... acetylene-propadiene mixture must have a refrigeration system that does not compress the cargo vapor or...

  6. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Methyl acetylene-propadiene mixture. 151.50-79 Section... acetylene-propadiene mixture. (a) The composition of the methyl acetylene-propadiene mixture at loading must... acetylene-propadiene mixture must have a refrigeration system that does not compress the cargo vapor or...

  7. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Methyl acetylene-propadiene mixture. 151.50-79 Section... acetylene-propadiene mixture. (a) The composition of the methyl acetylene-propadiene mixture at loading must... acetylene-propadiene mixture must have a refrigeration system that does not compress the cargo vapor or...

  8. Photocatalytic degradation and drug activity reduction of Chloramphenicol.

    PubMed

    Chatzitakis, A; Berberidou, C; Paspaltsis, I; Kyriakou, G; Sklaviadis, T; Poulios, I

    2008-01-01

    The photocatalytic degradation of Chloramphenicol, an antibiotic drug, has been investigated in aqueous heterogeneous solutions containing n-type oxide semiconductors as photocatalysts. The disappearance of the organic molecule follows approximately a pseudo-first-order kinetics according to the Langmuir-Hinshelwood model. It was observed that, with TiO(2) P-25 as photocatalyst, quantitative degradation of the organic molecule occurs after 4h of illumination. During this time, the dechlorination of the substrate is complete, while the organic nitrogen was recovered in the form of nitrate and ammonium ions. The effect of temperature on the degradation rate of Chloramphenicol shows similar apparent activation energies for both TiO(2) P-25 and ZnO photocatalysts. The initial apparent photonic efficiency (zeta(0)) of the photo-oxidation and the mineralization under various experimental conditions have been calculated, while the Kirby-Bauer disc diffusion method showed a 100% reduction of the drug activity after 90 min of photocatalytic treatment.

  9. 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.

  10. Active Vibration Reduction of the Advanced Stirling Convertor

    NASA Technical Reports Server (NTRS)

    Wilson, Scott D.; Metscher, Jonathan F.; Schifer, Nicholas A.

    2016-01-01

    Stirling Radioisotope Power Systems (RPS) are being developed as an option to provide power on future space science missions where robotic spacecraft will orbit, flyby, land or rove. A Stirling Radioisotope Generator (SRG) could offer space missions a more efficient power system that uses one fourth of the nuclear fuel and decreases the thermal footprint compared to the current state of the art. The Stirling Cycle Technology Development (SCTD) Project is funded by the RPS Program to developing Stirling-based subsystems, including convertors and controller maturation efforts that have resulted in high fidelity hardware like the Advanced Stirling Radioisotope Generator (ASRG), Advanced Stirling Convertor (ASC), and ASC Controller Unit (ACU). The SCTD Project also performs research to develop less mature technologies with a wide variety of objectives, including increasing temperature capability to enable new environments, improving system reliability or fault tolerance, reducing mass or size, and developing advanced concepts that are mission enabling. Active vibration reduction systems (AVRS), or "balancers", have historically been developed and characterized to provide fault tolerance for generator designs that incorporate dual-opposed Stirling convertors or enable single convertor, or small RPS, missions. Balancers reduce the dynamic disturbance forces created by the power piston and displacer internal moving components of a single operating convertor to meet spacecraft requirements for induced disturbance force. To improve fault tolerance for dual-opposed configurations and enable single convertor configurations, a breadboard AVRS was implemented on the Advanced Stirling Convertor (ASC). The AVRS included a linear motor, a motor mount, and a closed-loop controller able to balance out the transmitted peak dynamic disturbance using acceleration feedback. Test objectives included quantifying power and mass penalty and reduction in transmitted force over a range of ASC

  11. Active Vibration Reduction of the Advanced Stirling Convertor

    NASA Technical Reports Server (NTRS)

    Wilson, Scott D.; Metscher, Jonathan F.; Schifer, Nicholas A.

    2016-01-01

    Stirling Radioisotope Power Systems (RPS) are being developed as an option to provide power on future space science missions where robotic spacecraft will orbit, flyby, land or rove. A Stirling Radioisotope Generator (SRG) could offer space missions a more efficient power system that uses one fourth of the nuclear fuel and decreases the thermal footprint compared to the current state of the art. The Stirling Cycle Technology Development (SCTD) Project is funded by the RPS Program to developing Stirling-based subsystems, including convertors and controller maturation efforts that have resulted in high fidelity hardware like the Advanced Stirling Radioisotope Generator (ASRG), Advanced Stirling Convertor (ASC), and ASC Controller Unit (ACU). The SCTD Project also performs research to develop less mature technologies with a wide variety of objectives, including increasing temperature capability to enable new environments, improving system reliability or fault tolerance, reducing mass or size, and developing advanced concepts that are mission enabling. Active vibration reduction systems (AVRS), or "balancers", have historically been developed and characterized to provide fault tolerance for generator designs that incorporate dual-opposed Stirling convertors or enable single convertor, or small RPS, missions. Balancers reduce the dynamic disturbance forces created by the power piston and displacer internal moving components of a single operating convertor to meet spacecraft requirements for induced disturbance force. To improve fault tolerance for dual-opposed configurations and enable single convertor configurations, a breadboard AVRS was implemented on the Advanced Stirling Convertor (ASC). The AVRS included a linear motor, a motor mount, and a closed-loop controller able to balance out the transmitted peak dynamic disturbance using acceleration feedback. Test objectives included quantifying power and mass penalty and reduction in transmitted force over a range of ASC

  12. Treatment of activated carbon to enhance catalytic activity for reduction of nitric oxide with ammonia

    SciTech Connect

    Ku, B.J.; Rhee, H.K. . Dept. of Chemical Engineering); Lee, J.K.; Park, D. )

    1994-11-01

    Catalytic activity of activated carbon treated with various techniques was examined in a fixed bed reactor for the reduction of nitric oxide with ammonia at 150 C. Activated carbon derived from coconut shell impregnated with an aqueous solution of ammonium sulfate, further treated with sulfuric acid, dried at 120 C, and then heated in an inert gas stream at 400 C, showed the highest catalytic activity within the range of experimental conditions. The enhancement of catalytic activity of modified activated carbon could be attributed to the increase in the amount of oxygen function groups which increased the adsorption site for ammonia. Catalytic activity of activated carbons depended on the surface area and the oxygen content as well.

  13. Evaluating the effectiveness of active noise reduction in flight helmets

    NASA Astrophysics Data System (ADS)

    Forshaw, S. E.; Rylands, J. M.; Crabtree, R. B.

    1988-08-01

    The advent of high powered fixed- and rotary-wing aircraft and tracked armoured fighting vehicles has increased the level of noise to which crews are exposed. Active noise reduction (ANR) offers a means of increasing the attenuation at low and mid frequencies. It relies on sensing the sound inside a circumaural device and cancelling it by means of negative feedback through a miniature speaker inside the enclosed volume. This study was carried out to investigate laboratory procedures appropriate for measuring the effectiveness of ANR devices. The procedures were: ear-canal measurements using an acoustic test fixture (an objective procedure), and masked threshold and loudness balance tests (psycho-physical procedures). In addition, the effect of ANR on signal detection and speech reception was investigated. The results do not clearly permit one procedure to be recommended for the evaluation of ANR systems. Signal detection performance and speech intelligibility may be used, but the results are specific to the acoustic environment of the listener and the detection task or speech-system parameters of the evaluation. When the attenuation of the ANR system is measured objectively with a transducer inside the earmuff/ear-canal volume, the location of the transducer affects the observed ANR attenuations.

  14. The SIM Lite Astrometric Observatory: engineering risk reduction activity

    NASA Astrophysics Data System (ADS)

    Goullioud, Renaud; Dekens, Frank; Nemati, Bijan; An, Xin; Hovland, Larry

    2010-07-01

    The SIM Lite Astrometric Observatory is a mission concept for a space-borne instrument to perform micro-arcsecond narrow-angle astrometry to search 60 to 100 nearby stars for Earth-like planets, and to perform global astrometry for a broad astrophysics program. The main enabling technology development for the mission was completed during phases A & B. While the project is waiting for the results of the ASTRO2010 Decadal Survey to proceed into flight implementation, the instrument team is currently converting the developed technology onto flight-ready engineering models. These key engineering tasks will significantly reduce the implementation risks during the flight phases C & D of the mission. The main optical interferometer components, including the astrometric beam combiner (ABC), the fine steering mechanism (FSM), the path-length control and modulation optical mechanisms (POM & MOM), focal plane camera electronics (ATC & FTC), camera cooling cryo-heat pipe, and the siderostat mechanism are currently under development. Main assemblies are built to meet flight requirements and have been or will be subjected to flight qualification level environmental testing (random vibration and thermal cycling) and performance testing. The Spectral Calibration Development Unit (SCDU), a white light interferometer testbed has recently demonstrated how to perform the spectral calibration of the instrument. The Guide 2 Telescope testbed (G2T) has demonstrated the 50 micro-arcsecond angle monitoring capability required by SIM Lite to perform astrometry. This paper summarizes recent progress in engineering risk reduction activities.

  15. Growth of ammonia-oxidizing archaea in soil microcosms is inhibited by acetylene.

    PubMed

    Offre, Pierre; Prosser, James I; Nicol, Graeme W

    2009-10-01

    Autotrophic ammonia-oxidizing bacteria were considered to be responsible for the majority of ammonia oxidation in soil until the recent discovery of the autotrophic ammonia-oxidizing archaea. To assess the relative contributions of bacterial and archaeal ammonia oxidizers to soil ammonia oxidation, their growth was analysed during active nitrification in soil microcosms incubated for 30 days at 30 degrees C, and the effect of an inhibitor of ammonia oxidation (acetylene) on their growth and soil nitrification kinetics was determined. Denaturing gradient gel electrophoresis (DGGE) analysis of bacterial ammonia oxidizer 16S rRNA genes did not detect any change in their community composition during incubation, and quantitative PCR (qPCR) analysis of bacterial amoA genes indicated a small decrease in abundance in control and acetylene-containing microcosms. DGGE fingerprints of archaeal amoA and 16S rRNA genes demonstrated changes in the relative abundance of specific crenarchaeal phylotypes during active nitrification. Growth was also indicated by increases in crenarchaeal amoA gene copy number, determined by qPCR. In microcosms containing acetylene, nitrification and growth of the crenarchaeal phylotypes were suppressed, suggesting that these crenarchaea are ammonia oxidizers. Growth of only archaeal but not bacterial ammonia oxidizers occurred in microcosms with active nitrification, indicating that ammonia oxidation was mostly due to archaea in the conditions of the present study.

  16. Functionalized acetylenic compounds via 1-bromo- 1,2-dienes and organocopper reagents

    SciTech Connect

    Caporusso, A.M.; Iodice, A.; Lardicci, L.; Salvadori, P.

    1995-12-31

    The acetylenic unity provides a convenient handle which may be converted into a variety of functionalities. In this frame, the authors developed a general and efficient method for the synthesis of chiral 1-alkynes, with a tertiary or a quaternary asymmetric carbon atom in the {alpha} position to the triple bond, by stereoselective cross-coupling of bromocuprates [(RCuBr)MaBr LiBr R=Alkyl, aryl] with optically active 1-bromo-1,2-dienes. This method provides terminal acetylenes which can easily converted into biologically active compounds, such as the antiphlogistic (+)-Ibuprofen. The authors report here that this procedure can be extended to the preparation of a large variety of functionalized acetylenic systems. In fact, bromocuprates, obtained from protected functionalized Grignard reagents and LiCuBr{sub 2}, react with bromoallenes affording the 1-alkynes with high yields, regio- and stereoselectivity. Compounds are also conveniently obtained from cyanocuprates, prepared by reaction of functionalized zinc reagents with the cuprous cyanide/lithium chloride complex; the organozinc derivatives are directly obtained from organic halides and highly activated zinc powder, prepared by metal vapour technique.

  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. High pressure chemistry of substituted acetylenes

    SciTech Connect

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

    2011-01-25

    High pressure in situ synchrotron x-ray diffraction experiments were performed on substituted polyacetylenes: tert-butyl acetylene [TBA: (CH{sub 3}){sub 3}-C{triple_bond}CH] and ethynyl trimethylsilane [ETMS: (CH{sub 3}){sub 3}-Si{triple_bond}CH] to investigate pressure-induced chemical reactions. The starting samples were the low temperature crystalline phases which persisted metastably at room temperature and polymerized beyond 11 GPa and 26 GPa for TBA and ETMS respectively. These reaction onset pressures are considerably higher than what we observed in the shockwave studies (6.1 GPa for TBA and 6.6 GPa for ETMS). Interestingly, in the case of ETMS, it was observed with fluid ETMS as starting sample, reacts to form a semi-crystalline polymer (crystalline domains corresponding to the low-T phase) at pressures less than {approx}2 GPa. Further characterization using vibrational spectroscopy is in progress.

  19. Cation-π and CH-π Interactions in the Coordination and Solvation of Cu(+)(acetylene)n Complexes.

    PubMed

    Brathwaite, Antonio D; Ward, Timothy B; Walters, Richard S; Duncan, Michael A

    2015-06-04

    Copper-acetylene cation complexes of the form Cu(C2H2)n(+) (n = 1-8) are produced by laser ablation in a supersonic expansion of acetylene/argon. The ions are mass selected and studied via infrared laser photodissociation spectroscopy in the C-H stretching region (3000-3500 cm(-1)). The structure and bonding of these complexes are investigated through the number of infrared active bands, their relative intensities and their frequency positions. Density functional theory calculations are carried out in support of the experimental data. The combined data show that cation-π complexes are formed for the n = 1-3 species, resulting in red-shifted C-H stretches on the acetylene ligands. The coordination of the copper cation is completed with three acetylene ligands, forming a "propeller" structure with D3 symmetry. Surprisingly, complexes with even greater numbers of acetylenes than this (4-6) have distinctive infrared band patterns quite different from those of the smaller complexes. Experiment combined with theory establishes that there is a fascinating pattern of second-sphere solvation involving the binding of acetylenes in bifurcated CH-π binding sites at the apex of two core ligands. This binding motif leads to three equivalent sites for second-sphere ligands, which when filled form a highly symmetrical Cu(+)(C2H2)6 complex. Solvent binding in this complex induces a structural change to planarity in the core, producing an appealing "core-shell" structure with D(3h) symmetry.

  20. 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.

  1. 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.

  2. On the ionic states of vinylidene and acetylene

    NASA Astrophysics Data System (ADS)

    Rosmus, P.; Botchwina, P.; Maier, J. P.

    1981-11-01

    Electronic states of C 2H +2 cation (with acetylenic and vinylidenic structure) are investigated by ab initio SCF and PNO CEPA calculations. The lowest excited state of the acetylene cation is calculated to be 4A 2 in a strongly bent cis conformation, and a qualitative explanation is given for the lack of detectable emission from theà 2∑ g+ state. Only the radical anion with the vinylidenic structure is bound.

  3. Photo- and heterotrophic nitrogenase activity by the cyano-bacterium Nostoc in symbiosis with the bryophyte Anthoceros

    SciTech Connect

    Steinberg, N.A.; Meeks, J.C.

    1987-04-01

    In symbiosis with Anthoceros, Nostoc is thought to do little or no photosynthesis. However, light-dependent /sup 14/CO/sub 2/ fixation by symbiotic Nostoc, freshly isolated from pure cultures of the reconstituted Anthoceros-Nostoc association, was 16% of that by free-living Nostoc. A DCMU-resistant mutant of Nostoc was isolated that fixed CO/sub 2/ at rates comparable to wild-type in both symbiotic and free-living growth states. To determine if symbiotic Nostoc can use its photosynthate directly to fix nitrogen, acetylene reduction by Anthoceros associations reconstituted with wild-type Nostoc was compared to associations with the DCMU-resistant mutant. In wild-type Anthoceros-Nostoc acetylene reduction was inhibited 97% by 5 ..mu..M DCMU, while inhibition of the DCMU-resistant Nostoc association was only 63%. Additions of glucose, fructose, maltose or sucrose to wild-type associations completely restored DCMU-inhibited acetylene reduction in the light. Acetylene reduction in the dark was stimulated by glucose, attaining 84% of the uninhibited light-dependent value. The authors conclude that symbiotic Nostoc maintains a pool of photosynthate which supports nitrogenase activity. The pool can also be supplemented from plant sources.

  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. 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.

  6. 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

  7. Iran’s Activities on Prevention, Treatment and Harm Reduction of Drug Abuse

    PubMed Central

    Saberi Zafarghandi, Mohammad Bagher; Jadidi, Mohsen; Khalili, Narjes

    2015-01-01

    Context: In the present review study, authors investigated Iran’s activities regarding prevention, abuse and harm reduction of drugs nationwide. The issue appears to be important in order to show the trend of activities in the country. Evidence Acquisition: In this report, authors gathered data from different Farsi/English peer review journals issued both in printed and online versions. These journals have been indexed in PubMed, ISI, ISC, SID, Magiran, UN, etc. These are among the most referred and cited databases. Results: Summarizing the data led to three distinguished sections: 1) drug supply reduction activities; 2) drug demand reduction activities; 3) harm reduction activities. Conclusions: As the results showed, the trend of activities was encouraging and some additional activities could be included to future programs relying on early-onset preventions. PMID:26870709

  8. 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.

  9. The Synthesis and Isothermal Aging Behavior of Oxygen-Free Acetylene Terminated Quinoxalines

    DTIC Science & Technology

    1981-05-01

    AFWAL-TR-81-4004 THE SYNTHESIS AND ISOTHERMAL AGING BEHAVIOR OF OXYGEN-FREE ACETYLENE TERMINATED QUINOXALINES Polymer Branch Nonmetallic Materials...TYPE OF REPORT & PERIOD COVERED THE SYNTHESIS AND ISOTHERMAL AGING BEHAVIOR Final Technical Report OF OXYGEN-FREE ACETYLENE TERMINATED January 1979...Quinoxaline Acetylene Terminated Acetylene Cure Thermooxidative Stability Isothermal Aging 20. ABSTRACT (Continue on reverse side if necessary and identify by

  10. Reduction of structural weight, costs and complexity of a control system in the active vibration reduction of flexible structures

    NASA Astrophysics Data System (ADS)

    Daraji, A. H.; Hale, J. M.

    2014-09-01

    This paper concerns the active vibration reduction of a flexible structure with discrete piezoelectric sensors and actuators in collocated pairs bonded to its surface. In this study, a new fitness and objective function is proposed to determine the optimal number of actuators, based on variations in the average closed loop dB gain margin reduction for all of the optimal piezoelectric pairs and on the modes that are required to be attenuated using the optimal linear quadratic control scheme. The aim of this study is to find the minimum number of optimally located sensor/actuator pairs, which can achieve the same vibration reduction as a greater number, in order to reduce the cost, complexity and power requirement of the control system. This optimization was done using a genetic algorithm. The technique may be applied to any lightly damped structure, and is demonstrated here by attenuating the first six vibration modes of a flat cantilever plate. It is shown that two sensor/actuator pairs, located and controlled optimally, give almost the same vibration reduction as ten pairs. These results are validated by comparing the open and closed loop time responses and actuator feedback voltages for various numbers of piezoelectric pairs using the ANSYS finite element package and a proportional differential control scheme.

  11. 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.

  12. Active Flap Control of the SMART Rotor for Vibration Reduction

    NASA Technical Reports Server (NTRS)

    Hall, Steven R.; Anand, R. Vaidyanathan; Straub, Friedrich K.; Lau, Benton H.

    2009-01-01

    Active control methodologies were applied to a full-scale active flap rotor obtained during a joint Boeing/ DARPA/NASA/Army test in the Air Force National Full-Scale Aerodynamic Complex 40- by 80-foot anechoic wind tunnel. The active flap rotor is a full-scale MD 900 helicopter main rotor with each of its five blades modified to include an on-blade piezoelectric actuator-driven flap with a span of 18% of radius, 25% of chord, and located at 83% radius. Vibration control demonstrated the potential of active flaps for effective control of vibratory loads, especially normal force loads. Active control of normal force vibratory loads using active flaps and a continuous-time higher harmonic control algorithm was very effective, reducing harmonic (1-5P) normal force vibratory loads by 95% in both cruise and approach conditions. Control of vibratory roll and pitch moments was also demonstrated, although moment control was less effective than normal force control. Finally, active control was used to precisely control blade flap position for correlation with pretest predictions of rotor aeroacoustics. Flap displacements were commanded to follow specific harmonic profiles of 2 deg or more in amplitude, and the flap deflection errors obtained were less than 0.2 deg r.m.s.

  13. 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...

  14. 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...

  15. 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...

  16. 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...

  17. 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...

  18. Activity and Stability of Nanoscale Oxygen Reduction Catalysts

    SciTech Connect

    Shao-Horn, Yang

    2015-07-28

    Design of highly active and stable nanoscale catalysts for electro-oxidation of small organic molecules is of great importance to the development of efficient fuel cells. The amount and instability of Pt-based catalysts in the cathode limits the cost, efficiency and lifetime of proton exchange membrane fuel cells. We developed a microscopic understanding of the factors governing activity and stability in Pt and PtM alloys. Experimental efforts were focused on probing the size and shape dependence of ORR activity of Pt-based nanoparticles supported on carbon nanotubes. A microscopic understanding of the activity was achieved by correlating voltammetry and rotating ring disk electrodes to surface atomic and electronic structures, which were elucidated predominantly by high-resolution transmission electron microscopy (HRTEM), Scanning transmission electron microscopy energy dispersive X-ray Spectroscopy (STEM-EDS) and synchrotron X-ray absorption spectroscopy (XAS).

  19. Sustained Reduction of Cerebellar Activity in Experimental Epilepsy

    PubMed Central

    Rijkers, Kim; Moers-Hornikx, Véronique M. P.; Hemmes, Roelof J.; Aalbers, Marlien W.; Temel, Yasin; Vles, Johan S. H.; Hoogland, Govert

    2015-01-01

    Clinical and experimental evidence suggests a role for the cerebellum in seizure control, while no data are available on cerebellar activity between seizures. We hypothesized that interictal regional activity of the deep cerebellar nuclei is reduced in epilepsy and tested this in an animal model by using ΔFosB and cytochrome oxidase (COX) (immuno)histochemistry. The expression of these two markers of neuronal activity was analysed in the dentate nucleus (DN), interpositus nucleus (IN), and fastigial nucleus (FN) of the cerebellum of fully amygdala kindled rats that were sacrificed 48 hours after their last seizure. The DN and FN of kindled rats exhibited 25 to 29% less ΔFosB immunopositive cells than their respective counterpart in sham controls (P < 0.05). COX expression in the DN and FN of kindled animals was reduced by 32 to 33% compared to respective control values (P < 0.05). These results indicate that an epileptogenic state is characterized by decreased activity of deep cerebellar nuclei, especially the DN and FN. Possible consequences may include a decreased activation of the thalamus, contributing to further seizure spread. Restoration of FN activity by low frequency electrical stimulation is suggested as a possible treatment option in chronic epilepsy. PMID:26417599

  20. 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.

  1. 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.

  2. Design Activity in the Software Cost Reduction Project.

    DTIC Science & Technology

    1986-08-18

    PM Physical Model S G System Generation SS Shared Services SU System Utilities . NOV M N 1600SEP A 0 JUL TOTAL 14000 MAAR cc 100 FEB :IESGN 0o 10000...iy---- .... ;’ TESTING Jan 78 Jan 79 Jan 80 Jan 81 Jan 82 Jan 83 Jan 84 Jan 85 M3ITH Fig. 7 - Shared services activities A F 0 U E C 1600 G B T...DISCUSSING 200M Jan 78 Jan 79 Jan 80 Jan 81 Jan 82 Jan 83 Jan 84 Jan 85 Fig 13 - Shared services design activities 5.~ S% 12 ......,ooU7 . . NRL REPORT 8974 A

  3. 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.

  4. Exploration of Allosteric Agonism Structure-Activity Relationships within an Acetylene Series of Metabotropic Glutamate Receptor 5 (mGlu5) Positive Allosteric Modulators (PAMs): discovery of 5-((3-fluorophenyl)ethynyl)-N-(3-methyloxetan-3-yl)picolinamide (ML254)

    PubMed Central

    Turlington, Mark; Noetzel, Meredith J.; Chun, Aspen; Zhou, Ya; Gogliotti, Rocco D.; Nguyen, Elizabeth D.; Gregory, Karen J.; Vinson, Paige N.; Rook, Jerri M.; Gogi, Kiran K.; Xiang, Zixiu; Bridges, Thomas M.; Daniels, J. Scott; Jones, Carrie; Niswender, Colleen M.; Meiler, Jens; Conn, P. Jeffrey; Lindsley, Craig W.; Stauffer, Shaun R.

    2014-01-01

    Positive allosteric modulators (PAMs) of metabotropic glutamate receptor 5 (mGlu5) represent a promising therapeutic strategy for the treatment of schizophrenia. Both allosteric agonism and high glutamate fold-shift have been implicated in the neurotoxic profile of some mGlu5 PAMs; however, these hypotheses remain to be adequately addressed. To develop tool compounds to probe these hypotheses, the structure-activity relationship of allosteric agonism was examined within an acetylenic series of mGlu5 PAMs exhibiting allosteric agonism in addition to positive allosteric modulation (ago-PAMs). PAM 38t, a low glutamate fold-shift allosteric ligand (maximum fold-shift ~3.0), was selected as a potent PAM with no agonism in the in vitro system used for compound characterization and in two native electrophysiological systems using rat hippocampal slices. PAM 38t (ML254) will be useful to probe the relative contribution of cooperativity and allosteric agonism to the adverse effect liability and neurotoxicity associated with this class of mGlu5 PAMs. PMID:24050755

  5. Exploration of allosteric agonism structure-activity relationships within an acetylene series of metabotropic glutamate receptor 5 (mGlu5) positive allosteric modulators (PAMs): discovery of 5-((3-fluorophenyl)ethynyl)-N-(3-methyloxetan-3-yl)picolinamide (ML254).

    PubMed

    Turlington, Mark; Noetzel, Meredith J; Chun, Aspen; Zhou, Ya; Gogliotti, Rocco D; Nguyen, Elizabeth D; Gregory, Karen J; Vinson, Paige N; Rook, Jerri M; Gogi, Kiran K; Xiang, Zixiu; Bridges, Thomas M; Daniels, J Scott; Jones, Carrie; Niswender, Colleen M; Meiler, Jens; Conn, P Jeffrey; Lindsley, Craig W; Stauffer, Shaun R

    2013-10-24

    Positive allosteric modulators (PAMs) of metabotropic glutamate receptor 5 (mGlu5) represent a promising therapeutic strategy for the treatment of schizophrenia. Both allosteric agonism and high glutamate fold-shift have been implicated in the neurotoxic profile of some mGlu5 PAMs; however, these hypotheses remain to be adequately addressed. To develop tool compounds to probe these hypotheses, the structure-activity relationship of allosteric agonism was examined within an acetylenic series of mGlu5 PAMs exhibiting allosteric agonism in addition to positive allosteric modulation (ago-PAMs). PAM 38t, a low glutamate fold-shift allosteric ligand (maximum fold-shift ~ 3.0), was selected as a potent PAM with no agonism in the in vitro system used for compound characterization and in two native electrophysiological systems using rat hippocampal slices. PAM 38t (ML254) will be useful to probe the relative contribution of cooperativity and allosteric agonism to the adverse effect liability and neurotoxicity associated with this class of mGlu5 PAMs.

  6. Actively Controlled Landing Gear for Aircraft Vibration Reduction

    NASA Technical Reports Server (NTRS)

    Horta, Lucas G.; Daugherty, Robert H.; Martinson, Veloria J.

    1999-01-01

    Concepts for long-range air travel are characterized by airframe designs with long, slender, relatively flexible fuselages. One aspect often overlooked is ground induced vibration of these aircraft. This paper presents an analytical and experimental study of reducing ground-induced aircraft vibration loads using actively controlled landing gears. A facility has been developed to test various active landing gear control concepts and their performance. The facility uses a NAVY A6-intruder landing gear fitted with an auxiliary hydraulic supply electronically controlled by servo valves. An analytical model of the gear is presented including modifications to actuate the gear externally and test data is used to validate the model. The control design is described and closed-loop test and analysis comparisons are presented.

  7. 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

  8. Optimizing Estimated Loss Reduction for Active Sampling in Rank Learning

    DTIC Science & Technology

    2008-01-01

    ranging from the income level to age and her preference order over a set of products (e.g. movies in Netflix ). The ranking task is to learn a map- ping...learners in RankBoost. However, in both cases, the proposed strategy selects the samples which are estimated to produce a faster convergence from the...steps in Section 5. 2. Related Work A number of strategies have been proposed for active learning in the classification framework. Some of those center

  9. 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

  10. 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.

  11. Poly(acetylene) as a positive electrode in lithium sulfur oxyhalide cells

    NASA Astrophysics Data System (ADS)

    Calvert, Jeffrey M.; Weiner, Bryndyn; Smith, Jerry J.; Nowak, Robert J.

    1989-03-01

    Conductive poly(acetylene) film was employed as the positive electrode in primary lithium/thionyl chloride and lithium/sulfuryl chloride cells. Neutral (CH)x, doped to the metallic state upon in situ exposure to LiAlCl4/sulfur oxyhalide electrolytes, acts as a catalytic surface rather than as the active electrochemical element. Sulfur oxyhalides were reduced on(CH)x film at high rates as on PTFE-bonded Shawinigan carbon black felt. Electrode capacity was limited by the inability of the electrolyte to permeate the (CH)x film and the formation of a surface passive filmby discharge products.

  12. Real-Time Active Cosmic Neutron Background Reduction Methods

    SciTech Connect

    Mukhopadhyay, Sanjoy; Maurer, Richard; Wolff, Ronald; Mitchell, Stephen; Guss, Paul

    2013-09-01

    Neutron counting using large arrays of pressurized 3He proportional counters from an aerial system or in a maritime environment suffers from the background counts from the primary cosmic neutrons and secondary neutrons caused by cosmic ray-induced mechanisms like spallation and charge-exchange reaction. This paper reports the work performed at the Remote Sensing Laboratory–Andrews (RSL-A) and results obtained when using two different methods to reduce the cosmic neutron background in real time. Both methods used shielding materials with a high concentration (up to 30% by weight) of neutron-absorbing materials, such as natural boron, to remove the low-energy neutron flux from the cosmic background as the first step of the background reduction process. Our first method was to design, prototype, and test an up-looking plastic scintillator (BC-400, manufactured by Saint Gobain Corporation) to tag the cosmic neutrons and then create a logic pulse of a fixed time duration (~120 μs) to block the data taken by the neutron counter (pressurized 3He tubes running in a proportional counter mode). The second method examined the time correlation between the arrival of two successive neutron signals to the counting array and calculated the excess of variance (Feynman variance Y2F)1 in the neutron count distribution from Poisson distribution. The dilution of this variance from cosmic background values ideally would signal the presence of man-made neutrons.2 The first method has been technically successful in tagging the neutrons in the cosmic-ray flux and preventing them from being counted in the 3He tube array by electronic veto—field measurement work shows the efficiency of the electronic veto counter to be about 87%. The second method has successfully derived an empirical relationship between the percentile non-cosmic component in a neutron flux and the Y2F of the measured neutron count distribution. By using shielding materials alone, approximately 55% of the neutron flux

  13. Reductions in Northeast Refining Activity: Potential Implications for Petroleum Product Markets

    EIA Publications

    2011-01-01

    This report is the Energy Information Administration's (EIA) initial effort to provide information and analysis on the potential impacts on petroleum product markets from reductions in Northeast petroleum refining activity.

  14. A process for the purification of organochlorine contaminated activated carbon: Sequential solvent purging and reductive dechlorination.

    PubMed

    Lee, Matthew; Cord-Ruwisch, Ralf; Manefield, Mike

    2010-03-01

    A system for the purification of organochlorine contaminated activated carbon is described. The system involves a continuous flow of aqueous ethanol to purge organochlorines from activated carbon. The organochlorine laden solvent is simultaneously treated with zero valent zinc as the bulk electron source, water as the proton source and the electron shuttle cyanocobalamin as a catalyst for reductive dechlorination. The system was characterised by performing batch reactions and extractions before being applied in a continuous flow system. In particular the ratio of water to ethanol in the system needed to be optimised. Water is needed for the reductive dechlorination reaction whilst it is not conducive to the extraction process. An 80% ethanolic solution was found to give optimal reductive dechlorination rates without compromising extraction of organochlorines from activated carbon. Of three electron shuttles evaluated cyanocobalamin was discovered to be the most relevant to the system with respect to reductive dechlorination rates and its ability to avoid absorption to activated carbon.

  15. 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.

  16. ACTINIC MASK INSPECTION AT THE ALS: RISK REDUCTION ACTIVITIES FOR 2003

    SciTech Connect

    Barty, A; Levesque, R; Ayers, J; Liu, Y; Gullikson, E; Barale, P

    2004-01-05

    This document reports on risk reduction activities performed at the VNL during CY2003 as a part of the Lith-343 actinic inspection project funded by International SEMATECH. The risk reduction activities described in this document comprise deliverable items 3.1.3, 3.1.4, 3.1.5 and 3.1.6 of Amendment 6 to the VNL EUV mask blank technology transfer contract.

  17. Potential Impacts of Reductions in Refinery Activity on Northeast Petroleum Product Markets

    EIA Publications

    2012-01-01

    Potential Impacts of Reductions in Refinery Activity on Northeast Petroleum Product Markets is an update to a previous Energy Information Administration (EIA) report, Reductions in Northeast Refining Activity: Potential Implications for Petroleum Product Markets, released in December 2011. This update analyzes possible market responses and impacts in the event Sunoco's Philadelphia refinery closes this summer, in addition to the recently idled refineries on the East Coast and in the U.S. Virgin Islands.

  18. Reduction of interior sound fields in flexible cylinders by active vibration control

    NASA Technical Reports Server (NTRS)

    Jones, J. D.; Fuller, C. R.

    1988-01-01

    The mechanisms of interior sound reduction through active control of a thin flexible shell's vibrational response are presently evaluated in view of an analytical model. The noise source is a single exterior acoustic monopole. The active control model is evaluated for harmonic excitation; the results obtained indicate spatially-averaged noise reductions in excess of 20 dB over the source plane, for acoustic resonant conditions inside the cavity.

  19. Reactions of acetylenes in superbasic media. Recent advances

    NASA Astrophysics Data System (ADS)

    Trofimov, B. A.; Schmidt, E. Yu

    2014-07-01

    The main advances in the chemistry of acetylene in superbasic media achieved over the last five years are analyzed. Particular emphasis is placed on the ethynylation of aldehydes and ketones and C-, N- and O-vinylation. The cascade assembly of complex molecules in which ethynylation and vinylation are consecutive steps is considered. The bibliography includes 369 references.

  20. Acetylenic Coupling: A Powerful Tool in Molecular Construction.

    PubMed

    Siemsen; Livingston; Diederich

    2000-08-04

    Acetylenic coupling is currently experiencing some of the most intensive study of its long history. Rigid and sterically undemanding di- and oligoacetylene moieties, which are frequently encountered in natural products, are finding increasing application as key structural elements in synthetic receptors for molecular recognition. Interesting electronic and optical properties of extensively pi-conjugated systems have spurred research into new linear oligoalkynes and acetylenic carbon allotropes. The synthetic challenges associated with these efforts have in turn spawned new methods. While classical Glaser conditions are still frequently used for homocoupling, the demand for increasingly selective heterocoupling conditions has provided the focus of research over the past decades. These efforts have undoubtedly been hampered by a relatively poor mechanistic understanding of these processes. More recently, palladium-catalyzed coupling methods have led to improvements in both the selectivity and reliability of acetylenic homo- and heterocouplings and paved the way for their application to ever more complicated systems. The variety of acetylenic coupling protocols, the current mechanistic understanding, and their application in natural product and targeted synthesis are discussed comprehensively for the first time in this review, with an emphasis on the most recently developed methods, and their application to the synthesis of complex macromolecular structures.

  1. 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.

  2. 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.

  3. Acetylene absorption and binding in nonporous crystal lattice

    SciTech Connect

    Thallapally, Praveen K.; Dobrzanska, Liliana B.; Gingrich, Todd R.; Wirsig, Trevor B.; Barbour, Leonard J.; Atwood, Jerry L.

    2006-09-01

    Unusual storage: An organic nonporous material, p-tert-butylcalix[4]arene, sorbs acetylene with high storage density under ambient conditions. It is presumed that gas molecules diffuse through the seemingly nonporous lattice without disrupting the arrangement of the host molecules (see picture; red O, blue C, gray H, yellow void space).

  4. Nitrogen-doped Carbon Derived from ZIF-8 as a High-performance Metal-free Catalyst for Acetylene Hydrochlorination

    PubMed Central

    Chao, Songlin; Zou, Fang; Wan, Fanfan; Dong, Xiaobin; Wang, Yanlin; Wang, Yuxuan; Guan, Qingxin; Wang, Guichang; Li, Wei

    2017-01-01

    Acetylene hydrochlorination is a major industrial technology for manufacturing vinyl chloride monomer in regions with abundant coal resources; however, it is plagued by the use of mercury(II) chloride catalyst. The development of a nonmercury catalyst has been extensively explored. Herein, we report a N-doped carbon catalyst derived from ZIF-8 with both high activity and quite good stability. The acetylene conversion reached 92% and decreased slightly during a 200 h test at 220 °C and atmospheric pressure. Experimental studies and theoretical calculations indicate that C atoms adjacent to the pyridinic N are the active sites, and coke deposition covering pyridinic N is the main reason for catalyst deactivation. The performance of those N-doped carbons makes it possible for practical applications with further effort. Furthermore, the result also provides guidance for designing metal-free catalysts for similar reactions. PMID:28051131

  5. Nitrogen-doped Carbon Derived from ZIF-8 as a High-performance Metal-free Catalyst for Acetylene Hydrochlorination.

    PubMed

    Chao, Songlin; Zou, Fang; Wan, Fanfan; Dong, Xiaobin; Wang, Yanlin; Wang, Yuxuan; Guan, Qingxin; Wang, Guichang; Li, Wei

    2017-01-04

    Acetylene hydrochlorination is a major industrial technology for manufacturing vinyl chloride monomer in regions with abundant coal resources; however, it is plagued by the use of mercury(II) chloride catalyst. The development of a nonmercury catalyst has been extensively explored. Herein, we report a N-doped carbon catalyst derived from ZIF-8 with both high activity and quite good stability. The acetylene conversion reached 92% and decreased slightly during a 200 h test at 220 °C and atmospheric pressure. Experimental studies and theoretical calculations indicate that C atoms adjacent to the pyridinic N are the active sites, and coke deposition covering pyridinic N is the main reason for catalyst deactivation. The performance of those N-doped carbons makes it possible for practical applications with further effort. Furthermore, the result also provides guidance for designing metal-free catalysts for similar reactions.

  6. Nitrogen-doped Carbon Derived from ZIF-8 as a High-performance Metal-free Catalyst for Acetylene Hydrochlorination

    NASA Astrophysics Data System (ADS)

    Chao, Songlin; Zou, Fang; Wan, Fanfan; Dong, Xiaobin; Wang, Yanlin; Wang, Yuxuan; Guan, Qingxin; Wang, Guichang; Li, Wei

    2017-01-01

    Acetylene hydrochlorination is a major industrial technology for manufacturing vinyl chloride monomer in regions with abundant coal resources; however, it is plagued by the use of mercury(II) chloride catalyst. The development of a nonmercury catalyst has been extensively explored. Herein, we report a N-doped carbon catalyst derived from ZIF-8 with both high activity and quite good stability. The acetylene conversion reached 92% and decreased slightly during a 200 h test at 220 °C and atmospheric pressure. Experimental studies and theoretical calculations indicate that C atoms adjacent to the pyridinic N are the active sites, and coke deposition covering pyridinic N is the main reason for catalyst deactivation. The performance of those N-doped carbons makes it possible for practical applications with further effort. Furthermore, the result also provides guidance for designing metal-free catalysts for similar reactions.

  7. Revealing the Origin of Activity in Nitrogen-Doped Nanocarbons towards Electrocatalytic Reduction of Carbon Dioxide.

    PubMed

    Xu, Junyuan; Kan, Yuhe; Huang, Rui; Zhang, Bingsen; Wang, Bolun; Wu, Kuang-Hsu; Lin, Yangming; Sun, Xiaoyan; Li, Qingfeng; Centi, Gabriele; Su, Dangsheng

    2016-05-23

    Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO2 ). The investigation explores the origin of the catalyst's activity and the role of nitrogen chemical states therein. The catalysts show excellent performances, with about 90 % current efficiency for CO formation and stability over 60 hours. The Tafel analyses and density functional theory calculations suggest that the reduction of CO2 proceeds through an initial rate-determining transfer of one electron to CO2 , which leads to the formation of carbon dioxide radical anion (CO2 (.-) ). The initial reduction barrier is too high on pristine CNTs, resulting in a very high overpotentials at which the hydrogen evolution reaction dominates over CO2 reduction. The doped nitrogen atoms stabilize the radical anion, thereby lowering the initial reduction barrier and improving the intrinsic activity. The most efficient nitrogen chemical state for this reaction is quaternary nitrogen, followed by pyridinic and pyrrolic nitrogen.

  8. RFI Risk Reduction Activities Using New Goddard Digital Radiometry Capabilities

    NASA Technical Reports Server (NTRS)

    Bradley, Damon; Kim, Ed; Young, Peter; Miles, Lynn; Wong, Mark; Morris, Joel

    2012-01-01

    The Goddard Radio-Frequency Explorer (GREX) is the latest fast-sampling radiometer digital back-end processor that will be used for radiometry and radio-frequency interference (RFI) surveying at Goddard Space Flight Center. The system is compact and deployable, with a mass of about 40 kilograms. It is intended to be flown on aircraft. GREX is compatible with almost any aircraft, including P-3, twin otter, C-23, C-130, G3, and G5 types. At a minimum, the system can function as a clone of the Soil Moisture Active Passive (SMAP) ground-based development unit [1], or can be a completely independent system that is interfaced to any radiometer, provided that frequency shifting to GREX's intermediate frequency is performed prior to sampling. If the radiometer RF is less than 200MHz, then the band can be sampled and acquired directly by the system. A key feature of GREX is its ability to simultaneously sample two polarization channels simultaneously at up to 400MSPS, 14-bit resolution each. The sampled signals can be recorded continuously to a 23 TB solid-state RAID storage array. Data captures can be analyzed offline using the supercomputing facilities at Goddard Space Flight Center. In addition, various Field Programmable Gate Array (FPGA) - amenable radiometer signal processing and RFI detection algorithms can be implemented directly on the GREX system because it includes a high-capacity Xilinx Virtex-5 FPGA prototyping system that is user customizable.

  9. Lipase-catalyzed hydrolysis of TG containing acetylenic FA.

    PubMed

    Jie, Marcel S F Lie Ken; Fua, Xun; Lau, Maureen M L; Chye, M L

    2002-10-01

    Hydrolysis of symmetrical acetylenic TG of type AAA [viz., glycerol tri-(4-decynoate), glycerol tri-(6-octadecynoate), glycerol tri-(9-octadecynoate), glycerol tri-(10-undecynoate), and glycerol tri-(13-docosynoate)] in the presence of eight microbial lipases was studied. Novozyme 435 (Candida antarctica), an efficient enzyme for esterification, showed a significant resistance in the hydrolysis of glycerol tri-(9-octadecynoate) and glycerol tri-(13-docosynoate). Hydrolysis of acetylenic TG with Lipolase 100T (Humicola lanuginosa) was rapidly accomplished. Lipase PS-D (Pseudomonas cepacia) showed a fair resistance toward the hydrolysis of glycerol tri-(6-octadecynoate) only, which reflected its ability to recognize the delta6 positional isomer of 18:1. Lipase CCL (Candida cylindracea, syn. C. rugosa) and AY-30 (C. rugosa) were able to catalyze the release of 10-undecynoic acid and 9-octadecynoic acid from the corresponding TG, but less readily the 13-docosynoic acid in the case of glycerol tri-(13-docosynoate). The two lipases CCL and AY-30 were able to distinguish the small difference in structure of fatty acyl moieties in the TG substrate. To confirm this trend, three regioisomers of mixed acetylenic TG of type ABC (containing one each of delta6, delta9, and delta13 acetylenic FA in various positions) were prepared and hydrolyzed with CCL and AY-40. The results reconfirmed the observation that AY-30 and CCL were able to distinguish the slight differences in the molecular structure (position of the acetylenic bond and chain length) of the acyl groups in the TG during the hydrolysis of such TG substrates.

  10. 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.

  11. Enhanced activity and selectivity of carbon nanofiber supported Pd catalysts for nitrite reduction.

    PubMed

    Shuai, Danmeng; Choe, Jong Kwon; Shapley, John R; Werth, Charles J

    2012-03-06

    Pd-based catalyst treatment represents an emerging technology that shows promise to remove nitrate and nitrite from drinking water. In this work we use vapor-grown carbon nanofiber (CNF) supports in order to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). Results show that nitrite reduction activity increases by 3.1-fold and selectivity decreases by 8.0-fold, with decreasing Pd nanoparticle size from 1.4 to 9.6 nm. Both activity and selectivity are not significantly influenced by Pd interior versus exterior CNF loading. Consequently, turnover frequencies (TOFs) among all CNF catalysts are similar, suggesting nitrite reduction is not sensitive to Pd location on CNFs nor Pd structure. CNF-based catalysts compare favorably to conventional Pd catalysts (i.e., Pd on activated carbon or alumina) with respect to nitrite reduction activity and selectivity, and they maintain activity over multiple reduction cycles. Hence, our results suggest new insights that an optimum Pd nanoparticle size on CNFs balances faster kinetics with lower ammonia production, that catalysts can be tailored at the nanoscale to improve catalytic performance for nitrite, and that CNFs hold promise as highly effective catalyst supports in drinking water treatment.

  12. Acetylene hydrogenation on anatase TiO2(101) supported Pd4 cluster: oxygen deficiency effect.

    PubMed

    Yang, Jie; Cao, Li-Xin; Wang, Gui-Chang

    2012-07-01

    Acetylene hydrogenation on both the perfect and oxygen defective anatase TiO(2)(101) surfaces supported Pd(4) cluster has been studied using density functional theory calculations with a Hubbard U correction (DFT + U). The adsorbed Pd(4) cluster on the perfect surface prefers to form a tetrahedral structure, while it likely moves to the oxygen defective site to form a distorted tetrahedral structure by removing a bridging oxygen atom. For the defective surface, it exhibits a stronger ability to capture Pd(4) cluster as charge transfer is significantly performed due to the oxygen deficiency. Moreover, it is found that the oxygen defective surface shows higher activity for acetylene hydrogenation, and the possible reason may lie in the weaker adsorption strength between the Pd cluster and the adsorbed molecules on the defective surface as compared to the case on the perfect surface.

  13. 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…

  14. Retrievals of the Abundances of Acetylene and other Hydrocarbons in Titan's Upper Atmosphere

    NASA Astrophysics Data System (ADS)

    Fan, Siteng; Shemansky, D. E.; Yung, Yuk

    2016-10-01

    Acetylene abundance in the Titan upper atmosphere has been extracted from Cassini Ultraviolet Imaging Spectrograph (UVIS) stellar occultations. The data reduction process is based on simulation of the discrete spectral absorption in the far ultraviolet (FUV) region between 110 and 190 nm. Pointing drift is corrected by instrument simulation of the stellar image location on the instrument detector. Latitude and seasonal dependence of the vertical profiles has been examined. The observed spectra have been compared to atmospheric chemical model calculations (KINETICS) by predicting the occultation spectra, allowing the imposition of constraints on the model, and directly establishing the level of uncertainty in the extraction process. Hydrocarbon and nitrile vertical profiles have been extracted, with limits set on the precursors to aerosols. Aerosol continuum spectral structure is recognized in the extinction spectra, but physical chemistry modeling of aerosol precursors to date indicate higher abundances than the upper limits set by observation.

  15. DFT functional benchmarking on the energy splitting of chromium spin states and mechanistic study of acetylene cyclotrimerization over the Phillips Cr(II)/silica catalyst.

    PubMed

    Liu, Zhen; Cheng, Ruihua; He, Xuelian; Wu, Xiaojun; Liu, Boping

    2012-07-19

    In this work, a two-state reaction mechanism for the acetylene cyclotrimerization over a cluster model for the Phillips Cr(II)/silica catalyst were systematically investigated using density functional theory (DFT). Since spin crossover phenomenon was confirmed in the catalytic cycle, an accurate prediction of the energy gap between low- and high-spin states is crucial for the description of a reaction involving a two-state reactivity. Therefore, a massive DFT functional benchmarking test has been conducted on the cluster model by taking a CASPT2 energy gap as a reference. Consequently, B3PW91* with 28% Hartree-Fock exchange energy was selected for the following mechanistic investigation. Each of the possible potential energy surface including singlet, triplet, and quintet surfaces was explored. On the quintet surface, the reaction begins with a coordination of an acetylene on the chromium center to generate a π-coordinated complex. The following oxidative coupling through further coordination with a second acetylene was predicted to be a two-step reaction to generate a chromacyclopentadiene species. This transformation was found to be energetically prohibitive by the presence of the transition state (5)TS[C-E] (ΔG(‡) = 31.1 kcal/mol). On the triplet surface, however, the coordination of an acetylene generates a chromacyclopropene species without showing any activation barrier. The second acetylene incorporation proceeding via a coordination on the chromium center followed by an insertion into a Cr-C σ-bond of the chromacyclopropene was predicted to be a facile reaction pathway (ΔG(‡) = 10.2 kcal/mol). The third acetylene was captured by the cluster model through the formation of a hydrogen bond. The later transformation on the triplet surface was found to be an intermolecular [4 + 2] cycloaddition to finish the cyclization. The lack of the aromaticity of the benzene ring in (3)L results in an uncompleted reaction pathway on a single triplet surface

  16. Key Factors Influencing Rates of Heterotrophic Sulfate Reduction in Active Seafloor Hydrothermal Massive Sulfide Deposits

    PubMed Central

    Frank, Kiana L.; Rogers, Karyn L.; Rogers, Daniel R.; Johnston, David T.; Girguis, Peter R.

    2015-01-01

    Hydrothermal vents are thermally and geochemically dynamic habitats, and the organisms therein are subject to steep gradients in temperature and chemistry. To date, the influence of these environmental dynamics on microbial sulfate reduction has not been well constrained. Here, via multivariate experiments, we evaluate the effects of key environmental variables (temperature, pH, H2S, SO42−, DOC) on sulfate reduction rates and metabolic energy yields in material recovered from a hydrothermal flange from the Grotto edifice in the Main Endeavor Field, Juan de Fuca Ridge. Sulfate reduction was measured in batch reactions across a range of physico-chemical conditions. Temperature and pH were the strongest stimuli, and maximum sulfate reduction rates were observed at 50°C and pH 6, suggesting that the in situ community of sulfate-reducing organisms in Grotto flanges may be most active in a slightly acidic and moderate thermal/chemical regime. At pH 4, sulfate reduction rates increased with sulfide concentrations most likely due to the mitigation of metal toxicity. While substrate concentrations also influenced sulfate reduction rates, energy-rich conditions muted the effect of metabolic energetics on sulfate reduction rates. We posit that variability in sulfate reduction rates reflect the response of the active microbial consortia to environmental constraints on in situ microbial physiology, toxicity, and the type and extent of energy limitation. These experiments help to constrain models of the spatial contribution of heterotrophic sulfate reduction within the complex gradients inherent to seafloor hydrothermal deposits. PMID:26733984

  17. Communication: Observation of local-bender eigenstates in acetylene.

    PubMed

    Steeves, Adam H; Park, G Barratt; Bechtel, Hans A; Baraban, Joshua H; Field, Robert W

    2015-08-21

    We report the observation of eigenstates that embody large-amplitude, local-bending vibrational motion in acetylene by stimulated emission pumping spectroscopy via vibrational levels of the S1 state involving excitation in the non-totally symmetric bending modes. The N(b) = 14 level, lying at 8971.69 cm(-1) (J = 0), is assigned on the basis of degeneracy due to dynamical symmetry breaking in the local-mode limit. The level pattern for the N(b) = 16 level, lying at 10 218.9 cm(-1), is consistent with expectations for increased separation of ℓ = 0 and 2 vibrational angular momentum components. Increasingly poor agreement between our observations and the predicted positions of these levels highlights the failure of currently available normal mode effective Hamiltonian models to extrapolate to regions of the potential energy surface involving large-amplitude displacement along the acetylene ⇌ vinylidene isomerization coordinate.

  18. Enhanced Photoluminescence in Acetylene-Treated ZnO Nanorods.

    PubMed

    Jäppinen, Luke; Jalkanen, Tero; Sieber, Brigitte; Addad, Ahmed; Heinonen, Markku; Kukk, Edwin; Radevici, Ivan; Paturi, Petriina; Peurla, Markus; Shahbazi, Mohammad-Ali; Santos, Hélder A; Boukherroub, Rabah; Santos, Hellen; Lastusaari, Mika; Salonen, Jarno

    2016-12-01

    Zinc oxide (ZnO) nanorods were manufactured using the aqueous chemical growth (ACG) method, and the effect of thermal acetylene treatment on their morphology, chemical composition, and optical properties was investigated. Changes in the elemental content of the treated rods were found to be different than in previous reports, possibly due to the different defect concentrations in the samples, highlighting the importance of synthesis method selection for the process. Acetylene treatment resulted in a significant improvement of the ultraviolet photoluminescence of the rods. The greatest increase in emission intensity was recorded on ZnO rods treated at the temperature of 825 °C. The findings imply that the changes brought on by the treatment are limited to the surface of the ZnO rods.

  19. 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.

  20. 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.

  1. Effect of oxidation and catalytic reduction of trace organic contaminants on their activated carbon adsorption.

    PubMed

    Schoutteten, Klaas V K M; Hennebel, Tom; Dheere, Ellen; Bertelkamp, Cheryl; De Ridder, David J; Maes, Synthia; Chys, Michael; Van Hulle, Stijn W H; Vanden Bussche, Julie; Vanhaecke, Lynn; Verliefde, Arne R D

    2016-12-01

    The combination of ozonation and activated carbon (AC) adsorption is an established technology for removal of trace organic contaminants (TrOCs). In contrast to oxidation, reduction of TrOCs has recently gained attention as well, however less attention has gone to the combination of reduction with AC adsorption. In addition, no literature has compared the removal behavior of reduction vs. ozonation by-products by AC. In this study, the effect of pre-ozonation vs pre-catalytic reduction on the AC adsorption efficiency of five TrOCs and their by-products was compared. All compounds were susceptible to oxidation and reduction, however the catalytic reductive treatment proved to be a slower reaction than ozonation. New oxidation products were identified for dinoseb and new reduction products were identified for carbamazepine, bromoxynil and dinoseb. In terms of compatibility with AC adsorption, the influence of the oxidative and reductive pretreatments proved to be compound dependent. Oxidation products of bromoxynil and diatrizoic acid adsorbed better than their parent TrOCs, but oxidation products of atrazine, carbamazepine and dinoseb showed a decreased adsorption. The reductive pre-treatment showed an enhanced AC adsorption for dinoseb and a major enhancement for diatrizoic acid. For atrazine and bromoxynil, no clear influence on adsorption was noted, while for carbamazepine, the reductive pretreatment resulted in a decreased AC affinity. It may thus be concluded that when targeting mixtures of TrOCs, a trade-off will undoubtedly have to be made towards overall reactivity and removal of the different constituents, since no single treatment proves to be superior to the other.

  2. 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

    2005-03-07

    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.

  3. Gender-dependent reduction of spontaneous motor activity and growth in rats subjected to portacaval shunt.

    PubMed

    Conjeevaram, H S; Mullen, K D; May, E J; McCullough, A J

    1994-02-01

    Alterations in behavior are frequently described in rats subjected to portacaval shunt. Previous work has reported reduced spontaneous motor activity in various settings (nighttime, red light, decreased illumination) in this animal model. We investigated this phenomenon in rats of both genders subjected to portacaval shunt to determine whether our previously observed divergent growth patterns (males reduced, females unchanged) had any impact on the alterations in spontaneous motor activity in this model. Dietary intake, growth, motor activity and serum ammonia and amino acid concentrations were measured, in addition to final liver and spleen weights, in each animal after 3 to 4 wk of observation. Our results reconfirm the differential impact of portacaval shunt on growth in male (35% reduction p < 0.01) but not female rats (5% reduction, NS) compared with their respective-gender sham-operated controls. In addition, spontaneous motor activity was significantly reduced in male (congruent to 50%, p = 0.01) but not female rats subjected to portacaval shunt. The reduction of activity in male rats subjected to portacaval shunt did not correlate with any of the measured biochemical data or calculated nutritional/growth parameters. Thus we observed gender-dependent reduction in spontaneous motor activity after portacaval shunt in the rat. The mechanism for this phenomenon is unknown, but it is easily investigated with this reproducible model.

  4. Thermodynamic study on the formation of acetylene during coal pyrolysis in the arc plasma jet

    SciTech Connect

    Bao, W.; Li, F.; Cai, G.; Lu, Y.; Chang, L.

    2009-07-01

    Based on the principle of minimizing the Gibbs free energy, the composition of C-H-O-N-S equilibrium system about acetylene formation during the pyrolysis in arc plasma jet for four kinds of different rank-ordered coals such as Datong, Xianfeng, Yangcheng, and Luan was analyzed and calculated. The results indicated that hydrogen, as the reactive atmosphere, was beneficial to the acetylene formation. The coal ranks and the hydrogen, oxygen, nitrogen, and sulfur in coal all could obviously affect the acetylene yield. The mole fraction of acetylene is the maximum when the ratio value of atom H/C was 2. The content of oxygen was related to the acetylene yield, but it does not compete with CO formation. These agreed with the experimental results, and they could help to select the coal type for the production of acetylene through plasma pyrolysis process.

  5. Acetylene bubble-powered autonomous capsules: towards in situ fuel.

    PubMed

    Moo, James Guo Sheng; Wang, Hong; Pumera, Martin

    2014-12-28

    A fuel-free autonomous self-propelled motor is illustrated. The motor is powered by the chemistry of calcium carbide and utilising water as a co-reactant, through a polymer encapsulation strategy. Expulsion of acetylene bubbles powers the capsule motor. This is an important step, going beyond the toxic hydrogen peroxide fuel used normally, to find alternative propellants for self-propelled machines.

  6. Modeling encapsulation of acetylene molecules into carbon nanotubes.

    PubMed

    Tran-Duc, Thien; Thamwattana, Ngamta

    2011-06-08

    Polyacetylene is a well-known conductive polymer and when doped its conductivity can be altered by up to 12 orders of magnitude. However, due to entropy effects a polyacetylene chain usually suffers from distortions and interchain couplings which lead to unpredictable changes in its conducting property. Encapsulating a polyacetylene chain into a carbon nanotube can resolve these issues. Furthermore, since the carbon nanotube itself possesses excellent electrical conductivity, the combination of the carbon nanotube and polyacetylene may give rise to a new material with superior transport behavior. In this paper, we model mathematically the molecular interaction between an acetylene molecule and a carbon nanotube in order to determine conditions at which configurations of the acetylene molecule are accepted into the carbon nanotube as well as its equilibrium configurations inside various sizes of carbon nanotubes. For special cases of the acetylene molecule lying on the tube axis, standing vertically with its center on the tube axis and staying far inside the tube, explicit analytical expressions for the interaction energy are obtained.

  7. Quantifying Momentum Transfer Due to Blast Waves from Oxy-Acetylene Driven Shock Tubes

    DTIC Science & Technology

    2012-05-30

    Transfer Due to Blast Waves from Oxy - Acetylene Driven Shock Tubes 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d...and the response of materiel to blast loading. Recently, laboratory-scale shock tubes driven by oxy - acetylene were described. It was estimated that...later. In each case, most of the momentum transfer was due to the shock wave itself. The results support previous estimates that the oxy - acetylene

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

    NASA Astrophysics Data System (ADS)

    Culbertson, Charles W.; Strohmaier, Francis E.; Oremland, Ronald S.

    1988-12-01

    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.

  9. Thermodynamical Study on Production of Acetylene from Coal Pyrolysis in Hydrogen Plasma

    NASA Astrophysics Data System (ADS)

    Wang, Fei; Guo, Wenkang; Yuan, Xingqiu; Zhao, Taize

    2006-05-01

    The chemical thermodynamic equilibrium of acetylene production by coal pyrolysis in hydrogen plasma was studied. The thermodynamic equilibrium is obtained by using the method of free energy. Calculated results show that the hydrogen concentration in the equilibrium system is very important for the acetylene production by coal conversion and the energy consumption for the production of acetylene per-kilogram strongly depends on the hydrogen concentration and the temperature.

  10. 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

  11. Altered biologic activities of commercial polychlorinated biphenyl mixtures after microbial reductive dechlorination.

    PubMed Central

    Mousa, M A; Ganey, P E; Quensen, J F; Madhukar, B V; Chou, K; Giesy, J P; Fischer, L J; Boyd, S A

    1998-01-01

    The reductive dechlorination of polychlorinated biphenyls (PCBs) by anaerobic bacteria has recently been established as an important environmental fate of these compounds. This process removes chlorines directly from the biphenyl ring with replacement by hydrogen, resulting in a product mixture in which the average number of chlorines per biphenyl is reduced. In this study, dechlorination of commercial PCB mixtures (Aroclors 1242 and 1254) by microorganisms eluted from PCB-contaminated sediments of the River Raisin (Michigan) and Silver Lake (Massachusetts) caused a depletion in the proportion of highly chlorinated PCB congeners and an accumulation of lesser-chlorinated congeners. Dechlorination occurred primarily at the meta and, to a much lesser extent, para positions of biphenyl. The concentrations of the coplanar congeners including 3,3',4,4',5-pentachlorobiphenyl, the most potent dioxinlike congener, were significantly lowered by reductive dechlorination. Microbial reductive dechlorination of commercial PCB mixtures caused a substantial reduction in biologic activities in several instances. It significantly lowered or eliminated the inhibitory effects of Aroclors on fertilization of mouse gametes in vitro. Similarly, the dechlorinated product mixtures had substantially lower ethoxyresorufin-O-deethylase induction potencies and showed less ability to induce activating protein 1 transcription factor activity as compared to the unaltered Aroclors. In other assays the same dechlorinated product mixtures demonstrated biologic activities similar to the nondechlorinated Aroclors, including the ability of PCB mixtures to stimulate insulin secretion and cause neutrophil activation. The data presented here establish that the biologic activities of commercial PCB mixtures are altered by microbial reductive dechlorination and that an assessment of their toxic potential requires an array of tests that include the different mechanisms associated with PCBs. Images Figure 2

  12. Active Pt3Ni (111) Surface of Pt3Ni Icosahedron for Oxygen Reduction.

    PubMed

    Zhu, Jianbing; Xiao, Meiling; Li, Kui; Liu, Changpeng; Zhao, Xiao; Xing, Wei

    2016-11-09

    Highly active, durable oxygen reduction reaction (ORR) electrocatalysts are extremely important for fuel cell applications. Herein, we provide an efficient way to synthesis of activity Pt3M icosahedra by the one-pot hydrothermal method in the presence of glucosamine which can well adjust the reduction rate of Pt(4+) and efficiently control the morphology of final catalysts. Compared to Pt/C, the Pt3Ni icosahedra show 32-fold and 12-fold enhancement in specific and mass activity, respectively. Furthermore, robust durability was also observed in the accelerated durability test. Thus, this Pt3Ni icosahedron is found among the best Pt-based ORR catalysts, moreover, the findings also demonstrate how to mimic active extended surfaces in nanoscale.

  13. Reduction of Helicopter Blade-Vortex Interaction Noise by Active Rotor Control Technology

    NASA Technical Reports Server (NTRS)

    Yu, Yung H.; Gmelin, Bernd; Splettstoesser, Wolf; Brooks, Thomas F.; Philippe, Jean J.; Prieur, Jean

    1997-01-01

    Helicopter blade-vortex interaction noise is one of the most severe noise sources and is very important both in community annoyance and military detection. Research over the decades has substantially improved basic physical understanding of the mechanisms generating rotor blade-vortex interaction noise and also of controlling techniques, particularly using active rotor control technology. This paper reviews active rotor control techniques currently available for rotor blade vortex interaction noise reduction, including higher harmonic pitch control, individual blade control, and on-blade control technologies. Basic physical mechanisms of each active control technique are reviewed in terms of noise reduction mechanism and controlling aerodynamic or structural parameters of a blade. Active rotor control techniques using smart structures/materials are discussed, including distributed smart actuators to induce local torsional or flapping deformations, Published by Elsevier Science Ltd.

  14. 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.

  15. Rice (Oryza sativa L.) roots have iodate reduction activity in response to iodine

    PubMed Central

    Kato, Shota; Wachi, Takanori; Yoshihira, Kei; Nakagawa, Takuya; Ishikawa, Akifumi; Takagi, Daichi; Tezuka, Aya; Yoshida, Hideharu; Yoshida, Satoshi; Sekimoto, Hitoshi; Takahashi, Michiko

    2013-01-01

    Although iodine is not an essential nutrient for higher plants, their roots take up and transport the element. However, the exact mechanisms involved in iodine uptake and metabolism in higher plants have yet to be elucidated. In this study, we compared two cultivars differing in iodine tolerance (“Nipponbare” and “Gohyakumangoku”) to increasing levels of I− and IO−3 in the root solutions of water-cultured rice (Oryza sativa L.). We found that IO−3 added to the root solutions was converted to I− in the presence of roots. Iodate reduction occurred over the course of several hours. Furthermore, the iodate reduction activity of “Nipponbare” (iodine-sensitive) and “Gohyakumangoku” (iodine-tolerant) roots increased after adding IO−3 or I−. The roots of barley and soybean also showed iodate reduction activity and the activity responded to iodine treatment either with IO−3 and I−. This study suggests that plant roots biologically reduce iodate to iodide and indicates that the iodate reduction activity of roots responds to external iodine conditions. PMID:23847633

  16. RADON REDUCTION TECHNIQUES FOR EXISTING DETACHED HOUSES - TECHNICAL GUIDANCE (THIRD EDITION) FOR ACTIVE SOIL DEPRESSURIZATION SYSTEMS

    EPA Science Inventory

    This technical guidance document is designed to aid in the selection, design, installation and operation of indoor radon reduction techniques using soil depressurization in existing houses. Its emphasis is on active soil depressurization; i.e., on systems that use a fan to depre...

  17. Identification of intrinsic catalytic activity for electrochemical reduction of water molecules to generate hydrogen.

    PubMed

    Shinagawa, Tatsuya; Takanabe, Kazuhiro

    2015-06-21

    Insufficient hydronium ion activities at near-neutral pH and under unbuffered conditions induce diffusion-limited currents for hydrogen evolution, followed by a reaction with water molecules to generate hydrogen at elevated potentials. The observed constant current behaviors at near neutral pH reflect the intrinsic electrocatalytic reactivity of the metal electrodes for water reduction.

  18. QUANTITATIVE STRUCTURE-ACTIVITY RELATIONSHIPS FOR CHEMICAL REDUCTIONS OF ORGANIC CONTAMINANTS

    EPA Science Inventory

    Sufficient kinetic data on abiotic reduction reactions involving organic contaminants are now available that quantitative structure-activity relationships (QSARs) for these reactions can be developed. Over 50 QSARs have been reported, most in just the last few years, and they ar...

  19. Nickel-catalyzed reductive arylation of activated alkynes with aryl iodides

    PubMed Central

    Dorn, Stephanie C. M.; Olsen, Andrew K; Kelemen, Rachel E.; Shrestha, Ruja; Weix, Daniel J.

    2015-01-01

    The direct, regioselective, and stereoselective arylation of activated alkynes with aryl iodides using a nickel catalyst and manganese reductant is described. The reaction conditions are mild (40 °C in MeOH, no acid or base) and an intermediate organomanganese reagent is unlikely. Functional groups tolerated include halides and pseudohalides, free and protected anilines, and a benzyl alcohol. Other activated alkynes including an amide and a ketone also reacted to form arylated products in good yields. PMID:26028781

  20. Active breathing control (ABC): Determination and reduction of breathing-induced organ motion in the chest

    SciTech Connect

    Gagel, Bernd . E-mail: BGagel@UKAachen.de; Demirel, Cengiz M.P.; Kientopf, Aline; Pinkawa, Michael; Piroth, Marc; Stanzel, Sven; Breuer, Christian; Asadpour, Branka; Jansen, Thomas; Holy, Richard; Wildberger, Joachim E.; Eble, Michael J.

    2007-03-01

    Purpose: Extensive radiotherapy volumes for tumors of the chest are partly caused by interfractional organ motion. We evaluated the feasibility of respiratory observation tools using the active breathing control (ABC) system and the effect on breathing cycle regularity and reproducibility. Methods and Materials: Thirty-six patients with unresectable tumors of the chest were selected for evaluation of the ABC system. Computed tomography scans were performed at various respiratory phases starting at the same couch position without patient movement. Threshold levels were set at minimum and maximum volume during normal breathing cycles and at a volume defined as shallow breathing, reflecting the subjective maximal tolerable reduction of breath volume. To evaluate the extent of organ movement, 13 landmarks were considering using commercial software for image coregistration. In 4 patients, second examinations were performed during therapy. Results: Investigating the differences in a normal breathing cycle versus shallow breathing, a statistically significant reduction of respiratory motion in the upper, middle, and lower regions of the chest could be detected, representing potential movement reduction achieved through reduced breath volume. Evaluating interfraction reproducibility, the mean displacement ranged between 0.24 mm (chest wall/tracheal bifurcation) to 3.5 mm (diaphragm) for expiration and shallow breathing and 0.24 mm (chest wall) to 5.25 mm (diaphragm) for normal inspiration. Conclusions: By modifying regularity of the respiratory cycle through reduction of breath volume, a significant and reproducible reduction of chest and diaphragm motion is possible, enabling reduction of treatment planning margins.

  1. Reductive activation of mitomycin C by thiols: kinetics, mechanism, and biological implications.

    PubMed

    Paz, Manuel M

    2009-10-01

    The clinically used antitumor antibiotic mitomycin C requires a reductive activation to be converted to a bis-electrophile that forms several covalent adducts with DNA, including an interstrand cross-link which is considered to be the lesion responsible for the cytotoxic effects of the drug. Enzymes such as cytochrome P450 reductase and DT-diaphorase have traditionally been implicated in the bioreduction of mitomycin C, but recent reports indicate that enzymes containing a dithiol active site are also involved in the metabolism of mitomycin C. The reductive activation can also be effected in vitro with chemical reductants, but until now, mitomycin C was considered to be inert to thiols. We report here that mitomycin C can, in fact, be reductively activated by thiols. We show that the reaction is autocatalytic and that the end product is a relatively stable aziridinomitosene that can be trapped by adding several nucleophiles after the activation reaction. Kinetic studies show that the reaction is highly sensitive to pH and does not proceed or proceeds very slowly at neutral pH, an observation that explains the unsuccessful results on previous attempts to activate mitomycin C with thiols. The optimum pH for the reactions is around the pK(a) values of the thiols used in the activation. A mechanism for the reaction is hypothesized, involving the initial formation of a thiolate-mitomycin adduct, that then evolves to give the hydroquinone of mitomycin C and disulfide. The results presented here provide a chemical mechanism to explain how some biological dithiols containing an unusually acidic thiol group (deprotonated at physiological pH) participate in the modulation of mitomycin C cytotoxicity.

  2. Enhanced Activity and Stability of Pt catalysts on Functionalized Graphene Sheets for Electrocatalytic Oxygen Reduction

    SciTech Connect

    Kou, Rong; Shao, Yuyan; Wang, Donghai; Engelhard, Mark H.; Kwak, Ja Hun; Wang, Jun; Viswanathan, Vilayanur V.; Wang, Chong M.; Lin, Yuehe; Wang, Yong; Aksay, Ilhan A.; Liu, Jun

    2009-04-30

    Electrocatalysis of oxygen reduction using Pt nanoparticles supported on functionalized graphene sheets (FGSs) was studied. FGSs were prepared by thermal expansion of graphite oxide. Pt nanoparticles with average diameter of 2 nm were uniformly loaded on FGSs by impregnation methods. Pt-FGS showed a higher electrochemical surface area and oxygen reduction activity with improved stability as compared with commercial catalyst. Transmission electron microscopy, X-ray photoelectron spectroscopy, and electrochemical characterization suggest that the improved performance of Pt-FGS can be attributed to smaller particle size and less aggregation of Pt nanoparticles on the functionalized graphene sheets.

  3. Vibration reduction in helicopter rotors using an active control surface located on the blade

    NASA Technical Reports Server (NTRS)

    Millott, T. A.; Friedmann, P. P.

    1992-01-01

    A feasibility study of vibration reduction in a four-bladed helicopter rotor using individual blade control (IBC), which is implemented by an individually controlled aerodynamic surface located on each blade, is presented. For this exploratory study, a simple offset-hinged spring restrained model of the blade is used with fully coupled flap-lag-torsional dynamics for each blade. Deterministic controllers based on local and global system models are implemented to reduce 4/rev hub loads using both an actively controlled aerodynamic surface on each blade as well as conventional IBC, where the complete blade undergoes cyclic pitch change. The effectiveness of the two approaches for simultaneous reduction of the 4/rev hub shears and hub moments is compared. Conventional IBC requires considerably more power to achieve approximately the same level of vibration reduction as that obtained by implementing IBC using an active control surface located on the outboard segment of the blade. The effect of blade torsional flexibility on the vibration reduction effectiveness of the actively controlled surface was also considered and it was found that this parameter has a very substantial influence.

  4. Nitrous oxide reduction in nodules: denitrification or N/sub 2/ fixation

    SciTech Connect

    Coyne, M.S.; Focht, D.D.

    1987-05-01

    Detached cowpea nodules that contained a nitrous oxide reductase-positive (Nor/sup +/) rhizobium strain (8A55) and a nitrous oxide reductase-negative (Nor/sup -/) rhizobium strain (32H1) were incubated with 1% /sup 15/N/sub 2/O (95 atom% /sup 15/N) in the following three atmospheres: aerobic with C/sub 2/H/sub 2/ (10%), aerobic without C/sub 2/H/sub 2/, and anaerobic (argon atmosphere) without C/sub 2/H/sub 2/. The greatest production of /sup 15/N/sub 2/ occurred anaerobically with 8A55, yet very little was formed with 32H1. Although acetylene reduction activity was slightly higher with 32H1, about 10 times more /sup 15/N/sub 2/ was produced aerobically by 8A55 than by 32H1 in the absence of acetylene. The major reductive pathway of N/sub 2/O reduction by denitrifying rhizobium strain 8A55 is by nitrous oxide reductase rather than nitrogenase.

  5. Trend in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium

    SciTech Connect

    Dathar, Gopi Krishna Phani; Shelton Jr, William Allison; Xu, Ye

    2012-01-01

    Periodic density functional theory (DFT) calculations indicate that the intrinsic activity of Au, Ag, Pt, Pd, Ir, and Ru for the oxygen reduction reaction by Li (Li-ORR) forms a volcano-like trend with respect to the adsorption energy of oxygen, with Pt and Pd being the most active. The trend is based on two mechanisms: the reduction of molecular O{sub 2} on Au and Ag and of atomic O on the remaining metals. Step edges are found to be more active for catalyzing the Li-ORR than close-packed surfaces. Our findings identify important considerations in the design of catalyst-promoted air cathodes for nonaqueous Li-air batteries.

  6. Green synthesis of gold nanoparticles using aspartame and their catalytic activity for p-nitrophenol reduction

    NASA Astrophysics Data System (ADS)

    Wu, Shufen; Yan, Songjing; Qi, Wei; Huang, Renliang; Cui, Jing; Su, Rongxin; He, Zhimin

    2015-05-01

    We demonstrated a facile and environmental-friendly approach to form gold nanoparticles through the reduction of HAuCl4 by aspartame. The single-crystalline structure was illustrated by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared (FTIR) results indicated that aspartame played a pivotal role in the reduction and stabilization of the gold crystals. The crystals were stabilized through the successive hydrogen-bonding network constructed between the water and aspartame molecules. Additionally, gold nanoparticles synthesized through aspartame were shown to have good catalytic activity for the reduction of p-nitrophenol to p-aminophenol in the presence of NaBH4.

  7. Conjugation of glutathione and other thiols with bioreductively activated mitomycin C. Effect of thiols on the reductive activation rate.

    PubMed

    Sharma, M; Tomasz, M

    1994-01-01

    Mitomycin C (MC), a clinically used natural antitumor agent, was shown to form three monoconjugates (11a-13a) and two bisconjugates (14a, 15a) with GSH upon reductive activation by rat liver microsomes, purified NADPH-cytochrome c reductase, or NADH-cytochrome c reductase or chemical reduction using H2/PtO2. Rat liver cytosol/NADH activated MC only at acidic pH (5.8), resulting in the formation of a single GSH-MC monoconjugate, 13a. The reductase responsible for cytosolic activation of MC to form this conjugate was DT-diaphorase. GSH itself did not reduce MC, and unreduced MC did not form conjugates with GSH. A moderate catalytic effect by glutathione S-transferase was demonstrated on the cytosol-activated reaction. Mercaptoethanol and N-acetylcysteine gave analogous sets of five MC-thiol conjugates under cytochrome c reductase or H2/PtO2 activation conditions. The structures of all 15 MC-thiol conjugates (five each with GSH, mercaptoethanol, and N-acetylcysteine, respectively) were determined, using 1H-NMR, UV, and mass spectroscopies, combined with analytical chemical and radiolabeling methods. The mechanism of formation of the conjugates features SN2 displacement of the carbamate of the reduced MC by GS-. The MC-GSH conjugates were noncytotoxic to the tumor cells tested. The conjugation of GSH with activated MC is likely to represent detoxication in mammalian cells. As another effect, GSH accelerates the rate of reduction of MC by "slow" reducing agents such as cytochrome c reductases and H2/PtO2. A mechanism is proposed to explain this effect, which involves further reduction of the initially formed MC semiquinone free radical by GSH.

  8. Characterization of microbial activities and U reduction in a shallow aquifer contaminated by uranium mill tailings.

    PubMed

    Elias, D A; Krumholz, L R; Wong, D; Long, P E; Suflita, J M

    2003-07-01

    A characterization of the Shiprock, NM, uranium mill tailing site focused on the geochemical and microbiological factors governing in-situ uranium-redox reactions. Groundwater and aqueous extracts of sediment samples contained a wide concentration range of sulfate, nitrate, and U(VI) with median values of 21.2 mM, 16.1 micro M, and 2.7 micro M, respectively. Iron(III) was not detected in groundwater, but a median value of 0.3 mM in sediment extracts was measured. Bacterial diversity down gradient from the disposal pile reflected the predominant geochemistry with relatively high numbers of sulfate- and nitrate-reducing microorganisms, and smaller numbers of acetogenic, methanogenic, nitrate-dependent Fe(II)-oxidizing, Fe(III)-reducing, and sulfide-oxidizing bacteria. In aquifer slurry incubations, nitrate reduction was always preferred and had a negative impact on sulfate-, Fe(III)-, and U-reduction rates. We also found that sulfate-reduction rates decreased sharply in the presence of clay, while Fe(III)-reduction increased with no clear impact on U reduction. In the absence of clay, iron and sulfate reduction correlated with concentrations of Fe(III) and sulfate, respectively. Rates of U(VI) loss did not correlate with the concentration of any electron acceptor. With the exception of Fe(III), electron donor amendment was largely unsuccessful in stimulating electron acceptor loss over a 2-week incubation period, suggesting that endogenous forms of organic matter were sufficient to support microbial activity. Our findings suggest that efforts to accelerate biological U reduction should initially focus on stimulating nitrate removal.

  9. Suppression of oxygen reduction reaction activity on Pt-based electrocatalysts from ionomer incorporation

    SciTech Connect

    Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.; Kocha, Shyam S.

    2016-09-01

    The impact of Nafion on the oxygen reduction reaction (ORR) activity is studied for Pt/C and Pt-alloy/C catalysts using thin-film rotating disk electrode (TF-RDE) methods in 0.1 M HClO4. Ultrathin uniform catalyst layers and standardized activity measurement protocols are employed to obtain accurate and reproducible ORR activity. Nafion lowers the ORR activity which plateaus with increasing loading on Pt catalysts. Pt particle size is found not to have significant influence on the extent of the SA decrease upon Nafion incorporation. Catalysts using high surface area carbon (HSC) support exhibit attenuated activity loss resulting from lower ionomer coverage on catalyst particles located within the deep pores. The impact of metallic composition on the activity loss due to Nafion incorporation is also discussed.

  10. 49 CFR 173.303 - Charging of cylinders with compressed gas in solution (acetylene).

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Charging of cylinders with compressed gas in solution (acetylene). 173.303 Section 173.303 Transportation Other Regulations Relating to Transportation....303 Charging of cylinders with compressed gas in solution (acetylene). (a) Cylinder, filler...

  11. 49 CFR 173.303 - Charging of cylinders with compressed gas in solution (acetylene).

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Charging of cylinders with compressed gas in solution (acetylene). 173.303 Section 173.303 Transportation Other Regulations Relating to Transportation....303 Charging of cylinders with compressed gas in solution (acetylene). (a) Cylinder, filler...

  12. 49 CFR 173.303 - Charging of cylinders with compressed gas in solution (acetylene).

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Charging of cylinders with compressed gas in solution (acetylene). 173.303 Section 173.303 Transportation Other Regulations Relating to Transportation....303 Charging of cylinders with compressed gas in solution (acetylene). (a) Cylinder, filler...

  13. 49 CFR 173.303 - Charging of cylinders with compressed gas in solution (acetylene).

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Charging of cylinders with compressed gas in solution (acetylene). 173.303 Section 173.303 Transportation Other Regulations Relating to Transportation....303 Charging of cylinders with compressed gas in solution (acetylene). (a) Cylinder, filler...

  14. Complete genome sequences of two acetylene-fermenting Pelobacter acetylenicus strains

    USGS Publications Warehouse

    Sutton, John M.; Baesman, Shaun; Fierst, Janna L.; Poret-Peterson, Amisha T.; Oremland, Ronald S.; Dunlap, Darren S.; Akob, Denise M.

    2017-01-01

    Acetylene fermentation is a rare metabolism that was serendipitously discovered during C2H2-block assays of N2O reductase. Here, we report the genome sequences of two type strains of acetylene-fermenting Pelobacter acetylenicus, the freshwater bacterium DSM 3246 and the estuarine bacterium DSM 3247.

  15. Complete Genome Sequence of the Acetylene-Fermenting Pelobacter sp. Strain SFB93

    PubMed Central

    Baesman, Shaun M.; Fierst, Janna L.; Poret-Peterson, Amisha T.; Oremland, Ronald S.; Dunlap, Darren S.

    2017-01-01

    ABSTRACT Acetylene fermentation is a rare metabolism that was previously reported as being unique to Pelobacter acetylenicus. Here, we report the genome sequence of Pelobacter sp. strain SFB93, an acetylene-fermenting bacterium isolated from sediments collected in San Francisco Bay, CA. PMID:28183760

  16. Complete Genome Sequences of Two Acetylene-Fermenting Pelobacter acetylenicus Strains

    PubMed Central

    Baesman, Shaun M.; Fierst, Janna L.; Poret-Peterson, Amisha T.; Oremland, Ronald S.; Dunlap, Darren S.

    2017-01-01

    ABSTRACT Acetylene fermentation is a rare metabolism that was serendipitously discovered during C2H2-block assays of N2O reductase. Here, we report the genome sequences of two type strains of acetylene-fermenting Pelobacter acetylenicus, the freshwater bacterium DSM 3246 and the estuarine bacterium DSM 3247. PMID:28183759

  17. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... suction line. (c) The piping system, including the cargo refrigeration system, for tanks to be loaded with methyl acetylene-propadiene mixture must be completely separate from piping and refrigeration systems for other tanks. If the piping system for the tanks to be loaded with methyl acetylene-propadiene mixture...

  18. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... suction line. (c) The piping system, including the cargo refrigeration system, for tanks to be loaded with methyl acetylene-propadiene mixture must be completely separate from piping and refrigeration systems for other tanks. If the piping system for the tanks to be loaded with methyl acetylene-propadiene mixture...

  19. 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.

  20. Complete genome sequence of the acetylene-fermenting Pelobacter sp. strain SFB93

    USGS Publications Warehouse

    Sutton, John M.; Baesman, Shaun; Fierst, Janna L.; Poret-Peterson, Amisha T.; Oremland, Ronald S.; Dunlap, Darren S.; Akob, Denise M.

    2017-01-01

    Acetylene fermentation is a rare metabolism that was previously reported as being unique to Pelobacter acetylenicus. Here, we report the genome sequence of Pelobacter sp. strain SFB93, an acetylene-fermenting bacterium isolated from sediments collected in San Francisco Bay, CA.

  1. An infrared study of the bending region of acetylene

    NASA Astrophysics Data System (ADS)

    Hillman, J. J.; Jennings, D. E.; Halsey, G. W.; Nadler, Shachar; Blass, W. E.

    1991-04-01

    Acetylene spectra observed with instrumental resolutions of 0.0025 and 0.005 cm-1 were obtained at The National Optical Astronomy Observatory, Tucson, Arizona using the FTS spectrometer at the National Solar Observatory McMath telescope facility. These resolutions are factors of 6 and 3 times, respectively, that of the best prior study in the literature. The higher resolution allowed the assignment of many more low-J Q-branch transitions. The range of optical densities available in this study also allowed the extension of observed and assigned transitions to significantly higher J-values than reported in prior studies. Availability of improved standard lines resulted in high quality transition wavenumbers which are accurate to approximately +/-0.0001 cm-1. Using proven combination difference techniques and analysis software, this study produces the best available molecular parameters for the ν4 and ν5 states of acetylene. In addition, because acetylene has no permanent dipole moment, this study extends the precision of available ground state parameters B0 and D0 and produces for the first time an estimator of H0. In addition to H0 values for both isotopic species treated, we have obtained for the first time a value for H5 for the dominant isotopmer. The value of H5 for the 13C12CH2 was not determined and thus thought to be significantly smaller than H5 for 12C2H2. This study also obtains l-doubling parameters for both degenerate fundamental states in the lesser isotopmer for the first time as well as H4 for both isotopmers and B4 and D4 for the lesser isotopmer. NASA/ASEE Summer Faculty Fellow, NASA/Goddard Space Flight Center, 1986, 1987 (during which periods a portion of this work was completed).

  2. Neural Activity During Health Messaging Predicts Reductions in Smoking Above and Beyond Self-Report

    PubMed Central

    Falk, Emily B.; Berkman, Elliot T.; Whalen, Danielle; Lieberman, Matthew D.

    2011-01-01

    Objective The current study tested whether neural activity in response to messages designed to help smokers quit could predict smoking reduction, above and beyond self-report. Design Using neural activity in an a priori region of interest (a subregion of medial prefrontal cortex [MPFC]), in response to ads designed to help smokers quit smoking, we prospectively predicted reductions in smoking in a community sample of smokers (N = 28) who were attempting to quit smoking. Smoking was assessed via expired carbon monoxide (CO; a biological measure of recent smoking) at baseline and 1 month following exposure to professionally developed quitting ads. Results A positive relationship was observed between activity in the MPFC region of interest and successful quitting (increased activity in MPFC was associated with a greater decrease in expired CO). The addition of neural activity to a model predicting changes in CO from self-reported intentions, self-efficacy, and ability to relate to the messages significantly improved model fit, doubling the variance explained ( Rself−report2=.15,Rself−report+neuralactivity2=.35,Rchange2=.20). Conclusion: Neural activity is a useful complement to existing self-report measures. In this investigation, we extend prior work predicting behavior change based on neural activity in response to persuasive media to an important health domain and discuss potential psychological interpretations of the brain–behavior link. Our results support a novel use of neuroimaging technology for understanding the psychology of behavior change and facilitating health promotion. PMID:21261410

  3. State anxiety reduction and exercise: does hemispheric activation reflect such changes?

    PubMed

    Petruzzello, S J; Landers, D M

    1994-08-01

    Acute bouts of aerobic exercise have been consistently associated with significant reductions in anxiety, but explanations for this effect remain elusive. The cerebral lateralization hypothesis predicts that anxiety reductions would be caused by a postexercise decrease in anterior right, relative to left, hemisphere activation. A sample of 19 right-handed males ran at 75% of their VO2max for 30 min on a treadmill. Electroencephalogram (EEG; F3, F4, T3, T4) and state anxiety were collected before and following exercise. Compared with preexercise, anxiety was significantly (P < 0.05) reduced at 10, 20, and 30 min postexercise. Preexercise EEG alpha asymmetry was significantly related to trait anxiety and also predicted a significant amount of variance (30%; P = 0.008) in postexercise anxiety reduction. From pre- to postexercise, the relative activation of the left frontal area increased with respect to the homologous right frontal site. Within-subject correlations for the change in anxiety with corresponding EEG changes were small but in line with theoretical predictions. It is concluded that the cerebral lateralization hypothesis remains tenable for explaining anxiety reductions associated with exercise.

  4. Highly active Pd-In/mesoporous alumina catalyst for nitrate reduction.

    PubMed

    Gao, Zhenwei; Zhang, Yonggang; Li, Deyi; Werth, Charles J; Zhang, Yalei; Zhou, Xuefei

    2015-04-09

    The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd-In/Al2O3 with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO2-buffered water and under continuous H2 as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd-In ratio of 4, with a first-order rate constant (k(obs) = 0.241 L min(-1) g(cata)(-1)) that was 1.3× higher than that of conventional Pd-In/Al2O3 (5 wt% Pd; 0.19 L min(-1) g(cata)(-1)). The Pd-In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate.

  5. Effects of Extrinsic and Intrinsic Proton Activity on The Mechanism of Oxygen Reduction in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Zeller, Robert August

    Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2 *-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set

  6. Identification of glutathione conjugates of acetylene-containing positive allosteric modulators of metabotropic glutamate receptor subtype 5.

    PubMed

    Zhuo, Xiaoliang; Huang, Xiaohua Stella; Degnan, Andrew P; Snyder, Lawrence B; Yang, Fukang; Huang, Hong; Shu, Yue-Zhong; Johnson, Benjamin M

    2015-04-01

    A recent medicinal chemistry campaign to identify positive allosteric modulators (PAMs) of metabotropic glutamate receptor subtype 5 (mGluR5) led to the discovery of potent compounds featuring an oxazolidinone structural core flanked by biaryl acetylene and haloaryl moieties. However, biotransformation studies of some of these mGluR5 PAMs demonstrated the formation of glutathione (GSH) conjugates. The conjugates in question were formed independently of NADPH as the main products in liver microsomes and liver cytosol (rat and human) and exhibited masses that were 307 u greater than their respective substrates, indicating the involvement of a reductive step in the formation of these metabolites. To further characterize the relevant metabolic sequences, GSH conjugates of (4R,5R)-5-(3-fluorophenyl)-4-(5-(pyrazin-2-ylethynyl)pyridin-3-yl)oxazolidin-2-one and (4R,5R)-5-(4-fluorophenyl)-4-(6-((3-fluoropyridin-2-yl)ethynyl)pyridin-2-yl)oxazolidin-2-one were biosynthesized and isolated. Subsequent analysis by NMR showed that GSH had reacted with the acetylene carbon atoms of these mGluR5 PAMs, suggesting a conjugate addition mechanism and implicating cytosolic and microsomal GSH S-transferases (GSTs) in catalysis. Interestingly, five closely related mGluR5 PAMs were not similarly prone to the formation of GSH conjugates in vitro. These compounds also featured acetylenes, but were flanked by either phenyl or cyclohexyl rings, which indicated that the formation of GSH conjugates was influenced by proximal functional groups that modulated the electron density of the triple bond and/or differences in enzyme-substrate specificity. These results informed an ongoing drug-discovery effort to identify mGluR5 PAMs with drug-like properties and a low risk of reactivity with endogenous thiols.

  7. The reduction of rotorcraft power and vibration using optimally controlled active gurney flap

    NASA Astrophysics Data System (ADS)

    Bae, Eui Sung

    The main topic of the present study is the application of active control scheme for the reduction of rotorcraft main rotor power reduction and vibratory load. When the helicopter is operated near its flight boundary, the required power and vibratory loads rapidly increases which impose a limit on the helicopter operation. Various methods were proposed and studied in order to achieve performance improvement under such operating condition. The effect of active control scheme was examined for its impact on the performance improvement and vibration reduction in the present study. Numerical simulations are based on the UH-60A Blackhawk helicopter with an active Gurney flap spanning from 70%R to 80%R of the main rotor. For obtaining the aeroelastic response of the rotor blade, finite element method was used to represent elastic blade. The aerodynamic loads acting on the blade are provided by CFD based 2D lookup table. Prescribed wake model was used to resolve the induced inflow over the rotor disk. The unsteady aerodynamic behavior due to the higher harmonic actuation of active Gurney flap was resolved by the time-domain unsteady aerodynamic model. The first part of preliminary study covers parametric study using Gurney flap. Starting with simple rigid blade representation of the rotor blade, the effect of 1/rev Gurney flap actuation was examined on three different gross weights. The effect of active Gurney flap width, the chordwise location of active Gurney flap, the effect of unsteady aerodynamic model, and the effect of 2/rev actuation frequency were examined. The second part of preliminary study was conducted with the elastic blade model to include the effect of torsion dynamics. Performance improvement using active Gurney flap was examined for maximizing thrust capability at two flight speeds. 1/rev Gurney flap actuation increased the gross weight capability up to 1,000 lbs. Also, 1/rev actuation of Gurney flap increased maximum altitude limit of baseline rotor by 1

  8. Reactions of Cg10062, a cis-3-Chloroacrylic Acid Dehalogenase Homologue, with Acetylene and Allene Substrates: Evidence for a Hydration-Dependent Decarboxylation.

    PubMed

    Huddleston, Jamison P; Johnson, William H; Schroeder, Gottfried K; Whitman, Christian P

    2015-05-19

    Cg10062 is a cis-3-chloroacrylic acid dehalogenase (cis-CaaD) homologue from Corynebacterium glutamicum with an unknown function and an uninformative genomic context. It shares 53% pairwise sequence similarity with cis-CaaD including the six active site amino acids (Pro-1, His-28, Arg-70, Arg-73, Tyr-103, and Glu-114) that are critical for cis-CaaD activity. However, Cg10062 is a poor cis-CaaD: it lacks catalytic efficiency and isomer specificity. Two acetylene compounds (propiolate and 2-butynoate) and an allene compound, 2,3-butadienoate, were investigated as potential substrates. Cg10062 functions as a hydratase/decarboxylase using propiolate as well as the cis-3-chloro- and 3-bromoacrylates, generating mixtures of malonate semialdehyde and acetaldehyde. The two activities occur sequentially at the active site using the initial substrate. With 2,3-butadienoate and 2-butynoate, Cg10062 functions as a hydratase and converts both to acetoacetate. Mutations of the proposed water-activating residues (E114Q, E114D, and Y103F) have a range of consequences from a reduction in wild type activity to a switch of activities (i.e., hydratase into a hydratase/decarboxylase or vice versa). The intermediates for the hydration and decarboxylation products can be trapped as covalent adducts to Pro-1 when NaCNBH3 is incubated with the E114D mutant and 2,3-butadienoate or 2-butynoate, and the Y103F mutant and 2-butynoate. Three mechanisms are presented to explain these findings. One mechanism involves the direct attack of water on the substrate, whereas the other two mechanisms use covalent catalysis in which a covalent bond forms between Pro-1 and the hydration product or the substrate. The strengths and weaknesses of the mechanisms and the implications for Cg10062 function are discussed.

  9. Protonated acetylene - An important circumstellar and interstellar ion

    NASA Technical Reports Server (NTRS)

    Glassgold, A. E.; Omont, A.; Guelin, M.

    1992-01-01

    In a circumstellar envelope, a substantial amount of acetylene is transported in a wind to the outer envelope, where it can be photoionized by interstellar radiation and then converted into C2H3(+) by a low-temperature reaction with H2. New chemical modeling calculations indicate that sufficient C2H3(+) may be produced in the outer envelope of IRC + 10216 to be observable. Similar considerations suggest that C2H3(+) should also be detectable in interstellar clouds, provided its rotational spectrum has been measured accurately in the laboratory.

  10. Magnetic coupling in a hybrid Mn(ii) acetylene dicarboxylate.

    PubMed

    Hendon, Christopher H; Pradaux-Caggiano, Fabienne; Hatcher, Lauren E; Gee, William J; Wilson, Chick C; Butler, Keith T; Carbery, David R; Walsh, Aron; Melot, Brent C

    2016-12-07

    The design of ligands that mediate through-bond long range super-exchange in metal-organic hybrid materials would expand chemical space beyond the commonly observed short range, low temperature magnetic ordering. Here we examine acetylene dicarboxylate as a potential ligand that could install long range magnetic ordering due to its spatially continuous frontier orbitals. Using a known Mn(ii)-containing coordination polymer we compute and measure the electronic structure and magnetic ordering. In this case, the latter is weak owing to the sub-optimal ligand coordination geometry, with a critical temperature of 2.5 K.

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

    PubMed

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

    2013-03-07

    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.

  12. Electrically rechargeable anionically active reduction-oxidation electrical storage-supply system

    SciTech Connect

    Remick, R.J.; Ang, P.G.P.

    1984-11-27

    An electrically rechargeable anionically active reduction-oxidation electric storage-supply system and process is disclosed using a sodium or potassium sulfidepolysulfide anolyte reaction and an iodide-polyiodide, chloride-chlorine or bromide-bromine species catholyte reaction. The catholyte and anolyte are separated by an ion selective membrane permeable to positive sodium and potassium ions and substantially impermeable to negative bromide, chloride, iodide, sulfide and polysulfide ions. A flowing electrolyte system is disclosed with external electrolyte storage vessels. The apparatus and process provide an electrically rechargeable anionically active reduction-oxidation system in which the electrolytes may be maintained at near neutral or slightly basic pH, with virtually no parasitic side reactions upon charging, such as hydrogen or oxygen evolution, and the disclosed storage and supply system provides higher energy densities than referenced prior art systems.

  13. Synergy among manganese, nitrogen and carbon to improve the catalytic activity for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Kang, Jian; Wang, Hui; Ji, Shan; Key, Julian; Wang, Rongfang

    2014-04-01

    A highly active electrocatalyst for oxygen reduction reaction, manganese modified glycine derivative-carbon (Mn-CNx), is synthesized by a two-step carbonizing process. X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy are used to characterize structure and morphology of the catalysts. Electrochemical tests show that Mn-CNx has higher catalytic activity for oxygen reduction reaction than CNx derived glycine and Mn modified Vulcan carbon. Moreover, the half-wave potential of Mn-CNx is only 12 mV lower than that of commercial Pt/C. Mn-CNx also has excellent durability to methanol crossover in alkaline solution, and thus provides a promising low cost, non-precious metal cathode catalyst for fuel cells.

  14. Enhanced Oxygen Reduction Activity In Acid By Tin-Oxide Supported Au Nanoparticle Catalysts

    SciTech Connect

    Baker,W.; Pietron, J.; Teliska, M.; Bouwman, P.; Ramaker, D.; Swider-Lyons, K.

    2006-01-01

    Gold nanoparticles supported on hydrous tin-oxide (Au-SnO{sub x}) are active for the four-electron oxygen reduction reaction in an acid electrolyte. The unique electrocatalytic of the Au-SnO is confirmed by the low amount of peroxide detected with rotating ring-disk electrode voltammetry and Koutecky-Levich analysis. In comparison, 10 wt % Au supported on Vulcan carbon and SnO{sub x} catalysts both produce significant peroxide in the acid electrolyte, indicating only a two-electron reduction reaction. Characterization of the Au-SnO{sub x} catalyst reveals a high-surface area, amorphous support with 1.7 nm gold metal particles. The high catalytic activity of the Au-SnO is attributed to metal support interactions. The results demonstrate a possible path to non-Pt catalysts for proton exchange membrane fuel cell cathodes.

  15. INVITED PAPER: Application of an active device for helicopter noise reduction in JAXA

    NASA Astrophysics Data System (ADS)

    Saito, Shigeru; Kobiki, Noboru; Tanabe, Yasutada

    2010-02-01

    Important issues in noise problems for current helicopters are described. An active tab (AT) was developed as a new active device for noise/vibration reduction under research cooperation between Japan Aerospace Exploration Agency (JAXA) and Kawada Industries, Inc. The wind tunnel test was conducted in order to investigate the effectiveness of the AT on the aeroacoustic characteristics of a helicopter. From the wind tunnel test, the capability of reducing blade vortex interaction (BVI) noise by an AT was verified. A new control law using instantaneous pressure change on a blade during BVI phenomena was introduced and applied to the wind tunnel testing. This new control law shows reasonable controllability for helicopter noise reduction. Furthermore, in order to analyze noise characteristics, the advanced computational fluid dynamics (CFD) code named JAXA_ov3d was developed in JAXA and extended to include CFD-CSD (computational structure dynamics) coupling by using the beam theory for blade deformation.

  16. Reduction of the Radiating Sound of a Submerged Finite Cylindrical Shell Structure by Active Vibration Control

    PubMed Central

    Kim, Heung Soo; Sohn, Jung Woo; Jeon, Juncheol; Choi, Seung-Bok

    2013-01-01

    In this work, active vibration control of an underwater cylindrical shell structure was investigated, to suppress structural vibration and structure-borne noise in water. Finite element modeling of the submerged cylindrical shell structure was developed, and experimentally evaluated. Modal reduction was conducted to obtain the reduced system equation for the active feedback control algorithm. Three Macro Fiber Composites (MFCs) were used as actuators and sensors. One MFC was used as an exciter. The optimum control algorithm was designed based on the reduced system equations. The active control performance was then evaluated using the lab scale underwater cylindrical shell structure. Structural vibration and structure-borne noise of the underwater cylindrical shell structure were reduced significantly by activating the optimal controller associated with the MFC actuators. The results provide that active vibration control of the underwater structure is a useful means to reduce structure-borne noise in water. PMID:23389344

  17. Localized, Non-Harmonic Active Flap Motions for Low Frequency In-Plane Rotor Noise Reduction

    NASA Technical Reports Server (NTRS)

    Sim, Ben W.; Potsdam, Mark; Kitaplioglu, Cahit; LeMasurier, Philip; Lorber, Peter; Andrews, Joseph

    2012-01-01

    A first-of-its-kind demonstration of the use of localized, non-harmonic active flap motions, for suppressing low frequency, in-plane rotor noise, is reported in this paper. Operational feasibility is verified via testing of the full-scale AATD/Sikorsky/UTRC active flap demonstration rotor in the NFAC's 40- by 80-Foot anechoic wind tunnel. Effectiveness of using localized, non-harmonic active flap motions are compared to conventional four-per-rev harmonic flap motions, and also active flap motions derived from closed-loop acoustics implementations. All three approaches resulted in approximately the same noise reductions over an in-plane three-by-three microphone array installed forward and near in-plane of the rotor in the nearfield. It is also reported that using an active flap in this localized, non-harmonic manner, resulted in no more that 2% rotor performance penalty, but had the tendency to incur higher hub vibration levels.

  18. Reduction of the radiating sound of a submerged finite cylindrical shell structure by active vibration control.

    PubMed

    Kim, Heung Soo; Sohn, Jung Woo; Jeon, Juncheol; Choi, Seung-Bok

    2013-02-06

    In this work, active vibration control of an underwater cylindrical shell structure was investigated, to suppress structural vibration and structure-borne noise in water. Finite element modeling of the submerged cylindrical shell structure was developed, and experimentally evaluated. Modal reduction was conducted to obtain the reduced system equation for the active feedback control algorithm. Three Macro Fiber Composites (MFCs) were used as actuators and sensors. One MFC was used as an exciter. The optimum control algorithm was designed based on the reduced system equations. The active control performance was then evaluated using the lab scale underwater cylindrical shell structure. Structural vibration and structure-borne noise of the underwater cylindrical shell structure were reduced significantly by activating the optimal controller associated with the MFC actuators. The results provide that active vibration control of the underwater structure is a useful means to reduce structure-borne noise in water.

  19. Boosting oxygen reduction/evolution reaction activities with layered perovskite catalysts.

    PubMed

    Chen, Dengjie; Wang, Jian; Zhang, Zhenbao; Shao, Zongping; Ciucci, Francesco

    2016-08-25

    Layered PrBaMn2O5+δ (H-PBM) was simply prepared by annealing pristine Pr0.5Ba0.5MnO3-δ in H2. The oxygen reduction/evolution reaction activities are remarkably enhanced by employing H-PBM. The improvement can be ascribed to the introduction of additional oxygen vacancies, an optimized eg filling of Mn ions, and the facile incorporation of oxygen into layered H-PBM.

  20. Effect of the mechanical activation on size reduction of crystalline acetaminophen drug particles

    PubMed Central

    Biazar, Esmaeil; Beitollahi, Ali; Rezayat, S Mehdi; Forati, Tahmineh; Asefnejad, Azadeh; Rahimi, Mehdi; Zeinali, Reza; Ardeshir, Mahmoud; Hatamjafari, Farhad; Sahebalzamani, Ali; Heidari, Majid

    2009-01-01

    The decrease in particle size may offer new properties to drugs. In this study, we investigated the size reduction influence of the acetaminophen (C8H9O2N) particles by mechanical activation using a dry ball mill. The activated samples with the average size of 1 μm were then investigated in different time periods with the infrared (IR), inductively coupled plasma (ICP), atomic force microscopy (AFM), and X-ray diffraction (XRD) methods. The results of the IR and XRD images showed no change in the drug structure after the mechanical activation of all samples. With the peak height at full width at half maximum from XRD and the Scherrer equation, the size of the activated crystallite samples illustrated that the AFM images were in sound agreement with the Scherrer equation. According to the peaks of the AFM images, the average size of the particles in 30 hours of activation was 24 nm with a normal particle distribution. The ICP analysis demonstrated the presence of tungsten carbide particle impurities after activation from the powder sample impacting with the ball and jar. The greatest reduction in size was after milling for 30 hours. PMID:20054432

  1. Stable platinum nanoclusters on genomic DNA-graphene oxide with a high oxygen reduction reaction activity.

    PubMed

    Tiwari, Jitendra N; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N; Kemp, K Christian; Le, Nhien H; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S

    2013-01-01

    Nanosize platinum clusters with small diameters of 2-4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA-graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA-graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA-graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries.

  2. Effects of pathogen reduction systems on platelet microRNAs, mRNAs, activation, and function.

    PubMed

    Osman, Abdimajid; Hitzler, Walter E; Meyer, Claudius U; Landry, Patricia; Corduan, Aurélie; Laffont, Benoit; Boilard, Eric; Hellstern, Peter; Vamvakas, Eleftherios C; Provost, Patrick

    2015-01-01

    Pathogen reduction (PR) systems for platelets, based on chemically induced cross-linking and inactivation of nucleic acids, potentially prevent transfusion transmission of infectious agents, but can increase clinically significant bleeding in some clinical studies. Here, we documented the effects of PR systems on microRNA and mRNA levels of platelets stored in the blood bank, and assessed their impact on platelet activation and function. Unlike platelets subjected to gamma irradiation or stored in additive solution, platelets treated with Intercept (amotosalen+ ultraviolet-A [UVA] light) exhibited significantly reduced levels of 6 of the 11 microRNAs, and 2 of the 3 anti-apoptotic mRNAs (Bcl-xl and Clusterin) that we monitored, compared with platelets stored in plasma. Mirasol (riboflavin+ UVB light) treatment of platelets did not produce these effects. PR neither affected platelet microRNA synthesis or function nor induced cross-linking of microRNA-sized endogenous platelet RNA species. However, the reduction in the platelet microRNA levels induced by Intercept correlated with the platelet activation (p < 0.05) and an impaired platelet aggregation response to ADP (p < 0.05). These results suggest that Intercept treatment may induce platelet activation, resulting in the release of microRNAs and mRNAs from platelets. The clinical implications of this reduction in platelet nucleic acids secondary to Intercept remain to be established.

  3. Effects of pathogen reduction systems on platelet microRNAs, mRNAs, activation, and function

    PubMed Central

    Osman, Abdimajid; Hitzler, Walter E.; Meyer, Claudius U.; Landry, Patricia; Corduan, Aurélie; Laffont, Benoit; Boilard, Eric; Hellstern, Peter; Vamvakas, Eleftherios C.

    2015-01-01

    Pathogen reduction (PR) systems for platelets, based on chemically induced cross-linking and inactivation of nucleic acids, potentially prevent transfusion transmission of infectious agents, but can increase clinically significant bleeding in some clinical studies. Here, we documented the effects of PR systems on microRNA and mRNA levels of platelets stored in the blood bank, and assessed their impact on platelet activation and function. Unlike platelets subjected to gamma irradiation or stored in additive solution, platelets treated with Intercept (amotosalen + ultraviolet-A [UVA] light) exhibited significantly reduced levels of 6 of the 11 microRNAs, and 2 of the 3 anti-apoptotic mRNAs (Bcl-xl and Clusterin) that we monitored, compared with platelets stored in plasma. Mirasol (riboflavin + UVB light) treatment of platelets did not produce these effects. PR neither affected platelet microRNA synthesis or function nor induced cross-linking of microRNA-sized endogenous platelet RNA species. However, the reduction in the platelet microRNA levels induced by Intercept correlated with the platelet activation (p < 0.05) and an impaired platelet aggregation response to ADP (p < 0.05). These results suggest that Intercept treatment may induce platelet activation, resulting in the release of microRNAs and mRNAs from platelets. The clinical implications of this reduction in platelet nucleic acids secondary to Intercept remain to be established. PMID:24749844

  4. Risk avoidance versus risk reduction: a framework and segmentation profile for understanding adolescent sexual activity.

    PubMed

    Hopkins, Christopher D; Tanner, John F; Raymond, Mary Anne

    2004-01-01

    The teen birthrate in the United States is twice that of other industrialized nations. Adolescents in the U.S. are among high-risk groups for HIV/AIDS and other sexually transmitted diseases. As a result, the Department of Health and Human Services changed its policy on the promotion of abstinence to teenagers from a focus on a risk reduction strategy to a focus on a risk avoidance strategy. In order to create more effective risk avoidance as well as risk reduction campaigns, this study proposes a framework to illustrate the distinction that teens make between spontaneous sexual activity and planned sexual activity, as well as those teens that make a commitment to abstinence versus abstinence by default. Furthermore, this study classifies teens into three behavior segments (abstemious, promiscuous and monogamous) and then assesses specific differences that exist within these groups relative to their attitudes and perceptions concerning abstinence, sexual activity, contraception, fear and norms. This change in focus from a risk reduction to a risk avoidance strategy has important implications for social marketing, public policy and marketing theory.

  5. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction.

    PubMed

    Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

    2014-09-17

    Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm(-2)) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst.

  6. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

    2014-09-01

    Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm-2) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst.

  7. Reduction of hexavalent chromium by Sphaerotilus natans a filamentous micro-organism present in activated sludges.

    PubMed

    Caravelli, Alejandro H; Giannuzzi, Leda; Zaritzky, Noemí E

    2008-08-15

    Wastewaters produced by various industries may contain undesirable amounts of hexavalent chromium (Cr(VI)), as chromate and dichromate, a hazardous metal affecting flora and animals of aquatic ecosystems as well as human health. One removal strategy comprises the microbial reduction of Cr(VI) to Cr(III), a less soluble chemical species that is less toxic than Cr(VI). In this work, the ability to reduce Cr(VI) of Sphaerotilus natans, a filamentous bacterium usually found in activated sludge systems, was evaluated. In aerobic conditions, S. natans was able to efficiently reduce Cr(VI) to Cr(III) from dichromate solutions ranging between 4.5 and 80 mg Cr(VI)l(-1) in the presence of a carbonaceous source. A simultaneous evaluation of the microbial respiratory activity inhibition was also carried out to analyze the toxic effect of Cr(VI). Cr(VI) reduction by S. natans was mathematically modeled; chromium(VI) reduction rate depended on both Cr(VI) concentration and active biomass concentration. Although it is known that S. natans removes heavy metal cations such as Cr(III) by biosorption, the ability of this micro-organism to reduce Cr(VI), which behaves as an oxyanion in aqueous solutions, is a novel finding. The distinctive capacity to reduce Cr(VI) to Cr(III) than remain soluble or precipitated becomes S. natans a potential micro-organism to decontaminate wastewaters.

  8. Catalytic Activity of Platinum Monolayer on Iridium and Rhenium Alloy Nanoparticles for the Oxygen Reduction Reaction

    SciTech Connect

    Karan, Hiroko I.; Sasaki, Kotaro; Kuttiyiel, Kurian; Farberow, Carrie A.; Mavrikakis, Manos; Adzic, Radoslav R.

    2012-05-04

    A new type of electrocatalyst with a core–shell structure that consists of a platinum monolayer shell placed on an iridium–rhenium nanoparticle core or platinum and palladium bilayer shell deposited on that core has been prepared and tested for electrocatalytic activity for the oxygen reduction reaction. Carbon-supported iridium–rhenium alloy nanoparticles with several different molar ratios of Ir to Re were prepared by reducing metal chlorides dispersed on Vulcan carbon with hydrogen gas at 400 °C for 1 h. These catalysts showed specific electrocatalytic activity for oxygen reduction reaction comparable to that of platinum. The activities of PtML/PdML/Ir2Re1, PtML/Pd2layers/Ir2Re1, and PtML/Pd2layers/Ir7Re3 catalysts were, in fact, better than that of conventional platinum electrocatalysts, and their mass activities exceeded the 2015 DOE target. Our density functional theory calculations revealed that the molar ratio of Ir to Re affects the binding strength of adsorbed OH and, thereby, the O2 reduction activity of the catalysts. The maximum specific activity was found for an intermediate OH binding energy with the corresponding catalyst on the top of the volcano plot. The monolayer concept facilitates the use of much less platinum than in other approaches. Finally, the results with the PtML/PdML/Ir2Re electrocatalyst indicate that it is a promising alternative to conventional Pt electrocatalysts in low-temperature fuel cells.

  9. Ag-Fe2O3 nanocomposites with enhanced catalytic activity for reduction of 4-nitrophenol

    NASA Astrophysics Data System (ADS)

    Liu, Shiben; Chen, Yingjie; Dong, Lifeng

    2016-07-01

    Hybrid nanostructures can be multifunctional and even possess enhanced properties. Ag-Fe2O3 nanocomposites and Ag nanoparticles (NPs) were fabricated and applied to catalyze the reduction of 4-nitrophenol. Compared with Ag NPs, Ag-Fe2O3 nanocomposites demonstrated enhanced catalytic activities. Furthermore, due to their magnetic properties, Ag-Fe2O3 nanocomposites could be easily separated from the reaction mixture and recycled through an external magnetic field. These findings will help us design hybrid nanostructures with catalytic activity and explore other potential applications of magnetic nanocomposites.

  10. Hexagonal 2H-MoSe2 broad spectrum active photocatalyst for Cr(VI) reduction

    PubMed Central

    Chu, Haipeng; Liu, Xinjuan; Liu, Baibai; Zhu, Guang; Lei, Wenyan; Du, Huigang; Liu, Junying; Li, Jianwei; Li, Can; Sun, Changqing

    2016-01-01

    To make full use of the solar energy, exploring broad spectrum active photocatalysts has become one of the core issues for photocatalysis. Here we report a novel hexagonal 2H-MoSe2 photocatalyst with ultraviolet (UV)-visible-near infrared (NIR) light response for the first time. The results indicate that the MoSe2 displays excellent photo-absorption and photocatalytic activity in the reduction of Cr(VI) under UV and visible even NIR light irradiation. MoSe2 synthesized at pH value of 2 achieves the highest Cr(VI) reduction rates of 99%, 91% and 100% under UV, visible and NIR light irradiation, respectively, which should be attributed to its comparatively higher light absorption, efficient charge separation and transfer as well as relatively large number of surface active sites. The excellent broad spectrum active photocatalytic activity makes the MoSe2 to be a promising photocatalyst for the effective utilization of solar energy. PMID:27734974

  11. The validation of an active control intervention for Mindfulness Based Stress Reduction (MBSR).

    PubMed

    MacCoon, Donal G; Imel, Zac E; Rosenkranz, Melissa A; Sheftel, Jenna G; Weng, Helen Y; Sullivan, Jude C; Bonus, Katherine A; Stoney, Catherine M; Salomons, Tim V; Davidson, Richard J; Lutz, Antoine

    2012-01-01

    Most of the extant literature investigating the health effects of mindfulness interventions relies on wait-list control comparisons. The current article specifies and validates an active control condition, the Health Enhancement Program (HEP), thus providing the foundation necessary for rigorous investigations of the relative efficacy of Mindfulness Based Stress Reduction (MBSR) and for testing mindfulness as an active ingredient. 63 participants were randomized to either MBSR (n = 31) or HEP (n = 32). Compared to HEP, MBSR led to reductions in thermal pain ratings in the mindfulness- but not the HEP-related instruction condition (η(2) = .18). There were significant improvements over time for general distress (η(2) = .09), anxiety (η(2) = .08), hostility (η(2) = .07), and medical symptoms (η(2) = .14), but no effects of intervention. Practice was not related to change. HEP is an active control condition for MBSR while remaining inert to mindfulness. These claims are supported by results from a pain task. Participant-reported outcomes (PROs) replicate previous improvements to well-being in MBSR, but indicate that MBSR is no more effective than a rigorous active control in improving these indices. These results emphasize the importance of using an active control condition like HEP in studies evaluating the effectiveness of MBSR.

  12. Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

    SciTech Connect

    Sun-Mi Hwang; Choi, YongMan; Kim, Min Gyu; Sohn, Young-Jun; Cheon, Jae Yeong; Joo, Sang Hoon; Yim, Sung-Dae; Kuttiyiel, Kurian A.; Sasaki, Kotaro; Adzic, Radoslav R.; Park, Gu-Gon

    2016-03-08

    The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities compared to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. Finally, in terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.

  13. Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

    DOE PAGES

    Sun-Mi Hwang; Choi, YongMan; Kim, Min Gyu; ...

    2016-03-08

    The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities comparedmore » to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. Finally, in terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.« less

  14. An ene reductase from Clavispora lusitaniae for asymmetric reduction of activated alkenes.

    PubMed

    Ni, Yan; Yu, Hui-Lei; Lin, Guo-Qiang; Xu, Jian-He

    2014-03-05

    A putative ene reductase gene from Clavispora lusitaniae was heterologously overexpressed in Escherichia coli, and the encoded protein (ClER) was purified and characterized for its biocatalytic properties. This NADPH-dependent flavoprotein was identified with reduction activities toward a diverse range of activated alkenes including conjugated enones, enals, maleimide derivative and α,β-unsaturated carboxylic esters. The purified ClER exhibited a relatively high activity of 7.3 U mg(prot)⁻¹ for ketoisophorone while a remarkable catalytic efficiency (k(cat)/K(m)=810 s⁻¹ mM⁻¹) was obtained for 2-methyl-cinnamaldehyde due to the high affinity. A series of prochiral activated alkenes were stereoselectively reduced by ClER furnishing the corresponding saturated products in up to 99% ee. The practical applicability of ClER was further evaluated for the production of (R)-levodione, a valuable chiral compound, from ketoisophorone. Using the crude enzyme of ClER and glucose dehydrogenase (GDH), 500 mM of ketoisophorone was efficiently converted to (R)-levodione with excellent stereoselectivity (98% ee) within 1h. All these positive features demonstrate a high synthetic potential of ClER in the asymmetric reduction of activated alkenes.

  15. Hexagonal 2H-MoSe2 broad spectrum active photocatalyst for Cr(VI) reduction.

    PubMed

    Chu, Haipeng; Liu, Xinjuan; Liu, Baibai; Zhu, Guang; Lei, Wenyan; Du, Huigang; Liu, Junying; Li, Jianwei; Li, Can; Sun, Changqing

    2016-10-13

    To make full use of the solar energy, exploring broad spectrum active photocatalysts has become one of the core issues for photocatalysis. Here we report a novel hexagonal 2H-MoSe2 photocatalyst with ultraviolet (UV)-visible-near infrared (NIR) light response for the first time. The results indicate that the MoSe2 displays excellent photo-absorption and photocatalytic activity in the reduction of Cr(VI) under UV and visible even NIR light irradiation. MoSe2 synthesized at pH value of 2 achieves the highest Cr(VI) reduction rates of 99%, 91% and 100% under UV, visible and NIR light irradiation, respectively, which should be attributed to its comparatively higher light absorption, efficient charge separation and transfer as well as relatively large number of surface active sites. The excellent broad spectrum active photocatalytic activity makes the MoSe2 to be a promising photocatalyst for the effective utilization of solar energy.

  16. Field-scale reduction of PCB bioavailability with activated carbon amendment to river sediments.

    PubMed

    Beckingham, Barbara; Ghosh, Upal

    2011-12-15

    Remediation of contaminated sediments remains a technological challenge because traditional approaches do not always achieve risk reduction goals for human health and ecosystem protection and can even be destructive for natural resources. Recent work has shown that uptake of persistent organic pollutants such as polychlorinated biphenyls (PCBs) in the food web is strongly influenced by the nature of contaminant binding, especially to black carbon surfaces in sediments. We demonstrate for the first time in a contaminated river that application of activated carbon to sediments in the field reduces biouptake of PCBs in benthic organisms. After treatment with activated carbon applied at a dose similar to the native organic carbon of sediment, bioaccumulation in freshwater oligochaete worms was reduced compared to preamendment conditions by 69 to 99%, and concentrations of PCBs in water at equilibrium with the sediment were reduced by greater than 93% at all treatment sites for up to three years of monitoring. By comparing measured reductions in bioaccumulation of tetra- and penta-chlorinated PCB congeners resulting from field application of activated carbon to a laboratory study where PCBs were preloaded onto activated carbon, it is evident that equilibrium sorption had not been achieved in the field. Although other remedies may be appropriate for some highly contaminated sites, we show through this pilot study that PCB exposure from moderately contaminated river sediments may be managed effectively through activated carbon amendment in sediments.

  17. Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction

    SciTech Connect

    Lim, B.; Tao, J.; Jiang, M.; Camargo, P.H.C.; Cho, E.C.; Lu, X.; Zhu, Y.; Xia, Y.

    2009-06-05

    Controlling the morphology of Pt nanostructures can provide a great opportunity to improve their catalytic properties and increase their activity on a mass basis. We synthesized Pd-Pt bimetallic nanodendrites consisting of a dense array of Pt branches on a Pd core by reducing K{sub 2}PtCl{sub 4} with L-ascorbic acid in the presence of uniform Pd nanocrystal seeds in an aqueous solution. The Pt branches supported on faceted Pd nanocrystals exhibited relatively large surface areas and particularly active facets toward the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel cell. The Pd-Pt nanodendrites were two and a half times more active on the basis of equivalent Pt mass for the ORR than the state-of-the-art Pt/C catalyst and five times more active than the first-generation supportless Pt-black catalyst.

  18. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    DOEpatents

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  19. Catalytic activity of various pepsin reduced Au nanostructures towards reduction of nitroarenes and resazurin

    NASA Astrophysics Data System (ADS)

    Sharma, Bhagwati; Mandani, Sonam; Sarma, Tridib K.

    2015-01-01

    Pepsin, a digestive protease enzyme, could function as a reducing as well as stabilizing agent for the synthesis of Au nanostructures of various size and shape under different reaction conditions. The simple tuning of the pH of the reaction medium led to the formation of spherical Au nanoparticles, anisotropic Au nanostructures such as triangles, hexagons, etc., as well as ultra small fluorescent Au nanoclusters. The activity of the enzyme was significantly inhibited after its participation in the formation of Au nanoparticles due to conformational changes in the native structure of the enzyme which was studied by fluorescence, circular dichroism (CD), and infra red spectroscopy. However, the Au nanoparticle-enzyme composites served as excellent catalyst for the reduction of p-nitrophenol and resazurin, with the catalytic activity varying with size and shape of the nanoparticles. The presence of pepsin as the surface stabilizer played a crucial role in the activity of the Au nanoparticles as reduction catalysts, as the approach of the reacting molecules to the nanoparticle surface was actively controlled by the stabilizing enzyme.

  20. Enhanced catalytic activity of solid and hollow platinum-cobalt nanoparticles towards reduction of 4-nitrophenol

    NASA Astrophysics Data System (ADS)

    Krajczewski, Jan; Kołątaj, Karol; Kudelski, Andrzej

    2016-12-01

    Previous investigations of hollow platinum nanoparticles have shown that such nanostructures are more active catalysts than their solid counterparts towards the following electrochemical reactions: reduction of oxygen, evolution of hydrogen, and oxidation of borohydride, methanol and formic acid. In this work we show that synthesised using standard galvanic replacement reaction (with Co templates) hollow platinum nanoparticles exhibit enhanced catalytic activity also towards reduction of 4-nitrophenol by sodium borohydride in water. Unlike in the case of procedures involving hollow platinum catalysts employed so far to carry out this reaction it is not necessary to couple analysed platinum nanoparticles to the surface of an electrode. Simplification of the analyzed reaction may eliminate same experimental errors. We found that the enhanced catalytic activity of hollow Pt nanoparticles is not only connected with generally observed larger surface area of hollow nanostructures, but is also due to the contamination of formed hollow nanostructures with cobalt, from which sacrificial templates used in the synthesis of hollow Pt nanostrustures have been formed. Because using sacrificial templates is a typical method of synthesis of hollow metal nanostructures, formed hollow nanoparticles are probably often contaminated, which may significantly influence their catalytic activity.

  1. Influence of ammonium chloride on the nitrogenase activity of nodulated pea plants (Pisum sativum).

    PubMed Central

    Houwaard, F

    1978-01-01

    A study was made on the short-term effect of ammonium ions on the nitrogenase activity of pea root nodules. Nodulated pea plants (Pisum sativum), having reached maximum acetylene-reducing activity, were supplied with NH4Cl (20 mM). Nitrogenase activity of intact plants, detached nodules, and isolated bacteroids was measured at differed time intervals. A significant drop (20 to 40%) in the acetylene-reducing activity of treated intact plants and their detached nodules was observed after 1 day. No drop in the nitrogenase activity of bacteroids (assayed aerobically, or anaerobically after treatment with ethylenediaminetetraacetic acid-toluene) occurred for 2 to 4 days after the addition of NH4+ to the plants, depending on cultural conditions. From these results it is concluded that the adverse effect of NH4+ on acetylene reduction by intact plants and detached nodules during the first 2 days is not due to a decrease in the amount of nitrogenase in the bacteroids. It is suggested that the effect has to be attributed to a reduced supply to the bacteroids of energy-delivery photosynthates. PMID:677873

  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

    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.

  4. 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.

  5. A modified oxic-settling-anaerobic activated sludge process using gravity thickening for excess sludge reduction

    PubMed Central

    Wang, Jun; Li, Shi-Yu; Jiang, Feng; Wu, Ke; Liu, Guang-Li; Lu, Hui; Chen, Guang-Hao

    2015-01-01

    Oxic-settling-anaerobic process (OSA) was known as a cost-effective way to reduce the excess sludge production with simple upgrade of conventional activated sludge process (CAS). A low oxidation-reduction potential (ORP) level was the key factor to sludge decay and lysis in the sludge holding tank of the OSA process. However, the ORP control with nitrogen purge or chemical dosing in the OSA process would induce extra expense and complicate the operation. Hence, in this study, a sludge holding tank using gravity thickening was applied to OSA process to reduce the excess sludge production without any ORP control. Results showed that the modified OSA process not only reduced the excess sludge production effectively but also improved the sludge settleability without affected the treatment capacity. The reduction of the excess sludge production in the modified OSA process resulted from interactions among lots of factors. The key element of the process was the gravity thickening sludge holding tank. PMID:26350761

  6. A modified oxic-settling-anaerobic activated sludge process using gravity thickening for excess sludge reduction

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Li, Shi-Yu; Jiang, Feng; Wu, Ke; Liu, Guang-Li; Lu, Hui; Chen, Guang-Hao

    2015-09-01

    Oxic-settling-anaerobic process (OSA) was known as a cost-effective way to reduce the excess sludge production with simple upgrade of conventional activated sludge process (CAS). A low oxidation-reduction potential (ORP) level was the key factor to sludge decay and lysis in the sludge holding tank of the OSA process. However, the ORP control with nitrogen purge or chemical dosing in the OSA process would induce extra expense and complicate the operation. Hence, in this study, a sludge holding tank using gravity thickening was applied to OSA process to reduce the excess sludge production without any ORP control. Results showed that the modified OSA process not only reduced the excess sludge production effectively but also improved the sludge settleability without affected the treatment capacity. The reduction of the excess sludge production in the modified OSA process resulted from interactions among lots of factors. The key element of the process was the gravity thickening sludge holding tank.

  7. [The development of acetylene on-line monitoring technology based on laser absorption spectrum].

    PubMed

    He, Ying; Zhang, Yu-jun; Kan, Rui-feng; Xia, Hui; Wang, Min; Cui, Xiao-juan; Chen, Jiu-ying; Chen, Dong; Liu, Wen-qing; Liu, Jian-guo

    2008-10-01

    As one of the materials in organic chemical industry, acetylene has been used in many aspects of chemical industry. But acetylene is a very dangerous inflammable and explosive gas, so it needs in-situ monitoring during industrial storage and production. Tunable diode laser absorption spectroscopy (TDLAS) technology has been widely used in atmospheric trace gases detection, because it has a lot of advantageous characteristics, such as high sensitivity, good selectivity, and rapid time response. The distribution characteristics of absorption lines of acetylene in near infrared band were studied, and then the system designing scheme of acetylene on-line monitoring based on near infrared tunable diode laser absorption spectroscopy technology was discussed in detail. Moreover, the system of experiment measurement was set up and the method of signal detection and the algorithm of concentration inversion were studied. In addition, the sample cell with a path length of 10 cm, and the acetylene of different known concentrations were measured. As a result, the detection limit obtained reached 1.46 cm3 x m(-3). Finally the dynamic detection experiment was carried out, and the measurement result is stable and reliable, so the design of the system is practicable through experiment analysis. On-line acetylene leakage monitoring system was developed based on the experiment, and it is suitable for giving a leakage alarm of acetylene during its storage, transportation and use.

  8. Real-time monitoring of nucleation-growth cycle of carbon nanoparticles in acetylene plasmas

    NASA Astrophysics Data System (ADS)

    Hundt, Morten; Sadler, Patrick; Levchenko, Igor; Wolter, Matthias; Kersten, Holger; Ostrikov, Kostya (Ken)

    2011-06-01

    Quantum cascade laser absorption spectroscopy was used to measure the absolute concentration of acetylene in situ during the nanoparticle growth in Ar + C2H2 RF plasmas. It is demonstrated that the nanoparticle growth exhibits a periodical behavior, with the growth cycle period strongly dependent on the initial acetylene concentration in the chamber. Being 300 s at 7.5% of acetylene in the gas mixture, the growth cycle period decreases with the acetylene concentration increasing; the growth eventually disappears when the acetylene concentration exceeds 32%. During the nanoparticle growth, the acetylene concentration is small and does not exceed 4.2% at radio frequency (RF) power of 4 W, and 0.5% at RF power of 20 W. An injection of a single acetylene pulse into the discharge also results in the nanoparticle nucleation and growth. The absorption spectroscopy technique was found to be very effective for the time-resolved measurement of the hydrocarbon content in nanoparticle-generating plasmas.

  9. Controlled reduction of red mud waste to produce active systems for environmental applications: heterogeneous Fenton reaction and reduction of Cr(VI).

    PubMed

    Costa, Regina C C; Moura, Flávia C C; Oliveira, Patrícia E F; Magalhães, Fabiano; Ardisson, José D; Lago, Rochel M

    2010-02-01

    In this work, controlled reduction of red mud with H(2) was used to produce active systems for two different environmental applications, i.e. the heterogeneous Fenton reaction and the reduction of Cr(VI). Mössbauer, powder X-ray diffraction, thermal analyses and scanning electron microscopy analyses showed that at different temperatures, i.e. 300, 400, 500 and 600 degrees C, H(2) reduces red mud to different phases, mainly Fe(3)O(4), Fe(0)/Fe(3)O(4) and Fe(0). These Fe phases are dispersed on Al, Si and Ti oxides present in the red mud and show high reactivity towards two environmental applications, i.e. the heterogeneous Fenton reaction and the reduction of Cr(VI). Reduction with H(2) at 400 degrees C showed the best results for the oxidation of the model dye methylene blue with H(2)O(2) at neutral pH due to the presence of the composite Fe(0)/Fe(3)O(4). The reduced red mud at 500-600 degrees C produced Fe(0) highly active for the reduction of Cr(VI) in aqueous medium. Another feature of these red mud based system is that after deactivation due to extensive use they can be completely regenerated by simple treatment with H(2).

  10. 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.

  11. Analysis of acetylene in blood and urine using cryogenic gas chromatography-mass spectrometry.

    PubMed

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

    2009-09-01

    A method for quantitative analysis of acetylene in blood and urine samples was investigated. Using cryogenic gas chromatography-mass spectrometry (GC-MS), acetylene was measured with isobutane as the internal standard in the headspace method, which revealed a linear response over the entire composite range with an excellent correlation coefficient, both in blood (R = 0.9968, range = 5.39-43.1 microg/ml) and urine (R = 0.9972, range = 2.16-10.8 microg/ml). The coefficients of variation (CV) for blood ranged from 2.62 to 11.6% for intra-day and 4.55 to 10.4% for inter-day. The CV for urine ranged from 2.38 to 3.10% for intra-day and 4.83 to 11.0% for inter-day. The recovery rate as an index of accuracy ranged from 83 to 111%. The present method showed good reliability, and is also simple and rapid. In actual samples from a charred cadaver due to acetylene explosion, the measured concentrations of acetylene by this method were 21.5 microg/ml for femoral vein blood, 17.9 microg/ml for right atrial blood, 25.5 microg/ml for left atrial blood and 7.49 microg/ml for urine. Quantification of acetylene provides important information, because the acetylene concentration is a vital reaction or sign. For example, when acetylene is filled in a closed space and then explodes, in antemortem explosion, the blood acetylene concentration of the cadaver might be significant. On the other hand, in postmortem explosion, acetylene is not detected in blood. Furthermore, when several victims are involved in one explosion, comparison of the sample concentrations can also provide useful information to establish the conditions at the accident scene; therefore, the present method is useful in forensics.

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

    NASA Astrophysics Data System (ADS)

    Kočišek, J.; Lengyel, J.; Fárník, M.

    2013-03-01

    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 (C_2H_2)_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 C3 H_3^+ 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 C6 H_6^+ 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 Ar_{n ≥ 2}(C2 H2)_{m≥ 2}^+ at ≈13.7 eV is discussed in terms of an exciton transfer mechanism.

  13. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    SciTech Connect

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; Mavrikakis, Manos; Xia, Younan

    2015-07-02

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.

  14. Thermal Noise Reduction of Mechanical Oscillators by Actively Controlled External Dissipative Forces

    NASA Technical Reports Server (NTRS)

    Liang, Shoudan; Medich, David; Czajkowsky, Daniel M.; Sheng, Sitong; Yuan, Jian-Yang; Shao, Zhifeng

    1999-01-01

    We show that the thermal fluctuations of very soft mechanical oscillators, such as the cantilever in an atomic force microscope (AFM), can be reduced without changing the stiffness of the spring or having to lower the environment temperature. We derive a theoretical relationship between the thermal fluctuations of an oscillator and an actively external-dissipative force. This relationship is verified by experiments with an AFM cantilever where the external active force is coupled through a magnetic field. With simple instrumentation, we have reduced the thermal noise amplitude of the cantilever by a factor of 3.4, achieving an apparent temperature of 25 K with the environment at 295K. This active noise reduction approach can significantly improve the accuracy of static position or static force measurements in a number of practical applications.

  15. Palladium-platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction.

    PubMed

    Wang, Xue; Choi, Sang-Il; Roling, Luke T; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A; Mavrikakis, Manos; Xia, Younan

    2015-07-02

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. These results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.

  16. Active sound reduction: A study of recent developments and some future possibilities

    NASA Astrophysics Data System (ADS)

    Lindqvist, E.

    1983-11-01

    It is suggested that active sound reduction is easiest to implement and most effective at low frequencies and in a duct rather than in a room or a free field. The prospects for success are considerably improved if the sound to be attenuated is periodic. Symmetry of the sound field can sometimes be exploited. The physical mechanisms of sound attenuation include reflection of sound by secondary sources, creation of higher order sources in order to reduce the energy radiated and conversion of acoustic energy. Active techniques can also be applied to prevent transmission of sound or vibrations from one sub-field to another. Microelectronics and digital filtering techniques are expected to greatly influence active sound attenuators.

  17. 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

  18. Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases

    NASA Astrophysics Data System (ADS)

    Bhagi-Damodaran, Ambika; Michael, Matthew A.; Zhu, Qianhong; Reed, Julian; Sandoval, Braddock A.; Mirts, Evan N.; Chakraborty, Saumen; Moënne-Loccoz, Pierre; Zhang, Yong; Lu, Yi

    2016-11-01

    Haem-copper oxidase (HCO) catalyses the natural reduction of oxygen to water using a haem-copper centre. Despite decades of research on HCOs, the role of non-haem metal and the reason for nature's choice of copper over other metals such as iron remains unclear. Here, we use a biosynthetic model of HCO in myoglobin that selectively binds different non-haem metals to demonstrate 30-fold and 11-fold enhancements in the oxidase activity of Cu- and Fe-bound HCO mimics, respectively, as compared with Zn-bound mimics. Detailed electrochemical, kinetic and vibrational spectroscopic studies, in tandem with theoretical density functional theory calculations, demonstrate that the non-haem metal not only donates electrons to oxygen but also activates it for efficient O-O bond cleavage. Furthermore, the higher redox potential of copper and the enhanced weakening of the O-O bond from the higher electron density in the d orbital of copper are central to its higher oxidase activity over iron. This work resolves a long-standing question in bioenergetics, and renders a chemical-biological basis for the design of future oxygen-reduction catalysts.

  19. Enhanced Activity of Supported Ni Catalysts Promoted by Pt for Rapid Reduction of Aromatic Nitro Compounds

    PubMed Central

    Shang, Huishan; Pan, Kecheng; Zhang, Lu; Zhang, Bing; Xiang, Xu

    2016-01-01

    To improve the activities of non-noble metal catalysts is highly desirable and valuable to the reduced use of noble metal resources. In this work, the supported nickel (Ni) and nickel-platinum (NiPt) nanocatalysts were derived from a layered double hydroxide/carbon composite precursor. The catalysts were characterized and the role of Pt was analysed using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDS) mapping, and X-ray photoelectron spectroscopy (XPS) techniques. The Ni2+ was reduced to metallic Ni0 via a self-reduction way utilizing the carbon as a reducing agent. The average sizes of the Ni particles in the NiPt catalysts were smaller than that in the supported Ni catalyst. The electronic structure of Ni was affected by the incorporation of Pt. The optimal NiPt catalysts exhibited remarkably improved activity toward the reduction of nitrophenol, which has an apparent rate constant (Ka) of 18.82 × 10−3 s−1, 6.2 times larger than that of Ni catalyst and also larger than most of the reported values of noble-metal and bimetallic catalysts. The enhanced activity could be ascribed to the modification to the electronic structure of Ni by Pt and the effect of exposed crystal planes. PMID:28335231

  20. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal-nitrogen coordination.

    PubMed

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-06-10

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon-nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation.

  1. Asymmetric reduction of activated alkenes using an enoate reductase from Gluconobacter oxydans.

    PubMed

    Richter, Nina; Gröger, Harald; Hummel, Werner

    2011-01-01

    A recombinant enoate reductase from Gluconobacter oxydans was heterologously expressed, purified, characterised and applied in the asymmetric reduction of activated alkenes. In addition to the determination of the kinetic properties, the major focus of this work was to utilise the enzyme in the biotransformation of different interesting compounds such as 3,5,5-trimethyl-2-cyclohexen-1,4-dione (ketoisophorone) and (E/Z)-3,7-dimethyl-2,6-octadienal (citral). The reaction proceeded with excellent stereoselectivities (>99% ee) as well as absolute chemo- and regioselectivity, only the activated C=C bond of citral was reduced by the enoate reductase, while non-activated C=C bond and carbonyl moiety remained untouched. The described strategy can be used for the production of enantiomerically pure building blocks, which are difficult to prepare by chemical means. In general, the results show that the investigated enoate reductase is a promising catalyst for the use in asymmetric C=C bond reductions.

  2. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal–nitrogen coordination

    PubMed Central

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-01-01

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon–nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation. PMID:26059552

  3. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resulting in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.

  4. Antidepressant activity of memory-enhancing drugs in the reduction of submissive behavior model.

    PubMed

    Knapp, Richard J; Goldenberg, Rachel; Shuck, Caroline; Cecil, Alicia; Watkins, Jeff; Miller, Cortland; Crites, Glenda; Malatynska, Ewa

    2002-04-05

    The present study tests the activity of nootropic drugs in a behavioral test linked to depression. This test measures the reduction of submissive behavior in a competition test as the relative success of two food-restricted rats to gain access to a feeder. Nootropic drugs tested include piracetam (2-oxo-1-pyrrolidineacetamide), aniracetam (1-(4-methoxybenzoyl)-2-pyrrolidinone), the Ampakine, Ampalex, 1-(quinoxalin-6-ylcarbonyl)piperidine, and analogs were compared to the antidepressants, fluoxetine ((+/-)-N-methyl-gamma-(4-[trifluoromethyl]phenoxy)-benzenepropanamine) and desimpramine (5H-dibenz[b,f]azepine-5-propanamine, 10,11-dihydro-N-methyl-, monohydrochloride), while the anxiolytic diazepam (7-chloro-1-methyl-5-phenyl-3H-1,4-benzodiazepin-2(1H)-one) served as a control. Drugs were given intraperitoneally for 3 weeks. The antidepressant and nootropic drugs reduced submissive behavior over time. The effect was dose dependent as measured for fluoxetine and Ampakines. The reduction of submissive behavior by Ampakines gradually faded after cessation of treatment and had a more rapid onset of activity (during the 1st week of treatment) than fluoxetine (after 2 weeks). The results suggest that Ampakines may have antidepressant activity. The potential of depression treatment with memory-enhancing drugs is hypothesized and the link between cognition and depression is discussed.

  5. Enhanced Activity of Supported Ni Catalysts Promoted by Pt for Rapid Reduction of Aromatic Nitro Compounds.

    PubMed

    Shang, Huishan; Pan, Kecheng; Zhang, Lu; Zhang, Bing; Xiang, Xu

    2016-06-04

    To improve the activities of non-noble metal catalysts is highly desirable and valuable to the reduced use of noble metal resources. In this work, the supported nickel (Ni) and nickel-platinum (NiPt) nanocatalysts were derived from a layered double hydroxide/carbon composite precursor. The catalysts were characterized and the role of Pt was analysed using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDS) mapping, and X-ray photoelectron spectroscopy (XPS) techniques. The Ni(2+) was reduced to metallic Ni⁰ via a self-reduction way utilizing the carbon as a reducing agent. The average sizes of the Ni particles in the NiPt catalysts were smaller than that in the supported Ni catalyst. The electronic structure of Ni was affected by the incorporation of Pt. The optimal NiPt catalysts exhibited remarkably improved activity toward the reduction of nitrophenol, which has an apparent rate constant (Ka) of 18.82 × 10(-3) s(-1), 6.2 times larger than that of Ni catalyst and also larger than most of the reported values of noble-metal and bimetallic catalysts. The enhanced activity could be ascribed to the modification to the electronic structure of Ni by Pt and the effect of exposed crystal planes.

  6. Enhancing oxygen reduction reaction activity of Pt-shelled catalysts via subsurface alloying.

    PubMed

    Cheng, Daojian; Qiu, Xiangguo; Yu, Haiyan

    2014-10-14

    Despite remarkable efforts have been put into the field of Pt-shelled catalysts containing an atomically thin Pt surface layer for the oxygen reduction reaction (ORR) in the last decade, further development of new Pt-shelled catalysts is still necessary. Here, a new set of Pt-shelled catalysts by subsurface alloying with early transition metals such as Mn and Fe is predicted to be a good candidate for the ORR by using density functional theory (DFT) calculations. Trends in oxygen reduction activity of Pt-alloy catalysts are determined with calculations of oxygen binding by using the slab and cluster models. It is found that the subsurface alloys by the incorporation of submonolayer M (M = Mn and Fe) into Pt(111) in the slab model result in the enhancement of ORR activity, compared with the well-known Pt(111)-skin-M, pure Pt, and Pt3M alloy catalysts. For the cluster model, the Pt12Mn and Pt12Fe clusters are also found to be the optimal catalysts for the ORR. It is expected that this work can open up new opportunities for enhancing the ORR activity of Pt-alloy catalysts by subsurface alloying.

  7. Activity reductions in perirhinal cortex predict conceptual priming and familiarity-based recognition.

    PubMed

    Wang, Wei-Chun; Ranganath, Charan; Yonelinas, Andrew P

    2014-01-01

    Although it is well established that regions in the medial temporal lobes are critical for explicit memory, recent work has suggested that one medial temporal lobe subregion--the perirhinal cortex (PRC)--may also support conceptual priming, a form of implicit memory. Here, we sought to investigate whether activity reductions in PRC, previously linked to familiarity-based recognition, might also support conceptual implicit memory retrieval. Using a free association priming task, the current study tested the prediction that PRC indexes conceptual priming independent of contributions from perceptual and response repetition. Participants first completed an incidental semantic encoding task outside of the MRI scanner. Next, they were scanned during performance of a free association priming task, followed by a recognition memory test. Results indicated successful conceptual priming was associated with decreased PRC activity, and that an overlapping region within the PRC also exhibited activity reductions that covaried with familiarity during the recognition memory test. Our results demonstrate that the PRC contributes to both conceptual priming and familiarity-based recognition, which may reflect a common role of this region in implicit and explicit memory retrieval.

  8. Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases.

    PubMed

    Bhagi-Damodaran, Ambika; Michael, Matthew A; Zhu, Qianhong; Reed, Julian; Sandoval, Braddock A; Mirts, Evan N; Chakraborty, Saumen; Moënne-Loccoz, Pierre; Zhang, Yong; Lu, Yi

    2017-03-01

    Haem-copper oxidase (HCO) catalyses the natural reduction of oxygen to water using a haem-copper centre. Despite decades of research on HCOs, the role of non-haem metal and the reason for nature's choice of copper over other metals such as iron remains unclear. Here, we use a biosynthetic model of HCO in myoglobin that selectively binds different non-haem metals to demonstrate 30-fold and 11-fold enhancements in the oxidase activity of Cu- and Fe-bound HCO mimics, respectively, as compared with Zn-bound mimics. Detailed electrochemical, kinetic and vibrational spectroscopic studies, in tandem with theoretical density functional theory calculations, demonstrate that the non-haem metal not only donates electrons to oxygen but also activates it for efficient O-O bond cleavage. Furthermore, the higher redox potential of copper and the enhanced weakening of the O-O bond from the higher electron density in the d orbital of copper are central to its higher oxidase activity over iron. This work resolves a long-standing question in bioenergetics, and renders a chemical-biological basis for the design of future oxygen-reduction catalysts.

  9. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    DOE PAGES

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; ...

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

  10. Activity reductions in perirhinal cortex predict conceptual priming and familiarity-based recognition

    PubMed Central

    Wang, Wei-chun; Ranganath, Charan; Yonelinas, Andrew P

    2013-01-01

    Although it is well established that regions in the medial temporal lobes are critical for explicit memory, recent work has suggested that one medial temporal lobe subregion – the perirhinal cortex (PRC) – may also support conceptual priming, a form of implicit memory. Here, we sought to investigate whether activity reductions in PRC, previously linked to familiarity-based recognition, might also support conceptual implicit memory retrieval. Using a free association priming task, the current study tested the prediction that PRC indexes conceptual priming independent of contributions from perceptual and response repetition. Participants first completed an incidental semantic encoding task outside of the MRI scanner. Next, they were scanned during performance of a free association priming task, followed by a recognition memory test. Results indicated successful conceptual priming was associated with decreased PRC activity, and that an overlapping region within the PRC also exhibited activity reductions that covaried with familiarity during the recognition memory test. Our results demonstrate that the PRC contributes to both conceptual priming and familiarity-based recognition, which may reflect a common role of this region in implicit and explicit memory retrieval. PMID:24157537

  11. Effects of Air/Nitrogen Cure on An Acetylene Terminated Quinoxaline Thermoset System

    DTIC Science & Technology

    1981-06-01

    AFWAL-TR-81-401 2 FILE Copy EFFECTS OF AIR/NITROGEN CURE ON AN ACETYLENE TERMINATED QUINOXALINE THERMOSET SYSTEM Polymer Branch Nonmetallic Materials...RECIPIENT’S CATALOG NUMBER AFWAL-TR- 81-4012 4. TITLE (and Subtitle) 5. TYPE OF REPORT & PERIOD COVERED Effects of Air/Nitrogen Cure on an Acetylene ...81-4012 SECTION I INTRODUCTION The Air Force has an interest in the development of acetylene - terminated (AT) resins as a new technology to form high

  12. Acetylene in breath: background levels and real-time elimination kinetics after smoking.

    PubMed

    Metsälä, M; Schmidt, F M; Skyttä, M; Vaittinen, O; Halonen, L

    2010-12-01

    We have measured the acetylene concentration in the exhaled breath of 40 volunteers (31 non-smokers, nine smokers) using near-infrared cavity ring-down spectroscopy. The acetylene levels were found to be the same as in ambient air for non-smokers, whereas elevated levels were observed for smokers. Real-time measurements with sub-second time resolution have been applied to measure the elimination kinetics of acetylene in breath after exposure to tobacco smoke. Three exponential time constants can be distinguished from the data and these can be used to define the residence times for different compartments, according to the multi-compartment model of the human body.

  13. 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.

  14. Active Vibration Control for Helicopter Interior Noise Reduction Using Power Minimization

    NASA Technical Reports Server (NTRS)

    Mendoza, J.; Chevva, K.; Sun, F.; Blanc, A.; Kim, S. B.

    2014-01-01

    This report describes work performed by United Technologies Research Center (UTRC) for NASA Langley Research Center (LaRC) under Contract NNL11AA06C. The objective of this program is to develop technology to reduce helicopter interior noise resulting from multiple gear meshing frequencies. A novel active vibration control approach called Minimum Actuation Power (MAP) is developed. MAP is an optimal control strategy that minimizes the total input power into a structure by monitoring and varying the input power of controlling sources. MAP control was implemented without explicit knowledge of the phasing and magnitude of the excitation sources by driving the real part of the input power from the controlling sources to zero. It is shown that this occurs when the total mechanical input power from the excitation and controlling sources is a minimum. MAP theory is developed for multiple excitation sources with arbitrary relative phasing for single or multiple discrete frequencies and controlled by a single or multiple controlling sources. Simulations and experimental results demonstrate the feasibility of MAP for structural vibration reduction of a realistic rotorcraft interior structure. MAP control resulted in significant average global vibration reduction of a single frequency and multiple frequency excitations with one controlling actuator. Simulations also demonstrate the potential effectiveness of the observed vibration reductions on interior radiated noise.

  15. Hybrid feedforward-feedback active noise reduction for hearing protection and communication.

    PubMed

    Ray, Laura R; Solbeck, Jason A; Streeter, Alexander D; Collier, Robert D

    2006-10-01

    A hybrid active noise reduction (ANR) architecture is presented and validated for a circumaural earcup and a communication earplug. The hybrid system combines source-independent feedback ANR with a Lyapunov-tuned leaky LMS filter (LyLMS) improving gain stability margins over feedforward ANR alone. In flat plate testing, the earcup demonstrates an overall C-weighted total noise reduction of 40 dB and 30-32 dB, respectively, for 50-800 Hz sum-of-tones noise and for aircraft or helicopter cockpit noise, improving low frequency (<100 Hz) performance by up to 15 dB over either control component acting individually. For the earplug, a filtered-X implementation of the LyLMS accommodates its nonconstant cancellation path gain. A fast time-domain identification method provides a high-fidelity, computationally efficient, infinite impulse response cancellation path model, which is used for both the filtered-X implementation and communication feedthrough. Insertion loss measurements made with a manikin show overall C-weighted total noise reduction provided by the ANR earplug of 46-48 dB for sum-of-tones 80-2000 Hz and 40-41 dB from 63 to 3000 Hz for UH-60 helicopter noise, with negligible degradation in attenuation during speech communication. For both hearing protectors, a stability metric improves by a factor of 2 to several orders of magnitude through hybrid ANR.

  16. Mechanisms of Active Aerodynamic Load Reduction on a Rotorcraft Fuselage With Rotor Effects

    NASA Technical Reports Server (NTRS)

    Schaeffler, Norman W.; Allan, Brian G.; Jenkins, Luther N.; Yao, Chung-Sheng; Bartram, Scott M.; Mace, W. Derry; Wong, Oliver D.; Tanner, Philip E.

    2016-01-01

    The reduction of the aerodynamic load that acts on a generic rotorcraft fuselage by the application of active flow control was investigated in a wind tunnel test conducted on an approximately 1/3-scale powered rotorcraft model simulating forward flight. The aerodynamic mechanisms that make these reductions, in both the drag and the download, possible were examined in detail through the use of the measured surface pressure distribution on the fuselage, velocity field measurements made in the wake directly behind the ramp of the fuselage and computational simulations. The fuselage tested was the ROBIN-mod7, which was equipped with a series of eight slots located on the ramp section through which flow control excitation was introduced. These slots were arranged in a U-shaped pattern located slightly downstream of the baseline separation line and parallel to it. The flow control excitation took the form of either synthetic jets, also known as zero-net-mass-flux blowing, and steady blowing. The same set of slots were used for both types of excitation. The differences between the two excitation types and between flow control excitation from different combinations of slots were examined. The flow control is shown to alter the size of the wake and its trajectory relative to the ramp and the tailboom and it is these changes to the wake that result in a reduction in the aerodynamic load.

  17. Risk reduction activities for an F-1-based advanced booster for NASA's Space Launch System

    NASA Astrophysics Data System (ADS)

    Crocker, A. M.; Doering, K. B.; Cook, S. A.; Meadows, R. G.; Lariviere, B. W.; Bachtel, F. D.

    For NASA's Space Launch System (SLS) Advanced Booster Engineering Demonstration and/or Risk Reduction (ABEDRR) procurement, Dynetics, Inc. and Pratt & Whitney Rocketdyne (PWR) formed a team to offer a wide-ranging set of risk reduction activities and full-scale, system-level demonstrations that support NASA's goal of enabling competition on an affordable booster that meets the evolved capabilities of the SLS. During the ABEDRR effort, the Dynetics Team will apply state-of-the-art manufacturing and processing techniques to the heritage F-1, resulting in a low recurring cost engine while retaining the benefits of Apollo-era experience. ABEDRR will use NASA test facilities to perform full-scale F-1 gas generator and powerpack hot-fire test campaigns for engine risk reduction. Dynetics will also fabricate and test a tank assembly to verify the structural design. The Dynetics Team is partnered with NASA through Space Act Agreements (SAAs) to maximize the expertise and capabilities applied to ABEDRR.

  18. Effects of a TiC substrate on the catalytic activity of Pt for NO reduction.

    PubMed

    Chu, Xingli; Fu, Zhaoming; Li, Shasha; Zhang, Xilin; Yang, Zongxian

    2016-05-11

    Density functional theory calculations are used to elucidate the catalytic properties of a Pt monolayer supported on a TiC(001) substrate (Pt/TiC) toward NO reduction. It is found that the compound system of Pt/TiC has a good stability due to the strong Pt-TiC interaction. The diverse dissociation paths (namely the direct dissociation mechanism and the dimeric mechanism) are investigated. The transition state searching calculations suggest that NO has strong diffusion ability and small activation energy for dissociation on the Pt/TiC. For NO reduction on the Pt/TiC surface, we have found that the direct dissociation mechanisms (NO + N + O → NO2 + N and NO + N + O → N2 + O + O) are easier with a smaller dissociation barrier than those on the Pt(111) surface; and the dimeric process (NO + NO → (NO)2 → N2O + O → N2 + O + O) is considered to be dominant or significant with even a lower energy barrier than that of the direct dissociation. The results show that Pt/TiC can serve as an efficient catalyst for NO reduction.

  19. Atomic Ordering Enhanced Electrocatalytic Activity of Nanoalloys for Oxygen Reduction Reaction

    SciTech Connect

    Loukrakpam, Rameshwori; Shan, Shiyao; Petkov, Valeri; Yang, Lefu; Luo, Jin; Zhong, Chuan-Jian

    2013-10-01

    For oxygen reduction reaction (ORR) over alloy electrocatalysts, the understanding of how the atomic arrangement of the metal species in the nanocatalysts is responsible for the catalytic enhancement is challenging for achieving better design and tailoring of nanoalloy catalysts. This paper reports results of an investigation of the atomic structures and the electrocatalytic activities of ternary and binary nanoalloys, aiming at revealing a fundamental insight into the unique atomic-scale structure-electrocatalytic activity relationship. PtIrCo catalyst and its binary counterparts (PtCo and PtIr) are chosen as a model system for this study. The effect of thermochemical treatment temperature on the atomic-scale structure of the catalysts was examined as a useful probe to the structure-activity correlation. The structural characterization of the binary and ternary nanoalloy catalysts was performed by combining surface sensitive techniques such as XPS and 3D atomic ordering sensitive techniques such as high-energy X-ray diffraction (HE-XRD) coupled to atomic pair distribution function (PDF) analysis (HE-XRD/PDFs) and computer simulations. The results show that the thermal treatment temperature tunes the nanoalloy’s atomic and chemical ordering in a different way depending on the chemical composition, leading to differences in the nanoalloy’s mass and specific activities. A unique structural tunability of the atomic ordering in a platinum-iridium-cobalt nanoalloy has been revealed for enhancing greatly the electrocatalytic activity toward oxygen reduction reaction, which has significant implication for rational design and nanoengineering of advanced catalysts for electrochemical energy conversion and storage.

  20. A Computational Study of BVI Noise Reduction Using Active Twist Control

    NASA Technical Reports Server (NTRS)

    Fogarty, David E.; Wilbur, Matthew L.; Sekula, Martin K.

    2010-01-01

    The results of a computational study examining the effects of active-twist control on blade-vortex interaction (BVI) noise using the Apache Active Twist Rotor are presented. The primary goal of this activity is to reduce BVI noise during a low-speed descent flight condition using active-twist control. Rotor aeroelastic behavior was modeled using the Comprehensive Analytical Model of Rotorcraft Aerodynamics and Dynamics code and the rotor noise was predicted using the acoustics code PSU-WOPWOP. The accuracy of the analysis was validated through comparisons with experimental acoustic data for the first generation Active Twist Rotor at an advance ratio of mu=0.14. The application of active-twist to the main rotor blade system consisted of harmonic actuation frequencies ranging from 2P to 5P, control phase angles from 0' to 360 , and tip-twist amplitudes ranging from 0.5 to 4.0 . The acoustic analysis was conducted for a single low-speed flight condition of advance ratio =0.14 and shaft angle-of-attack, c^=+6 , with BVI noise levels predicted on a flat plane of observers located 1.1 rotor diameters beneath the rotor. The results indicated reductions of up to 11dB in BVI noise using 1.25 tip-twist amplitude with negligible effects on 4P vertical hub shear.

  1. Activity Trends of Binary Silver Alloy Nanocatalysts for Oxygen Reduction Reaction in Alkaline Media.

    PubMed

    Wu, Xiaoqiang; Chen, Fuyi; Zhang, Nan; Lei, Yimin; Jin, Yachao; Qaseem, Adnan; Johnston, Roy L

    2017-02-02

    The electrocatalytic activity of Pt-based alloys exhibits a strong dependence on their electronic structures, but a relationship between electronic structure and oxygen reduction reaction (ORR) activity in Ag-based alloys is still not clear. Here, a vapor deposition based approach is reported for the preparation of Ag75 M25 (M = Cu, Co, Fe, and In) and Agx Cu100-x (x = 0, 25, 45, 50, 55, 75, 90, and 100) nanocatalysts and their electronic structures are determined by valence band spectra. The relationship of the d-band center and ORR activity exhibits volcano-shape behaviors, where the maximum catalytic activity is obtained for Ag75 Cu25 alloys. The ORR enhancement of Ag75 Cu25 alloys originates from the 0.12 eV upshift in d-band center relative to pure Ag, which is different from the downshift in the d-band center in Pt-based alloys. The activity trend for these Ag75 M25 alloys is in the order of Ag75 Cu25 > Ag75 Fe25 > Ag75 Co25 . These results provide an insight to understand the activity and stability enhancement of Ag75 Cu25 and Ag50 Cu50 catalysts by alloying.

  2. 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

  3. Decoupling in the line mixing of acetylene infrared Q branches

    NASA Technical Reports Server (NTRS)

    Pine, A. S.; Looney, J. P.

    1990-01-01

    A difference-frequency laser spectrometer was used to record the Q-branch profiles of the nu1 + nu5, nu3 + nu4, and nu2 + 2nu4 + nu5 Pi(u)-Sigma(g) combination bands in the 2.5 micron C-H stretch-bend region of acetylene. The experiment was carried out at pressures in the range of 1 to 500 Torr. It is shown that line mixing causes substantial deviation of collisionally overlapped Q-branch profiles from the independently additive superposition of Lorentzian line shapes. It is also found that the degree of line mixing is greatly reduced from that assuming all the broadening arises from rotationally inelastic collisions coupling Q-branch lines only to one another.

  4. 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.

  5. Detection of acetylene in the infrared spectrum of comet Hyakutake

    NASA Technical Reports Server (NTRS)

    Brooke, T. Y.; Tokunaga, A. T.; Weaver, H. A.; Crovisier, J.; Bockelee-Morvan, D.; Crisp, D.

    1996-01-01

    Comets are rich in volatile materials, of which roughly 80% (by number) are water molecules. Considerable progress is being made in identifying the other volatile species, the abundances of which should enable us to determine whether comets formed primarily from ice-covered interstellar grains, or from material that was chemically processed in the early solar nebula. Here we report the detection of acetylene (C2H2) in the infrared spectrum of comet C/1996 B2 (Hyakutake). The estimated abundance is 0.3-0.9%, relative to water, which is comparable to the predicted solid-phase abundance in cold interstellar clouds. This suggests that the volatiles in comet Hyakotake may have come from ice-covered interstellar grains, rather than material processed in the accretion disk out of which the Solar System formed.

  6. 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.

  7. 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.

  8. Organogermanium Chemistry: Germacyclobutanes and digermane Additions to Acetylenes

    SciTech Connect

    Chubb, Andrew Michael

    2003-01-01

    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.

  9. Targeting Reductions in Sitting Time to Increase Physical Activity and Improve Health.

    PubMed

    Keadle, Sarah K; Conroy, David E; Buman, Matthew P; Dunstan, David W; Matthews, Charles E

    2017-03-08

    New evidence suggests that reductions in sedentary behavior may increase physical activity and improve health. These findings point to new behavioral targets for intervention and new ways to think about intervening to increase overall physical activity in the population. This report provides a knowledge update reflecting the rapid accumulation of new evidence related to sedentary behavior and health among adults. Recent observational studies suggest that leveraging the time-inverse relationship between sedentary and active behaviors by replacing sitting with standing, light or moderate-intensity activity can have important health benefits, particularly among less active adults. Clinical studies are providing evidence of the probable physiologic mechanisms underlying these associations, as well as insights into the cardiometabolic impact of breaking up and reducing sedentary behavior. In contrast to the well-established behavioral theories that guide the development and dissemination of evidence-based interventions to increase moderate-vigorous intensity physical activity (MVPA), much less is known about how to reduce sedentary time in order to increase daily activities. It has become clear that the environmental, social and individual level-determinants for sedentary time are distinct from those linked to the adoption and maintenance of MVPA. As a result, novel intervention strategies that focus on sitting and lower intensity activities by leveraging the surrounding environment (e.g., workplace, school, home) as well as individual-level cues and habits of sedentary behavior are being tested to increase the potency of interventions designed to increase overall physical activity. Herein we summarize the solutions-oriented research across the behavioral research framework, with a focus on highlighting areas of synergy across disciplines and identifying gaps for future research.

  10. Vortex lattices and defect-mediated viscosity reduction in active liquids

    NASA Astrophysics Data System (ADS)

    Slomka, Jonasz; Dunkel, Jorn

    2016-11-01

    Generic pattern-formation and viscosity-reduction mechanisms in active fluids are investigated using a generalized Navier-Stokes model that captures the experimentally observed bulk vortex dynamics in microbial suspensions. We present exact analytical solutions including stress-free vortex lattices and introduce a computational framework that allows the efficient treatment of previously intractable higher-order shear boundary conditions. Large-scale parameter scans identify the conditions for spontaneous flow symmetry breaking, defect-mediated low-viscosity phases and negative-viscosity states amenable to energy harvesting in confined suspensions. The theory uses only generic assumptions about the symmetries and long-wavelength structure of active stress tensors, suggesting that inviscid phases may be achievable in a broad class of non-equilibrium fluids by tuning confinement geometry and pattern scale selection.

  11. Porous Dendritic Platinum Nanotubes with Extremely High Activity and Stability for Oxygen Reduction Reaction

    PubMed Central

    Zhang, Gaixia; Sun, Shuhui; Cai, Mei; Zhang, Yong; Li, Ruying; Sun, Xueliang

    2013-01-01

    Controlling the morphology of Pt nanostructures can provide opportunities to greatly increase their activity and stability. Porous dendritic Pt nanotubes were successfully synthesized by a facile, cost-effective aqueous solution method at room temperature in large scale. These unique structures are porous, hollow, hierarchical, and single crystalline, which not only gives them a large surface area with high catalyst utilization, but also improves mass transport and gas diffusion. These novel Pt structures exhibited significantly improved catalytic activity (4.4 fold) for oxygen reduction reaction (ORR) and greatly enhanced durability (6.1 fold) over that of the state-of-the-art commercial Pt/C catalyst. This work provides a promising approach to the design of highly efficient next-generation electrocatalysts. PMID:23524665

  12. New mechanistically based model for predicting reduction of biosolids waste by ozonation of return activated sludge.

    PubMed

    Isazadeh, Siavash; Feng, Min; Urbina Rivas, Luis Enrique; Frigon, Dominic

    2014-04-15

    Two pilot-scale activated sludge reactors were operated for 98 days to provide the necessary data to develop and validate a new mathematical model predicting the reduction of biosolids production by ozonation of the return activated sludge (RAS). Three ozone doses were tested during the study. In addition to the pilot-scale study, laboratory-scale experiments were conducted with mixed liquor suspended solids and with pure cultures to parameterize the biomass inactivation process during exposure to ozone. The experiments revealed that biomass inactivation occurred even at the lowest doses, but that it was not associated with extensive COD solubilization. For validation, the model was used to simulate the temporal dynamics of the pilot-scale operational data. Increasing the description accuracy of the inactivation process improved the precision of the model in predicting the operational data.

  13. Enhanced oxygen reduction activity and solid oxide fuel cell performance with a nanoparticles-loaded cathode.

    PubMed

    Zhang, Xiaomin; Liu, Li; Zhao, Zhe; Tu, Baofeng; Ou, Dingrong; Cui, Daan; Wei, Xuming; Chen, Xiaobo; Cheng, Mojie

    2015-03-11

    Reluctant oxygen-reduction-reaction (ORR) activity has been a long-standing challenge limiting cell performance for solid oxide fuel cells (SOFCs) in both centralized and distributed power applications. We report here that this challenge has been tackled with coloading of (La,Sr)MnO3 (LSM) and Y2O3 stabilized zirconia (YSZ) nanoparticles within a porous YSZ framework. This design dramatically improves ORR activity, enhances fuel cell output (200-300% power improvement), and enables superior stability (no observed degradation within 500 h of operation) from 600 to 800 °C. The improved performance is attributed to the intimate contacts between nanoparticulate YSZ and LSM particles in the three-phase boundaries in the cathode.

  14. The Origin of the Catalytic Activity of a Metal Hydride in CO2 Reduction.

    PubMed

    Kato, Shunsuke; Matam, Santhosh Kumar; Kerger, Philipp; Bernard, Laetitia; Battaglia, Corsin; Vogel, Dirk; Rohwerder, Michael; Züttel, Andreas

    2016-05-10

    Atomic hydrogen on the surface of a metal with high hydrogen solubility is of particular interest for the hydrogenation of carbon dioxide. In a mixture of hydrogen and carbon dioxide, methane was markedly formed on the metal hydride ZrCoHx in the course of the hydrogen desorption and not on the pristine intermetallic. The surface analysis was performed by means of time-of-flight secondary ion mass spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy, for the in situ analysis. The aim was to elucidate the origin of the catalytic activity of the metal hydride. Since at the initial stage the dissociation of impinging hydrogen molecules is hindered by a high activation barrier of the oxidised surface, the atomic hydrogen flux from the metal hydride is crucial for the reduction of carbon dioxide and surface oxides at interfacial sites.

  15. Aircraft panel with sensorless active sound power reduction capabilities through virtual mechanical impedances

    NASA Astrophysics Data System (ADS)

    Boulandet, R.; Michau, M.; Micheau, P.; Berry, A.

    2016-01-01

    This paper deals with an active structural acoustic control approach to reduce the transmission of tonal noise in aircraft cabins. The focus is on the practical implementation of the virtual mechanical impedances method by using sensoriactuators instead of conventional control units composed of separate sensors and actuators. The experimental setup includes two sensoriactuators developed from the electrodynamic inertial exciter and distributed over an aircraft trim panel which is subject to a time-harmonic diffuse sound field. The target mechanical impedances are first defined by solving a linear optimization problem from sound power measurements before being applied to the test panel using a complex envelope controller. Measured data are compared to results obtained with sensor-actuator pairs consisting of an accelerometer and an inertial exciter, particularly as regards sound power reduction. It is shown that the two types of control unit provide similar performance, and that here virtual impedance control stands apart from conventional active damping. In particular, it is clear from this study that extra vibrational energy must be provided by the actuators for optimal sound power reduction, mainly due to the high structural damping in the aircraft trim panel. Concluding remarks on the benefits of using these electrodynamic sensoriactuators to control tonal disturbances are also provided.

  16. RF probe recovery time reduction with a novel active ringing suppression circuit

    PubMed Central

    Peshkovsky, A.S.; Forguez, J.; Cerioni, L.; Pusiol, D.J.

    2005-01-01

    A simple Q-damper device for active probe recovery time reduction is introduced along with a straightforward technique for the circuit's component value optimization. The device is inductively coupled to a probe through a coupling transformer positioned away from the main coil, which makes the design independent of the coil type being used. The Q-damper is a tuned circuit, which is resonant at the same frequency as the probe and can be actively interrupted. When the circuit is interrupted, it is detuned and, thereby, is uncoupled from the probe, which operates normally. Turning the device on leads to re-coupling of the circuits and causes splitting of the probe's resonance line, which can be observed through its drive port. A resistance of an appropriate value is introduced into the Q-damper circuit, resulting in smoothing of the resonance splitting into one broad line, representing the coupled system's low-Q state, in which the energy stored in the main coil is efficiently dissipated. The circuit's component values are optimized by monitoring the shape of this low-Q state. Probe recovery time reduction by, approximately, an order of magnitude has been obtained with this device. Application of the device during an NQR experiment led to an increase in the signal-to-noise ratio by a factor of 4.9. PMID:16111906

  17. Classic Maya civilization collapse associated with reduction in tropical cyclone activity

    NASA Astrophysics Data System (ADS)

    Medina, M. A.; Polanco-Martinez, J. M.; Lases-Hernández, F.; Bradley, R. S.; Burns, S. J.

    2013-12-01

    In light of the increased destructiveness of tropical cyclones observed over recent decades one might assume that an increase and not a decrease in tropical cyclone activity would lead to societal stress and perhaps collapse of ancient cultures. In this study we present evidence that a reduction in the frequency and intensity of tropical Atlantic cyclones could have contributed to the collapse of the Maya civilization during the Terminal Classic Period (TCP, AD. 800-950). Statistical comparisons of a quantitative precipitation record from the Yucatan Peninsula (YP) Maya lowlands, based on the stalagmite known as Chaac (after the Mayan God of rain and agriculture), relative to environmental proxy records of El Niño/Southern Oscillation (ENSO), tropical Atlantic sea surface temperatures (SSTs), and tropical Atlantic cyclone counts, suggest that these records share significant coherent variability during the TCP and that summer rainfall reductions between 30 and 50% in the Maya lowlands occurred in association with decreased Atlantic tropical cyclones. Analysis of modern instrumental hydrological data suggests cyclone rainfall contributions to the YP equivalent to the range of rainfall deficits associated with decreased tropical cyclone activity during the collapse of the Maya civilization. Cyclone driven precipitation variability during the TCP, implies that climate change may have triggered Maya civilization collapse via freshwater scarcity for domestic use without significant detriment to agriculture. Pyramid in Tikal, the most prominent Maya Kingdom that collapsed during the Terminal Classic Period (circa C.E. 800-950) Rainfall feeding stalagmites inside Rio Secreto cave system, Yucatan, Mexico.

  18. Porous Silica-Coated Gold Nanorods: A Highly Active Catalyst for the Reduction of 4-Nitrophenol.

    PubMed

    Mohanta, Jagdeep; Satapathy, Smithsagar; Si, Satyabrata

    2016-02-03

    The successful coating of thin porous silica layers of various thicknesses [(10±1), (12±1), and (14±1) nm] on cetyl trimethylammonium bromide (CTAB) capped gold nanorods was achieved through a modified Stöber procedure. The resulting material was applied as a novel catalyst for the reduction of 4-nitrophenol. The catalytic activities of the gold nanorods increased up to eight times after coating with a layer of porous silica and the reaction followed a zero-order kinetics, having a rate constant as high as 2.92×10(-1) mol L(-1) min(-1). The spectral changes during the reduction reaction of 4-nitrophenol were observed within a very short span of time and a complete conversion to 4-aminophenol occured within 5-6 mins, including the induction period of ≈2 mins. The reusability of the catalyst was studied by running the catalytic reaction during five consecutive cycles with good efficiency without destroying the nanostructure. The methodology can be effectively applied to the development of composite catalysts with highly enhanced catalytic activity.

  19. Ti(3+)-Promoted High Oxygen-Reduction Activity of Pd Nanodots Supported by Black Titania Nanobelts.

    PubMed

    Yuan, Xiaotao; Wang, Xin; Liu, Xiangye; Ge, Hongxin; Yin, Guoheng; Dong, Chenlong; Huang, Fuqiang

    2016-10-04

    One-dimensional nanocrystals favoring efficient charge transfer have attracted enormous attentions, and conductive nanobelts of black titania with a unique band structure and high electrical conductivity would be interestingly used in electrocatalysis. Here, Pd nanodots supported by two kinds of black titania, the oxygen-deficient titania (TiO2-x) and nitrogen-doped titania (TiO2-x:N), were synthesized as efficient composite catalysts for oxygen-reduction reaction (ORR). These composite catalysts show improved catalytic activity with lower overpotential and higher limited current, compared to the Pd nanodots supported on the white titania (Pd/TiO2). The improved activity is attributed to the relatively high conductivity of black titania nanobelts for efficient charge transfer (CT) between Ti(3+) species and Pd nanodots. The CT process enhances the strong metal-support interaction (SMSI) between Pd and TiO2, which lowers the absorption energy of O2 on Pd and makes it more suitable for oxygen reduction. Because of the stronger interaction between Pd and support, the Pd/TiO2-x:N also shows excellent durability and immunity to methanol poisoning.

  20. RF probe recovery time reduction with a novel active ringing suppression circuit.

    PubMed

    Peshkovsky, A S; Forguez, J; Cerioni, L; Pusiol, D J

    2005-11-01

    A simple Q-damper device for active probe recovery time reduction is introduced along with a straightforward technique for the circuit's component value optimization. The device is inductively coupled to a probe through a coupling transformer positioned away from the main coil, which makes the design independent of the coil type being used. The Q-damper is a tuned circuit, which is resonant at the same frequency as the probe and can be actively interrupted. When the circuit is interrupted, it is detuned and, thereby, is uncoupled from the probe, which operates normally. Turning the device on leads to re-coupling of the circuits and causes splitting of the probe's resonance line, which can be observed through its drive port. A resistance of an appropriate value is introduced into the Q-damper circuit, resulting in smoothing of the resonance splitting into one broad line, representing the coupled system's low-Q state, in which the energy stored in the main coil is efficiently dissipated. The circuit's component values are optimized by monitoring the shape of this low-Q state. Probe recovery time reduction by, approximately, an order of magnitude has been obtained with this device. Application of the device during an NQR experiment led to an increase in the signal-to-noise ratio by a factor of 4.9.

  1. Binary iron-carbon nanoparticle synthesis in photolysis of Fe(CO)5 with methane and acetylene

    NASA Astrophysics Data System (ADS)

    Eremin, A. V.; Gurentsov, E. V.; Mikheyeva, E. Yu; Musikhin, S. A.

    2016-11-01

    The experimental investigation of iron-carbon nanoparticles synthesis by joint laser photolysis of iron pentacarbonyl in the mixture with methane or acetylene has been carried out. The radiation source used for photo-dissociation of precursors was a pulsed Nd:Yag laser operated at a wavelength of 266 nm. Under uv radiation the molecules of Fe(CO)5 decomposed, forming atomic iron vapor and unsaturated carbonyls at well-known and readily controllable parameters. The subsequent condensation of supersaturated metal vapor resulted in small iron clusters and nanoparticles formation. It was assumed that the active catalytic surface of metal nanoparticles could activate the hydrocarbon molecules up to carbon layer formation on their surface. The growth process of the nanoparticles was observed by a method of laser light extinction. Additionally nanoparticle samples were investigated by a transmission electron microscope. The particle sizes were measured by microphotographs treatment. The sizes of synthesized particles from methane-iron-pentacarbonyl mixture were found to be in a range of 4-16 nm with a count median diameter of 8.9 nm and standard deviation of 1.13. These particles consisted of iron oxide without any carbon content. The particles formed in photolysis of acetylene-iron-pentacarbonyl mixture had the sizes of 3-7 nm with count median diameter of 4 nm and standard deviation of 1.28 and contained the essential amount of carbon. The iron cores were surrounded with a carbon shell.

  2. Reduction of beta-glucuronidase and nitroreductase activity by yoghurt in a murine colon cancer model.

    PubMed

    de Moreno de LeBlanc, A; Perdigón, G

    2005-04-01

    Yoghurt feeding inhibits induced colon cancer in mice. Several studies showed the immunomodulatory effect of yoghurt which can explain this inhibition. It is possible that yoghurt bacteria can also affect gut flora enzymes related to colon carcinogenesis as reported for other probiotics in different animal tumours. The aim of this work was to evaluate the role of yoghurt starter bacteria and their cell-free fermentation products on the reduction of procarcinogen enzyme activities (beta-glucuronidase and nitroreductase). Mice injected with 1,2-dimethylhydrazine (DMH) and fed with yoghurt were used for this study. Mice given milk or yoghurt supernatant (cell free extract) were used to evaluate if the yoghurt antitumour effect is due to the starter bacteria or other components released during fermentation, that could inhibit these enzymes. We determined that yoghurt by itself maintained enzymes activities similar or lower than non-treatment control group, and the enzyme activity was also lower than milk or yoghurt supernatant groups. DMH increased the activity of the enzymes. Mice injected with DMH and fed cyclically with yoghurt presented lower enzymes activities than the tumour control group. Feeding yoghurt decreased procarcinogenic enzyme levels in the large intestine contents of mice bearing colon tumour. The results of this study provide another mechanism by which yoghurt starter bacteria interact with the large intestine of the mice and prevent colon cancer.

  3. Tau reduction prevents Aβ-induced axonal transport deficits by blocking activation of GSK3β

    PubMed Central

    Xu, Jordan C.; Fomenko, Vira; Miyamoto, Takashi; Suberbielle, Elsa; Knox, Joseph A.; Ho, Kaitlyn; Kim, Daniel H.; Yu, Gui-Qiu

    2015-01-01

    Axonal transport deficits in Alzheimer’s disease (AD) are attributed to amyloid β (Aβ) peptides and pathological forms of the microtubule-associated protein tau. Genetic ablation of tau prevents neuronal overexcitation and axonal transport deficits caused by recombinant Aβ oligomers. Relevance of these findings to naturally secreted Aβ and mechanisms underlying tau’s enabling effect are unknown. Here we demonstrate deficits in anterograde axonal transport of mitochondria in primary neurons from transgenic mice expressing familial AD-linked forms of human amyloid precursor protein. We show that these deficits depend on Aβ1–42 production and are prevented by tau reduction. The copathogenic effect of tau did not depend on its microtubule binding, interactions with Fyn, or potential role in neuronal development. Inhibition of neuronal activity, N-methyl-d-aspartate receptor function, or glycogen synthase kinase 3β (GSK3β) activity or expression also abolished Aβ-induced transport deficits. Tau ablation prevented Aβ-induced GSK3β activation. Thus, tau allows Aβ oligomers to inhibit axonal transport through activation of GSK3β, possibly by facilitating aberrant neuronal activity. PMID:25963821

  4. Effect of microstructure of nitrogen-doped graphene on oxygen reduction activity in fuel cells.

    PubMed

    Zhang, Lipeng; Niu, Jianbing; Dai, Liming; Xia, Zhenhai

    2012-05-15

    The development of fuel cells as clean-energy technologies is largely limited by the prohibitive cost of the noble-metal catalysts needed for catalyzing the oxygen reduction reaction (ORR) in fuel cells. A fundamental understanding of catalyst design principle that links material structures to the catalytic activity can accelerate the search for highly active and abundant nonmetal catalysts to replace platinum. Here, we present a first-principles study of ORR on nitrogen-doped graphene in acidic environment. We demonstrate that the ORR activity primarily correlates to charge and spin densities of the graphene. The nitrogen doping and defects introduce high positive spin and/or charge densities that facilitate the ORR on graphene surface. The identified active sites are closely related to doping cluster size and dopant-defect interactions. Generally speaking, a large doping cluster size (number of N atoms >2) reduces the number of catalytic active sites per N atom. In combination with N clustering, Stone-Wales defects can strongly promote ORR. For four-electron transfer, the effective reversible potential ranges from 1.04 to 1.15 V/SHE, depending on the defects and cluster size. The catalytic properties of graphene could be optimized by introducing small N clusters in combination with material defects.

  5. Widespread reduction in sleep spindle activity in socially anxious children and adolescents.

    PubMed

    Wilhelm, Ines; Groch, Sabine; Preiss, Andrea; Walitza, Susanne; Huber, Reto

    2017-05-01

    Social anxiety disorder (SAD) is one of the most prevalent psychiatric diseases typically emerging during childhood and adolescence. Biological vulnerabilities such as a protracted maturation of prefrontal cortex functioning together with heightened reactivity of the limbic system leading to increased emotional reactivity are discussed as factors contributing to the emergence and maintenance of SAD. Sleep slow wave activity (SWA, 0.75-4.5 Hz) and sleep spindle activity (9-16 Hz) reflect processes of brain maturation and emotion regulation. We used high-density electroencephalography to characterize sleep SWA and spindle activity and their relationship to emotional reactivity in children and adolescents suffering from SAD and healthy controls (HC). Subjectively rated arousal was assessed using an emotional picture-word association task. SWA did not differ between socially anxious and healthy participants. We found a widespread reduction in fast spindle activity (13-16 Hz) in SAD patients compared to HC. SAD patients rated negative stimuli to be more arousing and these arousal ratings were negatively correlated with fast spindle activity. These results suggest electrophysiological alterations that are evident at an early stage of psychopathology and that are closely linked to one core symptom of anxiety disorders such as increased emotional reactivity. The role of disturbed GABAergic neurotransmission is discussed as an underlying factor.

  6. Microtubules Accelerate the Kinase Activity of Aurora-B by a Reduction in Dimensionality

    PubMed Central

    Noujaim, Michael; Bechstedt, Susanne; Wieczorek, Michal; Brouhard, Gary J.

    2014-01-01

    Aurora-B is the kinase subunit of the Chromosome Passenger Complex (CPC), a key regulator of mitotic progression that corrects improper kinetochore attachments and establishes the spindle midzone. Recent work has demonstrated that the CPC is a microtubule-associated protein complex and that microtubules are able to activate the CPC by contributing to Aurora-B auto-phosphorylation in trans. Aurora-B activation is thought to occur when the local concentration of Aurora-B is high, as occurs when Aurora-B is enriched at centromeres. It is not clear, however, whether distributed binding to large structures such as microtubules would increase the local concentration of Aurora-B. Here we show that microtubules accelerate the kinase activity of Aurora-B by a “reduction in dimensionality.” We find that microtubules increase the kinase activity of Aurora-B toward microtubule-associated substrates while reducing the phosphorylation levels of substrates not associated to microtubules. Using the single molecule assay for microtubule-associated proteins, we show that a minimal CPC construct binds to microtubules and diffuses in a one-dimensional (1D) random walk. The binding of Aurora-B to microtubules is salt-dependent and requires the C-terminal tails of tubulin, indicating that the interaction is electrostatic. We show that the rate of Aurora-B auto-activation is faster with increasing concentrations of microtubules. Finally, we demonstrate that microtubules lose their ability to stimulate Aurora-B when their C-terminal tails are removed by proteolysis. We propose a model in which microtubules act as scaffolds for the enzymatic activity of Aurora-B. The scaffolding activity of microtubules enables rapid Aurora-B activation and efficient phosphorylation of microtubule-associated substrates. PMID:24498282

  7. Silyl-acetylene polymers for use as precursors to silicon carbide fibers

    SciTech Connect

    Meyer, M.K.

    1991-12-20

    The steps involved in production of silicon carbide fiber using silyl acetylene polymer precursors can be separated into four processing steps: polymer synthesis, fiber spinning, fiber crosslinking, and pyrolysis. Practical experimental considerations in each step are discussed.

  8. 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.

  9. Fluorinated 5- and 7-membered carbacycle motifs by reaction of difluorocarbene with acetylene ethers.

    PubMed

    Chia, Poh Wai; Bello, Davide; Slawin, Alexandra M Z; O'Hagan, David

    2013-03-18

    The reaction of acetylene ethers with difluorocarbene (CF(2)), generated from the Ruppert-Prakash reagent, unexpectedly gave rise to co-produced fluorinated bicyclic [2.1.1]-hex-2-ene and cyclohepta-1,4-diene ring products.

  10. INHIBITION OF ALKYLBENZENE BIODEGRADATION UNDER DENITRIFYING CONDITIONS BY USING THE ACETYLENE BLOCK TECHNIQUE

    EPA Science Inventory

    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 degr...

  11. Comparing denitrification estimates for a Texas estuary by using acetylene inhibition and membrane inlet mass spectrometry.

    PubMed

    Bernot, Melody J; Dodds, Walter K; Gardner, Wayne S; McCarthy, Mark J; Sobolev, Dmitri; Tank, Jennifer L

    2003-10-01

    Characterizing denitrification rates in aquatic ecosystems is essential to understanding how systems may respond to increased nutrient loading. Thus, it is important to ensure the precision and accuracy of the methods employed for measuring denitrification rates. The acetylene (C2H2) inhibition method is a simple technique for estimating denitrification. However, potential problems, such as inhibition of nitrification and incomplete inhibition of nitrous oxide reduction, may influence rate estimates. Recently, membrane inlet mass spectrometry (MIMS) has been used to measure denitrification in aquatic systems. Comparable results were obtained with MIMS and C2H2 inhibition methods when chloramphenicol was added to C2H2 inhibition assay mixtures to inhibit new synthesis of denitrifying enzymes. Dissolved-oxygen profiles indicated that surface layers of sediment cores subjected to the MIMS flowthrough incubation remained oxic whereas cores incubated using the C2H2 inhibition methods did not. Analysis of the microbial assemblages before and after incubations indicated significant changes in the sediment surface populations during the long flowthrough incubation for MIMS analysis but not during the shorter incubation used for the C2H2 inhibition method. However, bacterial community changes were also small in MIMS cores at the oxygen transition zone where denitrification occurs. The C2H2 inhibition method with chloramphenicol addition, conducted over short incubation intervals, provides a cost-effective method for estimating denitrification, and rate estimates are comparable to those obtained by the MIMS method.

  12. A DFT+U study of acetylene selective hydrogenation on oxygen defective anatase (101) and rutile (110) TiO2 supported Pd4 cluster

    NASA Astrophysics Data System (ADS)

    Yang, Jie; Lv, Cun-Qin; Guo, Yong; Wang, Gui-Chang

    2012-03-01

    The reaction mechanisms for selective acetylene hydrogenation on three different supports, Pd4 cluster, oxygen defective anatase (101), and rutile (110) titania supported Pd4, cluster are studied using the density functional theory calculations with a Hubbard U correction (DFT+U). The present calculations show that the defect anatase support binds Pd4 cluster more strongly than that of rutile titania due to the existence of Ti3+ in anatase titania. Consequently, the binding energies of adsorbed species such as acetylene and ethylene on Pd4 cluster become weaker on anatase supported catalysts compared to the rutile supported Pd4 cluster. Anatase catalyst has higher selectivity of acetylene hydrogenation than rutile catalyst. On the one hand, the activation energies of ethylene formation are similar on the two catalysts, while they vary a lot on ethyl formation. The rutile supported Pd catalyst with lower activation energy is preferable for further hydrogenation. On the other hand, the relatively weak adsorption energy of ethylene is gained on anatase surface, which means it is easier for ethylene desorption, hence getting higher selectivity. For further understanding, the energy decomposition method and micro-kinetic analysis are also introduced.

  13. ESTIMATION OF MICROBIAL REDUCTIVE TRANSFORMATION RATES FOR CHLORINATED BENZENES AND PHENOLS USING A QUANTITATIVE STRUCTURE-ACTIVITY RELATIONSHIP APPROACH

    EPA Science Inventory

    A set of literature data was used to derive several quantitative structure-activity relationships (QSARs) to predict the rate constants for the microbial reductive dehalogenation of chlorinated aromatics. Dechlorination rate constants for 25 chloroaromatics were corrected for th...

  14. Reduction of adsorption capacity of coconut shell activated carbon for organic vapors due to moisture contents.

    PubMed

    Abiko, Hironobu; Furuse, Mitsuya; Takano, Tsuguo

    2010-01-01

    In occupational hygiene, activated carbon produced from coconut shell is a common adsorbent material for harmful substances including organic vapors due to its outstanding adsorption capacity and cost advantage. However, moisture adsorption of the carbon generally decreases the adsorption capacity for organic vapors. In a previous report, we prepared several coconut shell activated carbons which had been preconditioned by equilibration with moisture at different relative humidities and measured the breakthrough times for 6 kinds of organic vapor, in order to clarify the effect of preliminary moisture content in activated carbon on the adsorption capacity in detail. We found that the relative percent weight increase due to moisture adsorption of the carbon specimen had a quantitative effect, reducing the breakthrough time. In this report, we carried out further measurements of the effect of moisture content on the adsorption of 13 kinds of organic vapor, and investigated the relationship between moisture adsorption and the reduction of the breakthrough time of activated carbon specimens. We also applied the data to the Wood's breakthrough time estimation model which is an extension of the Wheeler-Jonas equation.

  15. Steps in reductive activation of the disulfide-generating enzyme Ero1p

    PubMed Central

    Heldman, Nimrod; Vonshak, Ohad; Sevier, Carolyn S; Vitu, Elvira; Mehlman, Tevie; Fass, Deborah

    2010-01-01

    Ero1p is the primary catalyst of disulfide bond formation in the yeast endoplasmic reticulum (ER). Ero1p contains a pair of essential disulfide bonds that participate directly in the electron transfer pathway from substrate thiol groups to oxygen. Remarkably, elimination of certain other Ero1p disulfides by mutation enhances enzyme activity. In particular, the C150A/C295A Ero1p mutant exhibits increased thiol oxidation in vitro and in vivo and interferes with redox homeostasis in yeast cells by hyperoxidizing the ER. Inhibitory disulfides of Ero1p are thus important for enzyme regulation. To visualize the differences between de-regulated and wild-type Ero1p, we determined the crystal structure of Ero1p C150A/C295A. The structure revealed local changes compared to the wild-type enzyme around the sites of mutation, but no conformational transitions within 25 Å of the active site were observed. To determine how the C150—C295 disulfide nonetheless participates in redox regulation of Ero1p, we analyzed using mass spectrometry the changes in Ero1p disulfide connectivity as a function of time after encounter with reducing substrates. We found that the C150—C295 disulfide sets a physiologically appropriate threshold for enzyme activation by guarding a key neighboring disulfide from reduction. This study illustrates the diverse and interconnected roles that disulfides can play in redox regulation of protein activity. PMID:20669236

  16. Experimental Study of Active Techniques for Blade/Vortex Interaction Noise Reduction

    NASA Astrophysics Data System (ADS)

    Kobiki, Noboru; Murashige, Atsushi; Tsuchihashi, Akihiko; Yamakawa, Eiichi

    This paper presents the experimental results of the effect of Higher Harmonic Control (HHC) and Active Flap on the Blade/Vortex Interaction (BVI) noise. Wind tunnel tests were performed with a 1-bladed rotor system to evaluate the simplified BVI phenomenon avoiding the complicated aerodynamic interference which is characteristically and inevitably caused by a multi-bladed rotor. Another merit to use this 1-bladed rotor system is that the several objective active techniques can be evaluated under the same condition installed in the same rotor system. The effects of the active techniques on the BVI noise reduction were evaluated comprehensively by the sound pressure, the blade/vortex miss distance obtained by Laser light Sheet (LLS), the blade surface pressure distribution and the tip vortex structure by Particle Image Velocimetry (PIV). The correlation among these quantities to describe the effect of the active techniques on the BVI conditions is well obtained. The experiments show that the blade/vortex miss distance is more dominant for BVI noise than the other two BVI governing factors, such as blade lift and vortex strength at the moment of BVI.

  17. Reduction of protein translation and activation of autophagy protect against PINK1 pathogenesis in Drosophila melanogaster.

    PubMed

    Liu, Song; Lu, Bingwei

    2010-12-09

    Mutations in PINK1 and Parkin cause familial, early onset Parkinson's disease. In Drosophila melanogaster, PINK1 and Parkin mutants show similar phenotypes, such as swollen and dysfunctional mitochondria, muscle degeneration, energy depletion, and dopaminergic (DA) neuron loss. We previously showed that PINK1 and Parkin genetically interact with the mitochondrial fusion/fission pathway, and PINK1 and Parkin were recently proposed to form a mitochondrial quality control system that involves mitophagy. However, the in vivo relationships among PINK1/Parkin function, mitochondrial fission/fusion, and autophagy remain unclear; and other cellular events critical for PINK1 pathogenesis remain to be identified. Here we show that PINK1 genetically interacted with the protein translation pathway. Enhanced translation through S6K activation significantly exacerbated PINK1 mutant phenotypes, whereas reduction of translation showed suppression. Induction of autophagy by Atg1 overexpression also rescued PINK1 mutant phenotypes, even in the presence of activated S6K. Downregulation of translation and activation of autophagy were already manifested in PINK1 mutant, suggesting that they represent compensatory cellular responses to mitochondrial dysfunction caused by PINK1 inactivation, presumably serving to conserve energy. Interestingly, the enhanced PINK1 mutant phenotype in the presence of activated S6K could be fully rescued by Parkin, apparently in an autophagy-independent manner. Our results reveal complex cellular responses to PINK1 inactivation and suggest novel therapeutic strategies through manipulation of the compensatory responses.

  18. The adsorption of acetylene on rhodium-modified colloidal silver, a surface-enhanced Raman study

    NASA Astrophysics Data System (ADS)

    Feilchenfeld, Hannah; Luckier, Miguel; Efron, Leah; Willner, Bilha

    Surface-enhanced Raman scattering (SERS) from molecules adsorbed on rhodium-modified colloidal silver particles is reported for the first time. Deposition of thin layers of metallic rhodium on the silver surface led to fast aggregation of the sol and to modifications of its SERS spectrum. An intense new band, assigned to the RhO stretching vibration of citrate ions bound to rhodium sites, appeared at 530 cm -1 in the Raman spectrum after rhodium addition to the suspension. The spectra of acetylene adsorbed on both unmodified silver particles and silver modified by an overlayer of rhodium indicated that acetylene displaced the citrate ions from their adsorption sites. All acetylene spectra were characterized by weak bands at 1990, 2050 and 2150 cm -1 assigned to σ π-complexes between acetylene and silver, by a silver acetylide peak at 1800 cm -1 and by an intense band at 1550 cm -1 due to C=C containing species formed on the surface. However, on the rhodium-modified colloid an additional band, attributed to acetylene σ π-bound to rhodium sites, was observed at 1910-1920 cm -1. The intensity of the new band was a direct function of the amount of rhodium deposited on the silver. It increased immediately after acetylene adsorption, and later slowly diminished, while simultaneously the 1550 cm -1 peak became more important. This time evolution was ascribed to a reaction taking place on the surface.

  19. 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

  20. Phosphine-mediated cascade reaction of azides with MBH-acetates of acetylenic aldehydes to substituted pyrroles: a facile access to N-fused pyrrolo-heterocycles.

    PubMed

    Reddy, Chada Raji; Reddy, Motatipally Damoder; Srikanth, Boinapally

    2012-06-07

    One-pot synthesis of substituted pyrroles by a cascade reaction of azides with Morita-Baylis-Hillman acetates of acetylenic aldehydes is described and the reaction is efficiently mediated by triphenyl phosphine at room temperature. Sodium azide is successfully used to provide N-unsubstituted pyrroles, while alkyl azides afforded the corresponding N-alkylated pyrroles through a sequence of allylic substitution/azide reduction/cycloisomerization reactions. The obtained products have provided a new entry to indolizino indoles, pyrrolo isoquinolines and 8-oxo-5,6,7,8-tetrahydroindolizine.

  1. Glycine cleavage system in ketotic hyperglycinemia: a reduction of H-protein activity.

    PubMed

    Hayasaka, K; Narisawa, K; Satoh, T; Tateda, H; Metoki, K; Tada, K; Hiraga, K; Aoki, T; Kawakami, T; Akamatsu, H; Matsuo, N

    1982-01-01

    Glycine cleavage activity was compared in the livers from three cases of ketotic hyperglycinemia (two cases of propionic acidemia and one case of methylmalonic acidemia) and three controls. In one case of propionic acidemia, glycine cleavage activity (5.2 nmole/mg protein/hr) was normal in the liver obtained at biopsy when the patient was well controlled by the treatment with low protein diet (0.8 g/kg/day) and the level of serum glycine was lowered to normal. In the two other cases of ketotic hyperglycinemia, glycine cleavage activity was significantly reduced in the liver obtained at autopsy when the patients died in the state of metabolic acidosis. Its activity in the liver of one case of propionic acidemia (0.7 nmole/mg protein/hr) was 6-26% of that in controls (2.7-10.8 nmole/mg protein/hr), and 2-7% in the case of methylmalonic acidemia (0.2 nmole/mg protein/hr). Analysing of the individual components of the glycine cleavage system, a marked decrease in the activity of H-protein was revealed in the livers of the both patients; it (0.2 nmole/mg protein/hr) was only 3-4% of that in controls (4.9-6.3 nmole/mg Protein/hr). These findings suggest that the reduction of the glycine cleavage system in the liver of ketotic hyperglycinemia occurs secondarily as speculated previously and is caused mainly by a decrease of H-protein activity.

  2. Optimization of actuator and sensor positions for an active noise reduction system

    NASA Astrophysics Data System (ADS)

    Böhme, Sten; Sachau, Delf; Breitbach, Harald

    2006-03-01

    Different systems and strategies have been invented in order to reduce the noise level inside the fuselage of aircrafts. First of all passive methods like adding materials with high damping or vibration absorbing qualities were used. Due to mass reduction as a major aspect in aircraft design a lot of research is focused on active noise reduction (ANR). The level of attenuation gained by an ANR - system is depending on several attributes of the system like hardware and software in use. Another important parameter, which has a great impact on the performance, is the positioning of the actuators and sensors. Because of the high number of possible arrangements of actuators and sensors in three dimensional spaces, it is almost impossible to determine the optimal positions by experimental work. Therefore numerical optimization is applied. In this paper a hybrid evolutionary algorithm is introduced for the calculation of appropriate configurations for a fixed number of actuator and sensors out of a high number of possible positions for an ANR - system within a military aircraft. The presented COSA - algorithm (cooperative simulated annealing) connects qualities of two well known optimization algorithms, the simulated annealing (SA) and genetic algorithm (GA). A general description of the algorithm and the acoustical basics will be provided together with an overview of the results.

  3. Reductive dehalogenation activity of indigenous microorganism in sediments of the Hackensack River, New Jersey.

    PubMed

    Sohn, Seo Yean; Häggblom, Max M

    2016-07-01

    Organohalogen pollutants are of concern in many river and estuarine environments, such as the New York-New Jersey Harbor estuary and its tributaries. The Hackensack River is contaminated with various metals, hydrocarbons and halogenated organics, including polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins. In order to examine the potential for microbial reductive dechlorination by indigenous microorganisms, sediment samples were collected from five different estuarine locations along the Hackensack River. Hexachlorobenzene (HCB), hexabromobenzene (HBB), and pentachloroaniline (PCA) were selected as model organohalogen pollutants to assess anaerobic dehalogenating potential. Dechlorinating activity of HCB and PCA was observed in sediment microcosms for all sampling sites. HCB was dechlorinated via pentachlorobenzene (PeCB) and trichlorobenzene (TriCB) to dichlorobenzene (DCB). PCA was dechlorinated via tetrachloroaniline (TeCA), trichloroanilines (TriCA), and dichloroanilines (DCA) to monochloroaniline (MCA). No HBB debromination was observed over 12 months of incubation. However, with HCB as a co-substrate slow HBB debromination was observed with production of tetrabromobenzene (TeBB) and tribromobenzene (TriBB). Chloroflexi specific 16S rRNA gene PCR-DGGE followed by sequence analysis detected Dehalococcoides species in sediments of the freshwater location, but not in the estuarine site. Analysis targeting 12 putative reductive dehalogenase (rdh) genes showed that these were enriched concomitant with HCB or PCA dechlorination in freshwater sediment microcosms.

  4. Electrocatalytic activities of alkyne-functionalized copper nanoparticles in oxygen reduction in alkaline media

    NASA Astrophysics Data System (ADS)

    Liu, Ke; Song, Yang; Chen, Shaowei

    2014-12-01

    Stable alkyne-capped copper nanoparticles were prepared by chemical reduction of copper acetate with sodium borohydride in the presence of alkyne ligands. Transmission electron microscopic measurements showed that nanoparticles were well dispersed with a diameter in the range of 4-6 nm. FTIR and photoluminescence spectroscopic measurements confirmed the successful attachment of the alkyne ligands onto the nanoparticle surface most likely forming Cu-Ctbnd interfacial bonds. XPS measurements indicated the formation of a small amount of CuO in the nanoparticles with a satellite peak where the binding energy red-shifted with increasing Cu(II) concentration. Cu2O was also detected in the nanoparticles. Similar results were observed with commercial CuO nanoparticles. Electrochemical studies showed that the as-prepared alkyne-capped copper nanoparticles exhibited apparent electrocatalytic activity in oxygen reduction in alkaline media, a performance that was markedly better than those reported earlier with poly- or single-crystalline copper electrodes; and the fraction of peroxides in the final products decreased with decreasing concentration of oxide components in the nanoparticles.

  5. Active Aerodynamic Load Reduction on a Rotorcraft Fuselage With Rotor Effects: A CFD Validation Effort

    NASA Technical Reports Server (NTRS)

    Allan, Brian G.; Schaeffler, Norman W.; Jenkins, Luther N.; Yao, Chung-Sheng; Wong, Oliver D.; Tanner, Philip E.

    2015-01-01

    A rotorcraft fuselage is typically designed with an emphasis on operational functionality with aerodynamic efficiency being of secondary importance. This results in a significant amount of drag during high-speed forward flight that can be a limiting factor for future high-speed rotorcraft designs. To enable higher speed flight, while maintaining a functional fuselage design (i.e., a large rear cargo ramp door), the NASA Rotary Wing Project has conducted both experimental and computational investigations to assess active flow control as an enabling technology for fuselage drag reduction. This paper will evaluate numerical simulations of a flow control system on a generic rotorcraft fuselage with a rotor in forward flight using OVERFLOW, a structured mesh Reynolds-averaged Navier-Stokes flow solver developed at NASA. The results are compared to fuselage forces, surface pressures, and PN flow field data obtained in a wind tunnel experiment conducted at the NASA Langley 14-by 22-Foot Subsonic Tunnel where significant drag and download reductions were demonstrated using flow control. This comparison showed that the Reynolds-averaged Navier-Stokes flow solver was unable to predict the fuselage forces and pressure measurements on the ramp for the baseline and flow control cases. While the CFD was able to capture the flow features, it was unable to accurately predict the performance of the flow control.

  6. Heterogeneous Au-Pt nanostructures with enhanced catalytic activity toward oxygen reduction.

    PubMed

    Ye, Feng; Liu, Hui; Hu, Weiwei; Zhong, Junyu; Chen, Yingying; Cao, Hongbin; Yang, Jun

    2012-03-14

    Heterogeneous Au-Pt nanostructures have been synthesized using a sacrificial template-based approach. Typically, monodispersed Au nanoparticles are prepared first, followed by Ag coating to form core-shell Au-Ag nanoparticles. Next, the galvanic replacement reaction between Ag shells and an aqueous H(2)PtCl(6) solution, whose chemical reaction can be described as 4Ag + PtCl(6)(2-)→ Pt + 4AgCl + 2Cl(-), is carried out at room temperature. Pure Ag shell is transformed into a shell made of Ag/Pt alloy by galvanic replacement. The AgCl formed simultaneously roughens the surface of alloy Ag-Pt shells, which can be manipulated to create a porous Pt surface for oxygen reduction reaction. Finally, Ag and AgCl are removed from core-shell Au-Ag/Pt nanoparticles using bis(p-sulfonatophenyl)phenylphosphane dihydrate dipotassium salt to produce heterogeneous Au-Pt nanostructures. The heterogeneous Au-Pt nanostructures have displayed superior catalytic activity towards oxygen reduction in direct methanol fuel cells because of the electronic coupling effect between the inner-placed Au core and the Pt shell.

  7. Particle size reduction effectively enhances the cholesterol-lowering activities of carrot insoluble fiber and cellulose.

    PubMed

    Chou, Sze-Yuan; Chien, Po-Jung; Chau, Chi-Fai

    2008-11-26

    This study investigated and compared the effects of particle size reduction on the cholesterol-lowering activities of carrot insoluble fiber-rich fraction (IFF) and plant cellulose. Our results demonstrated that micronization treatment effectively pulverized the particle sizes of these insoluble fibers to different microsizes. Feeding the micronized insoluble fibers, particularly the micronized carrot IFF, significantly (p < 0.05) improved their abilities in lowering the concentrations of serum triglyceride (18.6-20.0%), serum total cholesterol (15.5-19.5%), and liver lipids (16.7-20.3%) to different extents by means of enhancing (p < 0.05) the excretion of lipids (124-131%), cholesterol (120-135%), and bile acids (130-141%) in feces. These results suggested that particle size was one of the crucial factors in affecting the characteristics and physiological functions of insoluble fibers. Therefore, particle size reduction by micronization might offer the industry an opportunity to improve the physiological functions of insoluble fibers, particularly the carrot IFF, in health food applications.

  8. Size effect of silver nanoclusters on their catalytic activity for oxygen electro-reduction

    NASA Astrophysics Data System (ADS)

    Lu, Yizhong; Chen, Wei

    2012-01-01

    Two different sized silver nanoclusters are prepared by two different synthetic routs. First, a small nanocluster (NC) which is 0.7 nm in diameter was synthesized by using meso-2, 3-dimercapto-succinic acid (DMSA) as a capping ligand, and second a larger nanoparticle (NP) which is 3.3 nm in diameter was prepared by chemical reduction and coated with DMSA. The as-prepared silver nanoclusters or nanoparticles are then loaded onto a glassy carbon electrode and the size effect on their electrocatalytic activity toward oxygen reduction reaction (ORR) is investigated with electrochemical techniques in alkaline electrolyte. The cyclic voltammetric (CV) studies show that the onset potential of ORR on 0.7 nm silver nanoclusters is 150 mV more positive than that from 3.3 nm silver nanoparticles. And compared to the larger nanoparticles, five times higher current density of ORR at -0.80 V is obtained from the 0.7 nm silver nanoclusters. These CV results indicate that the smaller Ag nanoclusters exhibit higher catalytic performance for ORR. Rotating disk voltammetric studies show ORR on both DMSA monolayer-protected silver clusters is dominated first by a two-electron transfer pathway to produce H2O2 and then peroxide is reduced by 2 more electrons to produce water.

  9. Effect of temperature on the kinetics of acetylene decomposition over reduced iron oxide catalyst for the production of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Khedr, M. H.; Abdel Halim, K. S.; Soliman, N. K.

    2008-12-01

    Carbon nanotubes (CNTs) were synthesized by the catalytic decomposition of acetylene over nanosized metallic iron. A high metal loading was chosen in order to obtain a longer catalytic activity. Different nanosized iron oxides were prepared using chemical methods. A catalyst of the composition 40% Fe 2O 3:60% Al 2O 3 is prepared by wet impregnation method. The prepared samples of iron oxides supported in alumina were completely reduced by hydrogen gas at 500 °C and then constant rate of acetylene gas was passed over the freshly reduced samples at different reaction conditions. The kinetics of CNTs synthesis on reduced nanosized Fe 2O 3 supported on alumina was investigated as a function of crystal size of iron oxide catalyst (35-150 nm) and decomposition temperature (400-700 °C). The microstructure and morphology of the synthesized catalyst and CNTs were characterized using scanning electron microscope (SEM), high-resolution transmission electron microscope (HR-TEM) and XRD analysis. The results revealed that both the crystal size of iron oxide and decomposition temperature have a significant effect on the percentage yield of carbon deposited. It increased by decreasing crystal size of the catalyst and increasing decomposition temperature to certain limit. The maximum yield of carbon deposited (426%) was obtained at decomposition temperature 600 °C and over nanosized iron oxide catalyst with crystal size of average 35 nm.

  10. Coke formation and its effect on internal mass transfer and selectivity in Pd-catalysed acetylene hydrogenation

    SciTech Connect

    Asplund, S.

    1996-01-01

    Catalyst aging by coke formation has been studied for the selective hydrogenation of acetylene in the presence of excess ethylene on supported palladium catalysts. Deposited coke was found to have a substantial influence on the effective diffusivity, which decreased about one order of magnitude during 100 h of operation. As has been observed previously the selectivity for the undesired ethane was higher on aged catalysts, while the activity for acetylene hydrogenation was almost constant. These effects, however, were strongly dependent on the catalyst particle size, although the behaviour of fresh catalysts was unaffected by mass transfer limitations. When the catalyst used was Pd/{alpha}-Al{sub 2}O{sub 3} the change in selectivity with aging could be explained solely as a consequence of the increased diffusion resistance. The mass transfer effects were important also on Pd/{gamma}-Al{sub 2}O{sub 3}, but on this catalyst there was an additional increase in ethane selectivity that could not be attributed to diffusion limitations. Calculations and experimental tests showed that the observed phenomena are relevant also for the shell-type catalysts normally used industrially. The coke formation itself was about four to five times faster on Pd/{gamma}-Al{sub 2}O{sub 3} compared to the {alpha}-Al{sub 2}O{sub 3}-supported catalyst. The coke was generally concentrated towards the pellet periphery showing the influence of diffusion resistance also on the coke-forming reactions. 27 refs., 10 figs., 5 tabs.

  11. Rapid analysis of dissolved methane, ethylene, acetylene and ethane using partition coefficients and headspace-gas chromatography.

    PubMed

    Lomond, Jasmine S; Tong, Anthony Z

    2011-01-01

    Analysis of dissolved methane, ethylene, acetylene, and ethane in water is crucial in evaluating anaerobic activity and investigating the sources of hydrocarbon contamination in aquatic environments. A rapid chromatographic method based on phase equilibrium between water and its headspace is developed for these analytes. The new method requires minimal sample preparation and no special apparatus except those associated with gas chromatography. Instead of Henry's Law used in similar previous studies, partition coefficients are used for the first time to calculate concentrations of dissolved hydrocarbon gases, which considerably simplifies the calculation involved. Partition coefficients are determined to be 128, 27.9, 1.28, and 96.3 at 30°C for methane, ethylene, acetylene, and ethane, respectively. It was discovered that the volume ratio of gas-to-liquid phase is critical to the accuracy of the measurements. The method performance can be readily improved by reducing the volume ratio of the two phases. Method validation shows less than 6% variation in accuracy and precision except at low levels of methane where interferences occur in ambient air. Method detection limits are determined to be in the low ng/L range for all analytes. The performance of the method is further tested using environmental samples collected from various sites in Nova Scotia.

  12. N2O reduction by the mu4-sulfide-bridged tetranuclear CuZ cluster active site.

    PubMed

    Chen, Peng; Gorelsky, Serge I; Ghosh, Somdatta; Solomon, Edward I

    2004-08-13

    Nitrous oxide (N2O) reduction is a chemical challenge both in the selective oxidation of organic substrates by N2O and in the removal of N2O as a green-house gas. The reduction of N2O is thermodynamically favorable but kinetically inert, and requires activating transition-metal centers. In biological systems, N2O reduction is the last step in the denitrification process of the bacterial nitrogen cycle and is accomplished by the enzyme nitrous oxide reductase, whose active site consists of a micro4-sulfide-bridged tetranuclear CuZ cluster which has many unusual spectroscopic features. Recent studies have developed a detailed electronic-structure description of the resting CuZ cluster, determined its catalytically relevant state, and provided insight into the role of this tetranuclear copper cluster in N2O activation and reduction.

  13. Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

    DOE PAGES

    Christ, J. M.; Neyerlin, K. C.; Richards, R.; ...

    2014-10-04

    A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA weremore » more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.« less

  14. Reduction of Free Edge Peeling Stress of Laminated Composites Using Active Piezoelectric Layers

    PubMed Central

    Huang, Bin; Kim, Heung Soo

    2014-01-01

    An analytical approach is proposed in the reduction of free edge peeling stresses of laminated composites using active piezoelectric layers. The approach is the extended Kantorovich method which is an iterative method. Multiterms of trial function are employed and governing equations are derived by taking the principle of complementary virtual work. The solutions are obtained by solving a generalized eigenvalue problem. By this approach, the stresses automatically satisfy not only the traction-free boundary conditions, but also the free edge boundary conditions. Through the iteration processes, the free edge stresses converge very quickly. It is found that the peeling stresses generated by mechanical loadings are significantly reduced by applying a proper electric field to the piezoelectric actuators. PMID:25025088

  15. Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Richards, R.; Dinh, H. N.

    2014-10-04

    A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA were more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.

  16. Repetition-Related Reductions in Neural Activity during Emotional Simulations of Future Events

    PubMed Central

    2015-01-01

    Simulations of future experiences are often emotionally arousing, and the tendency to repeatedly simulate negative future outcomes has been identified as a predictor of the onset of symptoms of anxiety. Nonetheless, next to nothing is known about how the healthy human brain processes repeated simulations of emotional future events. In this study, we present a paradigm that can be used to study repeated simulations of the emotional future in a manner that overcomes phenomenological confounds between positive and negative events. The results show that pulvinar nucleus and orbitofrontal cortex respectively demonstrate selective reductions in neural activity in response to frequently as compared to infrequently repeated simulations of negative and positive future events. Implications for research on repeated simulations of the emotional future in both non-clinical and clinical populations are discussed. PMID:26390294

  17. NASA Propulsion Concept Studies and Risk Reduction Activities for Resource Prospector Lander

    NASA Technical Reports Server (NTRS)

    Trinh, Huu P.; Williams, Hunter; Burnside, Chris

    2015-01-01

    The Resource Prospector mission is to investigate the Moon's polar regions in search of volatiles. The government-version lander concept for the mission is composed of a braking stage and a liquid-propulsion lander stage. A propulsion trade study concluded with a solid rocket motor for the braking stage while using the 4th-stage Peacekeeper (PK) propulsion components for the lander stage. The mechanical design of the liquid propulsion system was conducted in concert with the lander structure design. A propulsion cold-flow test article was fabricated and integrated into a lander development structure, and a series of cold flow tests were conducted to characterize the fluid transient behavior and to collect data for validating analytical models. In parallel, RS-34 PK thrusters to be used on the lander stage were hot-fire tested in vacuum conditions as part of risk reduction activities.

  18. CATION-π and CH-π Interactions in the Coordination and Solvation of Cu+ (ACETYLENE)n (n=1-6) Complexes Investigated via Infrared Photodissociation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Brathwaite, Antonio David; Walters, Richard S.; Ward, Timothy B.; Duncan, Michael A.

    2015-06-01

    Mass-selected copper-acetylene cation complexes of the form Cu(C2H2)n+ are produced by laser ablation and studied via infrared laser photodissociation spectroscopy in the C-H stretching region (3000-3500 wn). Spectra for larger species are measured via ligand elimination, whereas argon tagging is employed to enhance dissociation yields in smaller complexes. The number of infrared active bands, their frequency positions and their relative intensities provide insight into the structure and bonding of these ions. Density functional theory calculations are carried out in support of this work. The combined data show that cation-π bonds are formed for the n=1-3 species, resulting in red-shifted C-H stretches on the acetylene ligands. Three acetylene ligands complete the coordination of the copper cation. Additional ligands (n=4-6) solvate the n=3 core by forming CH-pi bonds. Distinctive vibrational patterns are exhibited for coordinated vs. solvent ligands. Theory reproduces these results.

  19. Synthesis and biological evaluation of 1-(benzenesulfonamido)-2-[5-(N-hydroxypyridin-2(1H)-one)]acetylene regioisomers: a novel class of 5-lipoxygenase inhibitors.

    PubMed

    Chowdhury, Morshed Alam; Chen, Hua; Abdellatif, Khaled R A; Dong, Ying; Petruk, Kenneth C; Knaus, Edward E

    2008-07-15

    A hitherto unknown class of linear acetylene regioisomers were designed such that a SO(2)NH(2) group was located at the ortho-, meta-, or para-position of the acetylene C-1 phenyl ring, and a N-hydroxypyridin-2(1H)-one moiety was attached via its C-5 position to the C-2 position on an acetylene template (scaffold). All three regioisomers inhibited 5-lipoxygenase (5-LOX), where the relative potency order was 2-SO(2)NH(2) (IC(50)=10 microM) >3-SO(2)NH(2) (IC(50)=15 microM) >4-SO(2)NH(2) (IC(50)=68 microM) relative to the reference drug nordihydroguaiaretic acid (NDGA; IC(50)=35 microM). The 2-SO(2)NH(2) regioisomer (ED(50)=86.0mg/kg po) exhibited excellent oral anti-inflammatory (AI) activity that was more potent than aspirin (ED(50)=128.9 mg/kg) and marginally less potent than ibuprofen (ED(50)=67.4 mg/kg). The N-hydroxypyridin-2(1H)one moiety provides a novel pharmacophore for the design of cyclic hydroxamic mimetics capable of chelating 5-LOX iron for exploitation in the design of 5-LOX inhibitory AI drugs.

  20. Phoretic drag reduction of chemically active homogeneous spheres under force fields and shear flows

    NASA Astrophysics Data System (ADS)

    Yariv, Ehud; Kaynan, Uri

    2017-01-01

    Surrounded by a spherically symmetric solute cloud, chemically active homogeneous spheres do not undergo conventional autophoresis when suspended in an unbounded liquid domain. When exposed to external flows, solute advection deforms that cloud, resulting in a generally asymmetric distribution of diffusio-osmotic slip which, in turn, modifies particle motion. Inspired by classical forced-convection analyses [Acrivos and Taylor, Phys. Fluids 5, 387 (1962), 10.1063/1.1706630; Frankel and Acrivos, Phys. Fluids 11, 1913 (1968), 10.1063/1.1692218] we illustrate this phoretic phenomenon using two prototypic configurations, one where the particle sediments under a uniform force field and one where it is subject to a simple shear flow. In addition to the Péclet number Pe associated with the imposed flow, the governing nonlinear problem also depends upon α , the intrinsic Péclet number associated with the chemical activity of the particle. As in the forced-convection problems, the small-Péclet-number limit is nonuniform, breaking down at large distances away from the particle. Calculation of the leading-order autophoretic effects thus requires use of matched asymptotic expansions, the outer region being at distances that scale inversely with Pe and Pe1 /2 in the respective sedimentation and shear problems. In the sedimentation problem we find an effective drag reduction of fractional amount α /8 ; in the shear problem we find that the magnitude of the stresslet is decreased by a fractional amount α /4 . For a dilute particle suspension the latter result is manifested by a reduction of the effective viscosity.

  1. In situ probing of the active site geometry of ultrathin nanowires for the oxygen reduction reaction

    SciTech Connect

    Liu, Haiqing; Wong, Stanislaus S.; An, Wei; Li, Yuanyuan; Frenkel, Anatoly I.; Sasaki, Kotaro; Koenigsmann, Christopher; Su, Dong; Anderson, Rachel M.; Crooks, Richard M.; Adzic, Radoslav R.; Liu, Ping

    2015-09-24

    To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (~2 nm) core–shell Pt~Pd9Au nanowires, which have been previously shown to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu~Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Thus, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.

  2. Early reduction in toe flexor strength is associated with physical activity in elderly men

    PubMed Central

    Suwa, Masataka; Imoto, Takayuki; Kida, Akira; Yokochi, Takashi

    2016-01-01

    [Purpose] To compare the toe flexor, hand grip and knee extensor strengths of young and elderly men, and to examine the association between toe flexor strength and physical activity or inactivity levels. [Subjects and Methods] Young (n=155, 18–23 years) and elderly (n=60, 65–88 years) men participated in this study. Toe flexor, hand grip, and knee extensor strength were measured. Physical activity (time spent standing/walking per day) and inactivity (time spent sitting per day) were assessed using a self-administered questionnaire. [Results] Toe flexor, hand grip, and knee extensor strength of the elderly men were significantly lower than those of the young men. Standing/walking and sitting times of the elderly men were lower than those of the young men. Toe flexor strength correlated with hand grip and knee extensor strength in both groups. In elderly men, toe flexor strength correlated with standing/walking time. In comparison to the young men’s mean values, toe flexor strength was significantly lower than knee extensor and hand grip strength in the elderly group. [Conclusion] The results suggest that age-related reduction in toe flexor strength is greater than those of hand grip and knee extensor strengths. An early loss of toe flexor strength is likely associated with reduced physical activity in elderly men. PMID:27313353

  3. Meso-structured platinum thin films: active and stable electrocatalysts for the oxygen reduction reaction.

    PubMed

    Kibsgaard, Jakob; Gorlin, Yelena; Chen, Zhebo; Jaramillo, Thomas F

    2012-05-09

    Improving both the activity and the stability of the cathode catalyst in platinum-based polymer electrolyte fuel cells is a key technical challenge. Here, we synthesize a high surface area meso-structured Pt thin film that exhibits higher specific activity for the oxygen reduction reaction (ORR) than commercial carbon-supported Pt nanoparticles (Pt/C). An accelerated stability test demonstrates that the meso-structured Pt thin film also displays significantly enhanced stability as compared to the commercial Pt/C catalyst. Our study reveals the origin of the high turnover frequency (TOF), and excellent durability is attributed to the meso-structure, which yields a morphology with fewer undercoordinated Pt sites than Pt/C nanoparticles, a key difference with substantial impact to the surface chemistry. The improved catalyst activity and stability could enable the development of a high-performance gas diffusion electrode that is resistant to corrosion even under the harsh conditions of start-up, shut-down, and/or hydrogen starvation.

  4. Shell-anchor-core structures for enhanced stability and catalytic oxygen reduction activity

    NASA Astrophysics Data System (ADS)

    Ramirez-Caballero, Gustavo E.; Hirunsit, Pussana; Balbuena, Perla B.

    2010-10-01

    Density functional theory is used to evaluate activity and stability properties of shell-anchor-core structures. The structures consist of a Pt surface monolayer and a composite core having an anchor bilayer where C atoms in the interstitial sites lock 3d metals in their locations, thus avoiding their surface segregation and posterior dissolution. The modified subsurface geometry induces less strain on the top surface, thus exerting a favorable effect on the surface catalytic activity where the adsorption strength of the oxygenated species becomes more moderate: weaker than on pure Pt(111) but stronger than on a Pt monolayer having a 3d metal subsurface. Here we analyze the effect of changing the nature of the 3d metal in the subsurface anchor bilayer, and we also test the use of a Pd monolayer instead of Pt on the surface. It is found that a subsurface constituted by two layers with an approximate composition of M2C (M=Fe, Ni, and Co) provides a barrier for the migration of subsurface core metal atoms to the surface. Consequently, an enhanced resistance against dissolution in parallel to improved oxygen reduction activity is expected, as given by the values of adsorption energies of reaction intermediates, delayed onset of water oxidation, and/or low coverage of oxygenated species at surface oxidation potentials.

  5. In Situ Probing of the Active Site Geometry of Ultrathin Nanowires for the Oxygen Reduction Reaction.

    PubMed

    Liu, Haiqing; An, Wei; Li, Yuanyuan; Frenkel, Anatoly I; Sasaki, Kotaro; Koenigsmann, Christopher; Su, Dong; Anderson, Rachel M; Crooks, Richard M; Adzic, Radoslav R; Liu, Ping; Wong, Stanislaus S

    2015-10-07

    To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (∼2 nm) core-shell Pt∼Pd9Au nanowires, which have been previously shown to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu∼Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Hence, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.

  6. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    DOE PAGES

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; ...

    2015-07-02

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can bemore » attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.« less

  7. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    PubMed Central

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; Mavrikakis, Manos; Xia, Younan

    2015-01-01

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. These results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability. PMID:26133469

  8. Cerebral Activity Associated with Transient Sleep-Facilitated Reduction in Motor Memory Vulnerability to Interference

    PubMed Central

    Albouy, Geneviève; King, Bradley R.; Schmidt, Christina; Desseilles, Martin; Dang-Vu, Thien Thanh; Balteau, Evelyne; Phillips, Christophe; Degueldre, Christian; Orban, Pierre; Benali, Habib; Peigneux, Philippe; Luxen, André; Karni, Avi; Doyon, Julien; Maquet, Pierre; Korman, Maria

    2016-01-01

    Motor memory consolidation is characterized, in part, by a sleep-facilitated decrease in susceptibility to subsequent interfering experiences. Surprisingly, the cerebral substrates supporting this phenomenon have never been examined. We used fMRI to investigate the neural correlates of the influence of sleep on interference to motor memory consolidation. Healthy young adults were trained on a sequential motor task, and subsequently practiced a second competing sequence after an interval including diurnal sleep or wakefulness. Participants were then retested on the initial sequence 8 h and 24 h (including nocturnal sleep) after training. Results demonstrated that a post-training nap significantly protected memory against interference at 8 h and modulated the link between cerebral activity and behavior, such that a smaller post-interference decrease in cortico-striatal activity was associated with better performance. Interestingly, the protective effect of a nap was only transitory, as both groups performed similarly at 24 h. Activity in cortico-striatal areas that was disrupted during the day, presumably due to interference and accentuated in the absence of a nap, was restored overnight. Altogether, our findings offer the first evidence that cortico-striatal areas play a critical role in the transient sleep-facilitated reduction in motor memory vulnerability and in the overnight restoration of previously degraded memories. PMID:27725727

  9. In situ probing of the active site geometry of ultrathin nanowires for the oxygen reduction reaction

    DOE PAGES

    Liu, Haiqing; Wong, Stanislaus S.; An, Wei; ...

    2015-09-24

    To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (~2 nm) core–shell Pt~Pd9Au nanowires, which have been previously shownmore » to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu~Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Thus, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.« less

  10. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun; Liu, Baocang; Gong, Xia; Zheng, Dafang; Zhang, Jun; Wang, Qin

    2016-12-01

    The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg-1) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  11. Cerebral Activity Associated with Transient Sleep-Facilitated Reduction in Motor Memory Vulnerability to Interference.

    PubMed

    Albouy, Geneviève; King, Bradley R; Schmidt, Christina; Desseilles, Martin; Dang-Vu, Thien Thanh; Balteau, Evelyne; Phillips, Christophe; Degueldre, Christian; Orban, Pierre; Benali, Habib; Peigneux, Philippe; Luxen, André; Karni, Avi; Doyon, Julien; Maquet, Pierre; Korman, Maria

    2016-10-11

    Motor memory consolidation is characterized, in part, by a sleep-facilitated decrease in susceptibility to subsequent interfering experiences. Surprisingly, the cerebral substrates supporting this phenomenon have never been examined. We used fMRI to investigate the neural correlates of the influence of sleep on interference to motor memory consolidation. Healthy young adults were trained on a sequential motor task, and subsequently practiced a second competing sequence after an interval including diurnal sleep or wakefulness. Participants were then retested on the initial sequence 8 h and 24 h (including nocturnal sleep) after training. Results demonstrated that a post-training nap significantly protected memory against interference at 8 h and modulated the link between cerebral activity and behavior, such that a smaller post-interference decrease in cortico-striatal activity was associated with better performance. Interestingly, the protective effect of a nap was only transitory, as both groups performed similarly at 24 h. Activity in cortico-striatal areas that was disrupted during the day, presumably due to interference and accentuated in the absence of a nap, was restored overnight. Altogether, our findings offer the first evidence that cortico-striatal areas play a critical role in the transient sleep-facilitated reduction in motor memory vulnerability and in the overnight restoration of previously degraded memories.

  12. Update on Risk Reduction Activities for a Liquid Advanced Booster for NASA's Space Launch System

    NASA Technical Reports Server (NTRS)

    Crocker, Andrew M.; Doering, Kimberly B; Meadows, Robert G.; Lariviere, Brian W.; Graham, Jerry B.

    2015-01-01

    The stated goals of NASA's Research Announcement for the Space Launch System (SLS) Advanced Booster Engineering Demonstration and/or Risk Reduction (ABEDRR) are to reduce risks leading to an affordable Advanced Booster that meets the evolved capabilities of SLS; and enable competition by mitigating targeted Advanced Booster risks to enhance SLS affordability. Dynetics, Inc. and Aerojet Rocketdyne (AR) formed a team to offer a wide-ranging set of risk reduction activities and full-scale, system-level demonstrations that support NASA's ABEDRR goals. For NASA's SLS ABEDRR procurement, Dynetics and AR formed a team to offer a series of full-scale risk mitigation hardware demonstrations for an affordable booster approach that meets the evolved capabilities of the SLS. To establish a basis for the risk reduction activities, the Dynetics Team developed a booster design that takes advantage of the flight-proven Apollo-Saturn F-1. Using NASA's vehicle assumptions for the SLS Block 2, a two-engine, F-1-based booster design delivers 150 mT (331 klbm) payload to LEO, 20 mT (44 klbm) above NASA's requirements. This enables a low-cost, robust approach to structural design. During the ABEDRR effort, the Dynetics Team has modified proven Apollo-Saturn components and subsystems to improve affordability and reliability (e.g., reduce parts counts, touch labor, or use lower cost manufacturing processes and materials). The team has built hardware to validate production costs and completed tests to demonstrate it can meet performance requirements. State-of-the-art manufacturing and processing techniques have been applied to the heritage F-1, resulting in a low recurring cost engine while retaining the benefits of Apollo-era experience. NASA test facilities have been used to perform low-cost risk-reduction engine testing. In early 2014, NASA and the Dynetics Team agreed to move additional large liquid oxygen/kerosene engine work under Dynetics' ABEDRR contract. Also led by AR, the

  13. Density Functional Theory Study of Oxygen Reduction Activity on Ultrathin Platinum Nanotubes

    SciTech Connect

    Matanovic, Ivana; Kent, Paul; Garzon, Fernando; Henson, Neil J.

    2012-07-13

    The structure, stability, and catalytic activity of a number of single- and double-wall platinum (n,m) nanotubes ranging in diameter from 0.3 to 2.0 nm were studied using plane-wave based density functional theory in the gas phase and water environment. The change in the catalytic activity toward the oxygen reduction reaction (ORR) with the size and chirality of the nanotube was studied by calculating equilibrium adsorption potentials for ORR intermediates and by constructing free energy diagrams in the ORR dissociative mechanism network. In addition, the stability of the platinum nanotubes is investigated in terms of electrochemical dissolution potentials and by determining the most stable state of the material as a function of pH and potential, as represented in Pourbaix diagrams. Our results show that the catalytic activity and the stability toward electrochemical dissolution depend greatly on the diameter and chirality of the nanotube. On the basis of the estimated overpotentials for ORR, we conclude that smaller, approximately 0.5 nm in diameter single-wall platinum nanotubes consistently show a huge, up to 400 mV larger overpotential than platinum, indicating very poor catalytic activity toward ORR. This is the result of substantial structural changes induced by the adsorption of any chemical species on these tubes. Single-wall n = m platinum nanotubes with a diameter larger than 1 nm have smaller ORR overpotentials than bulk platinum for up to 180 mV and thus show improved catalytic activity relative to bulk. We also predict that these nanotubes can endure the highest cell potentials but dissolution potentials are still for 110 mV lower than for the bulk, indicating a possible corrosion problem.

  14. Early active motion protocol following open reduction internal fixation of the scaphoid: A pilot study.

    PubMed

    Dunn, J-C; Kusnezov, N; Fares, A; Buccino, Z; Esquivel, D; Mitchell, J

    2017-02-01

    Scaphoid fractures are common injuries which traditionally have been treated with long periods of immobilization even after open reduction and internal fixation (ORIF). The purpose of this pilot investigation was two-fold: 1) describe a precise postoperative Early Active Motion (EAM) rehabilitation protocol following ORIF of scaphoid fractures and 2) record the outcomes of the EAM protocol. Eight consecutive patients having undergone ORIF of the scaphoid were enrolled in the EAM and followed for a minimum of 1 year. At 12 weeks, Disabilities of the Arm Shoulder and Hand (DASH) score, Mayo Wrist score, and range of motion values were obtained. At 1 year, a telephone survey was conducted and several data points were obtained including DASH and Mayo Wrist score, number of push-ups, satisfaction with surgery and ability to remain on active duty. All 8 patients were male, on active duty, with an average age of 26 years. Two patients used tobacco products and none had major health problems. All patients completed the EAM protocol and obtained CT; all CT exams demonstrated healing at 8 weeks. At 12 weeks postoperatively, the average DASH score was 8.8±16 (range: 0-47.5), Mayo wrist score was 88±10 (range: 75-100) and range of motion nearly symmetrical. At a mean final follow-up of 15.4 months postoperatively, the average DASH score was 1.1±1.7 (Range: 0-4.5), Mayo wrist score was 97.5±4 (range 90-100), average number of push-ups was 57 (40-70) at the prior Army Physical Fitness Test. All patients were satisfied with surgery and all remained on active duty at 1 year. There were no reported complications. The EAM protocol following scaphoid fracture ORIF is safe and effective. The EAM can reliably return patients back to high demand activity earlier than a traditional protocol.

  15. Effect of radiation-induced reduction of nitroimidazoles on biologically active DNA

    SciTech Connect

    Lafleur, M.V.; Pluijmackers-Westmijze, E.J.; Loman, H.

    1986-07-01

    Radiation-chemical reductions have been carried out with several nitroimidazoles. Reduction of these drugs in the presence of single-stranded phi chi 174 DNA causes extensive lethal damage. However, relatively stable (end) products, do not contribute to the damage, although glyoxal is potentially toxic. This demonstrates that a short-lived intermediate in the reduction process is responsible. Further, the quantity of damage in the DNA depends on both dose (reduction)-rate and also the nature of the drug.

  16. Antitrypanosomal Acetylene Fatty Acid Derivatives from the Seeds of Porcelia macrocarpa (Annonaceae).

    PubMed

    de Á Santos, Luciana; Cavalheiro, Alberto J; Tempone, Andre G; Correa, Daniela S; Alexandre, Tatiana R; Quintiliano, Natalia F; Rodrigues-Oliveira, André F; Oliveira-Silva, Diogo; Martins, Roberto Carlos C; Lago, João Henrique G

    2015-05-07

    Chagas' disease is caused by a parasitic protozoan and affects the poorest population in the world, causing high mortality and morbidity. As a result of the toxicity and long duration of current treatments, the discovery of novel and more efficacious drugs is crucial. In this work, the hexane extract from seeds of Porcelia macrocarpa R.E. Fries (Annonaceae) displayed in vitro antitrypanosomal activity against trypomastigote forms of T. cruzi by the colorimetric MTT assay (IC50 of 65.44 μg/mL). Using chromatographic fractionation over SiO2, this extract afforded a fraction composed by one active compound (IC50 of 10.70 µg/mL), which was chemically characterized as 12,14-octadecadiynoic acid (macrocarpic acid). Additionally, two new inactive acetylene compounds (α,α'-dimacro-carpoyl-β-oleylglycerol and α-macrocarpoyl-α'-oleylglycerol) were also isolated from the hexane extract. The complete characterization of the isolated compounds was performed by analysis of NMR and MS data as well as preparation of derivatives.

  17. Skeletal muscle regeneration is delayed by reduction in Xin expression: consequence of impaired satellite cell activation?

    PubMed

    Nissar, Aliyah A; Zemanek, Bart; Labatia, Rita; Atkinson, Daniel J; van der Ven, Peter F M; Fürst, Dieter O; Hawke, Thomas J

    2012-01-01

    Xin is a striated muscle-specific actin-binding protein whose mRNA expression has been observed in damaged skeletal muscle. Here we demonstrate increased Xin protein expression early postinjury (≤ 12 h) and localization primarily to the periphery of damaged myofibers. At 1 day postinjury, Xin is colocalized with MyoD, confirming expression in activated satellite cells (SCs). By 5 days postinjury, Xin is evident in newly regenerated myofibers, with a return to preinjury levels by 14 days of regeneration. To determine whether the increased Xin expression is functionally relevant, tibialis anterior muscles of wild-type mice were infected with Xin-short hairpin RNA (shRNA) adenovirus, whereas the contralateral tibialis anterior received control adenovirus (Control). Four days postinfection, muscles were harvested or injured with cardiotoxin and collected at 3, 5, or 14 days thereafter. When compared with Control, Xin-shRNA infection attenuated muscle regeneration as demonstrated by Myh3 expression and fiber areas. Given the colocalization of Xin and MyoD, we isolated single myofibers from infected muscles to investigate the effect of silencing Xin on SC function. Relative to Control, SC activation, but not proliferation, was significantly impaired in Xin-shRNA-infected muscles. To determine whether Xin affects the G0-G1 transition, cell cycle reentry was assessed on infected C2C12 myoblasts using a methylcellulose assay. No difference in reentry was noted between groups, suggesting that Xin contributes to SC activation by means other than affecting G0-G1 transition. Together these data demonstrate a critical role for Xin in SC activation and reduction in Xin expression results in attenuated skeletal muscle repair.

  18. Activation of oxygen evolving perovskites for oxygen reduction by functionalization with Fe-N(x)/C groups.

    PubMed

    Rincón, Rosalba A; Masa, Justus; Mehrpour, Sara; Tietz, Frank; Schuhmann, Wolfgang

    2014-12-07

    The incorporation of Fe-Nx/C moieties into perovskites remarkably activates them for the oxygen reduction reaction (ORR) and also leads to notable improvement of their activity towards the oxygen evolution reaction (OER) thus presenting a new route for realizing high performance, low cost bifunctional catalysts for reversible oxygen electrodes.

  19. Reduction of COD in refinery wastewater through adsorption on date-pit activated carbon.

    PubMed

    El-Naas, Muftah H; Al-Zuhair, Sulaiman; Abu Alhaija, Manal

    2010-01-15

    Experiments were carried out to evaluate the batch adsorption of COD from petroleum refinery wastewater on a locally prepared date-pit activated carbon (DP-AC), and its adsorption effectiveness was compared to that of commercially available BDH activated carbon (BDH-AC). Adsorption equilibrium and kinetic data were determined for both adsorbents and fitted to several adsorption isotherm and kinetics models, respectively. The Langmuir monolayer isotherm fitted well the equilibrium data of COD on both adsorbents; whereas, the kinetics data were best fitted by the pseudo-second order model. Modeling of the controlling mechanisms indicated that both intrinsic kinetics and mass transfer contributed to controlling the adsorption process. Mass transfer seemed to be the dominant mechanism at low COD content, while intrinsic kinetics dominates at high concentrations. In general, the adsorption effectiveness of locally prepared DP-AC was proven to be comparable to that of BDH-AC. Therefore, DP-AC can be utilized as an effective and less expensive adsorbent for the reduction of COD in refinery wastewater.

  20. Reduction of computational complexity in the image/video understanding systems with active vision

    NASA Astrophysics Data System (ADS)

    Kuvich, Gary

    2003-10-01

    The vision system evolved not only as a recognition system, but also as a sensory system for reaching, grasping and other motion activities. In advanced creatures, it became a component of prediction function, allowing creation of environmental models and activity planning. Fast information processing and decision making is vital for any living creature, and requires reduction of informational and computational complexities. The brain achieves this goal using symbolic coding, hierarchical compression, and selective processing of visual information. Network-Symbolic representation, where both systematic structural / logical methods and neural / statistical methods are the parts of a single mechanism, is the most feasible for such models. It converts visual information into the relational Network-Symbolic structures, instead of precise computations of a 3-dimensional models. Narrow foveal vision provides separation of figure from ground, object identification, semantic analysis, and precise control of actions. Rough wide peripheral vision identifies and tracks salient motion, guiding foveal system to salient objects. It also provides scene context. Objects with rigid bodies and other stable systems have coherent relational structures. Hierarchical compression and Network-Symbolic transformations derive more abstract structures that allow invariably recognize a particular structure as an exemplar of class. Robotic systems equipped with such smart vision will be able effectively navigate in any environment, understand situation, and act accordingly.

  1. Subjective evaluation of an active crosstalk reduction system for mobile autostereoscopic displays

    NASA Astrophysics Data System (ADS)

    Chappuis, Alexandre; Rerabek, Martin; Hanhart, Philippe; Ebrahimi, Touradj

    2014-03-01

    The Quality of Experience (QoE) provided by autostereoscopic 3D displays strongly depends on the user position. For an optimal image quality, the observer should be located at one of the relevant positions, called sweet spots, where artifacts reducing the QoE, such as crosstalk, are minimum. In this paper, we propose and evaluate a complete active crosstalk reduction system running on an HTC EVO 3D smartphone. To determine the crosstalk level at each position, a full display characterization was performed. Based on the user position and crosstalk profile, the system first helps the user to find the sweet spot using visual feedback. If the user moves away from the sweet spot, then the active crosstalk compensation is performed and reverse stereo phenomenon is corrected. The user preference between standard 2D and 3D modes, and the proposed system was evaluated through a subjective quality assessment. Results show that in terms of depth perception, the proposed system clearly outperforms the 3D and 2D modes. In terms of image quality, 2D mode was found to be best, but the proposed system outperforms 3D mode.

  2. Proteolytic activity of Enterococcus faecalis VB63F for reduction of allergenicity of bovine milk proteins.

    PubMed

    Biscola, V; Tulini, F L; Choiset, Y; Rabesona, H; Ivanova, I; Chobert, J-M; Todorov, S D; Haertlé, T; Franco, B D G M

    2016-07-01

    With the aim of screening proteolytic strains of lactic acid bacteria to evaluate their potential for the reduction of allergenicity of the major bovine milk proteins, we isolated a new proteolytic strain of Enterococcus faecalis (Ent. faecalis VB63F) from raw bovine milk. The proteases produced by this strain had strong activity against caseins (αS1-, αS2-, and β-casein), in both skim milk and sodium caseinate. However, only partial hydrolysis of whey proteins was observed. Proteolysis of Na-caseinate and whey proteins, observed after sodium dodecyl sulfate-PAGE, was confirmed by analysis of peptide profiles by reversed-phase HPLC. Inhibition of proteolysis with EDTA indicated that the proteases produced by Ent. faecalis VB63F belonged to the group of metalloproteases. The optimal conditions for their activity were 42°C and pH 6.5. The majority of assessed virulence genes were absent in Ent. faecalis VB63F. The obtained results suggest that Ent. faecalis VB63F could be efficient in reducing the immunoreactivity of bovine milk proteins.

  3. Reduction of transition metals by human (THP-1) monocytes is enhanced by activators of protein kinase C.

    PubMed

    Wood, J L; Graham, A

    1999-11-01

    Macrophages oxidize low density lipoprotein (LDL) by enzymatic and non-enzymatic mechanisms; however, it is evident that macrophage reduction of transition metals can accelerate LDL oxidation in vitro, and possibly in vivo. Distinct cellular pathways contribute to this process, including trans-plasma membrane electron transport (TPMET), and production of free thiols or superoxide. Here, we explore the role of protein kinase C (PKC) in regulating transition metal reduction by each of these redox-active pathways, in human (THP-1) monocytes. We demonstrate that PKC agonists and/or inhibitors modulate reduction of transition metals by monocytes: both thiol-independent (direct) and thiol-dependent (indirect) pathways for transition metal reduction are enhanced by PKC activation, suggesting a potential strategy for therapeutic intervention.

  4. 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.

  5. 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.

  6. Acetylene hydrogenation over structured Au-Pd catalysts.

    PubMed

    McCue, Alan J; Baker, Richard T; Anderson, James A

    2016-07-04

    AuPd nanoparticles were prepared following a methodology designed to produce core-shell structures (an Au core and a Pd shell). Characterisation suggested that slow addition of the shell metal favoured deposition onto the pre-formed core, whereas more rapid addition favoured the formation of a monometallic Pd phase in addition to some nanoparticles with the core-shell morphology. When used for the selective hydrogenation of acetylene, samples that possessed monometallic Pd particles favoured over-hydrogenation to form ethane. A sample prepared by the slow addition of a small amount of Pd resulted in the formation of a core-shell structure but with an incomplete Pd shell layer. This material exhibited a completely different product selectivity with ethylene and oligomers forming as the major products as opposed to ethane. The improved performance was thought to be as a result of the absence of Pd particles, which are capable of forming a Pd-hydride phase, with enhanced oligomer selectivity associated with reaction on uncovered Au atoms.

  7. Studies of Cobalt-Mediated Electrocatalytic CO2 Reduction Using a Redox-Active Ligand

    PubMed Central

    2015-01-01

    The cobalt complex [CoIIIN4H(Br)2]+ (N4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene) was used for electrocatalytic CO2 reduction in wet MeCN with a glassy carbon working electrode. When water was employed as the proton source (10 M in MeCN), CO was produced (fCO= 45% ± 6.4) near the CoI/0 redox couple for [CoIIIN4H(Br)2]+ (E1/2 = −1.88 V FeCp2+/0) with simultaneous H2 evolution (fH2= 30% ± 7.8). Moreover, we successfully demonstrated that the catalytically active species is homogeneous through the use of control experiments and XPS studies of the working glassy-carbon electrodes. As determined by cyclic voltammetry, CO2 catalysis occurred near the formal CoI/0redox couple, and attempts were made to isolate the triply reduced compound (“[Co0N4H]”). Instead, the doubly reduced (“CoI”) compounds [CoN4] and [CoN4H(MeCN)]+ were isolated and characterized by X-ray crystallography. Their molecular structures prompted DFT studies to illuminate details regarding their electronic structure. The results indicate that reducing equivalents are stored on the ligand, implicating redox noninnocence in the ligands for H2 evolution and CO2 reduction electrocatalysis. PMID:24773584

  8. Mechanism of enhanced nitrate reduction via micro-electrolysis at the powdered zero-valent iron/activated carbon interface.

    PubMed

    Luo, Jinghuan; Song, Guangyu; Liu, Jianyong; Qian, Guangren; Xu, Zhi Ping

    2014-12-01

    Nitrate reduction by zero-valent iron (Fe(0)) powder always works well only at controlled pH lower than 4 due to the formation of iron (hydr)oxides on its surface. Fe(0) powder combined with activated carbon (AC), i.e., Fe(0)/AC micro-electrolysis system, was first introduced to enhance nitrate reduction in aqueous solution. Comparative study was carried out to investigate nitrate reduction by Fe(0)/AC system and Fe(0) under near-neutral conditions, showing that the Fe(0)/AC system successfully reduced nitrate even at initial pH 6 with the reduction efficiency of up to 73%, whereas for Fe(0) only ∼10%. The effect of Fe(0) to AC mass ratio on nitrate reduction efficiency was examined. Easier nitrate reduction was achieved with more contact between Fe(0) and AC as the result of decreasing Fe(0) to AC mass ratio. Ferrous ion and oxidation-reduction potential were measured to understand the mechanism of enhanced nitrate reduction by Fe(0)/AC micro-electrolysis. The results suggest that a relative potential difference drives much more electrons from Fe(0) to AC, thus generating adsorbed atomic hydrogen which makes it possible for nitrate to be reduced at near-neural pH. Fe(0)/AC micro-electrolysis thus presents a great potential for practical application in nitrate wastewater treatment without excessive pH adjustment.

  9. Titanium cobalt nitride supported platinum catalyst with high activity and stability for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Xiao, Yonghao; Zhan, Guohe; Fu, Zhenggao; Pan, Zhanchang; Xiao, Chumin; Wu, Shoukun; Chen, Chun; Hu, Guanghui; Wei, Zhigang

    2015-06-01

    We describe a facile route to the development of novel robust non-carbon titanium cobalt nitride (Ti0.9Co0.1N) used as a support for Pt, and the catalyst exhibits high activity and stability for the oxygen reduction reaction (ORR). XRD and TEM results show that the synthesized Ti0.9Co0.1N is formed as a single-phase solid solution with high purity. The XPS measurements verified the strong metal/support interaction between Pt nanoparticles (NPs) and the Ti0.9Co0.1N support. Most importantly, Ti0.9Co0.1N supported Pt catalyst (Pt/Ti0.9Co0.1N) exhibits a much higher mass activity and durability than that of the commercial JM Pt/C electrocatalyst for ORR. The accelerated durability test (ADT) reveals that the novel Ti0.9Co0.1N support can dramatically enhance the durability of the catalyst and maintain the electrochemical surface area (ECSA) of Pt. Pt/Ti0.9Co0.1N shows great improvement in ECSA preservation, with only 35% of the initial ECSA drop even after 10 000 ADT cycles. The experimental data indicate that the electronic structure of Pt can be modified by Co doping, and there exists a strong interaction between Pt and the Ti0.9Co0.1N support, both of them are playing an important role in improving the activity and durability of the Pt/Ti0.9Co0.1N catalyst.

  10. Reduction of training costs using active classification in fused hyperspectral and LiDAR data

    NASA Astrophysics Data System (ADS)

    Wuttke, Sebastian; Schilling, Hendrik; Middelmann, Wolfgang

    2012-11-01

    This paper presents a novel approach for the reduction of training costs in classification with co-registered hyperspectral (HS) and Light Detection and Ranging (LiDAR) data using an active classification framework. Fully automatic classification can be achieved by unsupervised learning, which is not suited for adjustment to specific classes. On the other hand, supervised classification with predefined classes needs a lot of training examples, which need to be labeled with the ground truth, usually at a significant cost. The concept of active classification alleviates these problems by the use of a selection strategy: only selected samples are ground truth labeled and used as training data. One common selection strategy is to incorporate in a first step the current state of the classification algorithm and choose only the examples for which the expected information gain is maximized. In the second step a conventional classification algorithm is trained using this data. By alternating between these two steps the algorithm reaches high classification accuracy results with less training samples and therefore lower training costs. The approach presented in this paper involves the user in the active selection strategy and the k-NN algorithm is chosen for classification. The results further benefit from fusing the heterogeneous information of HS and LiDAR data within the classification algorithm. For this purpose, several HS features, such as vegetation indices, and LiDAR features, such as relative height and roughness, are extracted. This increases the separability between different classes and reduces the dimensionality of the HS data. The practicability and performance of this framework is shown for the detection and separation of different kinds of vegetation, e.g. trees and grass in an urban area of Berlin. The HS data was obtained by the SPECIM AISA Eagle 2 sensor, LiDAR data by Riegl LMS Q560.

  11. Trichloramine Removal with Activated Carbon Is Governed by Two Reductive Reactions: A Theoretical Approach with Diffusion-Reaction Models.

    PubMed

    Matsushita, Taku; Matsui, Yoshihiko; Ikekame, Shohei; Sakuma, Miki; Shirasaki, Nobutaka

    2017-04-06

    Mechanisms underlying trichloramine removal with activated carbon treatment were proven by batch experiments and theoretical analysis with diffusion-reaction models. The observed values of trichloramine and free chlorine were explained only by the model in which (1) both trichloramine and free chlorine were involved as reactants, (2) the removals of reactants were affected both by the intraparticle diffusion and by the reaction with activated carbon, and (3) trichloramine decomposition was governed by two distinct reductive reactions. One reductive reaction was expressed as a first-order reaction: the reductive reaction of trichloramine with the basal plane of PAC, which consists of graphene sheets. The other reaction was expressed as a second-order reaction: the reductive reaction of trichloramine with active functional groups located on the edge of the basal plane. Free chlorine competitively reacted with both the basal plane and the active functional groups. The fact that the model prediction succeeded even in experiments with different activated carbon doses, with different initial trichloramine concentrations, and with different sizes of activated carbon particles clearly proved that the mechanisms described in the model were reasonable for explaining trichloramine removal with activated carbon treatment.

  12. Protonation of the binuclear active site in cytochrome c oxidase decreases the reduction potential of CuB.

    PubMed

    Blomberg, Margareta R A; Siegbahn, Per E M

    2015-10-01

    One of the remaining mysteries regarding the respiratory enzyme cytochrome c oxidase is how proton pumping can occur in all reduction steps in spite of the low reduction potentials observed in equilibrium titration experiments for two of the active site cofactors, CuB(II) and Fea3(III). It has been speculated that, at least the copper cofactor can acquire two different states, one metastable activated state occurring during enzyme turnover, and one relaxed state with lower energy, reached only when the supply of electrons stops. The activated state should have a transiently increased CuB(II) reduction potential, allowing proton pumping. The relaxed state should have a lower reduction potential, as measured in the titration experiments. However, the structures of these two states are not known. Quantum mechanical calculations show that the proton coupled reduction potential for CuB is inherently high in the active site as it appears after reaction with oxygen, which explains the observed proton pumping. It is suggested here that, when the flow of electrons ceases, a relaxed resting state is formed by the uptake of one extra proton, on top of the charge compensating protons delivered in each reduction step. The extra proton in the active site decreases the proton coupled reduction potential for CuB by almost half a volt, leading to agreement with titration experiments. Furthermore, the structure for the resting state with an extra proton is found to have a hydroxo-bridge between CuB(II) and Fea3(III), yielding a magnetic coupling that can explain the experimentally observed EPR silence.

  13. 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

  14. Bio-inspired electron-delivering system for reductive activation of dioxygen at metal centres towards artificial flavoenzymes

    PubMed Central

    Roux, Yoann; Ricoux, Rémy; Avenier, Frédéric; Mahy, Jean-Pierre

    2015-01-01

    Development of artificial systems, capable of delivering electrons to metal-based catalysts for the reductive activation of dioxygen, has been proven very difficult for decades, constituting a major scientific lock for the elaboration of environmentally friendly oxidation processes. Here we demonstrate that the incorporation of a flavin mononucleotide (FMN) in a water-soluble polymer, bearing a locally hydrophobic microenvironment, allows the efficient reduction of the FMN by NADH. This supramolecular entity is then capable of catalysing a very fast single-electron reduction of manganese(III) porphyrin by splitting the electron pair issued from NADH. This is fully reminiscent of the activity of natural reductases such as the cytochrome P450 reductases with kinetic parameters, which are three orders of magnitude faster compared with other artificial systems. Finally, we show as a proof of concept that the reduced manganese porphyrin activates dioxygen and catalyses the oxidation of organic substrates in water. PMID:26419885

  15. 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.

  16. Cycloheximide prevents the de novo polypeptide synthesis required to recover from acetylene inhibition in Nitrosopumilus maritimus.

    PubMed

    Vajrala, Neeraja; Bottomley, Peter J; Stahl, David A; Arp, Daniel J; Sayavedra-Soto, Luis A

    2014-06-01

    Developing methods to differentiate the relative contributions of ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB) to ammonia (NH3) oxidation has been challenging due to the lack of compounds that selectively inhibit AOA. In this study, we investigated the effects of specific bacteria- and eukaryote-selective protein synthesis inhibitors on the recovery of acetylene (C2H2)-inactivated NH3 oxidation in the marine AOA Nitrosopumilus maritimus and compared the results with recovery of the AOB Nitrosomonas europaea. C2 H2 irreversibly inhibited N. maritimus NH3 oxidation in a similar manner to what was observed previously with N. europaea. However, cycloheximide (CHX), a widely used eukaryotic protein synthesis inhibitor, but not bacteria-specific protein synthesis inhibitors (kanamycin and gentamycin), inhibited the recovery of NH3-oxidizing activity in N. maritimus. CHX prevented the incorporation of (14)CO2 -labeling into cellular proteins, providing further evidence that CHX acts as a protein synthesis inhibitor in N. maritimus. If the effect of CHX on protein synthesis can be confirmed among other isolates of AOA, the combination of C2H2 inactivation followed by recovery of NH3 oxidation either in the presence of bacteria-selective protein synthesis inhibitors or CHX might be used to estimate the relative contributions of AOB and AOA to NH3 oxidation in natural environments.

  17. [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.

  18. Acetylene reaction with the Si(111) surface: A semiempirical quantum chemical study

    NASA Astrophysics Data System (ADS)

    Weiner, B.; Carmer, C. S.; Frenklach, M.

    1991-01-01

    The interaction between the acetylene molecule and the Si(111) surface was modeled using the geometry optimization pathway of the Zerner intermediate neglect of differential overlap semiempirical quantum chemical program. The surface was represented by a 49-atom cluster containing four layers of silicon atoms. To determine the effect of the interaction upon the silicon surface, 12 central atoms from the top two layers were allowed to move to stable positions. The geometry of the silicon surface was initially optimized without acetylene, resulting in a significant rearrangement of the mobile atoms. Nine separate calculations were then performed, differing in the initial position and orientation of the acetylene molecule above the surface. The geometry of the resulting surface structures was found to be highly dependent upon the initial placement and orientation of the acetylene. In each case, the acetylene was found to react with the silicon surface by the formation of Si-C bonds. An analysis of the Wiberg bond indices revealed that the initial triple bond between carbon atoms was reduced to approximately a single bond, the exact bond order varying slightly from case to case. It was also found that Si-Si bonds surrounding the reaction site were weakened, and in some cases broken, due to the strain induced by the Si-C bond formation. The degree to which the surfaces were rearranged was found to correlate with the final energies, indicating that the most distorted surfaces were the most energetically favorable.

  19. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction

    NASA Astrophysics Data System (ADS)

    Parnell, Charlette M.; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A.; Mudalige, Thilak K.; Biris, Alexandru S.; Ghosh, Anindya

    2016-08-01

    Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material’s ‑0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 106 mol‑1s‑1 was observed for the polydopamine-coated material–over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells.

  20. Report on INL Activities for UncertaintyReduction Analysis of FY10

    SciTech Connect

    G. Palmiotti; H. Hiruta; M. Salvatores

    2010-09-01

    The work scope of this project related to the Work Packages of “Uncertainty Reduction Analyses” with the goal of reducing nuclear data uncertainties is to produce a set of improved nuclear data to be used both for a wide range of validated advanced fast reactor design calculations, and for providing guidelines for further improvements of the ENDF/B files (i.e. ENDF/B-VII, and future releases). This report presents the status of activities performed at INL under the FC R&D Work Package previously mentioned. First an analysis of uncertainty evaluation is presented using the new covariance data (AFCI version 1.2) made available by BNL. Then, analyses of a number of experiments, among those selected in the previous fiscal year and available, are presented making use of ENDF/B-VII data. These experiments include: updating of the ZPR-6/7 assembly (improved model and spectral indices), ZPPR-9 assembly (only simplified model available), ZPPR-10 (full detailed model), and irradiation experiments. These last experiments include PROFIL-1 were a new methodology has been employed in the Monte Carlo calculations, and also a deterministic analysis has been performed. This is the first time the Monte Carlo approach and ENDF/B-VII have been used for the PROFIL experiments. The PROFIL-2 and TRAPU experiments have been for the moment only modeled and a full analysis of the irradiation results will be finalized next fiscal year.

  1. Recent Status of SIM Lite Astrometric Observatory Mission: Flight Engineering Risk Reduction Activities

    NASA Technical Reports Server (NTRS)

    Goullioud, Renaud; Dekens, Frank; Nemati, Bijan; An, Xin; Carson, Johnathan

    2010-01-01

    The SIM Lite Astrometric Observatory is a mission concept for a space-borne instrument to perform micro-arc-second narrow-angle astrometry to search 60 to 100 nearby stars for Earth-like planets, and to perform global astrometry for a broad astrophysics program. The instrument consists of two Michelson stellar interferometers and a telescope. The first interferometer chops between the target star and a set of reference stars. The second interferometer monitors the attitude of the instrument in the direction of the target star. The telescope monitors the attitude of the instrument in the other two directions. The main enabling technology development for the mission was completed during phases A & B. The project is currently implementing the developed technology onto flight-ready engineering models. These key engineering tasks will significantly reduce the implementation risks during the flight phases C & D of the mission. The main optical interferometer components, including the astrometric beam combiner, the fine steering optical mechanism, the path-length-control and modulation optical mechanisms, focal-plane camera electronics and cooling heat pipe, are currently under development. Main assemblies are built to meet flight requirements and will be subjected to flight qualification level environmental testing (random vibration and thermal cycling) and performance testing. This paper summarizes recent progress in engineering risk reduction activities.

  2. False Alarm Reduction in BSN-Based Cardiac Monitoring Using Signal Quality and Activity Type Information

    PubMed Central

    Tanantong, Tanatorn; Nantajeewarawat, Ekawit; Thiemjarus, Surapa

    2015-01-01

    False alarms in cardiac monitoring affect the quality of medical care, impacting on both patients and healthcare providers. In continuous cardiac monitoring using wireless Body Sensor Networks (BSNs), the quality of ECG signals can be deteriorated owing to several factors, e.g., noises, low battery power, and network transmission problems, often resulting in high false alarm rates. In addition, body movements occurring from activities of daily living (ADLs) can also create false alarms. This paper presents a two-phase framework for false arrhythmia alarm reduction in continuous cardiac monitoring, using signals from an ECG sensor and a 3D accelerometer. In the first phase, classification models constructed using machine learning algorithms are used for labeling input signals. ECG signals are labeled with heartbeat types and signal quality levels, while 3D acceleration signals are labeled with ADL types. In the second phase, a rule-based expert system is used for combining classification results in order to determine whether arrhythmia alarms should be accepted or suppressed. The proposed framework was validated on datasets acquired using BSNs and the MIT-BIH arrhythmia database. For the BSN dataset, acceleration and ECG signals were collected from 10 young and 10 elderly subjects while they were performing ADLs. The framework reduced the false alarm rate from 9.58% to 1.43% in our experimental study, showing that it can potentially assist physicians in diagnosing a vast amount of data acquired from wireless sensors and enhance the performance of continuous cardiac monitoring. PMID:25671512

  3. Catechin-capped gold nanoparticles: green synthesis, characterization, and catalytic activity toward 4-nitrophenol reduction

    NASA Astrophysics Data System (ADS)

    Choi, Yoonho; Choi, Myung-Jin; Cha, Song-Hyun; Kim, Yeong Shik; Cho, Seonho; Park, Youmie

    2014-03-01

    An eco-friendly approach is described for the green synthesis of gold nanoparticles using catechin as a reducing and capping agent. The reaction occurred at room temperature within 1 h without the use of any external energy and an excellent yield (99%) was obtained, as determined by inductively coupled plasma mass spectrometry. Various shapes of gold nanoparticles with an estimated diameter of 16.6 nm were green-synthesized. Notably, the capping of freshly synthesized gold nanoparticles by catechin was clearly visualized with the aid of microscopic techniques, including high-resolution transmission electron microscopy, atomic force microscopy, and field emission scanning electron microscopy. Strong peaks in the X-ray diffraction pattern of the as-prepared gold nanoparticles confirmed their crystalline nature. The catalytic activity of the as-prepared gold nanoparticles was observed in the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4. The results suggest that the newly prepared gold nanoparticles have potential uses in catalysis.

  4. Enhancing pyridinic nitrogen level in graphene to promote electrocatalytic activity for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Sun, Jiaguang; Wang, Lan; Song, Ranran; Yanga, Shubin

    2016-02-01

    We develop an efficient approach to fabricate nitrogen-doped graphene with tunable pyridinic nitrogen levels (from 1.1 to 1.8 at.%), abundant in-plane holes and high surface areas (623 m2 g-1) via a hydrothermal treatment of graphene oxide with hydrogen peroxide and subsequent annealing under ammonia gas. It is found that the chemical etching is beneficial to the formation of pyridinic nitrogen in graphene during the nitrogen-doping process, which is crucial to enhancing the electrocatalytic properties of graphene for oxygen reduction reaction (ORR). Hence, the optimized NG exhibits good electrocatalytic activity, more positive onset potential than Pt-C (-0.08 V versus -0.09 V), good durability, and high selectivity when it is employed as a metal-free catalyst for ORR. This approach may uncover a mechanism in escalation of pyridinic N atoms doped on the graphene basal edge and provide an efficient platform for the synthesis of a series of heteroatom-doped graphene with tunable heteroatom content for broad applications.

  5. Physiological selectivity and activity reduction of insecticides by rainfall to predatory wasps of Tuta absoluta.

    PubMed

    Barros, Emerson C; Bacci, Leandro; Picanco, Marcelo C; Martins, Júlio C; Rosado, Jander F; Silva, Gerson A

    2015-01-01

    In this study, we carried out three bioassays with nine used insecticides in tomato crops to identify their efficiency against tomato leaf miner Tuta absoluta, the physiological selectivity and the activity reduction of insecticides by three rain regimes to predatory wasps Protonectarina sylveirae and Polybia scutellaris. We assessed the mortality caused by the recommended doses of abamectin, beta-cyfluthrin, cartap, chlorfenapyr, etofenprox, methamidophos, permethrin, phenthoate and spinosad to T. absoluta and wasps at the moment of application. In addition, we evaluated the wasp mortality due to the insecticides for 30 days on plants that did not receive rain and on plants that received 4 or 125 mm of rain. Spinosad, cartap, chlorfenapyr, phenthoate, abamectin and methamidophos caused mortality higher than 90% to T. absoluta, whereas the pyrethroids beta-cyfluthrin, etofenprox and permethrin caused mortality between 8.5% and 46.25%. At the moment of application, all the insecticides were highly toxic to the wasps, causing mortality higher than 80%. In the absence of rain, all the insecticides continued to cause high mortality to the wasps for 30 days after the application. The toxicity of spinosad and methamidophos on both wasp species; beta-cyfluthrin on P. sylveirae and chlorfenapyr and abamectin on P. scutellaris, decreased when the plants received 4 mm of rain. In contrast, the other insecticides only showed reduced toxicity on the wasps when the plants received 125 mm of rain.

  6. Voice communications in the cockpit noise environment: The role of active noise reduction

    NASA Astrophysics Data System (ADS)

    Wheeler, Peter David

    The topic of voice communications in the cockpit noise environment of modern fast-jet aircraft and helicopters is addressed, and in particular, research undertaken in support of the development of a system for reducing the noise level at the operators' ear is described by acoustic cancellation within the ear defender, known as active noise reduction (ANR). The internal noise spectra of today's high performance fast-jet aircraft and military helicopters is described, and the complex interaction of acoustic noise transmission, speech, and microphone noise pick-up, which produces the total acoustic environment at the aircrews' ears, is discussed. Means of mathematically modelling the audio channel, quantifying the components identified above, and identifying areas of shortfall in performance are derived, leading to a procedure for the development of attenuation requirements, described as the communications audit. A model of the electroacoustic characteristics of the ANR ear defender assembly is presented and the sound field distribution within the ear defender/ear cavity, and its effect upon cancellation performance, is discussed. The extensive laboratory and flight testing of the ANR system that was undertaken is reviewed, paying particular attention to the measurement and analysis techniques employed in such testing. Finally, the performance characteristics of ANR are discussed and compared with the requirements previously established. Design limitations placed upon the system by the constraints of its area of application are described, and the scope for future improvements is considered.

  7. Growth and Deposition of Au Nanoclusters on Polymer-wrapped Graphene and Their Oxygen Reduction Activity

    PubMed Central

    Fujigaya, Tsuyohiko; Kim, ChaeRin; Hamasaki, Yuki; Nakashima, Naotoshi

    2016-01-01

    The development of a non-Pt electrocatalyst with a high performance for the oxygen reduction reaction (ORR) is one of the central issues in polymer electrolyte fuel cells science. Au-nanoparticles (Au-NPs) with a diameter of <2 nm are one of the promising substitutes of Pt-NPs; however, it is still a challenge to synthesize such a small-sized Au-NPs with a narrow diameter distribution on a carbon support without using capping agents. We here describe a facile method to deposit uniform Au-NPs (diameter = 1.6 nm and 3.3 nm) on the stacked-graphene (<10 layers) coated with poly[2,2′-(2,6-pyridine)-5,5′-bibenzimidazole] without using any capping agents. The obtained Au-NPs exhibit an excellent ORR activity with the onset potential at −0.11 V and −0.09 V (vs. Ag/AgCl) for 1.6 nm and 3.3 nm, respectively. On the other hand, inhomogeneous Au-NPs with 4.6 nm in average diameter shows the onset potential at −0.15 V (vs. Ag/AgCl). PMID:26899591

  8. An Overview of Propulsion Concept Studies and Risk Reduction Activities for Robotic Lunar Landers

    NASA Technical Reports Server (NTRS)

    Trinh, Huu P.; Story, George; Burnside, Chris; Kudlach, Al

    2010-01-01

    In support of designing robotic lunar lander concepts, the propulsion team at NASA Marshall Space Flight Center (MSFC) and the Johns Hopkins University Applied Physics Laboratory (APL), with participation from industry, conducted a series of trade studies on propulsion concepts with an emphasis on light-weight, advanced technology components. The results suggest a high-pressure propulsion system may offer some benefits in weight savings and system packaging. As part of the propulsion system, a solid rocket motor was selected to provide a large impulse to reduce the spacecraft s velocity prior to the lunar descent. In parallel to this study effort, the team also began technology risk reduction testing on a high thrust-to-weight descent thruster and a high-pressure regulator. A series of hot-fire tests was completed on the descent thruster in vacuum conditions at NASA White Sands Test Facility (WSTF) in New Mexico in 2009. Preparations for a hot-fire test series on the attitude control thruster at WSTF and for pressure regulator testing are now underway. This paper will provide an overview of the concept trade study results along with insight into the risk mitigation activities conducted to date.

  9. Reactivity Descriptors for the Activity of Molecular MN4 Catalysts for the Oxygen Reduction Reaction.

    PubMed

    Zagal, José H; Koper, Marc T M

    2016-11-14

    Similarities are established between well-known reactivity descriptors of metal electrodes for their activity in the oxygen reduction reaction (ORR) and the reactivity of molecular catalysts, in particular macrocyclic MN4 metal complexes confined to electrode surfaces. We show that there is a correlation between the M(III) /M(II) redox potential of MN4 chelates and the M-O2 binding energies. Specifically, the binding energy of O2 (and other O species) follows the M(III) -OH/M(II) redox transition for MnN4 and FeN4 chelates. The ORR volcano plot for MN4 catalysts is similar to that for metal catalysts: catalysts on the weak binding side (mostly CoN4 chelates) yield mainly H2 O2 as the product, with an ORR onset potential independent of the pH value on the NHE scale (and therefore pH-dependent on the RHE scale); catalysts on the stronger binding side yield H2 O as the product with the expected pH-dependence on the NHE scale. The suggested descriptors also apply to heat-treated pyrolyzed MN4 catalysts.

  10. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction

    PubMed Central

    Parnell, Charlette M.; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A.; Mudalige, Thilak K.; Biris, Alexandru S.; Ghosh, Anindya

    2016-01-01

    Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material’s −0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 106 mol−1s−1 was observed for the polydopamine-coated material–over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells. PMID:27528439

  11. Haem propionates control oxidative and reductive activities of horseradish peroxidase by maintaining the correct orientation of the haem.

    PubMed Central

    Adak, S; Banerjee, R K

    1998-01-01

    The role of haem propionates in oxidative and reductive reactions catalysed by horseradish peroxidase (HRP) was studied after successful reconstitution of ferric protoporphyrin IX dimethyl ester (PPDME) into the apoperoxidase. The reconstituted enzyme oxidizes neither guaiacol (aromatic electron donor) nor iodide or thiocyanate (inorganic donor). Although the reconstituted enzyme binds guaiacol with a similar Kd (13 mM) to that of the native enzyme (10 mM), the Kd for SCN- binding (5 mM) is decreased 20-fold compared with that of the native enzyme (100 mM). This indicates that haem propionates hinder the entry or binding of inorganic anion to the active site of the native HRP. However, the reconstituted enzyme is catalytically inactive as it does not form spectroscopically detectable compound II with H2O2. CD measurements indicate a significant loss of haem CD spectrum of the reconstituted enzyme at 409 nm, suggesting a loss of asymmetry of the haem-protein interaction. Thus the inability of the reconstituted enzyme to form catalytic intermediates results from the change in orientation of the haem due to loss of interactions via the haem propionates. HRP also catalyses reductive reactions such as reduction of iodine (I+) in the presence of EDTA and H2O2. The reconstituted enzyme cannot catalyse I+ reduction because of the loss of I+ binding to the haem propionate. Since I+ reduction requires formation of the catalytically active enzyme-I+-EDTA ternary complex, the loss of reductive activity is primarily due to the loss of active enzyme formation. Haem propionates thus play a vital role in the oxidative and reductive reactions of HRP by favouring the formation of catalytic intermediates with H2O2 by maintaining the correct orientation of the haem with respect to the surrounding residues. PMID:9693101

  12. ACETYLENE INHIBITION OF TRICHLOROETHENE AND VINYL CHLORIDE REDUCTIVE DECHLORINATION. (R828772)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  13. Myopathic Lamin Mutations Cause Reductive Stress and Activate the Nrf2/Keap-1 Pathway

    PubMed Central

    Dialynas, George; Shrestha, Om K.; Ponce, Jessica M.; Zwerger, Monika; Thiemann, Dylan A.; Young, Grant H.; Moore, Steven A.; Yu, Liping; Lammerding, Jan; Wallrath, Lori L.

    2015-01-01

    Mutations in the human LMNA gene cause muscular dystrophy by mechanisms that are incompletely understood. The LMNA gene encodes A-type lamins, intermediate filaments that form a network underlying the inner nuclear membrane, providing structural support for the nucleus and organizing the genome. To better understand the pathogenesis caused by mutant lamins, we performed a structural and functional analysis on LMNA missense mutations identified in muscular dystrophy patients. These mutations perturb the tertiary structure of the conserved A-type lamin Ig-fold domain. To identify the effects of these structural perturbations on lamin function, we modeled these mutations in Drosophila Lamin C and expressed the mutant lamins in muscle. We found that the structural perturbations had minimal dominant effects on nuclear stiffness, suggesting that the muscle pathology was not accompanied by major structural disruption of the peripheral nuclear lamina. However, subtle alterations in the lamina network and subnuclear reorganization of lamins remain possible. Affected muscles had cytoplasmic aggregation of lamins and additional nuclear envelope proteins. Transcription profiling revealed upregulation of many Nrf2 target genes. Nrf2 is normally sequestered in the cytoplasm by Keap-1. Under oxidative stress Nrf2 dissociates from Keap-1, translocates into the nucleus, and activates gene expression. Unexpectedly, biochemical analyses revealed high levels of reducing agents, indicative of reductive stress. The accumulation of cytoplasmic lamin aggregates correlated with elevated levels of the autophagy adaptor p62/SQSTM1, which also binds Keap-1, abrogating Nrf2 cytoplasmic sequestration, allowing Nrf2 nuclear translocation and target gene activation. Elevated p62/SQSTM1 and nuclear enrichment of Nrf2 were identified in muscle biopsies from the corresponding muscular dystrophy patients, validating the disease relevance of our Drosophila model. Thus, novel connections were made

  14. L-Malate dehydrogenase activity in the reductive arm of the incomplete citric acid cycle of Nitrosomonas europaea.

    PubMed

    Deutch, Charles E

    2013-11-01

    The autotrophic nitrifying bacterium Nitrosomonas europaea does not synthesize 2-oxoglutarate (α-ketoglutarate) dehydrogenase under aerobic conditions and so has an incomplete citric acid cycle. L-malate (S-malate) dehydrogenase (MDH) from N. europaea was predicted to show similarity to the NADP(+)-dependent enzymes from chloroplasts and was separated from the NAD(+)-dependent proteins from most other bacteria or mitochondria. MDH activity in a soluble fraction from N. europaea ATCC 19718 was measured spectrophotometrically and exhibited simple Michaelis-Menten kinetics. In the reductive direction, activity with NADH increased from pH 6.0 to 8.5 but activity with NADPH was consistently lower and decreased with pH. At pH 7.0, the K m for oxaloacetate was 20 μM; the K m for NADH was 22 μM but that for NADPH was at least 10 times higher. In the oxidative direction, activity with NAD(+) increased with pH but there was very little activity with NADP(+). At pH 7.0, the K m for L-malate was 5 mM and the K m for NAD(+) was 24 μM. The reductive activity was quite insensitive to inhibition by L-malate but the oxidative activity was very sensitive to oxaloacetate. MDH activity was not strongly activated or inhibited by glycolytic or citric acid cycle metabolites, adenine nucleotides, NaCl concentrations, or most metal ions, but increased with temperature up to about 55 °C. The reductive activity was consistently 10-20 times higher than the oxidative activity. These results indicate that the L-malate dehydrogenase in N. europaea is similar to other NAD(+)-dependent MDHs (EC 1.1.1.37) but physiologically adapted for its role in a reductive biosynthetic sequence.

  15. Reductive behaviour of acid azo dye based wastewater: Biocatalyst activity in conjunction with enzymatic and bio-electro catalytic evaluation.

    PubMed

    Sreelatha, S; Nagendranatha Reddy, C; Velvizhi, G; Venkata Mohan, S

    2015-01-01

    Present study illustrates the significance of biocatalyst's reductive behaviour in the degradation of dye molecules using glucose as co-substrate. An anaerobic system was operated at a dye concentration of 50mg/l with an organic loading rate (OLR) of 1.36 kg COD/m(3)-day. Decolourization and COD removal efficiencies were observed to be 42% and 48% respectively. Azo reductase (18.9 U) and dehydrogenase enzyme (1.4 μg/ml) activities showed increment with operation time. Anaerobic microenvironment showed dye reduction converting them into aromatic amines. The presence of mediators viz., cytochromes, quinines and Fe-S proteins depicted in the cyclic voltammetry profiles played a crucial role in transfer of electrons for the reduction of dye molecules. Bio-electro kinetic profiles obtained through Tafel analysis showed persistent reduction behaviour, which is in good correlation with dye degradation in the anaerobic microenvironment.

  16. Nonluminous diffusion flame of diluted acetylene in oxygen-enriched air

    SciTech Connect

    Sugiyama, G.

    1994-12-31

    A soot-reducing mechanism of fuel dilution and oxygen enrichment in laminar diffusion flames is suggested. Analysis using the Burke-Schumann theory for the shape of over ventilated diffusion flames has shown that there is a critical ratio of stoichiometric coefficients of the fuel and the oxidizer under which the gas flows from the fuel side to the oxidizer side throughout the flame. When this condition is satisfied, the soot growth region vanishes. A similar result is also found in a numerical simulation for diffusion flames that do not satisfy the Burke-Schumann assumption of uniform flow field. KIVA code is used for that purpose. The theoretically predicted direction of gas-flow across the flame sheet is verified in an experiment in a coaxial-flow diffusion flame. Soot cloud and velocity fields are visualized through a laser sheet method in the experiment. The fuel is a mixture of acetylene and nitrogen. The oxidizer is a mixture of oxygen and nitrogen. The compositions of the reactants are controlled so that the adiabatic flame temperature is kept constant to avoid the effect of temperature change. Experimental results show substantial reduction of scattered light intensity by fuel dilution and oxygen enrichment. When a sufficient amount of nitrogen is added to the fuel, nonluminous blue flames are obtained. At higher oxygen concentrations, blue flames are obtained at higher flame temperature region. When oxygen concentration in the oxidizer is 70 vol.%, blue flames are obtained up to 2,250 K. The critical condition of the reactants for nonluminous flames agrees with the theoretical prediction when the oxidizer is ordinary air. In oxygen-enriched conditions, the fuel must be diluted more, than theoretically predicted.

  17. Report on INL Activities for Uncertainty Reduction Analysis of FY11

    SciTech Connect

    G. Plamiotti; H. Hiruta; M. Salvatores

    2011-09-01

    This report presents the status of activities performed at INL under the ARC Work Package on 'Uncertainty Reduction Analyses' that has a main goal the reduction of uncertainties associated with nuclear data on neutronic integral parameters of interest for the design of advanced fast reactors under consideration by the ARC program. First, an analysis of experiments was carried out. For both JOYO (the first Japanese fast reactor) and ZPPR-9 (a large size zero power plutonium fueled experiment performed at ANL-W in Idaho) the performance of ENDF/B-VII.0 is quite satisfying except for the sodium void configurations of ZPPR-9, but for which one has to take into account the approximation of the modeling. In fact, when one uses a more detailed model (calculations performed at ANL in a companion WP) more reasonable results are obtained. A large effort was devoted to the analysis of the irradiation experiments, PROFIL-1 and -2 and TRAPU, performed at the French fast reactor PHENIX. For these experiments a pre-release of the ENDF/B-VII.1 cross section files was also used, in order to provide validation feedback to the CSWEG nuclear data evaluation community. In the PROFIL experiments improvements can be observed for the ENDF/B-VII.1 capture data in 238Pu, 241Am, 244Cm, 97Mo, 151Sm, 153Eu, and for 240Pu(n,2n). On the other hand, 240,242Pu, 95Mo, 133Cs and 145Nd capture C/E results are worse. For the major actinides 235U and especially 239Pu capture C/E's are underestimated. For fission products, 105,106Pd, 143,144Nd and 147,149Sm are significantly underestimated, while 101Ru and 151Sm are overestimated. Other C/E deviations from unity are within the combined experimental and calculated statistical uncertainty. From the TRAPU analysis, the major improvement is in the predicted 243Cm build-up, presumably due to an improved 242Cm capture evaluation. The COSMO experiment was also analyzed in order to provide useful feedback on fission cross sections. It was found out that ENDF

  18. Aerobic Reduction of Arsenate by a Bacterium Isolated From Activated Sludge

    NASA Astrophysics Data System (ADS)

    Kozai, N.; Ohnuki, T.; Hanada, S.; Nakamura, K.; Francis, A. J.

    2006-12-01

    Microlunatus phosphovorus strain NM-1 is a polyphosphate-accumulating bacterium isolated from activated sludge. This bacterium takes up a large amount of polyphosphate under aerobic conditions and release phosphate ions by hydrolysis of polyphosphate to orthophosphate under anaerobic conditions to derive energy for taking up substrates. To understand the nature of this strain, especially, influence of potential contaminants in sewage and wastewater on growth, we have been investigating behavior of this bacterium in media containing arsenic. The present paper mainly reports reduction of arsenate by this bacterium under aerobic conditions. The strain NM-1 (JCM 9379) was aerobically cultured at 30 °C in a nutrient medium containing 2.5 g/l peptone, 0.5 g/l glucose, 1.5 g/l yeast extract, and arsenic [Na2HAsO4 (As(V)) or Na3AsO3 (As(III))] at concentrations between 0 and 50 mM. The cells collected from arsenic-free media were dispersed in buffer solutions containing 2mM HEPES, 10mM NaCl, prescribed concentrations of As(V), and 0-0.2 percent glucose. Then, this cell suspension was kept at 20 °C under aerobic or anaerobic conditions. The speciation of arsenic was carried out by ion chromatography and ICP-MS. The growth of the strain under aerobic conditions was enhanced by the addition of As(V) at the concentration between 1 and 10 mM. The maximum optical density of the culture in the medium containing 5mM As(V) was 1.4 times greater than that of the control culture. Below the As(V) concentration of 10mM, most of the As(V) was reduced to As(III). The growth of the strain under anaerobic conditions has not been observed so far. The cells in the buffer solutions reduced As(V) under aerobic condition. The reduction was enhanced by the addition of glucose. However, the cell did not reduce As(V) under anaerobic conditions. The strain NM-1 showed high resistance to As(V) and As(III). The maximum optical density of the culture grown in a medium containing 50 mM As(V) was only

  19. Inactivation of Escherichia coli by a combination of nisin, pulsed electric fields, and water activity reduction by sodium chloride.

    PubMed

    Terebiznik, M; Jagus, R; Cerrutti, P; de Huergo, M S; Pilosof, A M R

    2002-08-01

    The effect of nisin combined with pulsed electric fields (PEF) and water activity reduction by sodium chloride (NaCl) on the inactivation of E. coli in simulated milk ultrafiltrate media was studied with a Doehlert design and a response surface method. The reduction of water activity from 0.99 to 0.95 by the addition of NaCl (without any other hurdle) did not affect E. coli viability of approximately 10(8) CFU/ml. A reduction in PEF effectiveness occurred when the NaCl concentration was increased because of an increase in conductance, which reduced the pulse decay time. In cells submitted to PEF nisin activity was decreased, probably as a consequence of the nonspecific binding of nisin to cellular debris or the emergence of new binding sites in or from cells. However, the lethal effect due to nisin was reestablished and further improved when water activity was reduced to 0.95. A synergistic effect was evidenced when low-intensity PEF were applied. Decreasing water activity to 0.95 and applying PEF at 5 kV/cm (a nonlethal intensity when no other hurdle is used) with the further addition of nisin (1,200 IU/ml) resulted in a 5-log cycle reduction of the bacterial population.

  20. Gas Chromatographic Separation of an Acetylene Vinyl Fluoride-Difluoroethane Mixture on Triethylene Glycol and Silicone Oil,

    DTIC Science & Technology

    The purpose of the research was to study gas-chromatographic separation of impurities of acetylene and difluoroethane in vinyl fluoride obtained by...and difluoroethane . All the components are separated, and the criteria of separation of acetylene-vinyl fluoride and vinyl fluoride- difluoroethane

  1. Risk Reduction Activities for the Near-Earth Object Surveillance Satellite Project

    NASA Astrophysics Data System (ADS)

    Bédard, D.; Scott, L.; Wallace, B.; Harvey, W.

    every three minutes, for an average of 288 images for every 24 hours of operation. To ensure both science teams can employ the NEOSSat spacecraft to its full potential, the Mission Planning System (MPS) will automate the scheduling of both the HEOSS and NESS observation tasks. In another risk reduction effort for the NEOSSat project, a prototype of the MPS software has been developed to help in the definition of the system requirements as well as to identify and reduce the risks associated with the development of this software system. The paper will first provide an update on the status and schedule of the NEOSSat project. Then, we will present the results achieved (metrics and photometry) from the two tracked GPS spacecraft as well as the lessons learned that are being applied during the development of the joint DRDC and CSA NEOSSat micro-satellite. Finally, results obtained from the MPS prototype development will be presented with a special emphasis on the final system to be designed including a description of the functions judged to be critical based upon the risk reduction activity.

  2. Quantum Dynamics of Vinylidene Photodetachment on an Accurate Global Acetylene-Vinylidene Potential Energy Surface.

    PubMed

    Guo, Lifen; Han, Huixian; Ma, Jianyi; Guo, Hua

    2015-08-06

    Vinylidene is a high-energy isomer of acetylene, and the rearrangement of bonds in the two species serves as a prototype for isomerization reactions. Here, a full-dimensional quantum mechanical study of the vinylidene vibration is carried out on a recently developed global acetylene-vinylidene potential energy surface by simulating the photodetachment dynamics of the vinylidene anion. Several low-lying vibrational levels of the anion were first determined on a new ab initio based potential energy surface, and their photoelectron spectra were obtained within the Condon approximation. The vibrational features of the vinylidene isomer are found to agree well with the experiment in both positions and intensities, validating the global acetylene-vinylidene potential energy surface.

  3. 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.

  4. Structure-guided unravelling: Phenolic hydroxyls contribute to reduction of acrylamide using multiplex quantitative structure-activity relationship modelling.

    PubMed

    Zhang, Yu; Huang, Mengmeng; Wang, Qiao; Cheng, Jun

    2016-05-15

    We reported a structure-activity relationship study on unravelling phenolic hydroxyls instead of alcoholic hydroxyls contribute to the reduction of acrylamide formation by flavonoids. The dose-dependent study shows a close correlation between the number of phenolic hydroxyls of flavonoids and their reduction effects. In view of positions of hydroxyls, the 3',4'(ortho)-dihydroxyls in B cycle, 3-hydroxyl or hydroxyls of 3-gallate in C cycle, and 5,7(meta)-dihydroxyls in A cycle of flavonoid structures play an important role in the reduction of acrylamide. Flavone C-glycosides are more effective at reducing the formation of acrylamide than flavone O-glycosides when sharing the same aglycone. The current multiplex quantitative structure-activity relationship (QSAR) equations effectively predict the inhibitory rates of acrylamide using selected chemometric parameters (R(2): 0.835-0.938). This pioneer study opens a broad understanding on the chemoprevention of acrylamide contaminants on a structural basis.

  5. Facet-Dependent Catalytic Activity of Platinum Nanocrystals for Triiodide Reduction in Dye-Sensitized Solar Cells

    PubMed Central

    Zhang, Bo; Wang, Dong; Hou, Yu; Yang, Shuang; Yang, Xiao Hua; Zhong, Ju Hua; Liu, Jian; Wang, Hai Feng; Hu, P.; Zhao, Hui Jun; Yang, Hua Gui

    2013-01-01

    Platinum (Pt) nanocrystals have demonstrated to be an effective catalyst in many heterogeneous catalytic processes. However, pioneer facets with highest activity have been reported differently for various reaction systems. Although Pt has been the most important counter electrode material for dye-sensitized solar cells (DSCs), suitable atomic arrangement on the exposed crystal facet of Pt for triiodide reduction is still inexplicable. Using density functional theory, we have investigated the catalytic reaction processes of triiodide reduction over {100}, {111} and {411} facets, indicating that the activity follows the order of Pt(111) > Pt(411) > Pt(100). Further, Pt nanocrystals mainly bounded by {100}, {111} and {411} facets were synthesized and used as counter electrode materials for DSCs. The highest photovoltaic conversion efficiency of Pt(111) in DSCs confirms the predictions of the theoretical study. These findings have deepened the understanding of the mechanism of triiodide reduction at Pt surfaces and further screened the best facet for DSCs successfully. PMID:23670438

  6. Waste Reduction.

    ERIC Educational Resources Information Center

    Bray, Marilyn; And Others

    1996-01-01

    Presents activities that focus on waste reduction in the school and community. The ideas are divided into grade level categories. Sample activities include Techno-Trash, where children use tools to take apart broken appliances or car parts, then reassemble them or build new creations. Activities are suggested for areas including language arts and…

  7. Development of bioelectrocatalytic activity stimulates mixed-culture reduction of glycerol in a bioelectrochemical system

    PubMed Central

    Zhou, Mi; Freguia, Stefano; Dennis, Paul G; Keller, Jürg; Rabaey, Korneel

    2015-01-01

    In a microbial bioelectrochemical system (BES), organic substrate such as glycerol can be reductively converted to 1,3-propanediol (1,3-PDO) by a mixed population biofilm growing on the cathode. Here, we show that 1,3-PDO yields positively correlated to the electrons supplied, increasing from 0.27 ± 0.13 to 0.57 ± 0.09 mol PDO mol−1 glycerol when the cathodic current switched from 1 A m−2 to 10 A m−2. Electrochemical measurements with linear sweep voltammetry (LSV) demonstrated that the biofilm was bioelectrocatalytically active and that the cathodic current was greatly enhanced only in the presence of both biofilm and glycerol, with an onset potential of −0.46 V. This indicates that glycerol or its degradation products effectively served as cathodic electron acceptor. During long-term operation (> 150 days), however, the yield decreased gradually to 0.13 ± 0.02 mol PDO mol−1 glycerol, and the current–product correlation disappeared. The onset potentials for cathodic current decreased to −0.58 V in the LSV tests at this stage, irrespective of the presence or absence of glycerol, with electrons from the cathode almost exclusively used for hydrogen evolution (accounted for 99.9% and 89.5% of the electrons transferred at glycerol and glycerol-free conditions respectively). Community analysis evidenced a decreasing relative abundance of Citrobacter in the biofilm, indicating a community succession leading to cathode independent processes relative to the glycerol. It is thus shown here that in processes where substrate conversion can occur independently of the electrode, electroactive microorganisms can be outcompeted and effectively disconnected from the substrate. PMID:25817314

  8. Feasibility of measuring ferricyanide reduction by yeasts to estimate their activity during alcoholic fermentation in wine-making conditions.

    PubMed

    Roustan, Jean-Louis; Sablayrolles, Jean-Marie

    2003-01-01

    We assessed the feasibility of measuring the extracellular reduction of ferricyanide in the presence of an intermediate carrier (menadione) as a means of estimating the activity of yeasts during alcoholic fermentation. A spectrophotometric and a potentiometric approach were used. Comparison of specific reductase activity and gas production rate during the stationary phase indicated that measuring the menadione-catalyzed reduction of ferricyanide provides a good estimate of the total activity of the yeast cells in a fermenting must. The response observed following the addition of an electron acceptor (acetaldehyde) confirmed that the reductase activity of menadione is dependent on the availability of NADH. The stability of menadione in the fermentation medium, as assessed by the potentiometric method, suggested that electrochemical reoxidation of the ferrocyanide can act as a substitute for the addition of an electron acceptor when studying the redox regulation of fermenting yeasts.

  9. Synthesis of micro- and nanodiamonds by the method of oxy- acetylene combustion flame

    NASA Astrophysics Data System (ADS)

    Sabitov, S.; Mansurov, B.; Medyanova, B.; Partizan, G.; Koshanova, A.; Merkibayev, Ye; Mansurova, M.; Lesbayev, B.

    2016-08-01

    This work presents the results of experiments on synthesis of micro- and nanodiamonds by the method of oxy-acetylene torch on the surface of pre-deposited copper thin films. The influence of the thickness of the buffer copper film and the concentration ratio of oxygen and acetylene on the structure formation of the deposited samples was investigated during performed experiments. Studies by Raman scattering and scanning electron microscopy showed that the synthesis of micro- and nano-diamonds occurs under certain experimental conditions.

  10. 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.

  11. Efficient synthesis of β-chlorovinylketones from acetylene in chloroaluminate ionic liquids.

    PubMed

    Snelders, Dennis J M; Dyson, Paul J

    2011-08-05

    A method for the Friedel-Crafts-type insertion reaction of acetylene with acid chlorides in chloroaluminate ionic liquids is presented. The use of ionic liquids not only serves to avoid the use of carbon tetrachloride or 1,2-dichloroethane but also suppresses side reactions, notably the polymerization of acetylene, which occurs in these chlorinated solvents. Consequently, the products can be isolated using a simpler purification procedure, giving a range of aromatic and aliphatic β-chlorovinyl ketones in high yield and purity.

  12. 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.

  13. [Effect of permeabilization on sulfate reduction activity of Desulfovibrio vulgaris Hildenborough cells in the presence of different electron donors].

    PubMed

    Xu, Hui-Wei; Zhang, Xu; Li, Li-Ming; Zheng, Guang-Jie; Li, Guang-He

    2013-01-01

    The Desulfovibrio vulgaris Hildenborough (DvH) cells permeabilized with ethanol were used as biocatalysts to enhance hydrogenotrophic sulfate conversion. The effect of permeabilization extent of DvH cells on sulfate reduction was studied in the presence of different electron donors. When hydrogen was used as an electron donor, the highest level of sulfate reduction activity attained in cells treated with 10% ethanol (V/V), followed by 15% -ethanol treated cells. Furthermore, sulfate reduction activity markedly decreased when the ethanol concentration exceeded 15%. However, when lactate was used as the electron donor, the optimum ethanol concentration of the permeabilizing reagent was 20%, followed by 15% and 10%. Even when ethanol concentration reached 25%, DvH cells remained their partial activity with lactate. In a word, sulfate reduction activity of DvH cells responded differently in the presence of different donors. This was because the oxidation process of H2 and lactate occurred at different positions in DvH cells, and consequently intracellular electron transport pathway differed. To ensure the integrity of the electron transport chain between the donor and the accepter was a key factor for determining the permeabilization extent and for the application of cell permeabilization technology.

  14. Further Examination of the Vibratory Loads Reduction Results from the NASA/ARMY/MIT Active Twist Rotor Test

    NASA Technical Reports Server (NTRS)

    Wilbur, Matthew L.; Yeager, William T., Jr.; Sekula, Martin K.

    2002-01-01

    The vibration reduction capabilities of a model rotor system utilizing controlled, strain-induced blade twisting are examined. The model rotor blades, which utilize piezoelectric active fiber composite actuators, were tested in the NASA Langley Transonic Dynamics Tunnel using open-loop control to determine the effect of active-twist on rotor vibratory loads. The results of this testing have been encouraging, and have demonstrated that active-twist rotor designs offer the potential for significant load reductions in future helicopter rotor systems. Active twist control was found to use less than 1% of the power necessary to operate the rotor system and had a pronounced effect on both rotating- and fixed-system loads, offering reductions in individual harmonic loads of up to 100%. A review of the vibration reduction results obtained is presented, which includes a limited set of comparisons with results generated using the second-generation version of the Comprehensive Analytical Model of Rotorcraft Aerodynamics and Dynamics (CAMRAD II) rotorcraft comprehensive analysis.

  15. A feasibility study on assessing public health impacts of cumulative air pollution reduction activities in a small geographic area

    EPA Science Inventory

    Background and Objective: The rnain objective ofthis study was to examine the feasibility ofconducting a local (e.g., city level) assessment ofthe public health impacts ofcumulative air pollution reduction activities (a.k.a. accountability) from the federal, state, local and vo...

  16. Particle size dependence on oxygen reduction reaction activity of electrodeposited TaO(x) catalysts in acidic media.

    PubMed

    Seo, Jeongsuk; Cha, Dongkyu; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

    2014-01-21

    The size dependence of the oxygen reduction reaction activity was studied for TaO(x) nanoparticles electrodeposited on carbon black for application to polymer electrolyte fuel cells (PEFCs). Compared with a commercial Ta2O5 material, the ultrafine oxide nanoparticles exhibited a distinctively high onset potential different from that of the bulky oxide particles.

  17. 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.

  18. Report on INL Activities for Uncertainty Reduction Analysis of FY12

    SciTech Connect

    G. Palmiotti; M. Salvatores

    2012-09-01

    The work scope of this project related to the Work Packages of “Uncertainty Reduction Analyses” with the goal of reducing nuclear data uncertainties is to produce a set of improved nuclear data to be used both for a wide range of validated advanced fast reactor design calculations, and for providing guidelines for further improvements of the ENDF/B files (i.e. ENDF/B-VII, and future releases). Recent extensive sensitivity/uncertainty studies, performed within an international OECD-NEA initiative, have quantified for the first time the impact of current nuclear data uncertainties on design parameters of the major FCR&D and GEN-IV systems, and in particular on Na-cooled fast reactors with different fuels (oxide or metal), fuel composition (e.g. different Pu/TRU ratios) and different conversion ratios. These studies have pointed out that present uncertainties on the nuclear data should be significantly reduced, in order to get full benefit from the advanced modeling and simulation initiatives. Nuclear data plays a fundamental role in performance calculations of advanced reactor concepts. Uncertainties in the nuclear data propagate into uncertainties in calculated integral quantities, driving margins and costs in advanced system design, operation and safeguards. This package contributes to the resolution of technical, cost, safety, security and proliferation concerns in a multi-pronged, systematic, science-based R&D approach. The Nuclear Data effort identifies and develops small scale, phenomenon-specific experiments informed by theory and engineering to reduce the number of large, expensive integral experiments. The Nuclear Data activities are leveraged by effective collaborations between experiment and theory, between DOE programs and offices, at national laboratories and universities, both domestic and international. The primary objective is to develop reactor core sensitivity and uncertainty analyses that identify the improvement needs of key nuclear data which

  19. Vibration reduction in helicopter rotors using an actively controlled partial span trailing edge flap located on the blade

    NASA Technical Reports Server (NTRS)

    Millott, T. A.; Friedmann, P. P.

    1994-01-01

    This report describes an analytical study of vibration reduction in a four-bladed helicopter rotor using an actively controlled, partial span, trailing edge flap located on the blade. The vibration reduction produced by the actively controlled flap (ACF) is compared with that obtained using individual blade control (IBC), in which the entire blade is oscillated in pitch. For both cases a deterministic feedback controller is implemented to reduce the 4/rev hub loads. For all cases considered, the ACF produced vibration reduction comparable with that obtained using IBC, but consumed only 10-30% of the power required to implement IBC. A careful parametric study is conducted to determine the influence of blade torsional stiffness, spanwise location of the control flap, and hinge moment correction on the vibration reduction characteristics of the ACF. The results clearly demonstrate the feasibility of this new approach to vibration reduction. It should be emphasized than the ACF, used together with a conventional swashplate, is completely decoupled from the primary flight control system and thus it has no influence on the airworthiness of the helicopter. This attribute is potentially a significant advantage when compared to IBC.

  20. Synthesis of chitosan supported palladium nanoparticles and its catalytic activity towards 2-nitrophenol reduction

    NASA Astrophysics Data System (ADS)

    Dhanavel, S.; Nivethaa, E. A. K.; Esther, G.; Narayanan, V.; Stephen, A.

    2016-05-01

    Chitosan supported Palladium nanoparticles were synthesized by a simple cost effective chemical reduction method using NaBH4. The prepared nanocomposite was characterized by X-Ray diffraction analysis, FESEM and Energy dispersive spectroscopy analysis of X-rays (EDAX). The catalytic performance of the nanocomposite was evaluated on the reduction of 2-Nitrophenol to the 2-Amino phenol with rate constant 1.08 × 10-3 S-1 by NaBH4 using Spectrophotometer.