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Sample records for acetylene c2h2 ethylene

  1. The role of isovalency in the reactions of the cyano (CN), boron monoxide (BO), silicon nitride (SiN), and ethynyl (C2H) radicals with unsaturated hydrocarbons acetylene (C2H2) and ethylene (C2H4).

    PubMed

    Parker, D S N; Mebel, A M; Kaiser, R I

    2014-04-21

    The classification of chemical reactions based on shared characteristics is at the heart of the chemical sciences, and is well exemplified by Langmuir's concept of isovalency, in which 'two molecular entities with the same number of valence electrons have similar chemistries'. Within this account we further investigate the ramifications of the isovalency of four radicals with the same X(2)Σ(+) electronic structure - cyano (CN), boron monoxide (BO), silicon nitride (SiN), and ethynyl (C2H), and their reactions with simple prototype hydrocarbons acetylene (C2H2) and ethylene (C2H4). The fact that these four reactants own the same X(2)Σ(+) electronic ground state should dictate the outcome of their reactions with prototypical hydrocarbons holding a carbon-carbon triple and double bond. However, we find that other factors come into play, namely, atomic radii, bonding orbital overlaps, and preferential location of the radical site. These doublet radical reactions with simple hydrocarbons play significant roles in extreme environments such as the interstellar medium and planetary atmospheres (CN, SiN and C2H), and combustion flames (C2H, BO). PMID:24418936

  2. Direct measurements of collisional Raman line broadening in the S-branch transitions of acetylene (C2H2)

    NASA Astrophysics Data System (ADS)

    Hsu, Paul S.; Stauffer, Hans U.; Jiang, Naibo; Gord, James R.; Roy, Sukesh

    2013-10-01

    We report direct measurements of the self- and N2-broadened Raman S-branch linewidths of acetylene (C2H2), obtained by employing time-resolved picosecond rotational coherent anti-Stokes Raman scattering spectroscopy. Using broadband 115-ps pump and Stokes pulses (˜135 cm-1 bandwidth) and a spectrally narrowed 90-ps probe pulse (˜0.2 cm-1 bandwidth), Raman-coherence lifetimes are measured at room temperature for the S-branch (ΔJ = +2) transitions associated with rotational quantum number J = 3-25. These directly measured Raman-coherence lifetimes, when converted to collisional linewidth broadening coefficients, differ from the previously reported broadening coefficients extracted from theoretical calculations by 6%-35% for self-broadening for C2H2 and by up to 60% for N2-broadened C2H2.

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  4. 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.

  5. 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.

  6. Particle Generation And Evolution In Silane (SiH4)/Acetylene (C2H2) Flames In Microgravity

    NASA Technical Reports Server (NTRS)

    Keil, D. G.

    2003-01-01

    The objective of this experimental program is to advance the understanding of the coupling of particle formation with gas phase combustion processes. The work utilizes the unique SiH4/C2H2 combustion system which generates particulate products ranging from high purity, white SiC to carbonaceous soot depending on equivalence ratio (Ref. 1). A goal of this work is to identify gas phase or particle formation processes that provide the enthalpy release needed to drive the combustion wave, and to locate the steps of the particle formation process that determine SiC stoichiometry and crystallinity. In a real sense, these SiH4/C2H2 flames act like highly sooty hydrocarbon flames, but with simpler chemistry. This simplification is expected to allow them to be used as surrogates to advance understanding of soot formation in such rich hydrocarbon flames. It is also expected that this improved understanding of SiC particle generation and evolution in these self-sustaining flames will advance the commercial potential of the flame process for the generation of high purity SiC powders.

  7. Reactions of vanadium dioxide molecules with acetylene: infrared spectra of VO2(η(2)-C2H2)(x) (x = 1, 2) and OV(OH)CCH in solid neon.

    PubMed

    Zhou, Xiaojie; Chen, Mohua; Zhou, Mingfei

    2013-07-01

    Reactions of vanadium dioxide molecules with acetylene have been studied by matrix isolation infrared spectroscopy. Reaction intermediates and products are identified on the basis of isotopic substitutions as well as density functional frequency calculations. Ground state vanadium dioxide molecule reacts with acetylene in forming the side-on-bonded VO2(η(2)-C2H2) and VO2(η(2)-C2H2)2 complexes spontaneously on annealing in solid neon. The VO2(η(2)-C2H2) complex is characterized to have a (2)B2 ground state with C2v symmetry, whereas the VO2(η(2)-C2H2)2 complex has a (2)A ground state with C2 symmetry. The VO2(η(2)-C2H2) and VO2(η(2)-C2H2)2 complexes are photosensitive. The VO2(η(2)-C2H2) complex rearranges to the OV(OH)CCH molecule upon UV-vis light excitation. PMID:23718542

  8. Vibration-rotation alchemy in acetylene (12C2H2), ? at low vibrational excitation: from high resolution spectroscopy to fast intramolecular dynamics

    NASA Astrophysics Data System (ADS)

    Perry, David S.; Miller, Anthony; Amyay, Badr; Fayt, André; Herman, Michel

    2010-04-01

    The link between energy-resolved spectra and time-resolved dynamics is explored quantitatively for acetylene (12C2H2), ? with up to 8600 cm-1 of vibrational energy. This comparison is based on the extensive and reliable knowledge of the vibration-rotation energy levels and on the model Hamiltonian used to fit them to high precision [B. Amyay, S. Robert, M. Herman, A. Fayt, B. Raghavendra, A. Moudens, J. Thiévin, B. Rowe, and R. Georges, J. Chem. Phys. 131, 114301 (2009)]. Simulated intensity borrowing features in high resolution absorption spectra and predicted survival probabilities in intramolecular vibrational redistribution (IVR) are first investigated for the v 4 + v 5 and v 3 bright states, for J = 2, 30 and 100. The dependence of the results on the rotational quantum number and on the choice of vibrational bright state reflects the interplay of three kinds of off-diagonal resonances: anharmonic, rotational l-type, and Coriolis. The dynamical quantities used to characterize the calculated time-dependent dynamics are the dilution factor φ d, the IVR lifetime τ IVR , and the recurrence time τ rec. For the two bright states v 3 + 2v 4 and 7v 4, the collisionless dynamics for thermally averaged rotational distributions at T = 27, 270 and 500 K were calculated from the available spectroscopic data. For the 7v 4 bright state, an apparent irreversible decay of is found. In all cases, the model Hamiltonian allows a detailed calculation of the energy flow among all of the coupled zeroth-order vibration-rotation states.

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

    PubMed Central

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

    1988-01-01

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

  10. 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.

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

    PubMed

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

    2016-07-14

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  13. 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.

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

    PubMed

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

    2012-04-01

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

  15. Electron swarm parameters in pure C2H2 and in C2H2-Ar mixtures and electron collision cross sections for the C2H2 molecule

    NASA Astrophysics Data System (ADS)

    Nakamura, Yoshiharu

    2010-09-01

    Electron swarm parameters (the drift velocity and the longitudinal diffusion coefficient) were measured in pure C2H2 and also in C2H2-Ar mixtures containing 0.517% and 5.06% acetylene over wide E/N ranges. These swarm parameters were analysed using a Boltzmann equation analysis and a set of electron collision cross sections for the C2H2 molecule was derived so that it was consistent with the present swarm data and published ionization coefficient. The present result suggested the presence of a Ramsauer-Townsend minimum in the elastic momentum transfer cross section at 0.08 eV and prominent threshold and resonance peaks in the ν4/ν5 vibrational excitation cross section. The present cross section set was also confirmed to be consistent with the published experimental total cross section of C2H2.

  16. 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

  17. Laboratory IR Studies and Astrophysical Implications of C2H2-Containing Binary Ices

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

    Studies of molecular hot cores and protostellar environments have shown that the observed abundance of gas-phase acetylene (C2H2) cannot be matched by chemical models without the inclusion of C2H2 molecules subliming from icy grain mantles. Searches for infrared (IR) spectral features of solid-phase acetylene are under way, but few laboratory reference spectra of C2H2 in icy mixtures, which are needed for spectral fits to observational data, have been published. Here, we report a systematic study of the IR spectra of condensed-phase pure acetylene and acetylene in ices dominated by carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), and water (H2O). We present new spectral data for these ices, including band positions and intrinsic band strengths. For each ice mixture and concentration, we also explore the dependence of acetylene's ν5-band position (743 cm-1, 13.46 μm) and FWHM on temperature. Our results show that the ν5 feature is much more cleanly resolved in ices dominated by non-polar and low-polarity molecules, specifically CO, CO2, and CH4, than in mixtures dominated by H2O-ice. We compare our laboratory ice spectra with observations of a quiescent region in Serpens.

  18. The adsorption of small hydrocarbons on Cu(111): A combined He-atom scattering and x-ray absorption study for ethane, ethylene, and acetylene

    NASA Astrophysics Data System (ADS)

    Fuhrmann, D.; Wacker, D.; Weiss, K.; Hermann, K.; Witko, M.; Wöll, Ch.

    1998-02-01

    Ethane (C2H6), ethylene (C2H4), and acetylene (C2H2) adsorbed on Cu (111) are investigated using high-resolution helium atom scattering and x-ray absorption spectroscopy (NEXAFS). For C2H6/Cu(111) and C2H4/Cu(111) the excitation energies of the frustrated molecular translation normal to the surface (FTz) amount to 6.7 meV, suggesting the presence of a physisorbed species which is consistent with the NEXAFS data for ethylene. In contrast, for C2H2/Cu(111) the NEXAFS data indicate strong intramolecular distortions of the acetylene adsorbate compatible with a tilt of both CH ends away from the molecular axis. While the latter finding is in agreement with recent theoretical studies the theoretically predicted chemisorbed ethylene species could not be observed by the experiment. However, more detailed theoretical studies of the ethylene-Cu(111) interaction potential reveal two minima separated by an activation barrier. The minimum closer to the surface refers to strongly distorted chemisorbed C2H4 whereas the outer minimum is characterized by a free molecule-like physisorbed species. Thus the results from the present measurements are explained by the theoretically confirmed physisorbed species while chemisorbed C2H4 has to be excluded. Complementary results for ethylene and acetylene adsorbed on Pb(111) reveal a FTz-mode energy of 6.5 and 6.7 meV, respectively, thus revealing a much weaker acetylene-substrate binding than seen for Cu(111). Also in case of Pb(111) the FTz-mode showed an Einstein-like behavior with a flat dispersion curve, as for corresponding modes on the Cu(111)-substrate, see above.

  19. Quantitative C2H2 measurements in sooty flames using mid-infrared polarization spectroscopy

    NASA Astrophysics Data System (ADS)

    Sun, Z. W.; Li, Z. S.; Li, B.; Alwahabi, Z. T.; Aldén, M.

    2010-10-01

    Quantitative measurements of acetylene (C2H2) molecules as a combustion intermediate species in a series of rich premixed C2H4/air flames were non-intrusively performed, spatially resolved, using mid-infrared polarization spectroscopy (IRPS), by probing its fundamental ro-vibrational transitions. The flat sooty C2H4/air premixed flames with different equivalence ratios varying from 1.25 to 2.50 were produced on a 6 cm diameter porous-plug McKenna type burner at atmospheric pressure, and all measurements were performed at a height of 8.5 mm above the burner surface. IRPS excitation scans in different flame conditions were performed and rotational line-resolved spectra were recorded. Spectral features of acetylene molecules were readily recognized in the spectral ranges selected, with special attention to avoid the spectral interference from the large amount of coexisting hot water and other hydrocarbon molecules. On-line calibration of the optical system was performed in a laminar C2H2/N2 gas flow at ambient conditions. Using the flame temperatures measured by coherent anti-Stokes Raman spectroscopy in a previous work, C2H2 mole fractions in different flames were evaluated with collision effects and spectral overlap between molecular line and laser source being analyzed and taken into account. C2H2 IRPS signals in two different buffering gases, N2 and CO2, had been investigated in a tube furnace in order to estimate the spectral overlap coefficients and collision effects at different temperatures. The soot-volume fractions (SVF) in the studied flames were measured using a He-Ne laser-extinction method, and no obvious degrading of the IRPS technique due to the sooty environment has been observed in the flame with SVF up to ˜2×10-7. With the increase of flame equivalence ratios not only the SVF but also the C2H2 mole fractions increased.

  20. Numerical study of ethylene and acetylene laminar flame speeds

    SciTech Connect

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

    1995-03-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

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

  2. Direct Detection of C_2H_2 in Air and Human Breath by Cw-Crds

    NASA Astrophysics Data System (ADS)

    Schmidt, Florian M.; Vaittinen, Olavi; Metsälä, Markus; Halonen, Lauri

    2010-06-01

    Continuous wave cavity ring-down spectroscopy (cw-CRDS) is an established cavity-enhanced absorption technique that can provide the necessary sensitivity, selectivity and fast acquisition time for many applications involving the detection of trace species. We present a simple but highly sensitive cw-CRDS spectrometer based on an external cavity diode laser operating in the near-infrared region. This instrument allows us to directly detect acetylene (C_2H_2) mixing ratios in air with a detection limit of 120 parts per trillion by volume (pptv) measuring on a C_2H_2 absorption line at 6565.620 cm-1. Acetylene is a combustion product that is routinely used in environmental monitoring as a marker for anthropogenic emissions. In a recent work, the spectrometer was employed to measure the level of acetylene in indoor and outdoor air in Helsinki. Continuous flow measurements with high time resolution (one minute) revealed strong fluctuations in the acetylene mixing ratio in outdoor air during daytime. Due to its non-invasive nature and fast response time, the analysis of exhaled breath for medical diagnostics is an excellent and straightforward alternative to methods using urine or blood samples. In an ongoing study, the cw-CRDS instrument is used to establish the baseline level of acetylene in the breath of the healthy population. An elevated amount of acetylene in breath could indicate exposure to combustion exhausts or other volatile organic compound (VOC) rich sources. The latest results of this investigation will be presented. F. M. Schmidt, O. Vaittinen, M. Metsälä, P. Kraus and L. Halonen, submitted for publication in Appl. Phys. B.

  3. A compact laser-based spectrometer for detection of C2H2 in exhaled breath and HCN in vitro

    NASA Astrophysics Data System (ADS)

    Marchenko, D.; Neerincx, A. H.; Mandon, J.; Zhang, J.; Boerkamp, M.; Mink, J.; Cristescu, S. M.; Hekkert, S. te Lintel; Harren, F. J. M.

    2015-02-01

    We report on the development of a compact prototype near-infrared DBR laser-based spectrometer employing off-axis integrated cavity output spectroscopy. The spectrometer is capable of simultaneous detection of acetylene (C2H2) and CO2 at 1,529.2 nm as well as hydrogen cyanide (HCN) at 1,533.5 nm. The detection limits of 8 ppbv for C2H2 and 80 ppbv for HCN are achieved for the acquisition time of 1 s. The setup has been tested for online measurements of C2H2 in exhaled breath of a smoking subject and HCN resulting from the metabolism of Pseudomonas aeruginosa bacteria in vitro. Further improvements of the performance of the spectrometer are discussed.

  4. Probing anisotropic interaction potentials of unsaturated hydrocarbons with He*(2 3S) metastable atom: Attractive-site preference of σ-direction in C2H2 and π-direction in C2H4

    NASA Astrophysics Data System (ADS)

    Horio, Takuya; Hatamoto, Takuro; Maeda, Satoshi; Kishimoto, Naoki; Ohno, Koichi

    2006-03-01

    State-resolved collision energy dependence of Penning ionization cross sections of acetylene (C2H2) and ethylene (C2H4) with He*(2S3) metastable atoms was observed in a wide collision energy range from 20to350meV. A recently developed discharge nozzle source with a liquid N2 circulator was employed for the measurements in the low-energy range from 20to80meV. Based on classical trajectory calculations for the energy dependence of the partial ionization cross sections, anisotropic potential energy surfaces for the present systems were obtained by optimizing ab initio model potentials for the chemically related systems Li +C2H2 and C2H4. In the case of C2H2, the global minimum was found to be located around the H atom along the molecular axis with a well depth of 48meV (ca. 1.1kcal/mol). On the other hand, a dominant attractive well with a depth of 62meV (ca. 1.4kcal/mol) was found in the πCC electron region of C2H4. These findings were discussed in connection with orbital interactions between molecular orbitals of the target molecules and atomic orbitals of the metastable atom. It is concluded that σ-type unoccupied molecular orbitals of C2H2 and a πCC-type highest occupied molecular orbital of C2H4 play a significant role for the attractive-site preference of σ direction in C2H2 and π direction in C2H4, respectively.

  5. Finely tuning MOFs towards high performance in C2H2 storage: synthesis and properties of a new MOF-505 analogue with an inserted amide functional group.

    PubMed

    Zhang, Mingxing; Li, Bin; Li, Yunzhi; Wang, Qian; Zhang, Wenwei; Chen, Banglin; Li, Shuhua; Pan, Yi; You, Xiaozeng; Bai, Junfeng

    2016-06-01

    Aiming to improve the acetylene (C2H2) storage capability of MOFs, we successfully designed NJU-Bai 17, a new analogue of MOF-505 with an inserted amide functional group which exhibits almost record high C2H2 uptakes of 222.4 cm(3) g(-1) at 296 K and 296 cm(3) g(-1) at 273 K under 1 bar. This result has been further supported by the determination of the heat of C2H2 adsorption and Grand Canonical Monte Carlo (GCMC) and first-principle calculations. PMID:27173153

  6. 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.

  7. Herman-Wallis factors in the C2H2nu5 infrared fundamental near 14 microns

    NASA Technical Reports Server (NTRS)

    Maguire, William C.; Hillman, John J.; Weber, Mark; Blass, William E.

    1991-01-01

    The presence of acetylene has been confirmed for some time in the atmospheres of the outer planets Jupiter, Saturn, Neptune, and Saturn's satellite Titan. For these atmospheres, the determination of C2H2 abundances using its strong nu5 fundamental requires laboratory line position and intensity measurements. The 1-m Fourier transform spectrometer at McMath solar telescope of Kitt Peak National Observatory was used to measure C2H2 at an unapodized spectral resolution of 0.0025/cm. Synthetic spectra are generated by convolving a Voigt line shape with an instrument function and varying intensity parameters by means of a nonlinear least squares technique. Intensities of 37 nu5 lines spanning P18 through R20 were measured using 0.123 torr of gas in a 1-cm cell. A Herman-Wallis intensity correction parameter of 1.3(4) x 10 to the -3rd has been derived using a least squares linear fit.

  8. Muonium Addition Reactions and Kinetic Isotope Effects in the Gas Phase: k∞ Rate Constants for Mu + C2H2.

    PubMed

    Arseneau, Donald J; Garner, David M; Reid, Ivan D; Fleming, Donald G

    2015-07-16

    The kinetics of the addition reaction of muonium (Mu) to acetylene have been studied in the gas phase at N2 moderator pressures mainly from ∼800 to 1000 Torr and over the temperature range from 168 to 446 K, but also down to 200 Torr at 168 K and over a much higher range of pressures, from 10 to 44 bar at 295 K, demonstrating pressure-independent rate constants, kMu(T). Even at 200 Torr moderator pressure, the kinetics for Mu + C2H2 addition behave as if effectively in the high-pressure limit, giving k∞ = kMu due to depolarization of the muon spin in the MuC2H2 radical formed in the addition step. The rate constants kMu(T) exhibit modest Arrhenius curvature over the range of measured temperatures. Comparisons with data and with calculations for the corresponding H(D) + C2H2 addition reactions reveal a much faster rate for the Mu reaction at the lowest temperatures, by 2 orders of magnitude, in accord with the propensity of Mu to undergo quantum tunneling. Moreover, isotopic atom exchange, which contributes in a major way to the analogous D atom reaction, forming C2HD + H, is expected to be unimportant in the case of Mu addition, a consequence of the much higher zero-point energy and hence weaker C-Mu bond that would form, meaning that the present report of the Mu + C2H2 reaction is effectively the only experimental study of kinetic isotope effects in the high-pressure limit for H-atom addition to acetylene. PMID:25664674

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

    PubMed

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

    2016-07-01

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

  10. Ion-neutral reaction of the C2H2N+ cation with C2H2: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Fathi, P.; Geppert, W. D.; Kaiser, A.; Ascenzi, D.

    2016-03-01

    The ion-neutral reactions of the C2H2N+ cation with C2H2 have been investigated using a Guided Ion Beam Mass Spectrometer (GIB-MS). The following ionic products were observed: CH3+, C2H2+, C2H3+, HNC+ /HCN+ , HCNH+, C3H+ , C2N+ , C3H3+, HCCN+ and C4H2N+ . Theoretical calculations have been carried out to propose reaction pathways leading to the observed products. These processes are of relevance for the generation of long chain nitrogen-containing species and they may be of interest for the chemistry of Titan's ionosphere or circumstellar envelopes.

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

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

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

  12. Isomerization, Perturbations, Calculations and the S_{1} State of C_{2}H_{2}

    NASA Astrophysics Data System (ADS)

    Baraban, J. H.; Changala, P. B.; Berk, J. R. P.; Field, R. W.; Stanton, J. F.; Merer, A. J.

    2013-06-01

    Preliminary analysis of the energy region of the cis-trans isomerization transition state on the S_{1} surface of C_{2}H_{2} has revealed novel patterns and surprising perturbations, including unusually large (and high-order) anharmonicities, as well as K-staggerings of several vibrational levels. These effects complicate the analysis considerably, and require new models and calculations to account for and predict features of the observed spectra. The ˜{A}-˜{X} spectrum of acetylene has been studied both experimentally and theoretically for almost a century, and this cycle of unexpected phenomena eliciting innovative responses is found throughout its history. Especially in the last ten years, progress in understanding the S_{1} state rovibrational level structure and cis-trans isomerization has been accelerated by combining the information available from both ab initio computation and spectroscopic observations. The resulting dialogue has then frequently suggested fruitful avenues for further experiments and calculations. Current challenges and recent results in understanding the cis-trans isomerization transition state region will be discussed in this context.

  13. CO2 and C2H2 in cold nanodroplets of oxygenated organic molecules and water.

    PubMed

    Devlin, J Paul; Balcı, F Mine; Maşlakcı, Zafer; Uras-Aytemiz, Nevin

    2014-11-14

    Recent demonstrations of subsecond and microsecond timescales for formation of clathrate hydrate nanocrystals hint at future methods of control of environmental and industrial gases such as CO2 and methane. Combined results from cold-chamber and supersonic-nozzle [A. S. Bhabhe, "Experimental study of condensation and freezing in a supersonic nozzle," Ph.D. thesis (Ohio State University, 2012), Chap. 7] experiments indicate extremely rapid encagement of components of all-vapor pre-mixtures. The extreme rates are derived from (a) the all-vapor premixing of the gas-hydrate components and (b) catalytic activity of certain oxygenated organic large-cage guests. Premixing presents no obvious barrier to large-scale conditions of formation. Further, from sequential efforts of the groups of Trout and Buch, a credible defect-based model of the catalysis mechanism exists for guidance. Since the catalyst-generated defects are both mobile and abundant, it is often unnecessary for a high percentage of the cages to be occupied by a molecular catalyst. Droplets represent the liquid phase that bridges the premixed vapor and clathrate hydrate phases but few data exist for the droplets themselves. Here we describe a focused computational and FTIR spectroscopic effort to characterize the aerosol droplets of the all-vapor cold-chamber methodology. Computational data for CO2 and C2H2, hetero-dimerized with each of the organic catalysts and water, closely match spectroscopic redshift patterns in both magnitude and direction. Though vibrational frequency shifts are an order of magnitude greater for the acetylene stretch mode, both CO2 and C2H2 experience redshift values that increase from that for an 80% water-methanol solvent through the solvent series to approximately doubled values for tetrahydrofuran and trimethylene oxide (TMO) droplets. The TMO solvent properties extend to a 50 mol.% solution of CO2, more than an order of magnitude greater than for the water-methanol solvent mixture

  14. CO2 and C2H2 in cold nanodroplets of oxygenated organic molecules and water

    NASA Astrophysics Data System (ADS)

    Devlin, J. Paul; Balcı, F. Mine; Maşlakcı, Zafer; Uras-Aytemiz, Nevin

    2014-11-01

    Recent demonstrations of subsecond and microsecond timescales for formation of clathrate hydrate nanocrystals hint at future methods of control of environmental and industrial gases such as CO2 and methane. Combined results from cold-chamber and supersonic-nozzle [A. S. Bhabhe, "Experimental study of condensation and freezing in a supersonic nozzle," Ph.D. thesis (Ohio State University, 2012), Chap. 7] experiments indicate extremely rapid encagement of components of all-vapor pre-mixtures. The extreme rates are derived from (a) the all-vapor premixing of the gas-hydrate components and (b) catalytic activity of certain oxygenated organic large-cage guests. Premixing presents no obvious barrier to large-scale conditions of formation. Further, from sequential efforts of the groups of Trout and Buch, a credible defect-based model of the catalysis mechanism exists for guidance. Since the catalyst-generated defects are both mobile and abundant, it is often unnecessary for a high percentage of the cages to be occupied by a molecular catalyst. Droplets represent the liquid phase that bridges the premixed vapor and clathrate hydrate phases but few data exist for the droplets themselves. Here we describe a focused computational and FTIR spectroscopic effort to characterize the aerosol droplets of the all-vapor cold-chamber methodology. Computational data for CO2 and C2H2, hetero-dimerized with each of the organic catalysts and water, closely match spectroscopic redshift patterns in both magnitude and direction. Though vibrational frequency shifts are an order of magnitude greater for the acetylene stretch mode, both CO2 and C2H2 experience redshift values that increase from that for an 80% water-methanol solvent through the solvent series to approximately doubled values for tetrahydrofuran and trimethylene oxide (TMO) droplets. The TMO solvent properties extend to a 50 mol.% solution of CO2, more than an order of magnitude greater than for the water-methanol solvent mixture

  15. Meridional Variations of C2H2 and C2H6 in Jupiter's Atmosphere from Cassini CIRS Infrared Spectra

    NASA Technical Reports Server (NTRS)

    Nixon, C. A.; Achterberg, R. K.; Conrath, B. J.; Irwin, P. G. J.; Fouchet, T.; Parrish, P. D.; Romani, P. N.; Abbas, M.; LeClair, A.; Strobel, D.

    2004-01-01

    Hydrocarbons such as acetylene (C2H2) and ethane (C2H6) are important tracers in Jupiter's atmosphere, constraining our models of the chemical and dynamical processes. However, our knowledge of the vertical and meridional variations of their abundances has remained sparse. During the flyby of the Cassini spacecraft in December 2000, the Composite Infrared Spectrometer (CIRS) instrument was used to map the spatial variation of emissions from 10-1400 cm(sup -1) (1000-7 microns). In this paper we analyze a zonally-averaged set of CIRS spectra taken at the highest (0.5 cm(sup -1)) resolution, to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the v4 band of CH4, and in the troposphere at 150-400 mbar, via the H2 absorption at 600-800 cm(sup -1). Simultaneously, we retrieve the abundances of C2H2 and C2H6 via the v5 and vg bands respectively. Tropospheric absorption and stratospheric emission are highly anti-correlated at the CIRS resolution, introducing a non-uniqueness into the retrievals, such that vertical gradient and column abundance cannot both be found without additional constraints. Assuming profile gradients from photochemical calculations, we show that the column abundance of C2H2 decreases sharply towards the poles by a factor approximately 4, while C2H6 is unchanged in the north and increasing in the south, by a factor approximately 1.8. An explanation for the meridional trends is proposed in terms of a combination of photochemistry and dynamics. Poleward, the decreasing UV flux is predicted to decrease the abundances of C2H2 and C2H6 by factors 2.7 and 3.5 respectively at a latitude 70 deg. However, the lifetime of C2H6 in the stratosphere (5 x 10(exp 9)) is much longer than the dynamical timescale for meridional motions inferred from SL-9 debris (5 x 10(exp 8 s)), and therefore the constant or rising abundance towards high latitudes likely indicates that meridional mixing dominates over photochemical effects. For C2H2, the opposite

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

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

  18. The transcriptional regulator c2h2 accelerates mushroom formation in Agaricus bisporus.

    PubMed

    Pelkmans, Jordi F; Vos, Aurin M; Scholtmeijer, Karin; Hendrix, Ed; Baars, Johan J P; Gehrmann, Thies; Reinders, Marcel J T; Lugones, Luis G; Wösten, Han A B

    2016-08-01

    The Cys2His2 zinc finger protein gene c2h2 of Schizophyllum commune is involved in mushroom formation. Its inactivation results in a strain that is arrested at the stage of aggregate formation. In this study, the c2h2 orthologue of Agaricus bisporus was over-expressed in this white button mushroom forming basidiomycete using Agrobacterium-mediated transformation. Morphology, cap expansion rate, and total number and biomass of mushrooms were not affected by over-expression of c2h2. However, yield per day of the c2h2 over-expression strains peaked 1 day earlier. These data and expression analysis indicate that C2H2 impacts timing of mushroom formation at an early stage of development, making its encoding gene a target for breeding of commercial mushroom strains. PMID:27207144

  19. Meridional Variations of C2H2 and C2H6 in Jupiter's Atmosphere from Cassini CIRS Infrared Spectra

    NASA Technical Reports Server (NTRS)

    Nixon, C. A.; Achterberg, R. K.; Conrath, B. J.; Irwin, P. G. J.; Fouchet, T.; Parrish, P. D.; Abbas, M.; LeClaire, A.; Romani, P. N.; Simon-Miller, A. A.

    2004-01-01

    The abundances of hydrocarbons such as acetylene (C2H2) and ethane (C2H6) in Jupiter's atmosphere are important physical quantities, constraining our models of the chemical and dynamical processes. However, our knowledge of these quantities and their vertical and latitudinal variations has remained sparse. The flyby of the Cassini spacecraft with Jupiter at the end of 2000 provided an excellent opportunity to observe the infrared spectrum with the Composite Infrared Spectrometer (CIRS) instrument, mapping the spatial variation of emissions from 10-1400 cm-1. CIRS spectra taken at the highest resolution (0.5 cm-1) in early December 2000 have been analysed to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the v4 of CH4, and in the troposphere at 100-400 mbar, via the hydrogen collision-induced continuum absorption at 600-800 cm. Simultaneously, we have searched for meridional abundance variations in C2H2 and C2H6 via the v5 and vg bands respectively. Tropospheric absorption and stratospheric emission are highly anti-correlated at the CIM resolution, introducing a non-uniqueness into the retrievals, which means that vertical gradient and column abundance cannot be simultaneously found without additional constraints. If we assume the profile shapes from photochemical model calculations, we show that the column abundance of C2H2 must decrease sharply towards the poles, while C2H6 is constant or slightly increasing. The relevance of these results to current photochemical and dynamical knowledge of Jupiter's atmosphere is discussed.

  20. 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

  1. Observations of CH4, C2H6, and C2H2 in the stratosphere of Jupiter.

    PubMed

    Sada, P V; Bjoraker, G L; Jennings, D E; McCabe, G H; Romani, P N

    1998-12-01

    We have performed high-resolution spectral observations at mid-infrared wavelengths of CH4 (8.14 micrometers), C2H6 (12.16 micrometers), and C2H2 (13.45 micrometers) on Jupiter. These emission features probe the stratosphere of the planet and provide information on the carbon-based photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer CELESTE, in conjunction with the McMath-Pierce 1.5-m solar telescope between November 1994 and February 1995. We used the methane observations to derive the temperature profile of the jovian atmosphere in the 1-10 mbar region of the stratosphere. This profile was then used in conjunction with height-dependent mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. The resulting mixing ratios are 3.9(+1.9)(-1.3) x 10(-6) for C2H6 (5 mbar pressure level), and 2.3 +/- 0.5 x 10(-8) for C2H2 (8 mbar pressure level), where the quoted uncertainties are derived from model variations in the temperature profile which match the methane observation uncertainties. PMID:11878354

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

    PubMed

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

    2016-09-01

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

  3. 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.

  4. Analytical potential energy surface for O + C2H2 system

    NASA Astrophysics Data System (ADS)

    Garashchuk, Sophya; Rassolov, Vitaly A.; Braams, Bastiaan J.

    2013-11-01

    Full-dimensional analytical potential energy surfaces (PESs) for the O(1P) + C2H2 and O(3P) + C2H2 reactions are presented. The PESs are constructed by fitting thousands of ab initio data points using permutationally invariant polynomials [5]. Electronic structure data are obtained within the restricted coupled cluster theory with single and double excitations with perturbative triple corrections and correlation consistent basis set of triple-ζ with diffuse functions. Motivated by experiments, formation of DOCC and cyclic DCCO at collision energies of 2.5-4 eV is examined using quasi-classical trajectory dynamics on the triplet surface.

  5. Modeling of the nanoparticle coagulation in pulsed radio-frequency capacitively coupled C2H2 discharges

    NASA Astrophysics Data System (ADS)

    Liu, Xiang-Mei; Li, Qi-Nan; Li, Rui

    2015-07-01

    The role of pulse parameters on nanoparticle property is investigated self-consistently based on a couple of fluid model and aerosol dynamics model in a capacitively coupled parallel-plate acetylene (C2H2) discharge. In this model, the mass continuity equation, momentum balance equation, and energy balance equation for neutral gas are taken into account. Thus, the thermophoretic force arises when a gas temperature gradient exists. The typical results of this model are positive and negative ion densities, electron impact collisions rates, nanoparticle density, and charge distributions. The simulation is performed for duty ratio 0.4/0.7/1.0, as well as pulse modulation frequency from 40 kHz to 2.7 MHz for pure C2H2 discharges at a pressure of 500 mTorr. We find that the pulse parameters, especially the duty ratio, have a great affect on the dissociative attachment coefficient and the negative density. More importantly, by decreasing the duty ratio, nanoparticles start to diffuse to the wall. Under the action of gas flow, nanoparticle density peak is created in front of the pulse electrode, where the gas temperature is smaller. Project supported by the Natural Science Foundation of Heilongjiang Province, China (Grant Nos. A2015011 and A2015010), the Postdoctoral Scientific Research Developmental Fund of Heilongjiang Province, China (Grant No. LBH-Q14159), the National Natural Science Foundation of China (Grant No. 11404180), and the Program for Young Teachers Scientific Research in Qiqihar University, China (Grant No. 2014k-Z11).

  6. Can the fragmentation of hydrogen-bonded dimers be predicted: predissociation of C2H2-HX.

    PubMed

    McCaffery, Anthony J; Pritchard, Marisian; Reisler, Hanna

    2010-03-11

    HX rotational state distributions following vibrational predissociation (VP) of C(2)H(2)-HX (X = Cl, F, O) dimers are predicted by expressing the predissociation process as the joint probability of rovibrational excitation in the fragments following "internal collision" in the vibrationally excited dimer. Calculations of these joint probabilities for the T-shaped dimers of acetylene with HCl, DCl, HF, and OH using the angular momentum (AM) method reproduce experimental distributions with reasonable accuracy. In dimers of this complex, many different pathways for the disposal of initial energy and momentum exist in principle. The use of simple physical arguments based on (a) the direction of initial impulse upon excitation and (b) restricted relative geometries due to limited amplitude of relative motion of the dimer components allows the number of effective dissociation pathways to be much reduced. For these, the probability of rotational and rovibrational transfer into the fragments is calculated, a process that generally involves summing over a number of C(2)H(2) rovibrational states for each value of j(HX). In calculating relative rotational populations in the fragments, it was found essential to first calculate the threshold value of available energy for that transition and the threshold value of b(n), the effective impact parameter. Without these modifications, channels of lowest j(HX) and/or j(C(2)H(2)) dominate, which generally is not found experimentally. The need for these modifications is attributed to energy conservation in the dissociation and the limited range of relative orientations that the dimer pair can explore. The AM method is able to predict the very different fragment rotational excitations in this series of dimers fairly well using only readily available data. In addition, a number of new insights into the physical principles that control the dissociation of molecule-molecule dimers have emerged and are discussed. The results suggest that

  7. 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

  8. Mutant and overexpression analysis of a C2H2 single zinc finger gene of Arabidopsis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The goal of this work was to characterize an Arabidopsis C2H2 single zinc finger gene, named AtZFP11, that is similar to SUPERMAN (SUP) and RABBIT EARS (RBE). No altered phenotype was observed in mutants analyzed that were derived through TILLING, nor a T-DNA insertion into the exon of AtZFP11. Pl...

  9. An Adsorbate Discriminatory Gate Effect in a Flexible Porous Coordination Polymer for Selective Adsorption of CO2 over C2H2.

    PubMed

    Foo, Maw Lin; Matsuda, Ryotaro; Hijikata, Yuh; Krishna, Rajamani; Sato, Hiroshi; Horike, Satoshi; Hori, Akihiro; Duan, Jingui; Sato, Yohei; Kubota, Yoshiki; Takata, Masaki; Kitagawa, Susumu

    2016-03-01

    The adsorptive separation of C2H2 and CO2 via porous materials is nontrivial due to the close similarities of their boiling points and kinetic diameters. In this work, we describe a new flexible porous coordination polymer (PCP) [Mn(bdc)(dpe)] (H2bdc = 1,4-benzenedicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene) having zero-dimensional pores, which shows an adsorbate discriminatory gate effect. The compound shows gate opening type abrupt adsorption for C2H2 but not for CO2, leading to an appreciable selective adsorption of CO2 over C2H2 at near ambient temperature (273 K). The origin of this unique selectivity, as unveiled by in situ adsorption-X-ray diffraction experiments and density functional theory calculations, is due to vastly different orientations between the phenylene ring of bdc and each gas in the nanopores. The structural change by photochemical transformation of this PCP via [2 + 2] photodimerization leads to the removal of inverse CO2/C2H2 selectivity, verifying the mechanism of the guest discriminatory gate effect. PMID:26876504

  10. A novel flexible C2H2 gas sensor based on Ag-ZnO nanorods on PI/PTFE substrate

    NASA Astrophysics Data System (ADS)

    Uddin, A. S. M. Iftekhar; Chung, Gwiy-Sang

    2016-02-01

    In this work a novel flexible acetylene (C2H2) gas sensor based on Ag nanoparticles decorated vertical ZnO nanorods (Ag-ZnO NRs) on PI/PTFE substrate has been investigated. The grown structure was synthesized through a simple, rapid, and low-temperature hydrothermal-RF magnetron sputtering method. The successful immobilization of Ag nanoparticles (NPs) onto the surface of ZnO nanorods contributed large effective surface area and facilitated the charge transfer process. The as-fabricated sensor exhibited enhanced C2H2 sensing performances at low temperature (200°C) including a broad detection range (3 - 1000 ppm), and short recovery time (39 sec). Mechanical robustness and device flexibility were investigated at different curvature angle (0 - 90°) and several times bending-relaxing process (0 - 5 × 105 times). The sensor exhibited stable response magnitude with a negligible drift of ~ 2.1% for a maximum bending angle of 90o and a response drop of 8% after 5 × 104 bending/relaxing processes. The superior sensing features along with outstanding flexibility to extreme bending stress indicate the sensor a promising candidate for the development of practical flexible C2H2 gas sensors.

  11. Electron Impact Ionization and Dissociative Ionization of C2H2

    NASA Technical Reports Server (NTRS)

    Srivastava, S. K.

    1995-01-01

    By utilizing a crossed electron beam collision geometry, a combination of time-of-flight (TOF) and quadrupole mass spectrometers, and the relative flow technique1 normalized values of cross sections and appearance energies (AP) were obtained for the formation of singly and multiply ionized species resulting from the ionization and dissociation of C2H2. Details ont he apparatus and technique have been published previously.2,3.

  12. Terahertz Spectroscopy and Global Analysis of the Bending Vibrations of ^{12}C_2H_2 and ^{12}C_2D_2

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Drouin, Brian J.; Pearson, John C.; Pickett, Herbert M.; Lattanzi, Valerio; Walters, Adam

    2009-06-01

    Symmetric molecules have no permanent dipole moment and are undetectable by rotational spectroscopy. Their interstellar observations have previously been limited to mid-infrared vibration-rotation spectroscopy. Although relatively weak, vibrational difference bands provide a means for detection of non polar molecules by terahertz techniques with microwave precision. Herschel, SOFIA, and ALMA have the potential to identify a number of difference bands of light symmetric species, e.g., C_2H_2, CH_4 and C_3. This paper reports the results of the laboratory study on ^{12}C_2H_2 and ^{12}C_2D_2. The symmetric isotopomers of acetylene have two bending modes, the trans bending ν_4 (^1{π}_g), and the cis bending ν_5 (^1{π}_u). For ^{12}C_2H_2, the two bending modes occur at 612 and 729 cm^{-1}, respectively. For ^{12}C_2D_2, the two bending modes occur at 511 and 538 cm^{-1}. The ν_5-ν_4 difference bands are allowed and occur in the microwave, terahertz, and far-infrared wavelengths, with band origins at 117 cm^{-1} (3500 GHz) for ^{12}C_2H_2 and 27 cm^{-1} (900 GHz) for ^{12}C_2D_2. Two hundred and fifty-one ^{12}C_2D_2 transitions, which are from ν_5-ν_4, (ν_5+ν_4)-2ν_4 and 2ν_5-(ν_5+ν_4) bands, have been measured in the 0.2-1.6 THz region, and 202 of them were observed for the first time. The precision of these measurements is estimated to be from 50 kHz to 100 kHz. A multistate analysis was carried out for the bending vibrational modes ν_4 and ν_5 of ^{12}C_2D_2, which includes the lines observed in this work and prior microwave, far-infrared and infrared data on the pure bending levels. Significantly improved molecular parameters were obtained for ^{12}C_2D_2 by adding the new measurements to the old data set which had only 10 lines with microwave measurement precision. The experiments on ^{12}C_2H_2 are in progress and ten P branch lines have been observed. We will present the ^{12}C_2H_2 results to date.

  13. A structural approach reveals how neighbouring C2H2 zinc fingers influence DNA binding specificity

    PubMed Central

    Garton, Michael; Najafabadi, Hamed S.; Schmitges, Frank W.; Radovani, Ernest; Hughes, Timothy R.; Kim, Philip M.

    2015-01-01

    Development of an accurate protein–DNA recognition code that can predict DNA specificity from protein sequence is a central problem in biology. C2H2 zinc fingers constitute by far the largest family of DNA binding domains and their binding specificity has been studied intensively. However, despite decades of research, accurate prediction of DNA specificity remains elusive. A major obstacle is thought to be the inability of current methods to account for the influence of neighbouring domains. Here we show that this problem can be addressed using a structural approach: we build structural models for all C2H2-ZF–DNA complexes with known binding motifs and find six distinct binding modes. Each mode changes the orientation of specificity residues with respect to the DNA, thereby modulating base preference. Most importantly, the structural analysis shows that residues at the domain interface strongly and predictably influence the binding mode, and hence specificity. Accounting for predicted binding mode significantly improves prediction accuracy of predicted motifs. This new insight into the fundamental behaviour of C2H2-ZFs has implications for both improving the prediction of natural zinc finger-binding sites, and for prioritizing further experiments to complete the code. It also provides a new design feature for zinc finger engineering. PMID:26384429

  14. Gas-phase CO2, C2H2, and HCN toward Orion-KL

    NASA Astrophysics Data System (ADS)

    Boonman, A. M. S.; van Dishoeck, E. F.; Lahuis, F.; Doty, S. D.; Wright, C. M.; Rosenthal, D.

    2003-03-01

    The infrared spectra toward Orion-IRc2, Peak 1 and Peak 2 in the 13.5-15.5 mu m wavelength range are presented, obtained with the Short Wavelength Spectrometer on board the Infrared Space Observatory. The spectra show absorption and emission features of the vibration-rotation bands of gas-phase CO2, HCN, and C2H2, respectively. Toward the deeply embedded massive young stellar object IRc2 all three bands appear in absorption, while toward the shocked region Peak 2 CO2, HCN, and C2H2 are seen in emission. Toward Peak 1 only CO2 has been detected in emission. Analysis of these bands shows that the absorption features toward IRc2 are characterized by excitation temperatures of ~ 175-275 K, which can be explained by an origin in the shocked plateau gas. HCN and C2H2 are only seen in absorption in the direction of IRc2, whereas the CO2 absorption is probably more widespread. The CO2 emission toward Peak 1 and 2 is best explained with excitation by infrared radiation from dust mixed with the gas in the warm component of the shock. The similarity of the CO2 emission and absorption line shapes toward IRc2, Peak 1 and Peak 2 suggests that the CO2 is located in the warm component of the shock (T ~ 200 K) toward all three positions. The CO2 abundances of ~ 10-8 for Peak 1 and 2, and of a few times 10-7 toward IRc2 can be explained by grain mantle evaporation and/or reformation in the gas-phase after destruction by the shock. The HCN and C2H2 emission detected toward Peak 2 is narrower (T ~ 50-150 K) and originates either in the warm component of the shock or in the extended ridge. In the case of an origin in the warm component of the shock, the low HCN and C2H2 abundances of ~ 10-9 suggest that they are destroyed by the shock or have only been in the warm gas for a short time (t <~ 104 yr). In the case of an origin in the extended ridge, the inferred abundances are much higher and do not agree with predictions from current chemical models at low temperatures. Based on

  15. Adsorption and reaction of acetylene and ethylene on the Si(001)2×1 surface

    NASA Astrophysics Data System (ADS)

    Matsui, Fumihiko; Yeom, Han Woong; Matsuda, Iwao; Ohta, Toshiaki

    2000-08-01

    The electronic structures and the thermal reaction of chemisorbed C2H2 and C2H4 on the Si(001)2×1 surface have been investigated by carbon K-edge near-edge x-ray absorption fine structure (NEXAFS) and ultraviolet photoemission spectroscopy (UPS) using synchrotron radiation. The bonding and antibonding states due to the interaction of the molecules and the Si surface atoms are identified by detailed polarization-dependent UPS and NEXAFS measurements, respectively. These bonding and antibonding states are shown to originate from the hybridization between the occupied Si dangling bonds and the lowest unoccupied molecular orbitals (π*C-C) of C2H2 and C2H4 double-σ-bonded on the top of the Si dimer. The thermal evolution of mainly C2H2 is investigated in detail for a wide temperature range of 60-1500 K from the condensation to the surface alloy formation. The coexistence of the physisorbatelike and the chemisorbed molecular species is observed at 70-90 K for C2H2 and C2H4, for the coverages greater than ~0.25 monolayer (ML). The π*C-C resonance of those physisorbatelike C2H4 species in NEXAFS exhibits an unusual polarization dependence indicating adsorption with their molecular planes aligned perpendicular to the surface. The dissociation of C2H2 chemisorbates is shown to occur at 600-700 K as observed by UPS. After the dissociation of molecules, the atomic hydrogen adsorbates are identified by the monohydridelike surface resonance states in the UP spectra at 800-950 K. Most of the Si dangling bonds are passivated by, at least partly, the hydrogen adsorbates at this stage. At ~1000 K, the desorption of hydrogen occurs, which accompanies the appearance of a broad SiC-like feature in the UP spectra at ~3 eV below Fermi level.

  16. An ab initio and experimental study of vibrational effects in low energy O++C2H2 charge-transfer collisions

    NASA Astrophysics Data System (ADS)

    Fukuzawa, Kaori; Matsushita, Toshio; Morokuma, Keiji; Levandier, Dale J.; Chiu, Yu-hui; Dressler, Rainer A.; Murad, Edmond; Midey, Anthony; Williams, Skip; Viggiano, Albert A.

    2001-08-01

    Theoretical and experimental studies are performed to elucidate the low energy charge-transfer dynamics of the reaction, O+(4S)+C2H2(X 1Σg+)→O+C2H2+. In particular, the role of the low-frequency acetylene bending modes (612 and 730 cm-1) in promoting charge transfer was examined. High-temperature guided-ion beam measurements are carried out over the energy range from near-thermal to 3 eV at 310 and 610 K. The charge-transfer cross sections are found to decrease up to 0.5 eV, to have a constant value at intermediate energies between 0.5 and 1.5 eV, and then to dramatically increase above a threshold of a spin-allowed process determined to be at 1.7 eV. A bending vibrational enhancement of ˜8 is observed at intermediate energies. Thermal energy rate co-efficients are measured in a variable temperature-selected ion flow drift tube apparatus from 193 to 500 K. At each temperature, a negative energy dependence is observed. In order to elucidate the reaction mechanism in detail, high level ab initio calculations using Complete Active Space Self-Consistent Field and Multi-Reference Single- and Double-excitation Configuration Interaction methods have been performed. The results indicate that the charge transfer reaction occurs at an early stage via nonadiabatic transition between quartet and doublet states. There is a weak van der Waals minimum at the entrance channel between O+(4S) and C2H2 with the relative energy of -1.51 kcal/mol. The minimum of the quartet/doublet crossing seam (Q/D MSX), where the spin-forbidden nonadiabatic transition is most likely to take place, lies very near this minimum at RCO=4.06 Å, RCC=1.20 Å, and ∠CCH=166.6° with a relative energy of -1.48 kcal/mol. After the nonadiabatic transition, the system propagates on the doublet surface to reach the exothermic O(1D)+C2H2+(X˜2Πu) products. No energy barrier exists on the reaction pathway, strongly suggesting that the reaction should occur at low energy with a negative energy dependence

  17. Mining the Brassica oleracea genome for Q-type C2H2 zinc finger transcription factor proteins

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Q-type zinc finger proteins have been studied in several plant species and have been associated with response to stress. A whole genome analysis of Arabidopsis identified 176 putative C2H2 transcription factors (TF). Q-type C2H2 TFs containing the QALGGH motif and are a subset of these. In Arabidops...

  18. C2H2 type of zinc finger transcription factors in foxtail millet define response to abiotic stresses.

    PubMed

    Muthamilarasan, Mehanathan; Bonthala, Venkata Suresh; Mishra, Awdhesh Kumar; Khandelwal, Rohit; Khan, Yusuf; Roy, Riti; Prasad, Manoj

    2014-09-01

    C2H2 type of zinc finger transcription factors (TFs) play crucial roles in plant stress response and hormone signal transduction. Hence considering its importance, genome-wide investigation and characterization of C2H2 zinc finger proteins were performed in Arabidopsis, rice and poplar but no such study was conducted in foxtail millet which is a C4 Panicoid model crop well known for its abiotic stress tolerance. The present study identified 124 C2H2-type zinc finger TFs in foxtail millet (SiC2H2) and physically mapped them onto the genome. The gene duplication analysis revealed that SiC2H2s primarily expanded in the genome through tandem duplication. The phylogenetic tree classified these TFs into five groups (I-V). Further, miRNAs targeting SiC2H2 transcripts in foxtail millet were identified. Heat map demonstrated differential and tissue-specific expression patterns of these SiC2H2 genes. Comparative physical mapping between foxtail millet SiC2H2 genes and its orthologs of sorghum, maize and rice revealed the evolutionary relationships of C2H2 type of zinc finger TFs. The duplication and divergence data provided novel insight into the evolutionary aspects of these TFs in foxtail millet and related grass species. Expression profiling of candidate SiC2H2 genes in response to salinity, dehydration and cold stress showed differential expression pattern of these genes at different time points of stresses. PMID:24915771

  19. Vertical spectrum of the C2H2+ system. An open shell (SC)2-CAS-SDCI study.

    PubMed

    Pitarch-Ruiz, José; Sánchez-Marín, José; Maynau, Daniel

    2003-04-15

    The open shell (SC)(2)-CAS-SDCI method along with a basis set of atomic natural orbitals (ANO) has been applied for calculating the main ionization potentials of acetylene, as well as the manifold of excited states of the different symmetries up to 32 eV. In this method, the single and double excitations of a CAS space are generated and the corresponding CI matrix is corrected by means of the (SC)(2) procedure that cancels the size-extensivity error and adds some high order contributions. The mean absolute error for the outer-valence X (2)Pi(u)(1pi(u) (-1)), A (2)Sigma(g) (+)(3sigma(g) (-1)), and B (2)Sigma(u) (+)(2sigma(u) (-1)) states, and the inner-valence C (2)Sigma(g) (+)(2sigma(g) (-1)) state is 0.1 eV. The excited states of C(2)H(2) (+) corresponding to the Sigma(g) (+), Sigma(u) (+), Pi(g), Pi(u), Delta(g), and Delta(u) symmetries are reported and their composition is discussed. The results are thoroughly compared to the best available multireference CI calculations. Recent multichannel CI results by Wells and Lucchese [J Chem Phys 1999, 110, 6365] have been used also as a guide for the discussion of the results. Discrepancies in the description of many multiconfigurational states by means of the (SC)(2)-CAS-SDCI wave function as compared to previous large MR-CI calculations are significant and are, consequently, remarked on. A large mixing of the 3sigma(g) (-1) and 2sigma(g) (-1) processes is found in the A (2)Sigma(g) (+) and C (2)Sigma(g) (+) states, provided that the basis set is augmented with Rydberg functions. PMID:12632475

  20. An ignored but most favorable channel for NCO +C2H2 reaction

    NASA Astrophysics Data System (ADS)

    Xie, Hong-bin; Wang, Jian; Zhang, Shao-wen; Ding, Yi-hong; Sun, Chia-chung

    2006-09-01

    The NCO +C2H2 reaction has been considered as a prototype for understanding the chemical reactivity of the isocyanate radical towards unsaturated hydrocarbons in fuel-rich combustion. It has also been proposed to provide an effective route for formation of oxazole-containing compounds in organic synthesis, and might have potential applications in interstellar processes. Unfortunately, this reaction has met mechanistic controversy both between experiments and between experiments and theoretical calculations. In this paper, detailed theoretical investigations at the Becke's three parameter Lee-Yang-Parr-B3LYP /6-31G(d), B3LYP /6-311++G(d,p), quadratic configuration interaction with single and double excitations QCISD /6-31G(d), and Gaussian-3 levels are performed for the NCO +C2H2 reaction, covering various entrance, isomerization, and decomposition channels. Also, the highly cost-expensive coupled-cluster theory including single and double excitations and perturbative inclusion of triple excitations CCSD(T)/aug-cc-pVTZ single-point energy calculation is performed for the geometries obtained at the Becke's three parameter Lee-Yang-Parr-B3LYP /6-311++G(d,p) level. A previously ignored yet most favorable channel via a four-membered ring intermediate with allyl radical character is found. However, formation of P3 H +HCCNCO and the five-membered ring channel predicted by previous experimental and theoretical studies is kinetically much less competitive. With the new channel, master equation rate constant calculations over a wide range of temperatures (298-1500K) and pressures (10-560Torr) show that the predicted total rate constants exhibit a positive-temperature dependence and no distinct pressure dependence effect. This is in qualitative agreement with available experimental results. Under the experimental conditions, the predicted values are about 50% lower than the latest experimental results. Also, the branching ratio variations of the fragments P2 HCN +HCCO and P5

  1. Dual-laser absorption spectroscopy of C2H2 at 1.4 μ m

    NASA Astrophysics Data System (ADS)

    Fasci, E.; Odintsova, T. A.; Castrillo, A.; De Vizia, M. D.; Merlone, A.; Bertiglia, F.; Moretti, L.; Gianfrani, L.

    2016-04-01

    Spectroscopic parameters (line intensity factor, pressure self-broadening, and shifting coefficients) of C2H2 at 1.4 μ m were accurately measured using a dual-laser approach, based upon the technique of optical phase locking. This generated an absolute frequency scale underneath the absorption spectra. A pair of extended-cavity diode lasers was used. One of them, the probe laser, is forced to maintain a precise frequency offset from a reference laser, which is an optical frequency standard based on noise-immune cavity-enhanced optical heterodyne molecular spectroscopy. Laser-gas interaction takes place inside an isothermal multipass cell that is stabilized at the temperature of the triple point of water. The fidelity in the observation of the shape associated to the Pe(14) line of the 2 ν3+ν5 band allowed us to measure the spectroscopic parameters, with a global uncertainty for the line strength of 0.22%.

  2. The Dissociation Energies of CH4 and C2H2 Revisited

    NASA Technical Reports Server (NTRS)

    Partridge, Harry; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    The bond dissociation energies of CH4 and C2H2 and their fragments are investigated using basis set extrapolations and high levels of correlation. The computed bond dissociation energies (D(sub e)) are accurate to within 0.2 kcal/mol. The agreement with the experimental (D(sub 0)) values is excellent if we assume that the zero-point energy of C2H is 9.18 kcal/mol. The effect of core (1s) correlation on the bond dissociation energies of C-H bonds is shown to vary from 0.2 to 0.7 kcal/mol and that for C-C bonds varies from 0.4 to 2.2 kcal/mol.

  3. Direct growth of graphene on gallium nitride using C2H2 as carbon source

    NASA Astrophysics Data System (ADS)

    Wang, Bing; Zhao, Yun; Yi, Xiao-Yan; Wang, Guo-Hong; Liu, Zhi-Qiang; Duan, Rui-Rei; Huang, Peng; Wang, Jun-Xi; Li, Jin-Min

    2016-04-01

    Growing graphene on gallium nitride (GaN) at temperatures greater than 900°C is a challenge that must be overcome to obtain high quality of GaN epi-layers. We successfully met this challenge using C2H2 as the carbon source. We demonstrated that graphene can be grown both on copper and directly on GaN epi-layers. The Raman spectra indicated that the graphene films were about 4-5 layers thick. Meanwhile, the effects of the growth temperature on the growth of the graphene films were systematically studied, and 830°C was found to be the optimum growth temperature. We successfully grew high-quality graphene films directly on gallium nitride.

  4. 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

  5. Investigation of the C2H2-CO2 van der Waals complex in the overtone range using cw cavity ring-down spectroscopy

    NASA Astrophysics Data System (ADS)

    Lauzin, C.; Didriche, K.; Liévin, J.; Herman, M.; Perrin, A.

    2009-05-01

    A slit nozzle supersonic expansion containing acetylene [492 SCCM (SCCM denotes cubic centimeter per minute at STP)] and carbon dioxide (740 SCCM) seeded into Ar (837 SCCM) is investigated using cw-cavity ring-down spectroscopy, in the 1.5 μm range. The C2H2-CO2 van der Waals complex is observed around the ν1+ν3 acetylenic band. The rotational temperature is estimated to be close to 60 K from the comparison between observed and simulated spectra. The analysis of the main, perturbed B-type band centered near 6 549.280 cm-1, is performed. It is attributed to a dimer with the known planar, C2v geometry. The present overtone data, involving ground state levels with higher J /K states (J ≤35 and Ka≤20) than previously reported, are combined to 3 μm data [D. G. Prichard, R. N. Nandi, J. S. Muenter, and B. J. Howard, J. Chem. Phys. 89, 1245 (1988); Z. S. Huang and R. E. Miller, Chem. Phys. 132, 185 (1989)] to determine improved ground state parameters. The major perturbations affecting the upper state are accounted for through C-type Coriolis resonances involving one dark state, whose symmetry must therefore be A1. Upper state constants are obtained for the bright and dark states. The dependence upon vibrational excitation is demonstrated to arise from excitation in the acetylene unit, only, for the former, but cannot be unravelled for the latter.

  6. High-resolution, VUV (147-201 nm) photoabsorption cross sections for C2H2 at 195 and 295 K

    NASA Technical Reports Server (NTRS)

    Smith, Peter L.; Yoshino, Kouichi; Parkinson, W. H.; Ito, Kenji; Stark, Glenn

    1991-01-01

    Results of measurements of photoabsorption cross sections of acetylene at 195 and 295 K in the wavelength range of 147-201 nm are reported. Short-wavelength data are obtained at 0.002 nm intervals, but no structure was observed on that scale. Emission and absorption lines from contaminant species in xenon and hydrogen discharges are used to determine the correct wavelength scale for the data. The uncertainty in the relative wavelengths is estimated to be about 0.004 nm, whereas the absolute wavelength values are accurate to + or - 0.043 nm. No significant photodestruction of C2H2 was found during the measurements. Cross-section values determined at the beginning portions of the measurements are indistinguishable from the values determined at the ends, thus demonstrating that there was no loss of absorbers.

  7. Pressure dependence of the absolute rate constant for the reaction Cl + C2H2 from 210-361 K

    NASA Technical Reports Server (NTRS)

    Brunning, J.; Stief, L. J.

    1985-01-01

    In recent years, considerable attention has been given to the role of chlorine compounds in the catalytic destruction of stratospheric ozone. However, while some reactions have been studied extensively, the kinetic data for the reaction of Cl with C2H2 is sparse with only three known determinations of the rate constant k3. The reactions involved are Cl + C2H2 yields reversibly ClC2H2(asterisk) (3a) and ClC2H2(asterisk) + M yields ClC2H2 + M (3b). In the present study, flash photolysis coupled with chlorine atomic resonance fluorescence have been employed to determine the pressure and temperature dependence of k3 with the third body M = Ar. Room temperature values are also reported for M = N2. The pressure dependence observed in the experiments confirms the expectation that the reaction involves addition of Cl to the unsaturated C2H2 molecule followed by collisional stabilization of the resulting adduct radical.

  8. 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.

  9. Preparation of hydrogenated diamond-like carbon films using high-density pulsed plasmas of Ar/C2H2 and Ne/C2H2 mixture

    NASA Astrophysics Data System (ADS)

    Kimura, Takashi; Kamata, Hikaru

    2016-07-01

    Hydrogenated diamond-like carbon films are prepared using reactive high-density pulsed plasmas of Ar/C2H2 and Ne/C2H2 mixture in the total pressure range from 0.5 to 2 Pa. The plasmas are produced using a reactive high-power impulse magnetron sputtering (HiPIMS) system. A negative pulse voltage of ‑500 V is applied to the substrate for a period of 15 µs in the afterglow mode. The growth rate does not strongly depend on the type of ambient gas but it markedly increases to about 2.7 µm/h at a C2H2 fraction of 10% and a total pressure of 2 Pa with increasing C2H2 fraction. The marked increase in the growth rate means that the HiPIMS system can be regarded as a plasma source for the chemical vapor deposition process. The hardness of the films prepared by Ne/C2H2 plasmas is somewhat higher than that of the films prepared by Ar/C2H2 plasmas under the same operating conditions, and the difference becomes larger as the pressure increases. The hardness of the films prepared by Ne/C2H2 plasmas ranges between 11 and 18 GPa. In the Raman spectra, two very broad overlapping bands are assigned as the G (graphite) and D (disorder) bands. The peak position of the G band is roughly independent of the total pressure, whereas the FWHM of the G peak decreases with increasing total pressure as a whole.

  10. Characterization of mid-infrared emissions from C2H2, CO, CO2, and HCN-filled hollow fiber lasers

    NASA Astrophysics Data System (ADS)

    Jones, A. M.; Fourcade-Dutin, C.; Mao, C.; Baumgart, B.; Nampoothiri, A. V. V.; Campbell, N.; Wang, Y.; Benabid, F.; Rudolph, W.; Washburn, B. R.; Corwin, K. L.

    2012-02-01

    We have now demonstrated and characterized gas-filled hollow-core fiber lasers based on population inversion from acetylene (12C2H2) and HCN gas contained within the core of a kagome-structured hollow-core photonic crystal fiber. The gases are optically pumped via first order rotational-vibrational overtones near 1.5 μm using 1-ns pulses from an optical parametric amplifier. Transitions from the pumped overtone modes to fundamental C-H stretching modes in both molecules create narrow-band laser emissions near 3 μm. High gain resulting from tight confinement of the pump and laser light together with the active gas permits us to operate these lasers in a single pass configuration, without the use of any external resonator structure. A delay between the emitted laser pulse and the incident pump pulse has been observed and is shown to vary with pump pulse energy and gas pressure. Furthermore, we have demonstrated lasing beyond 4 μm from CO and CO2 using silver-coated glass capillaries, since fused silica based fibers do not transmit in this spectral region and chalcogenide fibers are not yet readily available. Studies of the laser pulse energy as functions of the pump pulse energy and gas pressure were performed. Efficiencies reaching ~ 20% are observed for both acetylene and CO2.

  11. 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}.

  12. 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.

  13. High resolution, low temperature photoabsorption cross-section of C2H2 with application to Saturn's atmosphere

    NASA Technical Reports Server (NTRS)

    Caldwell, John; Wu, C. Y. R.; Xia, T. J.; Judge, D. L.; Wagener, R.

    1990-01-01

    New laboratory observations of the VUV absorption cross-section of C2H2, obtained under physical conditions approximating stratospheres of the giant planets, were combined with IUE observations of the albedo of Saturn, for which improved data reduction techniques have been used, to produce new models for that atmosphere. When the effects of C2H2 absorption are accounted for, additional absorption by other molecules is required. The best-fitting model also includes absorption by PH3, H2O, C2H6 and CH4. A small residual disagreement near 1600 A suggests that an additional trace species may be required to complete the model.

  14. Quantum cascade laser investigations of CH4 and C2H2 interconversion in hydrocarbon/H2 gas mixtures during microwave plasma enhanced chemical vapor deposition of diamond

    NASA Astrophysics Data System (ADS)

    Ma, Jie; Cheesman, Andrew; Ashfold, Michael N. R.; Hay, Kenneth G.; Wright, Stephen; Langford, Nigel; Duxbury, Geoffrey; Mankelevich, Yuri A.

    2009-08-01

    CH4 and C2H2 molecules (and their interconversion) in hydrocarbon/rare gas/H2 gas mixtures in a microwave reactor used for plasma enhanced diamond chemical vapor deposition (CVD) have been investigated by line-of-sight infrared absorption spectroscopy in the wavenumber range of 1276.5-1273.1 cm-1 using a quantum cascade laser spectrometer. Parameters explored include process conditions [pressure, input power, source hydrocarbon, rare gas (Ar or Ne), input gas mixing ratio], height (z) above the substrate, and time (t) after addition of hydrocarbon to a pre-existing Ar/H2 plasma. The line integrated absorptions so obtained have been converted to species number densities by reference to the companion two-dimensional (r ,z) modeling of the CVD reactor described in Mankelevich et al. [J. Appl. Phys. 104, 113304 (2008)]. The gas temperature distribution within the reactor ensures that the measured absorptions are dominated by CH4 and C2H2 molecules in the cool periphery of the reactor. Nonetheless, the measurements prove to be of enormous value in testing, tensioning, and confirming the model predictions. Under standard process conditions, the study confirms that all hydrocarbon source gases investigated (methane, acetylene, ethane, propyne, propane, and butane) are converted into a mixture dominated by CH4 and C2H2. The interconversion between these two species is highly dependent on the local gas temperature and the H atom number density, and thus on position within the reactor. CH4→C2H2 conversion occurs most efficiently in an annular shell around the central plasma (characterized by 1400C2H2→CH4 is favored in the more distant regions where Tgas<1400 K. Analysis of the multistep interconversion mechanism reveals substantial net consumption of H atoms accompanying the CH4→C2H2 conversion, whereas the reverse C2H2→CH4 process only requires H atoms to drive the reactions; H atoms are not consumed by the overall

  15. Analysis of the High-Resolution Fourier Spectrum of the ν6 Band of the cis-C2h2d2 Molecule

    NASA Astrophysics Data System (ADS)

    Konov, I. A.; Chertavskikh, Yu. V.; Fomchenko, A. L.; Aslapovskaya, Yu. S.; Zhdanovich, S. A.; Sydow, C.

    2016-03-01

    The spectrum of the ν6 band of the cis-ethylene-d2 molecule (cis-C2H2D2) is recorded with a Bruker IFS 125 HR Fourier spectrometer in the range 580-1210 cm-1 with resolution of 0.0021 cm-1. An analysis of the experimental spectrum allows more than 1500 transitions belonging to this band to be assigned that by more than 2.5 times greater than it has been known in the literature so far. The obtained experimental data are then used to determine the model parameters of the molecule (the effective Hamiltonian in the A-reduction and I'- representation). Strong resonance interaction with the band ν4 forbidden in absorption by the symmetry of a molecule is taken into account. 10 parameters of the Hamiltonian obtained by solving inverse spectroscopic problem reproduce 427 initial experimental energies (more than 1500 transitions) with accuracy close to the experimental uncertainty.

  16. Theoretical study of the bonding of Nb(2+) to CH2, C2H2, and C2H4

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Partridge, Harry

    1991-01-01

    The bonding of Nb(2+) with CH2, C2H2, and C2H4 is studied by using electronic structure calculations that include high levels of electron correlation. The binding energy for NbCH2(2+) is in good agreement with the lower bound determined from the reaction with CH4 but is significantly smaller than the value determined from the binding energy and ionization potential of NbCH2(+). The calculations and a new interpretation of the experiment indicate that the larger value is in error primarily because the ionization potential of NbCH2(+) determined from bracketing charge-exchange reactions is too small. The computed binding energy of NbC2H2(2+) is in good agreement with experiment. The calculations show that the bonding is predominantly covalent in character for both NbCH2(2+) and NbC2H2(2+), whereas for NbC2H4(2+) the electronic states that are predominantly ionic and covalent are nearly degenerate. The trend in binding energies, CH2 greater than C2H2 greater than C2H4, is consistent with the energy required to prepare the ligands for bonding.

  17. Herbivory responsive C2H2 zinc finger transcription factor protein StZFP2 from potato

    Technology Transfer Automated Retrieval System (TEKTRAN)

    While C2H2 zinc finger transcription factors are often regulated by abiotic stress, their role during insect infestation has been overlooked. This study demonstrates that the transcripts of the zinc finger transcription factors StZFP1 and StZFP2 are induced in potato (Solanum tuberosum) upon infesta...

  18. Simulation of nanoparticle coagulation in radio-frequency C2H2/Ar microdischarges

    NASA Astrophysics Data System (ADS)

    Xiang-Mei, Liu; Qi-Nan, Li; Rui, Li

    2016-06-01

    The nanoparticle coagulation is investigated by using a couple of fluid models and aerosol dynamics model in argon with a 5% molecular acetylene admixture rf microdischarges, with the total input gas flow rate of 400 sccm. It co-exists with a homogeneous, secondary electron-dominated low temperature γ-mode glow discharges. The heat transfer equation and flow equation for neutral gas are taken into account. We mainly focused on investigations of the nanoparticle properties in atmospheric pressure microdischarges, and discussed the influences of pressure, electrode spacing, and applied voltage on the plasma density and nanoparticle density profiles. The results show that the characteristics of microdischarges are quite different from those of low pressure radio-frequency discharges. First, the nanoparticle density in the bulk plasma in microdischarges is much larger than that of low pressure discharges. Second, the nanoparticle density of 10 nm experiences an exponential increase as soon as the applied voltage increases, especially in the presheath. Finally, as the electrode spacing increases, the nanoparticle density decreased instead of increasing. Project supported by the Natural Science Foundation of Heilongjiang Province, China (Grant Nos. A2015011 and A2015010), the Postdoctoral Scientific Research Development Fund of Heilongjiang Province, China (Grant No. LBH-Q14159), the Program for Young Teachers Scientific Research in Qiqihar University (Grant No. 2014k-Z11), the National Natural Science Foundation of China (Grant No. 11404180), and the University Nursing Program for Yong Scholars with Creative Talents in Heilongjiang Province, China (Grant No. UNPYSCT-2015095).

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

    PubMed

    Kroneck, Peter M H

    2016-03-01

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

  20. Detection of acetylene impurities in ethylene and polyethylene manufacturing processes using tunable diode laser spectroscopy in the 3-μm range

    NASA Astrophysics Data System (ADS)

    Kluczynski, P.; Jahjah, M.; Nähle, L.; Axner, O.; Belahsene, S.; Fischer, M.; Koeth, J.; Rouillard, Y.; Westberg, J.; Vicet, A.; Lundqvist, S.

    2011-11-01

    Using recently developed GaInAsSb/AlGaInAsSb DFB lasers, tunable diode laser spectroscopy (TDLS) has been extended into the 3-μm wavelength region for the detection of acetylene impurities in hydrocarbon compounds encountered in ethylene manufacturing. Measurements of acetylene in pure polymer grade ethylene and in a gas mixture of ethylene and ethane typical of the process stream around a hydrogenation reactor have been performed. Using a procedure incorporating subtraction of a hydrocarbon background spectrum a detection limit of 5 ppb m was achieved under ordinary laboratory conditions. Under forced temperature cycling conditions, the detection limit deteriorated to 180 ppb m, due to temperature drift caused by optical interferences generated by reflections in the laser TO8 can.

  1. A Microporous Metal-Organic Framework with Lewis Basic Nitrogen Sites for High C2H2 Storage and Significantly Enhanced C2H2/CO2 Separation at Ambient Conditions.

    PubMed

    Wen, Hui-Min; Wang, Huizhen; Li, Bin; Cui, Yuanjing; Wang, Hailong; Qian, Guodong; Chen, Banglin

    2016-08-01

    A novel metal-organic framework (MOF), [Cu2L(H2O)2]·7DMF·4H2O [ZJU-40; H4L = 5,5'-(pyrazine-2,5-diyl)diisophthalic acid], with Lewis basic nitrogen sites has been constructed and structurally characterized. Owing to the combined features of high porosity, moderate pore sizes, and immobilized Lewis basic nitrogen sites, the activated ZJU-40a exhibits the second-highest gravimetric C2H2 uptake of 216 cm(3) g(-1) (at 298 K and 1 bar) among all of the reported MOFs so far. This value is not only much higher than that of the isoreticular NOTT-101a (184 cm(3) g(-1)), but also superior to those of two very promising MOFs, known as HKUST-1 (201 cm(3) g(-1)) and Co-MOF-74 (197 cm(3) g(-1)). Interestingly, the immobilized nitrogen sites in ZJU-40a have nearly no effect on the CO2 uptake, so ZJU-40a adsorbs a similar amount of CO2 (87 cm(3) g(-1)) compared with NOTT-101a (84 cm(3) g(-1)) at 298 K and 1 bar. As a result, ZJU-40a shows significantly enhanced adsorption selectivity for C2H2/CO2 separation (17-11.5) at ambient temperature compared to that of NOTT-101a (8-9), leading to a superior MOF material for highly selective C2H2/CO2 separation. PMID:27176900

  2. Structure and infrared absorption of the first layer C2H2 on the NaCl(100) single-crystal surface.

    PubMed

    Cabello-Cartagena, A G; Vogt, J; Weiss, H

    2010-02-21

    The adsorbate structure of the first layer acetylene on the NaCl(100) single-crystal surface is investigated using polarization infrared spectroscopy in combination with low-energy electron diffraction (LEED) experiments, and potential calculations on the basis of pair potentials. In agreement with a previous study, a triplet of infrared absorptions in the region of the asymmetric stretch vibration of C(2)H(2) was observed and assigned to an adsorbate phase with (3 square root 2 x square root 2)R45 degrees translational symmetry determined in the LEED experiment. The polarization dependence of the infrared spectra is consistent with a parallel orientation of the molecules with respect to the surface. The number of molecules per unit cell is four to six as determined by photometric considerations. Total energy minimizations support a new structure model which contains five inequivalent molecules per unit cell in a herringbone arrangement. The application of a vibrational exciton approach demonstrates that this new structure model can reproduce the triplet spectrum observed in the infrared experiments. PMID:20170243

  3. Herbivory responsive C2H2 zinc finger transcription factor protein StZFP2 from potato.

    PubMed

    Lawrence, Susan D; Novak, Nicole G; Jones, Richard W; Farrar, Robert R; Blackburn, Michael B

    2014-07-01

    While C2H2 zinc finger transcription factors (TF) are often regulated by abiotic stress, their role during insect infestation has been overlooked. This study demonstrates that the transcripts of the zinc finger transcription factors StZFP1 and StZFP2 are induced in potato (Solanum tuberosum L.) upon infestation by either the generalist tobacco hornworm (THW, Manduca sexta L.) or the specialist Colorado potato beetle (CPB, Leptinotarsa decemlineata Say). StZFP1 has been previously characterized as conferring salt tolerance to transgenic tobacco and its transcript is induced by Phytophthora infestans and several abiotic stresses. StZFP2 has not been characterized previously, but contains the hallmarks of a C2H2 zinc finger TF, with two conserved zinc finger domains and DLN motif, which encodes a transcriptional repressor domain. Expression studies demonstrate that StZFP2 transcript is also induced by tobacco hornworm and Colorado potato beetle. These observations expand the role of the C2H2 transcription factor in potato to include the response to chewing insect pests. PMID:24811678

  4. First-principles analysis of C2H2 molecule diffusion and its dissociation process on the ferromagnetic bcc-Fe(110) surface

    NASA Astrophysics Data System (ADS)

    Ikeda, Minoru; Yamasaki, Takahiro; Kaneta, Chioko

    2010-09-01

    Using the projector-augmented plane wave method, we study diffusion and dissociation processes of C2H2 molecules on the ferromagnetic bcc-Fe(110) surface and investigate the formation process of graphene created by C2H2 molecules. The most stable site for C2H2 on the Fe surface is a hollow site and its adsorption energy is - 3.5 eV. In order to study the diffusion process of the C2H2 molecule, the barrier height energies for the C atom, C2-dimer and CH as well as the C2H2 molecule are estimated using the nudged elastic band method. The barrier height energy for C2H2 is 0.71 eV and this indicates that the C2H2 diffuses easily on this FM bcc-Fe(110) surface. We further investigate the two step dissociation process of C2H2 on Fe. The first step is the dissociation of C2H2 into C2H and H, and the second step is that of C2H into C2 and H. Their dissociation energies are 0.9 and 1.2 eV, respectively. These energies are relatively small compared to the dissociation energy 7.5 eV of C2H2 into C2H and H in the vacuum. Thus, the Fe surface shows catalytic effects. We further investigate the initial formation process of graphene by increasing the coverage of C2H2. The formation process of the benzene molecule on the FM bcc(110) surface is also discussed. We find that there exists a critical coverage of C2H2 which characterizes the beginning of the formation of the graphene.

  5. 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.

  6. High acetylene/ethylene separation in a microporous zinc(II) metal-organic framework with low binding energy.

    PubMed

    Wen, Hui-Min; Li, Bin; Wang, Hailong; Krishna, Rajamani; Chen, Banglin

    2016-01-21

    A novel zinc(II) metal-organic framework UTSA-67a with narrow one-dimensional (1D) pore channels and inner cages of moderate size has been developed for highly selective separation of C2H2/C2H4 mixtures at room temperature. PMID:26597048

  7. A Soybean C2H2-Type Zinc Finger Gene GmZF1 Enhanced Cold Tolerance in Transgenic Arabidopsis

    PubMed Central

    Ma, Xue-Feng; Xu, Zhao-Shi; Liu, Meng-Meng; Shan, Shu-Guang; Cheng, Xian-Guo

    2014-01-01

    Zinc finger proteins were involved in response to different environmental stresses in plant species. A typical Cys2/His2-type (C2H2-type) zinc finger gene GmZF1 from soybean was isolated and was composed of 172 amino acids containing two conserved C2H2-type zinc finger domains. Phylogenetic analysis showed that GmZF1 was clustered on the same branch with six C2H2-type ZFPs from dicotyledonous plants excepting for GsZFP1, and distinguished those from monocotyledon species. The GmZF1 protein was localized at the nucleus, and has specific binding activity with EP1S core sequence, and nucleotide mutation in the core sequence of EPSPS promoter changed the binding ability between GmZF1 protein and core DNA element, implying that two amino acid residues, G and C boxed in core sequence TGACAGTGTCA possibly play positive regulation role in recognizing DNA-binding sites in GmZF1 proteins. High accumulation of GmZF1 mRNA induced by exogenous ABA suggested that GmZF1 was involved in an ABA-dependent signal transduction pathway. Over-expression of GmZF1 significantly improved the contents of proline and soluble sugar and decreased the MDA contents in the transgenic lines exposed to cold stress, indicating that transgenic Arabidopsis carrying GmZF1 gene have adaptive mechanisms to cold stress. Over-expression of GmZF1 also increased the expression of cold-regulated cor6.6 gene by probably recognizing protein-DNA binding sites, suggesting that GmZF1 from soybean could enhance the tolerance of Arabidopsis to cold stress by regulating expression of cold-regulation gene in the transgenic Arabidopsis. PMID:25286048

  8. Detection of HCN and C2H2 in ISO Spectra of Oxygen-Rich AGB Stars

    NASA Technical Reports Server (NTRS)

    Carbon, Duane F.; Chiar, Jean; Goorvitch, David; Kwak, Dochan (Technical Monitor)

    2002-01-01

    Cool oxygen-rich AGB stars were not expected to have organic molecules like HCN in either their photospheres or circumstellar envelopes (CSEs). The discovery of HCN and CS microwave emission from the shallowest CSE layers of these stars was a considerable surprise and much theoretical effort has been expended in explaining the presence of such organics. To further explore this problem, we have undertaken a systematic search of oxygen-rich AGB stellar spectra in the Infrared Space Observatory (ISO) data archive. Our purposes are to find evidence regarding critical molecular species that could be of value in choosing among the proposed theoretical models, to locate spectral features which might give clues to conditions deeper in the CSEs, and to lay the groundwork for future SIRTF (Space Infrared Telescope Facility) and SOFIA (Stratospheric Observatory for Infrared Astronomy) observations. Using carefully reduced observations, we have detected weak absorption features arising from HCN and possibly C2H2 in a small number of oxygen-rich AGB stars. The most compelling case is NML Cyg which shows both HCN (14 microns) and CO2 (15 microns). VY CMa, a similar star, shows evidence for HCN, but not CO2. Two S-type stars show evidence for the C-H bending transitions: W Aql at 14 microns (HCN) and both W Aql and S Cas at 13.7 microns (C2H2). Both W Aql and S Cas as well as S Lyr, a SC-type star, show 3 micron absorption which may arise from the C-H stretch of HCN and C2H2. In the case of NML Cyg, we show that the HCN and CO2 spectral features are formed in the CSE at temperatures well above those of the outermost CSE layers and derive approximate column densities. In the case of the S-stars, we discuss the evidence for the organic features and their photospheric origin.

  9. Probing the outer atmosphere of carbon stars - C2H2, HCN and C3 features in the SWS range

    NASA Astrophysics Data System (ADS)

    Loidl, R.; Hron, J.; Jorgensen, U. G.; Höfner, S.

    2000-11-01

    We have obtained ISO-SWS spectra of a number of carbon-rich AGB stars in the wavelength range 2.4 - 44 μm with a resolution of about 400. We compare these spectra with results of hydrostatic and dynamic model atmospheres. Of special interest are the features which are formed far out in the atmosphere like the C2H2, HCN and C3 features. For these outer regions of the atmosphere deviations from hydrostatic structures are to be expected.

  10. Infrared band extinctions and complex refractive indices of crystalline C2H2 and C4H2

    NASA Astrophysics Data System (ADS)

    Khanna, R. K.; Ospina, Mario J.; Zhao, Guizhi

    1988-03-01

    Thermal IR absorption intensities are obtained for thin films of crystalline C2H2 and C4H2 at 70 K, and their n and k complex refractive indices are ascertained by separating true film absorption from interface reflection on the basis of an analysis of the transmission spectrum ratio for two sample thicknesses. This method significantly simplifies the n and k iteration process. The n and k values determined in the laboratory will in most cases reproduce a given sample thickness' observed transmission to within + or - 5 percent.

  11. Infrared band extinctions and complex refractive indices of crystalline C2H2 and C4H2

    NASA Technical Reports Server (NTRS)

    Khanna, R. K.; Ospina, Mario J.; Zhao, Guizhi

    1988-01-01

    Thermal IR absorption intensities are obtained for thin films of crystalline C2H2 and C4H2 at 70 K, and their n and k complex refractive indices are ascertained by separating true film absorption from interface reflection on the basis of an analysis of the transmission spectrum ratio for two sample thicknesses. This method significantly simplifies the n and k iteration process. The n and k values determined in the laboratory will in most cases reproduce a given sample thickness' observed transmission to within + or - 5 percent.

  12. 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.

  13. Communication: An accurate calculation of the S1 C2H2 cis-trans isomerization barrier height

    NASA Astrophysics Data System (ADS)

    Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.

    2016-03-01

    A high level ab initio calculation of the cis-trans isomerization barrier height in the first excited singlet electronic state of acetylene is found to agree very well with a recent experimental determination.

  14. [Cloning and functional analysis of SCTF-1 encoding a C2H2-type Zinc finger protein from soybean].

    PubMed

    Song, Bing; Wang, Pi-Wu; Fu, Yong-Ping; Fan, Xu-Hong; Xia, Hai-Feng; Gao, Wei; Hong, Yang; Wang, He; Zhang, Zhuo; Ma, Jian

    2012-06-01

    The zinc finger protein is one of the proteins with finger-like domain. Some of them are transcription factors which play important role in plant growth and plant resistance to abiotic stresses. In this paper, a novel C2H2-type zinc finger protein gene SCTF-1 (GenBank accession number JQ692081) was isolated from soybean (Glycine max (L.) Merr.) This gene has a 699 bp ORF (open reading frame) with no intron and encodes a 24.9 kDa protein with 233 amino acids. Its isoelectric point (pI) is 8.33. The SCTF-1 protein contains two typical C2H2-type zinc finger domains. Both of them have highly conserved amino acid sequence-QALGGH which is a particular characteristic of plant. Transient expression of the GFP-SCTF-1 protein in onion epidermal cell showed that SCTF-1 was localized in cell nuclei. RT-PCR results showed that SCTF-1 gene was expressed with high levels in flowers and leaves in soybean, but low in roots and stems. The expression of SCTF-1 gene was strongly induced by low temperature in the soybean seedlings. Overexpression of SCTF-1 enhanced cold tolerance of transgenic tobacco (Nicotiana tabacum L.) compared to the control. PMID:22698747

  15. Permutationally invariant fitting of intermolecular potential energy surfaces: A case study of the Ne-C2H2 system

    NASA Astrophysics Data System (ADS)

    Li, Jun; Guo, Hua

    2015-12-01

    The permutation invariant polynomial-neural network (PIP-NN) approach is extended to fit intermolecular potential energy surfaces (PESs). Specifically, three PESs were constructed for the Ne-C2H2 system. PES1 is a full nine-dimensional PIP-NN PES directly fitted to ˜42 000 ab initio points calculated at the level of CCSD(T)-F12a/cc-pCVTZ-F12, while the other two consist of the six-dimensional PES for C2H2 [H. Han, A. Li, and H. Guo, J. Chem. Phys. 141, 244312 (2014)] and an intermolecular PES represented in either the PIP (PES2) or PIP-NN (PES3) form. The comparison of fitting errors and their distributions, one-dimensional cuts and two-dimensional contour plots of the PESs, as well as classical trajectory collisional energy transfer dynamics calculations shows that the three PESs are very similar. We conclude that full-dimensional PESs for non-covalent interacting molecular systems can be constructed efficiently and accurately by the PIP-NN approach for both the constituent molecules and intermolecular parts.

  16. Re-analysis of the high resolution FTIR spectrum of C2H2D2-cis in the region of 1280-1400 cm-1

    NASA Astrophysics Data System (ADS)

    Ulenikov, O. N.; Gromova, O. V.; Bekhtereva, E. S.; Konov, I. A.; Chertavskikh, Yu. V.; Maul, C.; Bauerecker, S.

    2016-02-01

    The high-resolution infrared spectrum of C2H2D2-cis ethylene was analyzed in the region of 1280-1400 cm-1, where the strong ν12 band is located. More than 2000 transitions (about three times more than it was made in the preceding studies) were assigned with the maximum values of the upper quantum numbers Jmax. = 45 and Kamax. = 19 (Jmax. = 31 and Kamax . = 13 in the preceding studies). For the first time, 22 transitions belonging to the 2ν10 weak band were assigned. For description of the assigned transitions (upper ro-vibrational energy levels), the Hamiltonian model was used which takes into account resonance interactions between the vibrational state (v12 = 1) and three other closely located states: (v10 = 2), (v8 =v10 = 1), and (v3 = 1). A set of 43 spectroscopic parameters obtained from a weighted least square fit reproduces the initial experimental data (817 upper energy values and more than 2000 transitions) with the drms = 2.2 ×10-4cm-1 which is close to experimental uncertainties and considerably better than in prior studies. Ground state rotational and centrifugal distortion parameters were improved on the basis of the IR experimental data of the present study and microwave data from the earlier literature.

  17. Genome-Wide Analysis of C2H2 Zinc-Finger Family Transcription Factors and Their Responses to Abiotic Stresses in Poplar (Populus trichocarpa)

    PubMed Central

    Liu, Quangang; Wang, Zhanchao; Xu, Xuemei; Zhang, Haizhen; Li, Chenghao

    2015-01-01

    Background C2H2 zinc-finger (C2H2-ZF) proteins are a large gene family in plants that participate in various aspects of normal plant growth and development, as well as in biotic and abiotic stress responses. To date, no overall analysis incorporating evolutionary history and expression profiling of the C2H2-ZF gene family in model tree species poplar (Populus trichocarpa) has been reported. Principal Findings Here, we identified 109 full-length C2H2-ZF genes in P. trichocarpa, and classified them into four groups, based on phylogenetic analysis. The 109 C2H2-ZF genes were distributed unequally on 19 P. trichocarpa linkage groups (LGs), with 39 segmental duplication events, indicating that segmental duplication has been important in the expansion of the C2H2-ZF gene family. Promoter cis-element analysis indicated that most of the C2H2-ZF genes contain phytohormone or abiotic stress-related cis-elements. The expression patterns of C2H2-ZF genes, based on heatmap analysis, suggested that C2H2-ZF genes are involved in tissue and organ development, especially root and floral development. Expression analysis based on quantitative real-time reverse transcription polymerase chain reaction indicated that C2H2-ZF genes are significantly involved in drought, heat and salt response, possibly via different mechanisms. Conclusions This study provides a thorough overview of the P. trichocarpa C2H2-ZF gene family and presents a new perspective on the evolution of this gene family. In particular, some C2H2-ZF genes may be involved in environmental stress tolerance regulation. PtrZFP2, 19 and 95 showed high expression levels in leaves and/or roots under environmental stresses. Additionally, this study provided a solid foundation for studying the biological roles of C2H2-ZF genes in Populus growth and development. These results form the basis for further investigation of the roles of these candidate genes and for future genetic engineering and gene functional studies in Populus. PMID

  18. Ab initio intermolecular potential of Ar-C2H2 refined using high-resolution spectroscopic data.

    PubMed

    Lauzin, Clément; Coudert, Laurent H; Herman, Michel; Liévin, Jacques

    2013-12-19

    The high-resolution infrared spectra of the ν1 + ν3 (2CH) band of the Ar-C2H2 complex has been recorded from 6544 to 6566 cm(-1). The previously reported K(a) = 1 ← 0, 2 ← 1, and 0 ← 1 subbands were observed and the K(a) = 1 ← 2, 2 ← 3, and 3 ← 2 subbands were assigned for the first time. The intermolecular potential energy surface of this complex has been calculated ab initio and optimized by fitting the new high-resolution data. Refined intermolecular potential energy surfaces have been obtained for the ground vibrational state and for the excited v1 = v3 = 1 stretching state. For the former state, the results of the analysis are satisfactory and the microwave transitions of the complex are reproduced with a root-mean-square deviation of 5 MHz. For the latter state, systematic discrepancies arise in the analysis. PMID:24111882

  19. Calculating the properties of C2H2-C9H16 alkynes, based on the additivity of energy contributions

    NASA Astrophysics Data System (ADS)

    Smolyakov, V. M.; Grebeshkov, V. V.

    2015-05-01

    A ten-constant additive model is obtained for calculating the physicochemical properties of a number of C n H2 n-2 alkynes, based on the group additivity method (with allowance for the initial atomic environment), two topological indices that allow for the second atomic environment, and pairwise non-valence interactions (in implicit form) between three atoms, four atoms, and so forth along the chain of a molecule. Two linear dependences are revealed. The obtained formula is used for numerical calculations of the normal heats of vaporization L NBT and normal boiling temperatures T b of C2H2-C9H16 alkynes, neither of which had been studied experimentally.

  20. Temperature dependent product yields for the spin forbidden singlet channel of the C(3P) + C2H2 reaction

    NASA Astrophysics Data System (ADS)

    Hickson, Kevin M.; Loison, Jean-Christophe; Wakelam, Valentine

    2016-08-01

    The atomic hydrogen formation channels of the C + C2H2 reaction have been investigated using a continuous supersonic flow reactor over the 52-296 K temperature range. H-atoms were detected directly at 121.567 nm by vacuum ultraviolet laser induced fluorescence. Absolute H-atom yields were determined by comparison with the H-atom signal generated by the C + C2H4 reaction. The product yields agree with earlier crossed beam experiments employing universal detection methods. Incorporating these branching ratios in a gas-grain model of dense interstellar clouds increases the c-C3H abundance. This reaction is a minor source of C3-containing molecules in the present simulations.

  1. Species-specific expansion of C2H2 zinc-finger genes and their expression profiles in silkworm, Bombyx mori.

    PubMed

    Duan, Jun; Xia, Qingyou; Cheng, Daojun; Zha, Xingfu; Zhao, Ping; Xiang, Zhonghuai

    2008-12-01

    Most C2H2 zinc-finger proteins (ZFPs) function as sequence-specific DNA-binding transcription factors, and play important roles in a variety of biology processes, such as development, differentiation, and tumor suppression. By searching the silkworm genome with a HMM model of C2H2 zinc-fingers, we have identified a total of 338 C2H2 ZFPs. Most of the ZFP genes were clustered on chromosomes and showed uneven distribution in the genome. Over one third of genes were concentrated on chromosome 11, 15 and 24. Phylogenetic analysis classified all silkworm C2H2 ZFPs into 75 families; 63 of which belong to evolutionarily conserved families. In addition, 188 C2H2 ZFP genes (55.6%) are species-specific to the silkworm. A species-specific expansion of a family with 39 members in a tandem array on chromosome 24 may explain the higher number of species-specific ZFPs in silkworm compared to other organisms. The expression patterns of C2H2 ZFP genes were also examined by microarray analysis. Most of these genes were actively expressed among different tissues on day 3 of the fifth instar. The results provide insight into the biological functions of the silkworm C2H2 ZFP genes in metamorphism and development. PMID:18835444

  2. Scattering cross sections for electrons in C2 H2F4 and its mixtures with Ar from measured transport coefficients

    NASA Astrophysics Data System (ADS)

    Šašić, Olivera; Dupljanin, Snježana; de Urquijo, Jaime; Petrović, Zoran Lj

    2013-08-01

    Previous measurements of the drift velocities, W, and the density-normalized effective ionization (multiplication) coefficients (ionization minus attachment), (α - η)/N, measured in C2H2F4 (1,1,1,2 tetrafluoroethane) and in C2H2F4-Ar mixtures have been analysed with a standard swarm procedure. As a result of this analysis a set of electron collision cross sections for the C2H2F4 molecule has been obtained. This set has been further used to calculate other transport parameters such as the characteristic energies and rate coefficients for individual processes.

  3. Covariance mapping of two-photon double core hole states in C2H2 and C2H6 produced by an x-ray free electron laser

    NASA Astrophysics Data System (ADS)

    Mucke, M.; Zhaunerchyk, V.; Frasinski, L. J.; Squibb, R. J.; Siano, M.; Eland, J. H. D.; Linusson, P.; Salén, P.; Meulen, P. v. d.; Thomas, R. D.; Larsson, M.; Foucar, L.; Ullrich, J.; Motomura, K.; Mondal, S.; Ueda, K.; Osipov, T.; Fang, L.; Murphy, B. F.; Berrah, N.; Bostedt, C.; Bozek, J. D.; Schorb, S.; Messerschmidt, M.; Glownia, J. M.; Cryan, J. P.; Coffee, R. N.; Takahashi, O.; Wada, S.; Piancastelli, M. N.; Richter, R.; Prince, K. C.; Feifel, R.

    2015-07-01

    Few-photon ionization and relaxation processes in acetylene (C2H2) and ethane (C2H6) were investigated at the linac coherent light source x-ray free electron laser (FEL) at SLAC, Stanford using a highly efficient multi-particle correlation spectroscopy technique based on a magnetic bottle. The analysis method of covariance mapping has been applied and enhanced, allowing us to identify electron pairs associated with double core hole (DCH) production and competing multiple ionization processes including Auger decay sequences. The experimental technique and the analysis procedure are discussed in the light of earlier investigations of DCH studies carried out at the same FEL and at third generation synchrotron radiation sources. In particular, we demonstrate the capability of the covariance mapping technique to disentangle the formation of molecular DCH states which is barely feasible with conventional electron spectroscopy methods.

  4. Covariance mapping of two-photon double core hole states in C 2 H 2 and C 2 H 6 produced by an x-ray free electron laser

    DOE PAGESBeta

    Mucke, M; Zhaunerchyk, V; Frasinski, L J; Squibb, R J; Siano, M; Eland, J H D; Linusson, P; Salén, P; Meulen, P v d; Thomas, R D; et al

    2015-07-01

    Few-photon ionization and relaxation processes in acetylene (C2H2) and ethane (C2H6) were investigated at the linac coherent light source x-ray free electron laser (FEL) at SLAC, Stanford using a highly efficient multi-particle correlation spectroscopy technique based on a magnetic bottle. The analysis method of covariance mapping has been applied and enhanced, allowing us to identify electron pairs associated with double core hole (DCH) production and competing multiple ionization processes including Auger decay sequences. The experimental technique and the analysis procedure are discussed in the light of earlier investigations of DCH studies carried out at the same FEL and at thirdmore » generation synchrotron radiation sources. In particular, we demonstrate the capability of the covariance mapping technique to disentangle the formation of molecular DCH states which is barely feasible with conventional electron spectroscopy methods.« less

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

    PubMed Central

    Gerbaud, Alain

    1990-01-01

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

  6. Hydrogenation of Acetylene-Ethylene Mixtures over Pd and Pd-Ag Alloys: First-Principles Based Kinetic Monte Carlo Simulations

    SciTech Connect

    Mei, Donghai; Neurock, Matthew; Smith, C Michael

    2009-10-22

    The kinetics for the selective hydrogenation of acetylene-ethylene mixtures over model Pd(111) and bimetallic Pd-Ag alloy surfaces were examined using first principles based kinetic Monte Carlo (KMC) simulations to elucidate the effects of alloying as well as process conditions (temperature and hydrogen partial pressure). The mechanisms that control the selective and unselective routes which included hydrogenation, dehydrogenation and C-C bond breaking pathways were analyzed using first-principle density functional theory (DFT) calculations. The results were used to construct an intrinsic kinetic database that was used in a variable time step kinetic Monte Carlo simulation to follow the kinetics and the molecular transformations in the selective hydrogenation of acetylene-ethylene feeds over Pd and Pd-Ag surfaces. The lateral interactions between coadsorbates that occur through-surface and through-space were estimated using DFT-parameterized bond order conservation and van der Waal interaction models respectively. The simulation results show that the rate of acetylene hydrogenation as well as the ethylene selectivity increase with temperature over both the Pd(111) and the Pd-Ag/Pd(111) alloy surfaces. The selective hydrogenation of acetylene to ethylene proceeds via the formation of a vinyl intermediate. The unselective formation of ethane is the result of the over-hydrogenation of ethylene as well as over-hydrogenation of vinyl to form ethylidene. Ethylidene further hydrogenates to form ethane and dehydrogenates to form ethylidyne. While ethylidyne is not reactive, it can block adsorption sites which limit the availability of hydrogen on the surface and thus act to enhance the selectivity. Alloying Ag into the Pd surface decreases the overall rated but increases the ethylene selectivity significantly by promoting the selective hydrogenation of vinyl to ethylene and concomitantly suppressing the unselective path involving the hydrogenation of vinyl to ethylidene

  7. An aminopyrimidine-functionalized cage-based metal-organic framework exhibiting highly selective adsorption of C2H2 and CO2 over CH4.

    PubMed

    Jiao, Jingjing; Dou, Li; Liu, Huimin; Chen, Fengli; Bai, Dongjie; Feng, Yunlong; Xiong, Shunshun; Chen, De-Li; He, Yabing

    2016-09-14

    There has been considerable interest in adsorptive separation of C2H2/CH4 and CO2/CH4 gas mixtures due to its industrial significance and scientific challenge. In this work, we have designed and synthesized a bent diisophthalate ligand functionalized with aminopyrimidine groups, and constructed via a solvothermal reaction, a porous copper-based framework. Single-crystal X-ray diffraction studies show that the framework is a three-dimensional network containing three different types of polyhedral nanocages, which are stacked together to form two distinct types of one-dimensional channels along the crystallographic c axis. The compound after activation shows exceptionally high C2H2 and CO2 uptakes of 211 and 120 cm(3) (STP) g(-1) at 295 K and 1 atm, as well as impressive adsorption selectivities towards C2H2 and CO2 over CH4. High C2H2 and CO2 uptake capacities as well as significant adsorption selectivities of C2H2 and CO2 over CH4 imply potential applications in the adsorptive separation and purification of C2H2/CH4 and CO2/CH4 gas mixtures, which have been verified by column breakthrough experiments. Several important binding sites for C2H2 and CO2 in ZJNU-54 were revealed by quantum chemical calculations, demonstrating that the organic linkers in ZJNU-54 form unique structures that facilitate the adsorption of C2H2, while the amine groups and the Lewis basic pyrimidine-ring nitrogen sites in the organic linker improve the adsorption energies for CO2, finally leading to the increase of adsorption capacities for these two gas molecules. This work provides an efficient strategy for incorporating specific functional groups into cage-based MOFs for generating new adsorbents for highly selective gas storage and separation. PMID:27483189

  8. Genome-wide identification and expression profiling of the C2H2-type zinc finger protein transcription factor family in tobacco.

    PubMed

    Minglei, Yang; Jiangtao, Chao; Dawei, Wang; Junhua, Hu; Hua, Wu; Daping, Gong; Guanshan, Liu

    2016-04-01

    C2H2 zinc finger protein transcription factor family members have important biological functions in eukaryotes. They not only bind DNA and RNA, but also interact with proteins. In this study, 118 members of the tobacco C2H2 zinc finger protein transcription factor family were identified from the N. tabacum genome database by using Pfam, SMART and Blastp. The analyses of phylogenetic tree, physical and chemical properties, chromosomal mapping, gene structures, protein three-dimensional structures and tissue expression patterns were performed. The results suggested that the peptide length of different subfamily members is significantly different. Phylogenetic and motif analysis revealed that the C2H2 zinc finger protein transcription factor family members can be divided into 5 subfamilies and each member has at least one C2H2 motif. Genes of the family members are distributed across the 22 chromosomes. C2H2 zinc finger protein transcription factor family members are expressed in different tissues although some have higher expression levels in leaves and roots. This study will be helpful for further analysis of the C2H2 zinc finger family proteins in other plants. PMID:27103457

  9. Photochemical deactivation process of HCFC-133a (C2H2F3Cl): a nonadiabatic dynamics study.

    PubMed

    Pereira Rodrigues, Gessenildo; Ventura, Elizete; do Monte, Silmar Andrade; Barbatti, Mario

    2014-12-26

    The photochemical deactivation process of HCFC-133a (C2H2F3Cl) was investigated by computing excited-state properties with a number of single-reference methods, including coupled cluster to approximated second order (CC2), algebraic diagrammatic construction to second order (ADC(2)), and time-dependent density functional theory (TDDFT). Excited states calculated with these methods, especially TDDFT, show good agreement with our previous multireference configuration interaction (MR-CISD) results. All tested methods were able to correctly predict the properties of the main series of excited states, the n-σ*, n-4p, and n-4s. Nonadiabatic dynamics in the gas phase considering 14 electronic states was simulated with TDDFT starting at the 10 ± 0.25 eV spectral window, to be compared to experimental data measured after 123.6 nm excitation. The excited-state lifetime is 137 fs. Internal conversion to the ground state occurred through several different reaction pathways with different products, including atomic elimination (Cl, F, or H), multifragmentation mechanisms (Cl+F, Cl+H, or F+H), and CC bond-fission mechanisms (alone or with Cl or H elimination). The main photochemical channels observed were Cl, Cl+H, and Cl+F eliminations, representing 54% of all processes. PMID:25310281

  10. Self-, N2- and Ar-broadening and line mixing in HCN and C2H2

    NASA Technical Reports Server (NTRS)

    Pine, A. S.

    1993-01-01

    Self-, N2- and Ar-broadening coefficients were measured for the stretch-bend infrared combination bands nu-1 + nu-1/2 (4004/cm) of HCN and nu-1 + nu-1/5 (4091/cm) of C2H2, using a tunable difference-frequency laser. At atmospheric pressures, the Q branches of these bands exhibit significant rotational narrowing or line mixing. The broadening coefficients are fit with empirical rotationally inelastic collision rate laws, which are then used to model the line mixing in the overlapped Q-branch profiles. Simple energy gap fitting laws appear to be suitable for the shorter-range intermolecular quadrupole-quadrupole and induction forces, whereas an energy-corrected-sudden scaling law works better for the longer-range dipole-dipole and dipole-quadrupole collision partners. In all cases, the line-coupling coefficients are substantially reduced from the rotationally inelastic rates fit to the broadening coefficients, indicating that 35-70 percent of the broadening may be due to other collisional mechanisms such as cross-relaxation to the degenerate H state vibrational level.

  11. Molecular Frame Photoelectron Angular Distributions for Core Ionization of CF4 and C2H2F2

    NASA Astrophysics Data System (ADS)

    Trevisan, C. S.; Williams, J. B.; Menssen, A. J.; Rescigno, T. N.; Dorner, R.; McCurdy, C. W.

    2015-05-01

    We present experimental and theoretical results for the angular dependence of electrons ejected from the core orbitals of tetrafluoromethane (CF4) which display a tendency to avoid molecular bonds if averaged over directions of polarization of the incident X-ray beam, in contrast to earlier cases (CH4, H2O and NH3) studied by the same methods. To investigate whether the imaging effect can be used to detect the creation of core holes by photoionization from one of two atoms of the same type in a molecule, we computed and measured MFPADs of difluoroethylene (C2H2F2). Good agreement with the experimentally measured angular distributions show that the MFPADs contain the clear signature of the core-hole origin of the photoelectron, and validate the use of computed MFPADs as promising tools for the interpretation of such experiments. Our measurements employ the COLTRIMS method and the calculations were performed with the Complex Kohn Variational method. Work supported in part by the USDOE, Office of Science, Office of WDTS under the Visiting Faculty Program.

  12. Buckybowls as adsorbents for CO2, CH4, and C2H2: Binding and structural insights from computational study.

    PubMed

    Hussain, M Althaf; Vijay, Dolly; Sastry, G Narahari

    2016-01-30

    Noncovalent functionalization of buckybowls sumanene (S), corannulene (R), and coronene (C) with greenhouse gases (GGs) such as CO2 , CH4 (M), and C2 H2 (A) has been studied using hybrid density functional theory. The propensity and preferences of these small molecules to interact with the concave and convex surfaces of the buckybowls has been quantitatively estimated. The results indicate that curvature plays a significant role in the adsorption of these small molecules on the π surface and it is observed that buckybowls have higher binding energies (BEs) compared with their planar counterpart coronene. The concave surface of the buckybowl is found to be more feasible for adsorption of small molecules. BEs of small molecules towards π systems is CO2  > A > M and the BEs of π systems toward small molecules is S > R > C. Obviously, the binding preference is dictated by the way in which various noncovalent interactions, such as π···π, lone pair···π, and CH···π manifest themselves on carbaneous surfaces. To delineate the intricate details of the interactions, we have employed Bader's quantum theory of atoms in molecule and localized molecular orbital energy decomposition analysis (LMO-EDA). LMO-EDA, which measures the contribution of various components and traces the physical origin of the interactions, indicates that the complexes are stabilized largely by dispersion interactions. PMID:26519620

  13. Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Nava, D. F.; Borokowski, R. P.; Payne, W. A.; Stief, L. J.

    1980-01-01

    The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.

  14. In situ spectroscopic characterization of Ni1-xZnx/ZnO catalysts and their selectivity for acetylene semihydrogenation in excess ethylene

    SciTech Connect

    Spanjers, Charles S.; Sim, Richard S.; Sturgis, Nicholas P.; Kabius, Bernd; Rioux, Robert M.

    2015-10-30

    The structures of ZnO-supported Ni catalysts were explored with in situ X-ray absorption spectroscopy, temperature-programmed reduction, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy, and electron energy loss spectroscopy. Calcination of nickel nitrate on a nanoparticulate ZnO support at 450 °C results in the formation of Zn-doped NiO (ca. N₀̣̣₈₅ Zn₀̣̣₁₅O) nanoparticles with the rock salt crystal structure. Subsequent in situ reduction monitored by X-ray absorption near-edge structure (XANES) at the Ni K edge reveals a direct transformation of the Zn-doped NiO nanoparticles to a face-centered cubic alloy, Ni1-xZnx, at ~400 °C with x increasing with increasing temperature. Both in situ XANES and ex situ HRTEM provide evidence for intermetallic β₁-NiZn formation at ~550 °C. In comparison to a Ni/SiO₂ catalyst, Ni/ZnO necessitates a higher temperature for the reduction of NiII to Ni⁰, which highlights the strong interaction between Ni and the ZnO support. The catalytic activity for acetylene removal from an ethylene feed stream is decreased by a factor of 20 on Ni/ZnO in comparison to Ni/SiO₂. The decrease in catalytic activity of Ni/ZnO is accompanied by a reduced absolute selectivity to ethylene. H–D exchange measurements demonstrate a reduced ability of Ni/ZnO to dissociate hydrogen in comparison to Ni/SiO₂.These results of the catalytic experiments suggest that the catalytic properties are controlled, in part, by the zinc oxide support and stress the importance of reporting absolute ethylene selectivity for the catalytic semihydrogenation of acetylene in excess ethylene.

  15. A C2H2 Zinc Finger Protein FEMU2 Is Required for fox1 Expression in Chlamydomonas reinhardtii

    PubMed Central

    Deng, Xiaodong; Yang, Jinghao; Wu, Xiaoxia; Li, YaJun; Fei, Xiaowen

    2014-01-01

    Chlamydomonas reinhardtii fox1 gene encodes a ferroxidase that is involved in cellular Fe uptake and highly induced during Fe deficient conditions. In an effort to identify fox1 promoter regulatory elements, an insertional library was generated in a transgenic Chlamydomonas strain (2A38) harboring an arylsulfatase (ARS) reporter gene driven by the fox1 promoter. Mutants with a defective response to low iron conditions were selected for further study. Among these, a strain containing a disrupted femu2 gene was identified. Activation of the fox1 promoter by the femu2 gene product was confirmed by silencing the femu2 gene using RNA interference. In three femu2 RNAi transgenic lines (IR3, IR6, and IR7), ARS reporter gene activities declined by 84.3%, 86.4%, and 88.8%, respectively under Fe deficient conditions. Furthermore, RT-PCR analysis of both the femu2 mutant and the RNAi transgenic lines showed significantly decreased transcript abundance of the endogenous fox1 gene under Fe deficient conditions. Amino acid sequence analysis of the femu2 gene product identified three potential C2H2 zinc finger (ZF) motifs and a nuclear localization study suggests that FEMU2 is localized to the nucleus. In addition, a potential FEMU2 binding site ((G/T)TTGG(G/T)(G/T)T) was identified using PCR-mediated random binding site selection. Taken together, this evidence suggests that FEMU2 is involved in up-regulation of the fox1 gene in Fe deficient cells. PMID:25485540

  16. Global distributions of C2H6, C2H2, HCN, and PAN retrieved from MIPAS reduced spectral resolution measurements

    NASA Astrophysics Data System (ADS)

    Wiegele, A.; Glatthor, N.; Höpfner, M.; Grabowski, U.; Kellmann, S.; Linden, A.; Stiller, G.; von Clarmann, T.

    2011-08-01

    Vertical profiles of mixing ratios of C2H6, C2H2, HCN, and PAN were retrieved from MIPAS reduced spectral resolution nominal mode limb emission measurements. The retrieval strategy followed that of the analysis of MIPAS high resolution measurements, with occasional adjustments to cope with the reduced spectral resolution under which MIPAS is operated since 2005. Largest mixing ratios are found in the troposphere, and reach 1.2 ppbv for C2H6, 1 ppbv for HCN, 600 pptv for PAN, and 450 pptv for C2H2. The estimated precision in case of significantly enhanced mixing ratios (including measurement noise and propagation of uncertain parameters randomly varying in the time domain) and altitude resolution are typically 10 %, 3-4.5 km for C2H6, 15 %, 4-6 km for HCN, 6 %, 2.5-3.5 km for PAN, and 7 %, 2.5-4 km for C2H2.

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

    PubMed

    Kočišek, J; Lengyel, J; Fárník, M

    2013-03-28

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

  18. Distortions of ethyne when complexed with a cuprous or argentous halide: the rotational spectrum of C2H2CuF.

    PubMed

    Zaleski, Daniel P; Stephens, Susanna L; Tew, David P; Bittner, Dror M; Walker, Nicholas R; Legon, Anthony C

    2015-07-15

    A new molecule C2H2CuF has been synthesized in the gas phase by means of the reaction of laser-ablated metallic copper with a pulse of gas consisting of a dilute mixture of ethyne and sulfur hexafluoride in argon. The ground-state rotational spectrum was detected by two types of Fourier-transform microwave spectroscopy, namely that conducted in a microwave Fabry-Perot cavity and the chirped-pulse broadband technique. The spectroscopic constants of the six isotopologues (12)C2H2(63)Cu(19)F, (12)C2H2(65)Cu(19)F, (13)C2H2(63)Cu(19)F, (13)C2H2(65)Cu(19)F, (12)C2D2(63)Cu(19)F and (12)C2D2(65)Cu(19)F were determined and interpreted to show that the molecule has a planar, T-shaped geometry belonging to the molecular point group C2v, with CuF forming the stem of the T. Quantitative interpretation reveals that the ethyne molecule is distorted when subsumed into the complex in such manner that the C[triple bond, length as m-dash]C bond lengthens (by δr) and the two H atoms cease to be collinear with the C[triple bond, length as m-dash]C internuclear line. The H atoms move symmetrically away from the approaching Cu atom of CuF, to increase each *[triple bond, length as m-dash]C-H angle by δA = 14.65(2)°, from 180° to 194.65(2)°. Ab initio calculations at the explicitly-correlated level of theory CCSD(T)(F12*)/aug-cc-pVTZ lead to good agreement with the experimental geometry. It is shown that similar distortions δr and δA, similarly determined, for four complexes C2H2MX (M = Cu or Ag; X = F, Cl or CCH) are approximately linearly related to the energies De for the dissociation process C2H2MX = C2H2 + MX. PMID:26134582

  19. On the reactivity of plasma-treated photo-catalytic TiO2 surfaces for oxidation of C2H2 and CO

    NASA Astrophysics Data System (ADS)

    Lopatik, D.; Marinov, D.; Guaitella, O.; Rousseau, A.; Röpcke, J.

    2013-06-01

    The objective of this study is to understand fundamental aspects of interactions of plasmas with catalytic surfaces. Based on this approach the reactivity of plasma treated and stimulated catalytic surfaces of TiO2 is studied by analysing the oxidation (i) of C2H2 to CO and CO2 and (ii) of CO to CO2. The inner surface of a Pyrex discharge tube is coated with TiO2 films impregnated with TiO2 nanoparticles, which provides a surface area of about 4 m2. In addition to the exposure of the TiO2 surface by low-pressure radio-frequency plasmas using O2, Ar or N2 (f = 13.56 MHz, p = 0.53 mbar, P = 17 W) the surfaces are stimulated by heating and UV radiation treatment. The temporal development of the concentrations of the precursor gases C2H2 or CO and of the reaction products is monitored using quantum cascade laser absorption spectroscopy, which provides multi-component detection in the mid-infrared spectral range. The C2H2 concentration was found to be nearly constant over time after a pre-treatment with Ar or N2 discharges using an initial gas mixture of 1% C2H2 in Ar. However, a strong decay of the concentration of C2H2 is observed for pure O2 plasma pre-treatment. In general, the decay is found to be nearly exponential with time constant in the order of about 10 min. The reactive adsorption of C2H2 molecules on the inner surface of the tube reactor showed a density of about 7.5 × 1012 C2H2 molecules cm-2. This behaviour demonstrates that the reaction (O_{ads} +C_{2} H_{2})_{{TiO}_{2}} produces some adsorbed intermediates, which can be thermally or photo-catalytically oxidized to CO2. In contrast, when 1% CO in Ar is used as an initial gas mixture no adsorption processes on the TiO2 surface could be detected. An effective destruction of CO took part via photo-catalytic oxidation.

  20. Theoretical study of the C-H bond dissociation energies of CH4, C2H2, C2H4, and H2C2O

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

    The successive C-H bond dissociation energies of CH4, C2H2, C2H4, and H2C2O (ketene) are determined using large-basis sets and a high level of correlation treatment. For CH4, C2H2, and C2H4 the computed values are in excellent agreement with experiment. Using these results, the values 107.9 + or - 2.0 and 96.7 + or - 2.0 kcal/mol are recommended for the C-H bond dissociation energies of H2C2O and HC2O, respectively.

  1. Distortion of ethyne on coordination to silver acetylide, C2H2⋅⋅⋅AgCCH, characterised by broadband rotational spectroscopy and ab initio calculations.

    PubMed

    Stephens, Susanna L; Zaleski, Daniel P; Mizukami, Wataru; Tew, David P; Walker, Nicholas R; Legon, Anthony C

    2014-03-28

    The rotational spectra of six isotopologues of a complex of ethyne and silver acetylide, C2H2⋅⋅⋅AgCCH, are measured by both chirped-pulse and Fabry-Perot cavity versions of Fourier-transform microwave spectroscopy. The complex is generated through laser ablation of a silver target in the presence of a gas sample containing 1% C2H2, 1% SF6, and 98% Ar undergoing supersonic expansion. Rotational, A0, B0, C0, and centrifugal distortion ΔJ and ΔJK constants are determined for all isotopologues of C2H2⋅⋅⋅AgCCH studied. The geometry is planar, C2v and T-shaped in which the C2H2 sub-unit comprises the bar of the "T" and binds to the metal atom through its π electrons. In the r0 geometry, the distance of the Ag atom from the centre of the triple bond in C2H2 is 2.2104(10) Å. The r(HC≡CH) parameter representing the bond distance separating the two carbon atoms and the angle, ∠(CCH), each defined within the C2H2 sub-unit, are determined to be 1.2200(24) Å and 186.0(5)°, respectively. This distortion of the linear geometry of C2H2 involves the hydrogen atoms moving away from the silver atom within the complex. The results thus reveal that the geometry of C2H2 changes measurably on coordination to AgCCH. A value of 59(4) N m(-1) is determined for the intermolecular force constant, kσ, confirming that the complex is significantly more strongly bound than hydrogen and halogen-bonded analogues. Ab initio calculations of the re geometry at the CCSD(T)(F12(*))/ACVTZ level of theory are consistent with the experimental results. The spectra of the (107)Ag(13)C(13)CH and (109)Ag(13)C(13)CH isotopologues of free silver acetylide are also measured for the first time allowing the geometry of the AgCCH monomer to be examined in greater detail than previously. PMID:24697444

  2. Five years of CO, HCN, C2H6, C2H2, CH3OH, HCOOH, and H2CO total columns measured in the Canadian High Arctic

    NASA Astrophysics Data System (ADS)

    Viatte, C.; Strong, K.; Walker, K. A.; Drummond, J. R.

    2013-12-01

    We present a five-year timeseries of seven tropospheric species measured using a ground-based Fourier Transform InfraRed (FTIR) spectrometer at the Polar Environment Atmospheric Research Laboratory (PEARL, Eureka, Nunavut, Canada, 80°05' N, 86°42' W) from 2007 to 2011. Total columns and temporal variabilities of carbon monoxide (CO), hydrogen cyanide (HCN), and ethane (C2H6), as well as the first derived total columns at Eureka of acetylene (C2H2), methanol (CH3OH), formic acid (HCOOH), and formaldehyde (H2CO) are investigated, providing a new dataset in the sparsely sampled high latitudes. Total columns are obtained using the SFIT2 retrieval algorithm based on the Optimal Estimation Method. The microwindows, as well as the a priori profiles and variabilities are selected to optimize the information content of the retrievals, and error analyses are performed for all seven species. Our retrievals show good sensitivities in the troposphere. The seasonal amplitudes of the timeseries, ranging from 34 to 104%, are captured while using a single a priori profile for each species. The timeseries of the CO, C2H6 and C2H2 total columns at PEARL exhibit strong seasonal cycles with maxima in winter and minima in summer, in opposite phase to the HCN, CH3OH, HCOOH and H2CO timeseries. These cycles result from the relative contributions of the photochemistry, oxidation, and transport, as well as biogenic and biomass burning emissions. Comparisons of the FTIR partial columns with coincident satellite measurements by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) show good agreement. The correlation coefficients and the slopes range from 0.56 to 0.97, and 0.50 to 3.35, respectively, for the seven target species. Our new dataset is compared with previous measurements found in the literature to assess atmospheric budgets of these tropospheric species in the high Arctic. The CO and C2H6 concentrations are consistent with negative trends observed over

  3. Five years of CO, HCN, C2H6, C2H2, CH3OH, HCOOH and H2CO total columns measured in the Canadian high Arctic

    NASA Astrophysics Data System (ADS)

    Viatte, C.; Strong, K.; Walker, K. A.; Drummond, J. R.

    2014-06-01

    We present a five-year time series of seven tropospheric species measured using a ground-based Fourier transform infrared (FTIR) spectrometer at the Polar Environment Atmospheric Research Laboratory (PEARL; Eureka, Nunavut, Canada; 80°05' N, 86°42' W) from 2007 to 2011. Total columns and temporal variabilities of carbon monoxide (CO), hydrogen cyanide (HCN) and ethane (C2H6) as well as the first derived total columns at Eureka of acetylene (C2H2), methanol (CH3OH), formic acid (HCOOH) and formaldehyde (H2CO) are investigated, providing a new data set in the sparsely sampled high latitudes. Total columns are obtained using the SFIT2 retrieval algorithm based on the optimal estimation method. The microwindows as well as the a priori profiles and variabilities are selected to optimize the information content of the retrievals, and error analyses are performed for all seven species. Our retrievals show good sensitivities in the troposphere. The seasonal amplitudes of the time series, ranging from 34 to 104%, are captured while using a single a priori profile for each species. The time series of the CO, C2H6 and C2H2 total columns at PEARL exhibit strong seasonal cycles with maxima in winter and minima in summer, in opposite phase to the HCN, CH3OH, HCOOH and H2CO time series. These cycles result from the relative contributions of the photochemistry, oxidation and transport as well as biogenic and biomass burning emissions. Comparisons of the FTIR partial columns with coincident satellite measurements by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) show good agreement. The correlation coefficients and the slopes range from 0.56 to 0.97 and 0.50 to 3.35, respectively, for the seven target species. Our new data set is compared to previous measurements found in the literature to assess atmospheric budgets of these tropospheric species in the high Arctic. The CO and C2H6concentrations are consistent with negative trends observed over the

  4. FTIR time-series of biomass burning products (HCN, C2H6, C2H2, CH3OH, and HCOOH) at Reunion Island (21° S, 55° E) and comparisons with model data

    NASA Astrophysics Data System (ADS)

    Vigouroux, C.; Stavrakou, T.; Whaley, C.; Dils, B.; Duflot, V.; Hermans, C.; Kumps, N.; Metzger, J.-M.; Scolas, F.; Vanhaelewyn, G.; Müller, J.-F.; Jones, D. B. A.; Li, Q.; De Mazière, M.

    2012-11-01

    Reunion Island (21° S, 55° E), situated in the Indian Ocean at about 800 km east of Madagascar, is appropriately located to monitor the outflow of biomass burning pollution from Southern Africa and Madagascar, in the case of short-lived compounds, and from other Southern Hemispheric landmasses such as South America, in the case of longer-lived species. Ground-based Fourier transform infrared (FTIR) solar absorption observations are sensitive to a large number of biomass burning products. We present in this work the FTIR retrieval strategies, suitable for very humid sites such as Reunion Island, for hydrogen cyanide (HCN), ethane (C2H6), acetylene (C2H2), methanol (CH3OH), and formic acid (HCOOH). We provide their total columns time-series obtained from the measurements during August-October 2004, May-October 2007, and May 2009-December 2010. We show that biomass burning explains a large part of the observed seasonal and interannual variability of the chemical species. The correlations between the daily mean total columns of each of the species and those of CO, also measured with our FTIR spectrometer at Reunion Island, are very good from August to November (R ≥ 0.86). This allows us to derive, for that period, the following enhancement ratios with respect to CO: 0.0047, 0.0078, 0.0020, 0.012, and 0.0046 for HCN, C2H6, C2H2, CH3OH, and HCOOH, respectively. The HCN ground-based data are compared to the chemical transport model GEOS-Chem, while the data for the other species are compared to the IMAGESv2 model. We show that using the HCN/CO ratio derived from our measurements (0.0047) in GEOS-Chem reduces the underestimation of the modeled HCN columns compared with the FTIR measurements. The comparisons between IMAGESv2 and the long-lived species C2H6 and C2H2 indicate that the biomass burning emissions used in the model (from the GFED3 inventory) are probably underestimated in the late September-October period for all years of measurements, and especially in

  5. Identification of Acetylene on Titan's Surface

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  6. Full-dimensional quantum dynamics study of the H2 + C2H → H + C2H2 reaction on an ab initio potential energy surface.

    PubMed

    Chen, Liuyang; Shao, Kejie; Chen, Jun; Yang, Minghui; Zhang, Dong H

    2016-05-21

    This work performs a time-dependent wavepacket study of the H2 + C2H → H + C2H2 reaction on a new ab initio potential energy surface (PES). The PES is constructed using neural network method based on 68 478 geometries with energies calculated at UCCSD(T)-F12a/aug-cc-pVTZ level and covers H2 + C2H↔H + C2H2, H + C2H2 → HCCH2, and HCCH2 radial isomerization reaction regions. The reaction dynamics of H2 + C2H → H + C2H2 are investigated using full-dimensional quantum dynamics method. The initial-state selected reaction probabilities are calculated for reactants in eight vibrational states. The calculated results showed that the H2 vibrational excitation predominantly enhances the reactivity while the excitation of bending mode of C2H slightly inhibits the reaction. The excitations of two stretching modes of C2H molecule have negligible effect on the reactivity. The integral cross section is calculated with J-shift approximation and the mode selectivity in this reaction is discussed. The rate constants over 200-2000 K are calculated and agree well with the experimental measured values. PMID:27208951

  7. Full-dimensional quantum dynamics study of the H2 + C2H → H + C2H2 reaction on an ab initio potential energy surface

    NASA Astrophysics Data System (ADS)

    Chen, Liuyang; Shao, Kejie; Chen, Jun; Yang, Minghui; Zhang, Dong H.

    2016-05-01

    This work performs a time-dependent wavepacket study of the H2 + C2H → H + C2H2 reaction on a new ab initio potential energy surface (PES). The PES is constructed using neural network method based on 68 478 geometries with energies calculated at UCCSD(T)-F12a/aug-cc-pVTZ level and covers H2 + C2H↔H + C2H2, H + C2H2 → HCCH2, and HCCH2 radial isomerization reaction regions. The reaction dynamics of H2 + C2H → H + C2H2 are investigated using full-dimensional quantum dynamics method. The initial-state selected reaction probabilities are calculated for reactants in eight vibrational states. The calculated results showed that the H2 vibrational excitation predominantly enhances the reactivity while the excitation of bending mode of C2H slightly inhibits the reaction. The excitations of two stretching modes of C2H molecule have negligible effect on the reactivity. The integral cross section is calculated with J-shift approximation and the mode selectivity in this reaction is discussed. The rate constants over 200-2000 K are calculated and agree well with the experimental measured values.

  8. Application of the Hartmann-Tran profile to precise experimental data sets of 12C2H2

    NASA Astrophysics Data System (ADS)

    Forthomme, D.; Cich, M. J.; Twagirayezu, S.; Hall, G. E.; Sears, T. J.

    2015-11-01

    Self- and nitrogen-broadened line shape data for the Pe(11) line of the ν1 +ν3 band of acetylene, recorded using a frequency comb-stabilized laser spectrometer, have been analyzed using the Hartmann-Tran profile (HTP) line shape model in a multispectrum fitting. In total, the data included measurements recorded at temperatures between 125 K and 296 K and at pressures between 4 and 760 Torr. New, sub-Doppler, frequency comb-referenced measurements of the positions of multiple underlying hot band lines have also been made. These underlying lines significantly affect the Pe(11) line profile at temperatures above 240 K and poorly known frequencies previously introduced errors into the line shape analyses. The behavior of the HTP model was compared to the quadratic speed dependent Voigt profile (QSDVP) expressed in the frequency and time domains. A parameter uncertainty analysis was carried out using a Monte Carlo method based on the estimated pressure, transmittance and frequency measurement errors. From the analyses, the Pe(11) line strength was estimated to be 1.2014(50) ×10-20 in cmmolecule-1 units at 296 K with the standard deviation in parenthesis. For analyzing these data, we found that a reduced form of the HTP, equivalent to the QSDVP, was most appropriate because the additional parameters included in the full HTP were not well determined. As a supplement to this work, expressions for analytic derivatives and a lineshape fitting code written in Matlab for the HTP are available.

  9. Application of the Hartmann–Tran profile to precise experimental data sets of 12C2H2

    DOE PAGESBeta

    Forthomme, D.; Cich, M. J.; Twagirayezu, S.; Hall, G. E.; Sears, T. J.

    2015-06-25

    Self- and nitrogen-broadened line shape data for the Pe(11) line of the ν₁ + ν₃ band of acetylene, recorded using a frequency comb-stabilized laser spectrometer, have been analyzed using the Hartmann–Tran profile (HTP) line shape model in a multispectrum fitting. In total, the data included measurements recorded at temperatures between 125 K and 296 K and at pressures between 4 and 760 Torr. New, sub-Doppler, frequency comb-referenced measurements of the positions of multiple underlying hot band lines have also been made. These underlying lines significantly affect the Pe(11) line profile at temperatures above 240 K and poorly known frequencies previouslymore » introduced errors into the line shape analyses. Thus, the behavior of the HTP model was compared to the quadratic speed dependent Voigt profile (QSDVP) expressed in the frequency and time domains. A parameter uncertainty analysis was carried out using a Monte Carlo method based on the estimated pressure, transmittance and frequency measurement errors. From the analyses, the Pe(11) line strength was estimated to be 1.2014(50) × 10-20 in cm.molecules⁻¹ units at 296 K with the standard deviation in parenthesis. For analyzing these data, we found that a reduced form of the HTP, equivalent to the QSDVP, was most appropriate because the additional parameters included in the full HTP were not well determined. As a supplement to this work, expressions for analytic derivatives and a lineshape fitting code written in Matlab for the HTP are available.« less

  10. Local Perturbations in the (10110) and (10101) Levels of C_2H_2 from Frequency Comb-Referenced Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sears, Trevor; Twagirayezu, Sylvestre; Forthomme, Damien; Hall, Gregory; Cich, Matthew

    2015-06-01

    In work reported by Twagirayezu et al. at this meeting, the rest frequencies of more than 100 lines in the ν_4 and ν_5 hot bands in the ν_1 + ν_3 combination band of acetylene have been measured by saturation dip spectroscopy using an extended cavity diode laser locked to a frequency comb. This work was orginally directed towards providing a set of accurate frequencies for the hot band line positions to aid in modeling the lineshapes of the main lines in the band. In analyzing the results, we find that many of the upper levels in the hot band transitions suffer small, and in some cases not so small, local perturbations. These arise because of J-dependent near degeneracies between the title levels and background levels of the same symmetry, mostly derived from zero order states involving multiple quanta of bending excitation. The vibration-rotation levels at the energies in question have previously been modeled using a polyad-based Hamiltonian and the present data can be interpreted on the basis of this model, but they also provide information which can be used to refine the model, and point to terms that may have previously been neglected. The most important result is that the high precision of the measurements gives the opportunity to calibrate the effects of background levels associated with high bending quantum numbers and angular momentun states that are otherwise very difficult to access. Acknowledgments: We are most grateful to D. S Perry (U. Akron) and M. Herman (U. Libre de Bruxelles) for helpful discussions. Work at Brookhaven National Laboratory is funded by the Division of Chemical Sciences, Geosciences and Biosciences within the Offices of Basic Energy Sciences, Office of Sciences, U.S. Department of Energy under Contract Nos. DE-AC02-98CH10886 and DE-SC0012704. M. Herman and D. S. Perry, Phys. Chem. Chem. Phys., 15, 9970-9993 (2013)

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

    PubMed

    Gautam, Seema; Sarkar, Abir De

    2016-05-18

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

  12. 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.

  13. Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies

    NASA Astrophysics Data System (ADS)

    Changala, P. Bryan; Baraban, Joshua H.; Merer, Anthony J.; Field, Robert W.

    2015-08-01

    We report novel experimental strategies that should prove instrumental in extending the vibrational and rotational assignments of the S1 state of acetylene, C2H2, in the region of the cis-trans isomerization barrier. At present, the assignments are essentially complete up to ˜500 cm-1 below the barrier. Two difficulties arise when the assignments are continued to higher energies. One is that predissociation into C2H + H sets in roughly 1100 cm-1 below the barrier; the resulting quenching of laser-induced fluorescence (LIF) reduces its value for recording spectra in this region. The other difficulty is that tunneling through the barrier causes a staggering in the K-rotational structure of isomerizing vibrational levels. The assignment of these levels requires data for K values up to at least 3. Given the rotational selection rule K' - ℓ'' = ± 1, such data must be obtained via excited vibrational levels of the ground state with ℓ'' > 0. In this paper, high resolution H-atom resonance-enhanced multiphoton ionization spectra are demonstrated to contain predissociated bands which are almost invisible in LIF spectra, while preliminary data using a hyperthermal pulsed nozzle show that ℓ'' = 2 states can be selectively populated in a jet, giving access to K' = 3 states in IR-UV double resonance.

  14. Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies.

    PubMed

    Changala, P Bryan; Baraban, Joshua H; Merer, Anthony J; Field, Robert W

    2015-08-28

    We report novel experimental strategies that should prove instrumental in extending the vibrational and rotational assignments of the S1 state of acetylene, C2H2, in the region of the cis-trans isomerization barrier. At present, the assignments are essentially complete up to ∼500 cm(-1) below the barrier. Two difficulties arise when the assignments are continued to higher energies. One is that predissociation into C2H + H sets in roughly 1100 cm(-1) below the barrier; the resulting quenching of laser-induced fluorescence (LIF) reduces its value for recording spectra in this region. The other difficulty is that tunneling through the barrier causes a staggering in the K-rotational structure of isomerizing vibrational levels. The assignment of these levels requires data for K values up to at least 3. Given the rotational selection rule K' - ℓ('') = ± 1, such data must be obtained via excited vibrational levels of the ground state with ℓ('') > 0. In this paper, high resolution H-atom resonance-enhanced multiphoton ionization spectra are demonstrated to contain predissociated bands which are almost invisible in LIF spectra, while preliminary data using a hyperthermal pulsed nozzle show that ℓ('') = 2 states can be selectively populated in a jet, giving access to K' = 3 states in IR-UV double resonance. PMID:26328846

  15. Reaction of C2H2+ (n.ν2, m.ν5) with NO2: Reaction on the singlet and triplet surfaces

    NASA Astrophysics Data System (ADS)

    Boyle, Jason M.; Bell, David M.; Anderson, Scott L.

    2011-01-01

    Integral cross sections and product recoil velocity distributions were measured for reaction of C2H2+ with NO2, in which the C2H2+ reactant was prepared in its ground state, and with mode-selective excitation in the cis-bend (2ν5) and CC stretch (n.ν2, n = 1, 2). Because both reactants have one unpaired electron, collisions can occur with either singlet or triplet coupling of these unpaired electrons, and the contributions are separated based on distinct recoil dynamics. For singlet coupling, reaction efficiency is near unity, with significant branching to charge transfer (NO2+), O- transfer (NO+), and O transfer (C2H2O+) products. For triplet coupling, reaction efficiency varies between 13% and 19%, depending on collision energy. The only significant triplet channel is NO+ + triplet ketene, generated predominantly by O- transfer, with a possible contribution from dissociative charge transfer at high collision energies. NO2+ formation (charge transfer) can only occur on the singlet surface, and appears to be mediated by a weakly bound complex at low energies. O transfer (C2H2O+) also appears to be dominated by reaction on the singlet surface, but is quite inefficient, suggesting a bottleneck limiting coupling to this product from the singlet reaction coordinate. The dominant channel is O- transfer, producing NO+, with roughly equal contributions from reaction on singlet and triplet surfaces. The effects of C2H2+ vibration are modest, but mode specific. For all three product channels (i.e., charge, O-, and O transfer), excitation of the CC stretch fundamental (ν2) has little effect, 2.ν2 excitation results in ˜50% reduction in reactivity, and excitation of the cis-bend overtone (2.ν5) results in ˜50% enhancement. The fact that all channels have similar mode dependence suggests that the rate-limiting step, where vibrational excitation has its effect, is early on the reaction coordinate, and branching to the individual product channels occurs later.

  16. Optical and electrical characterization of an atmospheric pressure microplasma jet for Ar /CH4 and Ar /C2H2 mixtures

    NASA Astrophysics Data System (ADS)

    Yanguas-Gil, A.; Focke, K.; Benedikt, J.; von Keudell, A.

    2007-05-01

    A rf microplasma jet working at atmospheric pressure has been characterized for Ar, He, and Ar /CH4 and Ar /C2H2 mixtures. The microdischarge has a coaxial configuration, with a gap between the inner and outer electrodes of 250μm. The main flow runs through the gap of the coaxial structure, while the reactive gases are inserted through a capillary as inner electrode. The discharge is excited using a rf of 13.56MHz, and rms voltages around 200-250V and rms currents of 0.4-0.6A are obtained. Electron densities around 8×1020m-3 and gas temperatures lower than 400K have been measured using optical emission spectroscopy for main flows of 3slm and inner capillary flows of 160SCCM. By adjusting the flows, the flow pattern prevents the mixing of the reactive species with the ambient air in the discharge region, so that no traces of air are found even when the microplasma is operated in an open atmosphere. This is shown in Ar /CH4 and Ar /C2H2 plasmas, where no CO and CN species are present and the optical emission spectroscopy spectra are mainly dominated by CH and C2 bands. The ratio of these two species follows different trends with the amount of precursor for Ar /CH4 and Ar /C2H2 mixtures, showing the presence of distinct chemistries in each of them. In Ar /C2H2 plasmas, CHx species are produced mainly by electron impact dissociation of C2H2 molecules, and the CHx/C2Hx ratio is independent of the precursor amount. In Ar /CH4 mixtures, C2Hx species are formed mainly by recombination of CHx species through three-body reactions, so that the CHx/C2Hx ratio depends on the amount of CH4 present in the mixture. All these properties make our microplasma design of great interest for applications such as thin film growth or surface treatment.

  17. 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

  18. MICROWAVE SPECTRA AND GEOMETRIES OF C2H_{2\\cdots AgI} and C2H_{4\\cdots AgI}

    NASA Astrophysics Data System (ADS)

    Stephens, Susanna L.; Tew, David Peter; Walker, Nick; Legon, Anthony

    2015-06-01

    A chirped-pulse Fourier transform microwave spectrometer has been used to measure the microwave spectra of both C2H_{2\\cdots AgI} and C2H_{4\\cdots AgI}. These complexes are generated via laser ablation at 532 nm of a silver surface in the presence of CF3I and either C2H_{2} or C2H_{4} and argon and are stabilized by a supersonic expansion. Rotational (A0, B0, C0) and centrifugal distortion constants (ΔJ and ΔJK) of each molecule have been determined as well the nuclear electric quadrupole coupling constants the iodine atom (χaa(I) and χbb-χcc(I)). The spectrum of each molecule is consistent with a C2v structure in which the metal atom interacts with the π-orbital of the ethene or ethyne molecule. Isotopic substitutions of atoms within the C2H_{2} or C2H_{4} subunits are in progress and in conjunction with high level ab initio calculations will allow for accurate determination of the geometry of each molecule. These to complexes are put in the context of the recently studied H2S\\cdots AgI, OC\\cdotsAgI, H3N\\cdots AgI and (CH3)_{3N\\cdots AgI}. S.Z. Riaz, S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, Chem. Phys. Let., 531, 1-12 (2012) S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, J. Chem. Phys., 136(6), 064306 (2012) D.M. Bittner, D.P. Zaleski, S.L. Stephens, N.R. Walker, A.C. Legon, Study in progress.

  19. Volumetric Properties of the Mixture Pentafluoroethane C2HF5 + C2H2F4 1,1,1,2-Tetrafluoroethane (VMSD1541, LB3231_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Pentafluoroethane C2HF5 + C2H2F4 1,1,1,2-Tetrafluoroethane (VMSD1541, LB3231_V)' providing data from direct measurement of thermodynamic speed of sound at variable pressure and constant temperature and mole fraction.

  20. Volumetric Properties of the Mixture Dichloromethane CH2Cl2 + C2H2Cl4 1,1,2,2-Tetrachloroethane (VMSD1212, LB4571_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dichloromethane CH2Cl2 + C2H2Cl4 1,1,2,2-Tetrachloroethane (VMSD1212, LB4571_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  1. ZNF1 Encodes a Putative C2H2 Zinc-Finger Protein Essential for Appressorium Differentiation by the Rice Blast Fungus Magnaporthe oryzae.

    PubMed

    Yue, Xiaofeng; Que, Yawei; Xu, Lin; Deng, Shuzhen; Peng, Youliang; Talbot, Nicholas J; Wang, Zhengyi

    2016-01-01

    The rice blast fungus Magnaporthe oryzae forms specialized infection structures called appressoria which are essential for gaining entry to plant tissue. Here, we report the identification of a novel nonpathogenic T-DNA-tagged mutant XF696 of M. oryzae with a single insertion in the promoter of ZNF1, which encodes a putative transcription factor (TF). Targeted gene deletion mutants of ZNF1 are nonpathogenic and unable to develop appressoria. However, Δznf1 mutants still respond to exogenous cyclic AMP on hydrophilic surfaces and can sense hydrophobic surfaces, initiating the differentiation of germ tubes. Interestingly, Δznf1 mutants also produce significantly more conidia compared with the isogenic wild-type strain. Quantitative reverse-transcription polymerase chain reaction analysis and green fluorescent protein fusion experiments revealed that expression of ZNF1 was highly induced during germination and appressorium development in M. oryzae and potentially regulated by the Pmk1 mitogen-activated protein kinase pathway. We observed that Δznf1 mutants are affected in mitosis and impaired in mobilization and degradation of lipid droplets and glycogen reserves during appressorium differentiation. Site-directed mutagenesis confirmed that three of the four C2H2 zinc-finger domains are essential for the function of Znf1. Taken together, we conclude that a C2H2 zinc-finger TF encoded by ZNF1 is essential for appressorium development by the rice blast fungus. PMID:26441322

  2. Ligand-dependent corepressor contributes to transcriptional repression by C2H2 zinc-finger transcription factor ZBRK1 through association with KRAB-associated protein-1

    PubMed Central

    Calderon, Mario R.; Verway, Mark; Benslama, Radia Ouelaa; Birlea, Mirela; Bouttier, Manuella; Dimitrov, Vassil; Mader, Sylvie; White, John H.

    2014-01-01

    We identified a novel interaction between ligand-dependent corepressor (LCoR) and the corepressor KRAB-associated protein-1 (KAP-1). The two form a complex with C2H2 zinc-finger transcription factor ZBRK1 on an intronic binding site in the growth arrest and DNA-damage-inducible α (GADD45A) gene and a novel site in the fibroblast growth factor 2 (FGF2) gene. Chromatin at both sites is enriched for histone methyltransferase SETDB1 and histone 3 lysine 9 trimethylation, a repressive epigenetic mark. Depletion of ZBRK1, KAP-1 or LCoR led to elevated GADD45A and FGF2 expression in malignant and non-malignant breast epithelial cells, and caused apoptotic death. Loss of viability could be rescued by simultaneous knockdowns of FGF2 and transcriptional coregulators or by blocking FGF2 function. FGF2 was not concurrently expressed with any of the transcriptional coregulators in breast malignancies, suggesting an inverse correlation between their expression patterns. We propose that ZBRK1, KAP-1 and LCoR form a transcriptional complex that silences gene expression, in particular FGF2, which maintains breast cell viability. Given the broad expression patterns of both LCoR and KAP-1 during development and in the adult, this complex may have several regulatory functions that extend beyond cell survival, mediated by interactions with ZBRK1 or other C2H2 zinc-finger proteins. PMID:24829459

  3. Vibrational energy transfer in CO2-C2H2n + 2 (n=0, 1, 2) mixtures from 220 to 300 K

    NASA Astrophysics Data System (ADS)

    Manzanares I., Carlos; Pinzon, Hernando; Fumero, Juan; Gonzalez, Carlos; Sanchez, Eugenio

    1983-05-01

    Time resolved laser induced infrared fluorescence studies have been performed to obtain the rate constants of energy transfer of CO2 (ν3) in mixtures with C2H2, C2H4, and C2H6 at temperatures between 220 and 300 K. A pulsed 10.6 μm CO2 laser light has been used to directly excite the CO2 molecules at low temperatures. The CO2 self-relaxation was measured and the results are in agreement with previous measurements. The rate constants for the transfer of energy in the CO2-C2H2 system show normal temperature behavior, (rate constant increases as the temperature increases) associated with large energy defect and caused by short-range repulsive forces. The rate constants for the systems CO2-C2H4 and CO2-C2H6 show an inverse temperature effect, (rate constant increases as the temperature decreases) associated with near resonant energy exchange and long-range attractive forces between the molecules. The observed behavior with temperature for the three systems is explained using a Morse potential which includes repulsive and attractive terms to describe the interaction between the molecules and a probability expression formulated by H. K. Shin, to calculate the energy transfer probabilities of some important reactions considered for each system.

  4. Vibronic valence and Rydberg transitions in geminal chloro-fluoro-ethene (1,1-C2H2FCl): a spectroscopic and quantum chemical investigation

    NASA Astrophysics Data System (ADS)

    Locht, R.; Dehareng, D.; Leyh, B.

    2014-06-01

    The vacuum ultraviolet photoabsorption spectrum of 1,1-C2H2FCl has been examined in detail between 5 and 15 eV photon energy by using synchrotron radiation dispersed by three different monochromators. Quantum chemical calculations are performed to help in the analysis of the valence/Rydberg transition region centred at 7.05 eV including the 3a″(π)→π* and the 3a″(π)→3s Rydberg transitions. Interactions between states involving transitions to the 3s, 4d and σ* orbitals are identified. A vibrational analysis is proposed for the structures belonging to these transitions. For the π(3a″)→π* transition, one vibrational progression is observed with ω3 = 1410 ± 50 cm-1 and its lowest excitation energy is determined at about 6.398 ± 0.003 eV. The π(3a″)→3s Rydberg transition is characterised by a single progression with ω3 = 1410 ± 80 cm-1 likely starting at about 6.45 eV. These vibrations are ascribed to the C=C stretching motion. The abundant structure observed in the spectrum between 7.8 and 10.5 eV has been analysed in terms of vibronic transitions to ns (δ = 0.97), np (δ = 0.63 and 0.40) and nd (δ = 0.13 and -0.11) Rydberg states, which belong to series converging to the 1,1-C2H2FCl+(?) ionic ground state. The analysis of the vibrational structure of the individual Rydberg states has been attempted leading to average values of the wave numbers ω3 = 1420 ± 20 cm-1, ω7 = 720 ± 50 cm-1 and ω9 = 390 ± 50 cm-1. Between 10.5 and 12.5 eV, nine other Rydberg states converging to the 1,1-C2H2FCl+(?) first excited state were analysed by the same way. The vibrational structure of these Rydberg states results from the excitation of one vibrational normal mode ν7 with an average value of ω7 = 520 ± 20 cm-1, which is assigned to the C-Cl stretching vibration as inferred from quantum chemical calculations.

  5. A SIFT ion-molecule study of some reactions in Titan's atmosphere. reactions of N(+), N(2)(+), and HCN(+) with CH(4), C(2)H(2), and C(2)H(4)

    NASA Technical Reports Server (NTRS)

    Anicich, Vincent G.; Wilson, Paul; McEwan, Murray J.

    2004-01-01

    The results of a study of the ion-molecule reactions of N(+), N(2)(+), and HCN(+) with methane, acetylene, and ethylene are reported. These studies were performed using the FA-SIFT at the University of Canterbury. The reactions studied here are important to understanding the ion chemistry in Titan's atmosphere. N(+) and N(2)(+) are the primary ions formed by photo-ionization and electron impact in Titan's ionosphere and drive Titan's ion chemistry. It is therefore very important to know how these ions react with the principal trace neutral species in Titan's atmosphere: Methane, acetylene, and ethylene. While these reactions have been studied before the product channels have been difficult to define as several potential isobaric products make a definitive answer difficult. Mass overlap causes difficulties in making unambiguous species assignments in these systems. Two discriminators have been used in this study to resolve the mass overlap problem. They are deuterium labeling and also the differences in reactivities of each isobar with various neutral reactants. Several differences have been found from the products in previous work. The HCN(+) ion is important in both Titan's atmosphere and in the laboratory.

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

    PubMed

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

    2006-09-27

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

  7. Characterization of the Minimum Energy Paths for the Reactions of CH(X(sup 2 Pi) and (1)CH2 with C2H2

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    The reactions of CH(sup 2 Pi) and singlet methylene (1)CH2 with acetylene lead to intermediates which may be important in soot formation. CH(sup 2 Pi) + acetylene leads to CHCHCH (C3H3), CHCCH (C3H2), and propargyl (CH2CCH). (1)CH2 + acetylene leads to cyclopropene and propargyl. All of these reaction products are formed with no barrier. Miller and Melius have previously discussed the dimerization of propargyl to give benzene. C3H3 and C3H2 can dimerize with no barrier to give benzene and para-benzyne, respectively. C3H3 and C3H2 can also add to smaller polynuclear aromatic hydrocarbons (PAH), and may be important species in forming larger PAH or fullerenes.

  8. Auger-electron angular distributions calculated without the two-step approximation: Calculation of angle-resolved resonant Auger spectra of C2 H2

    NASA Astrophysics Data System (ADS)

    Colle, Renato; Embriaco, Davide; Massini, Michol; Simonucci, Stefano; Taioli, Simone

    2004-10-01

    Analytic expressions for the direct, resonant, and interference contributions to the differential cross section of a resonant Auger process, produced by the inner-shell photoionization of a linear molecule either “fixed in space” or belonging to a gas of randomly oriented molecules, have been derived following Dill’s procedures [ Dill , Phys. Rev. Lett. 45, 1393 (1980) ], but going beyond the two-step approximation. Angle-resolved Auger spectra of the C2H2 molecule measured on top of the C1s→π* resonance [ Kivimäki , J. Phys. B 30, 4279 (1997) ] have been calculated together with asymmetry parameters, analyzing also the different contributions to the electron angular distributions.

  9. Discerning the direct and indirect ionization processes in the photo-double-ionization of 1, 1-C2H2F2 near and above threshold

    NASA Astrophysics Data System (ADS)

    Gaire, B.; Bocharova, I.; Sturm, F. P.; Gehrken, N.; Rist, J.; Belkacem, A.; Weber, Th.; Berry, B.; Zohrabi, M.; Ben-Itzhak, I.; Keiling, M.; Moradmand, A.; Landers, A.; Jahnke, T.; Schoeffler, M.; Sann, H.; Kunitski, M.; Doerner, R.

    2014-05-01

    We have studied the photo-double-ionization of 1, 1-C2H2F2 near and above threshold using linearly polarized single photons (40 to 70eV). Kinematically complete experiments were achieved for the nondissociative ionization (NDI) and all ionic two body break up channels by measuring the electrons and recoil ions in coincidence with the COLd Target Recoil Ion Momentum Spectroscopy (COLTRIMS) method. Using electron-ion and electron-electron energy correlation maps as well as asymmetry parameters and relative angles between the emitted electrons, we were able to trace the electronic states involved and distinguish between the direct and indirect ionization mechanisms of the NDI and the fragmentation processes. Supported by the Director, Office of Science, Office of Basic Energy Sciences, and by the Division of Chemical Sciences, Geosciences, and Biosciences of the U.S. Department of Energy at LBNL under Contract No. DE-AC02-05CH11231.

  10. Measurements in N2-CH4(C2H2) discharges of reaction rates and thermochemical constants for Titan atmosphere study.

    PubMed

    Ricard, A; Cernogora, G; Fitaire, M; Hochard, L; Kouassi, N; Speller, C; Vacher, J R

    1995-01-01

    The kinetic reactions in N2-xCH4(C2H2) gas discharges with x less than 1% have been studied by emission spectroscopy in the afterglow of D.C. discharges and by mass spectroscopy from radiolysis ionization using alpha particles. The pressure range is from several Torr to 100 Torr. At the end of N2 D.C. discharges at room temperature, for a residence time of about 10(-2) s, the dominant active species are the N atoms with density of 10(14)-10(15) cm-3 for N2 density of about 10(17) cm-3 (3 Torr), the N2(X,V) vibrational molecules with for example [N2(X,V = 10)] approximately 10(14) cm-3 and the electronic metastable molecules N2(A 3 sigma u +) with a density of 10(12) cm-3. In such conditions, the following kinetic reactions have been studied: N2(A) + N2(A) --> N2(C,B,V') + N2(X), N2(A) + N2(X,V>5) --> N2(X) + N2(B,V') in pure N2 post-discharges and N2(A) + CH4 --> products, C + N + M2 --> CN(B,V') + M2, N2(X,V>4) + CN --> N2(X) + CN(B,A,V'), in N2-1% CH4 post-discharges. The clustering reactions of N2-(1-5%)CH4(C2H2) gas mixtures after radiolysis ionization have been studied for the H2CN+ nN2 ions and the equilibrium constants have been determined in the temperature range T = 140-300 K. PMID:11538437

  11. A photochemical study of the kinetics of the reactions of NH2 with phosphine, ethylene, and acetylene using flash photolysis-laser induced fluorescence. Ph.D. Thesis Catholic Univ. of America; [ammonia in the atmosphere of Jupiter

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.

    1982-01-01

    The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.

  12. High-resolution spectroscopy of Saturn at 3 microns: CH 4, CH 3D, C 2H 2, C 2H 6, PH 3, clouds, and haze

    NASA Astrophysics Data System (ADS)

    Kim, Joo Hyeon; Kim, Sang J.; Geballe, Thomas R.; Kim, Sungsoo S.; Brown, Linda R.

    2006-12-01

    We report observation and analysis of a high-resolution 2.87-3.54 μm spectrum of the southern temperate region of Saturn obtained with NIRSPEC at Keck II. The spectrum reveals absorption and emission lines of five molecular species as well as spectral features of haze particles. The ν+ν band of CH 3D is detected in absorption between 2.87 and 2.92 μm; and we derived from it a mixing ratio approximately consistent with the Infrared Space Observatory result. The ν band of C 2H 2 also is detected in absorption between 2.95 and 3.05 μm; analysis indicates a sudden drop in the C 2H 2 mixing ratio at 15 mbar (130 km above the 1 bar level), probably due to condensation in the low stratosphere. The presence of the ν+ν+ν band of C 2H 6 near 3.07 μm, first reported by Bjoraker et al. [Bjoraker, G.L., Larson, H.P., Fink, U., 1981. Astrophys. J. 248, 856-862], is confirmed, and a C 2H 6 condensation altitude of 10 mbar (140 km) in the low stratosphere is determined. We assign weak emission lines within the 3.3 μm band of CH 4 to the ν band of C 2H 6, and derive a mixing ratio of 9±4×10 for this species. Most of the C 2H 6 3.3 μm line emission arises in the altitude range 460-620 km (at ˜μbar pressure levels), much higher than the 160-370 km range where the 12 μm thermal molecular line emission of this species arises. At 2.87-2.90 μm the major absorber is tropospheric PH 3. The cloud level determined here and at 3.22-3.54 is 390-460 mbar (˜30 km), somewhat higher than found by Kim and Geballe [Kim, S.J., Geballe, T.R., 2005. Icarus 179, 449-458] from analysis of a low resolution spectrum. A broad absorption feature at 2.96 μm, which might be due to NH 3 ice particles in saturnian clouds, is also present. The effect of a haze layer at about 125 km (˜12 mbar level) on the 3.20-3.54 μm spectrum, which was not apparent in the low resolution spectrum, is clearly evident in the high resolution data, and the spectral properties of the haze particles suggest that

  13. Electron impact induced anion production in acetylene.

    PubMed

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

    2014-02-28

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

  14. Infrared Spectra and Optical Constants of Astronomical Ices: II. Ethane and Ethylene

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie L.; Gerakines, Perry A.; Moore, M. H.

    2014-01-01

    Infrared spectroscopic observations have established the presence of hydrocarbon ices on Pluto and other TNOs, but the abundances of such molecules cannot be deduced without accurate optical constants (n, k) and reference spectra. In this paper we present our recent measurements of near- and mid-infrared optical constants for ethane (C2H6) and ethylene (C2H4) in multiple ice phases and at multiple temperatures. As in our recent work on acetylene (C2H2), we also report new measurements of the index of refraction of each ice at 670 nm. Comparisons are made to earlier work where possible, and electronic versions of our new results are made available.

  15. Infrared spectra and optical constants of astronomical ices: II. Ethane and ethylene

    NASA Astrophysics Data System (ADS)

    Hudson, R. L.; Gerakines, P. A.; Moore, M. H.

    2014-11-01

    Infrared spectroscopic observations have established the presence of hydrocarbon ices on Pluto and other TNOs, but the abundances of such molecules cannot be deduced without accurate optical constants (n, k) and reference spectra. In this paper we present our recent measurements of near- and mid-infrared optical constants for ethane (C2H6) and ethylene (C2H4) in multiple ice phases and at multiple temperatures. As in our recent work on acetylene (C2H2), we also report new measurements of the index of refraction of each ice at 670 nm. Comparisons are made to earlier work where possible, and electronic versions of our new results are made available.

  16. Inhibiting the combustion of air-acetylene mixtures

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  17. Activation of the Ustilagic Acid Biosynthesis Gene Cluster in Ustilago maydis by the C2H2 Zinc Finger Transcription Factor Rua1▿

    PubMed Central

    Teichmann, Beate; Liu, Lidan; Schink, Kay Oliver; Bölker, Michael

    2010-01-01

    The phytopathogenic basidiomycetous fungus Ustilago maydis secretes, under conditions of nitrogen starvation, large amounts of the biosurfactant ustilagic acid (UA). This secreted cellobiose glycolipid is toxic for many microorganisms and confers biocontrol activity to U. maydis. Recently, a large gene cluster that is responsible for UA biosynthesis was identified. Here, we show that expression of all cluster genes depends on Rua1, a nuclear protein of the C2H2 zinc finger family, whose gene is located within the gene cluster. While deletion of rua1 results in complete loss of UA production, overexpression of rua1 promotes increased UA synthesis even in the presence of a good nitrogen source. Bioinformatic analysis allowed us to identify a conserved sequence element that is present in the promoters of all structural genes involved in UA biosynthesis. Deletion analysis of several promoters within the cluster revealed that this DNA element serves as an upstream activating sequence (UAS) and mediates Rua1-dependent expression. We used the yeast one-hybrid system to demonstrate specific recognition of this DNA element by Rua1. Introduction of nucleotide exchanges into the consensus sequence interfered with Rua1-dependent activation, suggesting that this sequence element acts as a direct binding site for Rua1. PMID:20173069

  18. Precursor of N atoms of hydrogenated amorphous carbon nitride films formed from the microwave discharge of C2H2/N2 gas mixture

    NASA Astrophysics Data System (ADS)

    Ito, Haruhiko; Tsudome, Hiroki; Mogi, Nobuyoshi; Saitoh, Hidetoshi

    2016-01-01

    Hydrogenated amorphous carbon nitride films with the [N]/([N] + [C]) ratios of 0.29-0.44 were formed from the microwave discharge of the gas mixture of C2H2 with an excess amount of N2. The ratio of the fluxes, s = Φa-CN/ΦCN(X), was evaluated in this study, where Φa-CN was the flux of N atoms incorporated into the films and ΦCN(X) was that of CN radicals in the gas phase. ΦCN(X) was evaluated from the density of CN radicals using the A2Πi-X2Σ+ laser-induced fluorescence spectra and from the flow speed using the time-resolved emission, and Φa-CN from the film mass calibrated against atomic compositions. The s value was in the range of 0.22-0.78, being 1.2-1.7 times the sticking probability of CN radicals corrected in this study, 0.19-0.45. Then, the contribution of CN radicals was evaluated to be 60-80% of the N source of the films. The chemical structure and mechanical property of the films were analyzed in terms of Raman scattering, IR absorption, and nanoindentation measurements.

  19. Activation of the ustilagic acid biosynthesis gene cluster in Ustilago maydis by the C2H2 zinc finger transcription factor Rua1.

    PubMed

    Teichmann, Beate; Liu, Lidan; Schink, Kay Oliver; Bölker, Michael

    2010-04-01

    The phytopathogenic basidiomycetous fungus Ustilago maydis secretes, under conditions of nitrogen starvation, large amounts of the biosurfactant ustilagic acid (UA). This secreted cellobiose glycolipid is toxic for many microorganisms and confers biocontrol activity to U. maydis. Recently, a large gene cluster that is responsible for UA biosynthesis was identified. Here, we show that expression of all cluster genes depends on Rua1, a nuclear protein of the C(2)H(2) zinc finger family, whose gene is located within the gene cluster. While deletion of rua1 results in complete loss of UA production, overexpression of rua1 promotes increased UA synthesis even in the presence of a good nitrogen source. Bioinformatic analysis allowed us to identify a conserved sequence element that is present in the promoters of all structural genes involved in UA biosynthesis. Deletion analysis of several promoters within the cluster revealed that this DNA element serves as an upstream activating sequence (UAS) and mediates Rua1-dependent expression. We used the yeast one-hybrid system to demonstrate specific recognition of this DNA element by Rua1. Introduction of nucleotide exchanges into the consensus sequence interfered with Rua1-dependent activation, suggesting that this sequence element acts as a direct binding site for Rua1. PMID:20173069

  20. The threshold photoelectron spectrum of the geminal chloro-fluoro-ethene (1,1-C2H2FCl) isomer. Experiment and theory

    NASA Astrophysics Data System (ADS)

    Locht, R.; Dehareng, D.; Leyh, B.

    2014-04-01

    The threshold photoelectron spectrum (TPES) of 1,1-C2H2FCl has been measured for the first time using synchrotron radiation. It has been compared to the HeI PES obtained earlier (Tornow et al 1990 Chem. Phys. 146 115). Eight photoelectron bands have been observed at 10.22, 12.45, 13.28, 14.29, 14.99, 17.12, 17.67 and at 20.23 eV successively. Only the first three bands exhibit a rich and extensive vibrational structure. Their adiabatic ionization energies are measured and a detailed vibrational analysis is presented. The assignments of the electronic bands and of the vibrational wavenumbers were made by using ab initio quantum chemical calculations. These allowed us to provide the MO description of the eight electronic states in terms of ionization and double excitation. The good correlation between predicted vibrational wavenumbers and the experimental values provides a strong basis for the assignment of all the vibrational structures.

  1. Soybean C2H2-Type Zinc Finger Protein GmZFP3 with Conserved QALGGH Motif Negatively Regulates Drought Responses in Transgenic Arabidopsis

    PubMed Central

    Zhang, Dayong; Tong, Jinfeng; Xu, Zhaolong; Wei, Peipei; Xu, Ling; Wan, Qun; Huang, Yihong; He, Xiaolan; Yang, Jiayin; Shao, Hongbo; Ma, Hongxiang

    2016-01-01

    Plant response to environmental stresses is regulated by a complicated network of regulatory and functional genes. In this study, we isolated the putative stress-associated gene GmZFP3 (a C2H2-type Zinc finger protein gene) based on the previous finding that it was one of two genes located in the QTL region between the Satt590 and Satt567 markers related to soybean tolerance to drought. Temporal and spatial expression analysis using quantitative real-time PCR indicated that GmZFP3 was primarily expressed in roots, stems and leaf organs and was expressed at low levels in flowers and soybean pods. Moreover, GmZFP3 expression increased in response to polyethylene glycol (PEG) and Abscisic acid (ABA) treatments. In addition, subcellular localization analysis indicated that GmZFP3 was ubiquitously distributed in plant cells. Transgenic experiments indicated that GmZFP3 played a negative role in plant tolerance to drought. Analysis of ABA-related marker gene expression in Arabidopsis suggested that GmZFP3 might be involved in the ABA-dependent pathway during the drought stress response. Taken together, these results suggest that soybean GmZFP3 negatively regulates the drought response. PMID:27047508

  2. 10 kHz accuracy of an optical frequency reference based on (12)C2H2-filled large-core kagome photonic crystal fibers.

    PubMed

    Knabe, Kevin; Wu, Shun; Lim, Jinkang; Tillman, Karl A; Light, Philip S; Couny, Francois; Wheeler, Natalie; Thapa, Rajesh; Jones, Andrew M; Nicholson, Jeffrey W; Washburn, Brian R; Benabid, Fetah; Corwin, Kristan L

    2009-08-31

    Saturated absorption spectroscopy reveals the narrowest features so far in molecular gas-filled hollow-core photonic crystal fiber. The 48-68 mum core diameter of the kagome-structured fiber used here allows for 8 MHz full-width half-maximum sub-Doppler features, and its wavelength-insensitive transmission is suitable for high-accuracy frequency measurements. A fiber laser is locked to the (12)C2H2 nu(1); + nu(3) P(13) transition inside kagome fiber, and compared with frequency combs based on both a carbon nanotube fiber laser and a Cr:forsterite laser, each of which are referenced to a GPS-disciplined Rb oscillator. The absolute frequency of the measured line center agrees with those measured in power build-up cavities to within 9.3 kHz (1 sigma error), and the fractional frequency instability is less than 1.2 x 10(-11) at 1 s averaging time. PMID:19724600

  3. Soybean C2H2-Type Zinc Finger Protein GmZFP3 with Conserved QALGGH Motif Negatively Regulates Drought Responses in Transgenic Arabidopsis.

    PubMed

    Zhang, Dayong; Tong, Jinfeng; Xu, Zhaolong; Wei, Peipei; Xu, Ling; Wan, Qun; Huang, Yihong; He, Xiaolan; Yang, Jiayin; Shao, Hongbo; Ma, Hongxiang

    2016-01-01

    Plant response to environmental stresses is regulated by a complicated network of regulatory and functional genes. In this study, we isolated the putative stress-associated gene GmZFP3 (a C2H2-type Zinc finger protein gene) based on the previous finding that it was one of two genes located in the QTL region between the Satt590 and Satt567 markers related to soybean tolerance to drought. Temporal and spatial expression analysis using quantitative real-time PCR indicated that GmZFP3 was primarily expressed in roots, stems and leaf organs and was expressed at low levels in flowers and soybean pods. Moreover, GmZFP3 expression increased in response to polyethylene glycol (PEG) and Abscisic acid (ABA) treatments. In addition, subcellular localization analysis indicated that GmZFP3 was ubiquitously distributed in plant cells. Transgenic experiments indicated that GmZFP3 played a negative role in plant tolerance to drought. Analysis of ABA-related marker gene expression in Arabidopsis suggested that GmZFP3 might be involved in the ABA-dependent pathway during the drought stress response. Taken together, these results suggest that soybean GmZFP3 negatively regulates the drought response. PMID:27047508

  4. In situ TDLAS measurement of absolute acetylene concentration profiles in a non-premixed laminar counter-flow flame

    NASA Astrophysics Data System (ADS)

    Wagner, S.; Klein, M.; Kathrotia, T.; Riedel, U.; Kissel, T.; Dreizler, A.; Ebert, V.

    2012-06-01

    Acetylene (C2H2), as an important precursor for chemiluminescence species, is a key to understand, simulate and model the chemiluminescence and the related reaction paths. Hence we developed a high resolution spectrometer based on direct Tunable Diode Laser Absorption Spectroscopy (TDLAS) allowing the first quantitative, calibration-free and spatially resolved in situ C2H2 measurement in an atmospheric non-premixed counter-flow flame supported on a Tsuji burner. A fiber-coupled distributed feedback diode laser near 1535 nm was used to measure several absolute C2H2 concentration profiles (peak concentrations up to 9700 ppm) in a laminar non-premixed CH4/air flame ( T up to 1950 K) supported on a modified Tsuji counter-flow burner with N2 purge slots to minimize end flames. We achieve a fractional optical resolution of up to 5×10-5 OD (1 σ) in the flame, resulting in temperature-dependent acetylene detection limits for the P17e line at 6513 cm-1 of up to 2.1 ppmṡm. Absolute C2H2 concentration profiles were obtained by translating the burner through the laser beam using a DC motor with 100 μm step widths. Intercomparisons of the experimental C2H2 profiles with simulations using our new hydrocarbon oxidation mechanisms show excellent agreement in position, shape and in the absolute C2H2 values.

  5. Merging open metal sites and Lewis basic sites in a NbO-type metal-organic framework for improved C2H2/CH4 and CO2/CH4 separation.

    PubMed

    Song, Chengling; Hu, Jiayi; Ling, Yajing; Feng, Yunlong; Chen, De-Li; He, Yabing

    2015-09-01

    A new three-dimensional NbO-type porous metal-organic framework ZJNU-47 was synthesized via a solvothermal reaction of Cu(NO3)2·3H2O and a Lewis basic nitrogen donor site-rich tetracarboxylate, namely, 5,5'-(pyridazine-3,6-diyl)-diisophthalate, and the structure was characterized by single-crystal X-ray diffraction to be isostructural with NOTT-101. With the synergistic effect of open metal sites, Lewis basic sites and a suitable pore space, the MOF material ZJNU-47a after activation can take up a large amount of C2H2 and CO2. The gravimetric C2H2 uptake of 214 cm(3) (STP) g(-1) at room temperature and 1 atm is the highest among all reported MOFs to date, and the gravimetric CO2 uptake of 108 cm(3) (STP) g(-1) is also among the highest reported for MOFs. Compared to the isostructural MOF NOTT-101a, ZJNU-47a exhibits a significant increase in C2H2 and CO2 uptake and thus improved C2H2/CH4 and CO2/CH4 separations. Significantly, comprehensive DFT studies of C2H2 and CO2 adsorption have revealed that the open nitrogen donor sites are comparable and even superior to open metal sites regarding the adsorption sites. This work demonstrated that the simultaneous introduction of Lewis basic nitrogen donor sites and Lewis acidic metal sites into the framework is a promising approach to improve the gas sorption toward CO2 and C2H2 and thus to produce materials possessing enhanced C2H2/CH4 and CO2/CH4 separation performance. PMID:26223674

  6. Trajectory surface hopping study of the O(3P) + C2H2 reaction dynamics: Effect of collision energy on the extent of intersystem crossing

    NASA Astrophysics Data System (ADS)

    Rajak, Karunamoy; Maiti, Biswajit

    2014-01-01

    Intersystem crossing (ISC) dynamics plays an important role in determining the product branching in the O(3P) + C2H2 reaction despite the necessarily small spin-orbit coupling constant values. In this study we investigate the effect of collision energy on the extent of the contribution of a spin non-conserving route through ISC dynamics to the product distributions at the initial collision energies 8.2, 9.5, and 13.1 kcal/mol. A direct dynamics trajectory surface hopping method is employed with potential energy surfaces generated at the unrestricted B3LYP/6-31G(d,p) level of theory to perform nonadiabatic dynamics. To make our calculation simpler, nonadibatic transitions were only considered at the triplet-singlet intersections. At the crossing points, Landau-Zener transition probabilities were calculated using spin-orbit coupling constant values computed at the same geometry. The Landau-Zener model for the title reaction is validated against a more rigorous Tully's fewest switches method and found to be working reasonably well as expected because of weak spin-orbit coupling. We have compared our results with the recent crossed molecular beam experiments and observed a very good agreement with respect to the primary product branching ratios. Our calculation revealed that there is no noticeable effect of the initial collision energy on the overall product distributions that corroborates the recent experimental findings. Our calculation indicates, however, that the extent of intersystem crossing contributions varies significantly with collision energy, needed to be verified, experimentally.

  7. A Novel C2H2 Transcription Factor that Regulates gliA Expression Interdependently with GliZ in Aspergillus fumigatus

    PubMed Central

    Schoberle, Taylor J.; Nguyen-Coleman, C. Kim; Herold, Jennifer; Yang, Ally; Weirauch, Matt; Hughes, Timothy R.; McMurray, John S.; May, Gregory S.

    2014-01-01

    Secondary metabolites are produced by numerous organisms and can either be beneficial, benign, or harmful to humans. Genes involved in the synthesis and transport of these secondary metabolites are frequently found in gene clusters, which are often coordinately regulated, being almost exclusively dependent on transcription factors that are located within the clusters themselves. Gliotoxin, which is produced by a variety of Aspergillus species, Trichoderma species, and Penicillium species, exhibits immunosuppressive properties and has therefore been the subject of research for many laboratories. There have been a few proteins shown to regulate the gliotoxin cluster, most notably GliZ, a Zn2Cys6 binuclear finger transcription factor that lies within the cluster, and LaeA, a putative methyltransferase that globally regulates secondary metabolism clusters within numerous fungal species. Using a high-copy inducer screen in A. fumigatus, our lab has identified a novel C2H2 transcription factor, which plays an important role in regulating the gliotoxin biosynthetic cluster. This transcription factor, named GipA, induces gliotoxin production when present in extra copies. Furthermore, loss of gipA reduces gliotoxin production significantly. Through protein binding microarray and mutagenesis, we have identified a DNA binding site recognized by GipA that is in extremely close proximity to a potential GliZ DNA binding site in the 5′ untranslated region of gliA, which encodes an efflux pump within the gliotoxin cluster. Not surprisingly, GliZ and GipA appear to work in an interdependent fashion to positively control gliA expression. PMID:24784729

  8. The Arabidopsis C2H2 Zinc Finger INDETERMINATE DOMAIN1/ENHYDROUS Promotes the Transition to Germination by Regulating Light and Hormonal Signaling during Seed Maturation[W

    PubMed Central

    Feurtado, J. Allan; Huang, Daiqing; Wicki-Stordeur, Leigh; Hemstock, Laura E.; Potentier, Mireille S.; Tsang, Edward W.T.; Cutler, Adrian J.

    2011-01-01

    Seed development ends with a maturation phase that imparts desiccation tolerance, nutrient reserves, and dormancy degree. Here, we report the functional analysis of an Arabidopsis thaliana C2H2 zinc finger protein INDETERMINATE DOMAIN1 (IDD1)/ENHYDROUS (ENY). Ectopic expression of IDD1/ENY (2x35S:ENY) disrupted seed development, delaying endosperm depletion and testa senescence, resulting in an abbreviated maturation program. Consequently, mature 2x35S:ENY seeds had increased endosperm-specific fatty acids, starch retention, and defective mucilage extrusion. Using RAB18 promoter ENY lines (RAB18:ENY) to confine expression to maturation, when native ENY expression increased and peaked, resulted in mature seed with lower abscisic acid (ABA) content and decreased germination sensitivity to applied ABA. Furthermore, results of far-red and red light treatments of 2x35S:ENY and RAB18:ENY germinating seeds, and of artificial microRNA knockdown lines, suggest that ENY acts to promote germination. After using RAB18:ENY seedlings to induce ENY during ABA application, key genes in gibberellin (GA) metabolism and signaling were differentially regulated in a manner suggesting negative feedback regulation. Furthermore, GA treatment resulted in a skotomorphogenic-like phenotype in light-grown 2x35S:ENY and RAB18:ENY seedlings. The physical interaction of ENY with DELLAs and an ENY-triggered accumulation of DELLA transcripts during maturation support the conclusion that ENY mediates GA effects to balance ABA-promoted maturation during late seed development. PMID:21571950

  9. Trajectory surface hopping study of the O((3)P) + C2H2 reaction dynamics: effect of collision energy on the extent of intersystem crossing.

    PubMed

    Rajak, Karunamoy; Maiti, Biswajit

    2014-01-28

    Intersystem crossing (ISC) dynamics plays an important role in determining the product branching in the O((3)P) + C2H2 reaction despite the necessarily small spin-orbit coupling constant values. In this study we investigate the effect of collision energy on the extent of the contribution of a spin non-conserving route through ISC dynamics to the product distributions at the initial collision energies 8.2, 9.5, and 13.1 kcal/mol. A direct dynamics trajectory surface hopping method is employed with potential energy surfaces generated at the unrestricted B3LYP/6-31G(d,p) level of theory to perform nonadiabatic dynamics. To make our calculation simpler, nonadibatic transitions were only considered at the triplet-singlet intersections. At the crossing points, Landau-Zener transition probabilities were calculated using spin-orbit coupling constant values computed at the same geometry. The Landau-Zener model for the title reaction is validated against a more rigorous Tully's fewest switches method and found to be working reasonably well as expected because of weak spin-orbit coupling. We have compared our results with the recent crossed molecular beam experiments and observed a very good agreement with respect to the primary product branching ratios. Our calculation revealed that there is no noticeable effect of the initial collision energy on the overall product distributions that corroborates the recent experimental findings. Our calculation indicates, however, that the extent of intersystem crossing contributions varies significantly with collision energy, needed to be verified, experimentally. PMID:25669530

  10. Time-dependent density-functional study of the ionization and fragmentation of C2H2 and H2 by strong circularly polarized laser pulses

    NASA Astrophysics Data System (ADS)

    Russakoff, Arthur; Varga, Kálmán

    2015-11-01

    The ionization and fragmentation dynamics of acetylene and the hydrogen molecule driven by strong short circularly polarized laser pulses are investigated within the framework of the time-dependent density-functional theory coupled with the Ehrenfest dynamics. The effects of alignment are considered and the dynamics is compared to that driven by linearly polarized pulses. It is found that the coupled ion-electron dynamics of both molecules driven by circularly polarized pulses follows the enhanced ionization mechanism, as was found in previous theoretical studies with linearly polarized pulses. A moderate localization asymmetry in the ionization dynamics of the hydrogen molecule was also found, in qualitative agreement with previous experimental investigations.

  11. Frequency-comb referenced spectroscopy of v4- and v5-excited hot bands in the 1.5 μm spectrum of C2H2

    NASA Astrophysics Data System (ADS)

    Twagirayezu, Sylvestre; Cich, Matthew J.; Sears, Trevor J.; McRaven, Christopher P.; Hall, Gregory E.

    2015-10-01

    Doppler-free transition frequencies for v4- and v5-excited hot bands have been measured in the v1 + v3 band region of the spectrum of acetylene using saturation dip spectroscopy with an extended cavity diode laser referenced to a frequency comb. The frequency accuracy of the measured transitions, as judged from line shape model fits and comparison to known frequencies in the v1 + v3 band itself, is between 3 and 22 kHz. This is some three orders of magnitude improvement on the accuracy and precision of previous line position estimates that were derived from the analysis of high-resolution Fourier transform infrared absorption spectra. Comparison to transition frequencies computed from constants derived from published Fourier transform infrared spectra shows that some upper rotational energy levels suffer specific perturbations causing energy level shifts of up to several hundred MHz. These perturbations are due to energy levels of the same rotational quantum number derived from nearby vibrational levels that become degenerate at specific energies. Future identification of the perturbing levels will provide accurate relative energies of excited vibrational levels of acetylene in the 7100-7600 cm-1 energy region.

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

    PubMed

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

    1999-10-01

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

  13. Chanabayaite, Cu2(N3C2H2)Cl(NH3,Cl,H2O,□)4, a new mineral containing triazolate anion

    NASA Astrophysics Data System (ADS)

    Chukanov, N. V.; Zubkova, N. V.; Möhn, G.; Pekov, I. V.; Pushcharovsky, D. Yu.; Zadov, A. E.

    2015-12-01

    A new mineral, chanabayaite, has been discovered at a guano deposit located at Mt. Pabellón de Pica near the village of Chanabaya, Iquique Province, Tarapacá region, Chile. It is associated with salammoniac, halite, joanneumite, nitratine and earlier chalcopyrite. Chanabayaite occurs as blue translucent imperfect prismatic crystals, up to 0.05 × 0.1 × 0.5 mm in size, and their radial aggregates. Chanabayaite is brittle, with a Mohs' hardness of 2. The cleavage is perfect on (001) and imperfect on (100) and (010). D meas = 1.48(2) g/cm3, D calc = 1.464 g/cm3. The mineral is optically biaxial (-), α = 1.561(2), β = 1.615(3), γ = 1.620(2), 2 V meas = 25(10)°, 2 V calc = 33°. Pleochroism is strong, Z ≈ Y (deep blue) ≫ X (pale blue with gray tint). IR spectrum is given. The chemical composition (electron microprobe data for Cu, Fe and Cl; gas chromatography data for H, N, C and O) is as follows (wt %): 32.23 Cu, 1.14 Fe, 16.13 Cl, 3.1 H, 29.9 N, 12.2 C, 3.4 O, total is 98.1. The empirical formula is ( Z = 4): Cu1.92Fe0.08Cl1.72N8.09C3.85H11.66O0.81. The structural model was based on the single-crystal X-ray diffraction data ( R = 0.1627). Chanabayaite is orthorhombic, space group Imma, a = 19.484(3), b = 7.2136(10), c = 11.999(4) Å, V = 1686.5(7) Å3, Z = 2. In chanabayaite, chains of the corner-sharing Cu(l)-centered octahedra and single Cu(2)-centered octahedra are linked via 1,2,4-triazolate anions C2N3H2 -. NH3 and Cl- are additional ligands coordinating Cu2+. Chanabayaite is a transformational mineral species formed by leaching of Na and one third of Cl and partial dehydration of the protophase Na2Cu2Cl3(N3C2H2)2(NH3)2 • 4H2O. The strongest reflections in the powder X-ray diffraction pattern [ d, Å ( I, %) ( hkl)] are detected: 10.19 (100) (101), 6.189 (40) (011), 5.729 (23) (301), 5.216 (75) (211, 202), 4.964 (20) (400), 2.830 (20) (602, 413, 503), 2.611 (24) (123, 422, 404).

  14. C2H2 zinc finger proteins of the SP/KLF, Wilms tumor, EGR, Huckebein, and Klumpfuss families in metazoans and beyond.

    PubMed

    Pei, Jimin; Grishin, Nick V

    2015-11-15

    Specificity proteins (SPs) and Krüppel-Like Factors (KLFs) are C2H2-type zinc finger transcription factors that play essential roles in differentiation, development, proliferation and cell death. SP/KLF proteins, similarly to Wilms tumor protein 1 (WT1), Early Growth Response (EGR), Huckebein, and Klumpfuss, prefer to bind GC-rich sequences such as GC-box and CACCC-box (GT-box). We searched various genomes and transcriptomes of metazoans and single-cell holozoans for members of these families. Seven groups of KLFs (KLFA-G) and three groups of SPs (SPA-C) were identified in the three lineages of Bilateria (Deuterostomia, Ecdysozoa, and Lophotrochozoa). The last ancestor of jawed vertebrates was inferred to have at least 18 KLFs (group A: KLF1/2/4/17, group B: KLF3/8/12; group C: KLF5/5l; group D: KLF6/7; group E: KLF9/13/16; group F: KLF10/KLF11; group G: KLF15/15l) and 10 SPs (group A: SP1/2/3/4; group B: SP5/5l; group C: SP6/7/8/9), since they were found in both cartilaginous and boned fishes. Placental mammals have added KLF14 (group E) and KLF18 (group A), and lost KLF5l (KLF5-like) and KLF15l (KLF15-like). Multiple KLF members were found in basal metazoans (Ctenophora, Porifera, Placozoa, and Cnidaria). Ctenophora has the least number of KLFs and no SPs, which could be attributed to its proposed sister group relationship to other metazoans or gene loss. While SP, EGR and Klumpfuss were only detected in metazoans, KLF, WT1, and Huckebein are present in nonmetazoan holozoans. Of the seven metazoan KLF groups, only KLFG, represented by KLF15 in human, was found in nonmetazoans. In addition, two nonmetazoan groups of KLFs are present in Choanoflagellatea and Filasterea. WT1 could be evolutionarily the earliest among these GC/GT-box-binding families due to its sole presence in Ichthyosporea. PMID:26187067

  15. 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.

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

    NASA Astrophysics Data System (ADS)

    Manda, Abdullah Ahmed

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

  17. A Short-Term Decrease in Nitrogenase Activity (C2H2 Reduction) Is Induced by Exposure of Soybean Shoots to Their CO2 Compensation Point.

    PubMed Central

    Vidal, R.; Gerbaud, A.; Vidal, D.; Drevon, J. J.

    1995-01-01

    Photosynthesis and nitrogenase acetylene-reducing activity (ARA) were measured in soybeans (Glycine max [L.] Merr.) in which the shoots were exposed for 48 h to 60 [mu]L L-1 CO2, a value corresponding to their CO2 compensation point. Six hours after the beginning of the light period at low CO2, the ARA started to decrease, reaching a rate of 50% of the control rate in 14 to 24 h and 20% of the control rate in 34 to 38 h after the beginning of the CO2 treatment. At these times, there was no net photosynthesis, and the transpiration rate was 20% lower than that in the control plants. An increase in the partial pressure of O2 around the nodules alleviated this inhibition of ARA. The maximal ARA achieved at 40 kPaO2 was 3 times higher than that at 20 kPa O2 and similar to the maximal ARA of the control plants. It was argued that the decrease in ARA of soybean exposed to the CO2 compensation point was due to a decrease in the nodule's permeability to O2 diffusion. PMID:12228555

  18. Is the Reaction of C3N(-) with C2H2 a Possible Process for Chain Elongation in Titan's Ionosphere?

    PubMed

    Lindén, Fredrik; Alcaraz, Christian; Ascenzi, Daniela; Guillemin, Jean-Claude; Koch, Leopold; Lopes, Allan; Polášek, Miroslav; Romanzin, Claire; Žabka, Jan; Zymak, Illia; Geppert, Wolf D

    2016-07-14

    The reaction of C3N(-) with acetylene was studied using three different experimental setups, a triple quadrupole mass spectrometer (Trento), a tandem quadrupole mass spectrometer (Prague), and the "CERISES" guided ion beam apparatus at Orsay. The process is of astrophysical interest because it can function as a chain elongation mechanism to produce larger anions that have been detected in Titan's ionosphere by the Cassini Plasma Spectrometer. Three major products of primary processes, C2H(-), CN(-), and C5N(-), have been identified, whereby the production of the cyanide anion is probably partly due to collisional induced dissociation. The formations of all these products show considerable reaction thresholds and also display comparatively small cross sections. Also, no strong signals of anionic products for collision energies lower than 1 eV have been observed. Ab initio calculations have been performed to identify possible pathways leading to the observed products of the title reaction and to elucidate the thermodynamics of these processes. Although the productions of CN(-) and C5N(-) are exoergic, all reaction pathways have considerable barriers. Overall, the results of these computations are in agreement with the observed reaction thresholds. Due to the existence of considerable reaction energy barriers and the small observed cross sections, the title reaction is not very likely to play a major role in the buildup of large anions in cold environments like the interstellar medium or planetary and satellite ionospheres. PMID:27135984

  19. Reduced dimension rovibrational variational calculations of the S(1) state of C2H2. II. The S(1) rovibrational manifold and the effects of isomerization.

    PubMed

    Changala, P Bryan; Baraban, Joshua H; Stanton, John F; Merer, Anthony J; Field, Robert W

    2014-01-14

    Reduced dimension variational calculations have been performed for the rovibrational level structure of the S1 state of acetylene. The state exhibits an unusually complicated level structure, for various reasons. First, the potential energy surface has two accessible conformers, trans and cis. The cis conformer lies about 2700 cm(-1) above the trans, and the barrier to cis-trans isomerization lies about 5000 cm(-1) above the trans minimum. The trans vibrations ν4 (torsion) and ν6 (asym. bend) interact very strongly by Darling-Dennison and Coriolis resonances, such that their combination levels and overtones form polyads with unexpected structures. Both conformers exhibit very large x36 cross-anharmonicity since the pathway to isomerization is a combination of ν6 and ν3 (sym. bend). Near the isomerization barrier, the vibrational levels show an even-odd K-staggering of their rotational levels as a result of quantum mechanical tunneling through the barrier. The present calculations address all of these complications, and reproduce the observed K-structures of the bending and C-C stretching levels with good qualitative accuracy. It is expected that they will assist with the assignment of the irregular patterns near the isomerization barrier. PMID:24437883

  20. Least Squares Fitting of Perturbed Vibrational Polyads Near the Isomerization Barrier in the S_1 State of C_2H_2

    NASA Astrophysics Data System (ADS)

    Merer, A. J.; Baraban, J. H.; Changala, P. B.; Field, R. W.

    2013-06-01

    The S_1 electronic state of acetylene has recently been shown to have two potential minima, corresponding to cis- and trans-bent structures. The trans-bent isomer is the more stable, with the cis-bent isomer lying about 2670 cm^{-1} higher; the barrier to isomerization lies roughly 5000 cm^{-1} above the trans zero-point level. The ``isomerization coordinate'' (along which the molecule moves to get from the trans minimum to the barrier) is a combination of the ν_3 (trans bending) and ν_6 (cis bending) vibrational normal coordinates, but the spectrum is very confused because the ν_6 vibration interacts strongly with the ν_4 (torsion) vibration through Coriolis and Darling-Dennison resonances. Since the ν_4 and ν_6 fundamental frequencies are almost equal, the bending vibrational structure consists of polyads. At low vibrational energies the polyads where these three vibrations are excited can be fitted by least squares almost to experimental accuracy with a simple model of Coriolis and Darling-Dennison interactions, but at higher energies the huge x_{36} cross-anharmonicity, which is a symptom that the levels are approaching the isomerization barrier, progressively destroys the polyad structure; in addition the levels show an increasing even-odd staggering of their K-rotational structures, as predicted by group theory. It is not possible to fit the levels near the barrier with a simple model, though some success has been achieved with extended models. Progress with the fitting of the polyads near the barrier will be reviewed. A. L. Utz, J. D. Tobiason, E. Carrasquillo M., L. J. Sanders and F. F. Crim, J. Chem. Phys. {98}, 2742, 1993.

  1. 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

  2. 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.

  3. Electronic Spectroscopy and Dynamics of the Acetylene - Complex

    NASA Astrophysics Data System (ADS)

    Ju, Shan-Shan

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

  4. 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.

  5. 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.

  6. Vapor-Liquid Equilibrium in the Mixture 1,1,1,2-Tetrafluoroethane C2H2F4 + C4H10O2 2,5-Dioxahexane (EVLM1111, LB5748_E)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture 1,1,1,2-Tetrafluoroethane C2H2F4 + C4H10O2 2,5-Dioxahexane (EVLM1111, LB5748_E)' providing data from direct measurement of pressure at variable mole fraction in liquid phase and constant temperature.

  7. Vapor-Liquid Equilibrium in the Mixture Pentafluoroethane C2HF5 + C2H2F4 1,1,1,2-Tetrafluoroethane (EVLM1311, LB5632_E)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture Pentafluoroethane C2HF5 + C2H2F4 1,1,1,2-Tetrafluoroethane (EVLM1311, LB5632_E)' providing data from direct measurement of pressure at variable temperature and constant mole fraction in liquid phase.

  8. Vapor-Liquid Equilibrium in the Mixture 1,1,2,2-Tetrachloroethane C2H2Cl4 + C3H3N Propenenitrile (EVLM1211, LB5648_E)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'vapor-Liquid Equilibrium in the Mixture 1,1,2,2-Tetrachloroethane C2H2Cl4 + C3H3N Propenenitrile (EVLM1211, LB5648_E)' providing data from direct measurement of temperature at variable mole fraction in liquid phase and constant pressure.

  9. Threshold Ionization and Spin-Orbit Coupling of Ceracyclopropene Formed by Ethylene Dehydrogenation.

    PubMed

    Zhang, Yuchen; Schmidt, Michael W; Kumari, Sudesh; Gordon, Mark S; Yang, Dong-Sheng

    2016-09-01

    A Ce atom reaction with ethylene was carried out in a laser-vaporization metal cluster beam source. Ce(C2H2) formed by hydrogen elimination from ethylene was investigated by mass-analyzed threshold ionization (MATI) spectroscopy, isotopic substitutions, and relativistic quantum chemical computations. The theoretical calculations include a scalar relativistic correction, dynamic electron correlation, and spin-orbit coupling. The MATI spectrum exhibits two nearly identical band systems separated by 128 cm(-1). The separation is not affected by deuteration. The two-band systems are attributed to spin-orbit splitting and the vibrational bands to the symmetric metal-ligand stretching and in-plane carbon-hydrogen bending excitations. The spin-orbit splitting arises from interactions of a pair of nearly degenerate triplets and a pair of nearly degenerate singlets. The organolanthanide complex is a metallacyclopropene in C2v symmetry. The low-energy valence electron configurations of the neutral and ion species are Ce 4f(1)6s(1) and Ce 4f(1), respectively. The remaining two electrons that are associated with the isolated Ce atom or ion are spin paired in a molecular orbital that is a bonding combination between a 5d Ce orbital and a π* antibonding orbital of acetylene. PMID:27548080

  10. Near infrared diode laser spectroscopy of C2H2, H2O, CO2 and their isotopologues and the application to TDLAS, a tunable diode laser spectrometer for the martian PHOBOS-GRUNT space mission

    NASA Astrophysics Data System (ADS)

    Durry, G.; Li, J. S.; Vinogradov, I.; Titov, A.; Joly, L.; Cousin, J.; Decarpenterie, T.; Amarouche, N.; Liu, X.; Parvitte, B.; Korablev, O.; Gerasimov, M.; Zéninari, V.

    2010-04-01

    A near-infrared tunable diode laser spectrometer called TDLAS has been developed that combines telecommunication-type as well as new-generation antimonide laser diodes to measure C2H2, H2O, CO2 and their isotopologues in the near infrared. This sensor is devoted to the in situ analysis of the soil of the Martian satellite PHOBOS, within the framework of the Russian space mission PHOBOS-GRUNT. In the first part of the paper, we report accurate spectroscopic measurements of C2H2 and 13C12CH2 near 1.533 μm, of H2O and CO2 at 2.682 μm and of the isotopologues 13C16O2 and 16O12C18O near 2.041 μm and H2 17O, H2 18O and HDO near 2.642 μm. The achieved line strengths are thoroughly compared to data from molecular databases or from former experimental determinations. In the second part of the paper, we describe the TDLAS spectrometer for the PHOBOS-GRUNT mission.

  11. The composition of Saturn's atmosphere at northern temperate latitudes from Voyager IRIS spectra - NH3, PH3, C2H2, C2H6, CH3D, CH4, and the Saturnian D/H isotopic ratio

    NASA Technical Reports Server (NTRS)

    Courtin, R.; Gautier, D.; Marten, A.; Bezard, B.; Hanel, R.

    1984-01-01

    The vertical distributions and mixing ratios of minor constituents in the northern hemisphere of Saturn are investigated. Results are obtained for NH3, PH3, C2H2, C2H6, CH3D, and CH4; the D/H ratio is obtained from the CH4 and CH3D abundances. The NH3 mixing ratio in the upper atmosphere is found to be compatible with the saturated partial pressure. The inferred PH3/H2 ratio of 1.4 + or - 0.8 x 10 to the -6th is higher than the value derived from the solar P/H ratio. The stratospheric C2H2/H2 and C2H6/H2 ratios are, respectively, 2.1 + or - 1.4 x 10 to the -7th and 3.0 + or - 1.1 x 10 to the -6th; the latter decreases sharply below the 20-50 mbar level. The results for CH3D/H2 and CH4/H2 imply an enrichment of Saturn's upper atmosphere in carbon by a factor of at least three over the solar abundance. The interpretation of two NH3 lines in the five-micron window suggests a NH3/H2 ratio at the two bar level below the solar value.

  12. 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

  13. H2, He, and CO2 line-broadening coefficients, pressure shifts and temperature-dependence exponents for the HITRAN database. Part 1: SO2, NH3, HF, HCl, OCS and C2H2

    NASA Astrophysics Data System (ADS)

    Wilzewski, Jonas S.; Gordon, Iouli E.; Kochanov, Roman V.; Hill, Christian; Rothman, Laurence S.

    2016-01-01

    To increase the potential for use of the HITRAN database in astronomy, experimental and theoretical line-broadening coefficients, line shifts and temperature-dependence exponents of molecules of planetary interest broadened by H2, He, and CO2 have been assembled from available peer-reviewed sources. The collected data were used to create semi-empirical models so that every HITRAN line of the studied molecules has corresponding parameters. Since H2 and He are major constituents in the atmospheres of gas giants, and CO2 predominates in atmospheres of some rocky planets with volcanic activity, these spectroscopic data are important for remote sensing studies of planetary atmospheres. In this paper we make the first step in assembling complete sets of these parameters, thereby creating datasets for SO2, NH3, HF, HCl, OCS and C2H2.

  14. On the Stark effect in open shell complexes exhibiting partially quenched electronic angular momentum: Infrared laser Stark spectroscopy of OH-C2H2, OH-C2H4, and OH-H2O

    NASA Astrophysics Data System (ADS)

    Moradi, Christopher P.; Douberly, Gary E.

    2015-08-01

    The Stark effect is considered for polyatomic open shell complexes that exhibit partially quenched electronic angular momentum. Matrix elements of the Stark Hamiltonian represented in a parity conserving Hund's case (a) basis are derived for the most general case, in which the permanent dipole moment has projections on all three inertial axes of the system. Transition intensities are derived, again for the most general case, in which the laser polarization has projections onto axes parallel and perpendicular to the Stark electric field, and the transition dipole moment vector is projected onto all three inertial axes in the molecular frame. Simulations derived from this model are compared to experimental rovibrational Stark spectra of OH-C2H2, OH-C2H4, and OH-H2O complexes formed in helium nanodroplets.

  15. Properties of acetylene

    SciTech Connect

    Pavlovcak, J.T.

    1994-12-31

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

  16. A novel rice C2H2-type zinc finger protein, ZFP36, is a key player involved in abscisic acid-induced antioxidant defence and oxidative stress tolerance in rice

    PubMed Central

    Zhang, Hong; Liu, Yanpei; Wen, Feng; Yao, Dongmei; Wang, Lu; Guo, Jin; Ni, Lan; Zhang, Aying; Tan, Mingpu; Jiang, Mingyi

    2014-01-01

    C2H2-type zinc finger proteins (ZFPs) have been shown to play important roles in the responses of plants to oxidative and abiotic stresses, and different members of this family might have different roles during stresses. Here a novel abscisic acid (ABA)- and hydrogen peroxide (H2O2)-responsive C2H2-type ZFP gene, ZFP36, is identified in rice. The analyses of ZFP36-overexpressing and silenced transgenic rice plants showed that ZFP36 is involved in ABA-induced up-regulation of the expression and the activities of superoxide dismutase (SOD) and ascorbate peroxidase (APX). Overexpression of ZFP36 in rice plants was found to elevate the activities of antioxidant enzymes and to enhance the tolerance of rice plants to water stress and oxidative stress. In contrast, an RNA interference (RNAi) mutant of ZFP36 had lower activities of antioxidant enzymes and was more sensitive to water stress and oxidative stress. ABA-induced H2O2 production and ABA-activated mitogen-activated protein kinases (MAPKs) were shown to regulate the expression of ZFP36 in ABA signalling. On the other hand, ZFP36 also regulated the expression of NADPH oxidase genes, the production of H2O2, and the expression of OsMPK genes in ABA signalling. These results indicate that ZFP36 is required for ABA-induced antioxidant defence, for the tolerance of rice plants to water stress and oxidative stress, and for the regulation of the cross-talk between NADPH oxidase, H2O2, and MAPK in ABA signalling. PMID:25071223

  17. Negative regulation of the vacuole-mediated resistance to K(+) stress by a novel C2H2 zinc finger transcription factor encoded by aslA in Aspergillus nidulans.

    PubMed

    Park, Dong Soo; Yu, Yeong Man; Kim, Yong Jin; Maeng, Pil Jae

    2015-02-01

    In fungi and plants, vacuoles function as a storage and sequestration vessel for a wide variety of ions and are responsible for cytosolic ion homeostasis and responses to ionic shock. In the filamentous fungus Aspergillus nidulans, however, little is known about the molecular genetic mechanisms of vacuolar biogenesis and function. In the present study, we analyzed the function of the aslA gene (AN5583) encoding a novel C2H2-type zinc finger transcription factor (TF) in relation to K(+) stress resistance, vacuolar morphology, and vacuolar transporters. The mutant lacking aslA showed increased mycelial growth and decreased branching at high K(+) concentrations. Deletion of aslA also caused elevated K(+) stress-inducible expression of the genes, nhxA (AN2288), vnxA (AN6986), and vcxA (AN0471), encoding putative endosomal and vacuolar cation/H(+) exchangers, as well as cpyA and vpsA genes encoding the proteins involved in vacuolar biogenesis. Interestingly, vacuolar fragmentation induced by K(+) stress was alleviated by aslA deletion, resulting in persistence of unfragmented vacuoles. In the presence of bafilomycin, an inhibitor of vacuolar H(+)-ATPase, the mutant phenotype was suppressed in terms of growth rates and vacuolar morphology. These results together suggest that the C2H2-type zinc finger TF AslA attenuates the K(+) stress-inducible expression of the genes encoding the ion pumps involved in vacuolar sequestration of K(+) ions powered by vacuolar H(+)-ATPase, as well as the proteins that function in vacuolar biogenesis. PMID:25626364

  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. 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. Comparison of one-particle basis set extrapolation to explicitly correlated methods for the calculation of accurate quartic force fields, vibrational frequencies, and spectroscopic constants: application to H2O, N2H+, NO2+, and C2H2.

    PubMed

    Huang, Xinchuan; Valeev, Edward F; Lee, Timothy J

    2010-12-28

    One-particle basis set extrapolation is compared with one of the new R12 methods for computing highly accurate quartic force fields (QFFs) and spectroscopic data, including molecular structures, rotational constants, and vibrational frequencies for the H(2)O, N(2)H(+), NO(2)(+), and C(2)H(2) molecules. In general, agreement between the spectroscopic data computed from the best R12 and basis set extrapolation methods is very good with the exception of a few parameters for N(2)H(+) where it is concluded that basis set extrapolation is still preferred. The differences for H(2)O and NO(2)(+) are small and it is concluded that the QFFs from both approaches are more or less equivalent in accuracy. For C(2)H(2), however, a known one-particle basis set deficiency for C-C multiple bonds significantly degrades the quality of results obtained from basis set extrapolation and in this case the R12 approach is clearly preferred over one-particle basis set extrapolation. The R12 approach used in the present study was modified in order to obtain high precision electronic energies, which are needed when computing a QFF. We also investigated including core-correlation explicitly in the R12 calculations, but conclude that current approaches are lacking. Hence core-correlation is computed as a correction using conventional methods. Considering the results for all four molecules, it is concluded that R12 methods will soon replace basis set extrapolation approaches for high accuracy electronic structure applications such as computing QFFs and spectroscopic data for comparison to high-resolution laboratory or astronomical observations, provided one uses a robust R12 method as we have done here. The specific R12 method used in the present study, CCSD(T)(R12), incorporated a reformulation of one intermediate matrix in order to attain machine precision in the electronic energies. Final QFFs for N(2)H(+) and NO(2)(+) were computed, including basis set extrapolation, core-correlation, scalar

  1. Non-covalent C-Cl…π interaction in acetylene-carbon tetrachloride adducts: Matrix isolation infrared and ab initio computational studies.

    PubMed

    Ramanathan, N; Sundararajan, K; Vidya, K; Jemmis, Eluvathingal D

    2016-03-15

    Non-covalent halogen-bonding interactions between π cloud of acetylene (C2H2) and chlorine atom of carbon tetrachloride (CCl4) have been investigated using matrix isolation infrared spectroscopy and quantum chemical computations. The structure and the energies of the 1:1 C2H2-CCl4 adducts were computed at the B3LYP, MP2 and M05-2X levels of theory using 6-311++G(d,p) basis set. The computations indicated two minima for the 1:1 C2H2-CCl4 adducts; with the C-Cl…π adduct being the global minimum, where π cloud of C2H2 is the electron donor. The second minimum corresponded to a C-H…Cl adduct, in which C2H2 is the proton donor. The interaction energies for the adducts A and B were found to be nearly identical. Experimentally, both C-Cl…π and C-H…Cl adducts were generated in Ar and N2 matrixes and characterized using infrared spectroscopy. This is the first report on halogen bonded adduct, stabilized through C-Cl…π interaction being identified at low temperatures using matrix isolation infrared spectroscopy. Atoms in Molecules (AIM) and Natural Bond Orbital (NBO) analyses were performed to support the experimental results. The structures of 2:1 ((C2H2)2-CCl4) and 1:2 (C2H2-(CCl4)2) multimers and their identification in the low temperature matrixes were also discussed. PMID:26722673

  2. Non-covalent C-Cl…π interaction in acetylene-carbon tetrachloride adducts: Matrix isolation infrared and ab initio computational studies

    NASA Astrophysics Data System (ADS)

    Ramanathan, N.; Sundararajan, K.; Vidya, K.; Jemmis, Eluvathingal D.

    2016-03-01

    Non-covalent halogen-bonding interactions between π cloud of acetylene (C2H2) and chlorine atom of carbon tetrachloride (CCl4) have been investigated using matrix isolation infrared spectroscopy and quantum chemical computations. The structure and the energies of the 1:1 C2H2-CCl4 adducts were computed at the B3LYP, MP2 and M05-2X levels of theory using 6-311 ++G(d,p) basis set. The computations indicated two minima for the 1:1 C2H2-CCl4 adducts; with the C-Cl…π adduct being the global minimum, where π cloud of C2H2 is the electron donor. The second minimum corresponded to a C-H…Cl adduct, in which C2H2 is the proton donor. The interaction energies for the adducts A and B were found to be nearly identical. Experimentally, both C-Cl…π and C-H…Cl adducts were generated in Ar and N2 matrixes and characterized using infrared spectroscopy. This is the first report on halogen bonded adduct, stabilized through C-Cl…π interaction being identified at low temperatures using matrix isolation infrared spectroscopy. Atoms in Molecules (AIM) and Natural Bond Orbital (NBO) analyses were performed to support the experimental results. The structures of 2:1 ((C2H2)2-CCl4) and 1:2 (C2H2-(CCl4)2) multimers and their identification in the low temperature matrixes were also discussed.

  3. Acetylenic carbon allotrope

    SciTech Connect

    1999-11-16

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

  4. 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.

  5. 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.

  6. Acetylenic carbon allotrope

    DOEpatents

    Lagow, R.J.

    1998-02-10

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

  7. 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.

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

    SciTech Connect

    Tedeschi, R.J.

    1982-01-01

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

  9. Optimization, Yield Studies and Morphology of WO3Nano-Wires Synthesized by Laser Pyrolysis in C2H2and O2Ambients—Validation of a New Growth Mechanism

    PubMed Central

    2008-01-01

    Laser pyrolysis has been used to synthesize WO3nanostructures. Spherical nano-particles were obtained when acetylene was used to carry the precursor droplet, whereas thin films were obtained at high flow-rates of oxygen carrier gas. In both environments WO3nano-wires appear only after thermal annealing of the as-deposited powders and films. Samples produced under oxygen carrier gas in the laser pyrolysis system gave a higher yield of WO3nano-wires after annealing than the samples which were run under acetylene carrier gas. Alongside the targeted nano-wires, the acetylene-ran samples showed trace amounts of multi-walled carbon nano-tubes; such carbon nano-tubes are not seen in the oxygen-processed WO3nano-wires. The solid–vapour–solid (SVS) mechanism [B. Mwakikunga et al., J. Nanosci. Nanotechnol., 2008] was found to be the possible mechanism that explains the manner of growth of the nano-wires. This model, based on the theory from basic statistical mechanics has herein been validated by length-diameter data for the produced WO3nano-wires.

  10. Direct measurements of rate constants for the reactions of CH3 radicals with C2H6, C2H4, and C2H2 at high temperatures.

    PubMed

    Peukert, S L; Labbe, N J; Sivaramakrishnan, R; Michael, J V

    2013-10-10

    The shock tube technique has been used to study the reactions CH3 + C2H6 → C2H4 + CH4 + H (1), CH3 + C2H4 → Products + H (2), and CH3 + C2H2 → Products + H (3). Biacetyl, (CH3CO)2, was used as a clean high temperature thermal source for CH3-radicals for all the three reactions studied in this work. For reaction 1, the experiments span a T-range of 1153 K ≤ T ≤ 1297 K, at P ~ 0.4 bar. The experiments on reaction 2 cover a T-range of 1176 K ≤ T ≤ 1366 K, at P ~ 1.0 bar, and those on reaction 3 a T-range of 1127 K ≤ T ≤ 1346 K, at P ~ 1.0 bar. Reflected shock tube experiments performed on reactions 1-3, monitored the formation of H-atoms with H-atom Atomic Resonance Absorption Spectrometric (ARAS). Fits to the H-atom temporal profiles using an assembled kinetics model were used to make determinations for k1, k2, and k3. In the case of C2H6, the measurements of [H]-atoms were used to derive direct high-temperature rate constants, k1, that can be represented by the Arrhenius equation k1(T) = 5.41 × 10(-12) exp(-6043 K/T) cm(3) molecules(-1) s(-1) (1153 K ≤ T ≤ 1297 K) for the only bimolecular process that occurs, H-atom abstraction. TST calculations based on ab initio properties calculated at the CCSD(T)/CBS//M06-2X/cc-pVTZ level of theory show excellent agreement, within ±20%, of the measured rate constants. For the reaction of CH3 with C2H4, the present rate constant results, k2', refer to the sum of rate constants, k(2b) + k(2c), from two competing processes, addition-elimination, and the direct abstraction CH3 + C2H4 → C3H6 + H (2b) and CH3 + C2H4 → C2H2 + H + CH4 (2c). Experimental rate constants for k2' can be represented by the Arrhenius equation k2'(T) = 2.18 × 10(-10) exp(-11830 K/T) cm(3) molecules(-1) s(-1) (1176 K ≤ T ≤ 1366 K). The present results are in excellent agreement with recent theoretical predictions. The present study provides the only direct measurement for the high-temperature rate constants for these channels

  11. The C2H2 Transcription Factor REGULATOR OF SYMBIOSOME DIFFERENTIATION Represses Transcription of the Secretory Pathway Gene VAMP721a and Promotes Symbiosome Development in Medicago truncatula[W][OPEN

    PubMed Central

    Sinharoy, Senjuti; Torres-Jerez, Ivone; Bandyopadhyay, Kaustav; Kereszt, Attila; Pislariu, Catalina I.; Nakashima, Jin; Benedito, Vagner A.; Kondorosi, Eva; Udvardi, Michael K.

    2013-01-01

    Transcription factors (TFs) are thought to regulate many aspects of nodule and symbiosis development in legumes, although few TFs have been characterized functionally. Here, we describe REGULATOR OF SYMBIOSOME DIFFERENTIATION (RSD) of Medicago truncatula, a member of the Cysteine-2/Histidine-2 (C2H2) family of plant TFs that is required for normal symbiosome differentiation during nodule development. RSD is expressed in a nodule-specific manner, with maximal transcript levels in the bacterial invasion zone. A tobacco (Nicotiana tabacum) retrotransposon (Tnt1) insertion rsd mutant produced nodules that were unable to fix nitrogen and that contained incompletely differentiated symbiosomes and bacteroids. RSD protein was localized to the nucleus, consistent with a role of the protein in transcriptional regulation. RSD acted as a transcriptional repressor in a heterologous yeast assay. Transcriptome analysis of an rsd mutant identified 11 genes as potential targets of RSD repression. RSD interacted physically with the promoter of one of these genes, VAMP721a, which encodes vesicle-associated membrane protein 721a. Thus, RSD may influence symbiosome development in part by repressing transcription of VAMP721a and modifying vesicle trafficking in nodule cells. This establishes RSD as a TF implicated directly in symbiosome and bacteroid differentiation and a transcriptional regulator of secretory pathway genes in plants. PMID:24082011

  12. The C2H2-type transcription factor, FlbC, is involved in the transcriptional regulation of Aspergillus oryzae glucoamylase and protease genes specifically expressed in solid-state culture.

    PubMed

    Tanaka, Mizuki; Yoshimura, Midori; Ogawa, Masahiro; Koyama, Yasuji; Shintani, Takahiro; Gomi, Katsuya

    2016-07-01

    Aspergillus oryzae produces a large amount of secreted proteins in solid-state culture, and some proteins such as glucoamylase (GlaB) and acid protease (PepA) are specifically produced in solid-state culture, but rarely in submerged culture. From the disruption mutant library of A. oryzae transcriptional regulators, we successfully identified a disruption mutant showing an extremely low production level of GlaB but a normal level of α-amylase production. This strain was a disruption mutant of the C2H2-type transcription factor, FlbC, which is reported to be involved in the regulation of conidiospore development. Disruption mutants of other upstream regulators comprising a conidiation regulatory network had no apparent effect on GlaB production in solid-state culture. In addition to GlaB, the production of acid protease in solid-state culture was also markedly decreased by flbC disruption. Northern blot analyses revealed that transcripts of glaB and pepA were significantly decreased in the flbC disruption strain. These results suggested that FlbC is involved in the transcriptional regulation of genes specifically expressed under solid-state cultivation conditions, possibly independent of the conidiation regulatory network. PMID:26960315

  13. Optical emission spectroscopy study of premixed C2H4/O2 and C2H4/C2H2/O2 flames for diamond growth with and without CO2 laser excitation

    NASA Astrophysics Data System (ADS)

    He, X. N.; Gebre, T.; Shen, X. K.; Xie, Z. Q.; Zhou, Y. S.; Lu, Y. F.

    2010-02-01

    Optical emission spectroscopy (OES) measurements were carried out to study premixed C2H4/O2 and C2H4/C2H2/O2 combustion flame for diamond deposition with and without a CO2 laser excitation. Strong emissions from radicals C2 and CH were observed in the visible range in all the OES spectra acquired. By adding a continuous-wave CO2 laser to irradiate the flame at a wavelength of 10.591 μm, the common CO2 laser wavelength, it was discovered that the emission intensities of the C2 and CH radicals were increased due to the laser beam induced excitation. OES measurements of the C2 and CH radicals were performed using different gas combinations and laser powers. The rotational temperatures in the flame were determined by analyzing the spectra of the R-branch of the A2Δ-->X2Π (0, 0) electronic transition near 430 nm (CH band head). Information obtained from the OES spectra, including the emission intensities of the C2 and CH radicals, the intensity ratios, and the rotational temperatures, was integrated into the study of diamond deposition on tungsten carbide substrates for mechanism analysis of the laser induced vibrational excitation and laser-assisted diamond deposition.

  14. Isolation of a Novel Family of C2H2 Zinc Finger Proteins Implicated in Transcriptional Repression Mediated by Chicken Ovalbumin Upstream Promoter Transcription Factor (COUP-TF) Orphan Nuclear Receptors*

    PubMed Central

    Avram, Dorina; Fields, Andrew; Top, Karen Pretty On; Nevrivy, Daniel J.; Ishmael, Jane E.; Leid, Mark

    2010-01-01

    Two novel and related C2H2 zinc finger proteins that are highly expressed in the brain, CTIP1 and CTIP2 (COUP TF-interacting proteins 1 and 2, respectively), were isolated and shown to interact with all members of the chicken ovalbumin upstream promoter transcription factor (COUP-TF) subfamily of orphan nuclear receptors. The interaction of CTIP1 with ARP1 was studied in detail, and CTIP1 was found to harbor two independent ARP1 interaction domains, ID1 and ID2, whereas the putative AF-2 of ARP1 was required for interaction with CTIP1. CTIP1, which exhibited a punctate staining pattern within the nucleus of transfected cells, recruited cotransfected ARP1 to these foci and potentiated ARP1-mediated transcriptional repression of a reporter construct. However, transcriptional repression mediated by ARP1 acting through CTIP1 did not appear to involve recruitment of a trichostatin A-sensitive histone deacetylase(s) to the template, suggesting that this repression pathway may be distinct from that utilized by several other nuclear receptors. PMID:10744719

  15. Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units.

    PubMed

    Yao, Zizhu; Zhang, Zhangjing; Liu, Lizhen; Li, Ziyin; Zhou, Wei; Zhao, Yunfeng; Han, Yu; Chen, Banglin; Krishna, Rajamani; Xiang, Shengchang

    2016-04-11

    Acetylene separation is a very important but challenging industrial separation task. Here, through the solvothermal reaction of CuI and 5-triazole isophthalic acid in different solvents, two metal-organic frameworks (MOFs, FJU-21 and FJU-22) with open O donor sites and controllable robustness have been obtained for acetylene separation. They contain the same paddle-wheel {Cu2 (COO2 )4 } nodes and metal-ligand connection modes, but with different helical chains as secondary building units (SBUs), leading to different structural robustness for the MOFs. FJU-21 and FJU-22 are the first examples in which the MOFs' robustness is controlled by adjusting the helical chain SBUs. Good robustness gives the activated FJU-22 a, which has higher surface area and gas uptakes than the flexible FJU-21 a. Importantly, FJU-22 a shows extraordinary separation of acetylene mixtures under ambient conditions. The separation capacity of FJU-22 a for 50:50 C2 H2 /CO2 mixtures is about twice that of the high-capacity HOF-3, and its actual separation selectivity for C2 H2 /C2 H4 mixtures containing 1 % acetylene is the highest among reported porous materials. Based on first-principles calculations, the extraordinary separation performance of C2 H2 for FJU-22 a was attributed to hydrogen-bonding interactions between the C2 H2 molecules with the open O donors on the wall, which provide better recognition ability for C2 H2 than other functional sites, including open metal sites and amino groups. PMID:26934040

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

    PubMed

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

    2016-01-21

    Except for a few cases like water and carbon dioxide, identification and structural characterization of clusters with more than four monomers is rare. Here, we provide experimental and theoretical evidence for existence of box-like structures for a pentamer and a hexamer of mixed carbon dioxide-acetylene clusters. Two mid-infrared cluster absorption bands are observed in the CO2ν3 band region using a tunable diode laser to probe a pulsed supersonic jet. Each requires the presence of both carbon dioxide and acetylene in the jet, and (from observed rotational spacings) involves clusters containing about 4 to 7 molecules. Structures are predicted for mixed CO2 + C2H2 clusters using a distributed multipole model, and the bands are assigned to a specific pentamer, (CO2)3-(C2H2)2, and hexamer, (CO2)4-(C2H2)2. The hexamer has a box-like structure whose D2d symmetry is supported by observed intensity alternation in the spectrum. The pentamer has a closely related structure which is obtained by removing one CO2 molecule from the hexamer. These are among the largest mixed molecular clusters to be assigned by high-resolution spectroscopy. PMID:26315679

  17. Frequency-Comb Referenced Spectroscopy of νb{4} and νb{5} Hot Bands in the νb{1}+νb{3} Combination Band of C2H2

    NASA Astrophysics Data System (ADS)

    Twagirayezu, Sylvestre; Cich, Matthew; Sears, Trevor; McRaven, C.; Hall, Gregory

    2015-06-01

    Doppler-free transition frequencies for νb{4} and νb{5} hot bands in the band of C2H2 have been measured using saturation dip spectroscopy with an extended cavity diode laser referenced to a frequency comb. The frequency accuracy of the measured transitions, as judged from line shape model fits and the spectrometer stability, is better than 30 kHz. This is some 2-3 orders of magnitude improvement on the accuracy and precision of previous measurements of the line positions derived from the analysis of high-resolution Fourier transform infrared absorption spectra. The data were analyzed by determining the upper state energies, using known lower state level positions, and fitting them to a J(J+1) polynomial expansion to identify perturbations. The results reveal that the upper rotational energy level structure is mostly regular but suffers J-localized perturbations causing level shifts between one and several hundred MHz. These perturbations are due to accidental near degeneracies with energy levels of the same J and larger bending vibrational excitation. Acknowledgements: We are most grateful to Prof. D.S Perry (U. of Akron) and Prof. M. Herman (U. Libre de Bruxelles) for providing us with detailed results from their work and helpful discussions. Work at Brookhaven National Laboratory is funded by the Division of Chemical Sciences, Geosciences and Biosciences within the Offices of Basic Energy Sciences, Office of Sciences, U.S. Department of Energy under Contract Nos. DE-AC02-98CH10886 and DE-SC0012704.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  19. 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.

  20. 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.

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

    PubMed

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

    2015-10-15

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

  2. [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.

  3. Wavelength modulation spectroscopy at 1530.32 nm for measurements of acetylene based on Fabry-Perot tunable filter

    NASA Astrophysics Data System (ADS)

    Yun-Long, Li; Bing-Chu, Yang; Xue-Mei, Xu

    2016-02-01

    Sensitive detection of acetylene (C2H2) is performed by absorption spectroscopy and wavelength modulation spectroscopy (WMS) based on Fiber Fabry-Perot tunable filter (FFP-TF) at 1530.32 nm. After being calibrated by Fiber Bragg Grating (FBG), FFP-TF is frequency-multiplexed and modulated at 20 Hz and 2.5 kHz respectively to achieve wavelength modulation. The linearity with 0.9907 fitting coefficient is obtained by measuring different concentrations in a 100 ppmv-400 ppmv range. Furthermore, the stability of the system is analyzed by detecting 50 ppmv and 100 ppmv standard gases for 2 h under room temperature and ambient pressure conditions respectively. The precision of 11 ppmv is achieved by calculating the standard deviation. Therefore, the measuring system of C2H2 detection can be applied in practical applications. Project supported by the National Natural Science Foundation of China (Grant Nos. 61172047 and 61071025).

  4. The ancient mammalian KRAB zinc finger gene cluster on human chromosome 8q24.3 illustrates principles of C2H2 zinc finger evolution associated with unique expression profiles in human tissues

    PubMed Central

    2010-01-01

    Background Expansion of multi-C2H2 domain zinc finger (ZNF) genes, including the Krüppel-associated box (KRAB) subfamily, paralleled the evolution of tetrapodes, particularly in mammalian lineages. Advances in their cataloging and characterization suggest that the functions of the KRAB-ZNF gene family contributed to mammalian speciation. Results Here, we characterized the human 8q24.3 ZNF cluster on the genomic, the phylogenetic, the structural and the transcriptome level. Six (ZNF7, ZNF34, ZNF250, ZNF251, ZNF252, ZNF517) of the seven locus members contain exons encoding KRAB domains, one (ZNF16) does not. They form a paralog group in which the encoded KRAB and ZNF protein domains generally share more similarities with each other than with other members of the human ZNF superfamily. The closest relatives with respect to their DNA-binding domain were ZNF7 and ZNF251. The analysis of orthologs in therian mammalian species revealed strong conservation and purifying selection of the KRAB-A and zinc finger domains. These findings underscore structural/functional constraints during evolution. Gene losses in the murine lineage (ZNF16, ZNF34, ZNF252, ZNF517) and potential protein truncations in primates (ZNF252) illustrate ongoing speciation processes. Tissue expression profiling by quantitative real-time PCR showed similar but distinct patterns for all tested ZNF genes with the most prominent expression in fetal brain. Based on accompanying expression signatures in twenty-six other human tissues ZNF34 and ZNF250 revealed the closest expression profiles. Together, the 8q24.3 ZNF genes can be assigned to a cerebellum, a testis or a prostate/thyroid subgroup. These results are consistent with potential functions of the ZNF genes in morphogenesis and differentiation. Promoter regions of the seven 8q24.3 ZNF genes display common characteristics like missing TATA-box, CpG island-association and transcription factor binding site (TFBS) modules. Common TFBS modules partly

  5. Distortions of ethyne when complexed with a cuprous or argentous halide: the rotational spectrum of C2H2···CuF† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5cp02248g Click here for additional data file.

    PubMed Central

    Zaleski, Daniel P.; Stephens, Susanna L.; Tew, David P.; Bittner, Dror M.

    2015-01-01

    A new molecule C2H2···CuF has been synthesized in the gas phase by means of the reaction of laser-ablated metallic copper with a pulse of gas consisting of a dilute mixture of ethyne and sulfur hexafluoride in argon. The ground-state rotational spectrum was detected by two types of Fourier-transform microwave spectroscopy, namely that conducted in a microwave Fabry–Perot cavity and the chirped-pulse broadband technique. The spectroscopic constants of the six isotopologues 12C2H2···63Cu19F, 12C2H2···65Cu19F, 13C2H2···63Cu19F, 13C2H2···65Cu19F, 12C2D2···63Cu19F and 12C2D2···65Cu19F were determined and interpreted to show that the molecule has a planar, T-shaped geometry belonging to the molecular point group C 2v, with CuF forming the stem of the T. Quantitative interpretation reveals that the ethyne molecule is distorted when subsumed into the complex in such manner that the C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000

  6. 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.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  9. 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

  10. Synthesis of Highly Stable Silver-Loaded Vertical ZnO Nanowires Array and its Acetylene Sensing Properties

    NASA Astrophysics Data System (ADS)

    Uddin, Abu Sadat Mohammad Iftekhar; Chung, Gwiy-Sang

    2016-09-01

    A silver-loaded one-dimensional (1D) vertical ZnO nanowires (NWs) array synthesized by a facile seed mediated hydrothermal-RF magnetron sputtering method has been investigated for the fabrication of a highly stable and reproducible acetylene (C2H2) gas sensor. Successful immobilization of silver nanoparticles (NPs) as a sensitizer on the ZnO NWs array significantly enhanced the C2H2 sensing properties and showed a stable sensing performance. The grown structure exhibited high response magnitude (30.8 at 1000ppm), short response time (43s) and excellent selectivity at 220∘C. The enhanced performance can probably be accounted for the effect of combining the highly orientated ZnO NWs and catalytically active silver-based network. The superior sensing features toward C2H2 along with broad detection range (1-1000ppm), outstanding stability and excellent reproducibility indicate that the sensor is a promising candidate for practical applications.

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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

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

  12. Large amplitude motion of the acetylene molecule within acetylene-neon complexes hosted in helium droplets.

    PubMed

    Briant, M; Mengesha, E; de Pujo, P; Gaveau, M-A; Soep, B; Mestdagh, J-M; Poisson, L

    2016-06-28

    Superfluid helium droplets provide an ideal environment for spectroscopic studies with rotational resolution. Nevertheless, the molecular rotation is hindered because the embedded molecules are surrounded by a non-superfluid component. The present work explores the dynamical role of this component in the hindered rotation of C2H2 within the C2H2-Ne complex. A HENDI experiment was built and near-infrared spectroscopy of C2H2-Ne and C2H2 was performed in the spectral region overlapping the ν3/ν2 + ν4 + ν5 Fermi-type resonance of C2H2. The comparison between measured and simulated spectra helped to address the above issue. PMID:27263427

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

    PubMed

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

    2016-06-01

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

  14. 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.

  15. 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.

  16. Acetylene-Terminated Polyimide Siloxanes

    NASA Technical Reports Server (NTRS)

    St. Clair, Terry L.; Maudgal, Shubba

    1987-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

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

  18. Nonphysiological binding of ethylene by plants.

    PubMed

    Abeles, F B

    1984-03-01

    Ethylene binding to seedling tissue of Vicia faba, Phaseolus vulgaris, Glycine max, and Triticum aestivum was demonstrated by determining transit time required for ethylene to move through a glass tube filled with seedling tissue. Transit time for ethylene was greater than that for methane indicating that these tissues had an affinity for ethylene. However, the following observations suggest that the binding was not physiological. Inhibitors of ethylene action such as Ag(+) ions and CO(2) did not decrease binding. Mushrooms which have no known sites of ethylene action also demonstrated ethylene binding. The binding of acetylene, propylene, ethylene, propane, and ethane more closely followed their solubility in water than any known physiological activity. PMID:16663455

  19. Nonphysiological Binding of Ethylene by Plants

    PubMed Central

    Abeles, Fred B.

    1984-01-01

    Ethylene binding to seedling tissue of Vicia faba, Phaseolus vulgaris, Glycine max, and Triticum aestivum was demonstrated by determining transit time required for ethylene to move through a glass tube filled with seedling tissue. Transit time for ethylene was greater than that for methane indicating that these tissues had an affinity for ethylene. However, the following observations suggest that the binding was not physiological. Inhibitors of ethylene action such as Ag+ ions and CO2 did not decrease binding. Mushrooms which have no known sites of ethylene action also demonstrated ethylene binding. The binding of acetylene, propylene, ethylene, propane, and ethane more closely followed their solubility in water than any known physiological activity. PMID:16663455

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

    NASA Astrophysics Data System (ADS)

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

    2008-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2003-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

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

  6. 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.

  7. Absolute Integral Cross Sections for the State-selected Ion–Molecule Reaction N2+(X2Σg+ v+ = 0–2) + C2H2 in the Collision Energy Range of 0.03–10.00 eV

    NASA Astrophysics Data System (ADS)

    Xu, Yuntao; Xiong, Bo; Chung Chang, Yih; Ng, C. Y.

    2016-08-01

    Using the vacuum ultraviolet laser pulsed field ionization-photoion source, together with the double-quadrupole–double-octopole mass spectrometer developed in our laboratory, we have investigated the state-selected ion–molecule reaction {{{{N}}}2}+({X}2{{{{Σ }}}{{g}}}+; v + = 0–2, N+ = 0–9) + C2H2, achieving high internal-state selectivity and high kinetic energy resolution for reactant {{{{N}}}2}+ ions. The charge transfer (CT) and hydrogen-atom transfer (HT) channels, which lead to the respective formation of product {{{C}}}2{{{{H}}}2}+ and N2H+ ions, are observed. The vibrationally selected absolute integral cross sections for the CT [σ CT(v +)] and HT [[σ HT(v +)] channels obtained in the center-of-mass collision energy (E cm) range of 0.03–10.00 eV reveal opposite E cm dependences. The σ CT(v +) is found to increase as E cm is decreased, and is consistent with the long-range exothermic CT mechanism, whereas the E cm enhancement observed for the σ HT(v +) suggests effective coupling of kinetic energy to internal energy, enhancing the formation of N2H+. The σ HT(v +) curve exhibits a step at E cm = 0.70–1.00 eV, suggesting the involvement of the excited {{{C}}}2{{{{H}}}2}+({A}2{{{{Σ }}}{{g}}}+) state in the HT reaction. Contrary to the strong E cm dependences for σ CT(v +) and σ HT(v +), the effect of vibrational excitation of {{{{N}}}2}+ on both the CT and HT channels is marginal. The branching ratios and cross sections for the CT and HT channels determined in the present study are useful for modeling the atmospheric compositions of Saturn's largest moon, Titan. These cross sections and branching ratios are also valuable for benchmarking theoretical calculations on chemical dynamics of the titled reaction.

  8. Stable carbon isotope fractionation during bacterial acetylene fermentation: Potential for life detection in hydrocarbon-rich volatiles of icy planet(oid)s

    USGS Publications Warehouse

    Miller, Laurence; Baesman, Shaun; Oremland, Ron

    2015-01-01

    We report the first study of stable carbon isotope fractionation during microbial fermentation of acetylene (C2H2) in sediments, sediment enrichments, and bacterial cultures. Kinetic isotope effects (KIEs) averaged 3.7 ± 0.5‰ for slurries prepared with sediment collected at an intertidal mudflat in San Francisco Bay and 2.7 ± 0.2‰ for a pure culture of Pelobacter sp. isolated from these sediments. A similar KIE of 1.8 ± 0.7‰ was obtained for methanogenic enrichments derived from sediment collected at freshwater Searsville Lake, California. However, C2H2 uptake by a highly enriched mixed culture (strain SV7) obtained from Searsville Lake sediments resulted in a larger KIE of 9.0 ± 0.7‰. These are modest KIEs when compared with fractionation observed during oxidation of C1 compounds such as methane and methyl halides but are comparable to results obtained with other C2compounds. These observations may be useful in distinguishing biologically active processes operating at distant locales in the Solar System where C2H2 is present. These locales include the surface of Saturn's largest moon Titan and the vaporous water- and hydrocarbon-rich jets emanating from Enceladus.

  9. XPS and STM study of SiC synthesized by acetylene and disilane reaction with the Si(1 0 0)2 × 1 surface

    NASA Astrophysics Data System (ADS)

    Santoni, A.; Frycek, R.; Castrucci, P.; Scarselli, M.; De Crescenzi, M.

    2005-05-01

    The SiC formation on a ordered Si(1 0 0) substrate at low temperatures (980-1180 K) and low total pressures (10 -6 mbar) has been investigated by in situ X-ray photoemission spectroscopy (XPS) and ex situ scanning tunneling microscopy (STM). SiC was grown by chemical vapor deposition (CVD) from C 2H 2 and Si 2H 6 as the precursor gases. At all the temperatures and in presence of both C 2H 2 and Si 2H 6 XPS data showed the formation of sub-stoichiometric Si 1- xC x alloys characterized by excess silicon. By exposing to C 2H 2 only, stoichiometric SiC could be synthesized up to 1080 K. At 1180 K the formation of a Si 1- xC x alloy was observed. STM analysis has pointed out the role of silicon from the gas phase in the growth mechanisms and it has shown that uniform films with low roughness and small nanostructures can be obtained by tuning the acetylene/disilane ratios independently from the temperature selected in the investigated range.

  10. Stable Carbon Isotope Fractionation during Bacterial Acetylene Fermentation: Potential for Life Detection in Hydrocarbon-Rich Volatiles of Icy Planet(oid)s

    PubMed Central

    Baesman, Shaun M.; Oremland, Ronald S.

    2015-01-01

    Abstract We report the first study of stable carbon isotope fractionation during microbial fermentation of acetylene (C2H2) in sediments, sediment enrichments, and bacterial cultures. Kinetic isotope effects (KIEs) averaged 3.7 ± 0.5‰ for slurries prepared with sediment collected at an intertidal mudflat in San Francisco Bay and 2.7 ± 0.2‰ for a pure culture of Pelobacter sp. isolated from these sediments. A similar KIE of 1.8 ± 0.7‰ was obtained for methanogenic enrichments derived from sediment collected at freshwater Searsville Lake, California. However, C2H2 uptake by a highly enriched mixed culture (strain SV7) obtained from Searsville Lake sediments resulted in a larger KIE of 9.0 ± 0.7‰. These are modest KIEs when compared with fractionation observed during oxidation of C1 compounds such as methane and methyl halides but are comparable to results obtained with other C2 compounds. These observations may be useful in distinguishing biologically active processes operating at distant locales in the Solar System where C2H2 is present. These locales include the surface of Saturn's largest moon Titan and the vaporous water- and hydrocarbon-rich jets emanating from Enceladus. Key Words: Acetylene—Fermentation—Isotope fractionation—Enceladus—Life detection. Astrobiology 15, 977–986. PMID:26539733

  11. Satellite Boreal Measurements over Alaska and Canada During June-July 2004: Simultaneous Measurements of Upper Tropospheric CO, C2H6, HCN, CH3Cl, CH4, C2H2, CH2OH, HCOOH, OCS, and SF6 Mixing Ratios

    NASA Technical Reports Server (NTRS)

    Rinsland, Curtis P.; Dufour, Gaelle; Boone, Chris D.; Bernath, Peter F.; Chiou, Linda; Coheur, Pierre-Francois; Turquety, Solene; Clerbaux, Cathy

    2007-01-01

    Simultaneous ACE (Atmospheric Chemistry Experiment) upper tropospheric CO, C2H6, HCN, CH3Cl, CH4 , C2H2 , CH30H, HCOOH, and OCS measurements show plumes up to 185 ppbv (10 (exp -9) per unit volume) for CO, 1.36 ppbv for C2H6, 755 pptv (10(exp -12) per unit volume) for HCN, 1.12 ppbv for CH3C1, 1.82 ppmv, (10(exp -6) per unit volume) for CH4, 0.178 ppbv for C2H2, 3.89 ppbv for CH30H, 0.843 ppbv for HCOOH, and 0.48 ppbv for OCS in western Canada and Alaska at 50 deg N-68 deg N latitude between 29 June and 23 July 2004. Enhancement ratios and emission factors for HCOOH, CH30H, HCN, C2H6, and OCS relative to CO at 250-350 hPa are inferred from measurements of young plumes compared with lower mixing ratios assumed to represent background conditions based on a CO emission factor derived from boreal measurements. Results are generally consistent with the limited data reported for various vegetative types and emission phases measured in extratropical forests including boreal forests. The low correlation between fire product emission mixing ratios and the S176 mixing ratio is consistent with no significant SF6 emissions from the biomass fires.

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

    PubMed

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

    2011-02-10

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

  13. 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.

  14. 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.

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

    PubMed

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

    2014-07-15

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

  16. 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.

  17. Ethylene update

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The gaseous plant hormone ethylene is required for many aspects of plant growth, development and responses to the environment. Potato tubers produce low amounts of ethylene and are highly sensitive to ethylene in the atmosphere. Several responses of potato tubers to endogenous and exogenous ethylene...

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

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

  19. New assignments and a rare peculiarity in the high sensitivity CRDS spectrum of acetylene near 8000 cm-1

    NASA Astrophysics Data System (ADS)

    Kassi, S.; Lyulin, O. M.; Béguier, S.; Campargue, A.

    2016-08-01

    The absorption spectrum of acetylene has been recorded at room temperature (296 K) using high sensitivity Cavity Ring Down Spectroscopy in the 7914 and 8252 cm-1 interval. The noise equivalent absorption of the spectra is αmin ∼ 5×10-11 cm-1. A list of about 5600 absorption features was constructed. The smallest intensities are on the order of 10-29 cm/molecule. A total of 1325 rovibrational lines of 12C2H2 were assigned by comparison with accurate predictions provided by a global effective operator model. In addition, 132 rovibrational lines of 12C13CH2 present in natural isotopic abundance were assigned on the basis of their published positions. The assigned 12C2H2 lines belong to 12 new and 6 already known bands, for which additional J-lines were assigned. The line intensities of the three cold bands of 12C13CH2 are reported for the first time. The new data will be valuable to refine the parameters of the global effective Hamiltonian and dipole moments of 12C2H2 in the region. Spectroscopic parameters of the 12C2H2 and 12C13CH2 upper vibrational levels were derived from a band-by-band fit of the line positions (typical rms values are on the order of 0.001 cm-1). A few of the analyzed bands were found to be affected by rovibrational perturbations, which are discussed. In particular, the rotational structure of the 2ν1 + (ν4 + ν5)0 Σu+-Σg+ band near 7994 cm-1 exhibits a particularly surprising intensity distribution: while the P(19) and R(17) transitions share the same J = 18 upper level, the R(17) line has an intensity about 4 orders of magnitude smaller than the P(19) line. This unusual situation is quantitatively interpreted as resulting from a Coriolis interaction between the ν1 + 2ν2 + ν51 and 2ν1 + (ν4 + ν5)0 bands with a energy crossing at J = 18. The accidental nearly perfect cancelation of the two terms contributing to the line strength of the R(17) line leads to the near disappearance of this line.

  20. Giant macrocycles composed of thiophene, acetylene, and ethylene building blocks.

    PubMed

    Nakao, Kazumi; Nishimura, Masayuki; Tamachi, Tomoya; Kuwatani, Yoshiyuki; Miyasaka, Hitoshi; Nishinaga, Tohru; Iyoda, Masahiko

    2006-12-27

    Fully conjugated giant macrocyclic oligothiophenes with 60pi, 90pi,120pi, 150pi, and 180pi frames (1, 2, 3, 4 and 5) have been designed, and their butyl-substituted derivatives (1a, 2a, 3a, 4a, and 5a) have been synthesized using modified Sonogashira and McMurry coupling reactions as key steps. The 60-180pi systems 1-5 are circular with 1.8-6 nm inner cavities and 3.3-7.5 nm outside molecular diameters. Compound 1a containing ten 3,4-dibutyl-2,5-thienylene, eight ethynylene, and two vinylene units has been converted into macrocyclic oligo(3,4-dibutyl-2,5-thienylene-ethynylene) 6a using bromination/dehydrobromination procedure. Giant macrocycles 1a-6a exhibit a red shift of their absorption spectra and a fairly strong fluorescence with a large Stokes shift as compared to a linear conjugated counterpart having five thiophene rings. Compounds 1a-6a exhibit multistep reversible redox behaviors with fairly low first oxidation potentials, reflecting their cyclic conjugation. Furthermore, chemical oxidation of 1a-6a with FeCl3 shows drastic changes of spectroscopic properties due to intramolecular and intermolecular pi-pi interactions. Doping of 1a-3a with iodine forms semiconductor due to its pi-donor properties and pi-pi stacking ability. X-ray analysis of 1a confirmed a round, planar structure with nanoscale inner cavity, and revealed host ability for alkanes and unique packing structure. Interestingly, 2a and 3a self-aggregate in the solid state to form "molecular wires," which are about 200 nm thick and more than 1 mm long. The internal structures of fibrous aggregates have been investigated by optical microscope, scanning electron microscopy, atomic force microscopy, and X-ray diffraction analyses. PMID:17177424

  1. 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.

  2. Acetylene-terminated polyimide adhesives

    NASA Technical Reports Server (NTRS)

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

    1983-01-01

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

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

    SciTech Connect

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

    1994-12-31

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

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

    NASA Astrophysics Data System (ADS)

    Glein, Christopher R.; Shock, Everett L.

    2013-08-01

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

  5. 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.

  6. 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.

  7. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

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

    PubMed

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

    2007-02-15

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

  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. PMID:19488121

  11. 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

  12. Ethylene glycol

    Integrated Risk Information System (IRIS)

    Ethylene glycol ; CASRN 107 - 21 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

  13. Ethylene diamine

    Integrated Risk Information System (IRIS)

    Ethylene diamine ; CASRN 107 - 15 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

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

    PubMed

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

    2015-12-01

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

  15. 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…

  16. Living on acetylene. A primordial energy source.

    PubMed

    Ten Brink, Felix

    2014-01-01

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

  17. Rotationally Resolved Vacuum Ultraviolet Resonance-Enhanced Multiphoton Ionization (VUV REMPI) of Acetylene via the G̃ Rydberg State.

    PubMed

    Schmidt-May, Alice F; Grütter, Monika; Neugebohren, Jannis; Kitsopoulos, T N; Wodtke, Alec M; Harding, Dan J

    2016-07-14

    We present a 1 + 1' resonance-enhanced multiphoton ionization (REMPI) scheme for acetylene via the linear G̃ 4sσ (1)Πu Rydberg state, offering partial rotational resolution and the possibility to detect excitation in both the cis- and trans-bending modes. The resonant transition to the G̃ state is driven by a vacuum ultraviolet (VUV) photon, generated by resonant four-wave mixing (FWM) in krypton. Ionization from the short-lived G̃ state then occurs quickly, driven by the high intensity of the residual light from the FWM process. We have observed nine bands in the region between 79 200 cm(-1) and 80 500 cm(-1) in C2H2 and C2D2. We compare our results with published spectra in this region and suggest alternative assignments for some of the Renner-Teller split bands. Similar REMPI schemes should be applicable to other small molecules with picosecond lifetime Rydberg states. PMID:27073931

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

    NASA Astrophysics Data System (ADS)

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

    2002-07-01

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

  19. A mid-infrared absorption diagnostic for acetylene detection

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  20. Effects of compression with ethane, ethylene and their fluorinated derivatives on yeast growth

    NASA Astrophysics Data System (ADS)

    Kawachi, S.; Arao, T.; Hara, Y.; Suzuki, Y.; Tamura, K.

    2010-03-01

    The inhibitory effect of compressed gaseous C2 compounds on yeast growth was investigated quantitatively by microcalorimetry. The growth thermograms (heat output vs. incubation time) showed that all C2 compounds tested inhibited yeast growth. After quantification of yeast growth at various pressures, we determined the 50% inhibitory pressure (IP50) and the minimum inhibitory pressure (MIP) as indices which represent the inhibitory potency of gases. The lower the IP50 and MIP values, the greater the growth inhibitory effects of the gases. Based on these values, the inhibitory potency of the gases increased in the order: ethane (C2H6) < ethylene (C2H4) < pentafluoroethane (C2HF5) < 1,1,1,2-tetrafluoroethane (C2H2F4). Furthermore, transmission electron microscopy (TEM) of yeast cells treated with compressed ethylene showed that the inner structures of the cells, especially the nuclear membrane and cytoplasmic membrane, were damaged.

  1. Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

    NASA Technical Reports Server (NTRS)

    Payne, W. A.; Nava, D. F.; Brunning, J.; Stief, L. J.

    1986-01-01

    The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

  2. Acetylenes and fatty acids from Codonopsis pilosula

    PubMed Central

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

    2015-01-01

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

  3. Two new acetylenic compounds from Asparagus officinalis.

    PubMed

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

    2016-01-01

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

  4. 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.

  5. Photoabsorption cross section of acetylene in the EUV region

    NASA Technical Reports Server (NTRS)

    Wu, C. Y. R.; Judge, D. L.

    1985-01-01

    The measurement of the absolute photoabsorption cross sections of C2H2 in the 175-740 A region by means of a double ionization chamber is reported. The continuum background source is the synchrotron radiation emitted by the Wisconsin 240 MeV electron storage ring. It is found that the cross sections range from 2 to a maximum of 36 Mb. Two new Rydberg series are identified and the cross section data are applied in the analysis of various sum rules. From the rules, it is shown that the data of C2H2 in the 580-1088 A range may be too low, while the measured ionization transition moment may be too high.

  6. Ethylene Gas in Storage

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ethylene is a small volatile organic molecule that is produced by plants and many microbes. Potato tubers sense ethylene at concentrations of less than 1 ppm and respond to ethylene in ways that may be beneficial or detrimental for potato tuber storage. High concentrations of ethylene suppress sprou...

  7. Spectroscopic Characterization of Lanthanum-Mediated Dehydrogenation and C-C Bond Coupling of Ethylene.

    PubMed

    Kumari, Sudesh; Cao, Wenjin; Zhang, Yuchen; Roudjane, Mourad; Yang, Dong-Sheng

    2016-07-01

    La(C2H2) and La(C4H6) are observed from the reaction of laser-vaporized La atoms with ethylene molecules by photoionization time-of-flight mass spectrometry and characterized by mass-analyzed threshold ionization spectroscopy. La(C2H2) is identified as a metallacyclopropene and La(C4H6) as a metallacyclopentene. The three-membered ring is formed by concerted H2 elimination and the five-membered cycle by dehydrogenation and C-C bond coupling. Both metallacycles prefer a doublet ground state with a La 6s-based unpaired electron. Ionization of the neutral doublet state of either complex produces a singlet ion state by removing the La-based electron. The ionization allows accurate measurements of the adiabatic ionization energy of the neutral doublet state and metal-ligand and ligand-based vibrational frequencies of the neutral and ionic states. Although the La atom is in a formal oxidation state of +2, the ionization energies of these metal-hydrocarbon cycles are lower than that of the neutral La atom. Deuteration has a small effect on the ionization energies of the two cyclic radicals but distinctive effects on their vibrational frequencies. PMID:27322131

  8. 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.

  9. 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.

  10. 76 FR 75782 - Revising Standards Referenced in the Acetylene Standard

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-12-05

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

  11. 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

  12. Pressure-induced Polymerization in Substituted Acetylenes

    NASA Astrophysics Data System (ADS)

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

    2011-06-01

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

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

    PubMed

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

    2011-01-21

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

  14. C2H2F4 1,1,1,2-Tetrafluoroethane

    NASA Astrophysics Data System (ADS)

    Demaison, J.

    This document is part of Part 1 of Subvolume D 'Asymmetric Top Molecules' of Volume 29 'Molecular Constants Mostly from Microwave, Molecular Beam, and Sub-Doppler Laser Spectroscopy' of Landolt-Börnstein - Group II 'Molecules and Radicals'.

  15. C2H2F4 1,1,2,2-Tetrafluoroethane

    NASA Astrophysics Data System (ADS)

    Demaison, J.

    This document is part of Part 1 of Subvolume D 'Asymmetric Top Molecules' of Volume 29 'Molecular Constants Mostly from Microwave, Molecular Beam, and Sub-Doppler Laser Spectroscopy' of Landolt-Börnstein - Group II 'Molecules and Radicals'.

  16. Characterization of How DNA Modifications Affect DNA Binding by C2H2 Zinc Finger Proteins

    PubMed Central

    Patel, A.; Hashimoto, H.; Zhang, X.; Cheng, X.

    2016-01-01

    Much is known about vertebrate DNA methylation and oxidation; however, much less is known about how modified cytosine residues within particular sequences are recognized. Among the known methylated DNA-binding domains, the Cys2-His2 zinc finger (ZnF) protein superfamily is the largest with hundreds of members, each containing tandem ZnFs ranging from 3 to >30 fingers. We have begun to biochemically and structurally characterize these ZnFs not only on their sequence specificity but also on their sensitivity to various DNA modifications. Rather than following published methods of refolding insoluble ZnF arrays, we have expressed and purified soluble forms of ZnFs, ranging in size from a tandem array of two to six ZnFs, from seven different proteins. We also describe a fluorescence polarization assay to measure ZnFs affinity with oligonucleotides containing various modifications and our approaches for cocrystallization of ZnFs with oligonucleotides. PMID:27372763

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

    NASA Astrophysics Data System (ADS)

    Walker, Michael P.

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

  18. Improvements of anti-corrosion and mechanical properties of NiTi orthopedic materials by acetylene, nitrogen and oxygen plasma immersion ion implantation

    NASA Astrophysics Data System (ADS)

    Poon, Ray W. Y.; Ho, Joan P. Y.; Liu, Xuanyong; Chung, C. Y.; Chu, Paul K.; Yeung, Kelvin W. K.; Lu, William W.; Cheung, Kenneth M. C.

    2005-08-01

    Nickel-titanium shape memory alloys (NiTi) are useful materials in orthopedics and orthodontics due to their unique super-elasticity and shape memory effects. However, the problem associated with the release of harmful Ni ions to human tissues and fluids has been raising safety concern. Hence, it is necessary to produce a surface barrier to impede the out-diffusion of Ni ions from the materials. We have conducted acetylene, nitrogen and oxygen plasma immersion ion implantation (PIII) into NiTi alloys in an attempt to improve the surface properties. All the implanted and annealed samples surfaces exhibit outstanding corrosion and Ni out-diffusion resistance. Besides, the implanted layers are mechanically stronger than the substrate underneath. XPS analyses disclose that the layer formed by C2H2 PIII is composed of mainly TiCx with increasing Ti to C concentration ratios towards the bulk. The nitrogen PIII layer is observed to be TiN, whereas the oxygen PIII layer is composed of oxides of Ti4+, Ti3+ and Ti2+.

  19. Ethylene process design optimization

    SciTech Connect

    2001-09-01

    Integration of Advanced Technologies will Update Ethylene Plants. Nearly 93 million tons of ethylene are produced annually in chemical plants worldwide, using an energy intensive process that consumes 2.5 quadrillion Btu per year.

  20. 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.

  1. 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.

  2. Pyrethrum stabilization by inactivation of natural acetylenic impurities

    SciTech Connect

    Evans, A.J.

    1989-01-17

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

  3. 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.

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

    SciTech Connect

    Gabrielson, F.C.

    1982-01-01

    The winter annuals, crimson clover, rose clover, subterranean clover and hairy vetch, were evaluated for 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.

  5. Decomposition of ethylene oxide in the RF plasma environment.

    PubMed

    Liao, W T; Lee, W J; Chen, C Y; Shih, M

    2001-02-01

    A radio frequency (RF) plasma system was used to decompose the ethylene oxide (EO) contained gas in the EO/Ar, and EO/O2/Ar system, respectively. The reactants and final products were analyzed by using FTIR (Fourier transform infrared spectroscopy). The effects of plasma operational parameters, including input power wattage (W), total gas flow rate (Q), feeding concentration (C) of EO and operational pressure for EO decomposition were evaluated. Due to the importance of the high-energy electrons in the RF plasma system, the EO decomposition fraction in plasma reaction increased with decreasing operational pressure, while that of thermal reaction, reported by previous investigations, increased with increasing operational pressure. However, owing to the electrophilic characteristic of oxygen atoms in the EO molecule causing the effect of electron attachment, in conditions of higher EO feeding concentration, the pressure dependence became the same for both plasma- and thermal-reaction. The EO oxidation reaction has also been investigated, the result shows that EO almost completely oxidized at 600-692 K gas temperature. The main products for the EO/Ar system are CO, CH4, C2H6, C2H4, and C2H2, and those for the EO/O2/Ar system are CO2 and H2O. PMID:11349375

  6. A Green Process for High-Concentration Ethylene and Hydrogen Production from Methane in a Plasma-Followed-by-Catalyst Reactor

    NASA Astrophysics Data System (ADS)

    Wang, Kangjun; Li, Xiaosong; Zhu, Aimin

    2011-02-01

    A green process for the oxygen-free conversion of methane to high-concentration ethylene and hydrogen in a plasma-followed-by-catalyst (PFC) reactor is presented. Without any catalysts and with pure methane used as the feed gas, a stable kilohertz spark discharge leads to an acetylene yield of 64.1%, ethylene yield of 2.5% and hydrogen yield of 59.0% with 80.0% of methane conversion at a methane flow rate of 50 cm3/min and a specific input energy of 38.4 kJ/L. In the effluent gas from a stable kilohertz spark discharge reactor, the concentrations of acetylene, ethylene and hydrogen were 18.1%, 0.7% and 66.9%, respectively. When catalysts Pd-Ag/SiO2 were employed in the second stage with discharge conditions same as in the case of plasma alone, the PFC reactor provides an ethylene yield of 52.1% and hydrogen yield of 43.4%. The concentrations of ethylene and hydrogen in the effluent gas from the PFC reactor were found to be as high as 17.1% and 62.6%, respectively. Moreover, no acetylene was detected in the effluent gas. This means that a high concentration of ethylene and oxygen-free hydrogen can be co-produced directly from methane in the PFC reactor.

  7. Mortality of workers at acetylene production plants.

    PubMed Central

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

    1988-01-01

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

  8. 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.

  9. Process hydrogenates unwanted diolefins and acetylenes

    SciTech Connect

    Vora, B.V. )

    1988-12-05

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

  10. Ab initio calculations of one-electron-scattering properties of ethyne (acetylene) and ethylene molecules

    SciTech Connect

    Tripathi, A.N.; Smith, V.H. Jr. K7L3N6); Kaijser, P.; Siemens, A.G. ); Diercksen, G.H.F. )

    1990-03-01

    Isotropic scattering functions and Compton profiles together with their directional components for several directions relevant to the molecular structure of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} have been evaluated for {ital ab} {ital initio} self-consistent field and configuration-interaction wave functions. The internally folded density (reciprocal form factor) {ital B}({ital r}) is calculated and discussed as are various momentum expectation values. Comparison is made with available experimental and other theoretical results.

  11. AUTOMOTIVE EMISSIONS OF ETHYLENE DIBROMIDE

    EPA Science Inventory

    Ethylene dibromide, a suspected carcinogen, and ethylene dichloride are commonly used in leaded gasoline as scavengers. Ethylene dibromide emission rates were determined from seven automobiles which had a wide range of control devices, ranging from totally uncontrolled to evapora...

  12. Ethylene insensitive plants

    DOEpatents

    Ecker, Joseph R.; Nehring, Ramlah; McGrath, Robert B.

    2007-05-22

    Nucleic acid and polypeptide sequences are described which relate to an EIN6 gene, a gene involved in the plant ethylene response. Plant transformation vectors and transgenic plants are described which display an altered ethylene-dependent phenotype due to altered expression of EIN6 in transformed plants.

  13. 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.

  14. Temporally Varying Ethylene Emission on Jupiter

    NASA Technical Reports Server (NTRS)

    Romani, Paul N.; Jennings, Donald E.; Bjoraker, Gordon L.; Sada, Pedro V.; McCabe. Geprge; Boyle, Robert J.

    2008-01-01

    Ethylene (C2H4) emission has been measured in the poles and equator of Jupiter. The 949 cm(sup -1) spectra were recorded with a high resolution spectrometer at the McMath-Pierce telescope at Kitt Peak in October-November 1998 and at the Infrared Telescope Facility at Mauna Kea in June 2000. C2H4 is an important product of methane chemistry in the outer planets. Knowledge of its abundance can help discriminate among the various proposed sets of CH4 photolysis branching ratios at Ly-alpha, and determine the relative importance of the reaction pathways that produce C2H2 and C2H6. In the equatorial region the C2H4 emission is weak, and we were only able to detect it at high air-mass, near the limb. We derive a peak equatorial molar abundance of C2H4 of 4.5 x 10(exp -7) - 1.7 x 10(exp -6) near 2.2 x 10(exp -3) mbar, with a total column of 5.7 x 10(exp 14) - 2.2 x 10(exp 15) molecules cm(exp -2) above 10 mbar depending upon choice of thermal profile. We observed enhanced C2H4 emission from the poles in the regions where auroras are seen in X-ray, UV, and near infrared images. In 2000 we measured a short-term change in the distribution of polar C2H4 emission; the emission in the north IR auroral "hot spot" decreased by a factor of three over a two-day interval. This transient its contribution peak at 5-10 microbar suggests that the polar e is primarily a thermal effect coupled with vertical transport. Comparing our observations from Kitt Peak and Mauna Kea shows that the C2H4 emission of the northern non-"hot spot" auroral regions did not change over the three-year period while that in the southern polar regions decreased.

  15. Temporally varying ethylene emission on Jupiter

    NASA Astrophysics Data System (ADS)

    Romani, Paul N.; Jennings, Donald E.; Bjoraker, Gordon L.; Sada, Pedro V.; McCabe, George H.; Boyle, Robert J.

    2008-12-01

    Ethylene (C 2H 4) emission has been measured in the poles and equator of Jupiter. The 949 cm -1 spectra were recorded with a high resolution spectrometer at the McMath-Pierce telescope at Kitt Peak in October-November 1998 and at the Infrared Telescope Facility at Mauna Kea in June 2000. C 2H 4 is an important product of methane chemistry in the outer planets. Knowledge of its abundance can help discriminate among the various proposed sets of CH 4 photolysis branching ratios at Ly- α, and determine the relative importance of the reaction pathways that produce C 2H 2 and C 2H 6. In the equatorial region the C 2H 4 emission is weak, and we were only able to detect it at high air-mass, near the limb. We derive a peak equatorial molar abundance of C 2H 4 of 4.5×10-1.7×10 near 2.2×10 mbar, with a total column of 5.7×10-2.2×10 molecules cm -2 above 10 mbar depending upon choice of thermal profile. We observed enhanced C 2H 4 emission from the poles in the regions where auroras are seen in X-ray, UV, and near infrared images. In 2000 we measured a short-term change in the distribution of polar C 2H 4 emission; the emission in the north IR auroral "hot spot" decreased by a factor of three over a two-day interval. This transient behavior and the sensitivity of C 2H 4 emission to temperature changes near its contribution peak at 5-10 microbar suggests that the polar enhancement is primarily a thermal effect coupled with vertical transport. Comparing our observations from Kitt Peak and Mauna Kea shows that the C 2H 4 emission of the northern non-"hot spot" auroral regions did not change over the three-year period while that in the southern polar regions decreased.

  16. 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

  17. 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.

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

    PubMed

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

    1992-09-01

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

  19. Synthesis of functional acetylene derivatives from calcium carbide.

    PubMed

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

    2012-04-01

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

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

    PubMed

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

    2015-04-24

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

  1. ACR process for ethylene

    SciTech Connect

    Baldwin, R.L.; Kamm, G.R.

    1983-01-01

    Describes how the advanced cracking reactor process, which is ready for a logical commercial application, offers total liquids feedstock flexibility from light naphthenes through vacuum gas oils in the same production unit. Several processes are presently being developed which are aimed at maintaining olefin selectivity when cracking the heaviest feeds. Addresses the problems posed by such heavy feedstocks. The following trends favor the ACR process in the 1980s: natural gas price decontrol; limited natural gas reserves; few new domestic LPG-based ethylene plants will be built; an economic recovery will create the need for more ethylene capacity; modest increases in ''real'' crude oil prices; plentiful supplies of vacuum gas oil at prices making it an attractive ethylene feedstock; and increasing supplies of light naphtha at prices making it an attractive ethylene feedstock as well. Predicts that these factors will swing the preferred feedstocks for ethylene manufacture back to crude oil distillates before the end of the decade. Argues that in this environment, the ACR process can deliver the lowest cost ethylene in the industry. ACR has full-range feedstock flexibility, high selectivity to ethylene, and less sensitivity to feedstock costs and co-product credits.

  2. Ethylene production from methionine

    PubMed Central

    Lieberman, M.; Kunishi, A. T.; Mapson, L. W.; Wardale, D. A.

    1965-01-01

    1. A new reaction is described in which ethylene is formed from the Cu+-catalysed breakdown of methionine in phosphate buffer at 30° in air. Some of the other products of the reaction are methionine sulphone, methionine sulphoxide, homocysteic acid, homocystine, acrolein, dimethyl disulphide, methanethiol, ethyl methyl sulphide, methane and ethane. These are considered to be produced in different reaction pathways. 2. Hydrogen peroxide is an intermediate in this reaction and can support ethylene production in the model system in anaerobic atmospheres. Cuprous copper is the active form that catalyses the formation of ethylene from an oxidized intermediate. The initial reaction is probably a Strecker degradation, but the aldehyde product is further degraded to ethylene and other products. 3. Methional (CH3·S·CH2·CH2·CHO) is the most effective producer of ethylene in the model system and appears to be an intermediate in the reaction. 4. The evidence, from both tracer studies and from other precursors of ethylene in the reaction, indicates that ethylene is derived from the −CH2·CH2− group of methionine. PMID:16749150

  3. 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...

  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. 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...

  6. 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...

  7. 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...

  8. Ethylene glycol poisoning

    MedlinePlus

    ... attempt or as a substitute for drinking alcohol (ethanol). This article is for information only. Do NOT ... attempt or as a substitute for drinking alcohol (ethanol). Ethylene glycol is found in many household products, ...

  9. Ethylene by Naphta Cracking

    ERIC Educational Resources Information Center

    Wiseman, Peter

    1977-01-01

    Presents a discussion of the manufacture of ethylene by thermal cracking of hydrocarbon feedstocks that is useful for introducing the subject of industrial chemistry into a chemistry curriculum. (MLH)

  10. A All-Vacuum High Resolution Fourier Transform Spectrometer with Absorption Pathlengths up to 352 M: Acetylene Spectrum at 1.4-1.7 Microns.

    NASA Astrophysics Data System (ADS)

    Keppler, Karen Ann

    1995-01-01

    The spectra of acetylene (C_2H _2) and of water vapor have been recorded at room temperature with Doppler- or pressure -broadening-limited resolution at pathlengths up to 352m. The spectra were obtained with the combination of a FTIR (Fourier Transform Infrared) spectrometer, evacuated transfer optics, and a multipass cell of 4m base length. The measurements were performed at the Justus-Liebig-Universitat in Giessen, Germany, using the FTIR spectrometer at that university, the multipass cell assembled at The Ohio State University, and the vacuum transfer optics designed by the author. The regions in which the spectra were recorded are 5900-7150 cm^{-1} and 1850-6600 cm^{-1}. Calibration difficulties pertaining to the determination of the absolute accuracy of the data have been resolved, and molecular parameters have been extracted for the HCCH data. These calibration problems were not documented in earlier studies using high resolution Fourier transform spectrometers. For this reason, the dissertation addresses this matter in somewhat greater detail. This work contains a description of the technology used to obtain the data, and a description of the calibration of the spectra to make them suitable for future use as secondary wavenumber calibration standards. The bands detected for the first time in this study have been reported, and updated energy level diagrams for HCCH and H^{13}CCH have been included. The molecular parameters obtained from the HCCH spectra have been presented. The appendices include, among others, the basic observational data, a spectral map and associated wavenumber lists of HCCH, and a description of the weighting scheme developed by the author for Fourier Transform spectra.

  11. 46 CFR 154.1735 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

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

  12. 46 CFR 154.1735 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

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

  13. 46 CFR 154.1735 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

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

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

    PubMed

    Brvar, Miran

    2014-01-01

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

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

    PubMed

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

    2013-06-01

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

  16. Low energy electron impact vibrational excitation of acetylene

    NASA Astrophysics Data System (ADS)

    Patra, Sigma; Hargreaves, Leigh; Khakoo, Murtadha

    2016-05-01

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

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

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-08

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

  18. 76 FR 75840 - Revising Standards Referenced in the Acetylene Standard

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-12-05

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

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

    SciTech Connect

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

    2010-01-15

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

  20. Ethylene-Vapor Optrodes

    NASA Technical Reports Server (NTRS)

    Tabacco, Mary Beth; Zhou, Quan

    1993-01-01

    Porous optical fibers include sensing regions filled with reagents. Optical-fiber chemical sensors (optrodes) developed to measure concentrations of ethylene in air in enclosed artificial plant-growth environments. Such measurements needed because ethylene acts as plant-growth hormone affecting growth at concentrations less than or equal to 20 parts per billion. Optrodes small, but exhibit sensitivities comparable to those of larger instruments. Operated safely in potentially explosive atmospheres and neither cause, nor susceptible to, electrical interference at suboptical frequencies.

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

    PubMed Central

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

    2008-01-01

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

  2. Detonation engine fed by acetylene-oxygen mixture

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

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

    PubMed

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

    1976-01-01

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

  5. Recovery and purification of ethylene

    DOEpatents

    Reyneke, Rian; Foral, Michael J.; Lee, Guang-Chung; Eng, Wayne W. Y.; Sinclair, Iain; Lodgson, Jeffery S.

    2008-10-21

    A process for the recovery and purification of ethylene and optionally propylene from a stream containing lighter and heavier components that employs an ethylene distributor column and a partially thermally coupled distributed distillation system.

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

    PubMed

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

    2016-03-14

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

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

    PubMed

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

    2001-05-01

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

  8. Ethylene and Fruit Ripening

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Experiments designed to down-regulate specific tomato ethylene receptor isoforms using antisense suppression have been reported for LeETR1, NR and LeETR4. Down-regulation of LeETR1 expression in transgenic plants did not alter fruit ripening but resulted in plants with shorter internodes and reduce...

  9. Ethylene thiourea (ETU)

    Integrated Risk Information System (IRIS)

    Ethylene thiourea ( ETU ) ; CASRN 96 - 45 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarci

  10. ETHYLENE AND POSTHARVEST COMMODITIES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This paper is a review of the plant hormone ethylene, a simple two carbon molecule. This hormone is biologically active at low concentrations (part per billion to part per million range). Since it is a gas, it is easily transported long distances via diffusion from site of synthesis within the pla...

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

    SciTech Connect

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

    1987-10-06

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

  12. 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

  13. Acetylene frequency references in gas-filled hollow optical fiber and photonic microcells.

    PubMed

    Wang, Chenchen; Wheeler, Natalie V; Fourcade-Dutin, Coralie; Grogan, Michael; Bradley, Thomas D; Washburn, Brian R; Benabid, Fetah; Corwin, Kristan L

    2013-08-01

    Gas-filled hollow optical fiber references based on the P(13) transition of the ν1+ν3 band of 12C2H2 promise portability with moderate accuracy and stability. Previous realizations are corrected (<1σ) by using proper modeling of a shift due to line-shape. To improve portability, a sealed photonic microcell is characterized on the 12C2H2 ν1+ν3 P(23) transition with somewhat reduced accuracy and stability. Effects of the photonic crystal fiber, including surface modes, are explored. Both polarization-maintaining (PM) and non-PM 7-cell photonic bandgap fiber are shown to be unsuitable for kilohertz-level frequency references. PMID:23913062

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

    PubMed

    Petter, P J

    1989-02-01

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

  15. Ethylene Glycol Adsorption and Reaction over CeOX(111) Thin Films

    SciTech Connect

    Mullins, David R; Chen, Tsung-Liang

    2011-01-01

    This study reports the interaction of ethylene glycol with well-ordered CeO{sub x}(111) thin film surfaces. Ethylene glycol initially adsorbs on fully oxidized CeO{sub 2}(111) and reduced CeO{sub 2-x}(111) through the formation of one C-O-Ce bond and then forms a second alkoxy bond after annealing. On fully oxidized CeO{sub 2}(111) both recombination of ethylene glycol and water desorption occur at low temperature leaving stable -OCH{sub 2}CH{sub 2}O- (ethylenedioxy) intermediates and oxygen vacancies on the surface. This ethylenedioxy intermediate goes through C-C bond scission to produce formate species which then react to produce CO and CO{sub 2}. The formation of water results in the reduction of the ceria. On a reduced CeO{sub 2-x}(111) surface the reaction selectivity shifts toward a dehydration process. The ethylenedioxy intermediate decomposes by breaking a C-O bond and converts into an enolate species. Similar to the reaction of acetaldehyde on reduced CeO{sub 2-x}(111), the enolate reacts to produce acetaldehyde, acetylene, and ethylene. The loss of O from ethylene glycol leads to a small amount of oxidation of the reduced ceria.

  16. Ethylene Glycol Adsorption and Reaction over CeOX(111) Thin Films

    SciTech Connect

    T Chen; D Mullins

    2011-12-31

    This study reports the interaction of ethylene glycol with well-ordered CeO{sub x}(111) thin film surfaces. Ethylene glycol initially adsorbs on fully oxidized CeO{sub 2}(111) and reduced CeO{sub 2-x}(111) through the formation of one C-O-Ce bond and then forms a second alkoxy bond after annealing. On fully oxidized CeO{sub 2}(111) both recombination of ethylene glycol and water desorption occur at low temperature leaving stable -OCH{sub 2}CH{sub 2}O- (ethylenedioxy) intermediates and oxygen vacancies on the surface. This ethylenedioxy intermediate goes through C-C bond scission to produce formate species which then react to produce CO and CO{sub 2}. The formation of water results in the reduction of the ceria. On a reduced CeO{sub 2-x}(111) surface the reaction selectivity shifts toward a dehydration process. The ethylenedioxy intermediate decomposes by breaking a C-O bond and converts into an enolate species. Similar to the reaction of acetaldehyde on reduced CeO{sub 2-x}(111), the enolate reacts to produce acetaldehyde, acetylene, and ethylene. The loss of O from ethylene glycol leads to a small amount of oxidation of the reduced ceria.

  17. Salt tolerance function of the novel C2H2-type zinc finger protein TaZNF in wheat.

    PubMed

    Ma, Xiaoli; Liang, Wenji; Gu, Peihan; Huang, Zhanjing

    2016-09-01

    The expression profile chip of the wheat salt-tolerant mutant RH8706-49 was investigated under salt stress in our laboratory. Results revealed a novel gene induced by salt stress with unknown functions. The gene was named as TaZNF (Triticum aestivum predicted Dof zinc finger protein) because it contains the zf-Dof superfamily and was deposited in GenBank (accession no. KF307327). Further analysis showed that TaZNF significantly improved the salt-tolerance of transgenic Arabidopsis. Various physiological indices of the transgenic plant were improved compared with those of the control after salt stress. Non-invasive micro-test (NMT) detection showed that the root tip of transgenic Arabidopsis significantly expressed Na(+) excretion. TaZNF is mainly localized in the nucleus and exhibited transcriptional activity. Hence, this protein was considered a transcription factor. The TaZNF upstream promoter was then cloned and was found to contain three salts, one jasmonic acid methyl ester (MeJA), and several ABA-responsive elements. The GUS staining and quantitative results of different tissues in the full-length promoter in the transgenic plants showed that the promoter was not tissue specific. The promoter activity in the root, leaf, and flower was enhanced after induction by salt stress. Moreover, GUS staining and quantitative measurement of GUS activity showed that the promoter sequence contained the positive regulatory element of salt and MeJA after their respective elements were mutated in the full-length promoter. RNA-Seq result showed that 2727 genes were differentially expressed; most of these genes were involved in the metabolic pathway and biosynthesis of secondary metabolite pathway. PMID:27156137

  18. Platinum Metal-Free Catalysts for Selective Soft Oxidative Methane → Ethylene Coupling. Scope and Mechanistic Observations.

    PubMed

    Peter, Matthias; Marks, Tobin J

    2015-12-01

    Using abundant soft oxidants, a high methane-to-ethylene conversion might be achievable due to the low thermodynamic driving force for over-oxidation. Here we report on the oxidative coupling of methane by gaseous S2 (SOCM). The catalytic properties of Pd/Fe3O4 are compared with those of Fe3O4, and it is found that high ethylene selectivities can be achieved without noble metals; conversion and selectivity on Fe3O4 are stable for at least 48 h at SOCM conditions. SOCM data for 10 oxides are compared, and ethylene selectivities as high as 33% are found; the C2H4/C2H6 ratios of 9-12 observed at the highest S2 conversions are significantly higher than the C2H4/C2H6 ratios usually found in the CH4 coupling with O2. Complementary in-detail analytical studies show that, on Mg, Zr, Sm, W, and La catalysts, which strongly coke during the reaction, lower ethylene selectivities are observed than on Fe, Ti, and Cr catalysts, which only coke to a minor extent. Further catalyst-dependent changes during SOCM in surface area, surface composition, and partial conversion to oxysulfides and sulfides are discussed. Evidence concerning the reaction mechanism is obtained taking into account the selectivity for the different reaction products versus the contact time. CH4 coupling proceeds non-oxidatively with the evolution of H2 on some catalysts, and evidence is presented that C2H4 and C2H2 formation occur via C2H6 and C2H4 dehydrogenation, respectively. PMID:26551955

  19. [Chronic ethylene glycol poisoning].

    PubMed

    Kaiser, W; Steinmauer, H G; Biesenbach, G; Janko, O; Zazgornik, J

    1993-04-30

    Over a six-week period a 60-year-old patient had several unexplained intoxication-like episodes. He finally had severe abdominal cramps with changes in the level of consciousness and oligoanuric renal failure (creatinine 4.7 mg/dl). The history, marked metabolic acidosis (pH 7.15, HCO3- 2.2 mmol/l, pCO2 6.6 mmHg) as well as raised anion residue (43 mmol/l) and the presence of oxalates in urine suggested poisoning by ethylene glycol contained in antifreeze liquid. Intensive haemodialysis adequately eliminated ethylene glycol and its toxic metabolites (glycol aldehyde, glycolic acid). Renal function returned within 10 days, although the concentrating power of the kidney remained impaired for several weeks because of interstitial nephritis. The intoxication had been caused by a defective heating-pipe system from which the antifreeze had leaked into the hot-water boiler (the patient had habitually prepared hot drinks by using water from the hot-water tap). Gas chromatography demonstrated an ethylene glycol concentration of 21 g per litre of water. PMID:8482240

  20. Infrared study of matrix-isolated ethyl cyanide: simulation of the photochemistry in the atmosphere of Titan.

    PubMed

    Toumi, A; Piétri, N; Couturier-Tamburelli, I

    2015-11-11

    Low-temperature Ar matrix isolation has been carried out to investigate the infrared spectrum of ethyl cyanide (CH3CH2CN), a molecule present in the atmosphere of Titan. The λ > 120 nm and λ > 230 nm photolysis reactions of ethyl cyanide in an Ar matrix were also performed in order to compare the behaviour of this compound when it is submitted to high and low energetic radiations. These different wavelengths have been used with the aim to reproduce the radiation reaching the various parts of the atmosphere. Several photoproducts have been identified during photolysis such as vinyl cyanide (CH2[double bond, length as m-dash]CHCN), cyanoacetylene (HC3N), and ethylene/hydrogen cyanide (C2H4/HCN), ethylene/hydrogen isocyanide (C2H4/HNC), acetylene/hydrogen cyanide (C2H2/HCN), acetylene/hydrogen isocyanide (C2H2/HNC), and acetylene:methylenimine (C2H2:HNCH2) complexes. Ethyl isocyanide (CH3CH2NC) and a ketenimine form (CH3CH[double bond, length as m-dash]C[double bond, length as m-dash]NH) have been identified as well. Photoproduct identification and spectral assignments were done using previous studies and density functional theory (DFT) calculations with the B3LYP/cc-pVTZ basis set. PMID:26507585

  1. 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.

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

    PubMed Central

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

    1983-01-01

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

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

    PubMed

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

    2013-03-01

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

  4. Ethylene in mutualistic symbioses

    PubMed Central

    Khatabi, Behnam; Schäfer, Patrick

    2012-01-01

    Ethylene (ET) is a gaseous phytohormone that participates in various plant physiological processes and essentially contributes to plant immunity. ET conducts its functions by regulating the expression of ET-responsive genes or in crosstalk with other hormones. Several recent studies have shown the significance of ET in the establishment and development of plant-microbe interactions. Therefore, it is not surprising that pathogens and mutualistic symbionts target ET synthesis or signaling to colonize plants. This review introduces the significance of ET metabolism in plant-microbe interactions, with an emphasis on its role in mutualistic symbioses. PMID:23072986

  5. Interstellar Antifreeze: Ethylene Glycol

    NASA Astrophysics Data System (ADS)

    Hollis, J. M.; Lovas, F. J.; Jewell, P. R.; Coudert, L. H.

    2002-05-01

    Interstellar ethylene glycol (HOCH2CH2OH) has been detected in emission toward the Galactic center source Sagittarius B2(N-LMH) by means of several millimeter-wave rotational torsional transitions of its lowest energy conformer. The types and kinds of molecules found to date in interstellar clouds suggest a chemistry that favors aldehydes and their corresponding reduced alcohols-e.g., formaldehyde (H2CO)/methanol (CH3OH), acetaldehyde (CH3CHO)/ethanol (CH3CH2OH). Similarly, ethylene glycol is the reduced alcohol of glycolaldehyde (CH2OHCHO), which has also been detected toward Sgr B2(N-LMH). While there is no consensus as to how any such large complex molecules are formed in the interstellar clouds, atomic hydrogen (H) and carbon monoxide (CO) could form formaldehyde on grain surfaces, but such surface chemistry beyond that point is uncertain. However, laboratory experiments have shown that the gas-phase reaction of atomic hydrogen (H) and solid-phase CO at 10-20 K can produce formaldehyde and methanol and that alcohols and other complex molecules can be synthesized from cometary ice analogs when subject to ionizing radiation at 15 K. Thus, the presence of aldehyde/reduced alcohol pairs in interstellar clouds implies that such molecules are a product of a low-temperature chemistry on grain surfaces or in grain ice mantles. This work suggests that aldehydes and their corresponding reduced alcohols provide unique observational constraints on the formation of complex interstellar molecules.

  6. Interstellar Antifreeze: Ethylene Glycol

    NASA Technical Reports Server (NTRS)

    Hollis, J. M.; Lovas, F. J.; Jewell, P. R.; Coudert, L. H.

    2002-01-01

    Interstellar ethylene glycol (HOCH2CH2,OH) has been detected in emission toward the Galactic center source Sagittarius B2(N-LMH) by means of several millimeter-wave rotational torsional transitions of its lowest energy conformer. The types and kinds of molecules found to date in interstellar clouds suggest a chemistry that favors aldehydes and their corresponding reduced alcohols-e.g., formaldehyde (H2CO)/methanol (CH3OH), acetaldehyde (CH3CHO)/ethanol (CH3CH2OH). Similarly, ethylene glycol is the reduced alcohol of glycolaldehyde (CH2OHCHO), which has also been detected toward Sgr B2(N-LMH). While there is no consensus as to how any such large complex molecules are formed in the interstellar clouds, atomic hydrogen (H) and carbon monoxide (CO) could form formaldehyde on grain surfaces, but such surface chemistry beyond that point is uncertain. However, laboratory experiments have shown that the gas-phase reaction of atomic hydrogen (H) and solid-phase CO at 10-20 K can produce formaldehyde and methanol and that alcohols and other complex molecules can be synthesized from cometary ice analogs when subject to ionizing radiation at 15 K. Thus, the presence of aldehyde/ reduced alcohol pairs in interstellar clouds implies that such molecules are a product of a low-temperature chemistry on grain surfaces or in grain ice mantles. This work suggests that aldehydes and their corresponding reduced alcohols provide unique observational constraints on the formation of complex interstellar molecules.

  7. 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

  8. Microwave Enhanced Direct Cracking of Hydrocarbon Feedstock for Energy Efficient Production of Ethylene and Propylene.

    SciTech Connect

    Shulman, Holly; Fall, Morgana; Wagner, Eric; Bowlin, Ricardo

    2012-02-13

    This project demonstrated microwave cracking of ethane with good product conversion and ethylene selectivity, with a short residence time ({approx}0.001 sec). The laboratory scale equipment was designed and built, along with concept designs for larger scale implementation. The system was operated below atmospheric pressures, in the range of 15-55 torr, with argon as a carrier gas. The measured products included hydrogen, methane, acetylene, and ethylene. The results followed similar trends to those predicted by the modeling software SPYRO{reg_sign}, with the exception that the microwave appeared to produce slightly lower amounts of ethylene and methane, although enhanced analytical analysis should reduce the difference. Continued testing will be required to verify these results and quantify the energy consumption of microwave vs. conventional. The microwave cracking process is an attractive option due to the possibility of selectively heating the reaction volume rather than the reactor walls, which may allow novel reactor designs that result in more efficient production of ethylene. Supplemental studies are needed to continue the laboratory testing and refine processing parameters.

  9. Organogermanium Chemistry: Germacyclobutanes and digermane Additions to Acetylenes

    SciTech Connect

    Andrew Michael Chubb

    2003-12-12

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

  10. 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.

  11. Inclusion of 13C and D in protonated acetylene

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

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

    PubMed

    Oremland, Ronald S; Voytek, Mary A

    2008-02-01

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

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

    PubMed

    Olsen, R; Hørder, M

    1980-06-01

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

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

    PubMed Central

    Hutchins, S R

    1992-01-01

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

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

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

    PubMed

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

    2007-02-27

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

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

    NASA Astrophysics Data System (ADS)

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

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

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

    PubMed

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

    2015-01-01

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

  9. 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

  10. 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.

  11. Participation of ethylene in gravitropism

    NASA Technical Reports Server (NTRS)

    Harrison, M.; Pickard, B. G.

    1984-01-01

    In shoots of many plants, of which tomato (Lycopersicon esculentum Mill.) is an example, ethylene production is substantially increased during gravitropism. As a first step toward elucidating the role of ethylene in gravitropism, detailed time courses of ethylene production in isolated hypocotyl segments and whole plants were measured for gravistimulated and upright tomato seedlings. In the first experiment, seedlings were set upright or laid horizontal and then, at 15 min intervals, sets of hypocotyls were excised and sealed into gas tight vials. A steady long term rise in ethylene production begins after 15 min gravistimulation. It is possible that this increase is a consequence of the accumulation of indoleacetic acid (IAA) in the lower tissue of the hypocotyle. In a second kind of experiment, whole seedlings were enclosed in sealed chambers and air samples were withdrawn at 5 min intervals. Stimulated seedlings produced more ethylene than controls during the first 5 min interval, but not appreciably more during the second. This suggests the possibility that the ethylene production induced during the first 5 min occurs immediately rather than after a lag, and thus much too soon to be controlled by redistribution of IAA.

  12. Particle Generation and Evolution in Silane/Acetylene Flames in Microgravity

    NASA Technical Reports Server (NTRS)

    Keil, D. G.

    2001-01-01

    The objective of this new experimental program is to advance the understanding of the formation of particles from gas phase combustion processes. The work will utilize the unique SiH4/C2H2 combustion system which generates particulate products ranging from high purity, white SiC to carbonaceous soot depending on equivalence ratio. A key goal of this work is to identify gas phase or particle formation processes that provide the enthalpy release necessary to drive the combustion wave, and to locate the parts of the particle formation process that determine SiC stoichiometry and crystallinity. In a real sense, these SiH4/C2H2 flames act like "highly sooty" hydrocarbon flames, but with simpler chemistry. This simplification is expected to allow them to be used as surrogates to advance understanding of soot formation in such rich hydrocarbon flames. It is also expected that this improved understanding of SiC particle generation and evolution in these self-sustaining flames will advance the commercial potential of the flame process for the generation of high purity SiC powders.

  13. Ethylene C-H Bond Activation by Neutral Mn2O5 Clusters under Visible Light Irradiation.

    PubMed

    Yin, Shi; Bernstein, Elliot R

    2016-05-01

    A photo excitation fast flow reactor coupled with a single-photon ionization (118 nm, 10.5 eV) time-of-flight mass spectrometry (TOFMS) instrument is used to investigate reactions of neutral MnmOn clusters with C2H4 under visible (532 nm) light irradiation. Association products Mn2O5(C2H4) and Mn3O6,7(C2H4) are observed without irradiation. Under light irradiation, the Mn2O5(C2H4) TOFMS feature decreases, and a new species, Mn2O5H2, is observed. This light-activated reaction suggests that the visible radiation can induce the chemistry, Mn2O5 + C2H4 + hv(532 nm) → Mn2O5*(C2H4) → Mn2O5H2 + C2H2. High barriers (0.67 and 0.59 eV) are obtained on the ground-state potential energy surface (PES); the reaction is barrierless and thermodynamically favorable on the first excited-state PES, as performed by time-dependent density functional theory calculations. The calculational and experimental results suggest that Mn2O5-like structures on manganese oxide surfaces are the appropriate active catalytic sites for visible light photocatalysis of ethylene dehydrogenation. PMID:27099985

  14. BIOSYNTHESIS OF STRESS ETHYLENE IN SOYBEAN SEEDLINGS: SIMILARITIES TO ENDOGENOUS ETHYLENE BIOSYNTHESIS

    EPA Science Inventory

    The similarity of stress ethylene biosynthesis in whole plants to endogenous ethylene biosynthesis was investigated using two inhibitors of ethylene biosynthesis, amino-ethoxyvinylglycine (AVG) and cobalt chloride (Co2+); and the intermediates, methionine, S-adenosylmethionine (S...

  15. 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.

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

    PubMed

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

    2015-11-25

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

  17. 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.

  18. Spectroscopy of acetylene Rydberg states studied by VUV absorption and (3+1)-Resonantly Enhanced Multiphoton Ionisation

    NASA Astrophysics Data System (ADS)

    Boyé, Séverine; Campos, Andrea; Fillion, Jean-Hugues; Douin, Stéphane; Shafizadeh, Niloufar; Gauyacq, Dolores

    2004-03-01

    The ungerade ns+ nd Rydberg states of C 2H 2 converging to the ground state of the C 2H 2+ cation have been investigated in the energy range 74 000- 88 000 cm-1 by (3+1)-multiphoton ionisation (REMPI) and by VUV absorption spectroscopy at the Super-ACO synchrotron radiation facility. Both methods have allowed the selective analysis of the Rydberg transitions with rotational resolution. Mulliken's semi-united atom model, in which predissociation has been taken into account, was used to understand the relative three-photon intensities among the different electronic transitions within the same Rydberg supercomplex. Lifetimes have been evaluated and illustrate very different behaviours towards predissociation for the observed Rydberg states. To cite this article: S. Boyé et al., C. R. Physique 5 (2004).

  19. Ethylene monitoring and control system

    NASA Technical Reports Server (NTRS)

    Nelson, Bruce N. (Inventor); Richard, II, Roy V. (Inventor); Kane, James A. (Inventor)

    2001-01-01

    A system that can accurately monitor and control low concentrations of ethylene gas includes a test chamber configured to receive sample gas potentially containing an ethylene concentration and ozone, a detector configured to receive light produced during a reaction between the ethylene and ozone and to produce signals related thereto, and a computer connected to the detector to process the signals to determine therefrom a value of the concentration of ethylene in the sample gas. The supply for the system can include a four way valve configured to receive pressurized gas at one input and a test chamber. A piston is journaled in the test chamber with a drive end disposed in a drive chamber and a reaction end defining with walls of the test chamber a variable volume reaction chamber. The drive end of the piston is pneumatically connected to two ports of the four way valve to provide motive force to the piston. A manifold is connected to the variable volume reaction chamber, and is configured to receive sample gasses from at least one of a plurality of ports connectable to degreening rooms and to supply the sample gas to the reactive chamber for reaction with ozone. The apparatus can be used to monitor and control the ethylene concentration in multiple degreening rooms.

  20. Ethylene monitoring and control system

    NASA Technical Reports Server (NTRS)

    Nelson, Bruce N. (Inventor); Richard, II, Roy V. (Inventor); Kanc, James A. (Inventor)

    2000-01-01

    A system that can accurately monitor and control low concentrations of ethylene gas includes a test chamber configured to receive sample gas potentially containing an ethylene concentration and ozone, a detector configured to receive light produced during a reaction between the ethylene and ozone and to produce signals related thereto, and a computer connected to the detector to process the signals to determine therefrom a value of the concentration of ethylene in the sample gas. The supply for the system can include a four way valve configured to receive pressurized gas at one input and a test chamber. A piston is journaled in the test chamber with a drive end disposed in a drive chamber and a reaction end defining with walls of the test chamber a variable volume reaction chamber. The drive end of the piston is pneumatically connected to two ports of the four way valve to provide motive force to the piston. A manifold is connected to the variable volume reaction chamber, and is configured to receive sample gasses from at least one of a plurality of ports connectable to degreening rooms and to supply the sample gas to the reactive chamber for reaction with ozone. The apparatus can be used to monitor and control the ethylene concentration in multiple degreening rooms.

  1. Ethylene-producing bacteria that ripen fruit.

    PubMed

    Digiacomo, Fabio; Girelli, Gabriele; Aor, Bruno; Marchioretti, Caterina; Pedrotti, Michele; Perli, Thomas; Tonon, Emil; Valentini, Viola; Avi, Damiano; Ferrentino, Giovanna; Dorigato, Andrea; Torre, Paola; Jousson, Olivier; Mansy, Sheref S; Del Bianco, Cristina

    2014-12-19

    Ethylene is a plant hormone widely used to ripen fruit. However, the synthesis, handling, and storage of ethylene are environmentally harmful and dangerous. We engineered E. coli to produce ethylene through the activity of the ethylene-forming enzyme (EFE) from Pseudomonas syringae. EFE converts a citric acid cycle intermediate, 2-oxoglutarate, to ethylene in a single step. The production of ethylene was placed under the control of arabinose and blue light responsive regulatory systems. The resulting bacteria were capable of accelerating the ripening of tomatoes, kiwifruit, and apples. PMID:25393892

  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.

    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

  3. 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

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

    PubMed

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

    2015-08-21

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

  5. Portable Ethylene Oxide Sterilization Chamber

    PubMed Central

    Songer, J. R.; Mathis, R. G.

    1969-01-01

    A portable ethylene oxide sterilization chamber was designed, constructed, and tested for use in the sterilization of embolectomy catheters. The unit can accommodate catheters up to 40 inches (101.6 cm) in length and can be operated for less than 4 cents per cycle. A constant concentration of 500 mg of ethylene oxide per liter of space and holding periods of 4 and 6 hr at 43 and 22 C, respectively, were adequate when tested with B. subtilis spores. The estimated cost of construction was $165.00. If temperature control is unnecessary, the cost is approximately $80.00. Images PMID:4977644

  6. Grafting of poly(ethylene glycol) on click chemistry modified Si(100) surfaces.

    PubMed

    Flavel, Benjamin S; Jasieniak, Marek; Velleman, Leonora; Ciampi, Simone; Luais, Erwann; Peterson, Joshua R; Griesser, Hans J; Shapter, Joe G; Gooding, J Justin

    2013-07-01

    Poly(ethylene glycol) (PEG) is one of the most extensively studied antifouling coatings due to its ability to reduce protein adsorption and improve biocompatibility. Although the use of PEG for antifouling coatings is well established, the stability and density of PEG layers are often inadequate to provide optimum antifouling properties. To improve on these shortcomings, we employed the stepwise construction of PEG layers onto a silicon surface. Acetylene-terminated alkyl monolayers were attached to nonoxidized crystalline silicon surfaces via a one-step hydrosilylation procedure with 1,8-nonadiyne. The acetylene-terminated surfaces were functionalized via a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction of the surface-bound alkynes with an azide to produce an amine terminated layer. The amine terminated layer was then further conjugated with PEG to produce an antifouling surface. The antifouling surface properties were investigated by testing adsorption of human serum albumin (HSA) and lysozyme (Lys) onto PEG layers from phosphate buffer solutions. Detailed characterization of protein fouling was carried out with X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with principal component analysis (PCA). The results revealed no fouling of albumin onto PEG coatings whereas the smaller protein lysozyme adsorbed to a very low extent. PMID:23790067

  7. Colorometric detection of ethylene glycol vapor

    NASA Technical Reports Server (NTRS)

    Helm, C.; Mosier, B.; Verostko, C. E.

    1970-01-01

    Very low concentrations of ethylene glycol in air or other gases are detected by passing a sample through a glass tube with three partitioned compartments containing reagents which successively convert the ethylene glycol vapor into a colored compound.

  8. Ethylene binding site affinity in ripening apples

    SciTech Connect

    Blankenship, S.M. . Dept. of Horticultural Science); Sisler, E.C. )

    1993-09-01

    Scatchard plots for ethylene binding in apples (Malus domestica Borkh.), which were harvested weekly for 5 weeks to include the ethylene climacteric rise, showed C[sub 50] values (concentration of ethylene needed to occupy 50% of the ethylene binding sites) of 0.10, 0.11, 0.34, 0.40, and 0.57 [mu]l ethylene/liter[sup [minus]1], respectively, for each of the 5 weeks. Higher ethylene concentrations were required to saturate the binding sites during the climacteric rise than at other times. Diffusion of [sup 14]C-ethylene from the binding sites was curvilinear and did not show any indication of multiple binding sites. Ethylene was not metabolized by apple tissue.

  9. Ethylene oxide sterilisation--is it safe?

    PubMed Central

    Gillespie, E H; Jackson, J M; Owen, G R

    1979-01-01

    Tests show that ethylene oxide penetrates and can sterilise long narrow tubes in a hospital ethylene oxide steriliser. Residual ethylene oxide levels in plastic tubing after sterilisation have been estimated. Although initially the levels were very high, storage for four days at room temperature reduced them to a safe level. If adequate controls of the sterilising process and storage are carried out, sterilisation by ethylene oxide is considered to be safe for new plastics and clean equipment. Images Figure PMID:512032

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

    PubMed

    Rhee, Jong Uk; Krische, Michael J

    2006-08-23

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

  11. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  13. 49 CFR 173.323 - Ethylene oxide.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Ethylene oxide. 173.323 Section 173.323... SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.323 Ethylene oxide. (a) For packaging ethylene oxide in non-bulk packagings, silver mercury or any of its alloys or copper may not be used in...

  14. Optical frequency standard using acetylene-filled hollow-core photonic crystal fibers.

    PubMed

    Triches, Marco; Michieletto, Mattia; Hald, Jan; Lyngsø, Jens K; Lægsgaard, Jesper; Bang, Ole

    2015-05-01

    Gas-filled hollow-core photonic crystal fibers are used to stabilize a fiber laser to the 13C2H2 P(16) (ν1+ν3) transition at 1542 nm using saturated absorption. Four hollow-core fibers with different crystal structure are compared in terms of long term lock-point repeatability and fractional frequency instability. The locked fiber laser shows a fractional frequency instability below 4 × 10(-12) for averaging time up to 10(4) s. The lock-point repeatability over more than 1 year is 1.3 × 10(-11), corresponding to a standard deviation of 2.5 kHz. A complete experimental investigation of the light-matter interaction between the spatial modes excited in the fibers and the frequency of the locked laser is presented. A simple theoretical model that explains the interaction is also developed. PMID:25969219

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

    PubMed Central

    Anderson, Stephen J.; Phillips, Donald A.

    1976-01-01

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

  16. 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

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  19. 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.

  20. Ethylene effects in pea stem tissue

    SciTech Connect

    Steen, D.A.; Chadwick, A.V.

    1981-01-01

    The marked effects of ethylene on pea stem growth have been investigated. Low temperatures and colchicine, both known microtubule depolymerization agents, reverse the effects of ethylene in straight growth tests. Low temperature (6 C) also profoundly reduces the effects of gas in terms of swelling, hook curvature, and horizontal mutation. Deuterium oxide, an agent capable of rigidifying microtubular structure, mimics the effects of ethylene. Electron microscopy shows that microtubule orientation is strikingly altered by ethylene. These findings indicate that some of the ethylene responses may be due to a stabilizing effect on microtubules in plant cells.

  1. Ethylene and senescence in petals of tradescantia.

    PubMed

    Suttle, J C; Kende, H

    1978-08-01

    Flowers of Tradescantia (clone O2) which are ephemeral, produce ethylene during senescence with the maximum rates occurring during the initial period of fading. Senescing isolated petals produce ethylene in a similar manner, exhibit a loss of membrane semipermeability, and exogenous ethylene hastens the onset as well as the subsequent rate of this loss. The aminoethoxy analog of 0.1 millimolar rhizobitoxine completely inhibits ethylene production by isolated petals but only partially the loss of membrane semipermeability. Isolated petals acquire a sensitivity to ethylene as they mature, becoming fully sensitive on the day of anthesis. PMID:16660498

  2. 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.

  3. Acute hepatotoxicity of ethylene and halogenated ethylenes after PCB pretreatment.

    PubMed

    Conolly, R B; Jaeger, R J

    1977-12-01

    Previous studies from our laboratory have shown that ethylene, vinyl fluoride monomer (VFM), vinyl chloride monomer (VCM), and vinyl bromide monomer (VBM) are all acutely hepatotoxic in rats pretreated with polychlorinated biphenyl (PCB). The time course of hepatic injury development after exposure and several parameters, environmental and chemical, affecting this toxicity were evaluated in the work reported here. Liver injury, as measured by serum alanine-alpha-ketoglutarate transaminase (SAKT) or sorbitol dehydrogenase (SDH), develops progressively over a 24-hr period following a 4-hr inhalation exposure of PCB-pretreated rats to ethylene or VCM. Environmental temperature during exposure to VCM does not affect hepatotoxicity or mortality below 30.3 degrees C. At 33.8 degrees C, however, mortality and SAKT are dramatically increased. Overnight fasting, which depletes hepatic glutathione (GSH) of PCB-pretreated rats before exposure to ethylene or VCM, significantly increases the hepatotoxicity of these compounds as measured by SDH. The combined effects of fasting and of trichloropropane epoxide (TCPE), an inhibitor of epoxide hydrase (EH), were also examined. TCPE treatment of fasted PCB-pretreated rats immediately before exposure was synergistic in increasing the acute toxicity of ethylene and VCM. TCPE increased mortality in fed or fasted rats exposed to VFM, but there was no effect of fasting alone. Both fasting and TCPE increased the sensitivity of PCB-pretreated rats to VBM, but there was not a clearly synergistic effect of fasting plus TCPE. These data suggest that the acute toxicity of these compounds is mediated through epoxide intermediates. PMID:417916

  4. Ethylene glycol poisoning in sheep.

    PubMed

    2015-05-16

    Oxalate toxicity in sheep as a consequence of exposure to ethylene glycol. Chlamydophila abortus infection in a dairy cow. Neosporosis diagnosed in a newborn lamb with deformities. Yersiniosis affecting a 1000-strong goat herd. Porcine reproductive and respiratory syndrome causing blue ears in 14-week-old pigs. Avian tuberculosis diagnosed in an adult Mandarin duck. These are among matters discussed in the Animal and Plant Health Agency's (APHA's) disease surveillance report for January and February 2015. PMID:25977491

  5. 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...

  6. 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...

  7. 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...

  8. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

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

  9. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

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

  10. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

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

  11. 46 CFR 151.50-79 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

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

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

    Code of Federal Regulations, 2013 CFR

    2013-10-01

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

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

    EPA Science Inventory

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

  14. 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...

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

    PubMed

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

    2015-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  17. 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…

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

    PubMed

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

    2016-02-01

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

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

    EPA Science Inventory

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

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

    PubMed

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

    2010-12-28

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

  1. 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

  2. Ethylene oxide and acetaldehyde in hot cores

    NASA Astrophysics Data System (ADS)

    Occhiogrosso, A.; Vasyunin, A.; Herbst, E.; Viti, S.; Ward, M. D.; Price, S. D.; Brown, W. A.

    2014-04-01

    Context. Ethylene oxide (c-C2H4O), and its isomer acetaldehyde (CH3CHO), are important complex organic molecules because of their potential role in the formation of amino acids. The discovery of ethylene oxide in hot cores suggests the presence of ring-shaped molecules with more than 3 carbon atoms such as furan (c-C4H4O), to which ribose, the sugar found in DNA, is closely related. Aims: Despite the fact that acetaldehyde is ubiquitous in the interstellar medium, ethylene oxide has not yet been detected in cold sources. We aim to understand the chemistry of the formation and loss of ethylene oxide in hot and cold interstellar objects (i) by including in a revised gas-grain network some recent experimental results on grain surfaces and (ii) by comparison with the chemical behaviour of its isomer, acetaldehyde. Methods: We introduce a complete chemical network for ethylene oxide using a revised gas-grain chemical model. We test the code for the case of a hot core. The model allows us to predict the gaseous and solid ethylene oxide abundances during a cooling-down phase prior to star formation and during the subsequent warm-up phase. We can therefore predict at what temperatures ethylene oxide forms on grain surfaces and at what temperature it starts to desorb into the gas phase. Results: The model reproduces the observed gaseous abundances of ethylene oxide and acetaldehyde towards high-mass star-forming regions. In addition, our results show that ethylene oxide may be present in outer and cooler regions of hot cores where its isomer has already been detected. Our new results are compared with previous results, which focused on the formation of ethylene oxide only. Conclusions: Despite their different chemical structures, the chemistry of ethylene oxide is coupled to that of acetaldehyde, suggesting that acetaldehyde may be used as a tracer for ethylene oxide towards cold cores.

  3. Cooling in the tropics: ethylene glycol overdose.

    PubMed

    Holyoak, Adam L; Fraser, Todd A; Gelperowicz, Pascal

    2011-03-01

    Ethylene glycol is the active ingredient used in radiator antifreeze. Severe ingestions of ethylene glycol are uncommon in Australia, but if untreated, can result in multiorgan dysfunction, particularly renal failure and cerebral oedema. We report on a patient who consumed a large quantity of ethylene glycol. He was treated with enteral ethanol and went on to make a full recovery, despite an initial moribund state. We briefly review the pathophysiology and current treatment strategies for ethylene glycol intoxication, and discuss issues surrounding enteral versus parenteral ethanol administration. PMID:21355826

  4. Ethylene, Plant Senescence and Abscission 1

    PubMed Central

    Burg, Stanley P.

    1968-01-01

    Evidence supporting the hypothesis that ethylene is involved in the control of senescence and abscission is reviewed. The data indicate that ethylene causes abscission in vivo by inhibiting auxin synthesis and transport or enhancing auxin destruction, thus lowering the diffusible auxin level. Studies with isolated leaves and explants suggest that the gas also may influence abscission by accelerating senescence and through an action on plant cell walls. Freshly prepared explants produce ethylene at a rate which must be high enough to maximally affect the tissue and this may explain why these explants (stage I) cannot respond to applied ethylene. PMID:16657016

  5. Ethylene and pollination decrease transcript abundance of an ethylene receptor gene in Dendrobium petals.

    PubMed

    Thongkum, Monthathip; Burns, Parichart; Bhunchoth, Anjana; Warin, Nuchnard; Chatchawankanphanich, Orawan; van Doorn, Wouter G

    2015-03-15

    We studied the expression of a gene encoding an ethylene receptor, called Ethylene Response Sensor 1 (Den-ERS1), in the petals of Dendrobium orchid flowers. Transcripts accumulated during the young floral bud stage and declined by the time the flowers had been open for several days. Pollination or exposure to exogenous ethylene resulted in earlier flower senescence, an increase in ethylene production and a lower Den-ERS1 transcript abundance. Treatment with 1-methylcyclopropene (1-MCP), an inhibitor of the ethylene receptor, decreased ethylene production and resulted in high transcript abundance. The literature indicates two kinds of ethylene receptor genes with regard to the effects of ethylene. One group shows ethylene-induced down-regulated transcription, while the other has ethylene-induced up-regulation. The present gene is an example of the first group. The 5' flanking region showed binding sites for Myb and myb-like, homeodomain, MADS domain, NAC, TCP, bHLH and EIN3-like transcription factors. The binding site for the EIN3-like factor might explain the ethylene effect on transcription. A few other transcription factors (RAV1 and NAC) seem also related to ethylene effects. PMID:25590685

  6. Biocatalytic conversion of ethylene to ethylene oxide using an engineered toluene monooxygenase

    SciTech Connect

    Carlin, DA; Bertolani, SJ; Siegel, JB

    2015-01-01

    Mutants of toluene o-xylene monooxygenase are demonstrated to oxidize ethylene to ethylene oxide in vivo at yields of >99%. The best mutant increases ethylene oxidation activity by >5500-fold relative to the native enzyme. This is the first report of a recombinant enzyme capable of carrying out this industrially significant chemical conversion.

  7. Poly(ethylene oxide) functionalization

    DOEpatents

    Pratt, Russell Clayton

    2014-04-08

    A simple procedure is provided by which the hydroxyl termini of poly(ethylene oxide) can be appended with functional groups to a useful extent by reaction and precipitation. The polymer is dissolved in warmed toluene, treated with an excess of organic base and somewhat less of an excess of a reactive acylating reagent, reacted for several hours, then precipitated in isopropanol so that the product can be isolated as a solid, and salt byproducts are washed away. This procedure enables functionalization of the polymer while not requiring laborious purification steps such as solvent-solvent extraction or dialysis to remove undesirable side products.

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

    PubMed

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

    1999-08-01

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

  9. 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...

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

    PubMed

    Jensen, K M; Cox, R P

    1992-09-01

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

  11. On the radiolysis of ethylene ices by energetic electrons and implications to the extraterrestrial hydrocarbon chemistry

    SciTech Connect

    Zhou, Li; Maity, Surajit; Abplanalp, Matt; Turner, Andrew; Kaiser, Ralf I.

    2014-07-20

    The chemical processing of ethylene ices (C{sub 2}H{sub 4}) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH{sub 4}), the C2 species acetylene (C{sub 2}H{sub 2}), ethane (C{sub 2}H{sub 6}), the ethyl radical (C{sub 2}H{sub 5}), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C{sub 4}H{sub 8}) and n-butane (C{sub 4}H{sub 10}). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.

  12. CADMIUM-INDUCED ETHYLENE PRODUCTION IN BEAN PLANTS

    EPA Science Inventory

    Studies were conducted to (1) compare stress ethylene production from roots and shoots (2) determine the association between stress ethylene production and tissue Cd levels; and (3) investigate the time course of stress ethylene production following the rhizosphere application of...

  13. The interaction between soot and NO formation in a laminar axisymmetric coflow ethylene/air diffusion flame

    SciTech Connect

    Guo, Hongsheng; Smallwood, Gregory J.

    2007-04-15

    The interaction between soot and NO formation in a laminar axisymmetric coflow ethylene/air diffusion flame was investigated by numerical simulation. A detailed gas-phase reaction scheme and a simplified soot model were employed. The results show that the formation of NO has little effect on that of soot. However, the formation of soot in the flame significantly suppresses the formation of NO. The peak NO concentration and NO emission index are reduced by 28 and 46%, respectively, due to the formation of soot. The influence of soot on NO formation is caused by not only the radiation-induced thermal effect, but also the reaction-induced chemical effect. Relatively the thermal effect is more significant, causing 25 and 38% reduction, respectively, in peak NO concentration and NO emission index. The chemical effect is caused by the competition for acetylene (C{sub 2}H{sub 2}) between soot and NO formation. The formation of soot consumes acetylene in the flame and thus lowers the formation rate of radical CH. This reduces the reaction rate of CH + N{sub 2} = HCN + N, which is the rate-limiting step of the prompt NO formation route, the dominant route in the studied flame. (author)

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

    DOE PAGESBeta

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-10-01

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

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

    SciTech Connect

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

    1993-12-31

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

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

    NASA Astrophysics Data System (ADS)

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

    2001-10-01

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

  18. 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.

  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 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.

  20. Ethylene in Storage: The Phantom Menace

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ethylene is a small, gaseous, hydrocarbon that exists in the atmosphere at low concentrations. Plants, including potato tubers, produce ethylene as part of natural developmental processes and in response to some stresses, such as low temperature stress. Several lines of research have demonstrated th...

  1. Health Assessment Document for Ethylene Oxide

    EPA Science Inventory

    The largest single use of ethylene oxide is as an intermediate in the synthesis of ethylene glycol. However, small amounts of this epoxide are used as a sterilant or pesticide in commodities, pharmaceuticals, medical devices, tobacco, and other items, representing a considerable ...

  2. 21 CFR 573.440 - Ethylene dichloride.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Ethylene dichloride. 573.440 Section 573.440 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive Listing § 573.440 Ethylene...

  3. Ethylene glycol, hazardous substance in the household.

    PubMed

    Patocka, Jirí; Hon, Zdenek

    2010-01-01

    Ethylene glycol is a colorless, odorless, sweet-tasting but poisonous type of alcohol found in many household products. The major use of ethylene glycol is as an antifreeze in, for example, automobiles, in air conditioning systems, in de-icing fluid for windshields, and else. People sometimes drink ethylene glycol mistakenly or on purpose as a substitute for alcohol. Ethylene glycol is toxic, and its drinking should be considered a medical emergency. The major danger from ethylene glycol is following ingestion. Due to its sweet taste, peoples and occasionally animals will sometimes consume large quantities of it if given access to antifreeze. While ethylene glycol itself has a relatively low degree of toxicity, its metabolites are responsible for extensive cellular damage to various tissues, especially the kidneys. This injury is caused by the metabolites, glycolic and oxalic acid and their respective salts, through crystal formation and possibly other mechanisms. Toxic metabolites of ethylene glycol can damage the brain, liver, kidneys, and lungs. The poisoning causes disturbances in the metabolism pathways, including metabolic acidosis. The disturbances may be severe enough to cause profound shock, organ failure, and death. Ethylene glycol is a common poisoning requiring antidotal treatment. PMID:20608228

  4. Methods and compositions to modulate ethylene sensitivity

    DOEpatents

    Stepanova, Anna N.; Ecker, Joseph R.

    2007-01-30

    The field of the invention relates to plants and plant genes, including both plant mutants and transgenic plants containing a gene that confers an ethylene insensitive phenotype. Also encompassed by the invention are methods of using the disclosed plant gene to confer an ethylene insensitive phenotype.

  5. 29 CFR 1910.1047 - Ethylene oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 29 Labor 6 2014-07-01 2013-07-01 true Ethylene oxide. 1910.1047 Section 1910.1047 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR (CONTINUED) OCCUPATIONAL SAFETY AND HEALTH STANDARDS (CONTINUED) Toxic and Hazardous Substances § 1910.1047 Ethylene oxide. (a) Scope and...

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

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

    PubMed

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

    2007-05-01

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

  8. 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.

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

    NASA Astrophysics Data System (ADS)

    Fogg, Peter G. T.

    2013-03-01

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

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

    PubMed

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

    2011-09-15

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

  11. The ethylene response pathway in Arabidopsis

    NASA Technical Reports Server (NTRS)

    Kieber, J. J.; Evans, M. L. (Principal Investigator)

    1997-01-01

    The simple gas ethylene influences a diverse array of plant growth and developmental processes including germination, senescence, cell elongation, and fruit ripening. This review focuses on recent molecular genetic studies, principally in Arabidopsis, in which components of the ethylene response pathway have been identified. The isolation and characterization of two of these genes has revealed that ethylene sensing involves a protein kinase cascade. One of these genes encodes a protein with similarity to the ubiquitous Raf family of Ser/Thr protein kinases. A second gene shows similarity to the prokaryotic two-component histidine kinases and most likely encodes an ethylene receptor. Additional elements involved in ethylene signaling have only been identified genetically. The characterization of these genes and mutants will be discussed.

  12. Synthesis of p-xylene from ethylene.

    PubMed

    Lyons, Thomas W; Guironnet, Damien; Findlater, Michael; Brookhart, Maurice

    2012-09-26

    As oil supplies dwindle, there is a growing need to develop new routes to chemical intermediates that utilize alternative feedstocks. We report here a synthesis of para-xylene, one of the highest volume chemicals derived from petroleum, using only ethylene as a feedstock. Ethylene is an attractive alternative feedstock, as it can be derived from renewable biomass resources or harnessed from large domestic shale gas deposits. The synthesis relies on the conversion of hexene (from trimerization of ethylene) to 2,4-hexadiene followed by a Diels-Alder reaction with ethylene to form 3,6-dimethylcyclohexene. This monoene is readily dehydrogenated to para-xylene uncontaminated by the ortho and meta isomers. We report here a selective synthesis of para-xylene, uncontaminated by the ortho or meta isomers, using ethylene as the sole feedstock. PMID:22934909

  13. Ethylene synthesis and sensitivity in crop plants

    NASA Technical Reports Server (NTRS)

    Klassen, Stephen P.; Bugbee, Bruce

    2004-01-01

    Closed and semi-closed plant growth chambers have long been used in studies of plant and crop physiology. These studies include the measurement of photosynthesis and transpiration via photosynthetic gas exchange. Unfortunately, other gaseous products of plant metabolism can accumulate in these chambers and cause artifacts in the measurements. The most important of these gaseous byproducts is the plant hormone ethylene (C2H4). In spite of hundreds of manuscripts on ethylene, we still have a limited understanding of the synthesis rates throughout the plant life cycle. We also have a poor understanding of the sensitivity of intact, rapidly growing plants to ethylene. We know ethylene synthesis and sensitivity are influenced by both biotic and abiotic stresses, but such whole plant responses have not been accurately quantified. Here we present an overview of basic studies on ethylene synthesis and sensitivity.

  14. The ethylene signal transduction pathway in Arabidopsis

    NASA Technical Reports Server (NTRS)

    Kieber, J. J.; Evans, M. L. (Principal Investigator)

    1997-01-01

    The gaseous hormone ethylene is an important regulator of plant growth and development. Using a simple response of etiolated seedlings to ethylene as a genetic screen, genes involved in ethylene signal transduction have been identified in Arabidopsis. Analysis of two of these genes that have been cloned reveals that ethylene signalling involves a combination of a protein (ETR1) with similarity to bacterial histidine kinases and a protein (CTR1) with similarity to Raf-1, a protein kinase involved in multiple signalling cascades in eukaryotic cells. Several lines of investigation provide compelling evidence that ETR1 encodes an ethylene receptor. For the first time there is a glimpse of the molecular circuitry underlying the signal transduction pathway for a plant hormone.

  15. Enhancement of RNA Synthesis, Protein Synthesis, and Abscission by Ethylene

    PubMed Central

    Abeles, F. B.; Holm, R. E.

    1966-01-01

    Ethylene stimulated RNA and protein synthesis in bean (Phaseolus vulgaris L. var. Red Kidney) abscission zone explants prior to abscission. The effect of ethylene on RNA synthesis and abscission was blocked by actinomycin D. Carbon dioxide, which inhibits the effect of ethylene on abscission, also inhibited the influence of ethylene on protein synthesis. An aging period appears to be essential before bean explants respond to ethylene. Stimulation of protein synthesis by ethylene occurred only in receptive or senescent explants. Treatment of juvenile explants with ethylene, which has no effect on abscission also has no effect on protein synthesis. Evidence in favor of a hormonal role for ethylene during abscission is discussed. PMID:16656405

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

    SciTech Connect

    Takeichi, T.; Ogura, S.

    1993-12-31

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

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

    PubMed

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

    2016-07-26

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

  18. 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.

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

    PubMed

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

    2009-04-01

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

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

    PubMed

    Comandini, A; Malewicki, T; Brezinsky, K

    2012-03-15

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

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

    PubMed Central

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

    2013-01-01

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

  2. Effects of bending and bending angular momentum on reaction of NO2+ with C2H2: a quasi-classical trajectory study.

    PubMed

    Boyle, Jason M; Liu, Jianbo; Anderson, Scott L

    2009-04-23

    A large set of quasi-classical trajectories were calculated at the PBE1PBE/6-311G** level of theory, in an attempt to understand the mechanistic origins of the large, mode-specific enhancement of the O-transfer reaction by NO2+ bending vibration and the surprisingly large suppressing effect of bending angular momentum. The trajectories reproduce the magnitude of the absolute reaction cross section, and also get the dependence of reactivity on NO2+ vibrational state, and the vibrational state dependent scattering behavior qualitatively correct. Analysis of the trajectories shows that the bending effect is not simply a consequence of enhanced reactivity in bent geometries but, rather, that excitation of bending motion allows reaction in a wider range of orientation angles, even if the NO2+ is not bent at the onset of the collisional interaction. There is a strong interplay between NO2+ bending and transient charge transfer during the collisions. Such charge transfer enhances reactivity, but only if the reactants are oriented correctly. PMID:19182967

  3. A philosophical theory on human communication and modern physics: e(,2)c(,2)H('2)T energy-exchange and consciousness-change toward humanism, healing, and transformation

    NASA Astrophysics Data System (ADS)

    Jenkins-Tate, Marnishia Laverne

    This dissertation addresses the need for a body of human communication theory that can be useful toward advancing personal and social transformation. Of the humanistic genre, it suggests that there is a need to promote humanism, healing, and personal transformation in the non-clinical settings of everyday living. Three questions guide the effort. First, it asks: what kind of human communication theory might describe some of the underlying dynamics of human interaction, while also suggesting ways to improve the quality of interactions of any related philosophical theory be grounded by some scientific discipline? Then finally, it asks: how might these proposed concepts be captured in a manner that can be useful to human beings in everyday human interaction? Extending the work of modern physics to the realm of human communication, the theory integrates conceptual aspects of quantum theory, relativity theory, communication accommodation theory, and various nonverbal communication theory. Then, it proposes the philosophical framework for a new body of theory which it calls the energy-exchange theory of human communication. Treating human beings as living forms of matter, it suggests that ``energy'' is the life-force that sustains all human beings, and that ``consciousness'' is that qualitative level of development at which energy manifests itself in the human experience. It proposes that human beings have the capacity to exchange energy and influence consciousness during the human communication process, and that these interactions can advance humanism, healing, and transformation-which it proposes are the higher states and levels of human consciousness. Thus, this research effort sought to know and to describe a phenomenon that is the interactive human being; and to suggest useful ways that this volitional being can know and transform itself through human interaction. With verisimilitude as a driving factor in describing human beings as communicators, the research is ontology- centered. It suggests that human beings are most notably creatures of feeling and soul, and that it is through interaction involving these dimensions that one can best come to know the human being. Accordingly, the research employs a hermeneutic phenomenological approach toward participative inquiry and experiential knowing. With practicality as a driving factor in suggesting ways that the human phenomenon can know and transform itself, this work utilizes a pragmatic approach to theory- building. Pragmatism suggests that all theories are approximations that ultimately should be judged on their abilities to truthfully describe phenomena and to solve human problems. Thus, having undergone an inductive progression from data to theory-building, now this work must go from theory to data, such that next steps should involve formal assessment of its verisimilitude and pragmatism based on feedback gained through field research on various persons who may apply the theory and its model to everyday living. (Abstract shortened by UMI.)

  4. Nuclear localization of the C2H2 zinc finger protein Msn2p is regulated by stress and protein kinase A activity.

    PubMed

    Görner, W; Durchschlag, E; Martinez-Pastor, M T; Estruch, F; Ammerer, G; Hamilton, B; Ruis, H; Schüller, C

    1998-02-15

    Msn2p and the partially redundant factor Msn4p are key regulators of stress-responsive gene expression in Saccharomyces cerevisiae. They are required for the transcription of a number of genes coding for proteins with stress-protective functions. Both Msn2p and Msn4p are Cys2His2 zinc finger proteins and bind to the stress response element (STRE). In vivo footprinting studies show that the occupation of STREs is enhanced in stressed cells and dependent on the presence of Msn2p and Msn4p. Both factors accumulate in the nucleus under stress conditions, such as heat shock, osmotic stress, carbon-source starvation, and in the presence of ethanol or sorbate. Stress-induced nuclear localization was found to be rapid, reversible, and independent of protein synthesis. Nuclear localization of Msn2p and Msn4p was shown to be correlated inversely to cAMP levels and protein kinase A (PKA) activity. A region with significant homologies shared between Msn2p and Msn4p is sufficient to confer stress-regulated localization to a SV40-NLS-GFP fusion protein. Serine to alanine or aspartate substitutions in a conserved PKA consensus site abolished cAMP-driven nuclear export and cytoplasmic localization in unstressed cells. We propose stress and cAMP-regulated intracellular localization of Msn2p to be a key step in STRE-dependent transcription and in the general stress response. PMID:9472026

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

    SciTech Connect

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

    2008-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1996-02-01

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

  7. Effect of Ethylene Pathway Mutations upon Expression of the Ethylene Receptor ETR1 from Arabidopsis1

    PubMed Central

    Zhao, Xue-Chu; Qu, Xiang; Mathews, Dennis E.; Schaller, G. Eric

    2002-01-01

    The ethylene receptor family of Arabidopsis consists of five members, one of these being ETR1. The effect of ethylene pathway mutations upon expression of ETR1 was examined. For this purpose, ETR1 levels were quantified in mutant backgrounds containing receptor loss-of-function mutations, ethylene-insensitive mutations, and constitutive ethylene response mutations. Ethylene-insensitive mutations of ETR1 resulted in a posttranscriptional increase in levels of the mutant receptor. Treatment of seedlings with silver, which leads to ethylene insensitivity, also resulted in an increase in levels of ETR1. Loss-of-function mutations of ETR1 resulted in both transcriptional and posttranscriptional changes in levels of the receptor. Most other ethylene pathway mutations, including a newly isolated T-DNA insertion mutation in the gene encoding the ethylene receptor ERS1, had relatively minor effects upon the expression of ETR1. Our results indicate that mutations in ETR1 can affect expression at the posttranscriptional level, and suggest that these posttranscriptional changes may contribute to the phenotypes observed in the mutants. Our results also refine the model on how mutations in ethylene receptors are able to confer dominant ethylene insensitivity upon plants. PMID:12481081

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

  9. Ethylene and flower longevity in Alstroemeria: relationship between tepal senescence, abscission and ethylene biosynthesis.

    PubMed

    Wagstaff, Carol; Chanasut, Usawadee; Harren, Frans J M; Laarhoven, Luc-Jan; Thomas, Brian; Rogers, Hilary J; Stead, Anthony D

    2005-03-01

    Senescence of floral organs is broadly divided into two groups: those that exhibit sensitivity to exogenous ethylene and those that do not. Endogenous ethylene production from the former group is via a well-characterized biochemical pathway and is either due to developmental or pollination-induced senescence. Many flowers from the order Liliales are characterized as ethylene-insensitive since they do not appear to produce endogenous ethylene, or respond to exogenous ethylene treatments, however, the majority of cases studied are wilting flowers, rather than those where life is terminated by perianth abscission. The role of ethylene in the senescence and abscission of Alstroemeria peruviana cv. Rebecca and cv. Samora tepals was previously unclear, with silver treatments recommended for delaying leaf rather than flower senescence. In the present paper the effects of exogenous ethylene, 2-chloroethylphosphonic acid (CEPA) and silver thiosulphate (STS) treatments on tepal senescence and abscission have been investigated. Results indicate that sensitivity to ethylene develops several days after flower opening such that STS only has a limited ability to delay tepal abscission. Detachment force measurements indicate that cell separation events are initiated after anthesis. Endogenous ethylene production was measured using laser photoacoustics and showed that Alstroemeria senesce independently of ethylene production, but that an extremely small amount of ethylene (0.15 nl flower(-1) h(-1)) is produced immediately prior to abscission. Investigation of the expression of genes involved in ethylene biosysnthesis by semi-quantitative RT-PCR indicated that transcriptional regulation is likely to be at the level of ACC oxidase, and that the timing of ACC oxidase gene expression is coincident with development of sensitivity to exogenous ethylene. PMID:15689338

  10. Ethylene-forming enzyme and bioethylene production

    PubMed Central

    2014-01-01

    Worldwide, ethylene is the most produced organic compound. It serves as a building block for a wide variety of plastics, textiles, and chemicals, and a process has been developed for its conversion into liquid transportation fuels. Currently, commercial ethylene production involves steam cracking of fossil fuels, and is the highest CO2-emitting process in the chemical industry. Therefore, there is great interest in developing technology for ethylene production from renewable resources including CO2 and biomass. Ethylene is produced naturally by plants and some microbes that live with plants. One of the metabolic pathways used by microbes is via an ethylene-forming enzyme (EFE), which uses α-ketoglutarate and arginine as substrates. EFE is a promising biotechnology target because the expression of a single gene is sufficient for ethylene production in the absence of toxic intermediates. Here we present the first comprehensive review and analysis of EFE, including its discovery, sequence diversity, reaction mechanism, predicted involvement in diverse metabolic modes, heterologous expression, and requirements for harvesting of bioethylene. A number of knowledge gaps and factors that limit ethylene productivity are identified, as well as strategies that could guide future research directions. PMID:24589138

  11. Current methods for detecting ethylene in plants

    PubMed Central

    Cristescu, Simona M.; Mandon, Julien; Arslanov, Denis; De Pessemier, Jérôme; Hermans, Christian; Harren, Frans J. M.

    2013-01-01

    Background In view of ethylene's critical developmental and physiological roles the gaseous hormone remains an active research topic for plant biologists. Progress has been made to understand the ethylene biosynthesis pathway and the mechanisms of perception and action. Still numerous questions need to be answered and findings to be validated. Monitoring gas production will very often complete the picture of any ethylene research topic. Therefore the search for suitable ethylene measuring methods for various plant samples either in the field, greenhouses, laboratories or storage facilities is strongly motivated. Scope This review presents an update of the current methods for ethylene monitoring in plants. It focuses on the three most-used methods – gas chromatography detection, electrochemical sensing and optical detection – and compares them in terms of sensitivity, selectivity, time response and price. Guidelines are provided for proper selection and application of the described sensor methodologies and some specific applications are illustrated of laser-based detector for monitoring ethylene given off by Arabidopsis thaliana upon various nutritional treatments. Conclusions Each method has its advantages and limitations. The choice for the suitable ethylene sensor needs careful consideration and is driven by the requirements for a specific application. PMID:23243188

  12. Addition of in situ reduced amidinato-methylaluminium chloride to acetylenes.

    PubMed

    Chlupatý, T; Turek, J; De Proft, F; Růžičková, Z; Růžička, A

    2015-10-28

    Two ethylene-bridged methylaluminium amidinates and one aluminium amidinate containing three terminal trimethylstannyl-ethynyl groups interconnected by π-coordinated potassium ions were prepared in situ. The re-oxidation of the ethylene-bridged compound by iodine followed by further reduction using the same activation procedure demonstrated the versatility of the approach. The reactivity of an ethylene-bridged methylaluminum amidinate towards HCl was examined to demonstrate the building block concept. DFT calculations were performed to gain insight into the mechanism of the in situ activation of diphenylacetylene. PMID:26399401

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  14. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Ethylene-acrylic acid copolymers. 177.1310 Section... Use Food Contact Surfaces § 177.1310 Ethylene-acrylic acid copolymers. The ethylene-acrylic acid... for use in contact with food subject to the provisions of this section. (a) The ethylene-acrylic...

  15. 21 CFR 172.770 - Ethylene oxide polymer.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene oxide polymer. 172.770 Section 172.770... CONSUMPTION Other Specific Usage Additives § 172.770 Ethylene oxide polymer. The polymer of ethylene oxide may... conditions. (a) It is the polymer of ethylene oxide having a minimum viscosity of 1,500 centipoises in a...

  16. 21 CFR 172.770 - Ethylene oxide polymer.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ethylene oxide polymer. 172.770 Section 172.770... CONSUMPTION Other Specific Usage Additives § 172.770 Ethylene oxide polymer. The polymer of ethylene oxide may... conditions. (a) It is the polymer of ethylene oxide having a minimum viscosity of 1,500 centipoises in a...

  17. Ethylene Regulates the Physiology of the Cyanobacterium Synechocystis sp. PCC 6803 via an Ethylene Receptor.

    PubMed

    Lacey, Randy F; Binder, Brad M

    2016-08-01

    Ethylene is a plant hormone that plays a crucial role in the growth and development of plants. The ethylene receptors in plants are well studied, and it is generally assumed that they are found only in plants. In a search of sequenced genomes, we found that many bacterial species contain putative ethylene receptors. Plants acquired many proteins from cyanobacteria as a result of the endosymbiotic event that led to chloroplasts. We provide data that the cyanobacterium Synechocystis (Synechocystis sp. PCC 6803) has a functional receptor for ethylene, Synechocystis Ethylene Response1 (SynEtr1). We first show that SynEtr1 directly binds ethylene. Second, we demonstrate that application of ethylene to Synechocystis cells or disruption of the SynEtr1 gene affects several processes, including phototaxis, type IV pilus biosynthesis, photosystem II levels, biofilm formation, and spontaneous cell sedimentation. Our data suggest a model where SynEtr1 inhibits downstream signaling and ethylene inhibits SynEtr1. This is similar to the inverse-agonist model of ethylene receptor signaling proposed for plants and suggests a conservation of structure and function that possibly originated over 1 billion years ago. Prior research showed that SynEtr1 also contains a light-responsive phytochrome-like domain. Thus, SynEtr1 is a bifunctional receptor that mediates responses to both light and ethylene. To our knowledge, this is the first demonstration of a functional ethylene receptor in a nonplant species and suggests that that the perception of ethylene is more widespread than previously thought. PMID:27246094

  18. 49 CFR 173.323 - Ethylene oxide.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... and gaskets must be constructed of materials which are compatible with ethylene oxide and do not lower... the lading. (h) Neoprene, natural rubber and asbestos gaskets are prohibited. All packing and...

  19. 49 CFR 173.323 - Ethylene oxide.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... and gaskets must be constructed of materials which are compatible with ethylene oxide and do not lower... the lading. (h) Neoprene, natural rubber and asbestos gaskets are prohibited. All packing and...

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

    SciTech Connect

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

    1999-02-09

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