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Sample records for acetylene terminated aspartimides

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  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. 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.

  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. 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

  13. 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.

  14. 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.

  15. 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.

  16. C-Terminal acetylene derivatized peptides via silyl-based alkyne immobilization.

    PubMed

    Strack, Martin; Metzler-Nolte, Nils; Albada, H Bauke

    2013-06-21

    A new Silyl-based Alkyne Modifying (SAM)-linker for the synthesis of C-terminal acetylene-derivatized peptides is reported. The broad scope of this SAM2-linker is illustrated by manual synthesis of peptides that are side-chain protected, fully deprotected, and disulfide-bridged. Synthesis of a 14-meric (KLAKLAK)2 derivative by microwave-assisted automated SPPS and a one-pot cleavage click procedure yielding protected 1,2,3-triazole peptide conjugates are also described.

  17. Silyl-based alkyne-modifying linker for the preparation of C-terminal acetylene-derivatized protected peptides.

    PubMed

    Strack, Martin; Langklotz, Sina; Bandow, Julia E; Metzler-Nolte, Nils; Albada, H Bauke

    2012-11-16

    A novel linker for the synthesis of C-terminal acetylene-functionalized protected peptides is described. This SAM1 linker is applied in the manual Fmoc-based solid-phase peptide synthesis of Leu-enkephalin and in microwave-assisted automated synthesis of Maculatin 2.1, an antibacterial peptide that contains 18 amino acid residues. For the cleavage, treatment with tetramethylammonium fluoride results in protected acetylene-derivatized peptides. Alternatively, a one-pot cleavage-click procedure affords the protected 1,2,3-triazole conjugate in high yields after purification.

  18. 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…

  19. A General Preparation of Tailored-Length Acetylene Terminated Resins from Low-Cost Bisphenols

    DTIC Science & Technology

    1985-05-01

    bisphenols in 2, 4, 6-collidine with cuprous or cupric oxide to afford bromine terminated oligomer mixtures of stoichio- metrically tailored average lengths...preparation of 1,3-bis(3-bromophenoxy)benzene, cuprous oxide was replaced by an equivalent amount of cupric oxide. 4. Conversion of Bromine Terminated...either 1,3-dibromobenzene or 1,4-dibromobenzene, and cuprous oxide in 2,4,6-collidine, under conditions similar to those previously reported for the

  20. Synthesis of 3-iodoindoles by the Pd/Cu-catalyzed coupling of N,N-dialkyl-2-iodoanilines and terminal acetylenes, followed by electrophilic cyclization.

    PubMed

    Yue, Dawei; Yao, Tuanli; Larock, Richard C

    2006-01-06

    [reaction: see text] 3-Iodoindoles have been prepared in excellent yields by coupling terminal acetylenes with N,N-dialkyl-o-iodoanilines in the presence of a Pd/Cu catalyst, followed by an electrophilic cyclization of the resulting N,N-dialkyl-o-(1-alkynyl)anilines using I2 in CH2Cl2. Aryl-, vinylic-, alkyl-, and silyl-substituted terminal acetylenes undergo this process to produce excellent yields of 3-iodoindoles. The reactivity of the carbon-nitrogen bond cleavage during cyclization follows the following order: Me > n-Bu, Me > Ph, and cyclohexyl > Me. Subsequent palladium-catalyzed Sonogashira, Suzuki, and Heck reactions of the resulting 3-iodoindoles proceed smoothly in good yields.

  1. [omega]-Hydroxylation of Oleic Acid in Vicia sativa Microsomes (Inhibition by Substrate Analogs and Inactivation by Terminal Acetylenes).

    PubMed Central

    Pinot, F.; Bosch, H.; Alayrac, C.; Mioskowski, C.; Vendais, A.; Durst, F.; Salaun, J. P.

    1993-01-01

    Oleic acid (18:1) is hydroxylated exclusively on the terminal methyl by a microsomal cytochrome P-450-dependent system ([omega]-OAH) from clofibrate-induced Vicia sativa L. (var minor) seedlings (F. Pinot, J.-P. Salaun, H. Bosch, A. Lesot, C. Mioskowski, F. Durst [1992] Biochem Biophys Res Commun 184: 183-193). This reaction was inactivated by two terminal acetylenes: (Z)-9-octadecen-17-ynoic acid (17-ODCYA) and the corresponding epoxide, (Z)-9,10-epoxyoctadecan-17-ynoic acid (17-EODCYA). Inactivation was mechanism-based, with an apparent binding constant of 21 and 32 [mu]M and half-lives of 16 and 19 min for 17-ODCYA and 17-EODCYA, respectively. We have investigated the participation of one or more [omega]-hydroxylase isoforms in the oxidation of fatty acids in this plant system. Lauric acid (12:0) is [omega]-hydroxylated by the cytochrome P-450 [omega]-hydroxylase [omega]-LAH (J.-P. Salaun, A. Simon, F. Durst [1986] Lipids 21: 776-779). Half-lives of [omega]-OAH and [omega]-LAH in the presence of 40 [mu]M 17-ODCYA were 23 and 41 min, respectively. Inhibition of oleic acid [omega]-hydroxylation was competitive with linoleic acid (18:2), but noncompetitive with lauric acid (12:0). In contrast, oleic acid did not inhibit [omega]-hydroxylation of lauric acid. Furthermore, 1-pentadecyltriazole inhibited [omega]-hydroxylation of oleic acid but not of lauric acid. These results suggest that distinct monooxygenases catalyze [omega]-hydroxylation of medium- and long-chain fatty acids in V. sativa microsomes. PMID:12231907

  2. Characterization of peptide immobilization on an acetylene terminated surface via click chemistry

    NASA Astrophysics Data System (ADS)

    Shamsi, Fahimeh; Coster, Hans; Jolliffe, Katrina A.

    2011-10-01

    Peptide (A-A-A-A-G-G-G-E-R-G-D)1A: Alanine; D: Glutamic acid; E: Aspartic acid; G: Glycine; R: Arginine. conjugated surfaces were prepared on silicon surfaces through click chemistry. The amino acid sequence RGD is the cellular attachment site of a large number of extracellular matrices such as blood and cell surface proteins. Recent research has focused on developing RGD peptides which mimic cell adhesion proteins and integrins [1,2].The steps involved the formation of an alkyne-terminated monolayer on Si(111), followed by linking the peptide to 4-azidophenyl isothiocyanate via a specific and gentle reaction. This was followed by the attachment of the azido peptide to the surface-bound alkynes using the Cu (I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction. The surface structures of the alkyne terminated monolayer and the attached peptide were characterized using high resolution impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared (ATR-FTIR) Spectroscopy. EIS characterization revealed the alkyne layer and the hydrophobic and polar regions of the attached peptide. XPS analysis showed a high surface coverage of the peptide on the silicon substrates and this was confirmed by FTIR.Our results confirmed a specific covalent attachment of the peptide on the silicon surfaces. This approach offers a versatile, experimentally simple, method for the specific attachment of peptide ligands. This approach would have applications for cell attachment and biosensors.

  3. Preventing aspartimide formation in Fmoc SPPS of Asp-Gly containing peptides--practical aspects of new trialkylcarbinol based protecting groups.

    PubMed

    Behrendt, Raymond; Huber, Simon; White, Peter

    2016-02-01

    In our efforts to develop a universal solution to the problem of aspartimide formation in Fmoc SPPS, we investigated the application of our new β-trialkylmethyl protected aspartic acid building blocks to the synthesis of peptides containing the Asp-Gly motif. The N(α)-Fmoc aspartic acid β-tri-(ethyl/propyl/butyl)methyl esters were used in the synthesis of the classic model peptide scorpion toxin II (VKDGYI), and their effectiveness in minimising aspartimide formation during extended piperidine treatments was evaluated. Furthermore, we compared their efficacy against that of the commonly used approach of adding acids to the Fmoc deprotection solution. Finally, we applied our aspartic acid building blocks to the stepwise Fmoc SPPS of teduglutide, a human GLP-2 analogue, whose synthesis is made challenging by extensive aspartimide formation. In all experiments, our approach led to almost complete reduction of aspartimide formation with accompanied suppression of aspartic acid epimerisation.

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  5. Facile one-pot synthesis of 4,5-disubstituted 1,2,3-(NH)-triazoles through Sonogashira coupling/1,3-dipolar cycloaddition of acid chlorides, terminal acetylenes, and sodium azide.

    PubMed

    Li, Jihui; Wang, Dong; Zhang, Yuanqing; Li, Jiting; Chen, Baohua

    2009-07-16

    A novel and efficient way of synthesizing 4,5-disubstituted-1,2,3-(NH)-triazoles through palladium-catalyzed and ultrasonic promoted Sonogashira coupling/1,3-dipolar cycloaddition of acid chlorides, terminal acetylenes, and sodium azide in one pot is developed. The reaction scope is quite general, and the methodology can produce excellent yields. The regioselective 1,4,5-trisubstituted-1,2,3-(NH)-triazoles can be made easily from 4,5-disubstituted-1,2,3-(NH)-triazoles.

  6. Acetylene Terminated Sulfone Resin Development.

    DTIC Science & Technology

    1982-04-01

    lower heat of reaction (99.7 cal/g). High Performance Liquid Chromatography (HPLC) analysis disclosed that the sample was quite heterogeneous... Performance Liquid Chromatography Viscosity Mechanical Properties Gelation Vitrification Volatile Release Processing Prepreg Laminates 20. Abstract...When Daet Entered) UNCLASS IF IED SECURITY CLASSIFICATION OF THIS PAGE(Wh.n Data Ene,ed) 19. Key Words (Concluded) Dynamic Mechanical Analysis High

  7. 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.

  8. 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.

  9. Novel cytochrome p450 bioactivation of a terminal phenyl acetylene group: formation of a one-carbon loss benzaldehyde and other oxidative products in the presence of N-acetyl cysteine or glutathione.

    PubMed

    Subramanian, Raju; Tam, Janet; Aidasani, Divesh; Reid, Darren L; Skiles, Gary L

    2011-05-16

    Compounds 1 (N1-(3-ethynylphenyl)-6-methyl-N5-(3-(6-(methylamino)pyrimidin-4-yl)pyridin-2-yl) isoquinoline-1,5-diamine) and 2 (N-(3-ethynylphenyl)-6,7-bis(2-methoxyethoxy)quinazolin-4-amine; Erlotinib/Tarceva) are kinase inhibitors that contain a terminal phenyl acetylene moiety. When incubated in the presence of P450 and NADPH, the anticipated phenyl acetic acid metabolite was formed. When 10 mM of N-acetyl-l-cysteine was added to the incubation mixtures, the phenyl acetic acid product was reduced and at 25 mM or higher concentration of NAC, formation of the phenyl acetic acid was abolished. Instead, the phenyl acetylene moiety lost a carbon and formed a benzaldehyde product. Other oxidation products incorporating one or more equivalents of NAC were also observed. The identities of the metabolites were characterized by MS and NMR. Addition of deferoxamine or ascorbic acid diminished the formation of the NAC influenced products. Similar products were also observed when 1 or 2 were incubated in P450 reactions supplemented with GSH, in Fenton reactions supplemented with NAC or GSH, and in peroxidase reactions supplemented with NAC. We propose the thiols act as a pro-oxidant readily undergoing a one-electron oxidation to form thiyl radicals which in turn initiates the formation of other peroxy radicals that drive the reaction to the observed products. These in vitro findings suggest that one-electron oxidation of thiols may promote the cooxidation of xenobiotic substrates.

  10. The synthesis of monomers with pendent ethynyl group for modified high performance thermoplastics

    NASA Technical Reports Server (NTRS)

    Nwokogu, Godson C.; Antoine, Miquel D.; Ansong, Omari

    1992-01-01

    The objectives of this project were to develop synthetic schemes for the following classes of modified monomers: (1) difunctional triarylethanes with pendent acetylenic groups; and (2) tertiary aspartimides with terminal acetylene groups at the two ends. Our efforts have resulted in the successful development of high yield schemes for the syntheses of several diamino and bisphenolic analogs of difunctional triarylethanes with pendent ethynyl group. A scheme for one new tertiary aspartimide was also established. Multi-gram samples of all prepared new monomers were provided to our technical contact at NASA-LaRC and preliminary polymerization studies were encouraging. Details of the accomplished work within the last four years are described.

  11. Ultrasonic-assisted synthesis of 1,4-disubstituted 1,2,3-triazoles via various terminal acetylenes and azide and their quorum sensing inhibition.

    PubMed

    Zhang, Da-Wei; Zhang, Yu-Min; Li, Jing; Zhao, Tian-Qi; Gu, Qiang; Lin, Feng

    2017-05-01

    An efficient synthesis of 1,4-disubstituted 1,2,3-triazole derivatives was studied. 1,4-Disubstituted 1,2,3-triazoles containing isoxazole and thymidine structures were synthesized in 84-96% yields starting from various terminal isoxazole ether alkynes and β-thymidine azide derivatives via a 1,3-dispolar cycloaddition using copper acetate, sodium ascorbate as the catalyst under ultrasonic assisted condition. All the target compounds were characterized by HRMS, FT-IR, (1)H NMR and (13)C NMR spectroscopy. Furthermore, the quorum sensing inhibitory activities of synthesized compounds were evaluated with Chromobacterium violaceum (C. Violaceum CV026) based on their inhibition of violacein production, with compound C10-HSL as a positive control. The compounds 8a, 8c and 8f exhibited considerable levels of inhibitory activity against violacein production, and IC50 values were 217±19, 223±20 and 42.8±4.5μM, respectively, which highlighted the potential of these compounds as lead structures for further research towards the development of novel QS inhibitors.

  12. 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.

  13. Chemistry of Processible Acetylene-Terminated Imides

    DTIC Science & Technology

    1983-08-01

    and consultations in DSC -TGA analyses, FT-IR spectroscopy, NMR spectrometry, and HPLC-GPC analyses were provided by Mr. Philip G. Magallanes, Mr. Herman...11 Differential Scanning Calorimetry ( DSC ) for HR600P (Lot M1126-1) ........ 15 12 Differential Scanning Calorimetry ( DSC ) Curves for Thermid 600 and H...17 14 Gel Permeation Chromatogram for HR605P (Lot M1126-33A) .............. 18 15 Differential Scanning Calorimetry ( DSC ) for HR602P Oligomer (M1126-42

  14. New Acetylene-Terminated Quinoxaline Oligomers

    DTIC Science & Technology

    1982-03-01

    diketone . In this work, we tried other bases, but potassium t-butoxide and lithium t- butoxide gave unsatisfactory results. Synthesis of acetone adduct...the most expensive ingredient. We have previously been able to improve the synthesis of the bisglyoxals needed for these adhesives,2 and are now...general method of synthesis which have been developed is to first condense the quinoxallne oligomer with glyoxal end groups. 2 r ),-CO--CO-Ar--CO--C&O--j

  15. 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).

  16. 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.

  17. 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...

  18. 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...

  19. 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....

  20. 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....

  1. 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.

  2. 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.

  3. 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.

  4. 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....

  5. Specific surface modification of the acetylene-linked glycolipid vesicle by click chemistry.

    PubMed

    Ito, Hidehiro; Kamachi, Toshiaki; Yashima, Eiji

    2012-06-07

    A novel glycolipid with a terminal acetylene was synthesized and used to prepare unilamellar vesicles. Using these vesicles, a convenient method was developed for the specific modification of the vesicle surface using the photoresponsive copper complex [Cu(OH(2))(cage)] as the catalyst for a click reaction.

  6. 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...

  7. 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...

  8. 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...

  9. 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)...

  10. [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.

  11. 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

  12. New approach to phosphinoalkynes based on Pd- and Ni-catalyzed cross-coupling of terminal alkynes with chlorophosphanes.

    PubMed

    Beletskaya, Irina P; Afanasiev, Vladimir V; Kazankova, Marina A; Efimova, Irina V

    2003-11-13

    [reaction: see text] The first example of direct phosphination of terminal alkynes with chlorophosphanes catalyzed by Ni or Pd complexes is described. Both aromatic and aliphatic terminal acetylenes undergo the coupling reaction to give corresponding coupling product in high yield.

  13. Oxidative Degradation of Acetylene Terminated Sulfone (ATS) Resin

    DTIC Science & Technology

    1990-01-10

    encountered. Even so, the mercury manometer , depicted in Figure 20, was left open to the atmosphere during the course of experiments as a potential...Silicone Rubber D Dewar Flask M Mercury Manometer With Meter Stick T 1 Cr/Al Thermocouple To Oven Programmer T 2 Cr/Al Thermocouple To Recorder FIGURE 20b...storage reservoir Mercury manometer with meter stick for gas measurement/pressure relief FIGURE 25 GAS MANIPULATION MANIFOLD 73 KEY (-) Thermocouple

  14. Characterization of Acetylene Terminated Sulfone (ATS-G)

    DTIC Science & Technology

    1983-05-01

    probably produced by thermal isomerizations of the polyene chain to a most stable configuration. The cured Tg’s of fractions 2 - 7 are all between 200...scission process which partially volatilizes the sample leaving polyene centered aromatic clusters which fuze above 600’C to produce carbon monoxide...AFWAL-TS-83-4011 The stabilities of Fl - F3 with respect to Step 1 of degradation increase with polyene concentration (or cross link density) in the

  15. Synthesis and Properties of Acetylene Terminated Sulfone (ATS)

    DTIC Science & Technology

    1980-03-01

    reaction. The primary product was a white crystalline compound, identified as 3-(p-nitrophenoxy) phenylacet - ylene resulting from displacement at the...alkoxy styrenes have been readily obtained by the reaction of sodium alkoxides and phenylacetylene (Reference 15). The coupling con- stants of both...containing 23.7g (4.18 mmole) of (IV) in 250m1 of toluene was added, under a nitrogen atmosphere, 12g of sodium hydroxide and lOOml of methanol. The

  16. Acetylene (ethynyl) terminated polyimide siloxane and process for preparation thereof

    NASA Technical Reports Server (NTRS)

    Stclair, T. L.; ASI primers applied over ste (Inventor)

    1986-01-01

    Siloxane containing addition polyimides having improved physical property characteristics of flexibility, drape, tack, and toughness and the process for preparing and utilizing the same are disclosed. The novelty of this invention appears to reside in the composition and process of preparing addition type polyimides useful as structural adhesives as well as composite matrix materials and the process of preparing the same.

  17. 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.

  18. 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

  19. 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...

  20. 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...

  1. 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...

  2. 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...

  3. 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...

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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…

  10. 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

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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...

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. 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...

  8. 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...

  9. 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...

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. The methane-acetylene cycle Aerospace Plane - A promising candidate for earth to orbit transportation

    SciTech Connect

    Zubrin, R.M. )

    1992-01-01

    The methane-acetylene cycle Aerosapce Plane (MACASP) concept is proposed and its theoretical feasibility is shown. In this concept, methane fuel stored on-board the aircraft is run out within the wing leading edge in pipes at temperatures up to 1400 K. In the presence of catalyst, the heat provided by wing drag is used to drive the highly endothermic chemical reaction 2CH4 yields 3H2 + C2H2. The products of this reaction, hydrogen and acetylene, are then fed into a combustion chamber and burned in air. On the NASP, terminal acceleration to orbit beyond the critical Mach number of the scramjet can be enabled by rocket operation using a small on-board supply of LOx. The advantages of this concept are that the two highly energetic but difficult-to-store fuels can be used without on-board storage. It is shown that the MACASP concept offers significant promise for economical earth-to-orbit transportation. 5 refs.

  18. 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.

  19. 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.

  20. 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...

  1. 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...

  2. 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...

  3. 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...

  4. 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...

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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).

  15. 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.

  16. 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.

  17. Termination Documentation

    ERIC Educational Resources Information Center

    Duncan, Mike; Hill, Jillian

    2014-01-01

    In this study, we examined 11 workplaces to determine how they handle termination documentation, an empirically unexplored area in technical communication and rhetoric. We found that the use of termination documentation is context dependent while following a basic pattern of infraction, investigation, intervention, and termination. Furthermore,…

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  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. 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

  12. TRANSPORT AND THERMAL PROPERTIES OF POLY(ETHER IMIDE) ACETYLENE-TERMINATED MONOMER BLENDS. (R824727)

    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. 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...

  14. 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...

  15. 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...

  16. 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...

  17. 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.

  18. 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

  19. 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

  20. 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...

  1. 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...

  2. 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.

  3. 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.

  4. 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).

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. Time- and isomer-resolved measurements of sequential addition of acetylene to the propargyl radical

    DOE PAGES

    Savee, John D.; Selby, Talitha M.; Welz, Oliver; ...

    2015-10-06

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

  10. Bank Terminals

    NASA Technical Reports Server (NTRS)

    1978-01-01

    In the photo, employees of the UAB Bank, Knoxville, Tennessee, are using Teller Transaction Terminals manufactured by SCI Systems, Inc., Huntsville, Alabama, an electronics firm which has worked on a number of space projects under contract with NASA. The terminals are part of an advanced, computerized financial transaction system that offers high efficiency in bank operations. The key to the system's efficiency is a "multiplexing" technique developed for NASA's Space Shuttle. Multiplexing is simultaneous transmission of large amounts of data over a single transmission link at very high rates of speed. In the banking application, a small multiplex "data bus" interconnects all the terminals and a central computer which stores information on clients' accounts. The data bus replaces the maze-of wiring that would be needed to connect each terminal separately and it affords greater speed in recording transactions. The SCI system offers banks real-time data management through constant updating of the central computer. For example, a check is immediately cancelled at the teller's terminal and the computer is simultaneously advised of the transaction; under other methods, the check would be cancelled and the transaction recorded at the close of business. Teller checkout at the end of the day, conventionally a time-consuming matter of processing paper, can be accomplished in minutes by calling up a summary of the day's transactions. SCI manufactures other types of terminals for use in the system, such as an administrative terminal that provides an immediate printout of a client's account, and another for printing and recording savings account deposits and withdrawals. SCI systems have been installed in several banks in Tennessee, Arizona, and Oregon and additional installations are scheduled this year.

  11. 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.

  12. 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.

  13. 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.

  14. [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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Analysis of the seed oil of Heisteria silvanii (Olacaceae)--a rich source of a novel C18 acetylenic fatty acid.

    PubMed

    Spitzer, V; Tomberg, W; Hartmann, R; Aichholz, R

    1997-11-01

    Besides some usual fatty acids (FA), two conjugated ene-yne acetylenic FA [trans-10-heptadecen-8-ynoic acid (pyrulic acid) (7.4%), and trans-11-octadecen-9-ynoic acid (ximenynic acid) (3.5%)], a novel ene-yne-ene acetylenic FA [cis-7, trans-11-octadecadiene-9-ynoic acid (heisteric acid) (22.6%)], and 9,10-epoxystearic acid (0.6%) could be identified in the seed oil of Heisteria silvanii (Olacaceae). Two further conjugated acetylenic FA [9,11-octadecadiynoic acid (0.1%) and 13-octadecene-9,11-diynoic acid (0.4%)] were identified tentatively by their mass spectra. The FA mixture has been analyzed by gas chromatography/mass spectrometry (GC/MS) of their methyl ester and 4,4-dimethyloxazoline derivatives. The structure of heisteric acid was elucidated after isolation via preparative silver ion thin-layer chromatography and by various spectroscopic methods [ultraviolet; infrared; 1H, 13C nuclear magnetic resonance (NMR); 1H-1H and 1H-13C correlation spectroscopy]. To determine the position of the conjugated ene-yne-ene system, the NMR spectra were also measured after addition of the lanthanide shift reagent Resolve-Al EuFOD. Furthermore, the triyglyceride mixture was analyzed by high-temperature GC and high-temperature GC coupled with negative chemical ionization MS. A glass capillary column coated with a methoxy-terminated 50%-diphenyl-50%-dimethylpolysiloxane was used for the separation of the triacylglycerol (TAG) species. No evidence of decomposition of the TAG species containing conjugated ene-yne-ene FA was observed. Twenty-six species of the separated TAG were identified by means of their abundant quasi molecular ion [M - H]- and their corresponding carboxylate anions [RCOO]- of the fatty acids, respectively. The major molecular species of the TAG were found to be 16:0/18:1/18:1, 16:0/18:1/18:3 (heisteric acid), 17:2 (pyrulic acid)/18:1/18:1, 18:1/18:1/18:3 (heisteric acid). The TAG containing acetylenic FA showed an unexpected increase of the retention time in

  20. 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

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  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. Terminal structure

    DOEpatents

    Schmidt, Frank; Allais, Arnaud; Mirebeau, Pierre; Ganhungu, Francois; Lallouet, Nicolas

    2009-10-20

    A terminal structure (2) for a superconducting cable (1) is described. It consists of a conductor (2a) and an insulator (2b) that surrounds the conductor (2a), wherein the superconducting cable (1) has a core with a superconducting conductor (5) and a layer of insulation that surrounds the conductor (5), and wherein the core is arranged in such a way that it can move longitudinally in a cryostat. The conductor (2a) of the terminal structure (2) is electrically connected with the superconducting conductor (5) or with a normal conductor (6) that is connected with the superconducting conductor (5) by means of a tubular part (7) made of an electrically conductive material, wherein the superconducting conductor (5) or the normal conductor (6) can slide in the part (7) in the direction of the superconductor.

  10. Terminal Ballistics

    DTIC Science & Technology

    1976-02-01

    ballistics doe, little to c~plaini the workings of explosike pro jectiles. The termni,iaf phase (of di esplodling tbalfftic weapon is comiposed of esents...citterior, and terminal baillistic phases, and the study of this n’!w systemn hius useful parallel% it) the proiecoile ballistic sysStem. The...charge liner collapse Vi Jet velocity V, Slug velocity W Work Wp Weight of projecti!e Z A length variable a, bi Empirical constants. (In Chap. 5, Eq

  11. Termination unit

    DOEpatents

    Traeholt, Chresten; Willen, Dag; Roden, Mark; Tolbert, Jerry C.; Lindsay, David; Fisher, Paul W.; Nielsen, Carsten Thidemann

    2016-05-03

    Cable end section comprises end-parts of N electrical phases/neutral, and a thermally-insulation envelope comprising cooling fluid. The end-parts each comprises a conductor and are arranged with phase 1 innermost, N outermost surrounded by the neutral, electrical insulation being between phases and N and neutral. The end-parts comprise contacting surfaces located sequentially along the longitudinal extension of the end-section. A termination unit has an insulating envelope connected to a cryostat, special parts at both ends comprising an adapter piece at the cable interface and a closing end-piece terminating the envelope in the end-section. The special parts houses an inlet and/or outlet for cooling fluid. The space between an inner wall of the envelope and a central opening of the cable is filled with cooling fluid. The special part at the end connecting to the cryostat houses an inlet or outlet, splitting cooling flow into cable annular flow and termination annular flow.

  12. 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.

  13. 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.

  14. 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.

  15. 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...

  16. 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.

  17. 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.

  18. 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

  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. 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.

  1. 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

  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. Time- and isomer-resolved measurements of sequential addition of acetylene to the propargyl radical

    SciTech Connect

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

    2015-10-06

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

  4. 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

  5. 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.

  6. 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

  7. 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

  8. 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

  9. [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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. Aging, Terminal Decline, and Terminal Drop

    ERIC Educational Resources Information Center

    Palmore, Erdman; Cleveland, William

    1976-01-01

    Data from a 20-year longitudinal study of persons over 60 were analyzed by step-wise multiple regression to test for declines in function with age, for terminal decline (linear relationship to time before death), and for terminal drop (curvilinear relationship to time before death). There were no substantial terminal drop effects. (Author)

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

    SciTech Connect

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

    2007-06-28

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

  3. Computational study on C-H...π interactions of acetylene with benzene, 1,3,5-trifluorobenzene and coronene.

    PubMed

    Dinadayalane, Tandabany C; Paytakov, Guvanchmyrat; Leszczynski, Jerzy

    2013-07-01

    Meta-hybrid density functional theory calculations using M06-2X/6-31+G(d,p) and M06-2X/6-311+G(d,p) levels of theory have been performed to understand the strength of C-H(…)π interactions of two possible types for benzene-acetylene, 1,3,5-trifluorobenzene-acetylene and coronene-acetylene complexes. Our study reveals that the C-H(...)π interaction complex where acetylene located above to the center of benzene ring (classical T-shaped) is the lowest energy structure. This structure is twice more stable than the configuration characterized by H atom of benzene interacting with the π-cloud of acetylene. The binding energy of 2.91 kcal/mol calculated at the M06-2X/6-311+G(d,p) level for the lowest energy configuration (1A) is in very good agreement with the experimental binding energy of 2.7 ± 0.2 kcal/mol for benzene-acetylene complex. Interestingly, the C-H(...)π interaction of acetylene above to the center of the aromatic ring is not the lowest energy configuration for 1,3,5-trifluorobenzene-acetylene and coronene-acetylene complexes. The lowest energy configuration (2A) for the former complex possesses both C-H(...)π interaction and C-H(...)F hydrogen bond, while the lowest energy structure for the coronene-acetylene complex involves both π-π and C-H(...)π interactions. C-H stretching vibrational frequencies and the frequency shifts are reported and analyzed for all of the configurations. We observed red-shift of the vibrational frequency for the stretching mode of the C-H bond that interacts with the π-cloud. Acetylene in the lowest-energy structures of the complexes exhibits significant red-shift of the C-H stretching frequency and change in intensity of the corresponding vibrational frequency, compared to bare acetylene. We have examined the molecular electrostatic potential on the surfaces of benzene, 1,3,5-trifluorobenzene, coronene and acetylene to explain the binding strengths of various complexes studied here.

  4. Internal acetylene unit as a cross-link site for polyimides

    SciTech Connect

    Takeichi, T.; Tanikawa, M.

    1995-12-01

    We have been studying on the cross-linking behavior of internal acetylenes linked meta-meta to aromatic connecting units which were introduced into the polyimide backbone utilizing 3,3`-diaminodiphenylacetylene (m-intA). In this study, we studied on the cross-linking behavior of internal acetylenes linked para-para to aromatic connecting units. The internal acetylene units were introduced into the polyimide backbone by the reaction of 4,4`-diaminodiphenylacetylene (p-intA) with such acid anhydrides as biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA). The polyimides showed exotherm on DSC: The onset of the exotherm of p-intA appeared at around 330-390{degrees}C, which is 10-50{degrees}C higher than that of m-intA. The exotherm disappeared after thermal treatment at 400{degrees}C, suggesting the progress of crosslinking between acetylene units. The polyimides cured at 350{degrees}C or 400{degrees}C showed increased Tg and improved physical properties at high temperatures as confirmed by viscoelastic analyses. It was also made clear that polyimides containing p-intA showed higher modulus compared with polyimides containing m-intA, especially when coupled with BPDA and PMDA.

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

    EPA Science Inventory

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

  6. An upper limit to the acetylene abundance toward BN in the orion molecular cloud

    NASA Technical Reports Server (NTRS)

    Knacke, R. F.; Kim, Y. H.; Irvine, W. M.

    1989-01-01

    A search for the acetylene (C2H2) nu3 infrared vibration-rotation absorption near 3 microns toward the Becklin-Neugebauer source in the Orion molecular cloud is reported. The relative abundance of C2H2/CO in the quiescent gas is less than 0.003.

  7. Matrix Isolation and ab initio study of the noncovalent complexes between formamide and acetylene.

    PubMed

    Mardyukov, Artur; Sánchez-García, Elsa; Sander, Wolfram

    2009-02-12

    Matrix isolation spectroscopy in combination with ab initio calculations is a powerful technique for the identification of weakly bound intermolecular complexes. Here, weak complexes between formamide and acetylene are studied, and three 1:1 complexes with binding energies of -2.96, -2.46, and -1.79 kcal/mol have been found at the MP2 level of theory (MP2/cc-pVTZ + ZPE + BSSE). The two most stable dimers A and B are identified in argon and nitrogen matrices by comparison between the experimental and calculated infrared frequencies. Both complexes are stabilized by the formamide C=O...HC acetylene and H...pi interactions. Large shifts have been observed experimentally for the C-H stretching vibrations of the acetylene molecule, in very good agreement with the calculated values. Eight 1:2 FMA-acetylene trimers (T-A to T-H) with binding energies between -5.44 and -2.62 kcal/mol (MP2/aug-cc-pVDZ + ZPE + BSSE) were calculated. The two most stable trimers T-A and T-B are very close in energy and have similar infrared spectra. Several weak bands that are in agreement with the calculated frequencies of the trimers T-A and T-B are observed under matrix isolation conditions. However, the differences are too small for a definitive assignment.

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

    ERIC Educational Resources Information Center

    Cox, Marilyn Blagg; Krause, Paul

    1994-01-01

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

  9. Reaction of β-enaminones and acetylene dicarboxylates: synthesis of substituted 1,2-dihydropyridinones.

    PubMed

    Nagaraju, Vemu; Purnachander, Dalovai; Mangina, N S V M Rao; Suresh, Surisetti; Sridhar, Balasubramanian; Karunakar, Galla V

    2015-03-14

    Synthesis of substituted 1,2-dihydropyridinones is described in a one pot reaction of β-enaminones and acetylene dicarboxylates where new C-C and C-N bonds were formed. The title compounds were obtained in moderate to good yields.

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

    PubMed

    Quine, Zachary R; McNesby, Kevin L

    2009-06-01

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

  11. Incorporation of deuterium in coke formed on an acetylene hydrogenation catalyst

    SciTech Connect

    Larsson, M.; Jansson, J.; Asplund, S.

    1996-09-01

    In selective hydrogenation of acetylene in excess ethylene, considerable amounts of coke or {open_quotes}green oils{close_quotes} are formed and accumulate on the catalyst. A fraction of the acetylene undergoes oligomerization reactions producing C{sub 4}`s and larger hydrocarbons. Compounds larger than C{sub 8} are retained on the catalysts surface or as a condensed phase in the pore system. The reaction mechanism is largely unknown but several authors have postulated that oligomerization occurs through dissociatively adsorbed acetylene (2), i.e., C{sub 2}H(ads) and C{sub 2}(ads). In this paper a novel method of studying the coke formation on a catalyst is introduced. Deuterium is incorporated in the coke during hydrogenation of acetylene, and during temperature-programmed oxidation (TPO) experiments the deuterium content is analyzed. The objective is to shed some light on the mechanism for oligomer formation in this system. The catalyst, Pd/{alpha}-Al{sub 2}O{sub 3}, was prepared by the impregnation of {alpha}-alumina (Sued-Chemie) with a solution of Pd(NO{sub 3}){sub 2} in 30% HNO{sub 3}. 8 refs., 4 figs.

  12. 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.

  13. 49 CFR 178.60 - Specification 8AL steel cylinders with porous fillings for acetylene.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

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

  14. 49 CFR 178.60 - Specification 8AL steel cylinders with porous fillings for acetylene.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

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

  15. 49 CFR 178.60 - Specification 8AL steel cylinders with porous fillings for acetylene.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 3 2011-10-01 2011-10-01 false Specification 8AL steel cylinders with porous...) SPECIFICATIONS FOR PACKAGINGS Specifications for Cylinders § 178.60 Specification 8AL steel cylinders with porous fillings for acetylene. (a) Type and service pressure. A DOT 8AL cylinder is a seamless steel cylinder...

  16. 49 CFR 178.60 - Specification 8AL steel cylinders with porous fillings for acetylene.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

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

  17. Directional deprotonation ionization of acetylene in asymmetric two-color laser fields

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    We experimentally investigate the deprotonation dissociative double ionization of an acetylene molecule by an asymmetric two-color laser pulse. We find that the ejection direction of the proton, and hence the directional C-H bond breaking of a polyatomic hydrocarbon molecule, can be controlled by finely tuning the phase of a two-color laser pulse.

  18. [4 + 2] Annulation of Donor-Acceptor Cyclopropanes with Acetylenes Using 1,2-Zwitterionic Reactivity.

    PubMed

    Novikov, Roman A; Tarasova, Anna V; Denisov, Dmitry A; Borisov, Denis D; Korolev, Victor A; Timofeev, Vladimir P; Tomilov, Yury V

    2017-02-23

    A new process for the [4 + 2] annulation of donor-acceptor cyclopropanes with acetylenes under the effect of anhydrous GaCl3 using 1,2-zwitterion reactivity was elaborated. The reaction opens access to substituted dihydronaphthalenes, naphthalenes, and other fused carbocycles. The direction of the reaction can be efficiently controlled by temperature.

  19. 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

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

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

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

  1. A Plasma Display Terminal.

    ERIC Educational Resources Information Center

    Stifle, Jack

    A graphics terminal designed for use as a remote computer input/output terminal is described. Although the terminal is intended for use in teaching applications, it has several features which make it useful in many other computer terminal applications. These features include: a 10-inch square plasma display panel, permanent storage of information…

  2. Examining Contributions to Line Shapes in the ν_1 + ν_3 Band of Acetylene

    NASA Astrophysics Data System (ADS)

    Cich, Matthew J.; Caiola, Salvatore M.; Lee, Stephen W.; Lopez, Gary V.; Sears, Trevor J.; Forthomme, Damien; McRaven, C. P.; Hall, Gregory E.; Mantz, A. W.

    2013-06-01

    Using an extended cavity diode laser locked to a frequency comb, line shapes in the ν_1 + ν_3 combination band of acetylene have been studied. The frequency stability of this experiment produces high accuracy measurements that provide rigorous tests of line shape theories. Measurements of the P(11) line shape were made for pure acetylene and acetylene-nitrogen gas mixtures at a series of temperatures between 125 K and 296 K. Using the speed-dependent Voigt line shape model, parameters were determined by fitting data for all temperatures and pressures in a single multispectrum analysis. The resulting parameters successfully reproduce the measured line shapes and are valid for the acetylene-nitrogen system over the range of temperatures studied and combined pressures of up to 1 atmosphere. P(11) is isolated with respect to hot band transitions and neighboring transitions of the same band, but this is an unusual case. To explore the effects of overlapping lines, the P(1) transition was measured in a series of pure acetylene measurements in a congested spectral region. Overlapping hot band lines of measurable intensities were modeled and line shape paramters were simultaneously determined for these along with the P(1) line. Additionally, the effects of line mixing between overlapping ν_1 + ν_3 lines were explored using an appropriate line mixing model. Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences.

  3. 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...

  4. Numerical Study on the Acetylene Concentration in the Hydrogen-Carbon System in a Hydrogen Plasma Torch

    NASA Astrophysics Data System (ADS)

    Chen, Longwei; Shen, Jie; Shu, Xingsheng; Fang, Shidong; Zhang, Lipeng; Meng, Yuedong

    2009-06-01

    Effects of the hydrogen/carbon mole ratio and pyrolysis gas pressure on the acetylene concentration in the hydrogen-carbon system in a plasma torch were numerically calculated by using the chemical thermodynamic equilibrium method of Gibbs free energy. The calculated results indicate that the hydrogen concentration and the pyrolysis gas pressure play crucial roles in acetylene formation. Appropriately abundant hydrogen, with a mole ratio of hydrogen to carbon about 1 or 2, and a relatively high pyrolysis gas pressure can enhance the acetylene concentration. In the experiment, a compromised project consisting of an appropriate hydrogen flow rate and a feasible high pyrolysis gas pressure needs to be carried out to increase the acetylene concentration from coal pyrolysis in the hydrogen plasma torch.

  5. 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

  6. The photolysis of NH3 in the presence of substituted acetylenes - A possible source of oligomers and HCN on Jupiter

    NASA Technical Reports Server (NTRS)

    Ferris, James P.; Jacobson, Richard R.; Guillemin, Jean C.

    1992-01-01

    An NMR spectral study is presently conducted of NH3 photolysis in the presence of substituted acetylenes with NMR spectra and gas chromatography. Quantum yields and percentage conversions to products are reported. It is shown that acetylenic hydrocarbons generated during methane photolysis in Jupiter's stratosphere can react with radicals formed by NH3 photolysis to yield nonvolatile, yellow-brown polymers, alkylnitriles, and in due course, HCN, as observed on Jupiter.

  7. Unexpected hydrodeiodo Sonogashira-Heck-Casser coupling reaction of 2,2'-diiodobiphenyls with acetylenes.

    PubMed

    Chou, Meng-Yen; Mandal, Ashis Baran; Leung, Man-kit

    2002-03-08

    2,2'-Diiodobiphenyl-4,4'-dicarboxylic acid dimethyl ester (3) undergoes either a ring-closure reaction with phenylacetylene to give 4 or hydrodeiodo phenylethynylation to give 5 under the catalytic conditions of Pd(OAc)(2)/CuI/phosphine in amines. In these reactions, the amine and the phosphine ligands play important roles in controlling the reactivity. Among the ligands we used, tris(o-tolyl)phosphine is the best ligand for hydrodeiodo phenylethynylation, while the bidentate phosphine ligand retards both of the reactions. On the basis of our results, we propose that 5 is formed through a fast hydrodeiodination, followed by a Sonogashira phenylethynylation. The results of the deuterium labeling experiments show that proton exchange between the acetylenic proton and the alkyl protons of amine occurs effectively under the reaction conditions. In addition, the hydrogen that replaces the iodide in the hydrodeiodination process arises mainly from the acetylenic proton.

  8. Acetylene/Vinylidene Isomerization after Carbon K-shell Photo-Ionization

    NASA Astrophysics Data System (ADS)

    Osipov, Timut; Weber, T.; Jahnke, T.; Alnaser, A.; Landers, A.; Hertlein, M.; Jagutzki, O.; Schmidt, L.; Schöffler, M.; Prior, M.; Feinberg, B.; Cocke, C. L.; Dörner, R.; Belkacem, A.

    2006-05-01

    Comprehensive study of the acetylene/vinylidene isomerization dynamics after the carbon k-shell photoionization followed by the Auger decay was performed by means of the COLTRIMS (COLd Target Recoil Ion Momentum Spectroscopy) technique. The Auger electrons, produced in this reaction, were detected in coincidence with the products of the Coulomb explosion of the dication C2H2^2+. Measurement of the 3d vector momenta for all detected particles inferred the Auger electron energies and directions in the body fixed molecular frame along with the KER (Kinetic Energy Release) for different break up channels. This highly differential reaction cross-section study provided very unique information about the fragmentation pathways of the doubly charged acetylene molecule.

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

    SciTech Connect

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

    2012-01-01

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

  10. Unexpected chemistry from the reaction of naphthyl and acetylene at combustion-like temperatures.

    PubMed

    Parker, Dorian S N; Kaiser, Ralf I; Bandyopadhyay, Biswajit; Kostko, Oleg; Troy, Tyler P; Ahmed, Musahid

    2015-04-27

    The hydrogen abstraction/acetylene addition (HACA) mechanism has long been viewed as a key route to aromatic ring growth of polycyclic aromatic hydrocarbons (PAHs) in combustion systems. However, doubt has been drawn on the ubiquity of the mechanism by recent electronic structure calculations which predict that the HACA mechanism starting from the naphthyl radical preferentially forms acenaphthylene, thereby blocking cyclization to a third six-membered ring. Here, by probing the products formed in the reaction of 1- and 2-naphthyl radicals in excess acetylene under combustion-like conditions with the help of photoionization mass spectrometry, we provide experimental evidence that this reaction produces 1- and 2-ethynylnaphthalenes (C12 H8 ), acenaphthylene (C12 H8 ) and diethynylnaphthalenes (C14 H8 ). Importantly, neither phenanthrene nor anthracene (C14 H10 ) was found, which indicates that the HACA mechanism does not lead to cyclization of the third aromatic ring as expected but rather undergoes ethynyl substitution reactions instead.

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

    DOE PAGES

    Ma, Jianyi; Xu, Dingguo; Guo, Hua; ...

    2012-01-01

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

  12. Modeling of acetylene pyrolysis under steel vacuum carburizing conditions in a tubular flow reactor.

    PubMed

    Khan, Rafi Ullah; Bajohr, Siegfried; Graf, Frank; Reimert, Rainer

    2007-03-02

    In the present work, the pyrolysis of acetylene was studied under steel vacuum carburizing conditions in a tubular flow reactor. The pyrolysis temperature ranged from 650 degrees C to 1050 degrees C. The partial pressure of acetylene in the feed mixture was 10 and 20 mbar, respectively, while the rest of the mixture consisted of nitrogen. The total pressure of the mixture was 1.6 bar. A kinetic mechanism which consists of seven species and nine reactions has been used in the commercial computational fluid dynamics (CFD) software Fluent. The species transport and reaction model of Fluent was used in the simulations. A comparison of simulated and experimental results is presented in this paper.

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

    SciTech Connect

    Wang, H.; Frenklach, M.

    1997-07-01

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

  14. Line intensity measurements for acetylene between 8980 and 9420 cm-1

    NASA Astrophysics Data System (ADS)

    Béguier, S.; Lyulin, O. M.; Hu, S.-M.; Campargue, A.

    2017-03-01

    The absorption spectrum of acetylene is studied by high-resolution Fourier-transform spectroscopy (FTS) between 8980 and 9420 cm-1. Positions and intensities of 432 12C2H2 absorption lines are retrieved from a spectrum recorded at room temperature (298.5 K) with a pressure of 87.6 hPa and a 105 m path length. The measured lines belong to 11 bands including three bands observed for the first time. The obtained intensity dataset constitutes the first intensity information in the region. The Herman-Wallis coefficients are derived from a fit of the measured intensity values. The reported results will be valuable to complete the spectroscopic databases of acetylene.

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

    PubMed

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

    2012-01-07

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

  16. 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.

  17. 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.

  18. Laser-induced fluorescence study of the S1 state of doubly-substituted 13C acetylene and harmonic force field determination.

    PubMed

    Jiang, Jun; Baraban, Joshua H; Park, G Barratt; Clark, Michelle L; Field, Robert W

    2013-12-19

    In the first half of this study, rotational and vibrational constants of six Franck-Condon bright vibrational levels of S1 doubly-substituted (13)C acetylene are determined from laser-induced fluorescence spectra and an updated geometry of the trans conformer of S1 acetylene is obtained. In the second half, we determine the quadratic force field of S1 acetylene on the basis of the harmonic frequencies of four isotopologues of acetylene. The effects of both diagonal and off-diagonal x(ij) anharmonicities are removed from the input harmonic frequencies. Results from both experimental and theoretical studies of various isotopologues of acetylene (including those from the first half of this paper) are used to obtain a set of force constants that agrees well with ab initio calculations. Our set of force constants for S1 acetylene is an improvement over previous work by Tobiason et al., which did not include off-diagonal anharmonicities.

  19. ACTS Mobile Terminals

    NASA Technical Reports Server (NTRS)

    Abbe, Brian S.; Agan, Martin J.; Jedrey, Thomas C.

    1997-01-01

    The development of the Advanced Communications Technology Satellite (ACTS) Mobile Terminal (AMT) and its follow-on, the Broadband Aeronautical Terminal (BAT), have provided an excellent testbed for the evaluation of K- and Ka-band mobile satellite communications systems. An overview of both of these terminals is presented in this paper.

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  1. FAST TRACK COMMUNICATION: Fragmentation pathways for selected electronic states of the acetylene dication

    NASA Astrophysics Data System (ADS)

    Osipov, T.; Rescigno, T. N.; Weber, T.; Miyabe, S.; Jahnke, T.; Alnaser, A. S.; Hertlein, M. P.; Jagutzki, O.; Schmidt, L. Ph H.; Schöffler, M.; Foucar, L.; Schössler, S.; Havermeier, T.; Odenweller, M.; Voss, S.; Feinberg, B.; Landers, A. L.; Prior, M. H.; Dörner, R.; Cocke, C. L.; Belkacem, A.

    2008-05-01

    Coincident measurement of the Auger electron and fragment ion momenta emitted after carbon core-level photoionization of acetylene has yielded new understanding of how the dication fragments. Ab initio calculations and experimental data, including body-frame Auger angular distributions, are used to identify the parent electronic states and together yield a comprehensive map of the dissociation pathways which include surface crossings and barriers to direct dissociation. The Auger angular distributions for certain breakup channels show evidence of core-hole localization.

  2. Synthesis of 15R polytype of diamond in oxy-acetylene flame grown diamond thin films

    NASA Astrophysics Data System (ADS)

    Kapil, R.; Mehta, B. R.; Vankar, V. D.

    1996-04-01

    15R polytype of diamond has been synthesized using a specially designed oxy-acetylene flame system along with 3C diamond and cubic carbon on polycrystalline molybdenum substrates. X-ray diffraction has been used to detect the 15R phase as the dominant phase in these films. Rapid changes in the substrate temperature during the growth process are expected to be responsible for the growth of these phases.

  3. Polymerizations of Acetylenes and Cyclic Olefins Induced by Metal-Carbynes.

    DTIC Science & Technology

    1983-12-09

    of the American Chemical Society II to. KEy WORDS (Centinue en reoreo eide it neoedeary end idwntii& A, Weoek rwmbw) Polymers Metath~esis Polyalkenamer...and the polynorbornenamer produced when the initiator is the metal-carbyne are similar to those of the polymers produced when the initiator is penta...below, they cause acetylenes, to poly- merize, giving soluble, structurally homogeneous polymers in accord with equation 1. And they do this not only to

  4. Chemical Vapor Deposition Growth of Linked Carbon Monolayers with Acetylenic Scaffoldings on Silver Foil.

    PubMed

    Liu, Rong; Gao, Xin; Zhou, Jingyuan; Xu, Hua; Li, Zhenzhu; Zhang, Shuqing; Xie, Ziqian; Zhang, Jin; Liu, Zhongfan

    2017-03-02

    Graphdiyne analogs, linked carbon monolayers with acetylenic scaffoldings, are fabricated by adopting low-temperature chemical vapor deposition which provides a route for the synthesis of two-dimensional carbon materials via molecular building blocks. The electrical conductivity of the as-grown films can reach up to 6.72 S cm(-1) . Moreover, the films show potential as promising substrates for fluorescence suppressing and Raman advancement.

  5. Effect of acetylene and ammonia as reburn fuel additions to methane in nitric oxide reburning

    SciTech Connect

    Kumpaty, S.K.; Nokku, V.P.; Subramanian, K.

    1996-12-31

    Presented in this paper are the computational results of NO reburning with (a) a combination of methane and acetylene and (b) a combination of methane and ammonia. An updated reaction mechanism that was more comprehensive in terms of predicting the ammonia and isocyanic acid oxidation chemistry was employed to run the CKINTERP program. Using the binary file created by executing the above program and the input stoichiometric ratio conditions, the CHEMKIN package predicted the exit concentrations of various species involved in NO reburning.

  6. Imaging Mie ellipsometry: dynamics of nanodust clouds in an argon-acetylene plasma

    NASA Astrophysics Data System (ADS)

    Greiner, Franko; Carstensen, Jan; Köhler, Nils; Pilch, Iris; Ketelsen, Helge; Knist, Sascha; Piel, Alexander

    2012-12-01

    For the in situ analysis of nano-sized particles in a laboratory plasma, Mie ellipsometry is a well established technique. We present a simple setup with two CCD cameras to gain online spatiotemporal resolved information of the growth dynamics of particles which are produced by plasma chemical processes in an argon-acetylene plasma. Imaging Mie ellipsometry proves to be a powerful technique to study the growth processes of nanodust in all its details.

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

    SciTech Connect

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

    2016-09-15

    A novel 3D microporous metal-organic framework with NbO topology, [Cu{sub 2}(L)(H{sub 2}O){sub 2}]∙(DMF){sub 6}·(H{sub 2}O){sub 2} (ZJU-10, ZJU = Zhejiang University; H{sub 4}L =2′-hydroxy-[1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid; DMF =N,N-dimethylformamide), has been synthesized and structurally characterized. With suitable pore sizes and open Cu{sup 2+} sites, ZJU-10a exhibits high BET surface area of 2392 m{sup 2}/g, as well as moderately high C{sub 2}H{sub 2} volumetric uptake capacity of 132 cm{sup 3}/cm{sup 3}. Meanwhile, ZJU-10a is a promising porous material for separation of acetylene from methane and carbon dioxide gas mixtures at room temperature. - Graphical abstract: A new NbO-type microporous metal-organic framework ZJU-10 with suitable pore size and open Cu{sup 2+} sites was synthesized to realize the strong interaction with acetylene molecules, which can separate the acetylene from methane and carbon dioxane gas mixtures at room temperature. Display Omitted - Highlights: • A novel 3D NbO-type microporous metal-organic framework ZJU-10 was solvothermally synthesized and structurally characterized. • ZJU-10a exhibits high BET surface area of 2392 m{sup 2}/g. • ZJU-10a shows a moderately high C{sub 2}H{sub 2} gravimetric (volumetric) uptake capacity of 174 (132) cm{sup 3}/g at 298 K and 1 bar. • ZJU-10a can separate acetylene from methane and carbon dioxide gas mixtures at room temperature.

  8. 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

  9. 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.

  10. 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.

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

    PubMed

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

    2009-04-01

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

  12. Pulse-induced nonequilibrium dynamics of acetylene inside carbon nanotube studied by an ab initio approach.

    PubMed

    Miyamoto, Yoshiyuki; Zhang, Hong; Rubio, Angel

    2012-06-05

    Nanoscale molecular confinement substantially modifies the functionality and electronic properties of encapsulated molecules. Many works have approached this problem from the perspective of quantifying ground-state molecular changes, but little is known about the nonequilibrium dynamics of encapsulated molecular system. In this letter, we report an analysis of the nonequilibrium dynamics of acetylene (C(2)H(2)) inside a semiconducting carbon nanotube (CNT). An ultrashort high-intense laser pulse (2 fs width and 10(15) W/cm(2) intensity) brings the systems out of equilibrium. This process is modeled by comprehensive first-principles time-dependent density-functional simulations. When encapsulated, acetylene dimer, unlike a single acetylene molecule, exhibits correlated vibrational dynamics (C-C bond rotation and H-C-C bending) that is markedly different from the dynamics observed in the gas phase. This result highlights the role of CNT in modulating the optical electric field within the tube. At longer simulation timescales (> 20 fs) in the largest-diameter tube studied here [CNT(14,0)], we observe synchronized rotation about the C-C axes in the dimer and ultimately ejection of one of the four hydrogen atoms. Our results illustrate the richness of photochemical phenomena in confined geometries.

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

    PubMed

    Comandini, A; Malewicki, T; Brezinsky, K

    2012-03-15

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

  14. Imaging the C black formation by acetylene pyrolysis with molecular reactive force field simulations.

    PubMed

    Zhang, Chaoyang; Zhang, Chi; Ma, Yu; Xue, Xianggui

    2015-05-07

    C black is a class of substantial materials with a long history of applications. However, apart from some descriptions of primary reactions, subsequent processes leading up to the final formation mechanism remain unclear. This mechanism is also crucial for understanding the formation of other carbonaceous materials. In this work, we visualize C black formation by acetylene pyrolysis using molecular dynamics simulations with a molecular reactive force field named ReaxFF. We find that the formation undergoes four stages: (1) chain elongation by H abstraction and polymerization of small C species, (2) chain branching, (3) cyclization and ring densification, and (4) condensed ring folding. The simulated C black particle possesses a structure of folded graphite layers, which is in good accordance with experimental observations. Cyclization and condensation are derived from fusion between neighboring chains, significantly varying from common experimental observations at relatively low temperatures that abide by the mechanism of H abstraction and C2H2 addition. Moreover, polyyne and polyene are usually found during acetylene pyrolysis, suggesting that the pyrolysis of acetylene and other hydrocarbons may be a feasible method of obtaining carbyne, a novel carbonaceous material with a high value.

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

    SciTech Connect

    Han, Huixian; Li, Anyang; Guo, Hua

    2014-12-28

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

  16. 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

  17. Terminal automation system maintenance

    SciTech Connect

    Coffelt, D.; Hewitt, J.

    1997-01-01

    Nothing has improved petroleum product loading in recent years more than terminal automation systems. The presence of terminal automation systems (TAS) at loading racks has increased operational efficiency and safety and enhanced their accounting and management capabilities. However, like all finite systems, they occasionally malfunction or fail. Proper servicing and maintenance can minimize this. And in the unlikely event a TAS breakdown does occur, prompt and effective troubleshooting can reduce its impact on terminal productivity. To accommodate around-the-clock loading at racks, increasingly unattended by terminal personnel, TAS maintenance, servicing and troubleshooting has become increasingly demanding. It has also become increasingly important. After 15 years of trial and error at petroleum and petrochemical storage and transfer terminals, a number of successful troubleshooting programs have been developed. These include 24-hour {open_quotes}help hotlines,{close_quotes} internal (terminal company) and external (supplier) support staff, and {open_quotes}layered{close_quotes} support. These programs are described.

  18. 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.

  19. 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.

  20. 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.

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

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

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

  4. Hydrogen-Bonded Complexes of Phenylacetylene-Acetylene: Who is the Proton Donor?

    PubMed

    Verma, Kanupriya; Dave, Kapil; Viswanathan, K S

    2015-12-24

    Hydrogen-bonded complexes of C2H2 and phenylacetylene (PhAc) were studied using matrix isolation infrared spectroscopy and quantum chemical computations. Both C2H2 and PhAc, being potential proton donors, the question arises as to which of the two species would be the proton donor in the PhAc-C2H2 complex; a question that this work primarily addresses. The molecular structures, vibrational frequencies, and interaction energies of the PhAc-C2H2 complexes were calculated at the M06-2X and MP2 levels of theory, employing both 6-311++G(d,p) and aug-cc-pVDZ basis sets. At the M06-2X/aug-cc-pVDZ level, two nearly isoenergetic complexes (BSSE corrected) were indicated to be the global minima; one a C-H···π complex, where C2H2 served as a proton donor to the phenyl π-system in PhAc, and the other a C-H···π complex, where C2H2 served as a proton donor to the acetylene π-system in PhAc. Of the two, only the second complex was identified in the matrix, evidenced by a characteristic large shift in the ≡C-H stretch of C2H2. Experiments were also performed using PhAc deuterated at the acetylene hydrogen (PhAcD) to study the isotopic effects on the vibrational spectra of complexes. The isotopic studies further confirmed the structure of the complex trapped in the matrix, thereby presenting unambiguous evidence that C2H2 served as the proton donor to the acetylene π-system of PhAc. The theory of atoms-in-molecules (AIM), energy decomposition (EDA), and natural bond orbital (NBO) analysis were performed to understand the nature of the interactions involved in the complexes.

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

    PubMed

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

    2011-01-21

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

  6. 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.

  7. Unravelling exceptional acetylene and carbon dioxide adsorption within a tetra-amide functionalized metal-organic framework

    NASA Astrophysics Data System (ADS)

    Moreau, Florian; da Silva, Ivan; Al Smail, Nada H.; Easun, Timothy L.; Savage, Mathew; Godfrey, Harry G. W.; Parker, Stewart F.; Manuel, Pascal; Yang, Sihai; Schröder, Martin

    2017-02-01

    Understanding the mechanism of gas-sorbent interactions is of fundamental importance for the design of improved gas storage materials. Here we report the binding domains of carbon dioxide and acetylene in a tetra-amide functionalized metal-organic framework, MFM-188, at crystallographic resolution. Although exhibiting moderate porosity, desolvated MFM-188a exhibits exceptionally high carbon dioxide and acetylene adsorption uptakes with the latter (232 cm3 g-1 at 295 K and 1 bar) being the highest value observed for porous solids under these conditions to the best of our knowledge. Neutron diffraction and inelastic neutron scattering studies enable the direct observation of the role of amide groups in substrate binding, representing an example of probing gas-amide binding interactions by such experiments. This study reveals that the combination of polyamide groups, open metal sites, appropriate pore geometry and cooperative binding between guest molecules is responsible for the high uptakes of acetylene and carbon dioxide in MFM-188a.

  8. Characterization of magnetically confined low-pressure plasmas produced by an electromagnetic field in argon-acetylene mixtures

    NASA Astrophysics Data System (ADS)

    Makdessi, G. Al; Margot, J.; Clergereaux, R.

    2016-10-01

    Dust particles formation was investigated in magnetically confined low-pressure plasma produced in argon-acetylene mixtures. The plasma characteristics were measured in order to identify the species involved in the dust particles formation. Their dependence on the operating conditions including magnetic field intensity, acetylene fraction in the gas mixture and operating pressure was examined. In contrast with noble gases, in the presence of acetylene, the electron temperature increases with the magnetic field intensity, indicating additional charged particles losses in the plasma. Indeed, in these conditions, larger hydrocarbon ions are produced leading to the formation of dust particles in the plasma volume. The observed dependence of positive ion mass distribution and density and relative negative ion density on the operating parameters suggests that the dust particles are formed through different pathways, where negative and positive ions are both involved in the nucleation.

  9. Synthesis of novel E-2-chlorovinyltellurium compounds based on the stereospecific anti-addition of tellurium tetrachloride to acetylene.

    PubMed

    Musalova, Maria V; Potapov, Vladimir A; Amosova, Svetlana V

    2012-05-15

    The reaction of tellurium tetrachloride with acetylene proceeds in a stereospecific anti-addition manner to afford the novel products E-2-chlorovinyltellurium trichloride and E,E-bis(2-chlorovinyl)tellurium dichloride. Reaction conditions for the selective preparation of each of these products were found. The latter was obtained in 90% yield in CHCl(3) under a pressure of acetylene of 10-15 atm, whereas the former product was formed in up to 72% yield in CCl(4) under a pressure of acetylene of 1-3 atm. Synthesis of the previously unknown E,E-bis(2-chlorovinyl) telluride, E,E-bis(2-chlorovinyl) ditelluride, E-2-chlorovinyl 1,2,2-trichloroethyl telluride and E,E-bis(2-chlorovinyl)-tellurium dibromide is described.

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

    PubMed

    Hsu, Liang-Yan; Rabitz, Herschel

    2012-11-02

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

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

    SciTech Connect

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

    1987-01-20

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

  12. Superconducting Cable Termination

    DOEpatents

    Sinha, Uday K.; Tolbert, Jerry

    2005-08-30

    Disclosed is a termination that connects high temperature superconducting (HTS) cable immersed in pressurized liquid nitrogen to high voltage and neutral (shield) external bushings at ambient temperature and pressure. The termination consists of a splice between the HTS power (inner) and shield (outer) conductors and concentric copper pipes which are the conductors in the termination. There is also a transition from the dielectric tape insulator used in the HTS cable to the insulators used between and around the copper pipe conductors in the termination. At the warm end of the termination the copper pipes are connected via copper braided straps to the conventional warm external bushings which have low thermal stresses. This termination allows for a natural temperature gradient in the copper pipe conductors inside the termination which enables the controlled flashing of the pressurized liquid coolant (nitrogen) to the gaseous state. Thus the entire termination is near the coolant supply pressure and the high voltage and shield cold bushings, a highly stressed component used in most HTS cables, are eliminated. A sliding seal allows for cable contraction as it is cooled from room temperature to ˜72-82 K. Seals, static vacuum, and multi-layer superinsulation minimize radial heat leak to the environment.

  13. Potential energy and vibrational levels for local modes in water and acetylene

    NASA Astrophysics Data System (ADS)

    Wright, James S.; Donaldson, D. J.

    1985-03-01

    MRD Cl calculations are given for the potential energy along local X-H streching modes in water and acetylene, out to near dissolution. The Cl data points are accurately fitted by Morse functions up to half the well depth, but generalized (five-parameter) Morse functions are required to fit the whole range of data. The implications for the traetment of vibrational overtone levels are discussed, including a comparison of several treatments. Agreement with experimentally derived mode spectra is good, as is the agreement with bond distances and thermochemistry.

  14. Wavelength-modulation detection of acetylene with a near-infrared external-cavity diode laser

    NASA Astrophysics Data System (ADS)

    Oh, Daniel B.; Hovde, David Christian

    1995-10-01

    An external-cavity diode laser operating at 1500 nm was used to record the combination band of acetylene (C2H2). By combination of wavelength-modulation spectroscopy with a noise-canceler detection circuit, a minimum detectable absorbance of 4.8 \\times 10 -4 with a 300-ms time constant was achieved, although this result was limited by etalon fringes. When combined with this detection technique, continuous, widely tunable output from an external-cavity laser is ideally suited for high-resolution absorption spectroscopy with excellent sensitivity.

  15. Surface structures of high-quality diamond crystals synthesized by the oxy-acetylene flame method

    NASA Astrophysics Data System (ADS)

    Hirabayashi, Keiji; Amanuma, Shuji; Hirose, Yoichi

    1992-02-01

    The microstructures of the {111} surfaces of high-quality diamond crystals deposited by the oxy-acetylene flame method have been studied using a high-resolution scanning electron microscope to clear the mechanism of the crystal growth. On the {111} surfaces of the high-quality diamond crystals, the two-dimensional nucleation rate is suppressed and the two-dimensional crystal growth rate is promoted. The suppression of the two-dimensional nucleation rate and the promotion of the two-dimensional crystal growth rate reduce the number of faults, dislocations, and defects and result in the formation of high-quality diamond crystals.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  17. Quasiclassical trajectory study of fast H-atom collisions with acetylene.

    PubMed

    Han, Yong-Chang; Sharma, Amit R; Bowman, Joel M

    2012-06-07

    Translationally hot H collisions with the acetylene are investigated using quasiclassical trajectory calculations, on a recent full-dimensional ab initio-based potential energy surface. Three outcomes are focused on: non-reactive energy transfer via prompt collisions, non-reactive energy transfer via the formation of the vinyl complex, and reactive chemical H-atom exchange, also via complex formation. The details of these outcomes are presented and correlated with the collision lifetime. Large energy transfer is found via complex formation, which can subsequently decay back to reactants, a non-reactive event, or to new products, a reactive event. For the present system, these two events are experimentally indistinguishable.

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

    PubMed

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

    2016-03-01

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

  19. The 2Πg shape resonance of acetylene anion: an investigation with the RAC method

    NASA Astrophysics Data System (ADS)

    Čurík, Roman; Paidarová, Ivana; Horáček, Jiří

    2016-07-01

    Recently developed method of regularized analytic continuation (RAC) is applied to determination of the 2Πg resonance of acetylene anion. The method is based on continuation of the electron affinities calculated for the anion in presence of an external perturbation field. Its independence on the correlation treatment of the many-electron system allows application of accurate coupled-clusters methods for electronic structure calculations utilized in determination of the resonance position and width. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

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

    PubMed

    Hatua, Kaushik; Nandi, Prasanta K

    2015-10-01

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

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

    SciTech Connect

    Komives, E.A.

    1987-01-01

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

  2. 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.

  3. First principles potential for the acetylene dimer and refinement by fitting to experiments

    NASA Astrophysics Data System (ADS)

    Leforestier, Claude; Tekin, Adem; Jansen, Georg; Herman, Michel

    2011-12-01

    We report the definition and refinement of a new first principles potential for the acetylene dimer. The ab initio calculations were performed with the DFT-SAPT combination of symmetry-adapted intermolecular perturbation method and density functional theory, and fitted to a model site-site functional form. Comparison of the calculated microwave spectrum with experimental data revealed that the barriers to isomerization were too low. This potential was refined by fitting the model parameters in order to reproduce the observed transitions, an excellent agreement within ˜1 MHz being achieved.

  4. 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.

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

    NASA Technical Reports Server (NTRS)

    Tannenbaum, Stanley

    1957-01-01

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

  6. 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.

  7. 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).

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

    PubMed Central

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

    2013-01-01

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

  9. From the Lindlar catalyst to supported ligand-modified palladium nanoparticles: selectivity patterns and accessibility constraints in the continuous-flow three-phase hydrogenation of acetylenic compounds.

    PubMed

    Vilé, Gianvito; Almora-Barrios, Neyvis; Mitchell, Sharon; López, Núria; Pérez-Ramírez, Javier

    2014-05-12

    Site modification and isolation through selective poisoning comprise an effective strategy to enhance the selectivity of palladium catalysts in the partial hydrogenation of triple bonds in acetylenic compounds. The recent emergence of supported hybrid materials matching the stereo- and chemoselectivity of the classical Lindlar catalyst holds promise to revolutionize palladium-catalyzed hydrogenations, and will benefit from an in-depth understanding of these new materials. In this work, we compare the performance of bare, lead-poisoned, and ligand-modified palladium catalysts in the hydrogenation of diverse alkynes. Catalytic tests, conducted in a continuous-flow three-phase reactor, coupled with theoretical calculations and characterization methods, enable elucidation of the structural origins of the observed selectivity patterns. Distinctions in the catalytic performance are correlated with the relative accessibility of the active site to the organic substrate, and with the adsorption configuration and strength, depending on the ensemble size and surface potentials. This explains the role of the ligand in the colloidally prepared catalysts in promoting superior performance in the hydrogenation of terminal and internal alkynes, and short-chain alkynols. In contrast, the greater accessibility of the active surface of the Pd-Pb alloy and the absence of polar groups are shown to be favorable in the conversion of alkynes containing long aliphatic chains and/or ketone groups. These findings provide detailed insights for the advanced design of supported nanostructured catalysts.

  10. Flight Termination Criteria

    NASA Astrophysics Data System (ADS)

    Haber, Jerold M.; Larson, Erik

    2013-09-01

    The first line of defense in protecting the public against the threat of injury from a failing space booster is the flight termination system. Consequently, these systems must be highly reliable and the criteria for flight termination must be carefully formulated. Criteria must be developed based on observable data that allows adequate time for the data to be assessed and a flight termination action to be triggered. Criteria should be set so that 1) the chance a good vehicle will be terminated is small, 2) the chance of failing to terminate an errant vehicle before it can hazard population centers or valuable assets is minimal, and 3) there is assurance that the combination of the planned trajectory and mission rules do not induce excessive risks to land based populations, air lanes, and shipping lanes should the vehicle need to be terminated [1].This paper provides an overview of the approaches to developing and implement flight termination criteria and a tool for understanding risk implications of proposed criteria.

  11. Phenylethynyl terminated imide oligomers

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Bryant, Robert G. (Inventor); Jensen, Brian J. (Inventor); Havens, Stephen J. (Inventor)

    1995-01-01

    Four phenylethynyl amine compounds - 3 and 4-aminophenoxy-4'-phenylethynylbenzophenone, and 3 and 4-amino-4'-phenylethynylbenzophenone - were readily prepared and were used to endcap imide oligomers. Phenylethynyl-terminated amide acid oligomers and phenylethynyl-terminated imide oligomers with various molecular weights and compositions were prepared and characterized. These oligomers were cured at 300 to 400 C to provide crosslinked polyimides with excellent solvent resistance, high strength and modulus, and good high temperature properties. Adhesive panels, composites, films, and moldings from these phenylethynyl terminated imide oligomers gave excellent mechanical performance.

  12. Nonleaking battery terminals

    NASA Technical Reports Server (NTRS)

    Snider, W. E.; Nagle, W. J.

    1972-01-01

    Three different terminals were designed for usage in a 40 ampere/hour silver zinc battery which has a 45 percent KOH by weight electrolyte in a plastic battery case. Life tests, including thermal cycling, electrical charge and discharge for up to three years duration, were conducted on these three different terminal designs. Tests for creep rate and tensile strength were conducted on the polyphenylene oxide (PPO) plastic battery cases. Some cases were unused and others containing KOH electrolyte were placed on life tests. The design and testing of nonleaking battery terminals for use with a potassium hydroxide (KOH) electrolyte in a plastic case are discussed.

  13. Nonleaking battery terminals.

    NASA Technical Reports Server (NTRS)

    Snider, W. E.; Nagle, W. J.

    1972-01-01

    Three different terminals were designed for usage in a 40 ampere/hour silver zinc battery which has a 45% KOH by weight electrolyte in a plastic battery case. Life tests, including thermal cycling, electrical charge and discharge for up to three years duration, were conducted on these three different terminal designs. Tests for creep rate and tensile strength were conducted on the polyphenylene oxide plastic battery cases. Some cases were unused and others containing KOH electrolyte were placed on life tests. The design and testing of nonleaking battery terminals for use with a KOH electrolyte in a plastic case are considered.

  14. Intimacy and terminal care

    PubMed Central

    Gilley, Judy

    1988-01-01

    Four cases are summarized in which the general practitioner is involved in the terminal care of one partner of a stable marital relationship. The need to conceptualize the expectations of the patient, the family and the doctor in terminal care is stressed. An attempt is made to illustrate how the quality of the pre-existing sexual relationship, the dying person's own sexuality, and ultimately the capacity for physical expression of intimacy in the marriage profoundly influence choices in terminal care and the quality of dying. PMID:3204583

  15. 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.

  16. 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.

  17. Ammonia nitrogen removal from acetylene purification wastewater from a PVC plant by struvite precipitation.

    PubMed

    Zhu, Lei; Dong, DeMing; Hua, XiuYi; Guo, ZhiYong; Liang, DaPeng

    Acetylene purification wastewater (APW) usually contains high concentrations of ammonia nitrogen (NH4-N), which is generated during the production of acetylene in a polyvinylchloride manufacturing plant. In this study, a struvite precipitation method was selected to remove NH4-N from the APW. Laboratory-scale batch experiments were performed to investigate the effects of the initial APW pH, phosphate (PO4(3-)) concentration, magnesium (Mg(2+)) concentration, and sources of PO4(3-) and Mg(2+) on NH4-N removal. The results indicated that the initial APW pH had a significant effect on the removal of NH4-N, while the other factors had relatively minor effect. The NH4-N could be effectively removed at an optimum initial APW pH of 9.5, when Na2HPO4·12H2O and MgSO4·7H2O were both applied to NH4-N at a ratio of 1.2. Under these conditions, the efficiency of removal of NH4-N, total nitrogen and chemical oxygen demand were 85%, 84% and 18%, respectively. The X-ray diffraction analysis indicated that the precipitates were dominated by struvite. The scanning electron microscopy analysis of the precipitates showed a typical morphology of stick-like and prismatic crystals with coarse surface. The energy dispersive spectroscopy analysis indicated that the precipitates contained P, O, Mg and Ca.

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  20. Nontraumatic terminal ileal perforation

    PubMed Central

    Wani, Rauf A; Parray, Fazl Q; Bhat, Nadeem A; Wani, Mehmood A; Bhat, Tasaduq H; Farzana, Fowzia

    2006-01-01

    Background There is still confusion and controversy over the diagnosis and optimal surgical treatment of non traumatic terminal ileal perforation-a cause of obscure peritonitis. Methods This study was a prospective study aimed at evaluating the clinical profile, etiology and optimal surgical management of patients with nontraumatic terminal ileal perforation. Results There were 79 cases of nontraumatic terminal ileal perforation; the causes for perforation were enteric fever(62%), nonspecific inflammation(26%), obstruction(6%), tuberculosis(4%) and radiation enteritis (1%). Simple closure of the perforation (49%) and end to side ileotransverse anastomosis(42%) were the mainstay of the surgical management. Conclusion Terminal ileal perforation should be suspected in all cases of peritonitis especially in developing countries and surgical treatment should be optimized taking various accounts like etiology, delay in surgery and operative findings into consideration to reduce the incidence of deadly complications like fecal fistula. PMID:16759405

  1. Theoretical study of the bonding of the first- and second-row transition-metal positive ions to acetylene

    NASA Technical Reports Server (NTRS)

    Sodupe, M.; Bauschlicher, Charles W., Jr.

    1991-01-01

    The bonding of transition-metal ions to acetylene is studied by using a theoretical treatment that includes electron correlation. The ions on the left side of the first and second transition rows insert into the pi bond to form a three-membered ring. On the right side of the row the bonding is electrostatic. The trends in bonding are discussed.

  2. 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.

  3. High-temperature measurements of methane and acetylene using quantum cascade laser absorption near 8 μm

    NASA Astrophysics Data System (ADS)

    Sajid, M. B.; Javed, T.; Farooq, A.

    2015-04-01

    The mid-infrared wavelength region near 8 μm contains absorption bands of several molecules such as water vapor, hydrogen peroxide, nitrous oxide, methane and acetylene. A new laser absorption sensor based on the ν4 band of methane and the ν4+ν5 band of acetylene is reported for interference-free, time-resolved measurements under combustion-relevant conditions. A detailed line-selection procedure was used to identify optimum transitions. Methane and acetylene were measured at the line centers of Q12 (1303.5 cm-1) and P23 (1275.5 cm-1) transitions, respectively. High-temperature absorption cross sections of methane and acetylene were measured at peaks (on-line) and valleys (off-line) of the selected absorption transitions. The differential absorption strategy was employed to eliminate interference absorption from large hydrocarbons. Experiments were performed behind reflected shock waves over a temperature range of 1200-2200 K, between pressures of 1-4 atm. The diagnostics were then applied to measure the respective species time-history profiles during the shock-heated pyrolysis of n-pentane.

  4. Lewis base catalyzed [4+2] annulation of electron-deficient chromone-derived heterodienes and acetylenes.

    PubMed

    Dückert, Heiko; Khedkar, Vivek; Waldmann, Herbert; Kumar, Kamal

    2011-04-26

    Lewis base catalyzed [4+2] annulation reactions between electron-deficient chromone oxa- and azadienes and acetylene carboxylates provide tricyclic benzopyrones inspired by natural products. An asymmetric synthesis of the tricyclic benzopyrones was developed by using modified cinchona alkaloids as enantiodifferentiating Lewis base catalysts.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

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

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1995-01-01

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

  7. Vibration-rotation pattern in acetylene. II. Introduction of Coriolis coupling in the global model and analysis of emission spectra of hot acetylene around 3 microm.

    PubMed

    Amyay, Badr; Robert, Séverine; Herman, Michel; Fayt, André; Raghavendra, Balakrishna; Moudens, Audrey; Thiévin, Jonathan; Rowe, Bertrand; Georges, Robert

    2009-09-21

    A high temperature source has been developed and coupled to a high resolution Fourier transform spectrometer to record emission spectra of acetylene around 3 mum up to 1455 K under Doppler limited resolution (0.015 cm(-1)). The nu(3)-ground state (GS) and nu(2)+nu(4)+nu(5) (Sigma(u) (+) and Delta(u))-GS bands and 76 related hot bands, counting e and f parities separately, are assigned using semiautomatic methods based on a global model to reproduce all related vibration-rotation states. Significantly higher J-values than previously reported are observed for 40 known substates while 37 new e or f vibrational substates, up to about 6000 cm(-1), are identified and characterized by vibration-rotation parameters. The 3 811 new or improved data resulting from the analysis are merged into the database presented by Robert et al. [Mol. Phys. 106, 2581 (2008)], now including 15 562 lines accessing vibrational states up to 8600 cm(-1). A global model, updated as compared to the one in the previous paper, allows all lines in the database to be simultaneously fitted, successfully. The updates are discussed taking into account, in particular, the systematic inclusion of Coriolis interaction.

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

    PubMed

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

    2014-07-15

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

  9. 29 CFR 4043.24 - Termination or partial termination.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Secretary of the Treasury determines that there has been a termination or partial termination of a plan... 29 Labor 9 2010-07-01 2010-07-01 false Termination or partial termination. 4043.24 Section 4043.24 Labor Regulations Relating to Labor (Continued) PENSION BENEFIT GUARANTY CORPORATION PLAN...

  10. Infrared Spectroscopy of Deuterated Acetylene in Solid Parahydrogen and the Helium Recovery Initiative

    NASA Astrophysics Data System (ADS)

    Strom, Aaron I.; Anderson, David T.

    2016-06-01

    The linear tetratomic organic molecule acetylene, HCCH, has been studied extensively throughout the past century via numerous spectroscopic experiments, exploiting wavelengths across the electromagnetic spectrum. Both the mono- and di-deutero acetylene isotopologues have also been widely studied, namely HCCD and DCCD. In this presentation, I will present the Fourier transform infrared (FTIR) spectroscopy of DCCD in solid parahydrogen (pH2) in the low-temperature regime (1.5-5.0 K). We intend to perform UV photochemical studies on DCCD doped solid pH2 and, therefore, the infrared spectroscopy must be characterized prior. The FTIR spectrum of DCCD isolated in solid pH2 exhibits rich fine structure in the νb{3} asymmetric C-D stretch region. Some of the observed peaks may arise from the formation of weakly bound acetylene dimers, or potentially even larger clusters. We can test this hypothesis by varying the DCCD concentration in separate experiments and temperature cycling the matrix to look for irreversible cluster growth. In preliminary experiments we observe trace amounts of the lighter isotopologues (HCCD and HCCH) and so these species can also cluster with DCCD, adding to the complexity of the spectra. We remark that ortho-hydrogen clustering to DCCD may also be occurring and we have ways to check that as well. In order to make better sense of the FTIR spectrum of DCCD doped pH2, a comparison with the simulated low temperature gas-phase spectrum will also be presented. This will allow us to address issues related to the extent of the rotational motion of DCCD in solid pH2. A liquid helium bath cryostat is used to grow and maintain the DCCD doped pH2 crystals for spectroscopic characterization. Helium is a non-renewable resource and in recent years the Anderson group has been building a helium recovery system. This Helium Recovery Initiative (HRI) will be discussed in an effort to describe how we implemented this new experimental system in our laboratory and to

  11. In situ monitoring of the acetylene decomposition and gas temperature at reaction conditions for the deposition of carbon nanotubes using linear Raman scattering.

    PubMed

    Reinhold-López, Karla; Braeuer, Andreas; Popovska, Nadejda; Leipertz, Alfred

    2010-08-16

    To understand the reaction mechanisms taking place by growing carbon nanotubes via the catalytic chemical vapor deposition process, a strategy to monitor in situ the gas phase at reaction conditions was developed applying linear Raman spectroscopy. The simultaneous determination of the gas temperature and composition was possible by a new strategy of the evaluation of the Raman spectra. In agreement to the well-known exothermic decomposition of acetylene, a gas temperature increase was quantified when acetylene was added to the incident flow. Information about exhaust gas recirculation and location of the maximal acetylene conversion was derived from the composition measurements.

  12. Formation of nitrogen-containing polycyclic cations by gas-phase and intracluster reactions of acetylene with the pyridinium and pyrimidinium ions.

    PubMed

    Soliman, Abdel-Rahman; Hamid, Ahmed M; Attah, Isaac; Momoh, Paul; El-Shall, M Samy

    2013-01-09

    Here, we present evidence from laboratory experiments for the formation of nitrogen-containing complex organic ions by sequential reactions of acetylene with the pyridinium and pyrimidinium ions in the gas phase and within ionized pyridine-acetylene binary clusters. Additions of five and two acetylene molecules onto the pyridinium and pyrimidinium ions, respectively, at room temperature are observed. Second-order rate coefficients of the overall reaction of acetylene with the pyridinium and pyrimidinium ions are measured as 9.0 × 10(-11) and 1.4 × 10(-9) cm(3) s(-1), respectively, indicating reaction efficiencies of about 6% and 100%, respectively, at room temperature. At high temperatures, only two acetylene molecules are added to the pyridinium and pyrimidinium ions, suggesting covalent bond formation. A combination of ion dissociation and ion mobility experiments with DFT calculations reveals that the addition of acetylene into the pyridinium ion occurs through the N-atom of the pyridinium ion. The relatively high reaction efficiency is consistent with the absence of a barrier in the exothermic N-C bond forming reaction leading to the formation of the C(7)H(7)N(•+) covalent adduct. An exothermic addition/H-elimination reaction of acetylene with the C(7)H(7)N(•+) adduct is observed leading to the formation of a bicyclic quinolizinium cation (C(9)H(8)N(+)). Similar chemistry is observed in the sequential reactions of acetylene with the pyrimidinium ion. The second acetylene addition onto the pyrimidinium ion involves an exclusive addition/H-elimination reaction at room temperature leading to the formation of a bicyclic pyrimidinium cation (C(8)H(7)N(2)(+)). The high reactivity of the pyridinium and pyrimidinium ions toward acetylene is in sharp contrast to the very low reactivity of the benzene cation, which has a reaction efficiency of 10(-4)-10(-5). This indicates that the presence of a nitrogen atom within the aromatic ring enhances the ring growth

  13. The last glacial termination.

    PubMed

    Denton, G H; Anderson, R F; Toggweiler, J R; Edwards, R L; Schaefer, J M; Putnam, A E

    2010-06-25

    A major puzzle of paleoclimatology is why, after a long interval of cooling climate, each late Quaternary ice age ended with a relatively short warming leg called a termination. We here offer a comprehensive hypothesis of how Earth emerged from the last global ice age. A prerequisite was the growth of very large Northern Hemisphere ice sheets, whose subsequent collapse created stadial conditions that disrupted global patterns of ocean and atmospheric circulation. The Southern Hemisphere westerlies shifted poleward during each northern stadial, producing pulses of ocean upwelling and warming that together accounted for much of the termination in the Southern Ocean and Antarctica. Rising atmospheric CO2 during southern upwelling pulses augmented warming during the last termination in both polar hemispheres.

  14. Phenylethynyl terminated reactive oligomer

    NASA Technical Reports Server (NTRS)

    Bryant, Robert G. (Inventor); Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor)

    1995-01-01

    A composition of matter having the general structure: ##STR1## (wherein X is F, Cl, or NO.sub.2, and Y is CO, SO.sub.2 or C(CF.sub.3).sub.2) is employed to terminate a nucleophilic reagent, resulting in the exclusive production of phenylethynyl terminated reactive oligomers which display unique thermal characteristics. A reactive diluent having the general structure: ##STR2## (wherein R is any aliphatic or aromatic moiety) is employed to decrease the melt viscosity of a phenylethynyl terminated reactive oligomer and to subsequently react therewith to provide a thermosetting material of enhanced density. These materials have features which make them attractive candidates for use as composite matrices and adhesives.

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

    PubMed

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

    2009-02-24

    We report on an experimental approach that reveals crucial details of the composition of singlet-triplet mixed eigenstates in acetylene. Intersystem crossing in this prototypical polyatomic molecule embodies the mixing of the lowest excited singlet state (S(1)) with 3 triplet states (T(1), T(2), and T(3)). Using high-energy (157-nm) photons from an F(2) laser to record excited-state photoelectron spectra, we have decomposed the mixed eigenstates into their S(1), T(3), T(2), and T(1) constituent parts. One example of the interpretive power that ensues from the selective sensitivity of the experiment to the individual electronic state characters is the discovery and examination of destructive interference between two doorway-mediated intersystem crossing pathways. This observation of an interference effect in nonradiative decay opens up possibilities for rational coherent control over molecular excited state dynamics.

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

    NASA Technical Reports Server (NTRS)

    Yung, E.

    1974-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2005-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

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

  19. Infrared Spectra of Acetylene Diluted in Solid Nitrogen upon Irradiation with Vacuum Ultraviolet Light and Electrons

    NASA Astrophysics Data System (ADS)

    Wu, Yu-Jong; Chuang, Shiang-Jiun; Chen, Sian-Cong; Huang, Tzu-Ping

    2014-05-01

    Infrared spectra and chemical reactions of acetylene diluted in solid nitrogen at 10 K upon irradiation with vacuum ultraviolet (VUV) light and energetic electrons were investigated in separate experiments. Irradiation of the matrix sample with VUV light peaking at 160 and 121.6 nm yielded simple products, including C2H, CN, and isomers of C2N2. In contrast, electron irradiation of a similar sample generated N3, C2H, and various nitriles. The reaction mechanisms for photolysis and radiolysis of the matrix samples are discussed. Our results may help explain the distribution of trace species detected in the atmosphere of Titan. In addition, the UV absorption spectrum of the electron-bombarded icy sample was obtained and might be useful for future spectral investigations of Pluto by New Horizons.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  1. 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.

  2. Hydrothermal synthesis and acetylene sensing properties of variety low dimensional zinc oxide nanostructures.

    PubMed

    Zhou, Qu; Chen, Weigen; Peng, Shudi; Zeng, Wen

    2014-01-01

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

  3. 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.

  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. Shape and optical properties of aerosols formed by photolysis of acetylene, ethylene, and hydrogen cyanide

    NASA Astrophysics Data System (ADS)

    Bar-Nun, A.; Kleinfeld, I.; Ganor, E.

    1988-07-01

    The shapes and sizes of photochemically produced aerosol particles of polyacetylene, polyethylene, and polyhydrogen cyanide were studied experimentally. All of the single particles were found to be perfectly spherical and semiliquid. However, they aggregate readily, with a sticking coefficient near unity, to form nonspherical particles, which could give rise to the observed polarization from Titan's and Jupiter's upper haze layers. The absorbance of polyacetylene was remeasured and corrected, and it is now much closer to that of polyethylene. The measured real and imaginary indices of refraction of the two materials make them both suitable material for Titan's and Jupiter's upper haze layers. However, the larger abundance and higher rate of polymerization of acetylene would make it the dominant aerosol-forming material in both atmospheres.

  6. Shape and optical properties of aerosols formed by photolysis of acetylene, ethylene, and hydrogen cyanide

    SciTech Connect

    Bar-Nun, A.; Kleinfeld, I.; Ganor, E.

    1988-07-20

    The shapes and sizes of photochemically produced aerosol particles of polyacetylene, polyethylene, and polyhydrogen cyanide were studied experimentally. All of the single particles were found to be perfectly spherical and semiliquid. However, they aggregate readily, with a sticking coefficient near unity, to form nonspherical particles, which could give rise to the observed polarization from Titan's and Jupiter's upper haze layers. The absorbance of polyacetylene was remeasured and corrected, and it is now much closer to that of polyethylene. The measured real and imaginary indices of refraction of the two materials make them both suitable material for Titan's and Jupiter's upper haze layers. However, the larger abundance and higher rate of polymerization of acetylene would make it the dominant aerosol-forming material in both atmospheres. copyright American Geophysical Union 1988

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  8. Living polymerization of (o-(trimethylsilyl)phenyl)acetylene using `small alkoxide` molybdenum(VI) initiators

    SciTech Connect

    Schrock, R.R.; Luo, S.; Zanetti, N.C.; Fox, H.H.

    1994-09-01

    (o-(Trimethylsily)phenyl)acetylene (o-TM-SPA) is polymerized in a living manner by the new `small alkoxide` initiators Mo(CHCMe{sub 2}Ph)(N-1-adamantyl) [OCH(CF{sub 3}){sub 2}]{sub 2}(2,4-lutidine) (1b) and Mo(CHCMe{sub 2}-Ph)(NAr{prime})(OC{sub 6}F{sub 5}){sub 2}(quinulidine) (2; Ar{prime} = 2,6-C{sub 6}H{sub 3}Me{sub 2}) to give low-polydispersity polyenes containing up to 100 equiv of o-TMSPA. The thermodynamically most stable form of poly(o-TMSPA) that contains <25 double bonds is air-sensitive and has a significantly red-shifted {lambda}{sub max}. 29 refs., 1 fig., 1 tab.

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

    PubMed Central

    Chen, Weigen; Peng, Shudi; Zeng, Wen

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Cheng, Peifu; Hu, Yun Hang

    2016-07-01

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

  12. Laser induced vibration-rotation fluorescence and infrared forbidden transitions in acetylene

    NASA Astrophysics Data System (ADS)

    Jungner, Peter; Halonen, Lauri

    1997-08-01

    Laser induced fluorescence method has been used to study highly excited vibrational overtones in acetylene. A sample cell has been placed inside a Ti:Sapphire ring laser cavity and the total fluorescence collected by a parabolic mirror has been dispersed by a high-resolution FTIR spectrometer. The laser has pumped specific rotational states of the CH stretching vibrational overtone state ν1+3ν3(∑u+) and transitions to the symmetric state ν1+2ν3(∑g+) have been observed. The observations allow determining both the vibrational term value and the rotational constant of the symmetric state, which is not accessible from the ground vibrational state by one-photon absorption. The parameters obtained are in excellent agreement with simple local mode predictions.

  13. 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

  14. ALSEP termination report

    NASA Technical Reports Server (NTRS)

    Bates, J. R.; Lauderdale, W. W.; Kernaghan, H.

    1979-01-01

    The Apollo Lunar Surface Experiments Package (ALSEP) final report was prepared when support operations were terminated September 30, 1977, and NASA discontinued the receiving and processing of scientific data transmitted from equipment deployed on the lunar surface. The ALSEP experiments (Apollo 11 to Apollo 17) are described and pertinent operational history is given for each experiment. The ALSEP data processing and distribution are described together with an extensive discussion on archiving. Engineering closeout tests and results are given, and the status and configuration of the experiments at termination are documented. Significant science findings are summarized by selected investigators. Significant operational data and recommendations are also included.

  15. Electrical termination techniques

    NASA Technical Reports Server (NTRS)

    Oakey, W. E.; Schleicher, R. R.

    1976-01-01

    A technical review of high reliability electrical terminations for electronic equipment was made. Seven techniques were selected from this review for further investigation, experimental work, and preliminary testing. From the preliminary test results, four techniques were selected for final testing and evaluation. These four were: (1) induction soldering, (2) wire wrap, (3) percussive arc welding, and (4) resistance welding. Of these four, induction soldering was selected as the best technique in terms of minimizing operator errors, controlling temperature and time, minimizing joint contamination, and ultimately producing a reliable, uniform, and reusable electrical termination.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    The hydrogens in protonated acetylene are very mobile and can easily migrate around the C2 core by moving between classical and non-classical structures of the cation. The lowest energy structure is the T-shaped, non-classical cation with a hydrogen bridging the two carbons. Conversion to the classical H2CCH+ ion requires only 4 kcal/mol. The effect of circularly polarized light on the migration of hydrogens in oriented C2H3+ has been simulated by Born-Oppenheimer molecular dynamics. Classical trajectory calculations were carried out with the M062X/6-311+G(3df,2pd) level of theory using linearly and circularly polarized 32 cycle 7 μm cosine squared pulses with peak intensity of 5.6 × 1013 W/cm2 and 3.15 × 1013 W/cm2, respectively. These linearly and circularly polarized pulses transfer similar amounts of energy and total angular momentum to C2H3+. The average angular momentum vectors of the three hydrogens show opposite directions of rotation for right and left circularly polarized light, but no directional preference for linearly polarized light. This difference results in an appreciable amount of angular displacement of the three hydrogens relative to the C2 core for circularly polarized light, but only an insignificant amount for linearly polarized light. Over the course of the simulation with circularly polarized light, this corresponds to a propeller-like motion of the three hydrogens around the C2 core of protonated acetylene.

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

    NASA Technical Reports Server (NTRS)

    Greenberg, Paul S.; Ku, Jerry C.

    1997-01-01

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

  18. Stroke volume response during exercise measured by acetylene uptake and MRI.

    PubMed

    Groepenhoff, Herman; Holverda, Sebastiaan; Marcus, J Tim; Postmus, Pieter E; Boonstra, Anco; Vonk-Noordegraaf, Anton

    2007-01-01

    The intra-breath technique to measure acetylene absorption offers the possibility to determine augmentation of the pulmonary blood flow per heart beat (Q(C)) as an estimate of the stroke volume response during exercise. However, this method has not been compared with a validated test until now. Therefore, the aim of this study was to compare Q(C) with stroke volume (SV(MRI)) determined by magnetic resonance imaging (MRI) at rest and during exercise in healthy subjects and patients. For this purpose, ten healthy subjects and ten patients with idiopathic pulmonary arterial hypertension (iPAH) with expected impaired stoke volume response during exercise were measured by both methods. Exercise-induced changes in Q(C) and SV(MRI) were correlated in healthy controls (r = 0.75, p < 0.05). Compared to healthy controls, Q(C) increased less during exercise in iPAH patients (11 +/- 17 ml versus 33 +/- 12 ml, p < 0.05). A similar difference in stroke volume response to exercise between the two groups was measured by MRI (-0.6 +/- 8 ml versus 23 +/- 12 ml, p < 0.05, respectively). Hence, intra-breath and MRI measurements showed similar differences in exercise-induced changes in stroke volume between controls and patients. From these results it can be concluded that the intra-breath measurement of acetylene absorption might be of value as a non-invasive tool to estimate stroke volume augmentation during exercise and can detect differences in stroke volume responses between iPAH patients and healthy subjects.

  19. Prematurely terminated slug tests

    SciTech Connect

    Karasaki, K. )

    1990-07-01

    A solution of the well response to a prematurely terminated slug test (PTST) is presented. The advantages of a PTST over conventional slug tests are discussed. A systematized procedure of a PTST is proposed, where a slug test is terminated in the midpoint of the flow point, and the subsequent shut-in data is recorded and analyzed. This method requires a downhole shut-in device and a pressure transducer, which is no more than the conventional deep-well slug testing. As opposed to slug tests, which are ineffective when a skin is present, more accurate estimate of formation permeability can be made using a PTST. Premature termination also shortens the test duration considerably. Because in most cases no more information is gained by completing a slug test to the end, the author recommends that conventional slug tests be replaced by the premature termination technique. This study is part of an investigation of the feasibility of geologic isolation of nuclear wastes being carried out by the US Department of Energy and the National Cooperative for the Storage of Radioactive Waste of Switzerland.

  20. Navy Multiband Terminal (NMT)

    DTIC Science & Technology

    2015-12-01

    Selected Acquisition Report (SAR) RCS: DD-A&T(Q&A)823-290 Navy Multiband Terminal (NMT) As of FY 2017 President’s Budget Defense Acquisition...Research, Development, Test, and Evaluation SAR - Selected Acquisition Report SCP - Service Cost Position TBD - To Be Determined TY - Then Year UCR

  1. Trauma and termination.

    PubMed

    Ferraro, F

    1995-02-01

    The author suggests a particular reading of the thesis put forward by Freud in 'Analysis terminable and interminable' that an effective and more definitive conclusion may be expected in analyses of cases with traumatic aetiology. This reading shifts the emphasis from the patient's history to the possibility of its crystallising in focal nuclei emerging within the analytic relationship under the pressure of the termination. The revival of separation anxieties which cannot be worked through, and their crystallisation in precipitating traumatic events, may give rise to decisive psychic work allowing the analysis to be brought to a conclusion. Two case histories are presented to show how the end of the analysis assumes the form of a new trauma, which reactivates in the present, traumatic anxieties from the patient's own infantile history. In the first case a premature birth and in the second a miscarriage, originally experienced as isolated automatic events without time or history, are relived in the terminal phase as vicissitudes of the transference, so that new meaning can be assigned to them and they can be withdrawn from the somatic cycle of repetition. The powerful tendency to act out and the intense countertransference pressure on the analyst are discussed in the light of the specificities of this phase, which is crucial to the success of the analysis. This leads to a re-examination, in the concluding notes, of some theoretical questions inherent in the problem of the termination and, in particular, to a discussion of the ambiguous concept of a natural ending.

  2. Modeling Terminal Velocity

    ERIC Educational Resources Information Center

    Brand, Neal; Quintanilla, John A.

    2013-01-01

    Using a simultaneously falling softball as a stopwatch, the terminal velocity of a whiffle ball can be obtained to surprisingly high accuracy with only common household equipment. This classroom activity engages students in an apparently daunting task that nevertheless is tractable, using a simple model and mathematical techniques at their…

  3. Settings for Terminal Care.

    ERIC Educational Resources Information Center

    Corless, Inge B.

    1988-01-01

    Examines topics related to delivery of terminal care services: ability of various hospice programs to survive financially, contributions of various models of hospice care, impact of Medicare legislation on hospice movement, demonstration of unique hospice intervention, integration of spiritual care into hospice, and role of hospice in care of…

  4. Shipboard regasification terminal

    SciTech Connect

    Campbell, G.; Zednik, J.

    1999-07-01

    Mobil Technology Company and Mobil Shipping and Transportation Company have jointly developed a new combination of existing proven equipment to regasify LNG. Advantages of this Shipboard Regasification Terminal (SRT) include accelerated initial gas delivery schedule, low capital cost, delivery of smaller quantities of LNG at a competitive price and shorter term of LNG purchase and improved financing options. These advantages benefit both the supplier of LNG and the purchaser. SRT can be used as an interim supply to developing markets allowing the demand to grow while developing downstream infrastructure. This concept does not involve offshore transfer of cryogenic fluids while delivering near-ambient temperature pipeline quality gas at typical pipeline pressures. During times when gas is not required, the SRT ship can easily be returned to the trade of transporting and delivering LNG to conventional land based terminals. This paper will discuss the merits of Shipboard Regasification Terminals in general, cover the development of this concept and review the factors guiding the use of SRT vs. an onshore terminal.

  5. A model for the ethylene and acetylene adsorption on the surface of Cun(n = 10-15) nanoclusters: A theoretical study

    NASA Astrophysics Data System (ADS)

    Farmanzadeh, Davood; Abdollahi, Tahereh

    2016-11-01

    In this work, we report the results of density functional theory calculations of ethylene and acetylene adsorption on the most stable Cun (n = 10-15) nanoclusters, in two π and di- σ adsorption modes. Both the hydrocarbons molecularly adsorbed on the surface. Our results show that the quality of interaction of ethylene and acetylene with odd copper nanoclusters (n = 11, 13, 15) is different from what is found on even copper nanoclusters (n = 10, 12, 14). One of the interesting features of this adsorption is that acetylene never orient toward di-σ mode for Cusbnd Cu bond in odd copper nanoclusters. Also, for di- σ-CunC2H4, no stable structure is identified. The highest interaction and deformation energies are seen for the adsorption of acetylene and ethylene on Cu11 in π-mode.

  6. Reactions of 1-Naphthyl Radicals with Acetylene. Single-Pulse Shock Tube Experiments and Quantum Chemical Calculations. Differences and Similarities in the Reaction with Ethylene

    NASA Astrophysics Data System (ADS)

    Lifshitz, Assa; Tamburu, Carmen; Dubnikova, Faina

    2009-09-01

    The reactions of 1-naphthyl radicals with acetylene were studied behind reflected shock waves in a single-pulse shock tube, covering the temperature range 950-1200 K at overall densities behind the reflected shocks of ˜2.5 × 10-5 mol/cm3. 1-Iodonaphthalene served as the source for 1-naphthyl radicals. The [acetylene]/[1-iodonaphthalene] ratio in all of the experiments was ˜100 to channel the free radicals into reactions with acetylene rather than iodonaphthalene. Only two major products resulting from the reactions of 1-naphthyl radicals with acetylene and with hydrogen atoms were found in the post shock samples. They were acenaphthylene and naphthalene. Some low molecular weight aliphatic products at rather low concentrations, resulting from an attack of various free radicals on acetylene, were also found in the shocked samples. In view of the relatively low temperatures employed in the present experiments, the unimolecular decomposition rate of acetylene is negligible. One potential energy surface describes the production of acenaphthylene and 1-naphthyl acetylene, although the latter was not found experimentally due to the high barrier (calculated) required for its production. Using quantum chemical methods, the rate constants for three unimolecular elementary steps on the surface were calculated using transition state theory. A kinetics scheme containing 16 elementary steps was constructed, and computer modeling was performed. An excellent agreement between the experimental yields of the two major products and the calculated yields was obtained. Differences and similarities in the potential energy surfaces of 1-naphthyl radical + acetylene and those of ethylene are presented, and the kinetics mechanisms are discussed.

  7. 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

  8. 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.

  9. 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.

  10. Effects of hydrogen addition and growth-etch cycling on the oxy-acetylene torch deposition of homoepitaxial diamond

    NASA Astrophysics Data System (ADS)

    Weimer, R. A.; Thorpe, T. P.; Snail, K. A.; Merzbacher, C. E.

    1995-09-01

    Homoepitaxial diamond films were deposited onto (110) single crystal substrates using oxy-acetylene torch deposition at a constant substrate temperature of 1150 °C. Growth-etch cycling of the deposition increased the linear growth rates of the (100) and (111) faces by a factor of 2. The growth-etch films were shown to be less transparent in the infrared than the reference depositions as determined by microfocus Fourier transform infrared spectroscopy. Using the growth-etch technique, the growth rates of the (100), (111), and (110) faces decreased with increasing hydrogen addition to the combustion flame for hydrogen flow rates up to 50% of the acetylene flow rate. The additional hydrogen did not improve the growth-etch films' transparency.

  11. 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

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

    NASA Astrophysics Data System (ADS)

    Wierzbowska, Małgorzata; Sobolewski, Andrzej L.

    2016-03-01

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

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

    PubMed

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

    2013-12-15

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

  14. Homochiral [2]Catenane and Bis[2]catenane from Alleno-Acetylenic Helicates - A Highly Selective Narcissistic Self-Sorting Process.

    PubMed

    Gidron, Ori; Jirásek, Michael; Trapp, Nils; Ebert, Marc-Olivier; Zhang, Xiangyang; Diederich, François

    2015-10-07

    Homochiral strands of alternating alleno-acetylenes and phenanthroline ligands (P)-1 and (P2)-2, as well as their corresponding enantiomers, selectively assemble with the addition of silver(I) salt to yield dinuclear and trinuclear double helicates, respectively. Upon increasing the solvent polarity, the dinuclear and trinuclear helicates interlock to form a [2]catenane and bis[2]catenane, bearing 14 chirality elements, respectively. The solid-state structure of the [2]catenane reveals a nearly perfect fit of the interlocked strands, and the ECD spectra show a significant amplification of the chiroptical properties upon catenation, indicating stabilization of the helical secondary structure. Highly selective narcissistic self-sorting was demonstrated for a racemic mixture consisting of both short and long alleno-acetylenic strands, highlighting their potential for the preparation of linear catenanes of higher order.

  15. Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene.

    PubMed

    Xiang, Sheng-Chang; Zhang, Zhangjing; Zhao, Cong-Gui; Hong, Kunlun; Zhao, Xuebo; Ding, De-Rong; Xie, Ming-Hua; Wu, Chuan-De; Das, Madhab C; Gill, Rachel; Thomas, K Mark; Chen, Banglin

    2011-02-22

    Separation of acetylene and ethylene is an important industrial process because both compounds are essential reagents for a range of chemical products and materials. Current separation approaches include the partial hydrogenation of acetylene into ethylene over a supported Pd catalyst, and the extraction of cracked olefins using an organic solvent; both routes are costly and energy consuming. Adsorption technologies may allow separation, but microporous materials exhibiting highly selective adsorption of C(2)H(2)/C(2)H(4) have not been realized to date. Here, we report the development of tunable microporous enantiopure mixed-metal-organic framework (M'MOF) materials for highly selective separation of C(2)H(2) and C(2)H(4). The high selectivities achieved suggest the potential application of microporous M'MOFs for practical adsorption-based separation of C(2)H(2)/C(2)H(4).

  16. 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.

  17. 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.

  18. 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.

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

    PubMed Central

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

    2016-01-01

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

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

    DOE PAGES

    Wang, Jian -Tao; Chen, Changfeng; Li, Han -Dong; ...

    2016-04-18

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

  1. 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

  2. Dusty Termination Shocks

    SciTech Connect

    Ip, W.H.

    2004-09-15

    In astrophysical settings, termination shocks where strong stellar wind outflows interact with the surrounding environments tend to take place in dusty regions. Just to name a few, star formation regions, planetary nebulae, supernova remnants and active galactic nuclei are all good examples. Dynamics and evolution of the associated dust clouds could have important influences on the acceleration and composition of energetic particles resulting from the diffusive shock acceleration at the termination shocks. In this note we provide a brief review of previous work predating the recent detection of ACR Mg, Na, Si and S ions which might have originated from the Kuiper belt dust. Their compositional abundance might be diagnostic of the collisional history of the Kupier belt objects.

  3. Mobile Phone Terminal

    NASA Technical Reports Server (NTRS)

    1978-01-01

    In the photo, an employee of a real estate firm is contacting his office by means of HICOM, an advanced central terminal for mobile telephones. Developed by the Orlando Division of Martin Marietta Aerospace, Orlando, Florida, and manufactured by Harris Corporation's RF Division, Rochester, N.Y., HICOM upgrades service to users, provides better system management to telephone companies, and makes more efficient use of available mobile telephone channels through a computerized central control terminal. The real estate man, for example, was able to dial his office and he could also have direct-dialed a long distance number. Mobile phones in most areas not yet served by HICOM require an operator's assistance for both local and long distance calls. HICOM improves system management by automatically recording information on all calls for accurate billing, running continual performance checks on its own operation, and reporting any malfunctions to a central office.

  4. Shipboard fisheries management terminals

    NASA Technical Reports Server (NTRS)

    Nagler, R. G.; Sager, E. V.

    1980-01-01

    The needs of the National Marine Fisheries Service (NMGS), National Weather Service, and the U.S. Coast Guard for locational, biological, and environmental data were assessed. The fisheries conservation zones and the yellowfin tuna jurisdiction of the NMFS operates observer programs on foreign and domestic fishing vessels. Data input terminal and data transfer and processing technology are reviewed to establish available capability. A matrix of implementation options is generated to identify the benefits of each option, and preliminary cost estimates are made. Recommendations are made for incremental application of available off the shelf hardware to obtain improved performance and benefits within a well bounded cost. Terminal recommendations are made for three interdependent shipboard units emphasizing: (1) the determination of location and fishing activity; (2) hand held data inputting and formatting in the fishing work areas; and (3) data manipulation, merging, and editing.

  5. Ice age terminations.

    PubMed

    Cheng, Hai; Edwards, R Lawrence; Broecker, Wallace S; Denton, George H; Kong, Xinggong; Wang, Yongjin; Zhang, Rong; Wang, Xianfeng

    2009-10-09

    230Th-dated oxygen isotope records of stalagmites from Sanbao Cave, China, characterize Asian Monsoon (AM) precipitation through the ends of the third- and fourthmost recent ice ages. As a result, AM records for the past four glacial terminations can now be precisely correlated with those from ice cores and marine sediments, establishing the timing and sequence of major events. In all four cases, observations are consistent with a classic Northern Hemisphere summer insolation intensity trigger for an initial retreat of northern ice sheets. Meltwater and icebergs entering the North Atlantic alter oceanic and atmospheric circulation and associated fluxes of heat and carbon, causing increases in atmospheric CO2 and Antarctic temperatures that drive the termination in the Southern Hemisphere. Increasing CO2 and summer insolation drive recession of northern ice sheets, with probable positive feedbacks between sea level and CO2.

  6. Navy Multiband Terminal (NMT)

    DTIC Science & Technology

    2013-12-01

    Acquisition Management Information Retrieval Dev Est - Development Estimate DoD - Department of Defense DSN - Defense Switched Network Econ - Economic Eng...Memo Note for Shore (for MTBF and MTBCF): Represents IOT &E and Verification of Correction of Deficiencies testing results; mission impact deemed...insignificant due to multiple terminals at Shore site. Note for Sub (for MTBF, MTBCF and MTTR): Represents IOT &E hours; test duration limit for

  7. Amine terminated bisaspartimide polymer

    NASA Technical Reports Server (NTRS)

    Kumar, D. (Inventor); Fohlen, G. M. (Inventor); Parker, J. A. (Inventor)

    1986-01-01

    Novel amine terminated bisaspartimides are prepared by a Michael-type reaction of an aromatic bismalteimide and an aromatic diamine in an aprotic solvent. These bisaspartimides are thermally polymerized to yield tough, resinous polymers cross-lined through -NH- groups. Such polymers are useful in applications requiring materials with resistance to change at elevated temperatures, e.g., as lightweight laminates with graphite cloth, molding material prepregs, adhesives and insulating material.

  8. Remote terminal system evaluation

    NASA Technical Reports Server (NTRS)

    Phillips, T. L.; Grams, H. L.; Lindenlaub, J. C.; Schwingendorf, S. K.; Swain, P. H.; Simmons, W. R.

    1975-01-01

    An Earth Resources Data Processing System was developed to evaluate the system for training, technology transfer, and data processing. In addition to the five sites included in this project two other sites were connected to the system under separate agreements. The experience of these two sites is discussed. The results of the remote terminal project are documented in seven reports: one from each of the five project sites, Purdue University, and an overview report summarizing the other six reports.

  9. Copper(I)-catalyzed cycloaddition of silver acetylides and azides: incorporation of volatile acetylenes into the triazole core.

    PubMed

    Proietti Silvestri, Ilaria; Andemarian, Fikre; Khairallah, George N; Yap, Su Wan; Quach, Tim; Tsegay, Sammi; Williams, Craig M; O'Hair, Richard A J; Donnelly, Paul S; Williams, Spencer J

    2011-09-07

    Silver acetylides and organic azides react under copper(I) catalysis to afford 1,4-disubstituted 1,2,3-triazoles. Mechanistic studies implicate a process involving transmetallation to copper acetylides prior to cycloaddition. This work demonstrates that silver acetylides serve as suitable precursors for entry into copper-mediated coupling reactions. This methodology allows the incorporation of volatile and difficult-to-handle acetylenes into the triazole core.

  10. Extractive probe/TDLAS measurements of acetylene in atmospheric-pressure fuel-rich premixed methane/air flames

    SciTech Connect

    Gersen, S.; Mokhov, A.V.; Levinsky, H.B.

    2005-11-01

    The profiles of C{sub 2}H{sub 2} mole fractions were measured in flat atmospheric-pressure rich-premixed methane/air flames using microprobe gas sampling followed by tunable diode laser absorption spectroscopy (TDLAS), and compared the results with predictions of one-dimensional flame calculations. Acetylene concentrations are also determined by spontaneous Raman scattering to quantify possible uncertainties due to chemical reactions on the probe surface or acceleration of the combustion products into the probe.

  11. Growth of bridging carbon nanofibers in cracks formed by heat-treating iron oxide thin sheets in acetylene gas

    NASA Astrophysics Data System (ADS)

    Hikata, Takeshi; Okubo, Soichiro; Higashi, Yugo; Matsuba, Teruaki; Utsunomiya, Risa; Tsurekawa, Sadahiro; Murakami, Katsuhisa; Fujita, Jun-ichi

    2013-04-01

    We produced novel carbon nanofibers (CNFs) by oxidizing high-purity iron foil and then carburizing it in acetylene gas flow. This formed cracks in the heat-treated iron foil with CNFs bridging the two walls of each crack. The CNFs were drawn out from the walls as the crack opened during heat treatment. This will be a new method to grow and arrange carbon nanotubes and nanosheets without using metal nanoparticles or template substrates.

  12. Tracking hole localization in K -shell and core-valence-excited acetylene photoionization via body-frame photoelectron angular distributions

    NASA Astrophysics Data System (ADS)

    Rescigno, T. N.; Trevisan, C. S.; McCurdy, C. W.

    2015-02-01

    Asymmetry in the molecular-frame photoelectron angular distributions from core-hole- or core-valence-excited polyatomic targets with symmetry-equivalent atoms can provide direct evidence for core-hole localization. Using acetylene as an example, we contrast the small asymmetry that can be seen in direct core-level ionization, due to the competition between two competing pathways to the continuum, with ionization from core-valence-excited HCCH, which offers the prospect of observing markedly greater asymmetry.

  13. 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.

  14. 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.

  15. Unravelling exceptional acetylene and carbon dioxide adsorption within a tetra-amide functionalized metal-organic framework

    PubMed Central

    Moreau, Florian; da Silva, Ivan; Al Smail, Nada H.; Easun, Timothy L.; Savage, Mathew; Godfrey, Harry G. W.; Parker, Stewart F.; Manuel, Pascal; Yang, Sihai; Schröder, Martin

    2017-01-01

    Understanding the mechanism of gas-sorbent interactions is of fundamental importance for the design of improved gas storage materials. Here we report the binding domains of carbon dioxide and acetylene in a tetra-amide functionalized metal-organic framework, MFM-188, at crystallographic resolution. Although exhibiting moderate porosity, desolvated MFM-188a exhibits exceptionally high carbon dioxide and acetylene adsorption uptakes with the latter (232 cm3 g−1 at 295 K and 1 bar) being the highest value observed for porous solids under these conditions to the best of our knowledge. Neutron diffraction and inelastic neutron scattering studies enable the direct observation of the role of amide groups in substrate binding, representing an example of probing gas-amide binding interactions by such experiments. This study reveals that the combination of polyamide groups, open metal sites, appropriate pore geometry and cooperative binding between guest molecules is responsible for the high uptakes of acetylene and carbon dioxide in MFM-188a. PMID:28176793

  16. 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.

  17. Development of a New Detection Scheme to Probe Predissociated Levels of the S_1 State of Acetylene

    NASA Astrophysics Data System (ADS)

    Jiang, Jun; Erickson, Trevor J.; Merer, Anthony; Field, Robert W.

    2016-06-01

    A new spectroscopic scheme has been developed to probe the predissociated levels of the S_1 state of acetylene. Our new scheme is based on detection of visible fluorescence that is a result of multi-photon excitation of acetylene (resonantly through single rovibronic S_1 levels). The new detection scheme is not subject to decreases in fluorescence quantum yield of S_1 levels that lie above the predissociation limit, and laser scatter-light can be easily eliminated by a long-pass filter with a cutoff in the visible range. For the S_1 predissociated levels, the new detection scheme offers much improved signal-to-noise ratio compared to the conventional laser-induced fluorescence technique, based on detection of UV fluorescence from the S_1 levels. The new method is also easier to implement than various H-atom detection schemes, which involve one additional laser of different wavelength than the excitation wavelength. Based on the power dependence and lifetime of the fluorescence signals, electronically excited C_2H and/or C_2 fragments are the likely emitters of the detected visible fluorescence. The new method is currently being used to extend the vibrational and rotational assignments of both gerade and ungerade levels of the S_1 state of acetylene in the region of the cis-trans isomerization barrier, >1000 cm-1 above the onset of S_1 predissociation.

  18. 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.

  19. 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.

  20. 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

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

    NASA Technical Reports Server (NTRS)

    Woon, David E.

    2007-01-01

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

  2. Quantum chemical evaluation of the astrochemical significance of reactions between S atom and acetylene or ethylene.

    PubMed

    Woon, David E

    2007-11-08

    Addition-elimination reactions of S atom in its 3P ground state with acetylene (C2H2) and ethylene (C2H4) were characterized with both molecular orbital and density functional theory calculations employing correlation consistent basis sets in order to assess the likelihood that either reaction might play a general role in astrochemistry or a specific role in the formation of S2 (X3Sigmag-) via a mechanism proposed by Saxena, P. P.; Misra, A. Mon. Not. R. Astron. Soc. 1995, 272, 89. The acetylene and ethylene reactions proceed through C2H2S (3A' ') and C2H4S (3A' ') intermediates, respectively, to yield HCCS (2Pi) and C2H3S (2A'). Substantial barriers were found in the exit channels for every combination of method and basis set considered in this work, which effectively precludes hydrogen elimination pathways for both S + C2H2 and S + C2H4 in the ultracold interstellar medium where only very modest barriers can be surmounted and processes without barriers tend to predominate. However, if one or both intermediates are formed and stabilized efficiently under cometary or dense interstellar cloud conditions, they could serve as temporary reservoirs for the S atom and participate in reactions such as S + C2H2S --> S2 + C2H2 or S + C2H4S --> S2 + C2H4. For formation and stabilization to be efficient, the reaction must possess a barrier height small enough to be surmountable at low temperatures yet large enough to prevent redissociation to reactants. Barrier heights computed with B3LYP and large basis sets are very low, but more rigorous QCISD(T) and RCCSD(T) results indicate that the barrier heights are closer to 3-4 kcal/mol. The calculations therefore indicate that S + C2H2 or S + C2H4 could contribute to the formation of S2 in comets and may serve as a means to gauge coma temperature. The energetics of the ethylene reaction are more favorable.

  3. The Ethics of Terminal Care

    ERIC Educational Resources Information Center

    Agich, George J.

    1978-01-01

    Need for a critical and analytical approach to ethics of terminal care is suggested by considering a series of unexamined questions regarding justification of terminal care. If terminal care is a moral and ethical enterprise, such considerations must be given a more prominent place in discussions of the hospice movement. (Author)

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

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

  5. Terminal weather information management

    NASA Technical Reports Server (NTRS)

    Lee, Alfred T.

    1990-01-01

    Since the mid-1960's, microburst/windshear events have caused at least 30 aircraft accidents and incidents and have killed more than 600 people in the United States alone. This study evaluated alternative means of alerting an airline crew to the presence of microburst/windshear events in the terminal area. Of particular interest was the relative effectiveness of conventional and data link ground-to-air transmissions of ground-based radar and low-level windshear sensing information on microburst/windshear avoidance. The Advanced Concepts Flight Simulator located at Ames Research Center was employed in a line oriented simulation of a scheduled round-trip airline flight from Salt Lake City to Denver Stapleton Airport. Actual weather en route and in the terminal area was simulated using recorded data. The microburst/windshear incident of July 11, 1988 was re-created for the Denver area operations. Six experienced airline crews currently flying scheduled routes were employed as test subjects for each of three groups: (1) A baseline group which received alerts via conventional air traffic control (ATC) tower transmissions; (2) An experimental group which received alerts/events displayed visually and aurally in the cockpit six miles (approx. 2 min.) from the microburst event; and (3) An additional experimental group received displayed alerts/events 23 linear miles (approx. 7 min.) from the microburst event. Analyses of crew communications and decision times showed a marked improvement in both situation awareness and decision-making with visually displayed ground-based radar information. Substantial reductions in the variability of decision times among crews in the visual display groups were also found. These findings suggest that crew performance will be enhanced and individual differences among crews due to differences in training and prior experience are significantly reduced by providing real-time, graphic display of terminal weather hazards.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  7. Terminal Analysis Study

    DTIC Science & Technology

    1976-06-01

    processor cannot provide data at a rate which is fast enough to fill the link, fill bits are inserted until the next line is ready. Each line has the...JWICROPRCXESSOR r^Zl*" MODERATELV MODERATE 7 l I FAST I HIGH Figure 3.19. General Data Proofing Trode-Of* ^peed than the...standard, .p.cify the p.oper manner > which terminals may Interface this store- and- forword message switching network. A2.3 AUTOSEVOCOM The current

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  9. High-rate deposition of diamond films by oxy-acetylene torch

    NASA Astrophysics Data System (ADS)

    Hudson, Martin D.; Brierley, Crofton J.

    1992-12-01

    An oxy-acetylene flame can produce diamond films at significantly higher deposition rates than those associated with either microwave plasma or hot filament assisted chemical vapor deposition. We have established the growth conditions necessary to achieve good quality diamond on silicon substrates. The addition of hydrogen to the gas mixture has been shown to give good quality material at enhanced growth rates. The growth rate has been increased further by using a growth-etch cycling process. This is achieved by periodically pulsing extra oxygen into the gas stream to change from depositing to etching conditions. Under etching conditions the non-diamond carbon in the film is rapidly removed leaving the diamond behind. This allows the use of high rate growth conditions that would otherwise produce poor quality material. The morphology and Raman spectra of films produced by these techniques are presented. The scale-up of the deposition system to cover areas as large as 15 X 20 mm is reported. This is accomplished by rastering a burner consisting of a line of small flames.

  10. 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.

  11. Transition states from molecular symmetry groups: Analysis of non-rigid acetylene trimer

    NASA Astrophysics Data System (ADS)

    Bone, Richard G. A.; Rowlands, Timothy W.; Handy, Nicholas C.; Stone, Anthony J.

    We demonstrate that Longuet-Higgins' molecular symmetry (MS) group for describing non-rigid molecules allows deduction of the transition state for an intramolecular rearrangement and that the level of symmetry of the transition state is governed by very simple rules. Key pieces of information are the order of the MS group and the number of distinctly labelled forms represented by it. We also show that the local symmetry at stationary points on the potential energy surface is important and introduce natural definitions of narcissistic reactions and pathways using the laboratory-fixed inversion operation, giving examples of each. Inspection of normal modes is used to depict motion across the potential energy surface between a minimum-energy structure and a transition state. This analysis is applied to acetylene trimer, a recently observed van der Waals cluster. We elucidate the relationships between the stationary points identified by our earlier ab initio work. There are two transition state structures that together allow full interconversion between the 16 distinctly labelled forms of the global minimum.

  12. Vibration-rotation energy pattern in acetylene: 13CH12CH up to 6750 cm-1.

    PubMed

    Fayt, A; Robert, S; Di Lonardo, G; Fusina, L; Tamassia, F; Herman, M

    2007-03-21

    All known vibration-rotation absorption lines of 13CH12CH accessing levels up to 6750 cm-1 were gathered from the literature. They were fitted simultaneously to J-dependent Hamiltonian matrices exploiting the well known vibrational polyad or cluster block diagonalization, in terms of the pseudo-quantum-numbers Ns=v1+v2+v3 and Nr=5v1+3v2+5v3+v4+v5, and accounting also for l parity and ef symmetry properties. The anharmonic interaction coupling terms known to occur from a pure vibrational fit in this acetylene isotopologue [Robert et al., J. Chem. Phys. 123, 174302 (2005)] were included in the model. A total of 12 703 transitions accessing 158 different (v1v2v3v4v5,l4l5) vibrational states was fitted with a dimensionless standard deviation of 0.99, leading to the determination of 216 vibration-rotation parameters. The experimental data included very weak vibration-rotation transitions accessing 18 previously unreported states, some of them forming Q branches with very irregular patterns.

  13. Zwitterionic Surfactant Modified Acetylene Black Paste Electrode for Highly Facile and Sensitive Determination of Tetrabromobisphenol A

    PubMed Central

    Wei, Xiaoyun; Zhao, Qiang; Wu, Weixiang; Zhou, Tong; Jiang, Shunli; Tong, Yeqing; Lu, Qing

    2016-01-01

    A electrochemical sensor for the highly sensitive detection of tetrabromobisphenol A (TBBPA) was fabricated based on acetylene black paste electrode (ABPE) modified with 3-(N,N-Dimethylpalmitylammonio) propanesulfonate (SB3-16) in this study. The peak current of TBBPA was significantly enhanced at SB3-16/ABPE compared with unmodified electrodes. To further improve the electrochemical performance of the modified electrode, corresponding experimental parameters such as the length of hydrophobic chains of zwitterionic surfactant, the concentration of SB3-16, pH value, and accumulation time were examined. The peak currents of TBBPA were found to be linearly correlated with its concentrations in the range of 1 nM to 1 µM, with a detection limit of 0.4 nM. Besides, a possible mechanism was also discussed, and the hydrophobic interaction between TBBPA and the surfactants was suggested to take a leading role in enhancing the responses. Finally, this sensor was successfully employed to detect TBBPA in water samples. PMID:27657078

  14. Electrochemical determination of chrysophanol based on the enhancement effect of acetylene black nanoparticles.

    PubMed

    Zhang, Yuanyuan; Wang, Yanying; Wu, Kangbing; Zhang, Shichao; Zhang, Yu; Wan, Chidan

    2013-03-01

    Acetylene black (AB) nanoparticles were readily dispersed into water in the presence of dihexadecyl hydrogen phosphate. After evaporation of water, the surface of glassy carbon electrode (GCE) was coated with AB nanoparticles as confirmed from the scanning electron microscopy measurements. The transmission electron microscopy images indicated that AB nanoparticles possessed porous structure. Electrochemical behavior of chrysophanol was studied, and a sensitive oxidation peak was observed in pH 3.6 acetate buffer solution. Compared with the bare GCE, the AB nanoparticles-modified GCE greatly increased the oxidation peak current of chrysophanol, showing remarkable signal enhancement effect. The influences of pH value, amount of AB, accumulation potential and time on the signal enhancement of chrysophanol were studied. As a result, a novel electrochemical method was developed for the determination of chrysophanol. The linear range was from 1.5 to 200 μgL(-1), and the detection limit was 0.51 μgL(-1) (2.01 × 10(-9)M) after 2-min accumulation. Finally, this method was used in traditional Chinese medicines, and the results consisted with the values that obtained by high-performance liquid chromatography.

  15. Self-calibration wavelength modulation spectroscopy for acetylene detection based on tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Qin-Bin; Xu, Xue-Mei; Li, Chen-Jing; Ding, Yi-Peng; Cao, Can; Yin, Lin-Zi; Ding, Jia-Feng

    2016-11-01

    The expressions of the second harmonic (2f) signal are derived on the basis of absorption spectral and lock-in theories. A parametric study indicates that the phase shift between the intensity and wavelength modulation makes a great contribution to the 2f signal. A self-calibration wavelength modulation spectroscopy (WMS) method based on tunable diode laser absorption spectroscopy (TDLAS) is applied, combining the advantages of ambient pressure, temperature suppression, and phase-shift influences elimination. Species concentration is retrieved simultaneously from selected 2f signal pairs of measured and reference WMS-2f spectra. The absorption line of acetylene (C2H2) at 1530.36 nm near-infrared is selected to detect C2H2 concentrations in the range of 0-400 ppmv. System sensitivity, detection precision and limit are markedly improved, demonstrating that the self-calibration method has better detecting performance than the conventional WMS. Project supported by the National Natural Science Foundation of China (Grant Nos. 61172047, 61502538, and 61501525).

  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. 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.

  18. Conformations of propargyl alcohol and its interaction with acetylene: A matrix isolation infrared and DFT computations

    NASA Astrophysics Data System (ADS)

    Sundararajan, K.; Gopi, R.; Ramanathan, N.

    2016-10-01

    Conformations of propargyl alcohol (PA) were studied using matrix isolation infrared spectroscopy. DFT computations using 6-311++G(d,p) basis set on the PA molecule identified two minima; gauche (g-PA) and trans (t-PA). Comparison of infrared spectra of PA trapped in Ar, N2 and Xe matrices with computations showed the evidence of the ground state g-PA conformer. Four minima were optimized on the potential energy surface for the hydrogen-bonded interaction of g-PA and acetylene (C2H2), corresponding to complex A (Csbnd H⋯O), complex B (Osbnd H⋯π) and complex C and D (Csbnd H⋯π). The structure, energies and the vibrational wavenumbers were computed for these complexes at B3LYP/6-311++G (d,p) level of theory. The infrared spectra of the hydrogen-bonded complexes between C2H2 and g-PA were studied in Ar matrix. The infrared spectra recorded under matrix isolation conditions revealed the formation of two types of complexes A (Csbnd H⋯O) and B (Osbnd H⋯π). Formation of these complexes was evidenced from the shifts in the vibrational wavenumber of the modes involving the C2H2 and PA submolecules.

  19. DFT study of selective hydrogenation of acetylene to ethylene on Pd doping Ag nanoclusters

    NASA Astrophysics Data System (ADS)

    Liu, D.

    2016-11-01

    Recently, it has been reported that the reaction selectivity of catalytic hydrogenation of acetylene to ethylene can be significantly enhanced via the approach of Pd mono-atomic catalysis [Pei et al. ACS Catal. 5 (2015) 3717-3725]. To explain the catalytic mechanism of this binary alloy catalyst, C2H2 hydrogenation reactions on Pd doping Ag nanoclusters are studied using density functional theory simulations. The simulation results indicate that H2 and C2H2 can simultaneously bind with a single Pd doping atom no matter it is on vertex and edge sites of Ag clusters. The following H2 dissociation and C2H2 hydrogenation are not difficult since the corresponding reaction barrier values are no more than 0.58 eV. The generated C2H4 molecule can not be further hydrogenated since it locates on the top of Pd doping atom, which is the only adsorption site for H2. On two Pd doping atoms at contiguous sites of Ag clusters, C2H4 hydrogenation reactions can be carried out since there are enough sites for co-adsorption of H2 and C2H4.

  20. Infrared spectroscopy of acetylene, carbon monoxide, and deuterated hydrogen cyanide for planetary atmospheric applications

    NASA Astrophysics Data System (ADS)

    Esteki, Koorosh

    I present the results of three spectroscopic projects. First, we analysed spectra of acetylene diluted by carbon dioxide (CO2) in the R-branch region of the nu1+nu3 combination vibrational band (6470-6618 cm-1). The spectra were recorded over a range of pressures between 50 to 500 Torr and temperatures between 216 to 333 K. The objective was to obtain the CO2 broadened Lorentz half width, line-shift parameters as well as their temperature dependency for all measurable transitions. Second, we have re-analyzed high-resolution, room temperature spectra of pure CO and CO broadened by hydrogen recorded in the spectral range of the first overtone band. Self- and H2-broadened line parameters were obtained for 48 ro-vibrational transitions. Third, we studied the infrared emission spectra of Deuterium Cyanide (DCN) in the 450 to 850 wavenumbers range, recorded at 1370 K at the Justus-Liebig University, Giessen, Germany. We report the ro-vibrational constants for the DCN molecule.

  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. Successive lithiation of acetylene, ethylene and benzene: a comprehensive computational study of large static second hyperpolarizability.

    PubMed

    Mondal, Avijit; Hatua, Kaushik; Roy, Ria Sinha; Nandi, Prasanta K

    2017-02-08

    This work is a revisit of the study of the electron correlation effect of lithium substitution on the second hyperpolarizability (10(6) a.u.) of acetylene, ethylene and benzene. The large quenching of mean second hyperpolarizability has been addressed by CCSD calculations. The inclusion of triple excitation in the MP4 method generally overestimates second hyperpolarizability in comparison to the MP4SDQ method. The present CCSD γav value of C6Li6: 405 × 10(4) a.u. obtained with a relatively larger basis set established the earlier prediction of Sadlej et al. [Phys. Chem. Phys. Chem., 2000, 2, 3393-3399] where degenerate non-dipolar transitions in low lying excited states play the crucial role. The successive lithiation results in gradual red shifting of transition energy leading to significant enhancement of second hyperpolarizability. Most of the chosen DFT functionals predict the correct qualitative trend of second hyperpolarizability. The quantitatively different results may be attributed to the case when the ground state wave function cannot be approximated by a single SD.

  4. 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.

  5. 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.

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

    NASA Technical Reports Server (NTRS)

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  8. Prediction of electron and ion concentrations in low-pressure premixed acetylene and ethylene flames

    NASA Astrophysics Data System (ADS)

    Cancian, J.; Bennett, B. A. V.; Colket, M. B.; Smooke, M. D.

    2013-04-01

    Flame stabilisation and extinction in a number of different flows can be affected by application of electric fields. Electrons and ions are present in flames, and because of charge separation, weak electric fields can also be generated even when there is no externally applied electric field. In this work, a numerical model incorporating ambipolar diffusion and plasma kinetics has been developed to predict gas temperature, species, and ion and electron concentrations in laminar premixed flames without applied electric fields. This goal has been achieved by combining the existing CHEMKIN-based PREMIX code with a recently developed methodology for the solution of electron temperature and transport properties that uses a plasma kinetics model and a Boltzmann equation solver. A chemical reaction set has been compiled from seven sources and includes chemiionisation, ion-molecule, and dissociative-recombination reactions. The numerical results from the modified PREMIX code (such as peak number densities of positive ions) display good agreement with previously published experimental data for fuel-rich, non-sooting, low-pressure acetylene and ethylene flames without applied electric fields.

  9. A Cationic Unsaturated Platinum(II) Complex that Promotes the Tautomerization of Acetylene to Vinylidene.

    PubMed

    Ortega-Moreno, Laura; Peloso, Riccardo; López-Serrano, Joaquín; Iglesias-Sigüenza, Javier; Maya, Celia; Carmona, Ernesto

    2017-03-01

    Complex [PtMe2 (PMe2 ArDipp2 )] (1), which contains a tethered terphenyl phosphine (ArDipp2 =2,6-(2,6-(i) Pr2 C6 H3 )2 C6 H3 ), reacts with [H(Et2 O)2 ]BArF (BArF(-) =B[3,5-(CF3 )2 C6 H3 ]4(-) ) to give the solvent (S) complex [PtMe(S)(PMe2 ArDipp2 )](+) (2⋅S). Although the solvent molecule is easily displaced by a Lewis base (e.g., CO or C2 H4 ) to afford the corresponding adducts, treatment of 2⋅S with C2 H2 yielded instead the allyl complex [Pt(η(3) -C3 H5 )(PMe2 ArDipp2 )](+) (6) via the alkyne intermediate [PtMe(η(2) -C2 H2 )(PMe2 ArDipp2 )](+) (5). Deuteration experiments with C2 D2 , and kinetic and theoretical investigations demonstrated that the conversion of 5 into 6 involves a Pt(II) -promoted HC≡CH to :C=CH2 tautomerization in preference over acetylene migratory insertion into the Pt-Me bond.

  10. Termination: A Case Study.

    PubMed

    Friedberg, Ahron L

    2015-12-01

    In this article I posit and examine certain criteria and qualities for ending an analysis. The case study describes the end phase of a four-year psychoanalysis in which the patient's decision to move to another area forced the end of his analysis. We continued to explore and work through his core neurotic conflicts that included issues of competitive rivalry, dominance and submission, control, and anxiety about birth and death. A shift in the transference from me as a negative father to me as a supportive but competitive older brother was also examined in the context of ending treatment as well as other aspects of the transference. In addition, we analyzed the meaning of his ending treatment based on an extra-analytic circumstance. In discussing this phase of treatment, the definition and history of the term "termination" and its connotations are reviewed. Various criteria for completing an analysis are examined, and technical observations about this phase of treatment are investigated. It was found that while a significant shift in the transference occurred in this phase of the patient's analysis, conflicts related to the transference were not "resolved" in the classical sense. Terminating treatment was considered as a practical matter in which the patient's autonomy and sense of choice were respected and analyzed.

  11. Channel and terminal description of the ACTS mobile terminal

    NASA Technical Reports Server (NTRS)

    Abbe, B. S.; Agan, M. J.; Girardey, C. C.; Jedrey, T. C.

    1994-01-01

    The Advanced Communications Technology Satellite (ACTS) Mobile Terminal (AMT) is a proof-of-concept K/Ka-band mobile satellite communications terminal under development by NASA at JPL. Currently the AMT is undergoing systems integration and testing in preparation for a July 1993 ACTS launch and the subsequent commencement of mobile experiments in the fall of 1993. The AMT objectives are presented, followed by a discussion of the AMT communications channel and the mobile terminal's design and performance.

  12. Channel and terminal description of the ACTS mobile terminal

    NASA Technical Reports Server (NTRS)

    Abbe, B. S.; Agan, M. J.; Girardey, C. C.; Jedrey, T. C.

    1993-01-01

    The Advanced Communications Technology Satellite (ACTS) Mobile Terminal (AMT) is a proof-of-concept K/Ka-band mobile satellite communications terminal under development by NASA at JPL. Currently the AMT is undergoing system integration and test in preparation for a July 1993 ACTS launch and the subsequent commencement of mobile experiments in the fall of 1993. The AMT objectives are presented followed by a discussion of the AMT communications channel and mobile terminal design and performance.

  13. The Effects of Termination on the Menominee

    ERIC Educational Resources Information Center

    Deer, Ada E.

    1973-01-01

    Topics discussed in this article are: (1) a brief pre-termination history of the Menominee Indians; (2) the enactment of termination; (3) the effects of termination on the Menominee; and (4) the need to repudiate termination. (NQ)

  14. [Terminal ballistics. 3].

    PubMed

    Marini, F; Mangiante, G; Dagradi, V; Radin, S; Carolo, F; Giarolli, M; Della Giacoma, G; Tosi, D; Merico, G; Tenci, A

    1993-01-01

    This brief chapter, focusing essentially on a single topic, has been written in homage to Emile Theodor Kocker, a masterful exponent of the art of surgery and founder of the culture of terminal ballistics. For most of the literature we are indebted to Fackler and Dougherty, who, with the particular grasp, and fair of historians, act as guides on a trial which is only apparently retrograde, but which actually bears eloquent witness to the fact that even in the most physically tangible of arts, namely the art of surgery, inspired curiosity may help us to go well beyond the limits of our day and age. This chapter is also dedicated to the memory of another great surgeon, Vittorio Pettinari, who for one of the authors was an incomparable mentor and past-master of such curiosity.

  15. 75 FR 13644 - TORP Terminal LP, Bienville Offshore Energy Terminal Liquefied Natural Gas Deepwater Port License...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-22

    ... Maritime Administration TORP Terminal LP, Bienville Offshore Energy Terminal Liquefied Natural Gas...) for the TORP Terminal LP, Bienville Offshore Energy Terminal (BOET) Liquefied Natural Gas (LNG..., both are identified in FOR FURTHER INFORMATION CONTACT. Summary of the Application TORP Terminal...

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

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

    PubMed

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

    2012-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  20. Thermal decomposition mechanisms of the methoxyphenols: formation of phenol, cyclopentadienone, vinylacetylene, and acetylene.

    PubMed

    Scheer, Adam M; Mukarakate, Calvin; Robichaud, David J; Nimlos, Mark R; Ellison, G Barney

    2011-11-24

    The pyrolyses of the guaiacols or methoxyphenols (o-, m-, and p-HOC(6)H(4)OCH(3)) have been studied using a heated SiC microtubular (μ-tubular) reactor. The decomposition products are detected by both photoionization time-of-flight mass spectroscopy (PIMS) and matrix isolation infrared spectroscopy (IR). Gas exiting the heated SiC μ-tubular reactor is subject to a free expansion after a residence time of approximately 50-100 μs. The PIMS reveals that, for all three guaiacols, the initial decomposition step is loss of methyl radical: HOC(6)H(4)OCH(3) → HOC(6)H(4)O + CH(3). Decarbonylation of the HOC(6)H(4)O radical produces the hydroxycyclopentadienyl radical, C(5)H(4)OH. As the temperature of the μ-tubular reactor is raised to 1275 K, the C(5)H(4)OH radical loses a H atom to produce cyclopentadienone, C(5)H(4)═O. Loss of CO from cyclopentadienone leads to the final products, acetylene and vinylacetylene: C(5)H(4)═O → [CO + 2 HC≡CH] or [CO + HC≡C-CH═CH(2)]. The formation of C(5)H(4)═O, HCCH, and CH(2)CHCCH is confirmed with IR spectroscopy. In separate studies of the (1 + 1) resonance-enhanced multiphoton ionization (REMPI) spectra, we observe the presence of C(6)H(5)OH in the molecular beam: C(6)H(5)OH + λ(275.1 nm) → [C(6)H(5)OH Ã] + λ(275.1nm) → C(6)H(5)OH(+). From the REMPI and PIMS signals and previous work on methoxybenzene, we suggest that phenol results from a radical/radical reaction: CH(3) + C(5)H(4)OH → [CH(3)-C(5)H(4)OH]* → C(6)H(5)OH + 2H.

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

    PubMed

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

    2015-12-01

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

  2. Influence of resonant collisions on the self-broadening of acetylene

    NASA Astrophysics Data System (ADS)

    Lehmann, Kevin K.

    2017-03-01

    Iwakuni et al. [Phys. Rev. Lett. 117, 143902 (2016)] have reported an ortho-para alternation of ˜10% in the self pressure broadening coefficients for ro-vibrational lines of the C2H2 transitions in the ν1+ν3 C-H (local mode) overtone band near 197 THz (1.52 μm). These authors attributed this effect to the contribution of resonant collisions, where the rotational energy change of one molecule is exactly compensated by the rotational energy change of its collision partner. Resonant collisions are known to be important in the case of self pressure broadening of highly polar molecules, such as HCN, but have not previously been invoked in the case of nonpolar molecules, such as acetylene, where the long range potential is dominated by the quadrupole-quadrupole electrostatic interaction. In the present work, the simple semiclassical Anderson-theory approach is used to estimate the rates of C2H2-C2H2 rotationally inelastic collisions and these used to predict pressure broadening rates, ignoring other contributions to the broadening, which should not have resonant enhancements. It is found that exactly resonant collisions do not make a major contribution to the broadening and these calculations predict an ortho-para alternation of the pressure broadening coefficients far below what was inferred by Iwakuni et al. The present results are consistent with a large body of published work that reported self-broadening coefficients of C2H2 ro-vibrational transitions that found negligible dependence on the vibrational transition and no even-odd alternation, even for Q and S branch transitions where any such effect is predicted to be much larger than for the P and R branch transitions studied by Iwakuni et al.

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

    NASA Technical Reports Server (NTRS)

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

    2014-01-01

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

  4. Infrared analysis of soot produced from an acetylene-rich flame

    NASA Astrophysics Data System (ADS)

    Pino, Thomas; Dartois, Emmanuel; Cao, Anh Tuan; D'Hendecourt, Louis; Bréchignac, Philippe

    The ubiquitous unidentified infrared emission bands (UIBs), now referred to as aromatic infrared bands (AIBs), observed from a variety of regions of interstellar space have been recognized to involve carbonaceous material with an aromatic character. It is now widely accepted that these interstellar "nanograins" should have sizes intermediate between those of the PAHs easily accessible to laboratory studies and of the "standard" interstellar grains (ca 0.05μm or 50 nm). The nanometer size is related to their capability of being transiently heated upon absorption of UV starlight photons. We will present the preliminary results obtained with a new experimental set-up, devoted to the formation of carbonaceous nanoparticles and the characterization of their spectral properties in absorption and in emission, in the solid phase and in the gas phase, isolated in a van der Waals matrix or free-flying. The production of the species uses laboratory techniques and conditioning under specific interstellar processes such as coupling a chemical reactor to stellar-like UV irradiation. We have used in particular an acetylene-rich, premixed and flat, low-pressure flame as a reactor. When operated under low-pressure conditions, the spatial development of the flame allows us to sample its content at various stages of the particles growth. The analysis can be made by transmission spectroscopy of thin film deposits under infrared microscope or in rare gas matrices under FTIR spectroscopy, and by Time-Of-Flight mass spectrometry. The preliminary results reveal a strong evolution from aromatic materials containing aliphatic substituents to large polymer-like soot particules. The spectrum in Figure 1 is that of a deposition taken from a sooting flame at a C/O=2, burning at a pressure of 26.5mb, and sampled at 12mm from the flat burner. A tentative assignment is given.

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  7. Recovery of acetylene absorption line profile basing on tunable diode laser spectroscopy with intensity modulation and photoacoustic spectroscopy

    NASA Astrophysics Data System (ADS)

    Li, Li; Thursby, Graham; Stewart, George; Arsad, Norhana; Uttamchandani, Deepak; Culshaw, Brian; Wang, Yiding

    2010-04-01

    A novel and direct absorption line recovery technique based on tunable diode laser spectroscopy with intensity modulation is presented. Photoacoustic spectroscopy is applied for high sensitivity, zero background and efficient acoustic enhancement at a low modulation frequency. A micro-electromechanical systems (MEMS) mirror driven by an electrothermal actuator is used for generating laser intensity modulation (without wavelength modulation) through the external reflection. The MEMS mirror with 10μm thick structure material layer and 100nm thick gold coating is formed as a circular mirror of 2mm diameter attached to an electrothermal actuator and is fabricated on a chip that is wire-bonded and placed on a PCB holder. Low modulation frequency is adopted (since the resonant frequencies of the photoacoustic gas cell and the electrothermal actuator are different) and intrinsic high signal amplitude characteristics in low frequency region achieved from measured frequency responses for the MEMS mirror and the gas cell. Based on the property of photoacoustic spectroscopy and Beer's law that detectable sensitivity is a function of input laser intensity in the case of constant gas concentration and laser path length, a Keopsys erbium doped fibre amplifier (EDFA) with opto-communication C band and high output power up to 1W is chosen to increase the laser power. High modulation depth is achieved through adjusting the MEMS mirror's reflection position and driving voltage. In order to scan through the target gas absorption line, the temperature swept method is adopted for the tunable distributed feed-back (DFB) diode laser working at 1535nm that accesses the near-infrared vibration-rotation spectrum of acetylene. The profile of acetylene P17 absorption line at 1535.39nm is recovered ideally for ~100 parts-per-million (ppm) acetylene balanced by nitrogen. The experimental signal to noise ratio (SNR) of absorption line recovery for 500mW laser power was ~80 and hence the

  8. Selective hydrogenation of acetylene on SiO2 supported Ni-In bimetallic catalysts: Promotional effect of In

    NASA Astrophysics Data System (ADS)

    Chen, Yanjun; Chen, Jixiang

    2016-11-01

    Ni/SiO2 and the bimetallic NixIn/SiO2 catalysts with different Ni/In ratios were tested for the selective hydrogenation of acetylene, and their physicochemical properties before and after the reaction were characterized by means of N2-sorption, H2-TPR, XRD, TEM, XPS, H2 chemisorption, C2H4-TPD, NH3-TPD, FT-IR of adsorbed pyridine, and TG/DTA and Raman. A promotional effect of In on the performance of Ni/SiO2 was found, and NixIn/SiO2 with a suitable Ni/In ratio gave much higher acetylene conversion, ethylene selectivity and catalyst stability than Ni/SiO2. This is ascribed to the geometrical isolation of the reactive Ni atoms with the inert In ones and the charge transfer from the In atoms to Ni ones, both of which are favorable for reducing the adsorption strength of ethylene and restraining the Csbnd C hydrogenolysis and the polymerizations of acetylene and the intermediate compounds. On the whole, Ni6In/SiO2 and Ni10In/SiO2 had better performance. Nevertheless, with increasing the In content, the selectivity to the C4+ hydrocarbons tended to increase due to the enhanced catalyst acidity because of the charge transfer from the In atoms to Ni ones. As the Lewis acid ones, the In sites could promote the polymerization. The catalyst deactivation was also analyzed. We propose that the Ni/SiO2 deactivation is mainly attributed to the phase change from metallic Ni to nickel carbide. The introduction of In inhibited the formation of nickel carbide. However, as the In content increased, the carbonaceous deposit became the main reason for the NixIn/SiO2 deactivation due to the enhanced catalyst acidity.

  9. 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.

  10. 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.

  11. The electronic structure and second-order nonlinear optical properties of donor-acceptor acetylenes - A detailed investigation of structure-property relationships

    NASA Technical Reports Server (NTRS)

    Stiegman, A. E.; Graham, Eva; Khundkar, Lutfur R.; Perry, Joseph W.; Cheng, L.-T.; Perry, Kelly J.

    1991-01-01

    A series of donor-acceptor acetylene compounds was synthesized in which systematic changes in both the conjugation length and the donor-acceptor strength were made. The effect of these structural changes on the spectroscopic and electronic properties of the molecules and, ultimately, on the measured second-order molecular hyperpolarizabilities (beta) was investigated. It was found that increases in the donor-acceptor strength resulted in increases in the magnitude of beta. For this class of molecules, the increase is dominated by the energy of the intramolecular charge-transfer transition, while factors such as the ground to excited-state dipole moment change and the transition-moment integral are much less important. Increasing the conjugation length from one to two acetylene linkers did not result in an increase in the value of beta; however, beta increased sharply in going from two acetylenes to three. This increase is attributed to the superposition of several nearly isoenergetic excited states.

  12. Generation of the organo-rare gas dications HCCRg2+ (Rg = Ar and Kr) in the reaction of acetylene dications with rare gases.

    PubMed

    Ascenzi, Daniela; Tosi, Paolo; Roithová, Jana; Ricketts, Claire L; Schröder, Detlef; Lockyear, Jessica F; Parkes, Michael A; Price, Stephen D

    2008-12-21

    Using doubly ionized acetylene as a superelectrophilic reagent, the new rare-gas compounds HCCAr2+ and HCCKr2+ have been prepared for the first time in hyperthermal collisions of mass-selected C2H2(2+) with neutral rare gases (Rg). However, electron transfer from the rare gas to the acetylene dication as well as proton transfer from C2H2(2+) to the rare gas efficiently compete with formation of HCCRg2+. The computational investigations show that the formation of HCCRg2+ from acetylene dication is endothermic with Rg = He, Ne, Ar and Kr and only weakly exothermic with Xe. These energetic factors, as well as the pronounced competition with the other reactive channels help to explain why HCCRg2+ is only observed with Rg = Ar and Kr.

  13. Untangling the reaction dynamics of the silylidyne radical (SiH; X2Π) with acetylene (C2H2; X1Σg+)

    NASA Astrophysics Data System (ADS)

    Yang, Tao; Dangi, Beni B.; Thomas, Aaron M.; Kaiser, Ralf I.

    2016-06-01

    The chemical reaction dynamics of silylidyne (SiH; X2Π) with acetylene (C2H2; X1Σg+) were studied exploiting the crossed molecular beam approach, and compared with previous studies on D1-silylidyne with acetylene. The reaction is initiated by a barrierless addition of silylidyne to one or both carbons of acetylene leading to 1-sila-1-propene-1,3-diylidene and/or the cyclic 1-silacyclopropenyl with the former isomerizing to the latter. 1-Silacyclopropenyl eventually loses atomic hydrogen yielding silacyclopropenylidene (c-SiC2H2) in an overall exoergic reaction (experiment: -14.7 ± 8.5 kJ mol-1; theory: -13 ± 3 kJ mol-1). The enthalpy of formation for silacyclopropenylidene is determined to be 421.4 ± 9.3 kJ mol-1.

  14. Acetylene-substituted two-photon absorbing molecules with rigid elongated pi-conjugation: synthesis, spectroscopic properties and two-photon fluorescence cell imaging applications.

    PubMed

    Liu, Bo; Zhang, Hai-Li; Liu, Jun; Huang, Zhen-Li; Zhao, Yuan-Di; Luo, Qing-Ming

    2007-09-01

    Two asymmetrical molecules with substituted acetylene as central rigid elongated conjugation are reported as potential chromophores for two-photon microscopic imaging. These molecules consist of a typical D-pi-A structure, have different donors (D), the same pi-conjugated center (pi) and the same acceptor (A). Structural characterization and spectroscopic properties, including single-photon (linear) absorption, quantum yields, single-photon fluorescence, and two-photon absorption spectra, were studied in solvents with different polarity. These acetylene-substituted molecules were found to have high two-photon absorption cross-sections (for example, 690 GM for molecule 1 in toluene), which were determined by a two-photon induced fluorescence method using a femtosecond Ti: sapphire laser as excitation source. Single- and two-photon cellular imaging experiments demonstrate that the substituted acetylene derivatives could be one kind of promising two-photon fluorescence probes for cellular imaging.

  15. Degenerate four-wave mixing spectroscopy and spectral simulation of C2 in an atmospheric pressure oxy-acetylene flame

    NASA Astrophysics Data System (ADS)

    Kaminski, C. F.; Hughes, I. G.; Ewart, P.

    1997-04-01

    The d 3Πg↔a3Πu Swan bands of C2 have been recorded with high resolution using DFWM in the nearly Doppler free, phase conjugate geometry. C2 was probed in a standard oxy-acetylene welding flame with excellent signal-to-noise ratio and spectral resolution. Theoretical spectra were simulated and fitted directly to the complex overlapping spectra. The good agreement obtained shows that DFWM holds promise to become a robust and reliable tool for flame thermometry. Current theories of DFWM are reviewed in context of the present work and advantages and disadvantages of the technique are discussed.

  16. Research on the influence of transparent vacuum encapsulation quartz tuning fork on the photo-thermoelastic spectroscopy of acetylene

    NASA Astrophysics Data System (ADS)

    Zhang, Zhouqiang; Jia, Shuhai; Wang, Yonglin; Tang, Zhenhua; Wang, Fei

    2016-10-01

    In this paper, a transparent vacuum-encapsulated quartz tuning fork (QTF) is proposed for the first time to improve the quality factor and sensitivity of QTF sensors. Increasing the vacuum considerably improved the quality factor of QTF, and the resonance frequency was also shifted to higher values to 10 Hz. Subsequently, the spectroscopy detection of acetylene gas using an exposed QTF and a transparent vacuum-encapsulated QTF was investigated. The sensitivity of the detection system improved in the presence of the transparent vacuum-sealed QTF. The current findings represent a gateway to subsequent research in photo-thermoelastic spectroscopy.

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

    NASA Technical Reports Server (NTRS)

    Allen, Harrison, Jr.; Tannenbaum, Stanley

    1957-01-01

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

  18. The Power-Supply Control System in the Device of Acetylene Production by H-Plasma Pyrolysis Coal

    NASA Astrophysics Data System (ADS)

    Chen, Feiyun; Zhang, Ming; Fu, Peng; Weng, Peide

    2006-09-01

    The device of acetylene production by hydrogen (H-) plasma pyrolysis coal is examined and developed not only for studying the application of low temperature plasma but also for studying the clean use of coal. The power-supply control system is used to ensure supplying a steady energy to generate and maintain the plasma electric arc of the device. The hardware configuration and the software design of the system are described in this paper. Verified by experiments, this system can meet the requirements of real-time performance, reliability and extensibility for the device.

  19. Infrared spectra of the ethynyl metal hydrides produced in reactions of laser-ablated Mn and Re atoms with acetylene.

    PubMed

    Cho, Han-Gook; Andrews, Lester

    2011-05-19

    The ethynyl metal hydride molecules (HM-C≡CH) are identified in the matrix infrared spectra from reactions of laser-ablated Mn and Re atoms with acetylene using D and (13)C isotopic substitution and density functional computed frequencies. The assignment of strong M-H as well as C≡C bond stretching product absorptions suggests oxidative C-H insertion during reagent codeposition and subsequent photolysis. The unique linear structure calculated for HMn-C≡CH is parallel to C(3v) structures found recently for Mn complexes including CH(3)-MnF.

  20. 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

  1. Is Lake Tahoe Terminal?

    NASA Astrophysics Data System (ADS)

    Coats, R. N.; Reuter, J.; Heyvaert, A.; Lewis, J.; Sahoo, G. B.; Schladow, G.; Thorne, J. H.

    2014-12-01

    ) the climatic water deficit will increase, especially at high elevations that will be most affected by the loss of snow, with likely consequences for existing vegetation and fire frequency. Hydrologically, Lake Tahoe is intermittently terminal; in a medical sense it is not yet terminal, but its condition—especially its valued clarity and deep blue color--is serious.

  2. SCATHA mission termination report

    NASA Technical Reports Server (NTRS)

    Stakkestad, Kjell; Fennessey, Richard

    1993-01-01

    nearly complete lack of available telemetry data, large undamped motion of the long booms, inadequacies in attitude determination software, and an error in the fuel level calculation software. This paper discusses the various proposed termination plans and execution of the selected one. Attitude determination methodologies, nutation from maneuvers, and effects of the flexible booms on the termination mission are presented and analyzed from a satellite analyst point of view.

  3. SCATHA mission termination report

    NASA Astrophysics Data System (ADS)

    Stakkestad, Kjell; Fennessey, Richard

    1993-02-01

    nearly complete lack of available telemetry data, large undamped motion of the long booms, inadequacies in attitude determination software, and an error in the fuel level calculation software. This paper discusses the various proposed termination plans and execution of the selected one. Attitude determination methodologies, nutation from maneuvers, and effects of the flexible booms on the termination mission are presented and analyzed from a satellite analyst point of view.

  4. 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

  5. [Terminal ballistics. 1].

    PubMed

    Mangiante, G; Dagradi, V; Radin, S; Carolo, F; Giarolli, M; Tenci, A; Merico, G; Tosi, D; Acerbi, A; Della Giacoma, G

    1993-01-01

    We have chosen to conceive of terminal ballistics as a violent and extremely rapid confrontation between two forms of resistance before the final state of rest is reached. This definition, which cannot help but don the admittedly loud and outlandish garb of physics, is the most promising for the purposes of biological interpretation. The main characters on this stage are two, but only one of these really plays the lead, namely the human target, which acts out the basic roles inherent in its physical make-up; the other, the bullet, remains a background figure, frozen in its walk-on part, and ready for the next performance. This modus operandi, which is no simplification, but rather an academic necessity, enables us to focus on images which stand out more clearly as a result of an intensive macroscopic spotlight which brings out the features of the individual phenomena, broken down into a succession of close-ups, and subtracts them from the cold physical nature of this or that form of inert matter, which here is merely an occasional, disagreeable witness, or even more, a standing from time to time for but one of the infinite facets of the biological composite being. Here, then, faced with a kind of exploded macrophotograph of a complex kaleidoscope, we see the animal universe, of which we capture so far the plasticity, the subdivisibility, the anisotropy and the cavitation.

  6. Terminal Descent Sensor Simulation

    NASA Technical Reports Server (NTRS)

    Chen, Curtis W.

    2009-01-01

    Sulcata software simulates the operation of the Mars Science Laboratory (MSL) radar terminal descent sensor (TDS). The program models TDS radar antennas, RF hardware, and digital processing, as well as the physics of scattering from a coherent ground surface. This application is specific to this sensor and is flexible enough to handle end-to-end design validation. Sulcata is a high-fidelity simulation and is used for performance evaluation, anomaly resolution, and design validation. Within the trajectory frame, almost all internal vectors are represented in whatever coordinate system is used to represent platform position. The trajectory frame must be planet-fixed. The platform body frame is specified relative to arbitrary reference points relative to the platform (spacecraft or test vehicle). Its rotation is a function of time from the trajectory coordinate system specified via dynamics input (file for open loop, callback for closed loop). Orientation of the frame relative to the body is arbitrary, but constant over time. The TDS frame must have a constant rotation and translation from the platform body frame specified at run time. The DEM frame has an arbitrary, but time-constant, rotation and translation with respect to the simulation frame specified at run time. It has the same orientation as sigma0 frame, but is possibly translated. Surface sigma0 has the same arbitrary rotation and translation as DEM frame.

  7. Anchored terminal conductor

    SciTech Connect

    Milewski, M.A.; Delmolino, W.P.

    1986-08-19

    An electrochemical cell is described comprising a cell container which is closed by a resilient insulative cell top and an electrode conductor inserted through the cell top and into an electrode of the cell, with the electrode conductor being physically and electrically accessible to the exterior of the cell whereby it functions as a terminal for the electrode, and wherein a portion of the electrode conductor is enclosed within the cell top, characterized in that the cell further comprises means for substantially restraining movement of the electrode conductor relative to the cell top. The electrode conductor has a nail configuration comprising a head and a shank with the head of the nail providing the external physical and electrical accessibility, wherein the restraining means is integrated with the shank of the nail. The restraining means is positioned on the shank, interior to the cell container and below the interior surface of the cell top and in close juxtaposition to the interior surface. The restraining means comprises a circumferential barb longitudinally disposed on the shank and having an upper portion which engages the interior surface to provide the substantial restraining of movement.

  8. War Termination: A Selected Bibliography

    DTIC Science & Technology

    2010-10-01

    Peace Research 33, no. 4 (November 1996): 491-496. JSTOR Phinney, Catherine. "Enhancing Conflict Termination through Problem Solving...96." Journal of Peace Research 34, no. 3 (August 1997): 339-358. JSTOR Bibliographies Bibliography Branch, comp. Conflict Termination

  9. 49 CFR 1242.27 - Coal marine terminals, ore marine terminals, TOFC/COFC terminals, other marine terminals, motor...

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    .../COFC terminals, other marine terminals, motor vehicle loading and distribution facilities, and facilities for other specialized service operations (accounts XX-13-29 to XX-13-35, inclusive). 1242.27..., motor vehicle loading and distribution facilities, and facilities for other specialized...

  10. Discovery and Preclinical Characterization of 3-((4-(4-Chlorophenyl)-7-fluoroquinoline-3-yl)sulfonyl)benzonitrile, a Novel Non-acetylenic Metabotropic Glutamate Receptor 5 (mGluR5) Negative Allosteric Modulator for Psychiatric Indications.

    PubMed

    Galambos, János; Bielik, Attila; Krasavin, Mikhail; Orgován, Zoltán; Domány, György; Nógrádi, Katalin; Wágner, Gábor; Balogh, György T; Béni, Zoltán; Kóti, János; Szakács, Zoltán; Bobok, Amrita; Kolok, Sándor; Mikó-Bakk, Mónika L; Vastag, Mónika; Sághy, Katalin; Laszy, Judit; Halász, Attila Sándor; Balázs, Ottilia; Gál, Krisztina; Greiner, István; Szombathelyi, Zsolt; Keserű, György M

    2017-03-23

    Negative allosteric modulators (NAM) of metabotropic glutamate receptor 5 (mGluR5) have been implicated as a potential pharmacotherapy for a number of psychiatric diseases, including anxiety and depression. Most of the mGluR5 NAM clinical candidates can be characterized by the central acetylenic moiety that connects the terminal pharmacophores. Identification of a sulfoquinoline hit via high throughput screening (HTS) followed by optimization provided a 4-phenyl-3-aryl-sulfoquinoline lead compound with the minimal pharmacophore. Optimization of the core and aryl appendages was performed by scanning and matrix libraries synthesized by the multiple parallel synthesis approach. Biological evaluation of matrix libraries provided a number of potent, metabolically stable, and in vivo active compounds. One of these compounds, 25 showed high efficacy and safety in preclinical in vivo models; this allowed its nomination as a novel, nonacetylenic mGluR5 NAM clinical candidate. Compound 25 was advanced to first-in-man trials for the treatment of psychiatric conditions.

  11. 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

  12. The Application of Gas Dwell Time Control for Rapid Single Wall Carbon Nanotube Forest Synthesis to Acetylene Feedstock

    PubMed Central

    Matsumoto, Naoyuki; Oshima, Azusa; Sakurai, Shunsuke; Yamada, Takeo; Yumura, Motoo; Hata, Kenji; Futaba, Don N.

    2015-01-01

    One aspect of carbon nanotube (CNT) synthesis that remains an obstacle to realize industrial mass production is the growth efficiency. Many approaches have been reported to improve the efficiency, either by lengthening the catalyst lifetime or by increasing the growth rate. We investigated the applicability of dwell time and carbon flux control to optimize yield, growth rate, and catalyst lifetime of water-assisted chemical vapor deposition of single-walled carbon nanotube (SWCNT) forests using acetylene as a carbon feedstock. Our results show that although acetylene is a precursor to CNT synthesis and possesses a high reactivity, the SWCNT forest growth efficiency is highly sensitive to dwell time and carbon flux similar to ethylene. Through a systematic study spanning a wide range of dwell time and carbon flux levels, the relationship of the height, growth rate, and catalyst lifetime is found. Further, for the optimum conditions for 10 min growth, SWCNT forests with ~2500 μm height, ~350 μm/min initial growth rates and extended lifetimes could be achieved by increasing the dwell time to ~5 s, demonstrating the generality of dwell time control to highly reactive gases.

  13. Broad-band frequency references in the near-infrared: Accurate dual comb spectroscopy of methane and acetylene

    NASA Astrophysics Data System (ADS)

    Zolot, A. M.; Giorgetta, F. R.; Baumann, E.; Swann, W. C.; Coddington, I.; Newbury, N. R.

    2013-03-01

    The Doppler-limited spectra of methane between 176 THz and 184 THz (5870-6130 cm-1) and acetylene between 193 THz and 199 THz (6430-6630 cm-1) are acquired via comb-tooth resolved dual comb spectroscopy with frequency accuracy traceable to atomic standards. A least squares analysis of the measured absorbance and phase line shapes provides line center frequencies with absolute accuracy of 0.2 MHz, or less than one thousandth of the room temperature Doppler width. This accuracy is verified through comparison with previous saturated absorption spectroscopy of 37 strong isolated lines of acetylene. For the methane spectrum, the center frequencies of 46 well-isolated strong lines are determined with similar high accuracy, along with the center frequencies for 1107 non-isolated lines at lower accuracy. The measured methane line-center frequencies have an uncertainty comparable to the few available laser heterodyne measurements in this region but span a much larger optical bandwidth, marking the first broad-band measurements of the methane 2ν3 region directly referenced to atomic frequency standards. This study demonstrates the promise of dual comb spectroscopy to obtain high resolution broadband spectra that are comparable to state-of-the-art Fourier-transform spectrometer measurements but with much improved frequency accuracy.Work of the US government, not subject to US copyright.

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

    SciTech Connect

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

    2014-01-01

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

  15. Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene

    SciTech Connect

    Xiang, Sheng-Chang; Zhang, Zhangjing; Zhao, Cong-Gui; Hong, Kunlun; Zhao, Xuebo; Ding, De-Rong; Xie, Ming-Hua; Wu, Chuan-De; Madhab, Das; Gill, Rachel; Thomas, K Mark; Chen, Banglin

    2011-01-01

    Separation of acetylene and ethylene is an important industrial process because both compounds are essential reagents for a range of chemical products and materials. Current separation approaches include the partial hydrogenation of acetylene into ethylene over a supported Pd catalyst, and the extraction of cracked olefins using an organic solvent; both routes are costly and energy consuming. Adsorption technologies may allow separation, but microporous materials exhibiting highly selective adsorption of C{sub 2}H{sub 2}/C{sub 2}H{sub 4} have not been realized to date. Here, we report the development of tunable microporous enantiopure mixed-metal-organic framework (M'MOF) materials for highly selective separation of C{sub 2}H{sub 2} and C{sub 2}H{sub 4}. The high selectivities achieved suggest the potential application of microporous M'MOFs for practical adsorption-based separation of C{sub 2}H{sub 2}/C{sub 2}H{sub 4}.

  16. 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.

  17. Infrared spectra reveal box-like structures for a pentamer and hexamer of mixed carbon dioxide-acetylene clusters.

    PubMed

    Rezaei, Mojtaba; Norooz Oliaee, J; Moazzen-Ahmadi, N; McKellar, A R W

    2016-01-21

    Except for a few cases like water and carbon dioxide, identification and structural characterization of clusters with more than four monomers is rare. Here, we provide experimental and theoretical evidence for existence of box-like structures for a pentamer and a hexamer of mixed carbon dioxide-acetylene clusters. Two mid-infrared cluster absorption bands are observed in the CO2ν3 band region using a tunable diode laser to probe a pulsed supersonic jet. Each requires the presence of both carbon dioxide and acetylene in the jet, and (from observed rotational spacings) involves clusters containing about 4 to 7 molecules. Structures are predicted for mixed CO2 + C2H2 clusters using a distributed multipole model, and the bands are assigned to a specific pentamer, (CO2)3-(C2H2)2, and hexamer, (CO2)4-(C2H2)2. The hexamer has a box-like structure whose D2d symmetry is supported by observed intensity alternation in the spectrum. The pentamer has a closely related structure which is obtained by removing one CO2 molecule from the hexamer. These are among the largest mixed molecular clusters to be assigned by high-resolution spectroscopy.

  18. Direct synthesis of solid and hollow carbon nanospheres over NaCl crystals using acetylene by chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Chandra Kishore, S.; Anandhakumar, S.; Sasidharan, M.

    2017-04-01

    Carbon nanospheres (CNS) with hollow and solid morphologies have been synthesised by a simple chemical vapour deposition method using acetylene as a carbon precursor. Sodium chloride (NaCl) powder as a template was used for the direct growth of CNS via facile and low-cost approach. The effect of various temperatures (500 °C, 600 °C and 700 °C) and acetylene flow rates were investigated to study the structural evolution on the carbon products. The purified CNS thus obtained was characterized by various physicochemical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy, and cyclicvoltametry. The synthesised hollow nanospheres were investigated as anode materials for Li-ion batteries. After 25 cycles of repeated charge/discharge cycles, the discharge and charge capacities were found to be 574 mAh/g and 570 mAh/g, respectively which are significantly higher than the commercial graphite samples.

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  20. 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.

  1. 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.

  2. 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

  3. Cavity Ringdown Laser Asorption Spectroscopy(crlas) of Isotopically Labeled Acetylene Between 12,500 - 13,600 wn

    NASA Astrophysics Data System (ADS)

    Lue, Christopher J.; Sullivan, Michael N.; Draganjac, Mark E.; Reeve, Scott W.

    2011-06-01

    About five years ago, Arkansas State University created the Arkansas Center for Laser Applications and Science (ArCLAS) with the intention of making it a state-of-the-art facility for laser-based research and optical spectroscopy in the midSouth. Since that time, University and DoD support has lead to the acquisition of numerous laser based spectrometers including a novel three color picosecond system utilized primarily for STIRAP measurements of bulk gas samples. Over the past few months, we have begun collecting near infrared overtone and combination band spectra for the acetylene molecule with a pulsed cavity ringdown laser absorption spectrometer (CRDLAS) as part of the STIRAP support effort. Certainly acetylene has been extensively studied by a number of different spectroscopic methods. During these CRDLAS investigations a 13C_2H_2 band was discovered which we believe has not been previously reported. Here a complete rovibrational analysis of this band will be presented. See for example, Michel Herman, Jacques lievin, Jean Vander Auwera, and Alain Campargue, in Global and Accurate Vibration Hamiltonians from High Resolution Molecular Spectroscopy, Advances in Chemical Physics Volume 108, John Wiley and Sons, NY, NY (1999) and references therein.

  4. Forming a Two-Ring Polycyclic Aromatic Hydrocarbon without a Benzene Intermediate: the Reaction of Propargyl with Acetylene

    NASA Astrophysics Data System (ADS)

    Osborn, David; Savee, John; Selby, Talitha; Welz, Oliver; Taatjes, Craig

    The reaction of acetylene (HCCH) with a resonance-stabilized free radical is a commonly invoked mechanism for the generation of polycyclic aromatic hydrocarbons (PAH), which are likely precursors of soot particles in combustion. In this work, we examine the sequential addition of acetylene to the propargyl radical (H2CCCH) at temperatures of 800 and 1000 K. Using time-resolved multiplexed photoionization mass spectrometry with tunable ionizing radiation, we identified the isomeric forms of the C5H5 and C7H7 intermediates in this reaction sequence, and confirmed that the final C9H8 product is the two-ring aromatic compound indene. We identified two different resonance-stabilized C5H5 intermediates, with different temperature dependencies. Furthermore, the C7H7 intermediate is the tropyl radical (c-C7H7) , not the benzyl radical (C6H5CH2) , as is usually assumed in combustion environments. These experimental results are in general agreement with the latest electronic structure / master equation results of da Silva et al. This work shows a pathway for PAH formation that bypasses benzene / benzyl intermediates.

  5. 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.

  6. Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymers

    NASA Technical Reports Server (NTRS)

    Clarke, D. W.; Ferris, J. P.

    1997-01-01

    The structure and morphological properties of polymers produced photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been examined to evaluate their possible contribution to the haze layers found on Titan. A structural analysis of these polymers may contribute to our understanding of the data returned from the Huygens probe of the Cassini mission that will pass through the atmosphere of Titan in the year 2004. Infrared analysis, elemental analysis, and thermal methods (thermogravimetric analysis, thermolysis, pyrolysis) were used to examine structures of polycyanoacetylenes produced by irradiation of the gas phase HC3N at 185 and 254 nm. The resulting brown to black polymer, which exists as small particles, is believed to be a branched chain of conjugated carbon-carbon double bonds, which, on exposure to heat, cyclizes to form a graphitic structure. Similar methods of analysis were used to show that when HC3N is photolyzed in the presence of Titan's other atmospheric constituents (CH4, C2H6, C2H2, and CO), a copolymer is formed in which the added gases are incorporated as substituents on the polymer chain. Of special significance is the copolymer of HC3N and acetylene (C2H2). Even in experiments where C2H2 was absorbing nearly all of the incident photons, the ratio of C2H2 to HC3N found in the resulting polymer was only 2:1. Scanning electron microscopy was used to visually examine the polymer particles. While pure polyacetylene particles are amorphous spheres roughly 1 micrometer in diameter, polycyanoacetylenes appear to be strands of rough, solid particles slightly smaller in size. The copolymer of HC3N and C2H2 exhibits characteristics of both pure polymers. This is particularly important as pure polyacetylenes do not match the optical constants measured for Titan's atmospheric hazes. The copolymers produced by the incorporation of other minor atmospheric constituents, like HC3N, into the polyacetylenes are expected to have

  7. Differential solubility of ethylene and acetylene in room-temperature ionic liquids: a theoretical study.

    PubMed

    Zhao, Xu; Xing, Huabin; Yang, Qiwei; Li, Rulong; Su, Baogen; Bao, Zongbi; Yang, Yiwen; Ren, Qilong

    2012-04-05

    The room-temperature ionic liquids (RTILs) have potential in realizing the ethylene (C(2)H(4)) and acetylene (C(2)H(2)) separation and avoiding solvent loss and environmental pollution compared with traditional solvents. The interaction mechanisms between gases and RTILs are important for the exploration of new RTILs for gas separation; thus, they were studied by quantum chemical calculation and molecular dynamics simulation in this work. The optimized geometries were obtained for the complexes of C(2)H(4)/C(2)H(2) with anions (Tf(2)N(-), BF(4)(-), and OAc(-)), cation (bmim(+)), and their ion pairs, and the analysis for geometry, interaction energy, natural bond orbital (NBO), and atoms in molecules (AIM) was performed. The quantum chemical calculation results show that the hydrogen-bonding interaction between the gas molecule and anion is the dominant factor in determining the solubility of C(2)H(2) in RTILs. However, the hydrogen-bonding interaction, the p-π interaction in C(2)H(4)-anion, and the π-π interaction in C(2)H(4)-cation are weak and comparable, which all affect the solubility of C(2)H(4) in RTILs with comparable contribution. The calculated results for the distance of H(gas)···X (X = O or F in anions), the BSSE-corrected interaction energy, the electron density of H(gas)···X at the bond critical point (ρ(BCP)), and the relative second-order perturbation stabilization energy (E(2)) are consistent with the experimental data that C(2)H(2) is more soluble than C(2)H(4) in the same RTILs and the solubility of C(2)H(4) in RTILs has the following order: [bmim][Tf(2)N] > [bmim][OAc] > [bmim][BF(4)]. The calculated results also agree with the order of C(2)H(2) solubility in different RTILs that [bmim][OAc] > [bmim][BF(4)] > [bmim][Tf(2)N]. Furthermore, the calculation results indicate that there is strong C(2)H(2)-RTIL interaction, which cannot be negligible compared to the RTIL-RTIL interaction; thus, the regular solution theory is probably not

  8. Structure and hydration of the C4H4●+ ion formed by electron impact ionization of acetylene clusters.

    PubMed

    Momoh, Paul O; Hamid, Ahmed M; Abrash, Samuel A; El-Shall, M Samy

    2011-05-28

    Here we report ion mobility experiments and theoretical studies aimed at elucidating the identity of the acetylene dimer cation and its hydrated structures. The mobility measurement indicates the presence of more than one isomer for the C(4)H(4)(●+) ion in the cluster beam. The measured average collision cross section of the C(4)H(4)(●+) isomers in helium (38.9 ± 1 Å(2)) is consistent with the calculated cross sections of the four most stable covalent structures calculated for the C(4)H(4)(●+) ion [methylenecyclopropene (39.9 Å(2)), 1,2,3-butatriene (41.1 Å(2)), cyclobutadiene (38.6 Å(2)), and vinyl acetylene (41.1 Å(2))]. However, none of the single isomers is able to reproduce the experimental arrival time distribution of the C(4)H(4)(●+) ion. Combinations of cyclobutadiene and vinyl acetylene isomers show excellent agreement with the experimental mobility profile and the measured collision cross section. The fragment ions obtained by the dissociation of the C(4)H(4)(●+) ion are consistent with the cyclobutadiene structure in agreement with the vibrational predissociation spectrum of the acetylene dimer cation (C(2)H(2))(2)(●+) [R. A. Relph, J. C. Bopp, J. R. Roscioli, and M. A. Johnson, J. Chem. Phys. 131, 114305 (2009)]. The stepwise hydration experiments show that dissociative proton transfer reactions occur within the C(4)H(4)(●+)(H(2)O)(n) clusters with n ≥ 3 resulting in the formation of protonated water clusters. The measured binding energy of the C(4)H(4)(●+)H(2)O cluster, 38.7 ± 4 kJ/mol, is in excellent agreement with the G3(MP2) calculated binding energy of cyclobutadiene(●+)·H(2)O cluster (41 kJ/mol). The binding energies of the C(4)H(4)(●+)(H(2)O)(n) clusters change little from n = 1 to 5 (39-48 kJ/mol) suggesting the presence of multiple binding sites with comparable energies for the water-C(4)H(4)(●+) and water-water interactions. A significant entropy loss is measured for the addition of the fifth water

  9. Structure and hydration of the C4H4•+ ion formed by electron impact ionization of acetylene clusters

    NASA Astrophysics Data System (ADS)

    Momoh, Paul O.; Hamid, Ahmed M.; Abrash, Samuel A.; Samy El-Shall, M.

    2011-05-01

    Here we report ion mobility experiments and theoretical studies aimed at elucidating the identity of the acetylene dimer cation and its hydrated structures. The mobility measurement indicates the presence of more than one isomer for the C4H4•+ ion in the cluster beam. The measured average collision cross section of the C4H4•+ isomers in helium (38.9 ± 1 Å2) is consistent with the calculated cross sections of the four most stable covalent structures calculated for the C4H4•+ ion [methylenecyclopropene (39.9 Å2), 1,2,3-butatriene (41.1 Å2), cyclobutadiene (38.6 Å2), and vinyl acetylene (41.1 Å2)]. However, none of the single isomers is able to reproduce the experimental arrival time distribution of the C4H4•+ ion. Combinations of cyclobutadiene and vinyl acetylene isomers show excellent agreement with the experimental mobility profile and the measured collision cross section. The fragment ions obtained by the dissociation of the C4H4•+ ion are consistent with the cyclobutadiene structure in agreement with the vibrational predissociation spectrum of the acetylene dimer cation (C2H2)2•+ [R. A. Relph, J. C. Bopp, J. R. Roscioli, and M. A. Johnson, J. Chem. Phys. 131, 114305 (2009)], 10.1063/1.3212595. The stepwise hydration experiments show that dissociative proton transfer reactions occur within the C4H4•+(H2O)n clusters with n ≥ 3 resulting in the formation of protonated water clusters. The measured binding energy of the C4H4•+H2O cluster, 38.7 ± 4 kJ/mol, is in excellent agreement with the G3(MP2) calculated binding energy of cyclobutadiene•+.H2O cluster (41 kJ/mol). The binding energies of the C4H4•+(H2O)n clusters change little from n = 1 to 5 (39-48 kJ/mol) suggesting the presence of multiple binding sites with comparable energies for the water-C4H4•+ and water-water interactions. A significant entropy loss is measured for the addition of the fifth water molecule suggesting a structure with restrained water molecules, probably a

  10. Reaction Mechanism of the Symmetry-Forbidden [2+2] Addition of Ethylene and Acetylene to Amido-Substituted Digermynes and Distannynes Ph2N-EE-NPh2, (E = Ge, Sn): A Theoretical Study.

    PubMed

    Zhao, Lili; Jones, Cameron; Frenking, Gernot

    2015-08-24

    Quantum chemical calculations of reaction mechanisms for the formal [2+2] addition of ethylene and acetylene to the amido-substituted digermyne and distannyne Ph2N-EE-NPh2 (E = Ge, Sn) have been carried out by using density functional theory at the BP86/def2-TZVPP level. The nature and bonding situations were studied with the NBO method and with the charge and energy decomposition analysis EDA-NOCV. The addition of ethylene to Ph2N-EE-NPh2 takes place through an initial [2+1] addition to one metal atom and consecutive rearrangement to four-membered cyclic species, which feature a weak E-E bond. Rotation about the C-C bond with concomitant rupture of the E-E bond leads to the 1,2-disubstituted ethanes, which have terminal E(NPh2) groups. The overall reaction Ph2N-EE-NPh2+C2H4→(Ph2N)E-C2H4-E(NPh2) has very low activation barriers and is slightly exergonic for E = Ge but slightly endergonic for E = Sn. The analysis of the electronic structure shows that there is charge donation of nearly one electron to the ethylene moiety already in the first part of the reaction. The energy partitioning analysis suggests that the HOMO(Ph2N-EE-NPh2)→LUMO(C2H4) interaction has a similar strength as the HOMO(C2H4)→LUMO(Ph2N-EE-NPh2) interaction. The [2+2] addition of acetylene to Ph2N-EE-NPh2 also takes place through an initial [2+1] approach, which eventually leads to 1,2-disubstituted olefins (Ph2N)E-C2H2-E(NPh2). The formation of the energetically lowest lying conformations of cis-(Ph2N)E-C2H2-E(NPh2), which occurs with very low activation barriers, is clearly exergonic for the germanium and the tin compound. The trans-coordinated isomers of (Ph2N)E-C2H2-E(NPh2) are slightly lower in energy than the cis form but they are separated by a substantial energy barrier for the rotation about the C-C bond. The energy decomposition analysis indicates that the initial reaction takes place under formation of electron-sharing bonds between triplet fragments rather than HOMO

  11. The use of mobile satellite communication terminals

    NASA Astrophysics Data System (ADS)

    Law, P. A.

    The role of small portable terminals in military satellite systems is examined; the discussion embraces terminals with an antenna reflector diameter of seven meters or less. Emphasis is placed on the specification of MARMOSET (Marconi Mobile Satellite Earth Terminal). Also considered are ship-borne satellite terminals, the improved SCOT terminal, interoperability, reduced downlink power, and reliability and availability.

  12. 32 CFR 34.51 - Termination.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., in which case the two parties shall agree upon the termination conditions, including the effective date and, in the case of partial termination, the portion to be terminated. (3) By the recipient upon... effective date, and, in the case of partial termination, the portion to be terminated. The recipient...

  13. 32 CFR 32.61 - Termination.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... consent of the recipient, in which case the two parties shall agree upon the termination conditions, including the effective date and, in the case of partial termination, the portion to be terminated; or (3... for such termination, the effective date, and, in the case of partial termination, the portion to...

  14. Low Earth Orbiter: Terminal

    NASA Technical Reports Server (NTRS)

    Kremer, Steven E.; Bundick, Steven N.

    1999-01-01

    In response to the current government budgetary environment that requires the National Aeronautics and Space Administration (NASA) to do more with less, NASA/Goddard Space Flight Center's Wallops Flight Facility has developed and implemented a class of ground stations known as a Low Earth Orbiter-Terminal (LEO-T). This development thus provides a low-cost autonomous ground tracking service for NASA's customers. More importantly, this accomplishment provides a commercial source to spacecraft customers around the world to purchase directly from the company awarded the NASA contract to build these systems. A few years ago, NASA was driven to provide more ground station capacity for spacecraft telemetry, tracking, and command (TT&C) services with a decreasing budget. NASA also made a decision to develop many smaller, cheaper satellites rather than a few large spacecraft as done in the past. In addition, university class missions were being driven to provide their own TT&C services due to the increasing load on the NASA ground-tracking network. NASA's solution for this ever increasing load was to use the existing large aperture systems to support those missions requiring that level of performance and to support the remainder of the missions with the autonomous LEO-T systems. The LEO-T antenna system is a smaller, cheaper, and fully autonomous unstaffed system that can operate without the existing NASA support infrastructure. The LEO-T provides a low-cost, reliable space communications service to the expanding number of low-earth orbiting missions around the world. The system is also fostering developments that improve cost-effectiveness of autonomous-class capabilities for NASA and commercial space use. NASA has installed three LEO-T systems. One station is at the University of Puerto Rico, the second system is installed at the Poker Flat Research Range near Fairbanks, Alaska, and the third system is installed at NASA's Wallops Flight Facility in Virginia. This paper

  15. Smart sensor for terminal homing

    NASA Astrophysics Data System (ADS)

    Panda, D.; Aggarwal, R.; Hummel, R.

    1980-01-01

    The practical scene matching problem is considered to present certain complications which must extend classical image processing capabilities. Certain aspects of the scene matching problem which must be addressed by a smart sensor for terminal homing are discussed. First a philosophy for treating the matching problem for the terminal homing scenario is outlined. Then certain aspects of the feature extraction process and symbolic pattern matching are considered. It is thought that in the future general ideas from artificial intelligence will be more useful for terminal homing requirements of fast scene recognition and pattern matching.

  16. The small-scale production of (U-14C)acetylene from Ba14CO3: Application to labeling of ammonia monooxygenase in autotrophic nitrifying bacteria

    SciTech Connect

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

    1990-11-01

    A small-scale method has been adapted from an established procedure for the generation of (U-14C)acetylene from inexpensive and commonly available precursors. The method involves the fusing of Ba14CO3 with excess barium metal to produce Ba14C2. The BaC2 is reacted with water to generate acetylene which is then selectively dissolved into dimethyl sulfoxide (DMSO). The results presented demonstrate the effect of Ba:BaCO3 ratio on the concentrations of various gases released during the hydrolysis reaction and quantify the selectivity of the DMSO-trapping process for each gas. (U-14C)Acetylene generated by this method has been used to inactivate ammonia monooxygenase in three species of autotrophic nitrifying bacteria: Nitrosomonas europaea, Nitrosococcus oceanus, and Nitrosolobus multiformis. Our results demonstrate that acetylene inactivation of this enzyme in all three species results in the covalent incorporation of radioactive label into a polypeptide of apparent Mr of 25,000-27,000, as determined by sodium dodecylsulfate-polyacrylamide gel electrophoresis and fluorography.

  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. Structure, dynamics, and reactivity of an alkoxy intermediate formed from acetylene on zeolite catalysts: An in situ solid-state NMR study

    SciTech Connect

    Lazo, N.D.; White, J.L.; Munson, E.J.; Lambregts, M.; Haw, J.F. )

    1990-05-09

    Recently, there has been much interest in reactive intermediates formed by the adsorption of organic compounds on zeolites and alumina. In this communication, they present evidence for a vinyl alkoxy species, analogous to IV, which is formed at high temperatures from acetylene on zeolites HY and HZSM-5. Upon exposure of the catalyst to water, the intermediate was converted quantitatively to acetaldehyde.

  19. 77 FR 38128 - Withdrawal of TORP Terminal LP, Bienville Offshore Energy Terminal Liquefied Natural Gas (LNG...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-06-26

    ... Maritime Administration Withdrawal of TORP Terminal LP, Bienville Offshore Energy Terminal Liquefied... Terminal LP's (TORP) withdrawal of the deepwater port license application for the proposed Bienville Offshore Energy Terminal (BOET). All actions related to the processing and agency coordination...

  20. Balanced Branching in Transcription Termination

    NASA Technical Reports Server (NTRS)

    Harrington, K. J.; Laughlin, R. B.; Liang, S.

    2001-01-01

    The theory of stochastic transcription termination based on free-energy competition requires two or more reaction rates to be delicately balanced over a wide range of physical conditions. A large body of work on glasses and large molecules suggests that this should be impossible in such a large system in the absence of a new organizing principle of matter. We review the experimental literature of termination and find no evidence for such a principle but many troubling inconsistencies, most notably anomalous memory effects. These suggest that termination has a deterministic component and may conceivably be not stochastic at all. We find that a key experiment by Wilson and von Hippel allegedly refuting deterministic termination was an incorrectly analyzed regulatory effect of Mg(2+) binding.

  1. Terminal attractors in neural networks

    NASA Technical Reports Server (NTRS)

    Zak, Michail

    1989-01-01

    A new type of attractor (terminal attractors) for content-addressable memory, associative memory, and pattern recognition in artificial neural networks operating in continuous time is introduced. The idea of a terminal attractor is based upon a violation of the Lipschitz condition at a fixed point. As a result, the fixed point becomes a singular solution which envelopes the family of regular solutions, while each regular solution approaches such an attractor in finite time. It will be shown that terminal attractors can be incorporated into neural networks such that any desired set of these attractors with prescribed basins is provided by an appropriate selection of the synaptic weights. The applications of terminal attractors for content-addressable and associative memories, pattern recognition, self-organization, and for dynamical training are illustrated.

  2. Discovery Performs Terminal Initiation Burn

    NASA Video Gallery

    The terminal initiation burn, a left Orbital Maneuvering System engine firing that gave Discovery one last big push toward the space station, took place Feb. 26, 2011 at 10:33 a.m. The burn lasted ...

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

    SciTech Connect

    Mackenzie, Rebecca B.; Dewberry, Christopher T.; Leopold, Kenneth R. E-mail: david.tew@bristol.ac.uk; Coulston, Emma; Cole, George C.; Legon, Anthony C. E-mail: david.tew@bristol.ac.uk Tew, David P. E-mail: david.tew@bristol.ac.uk

    2015-09-14

    a-type rotational spectra of the hydrogen-bonded complex formed from pyridine and acetylene are reported. Rotational and {sup 14}N hyperfine constants indicate that the complex is planar with an acetylenic hydrogen directed toward the nitrogen. However, unlike the complexes of pyridine with HCl and HBr, the acetylene moiety in HCCH—NC{sub 5}H{sub 5} does not lie along the symmetry axis of the nitrogen lone pair, but rather, forms an average angle of 46° with the C{sub 2} axis of the pyridine. The a-type spectra of HCCH—NC{sub 5}H{sub 5} and DCCD—NC{sub 5}H{sub 5} are doubled, suggesting the existence of a low lying pair of tunneling states. This doubling persists in the spectra of HCCD—NC{sub 5}H{sub 5}, DCCH—NC{sub 5}H{sub 5}, indicating that the underlying motion does not involve interchange of the two hydrogens of the acetylene. Single {sup 13}C substitution in either the ortho- or meta-position of the pyridine eliminates the doubling and gives rise to separate sets of spectra that are well predicted by a bent geometry with the {sup 13}C on either the same side (“inner”) or the opposite side (“outer”) as the acetylene. High level ab initio calculations are presented which indicate a binding energy of 1.2 kcal/mol and a potential energy barrier of 44 cm{sup −1} in the C{sub 2v} configuration. Taken together, these results reveal a complex with a bent hydrogen bond and large amplitude rocking of the acetylene moiety. It is likely that the bent equilibrium structure arises from a competition between a weak hydrogen bond to the nitrogen (an n-pair hydrogen bond) and a secondary interaction between the ortho-hydrogens of the pyridine and the π electron density of the acetylene.

  4. 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

    Denitrification allows microorganisms to sustain respiration under anoxic conditions. The typical niche for denitrification is an environment with fluctuating oxygen concentrations such as soils and borders between anoxic and oxic zones of biofilms and sediments. In such environments, the organisms need adequate regulation of denitrification in response to changing oxygen availability to tackle both oxic and anoxic spells. The regulation of denitrification in soils has environmental implications, since it affects the proportions of N2, N2O and NO emitted to the atmosphere. The expression of denitrification enzymes is regulated by a complex regulatory network involving one or several positive feedback loops via the intermediate nitrogen oxides. Nitric oxide (NO) is known to induce denitrification in model organisms, but the quantitative effect of NO and its concentration dependency has not been assessed for denitrification in soils. NO is chemically unstable in the presence of oxygen due to autoxidation, and the oxidation of NO is accelerated by acetylene (C2H2) which is commonly used as an inhibitor of N2O reductase in denitrification studies. As a first step to a better understanding of NO's role in soil denitrification, we investigated NO oxidation kinetics for a closed "two phase" system (i.e. liquid phase + headspace) typically used for denitrification experiments with soil slurries, with and without acetylene present. Models were developed to adequately predict autoxidation and acetylene-accelerated oxidation. The minimum oxygen concentration in the headspace ([O2]min, mL L-1) for acetylene-accelerated NO oxidation was found to increase linearly with the NO concentration ([NO], mL L-1); [O2]min= 0.192 + [NO]*0.1 (r2=0.978). The models for NO oxidation were then used to assess NO-oxidation rates in denitrification experiments with batches of bacterial cells extracted from soil. The batches were exposed to low initial oxygen concentrations in gas tight serum

  5. Propagation Terminal Design and Measurements

    NASA Technical Reports Server (NTRS)

    Nessel, James

    2015-01-01

    The NASA propagation terminal has been designed and developed by the Glenn Research Center and is presently deployed at over 5 NASA and partner ground stations worldwide collecting information on the effects of the atmosphere on Ka-band and millimeter wave communications links. This lecture provides an overview of the fundamentals and requirements of the measurement of atmospheric propagation effects and, specifically, the types of hardware and digital signal processing techniques employed by current state-of-the-art propagation terminal systems.

  6. 15 CFR 286.12 - Terminations.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... STANDARDS AND TECHNOLOGY, DEPARTMENT OF COMMERCE ACCREDITATION AND ASSESSMENT PROGRAMS NATIONAL VOLUNTARY CONFORMITY ASSESSMENT SYSTEM EVALUATION (NVCASE) PROGRAM § 286.12 Terminations. (a) Voluntary termination. Any participant may voluntarily terminate participation at any time by written notification to...

  7. Acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces: a comprehensive periodic DFT study.

    PubMed

    Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres; Liu, Ping; Rodriguez, Jose A

    2017-01-04

    A comprehensive study of acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces was carried out by means of calculations based on periodic density functional theory, using the Perdew-Burke-Ernzerhof exchange-correlation functional. It was found that the bonding of acetylene was significantly affected by the electronic and structural properties of the carbide surfaces. The adsorbate interacted with metal and/or carbon sites of the carbide. The interaction of acetylene with the TiC(001) and ZrC(001) surfaces was strong (binding energies higher than -3.5 eV), while moderate acetylene adsorption energies were observed on δ-MoC(001) (-1.78 eV to -0.66 eV). Adsorption energies, charge density difference plots and Mulliken charges suggested that the binding of the hydrocarbon to the surface had both ionic and covalent contributions. According to the C-C bond lengths obtained, the adsorbed molecule was modified from acetylene-like into ethylene-like on the δ-MoC(001) surface (desired behavior for hydrogenation reactions) but into ethane-like on TiC(001) and ZrC(001). The obtained results suggest that the δ-MoC(001) surface is expected to have the best performance in selective hydrogenation reactions to convert alkynes into alkenes. Another advantage of δ-MoC(001) is that, after C2H2 adsorption, surface carbon sites remain available, which are necessary for H2 dissociation. However, these sites were occupied when C2H2 was adsorbed on TiC(001) and ZrC(001), limiting their application in the hydrogenation of alkynes.

  8. 7 CFR 1206.22 - Terminate.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... AND ORDERS; MISCELLANEOUS COMMODITIES), DEPARTMENT OF AGRICULTURE MANGO PROMOTION, RESEARCH, AND INFORMATION Mango Promotion, Research, and Information Order Definitions § 1206.22 Terminate. Terminate...

  9. 7 CFR 1206.22 - Terminate.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... AND ORDERS; MISCELLANEOUS COMMODITIES), DEPARTMENT OF AGRICULTURE MANGO PROMOTION, RESEARCH, AND INFORMATION Mango Promotion, Research, and Information Order Definitions § 1206.22 Terminate. Terminate...

  10. 7 CFR 1206.22 - Terminate.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... AND ORDERS; MISCELLANEOUS COMMODITIES), DEPARTMENT OF AGRICULTURE MANGO PROMOTION, RESEARCH, AND INFORMATION Mango Promotion, Research, and Information Order Definitions § 1206.22 Terminate. Terminate...

  11. 7 CFR 1206.22 - Terminate.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... AND ORDERS; MISCELLANEOUS COMMODITIES), DEPARTMENT OF AGRICULTURE MANGO PROMOTION, RESEARCH, AND INFORMATION Mango Promotion, Research, and Information Order Definitions § 1206.22 Terminate. Terminate...

  12. 7 CFR 1206.22 - Terminate.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... AND ORDERS; MISCELLANEOUS COMMODITIES), DEPARTMENT OF AGRICULTURE MANGO PROMOTION, RESEARCH, AND INFORMATION Mango Promotion, Research, and Information Order Definitions § 1206.22 Terminate. Terminate...

  13. A model of ethylene and acetylene adsorption on the (111) surfaces of platinum and nickel

    NASA Astrophysics Data System (ADS)

    Felter, T. E.; Weinberg, W. H.

    1981-02-01

    Despite the application of a variety of surface sensitive techniques to the adsorption of simple hydrocarbons on well characterized metallic surfaces, no consistent picture has appeared. We review briefly the published spectroscopic results of ultraviolet photoelectron spectroscopy (UPS) and electron energy loss spectroscopy (EELS) which probe, respectively, the electronic and vibrational structure of the surface-molecular complex, and we consider appropriate free molecular analogues, not only in their ground state but also in their first excited states. A simplified approach to determine the chemisorption geometry from UPS level shifts and EELS is presented. The technique allows an isolation of distortion induced shifts from the total relaxation shift, and we find that the true relaxation shift is rather constant, approximately 2.1 eV for the cases considered. These shifts can then be used to estimate the distance of the molecule to the surface. We concentrate primarily on four systems, C 2H 2 and C 2H 4 on Ni(111) and Pt(111), adsorbed at low temperature (below the onset of dissociation). Depending on the metal, the hydrocarbon can adsorb in a di-σ arrangement or with a distortion resembling the lowest energy configuration of the first excited state of the free molecule. We also consider briefly C 2H 4 on Ag and Cu in which no distortion occurs. The distortions that resemble the first excited states might occur as a consequence of donation of bonding (backbonding) electrons from (to) the normally filled π (empty π ∗) to (from) the empty (filled) d-band states of the metal. The net effect on the hydrocarbon to partially empty the π level and fill the π ∗ level, is analogous to a low excitation of the free molecule, π → π ∗. For C 2H 4 (planar in the ground state), the lowest excitation is the triplet T-state (3-4 eV) of minimal energy for a 90° twisted configuration with a lengthened C-C bond. Acetylene is a linear molecule in the ground state, but

  14. The infrared-ultraviolet dispersed fluorescence spectrum of acetylene: New classes of bright states

    NASA Astrophysics Data System (ADS)

    Hoshina, Kennosuke; Iwasaki, Atsushi; Yamanouchi, Kaoru; Jacobson, Matthew P.; Field, Robert W.

    2001-05-01

    Single rotational levels of ungerade vibrational levels, 2ν3'+ν6' and 3ν3'+ν6' (both with bu symmetry), in the à 1Au electronically excited state of acetylene were excited by an IR-UV double resonance scheme via the ν3″ fundamental level in the X˜ 1Σg+ state, and the rotationally resolved dispersed fluorescence (DF) spectra were recorded at 3.2-4.5 cm-1 resolution. The term values of the new ungerade levels were determined within an accuracy of 0.56 cm-1(1σ) through careful calibration achieved by frequency standard atomic Fe and Hg lines. A total of 111 new ungerade vibrational levels with Σu+, Σu-, and Δu symmetry below 10 000 cm-1 was identified in the high-resolution IR-UV-DF spectra, which provide access to new classes of X˜ 1Σg+ bright states: (i) (0,v2″,0,v4″1,1-1)Σu+, (0,v2″,0,v4″1,11)Δu, and (0,v2″,0,v4″3,1-1)Δu, which are the Franck-Condon (FC) bright levels from the nν3'+ν6' (n=2,3) levels in the à 1Au state; (ii) (0,v2″,0,v4″-1,11)Σu- levels which appear through the a-axis Corioris interaction between nν3'+ν6' and nν3'+ν4' (n=2,3) in the à 1Au state; and (iii) (0,v2″,1,v4″0,0)Σu+ and (0,v2″,1,v4″2,0)Δu levels which gain transition intensity from the Duschinsky effect associated with the bent-linear ÖX˜ transition. All observed ungerade term values and previously determined gerade and ungerade term values below 10 000 cm-1 were fitted by two effective model Hamiltonians, i.e., a pure-bend effective Hamiltonian and a stretch-bend effective Hamiltonian. The stretch-bend effective Hamiltonian is expressed in terms of 31 Dunham expansion parameters and 11 anharmonic resonance parameters associated with (i) five stretch-bend anharmonic resonances; (ii) one stretch-stretch and two bend-bend Darling-Dennison resonances; and (iii) one vibrational l resonance. The parameters in this Hamiltonian were determined from a least-squares fit of 287 vibrational term values (111 new ungerade levels, 128 levels from

  15. Thermometry of an oxy-acetylene flame using multiplex degenerate four-wave mixing of C2

    NASA Astrophysics Data System (ADS)

    Kaminski, C. F.; Hughes, I. G.; Lloyd, G. M.; Ewart, P.

    1996-01-01

    Thermometry of an oxy-acetylene flame using multiplex Degenerate Four-Wave Mixing (DFWM) of C2 is demonstrated. More than 100 rotational transitions in the d 3 Π g ← a 3 Π u (0,0) Swan band of C2 could be recorded simultaneously by use of a pulsed, broad bandwidth “modeless” laser. Temperatures were inferred by fitting temperature-dependent synthetic spectra of single- or multiple-shot averaged spectra. The strength and reliability of recorded signals together with the large number of rotational lines observed suggest that multiplex DFWM is a promising technique for minor species detection and for temporally resolved temperature measurements in luminous environments. Factors influencing the accuracy and precision of single-shot thermometry using the technique are discussed.

  16. Vibration-rotation spectroscopic database on acetylene, X ˜ 1 Σg + (12C2H2)

    NASA Astrophysics Data System (ADS)

    Amyay, B.; Fayt, A.; Herman, M.; Vander Auwera, J.

    2016-06-01

    A complete set of calculated vibration-rotation energies of 12C2H2 ( X ˜ 1 Σg + ) is provided for all vibrational states up to 13 000 cm-1 and some at higher energies, with rotational (J) and vibrational angular momentum (l) quantum numbers such that 0 ≤ J ≤ 100 and 0 ≤ |l| ≤ 20, respectively. The calculation is performed using a global effective Hamiltonian and related spectroscopic constants from the literature [B. Amyay et al., J. Mol. Spectrosc. 267, 80 (2011)], based on the polyad model. The numerical values of all related polyad matrix elements are also provided. The model and equations for the Hamiltonian matrix elements are gathered. The experimental acetylene database used for determining the parameters is listed.

  17. Histrionicotoxins: Roentgen-Ray Analysis of the Novel Allenic and Acetylenic Spiroalkaloids Isolated from a Colombian Frog, Dendrobates histrionicus

    PubMed Central

    Daly, John W.; Karle, Isabella; Myers, Charles W.; Tokuyama, Takashi; Waters, James A.; Witkop, Bernhard

    1971-01-01

    The structures and absolute configuration of two unique alkaloids isolated from the Colombian frog, Dendrobates histrionicus, have been elucidated by Roentgen-ray (x-ray) crystallography. Histrionicotoxin is (2pR, 6S, 7pS, 8aS)-7-(cis-1-buten-3-ynyl)-8-hydroxy-2-(cis-2-penten-4- ynyl)-1-azaspiro[5.5] undecane, while in dihydro-isohistrionicotoxin the acetylenic 2-pentenynyl side chain is replaced by an allenic 2-(3,4 pentadienyl) substituent. Dendrobates histrionicus exhibits remarkable interpopulational variations in amounts and composition of skin toxins, in behavior, and in phenotypic characters, aspects of which are illustrated in a color plate. The histrionico-toxins are the third class of alkaloids isolated from the defensive skin secretions of Neotropical (Dendrobatidae) frogs. Images PMID:5288773

  18. Metastable argon atom density in complex argon/acetylene plasmas determined by means of optical absorption and emission spectroscopy

    NASA Astrophysics Data System (ADS)

    Sushkov, Vladimir; Herrendorf, Ann-Pierra; Hippler, Rainer

    2016-10-01

    Optical emission and absorption spectroscopy has been utilized to investigate the instability of acetylene-containing dusty plasmas induced by growing nano-particles. The density of Ar(1s5) metastable atoms was derived by two methods: tunable diode laser absorption spectroscopy and with the help of the branching ratio method of emitted spectral lines. Results of the two techniques agree well with each other. The density of Ar(1s3) metastable atoms was also measured by means of optical emission spectroscopy. The observed growth instability leads to pronounced temporal variations of the metastable and other excited state densities. An analysis of optical line ratios provides evidence for a depletion of free electrons during the growth cycle but no indication for electron temperature variations.

  19. Self-assembled film of poly(4-carboxyphenyl)acetylene and diazoresin and its photoelectric conversion property.

    PubMed

    Yao, Guijun; Dong, Yuping; Cao, Tingbing; Yang, Shuming; Lam, Jacky Wing Yip; Tang, Benzhong

    2003-01-15

    A novel multilayer film was assembled from water-soluble poly(4-carboxyphenyl)acetylene sodium salt (PCPA) and diazoresin (DR) in aqueous solution via electrostatic attraction. Under UV irradiation, following the decomposition of the diazonium group between the adjacent interfaces of the multilayers, the ionic bonds of the self-assembled film convert to covalent bonds and the film becomes very stable toward electrolyte aqueous solutions. Thus, the photoelectric conversion property of PCPA-containing film can be measured in a conventional three-electrode photoelectrochemical cell, and 0.5 mol/l KCl solution can be used as the supporting electrolyte. The photocurrent spectroscopy response coincides with the absorption spectrum of the irradiated self-assembled film, which indicates that the irradiated DR/PCPA film is responsible for the photocurrent generation.

  20. 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.