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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

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Drouin, Brian J.; Pearson, John C.

    2009-11-01

    Twenty P-branch transitions of 12C2H2 have been measured in the 0.8-1.6 THz region of its bending vibrational difference band. The accuracy of these measurements is estimated to be 100 kHz. The 12C2H2 molecules were generated under room temperature by passing 150 mTorr H2O vapor through calcium carbide (CaC2) powder. The observed transitions were modeled together with prior far-infrared data involving the bending levels with ∑\

  4. 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.

  5. Acetylene (C2H2) and hydrogen cyanide (HCN) from IASI satellite observations: global distributions, validation, and comparison with model

    NASA Astrophysics Data System (ADS)

    Duflot, V.; Wespes, C.; Clarisse, L.; Hurtmans, D.; Ngadi, Y.; Jones, N.; Paton-Walsh, C.; Hadji-Lazaro, J.; Vigouroux, C.; De Mazière, M.; Metzger, J.-M.; Mahieu, E.; Servais, C.; Hase, F.; Schneider, M.; Clerbaux, C.; Coheur, P.-F.

    2015-09-01

    We present global distributions of C2H2 and hydrogen cyanide (HCN) total columns derived from the Infrared Atmospheric Sounding Interferometer (IASI) for the years 2008-2010. These distributions are obtained with a fast method allowing to retrieve C2H2 abundance globally with a 5 % precision and HCN abundance in the tropical (subtropical) belt with a 10 % (25 %) precision. IASI data are compared for validation purposes with ground-based Fourier transform infrared (FTIR) spectrometer measurements at four selected stations. We show that there is an overall agreement between the ground-based and space measurements with correlation coefficients for daily mean measurements ranging from 0.28 to 0.81, depending on the site. Global C2H2 and subtropical HCN abundances retrieved from IASI spectra show the expected seasonality linked to variations in the anthropogenic emissions and seasonal biomass burning activity, as well as exceptional events, and are in good agreement with previous spaceborne studies. Total columns simulated by the Model for Ozone and Related Chemical Tracers, version 4 (MOZART-4) are compared to the ground-based FTIR measurements at the four selected stations. The model is able to capture the seasonality in the two species in most of the cases, with correlation coefficients for daily mean measurements ranging from 0.50 to 0.86, depending on the site. IASI measurements are also compared to the distributions from MOZART-4. Seasonal cycles observed from satellite data are reasonably well reproduced by the model with correlation coefficients ranging from -0.31 to 0.93 for C2H2 daily means, and from 0.09 to 0.86 for HCN daily means, depending on the considered region. However, the anthropogenic (biomass burning) emissions used in the model seem to be overestimated (underestimated), and a negative global mean bias of 1 % (16 %) of the model relative to the satellite observations was found for C2H2 (HCN).

  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.

  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. Darling-Dennison resonance and Coriolis coupling in the bending overtones of the A 1A(u) state of acetylene, C2H2.

    PubMed

    Merer, Anthony J; Yamakita, Nami; Tsuchiya, Soji; Steeves, Adam H; Bechtel, Hans A; Field, Robert W

    2008-08-01

    Rotational analyses have been carried out for the overtones of the nu(4) (torsion) and nu(6) (in-plane cis-bend) vibrations of the A (1)A(u) state of C(2)H(2). The v(4)+v(6)=2 vibrational polyad was observed in high-sensitivity one-photon laser-induced fluorescence spectra and the v(4)+v(6)=3 polyad was observed in IR-UV double resonance spectra via the ground state nu(3) (Sigma(+) (u)) and nu(3)+nu(4) (Pi(u)) vibrational levels. The structures of these polyads are dominated by the effects of vibrational angular momentum: Vibrational levels of different symmetry interact via strong a-and b-axis Coriolis coupling, while levels of the same symmetry interact via Darling-Dennison resonance, where the interaction parameter has the exceptionally large value K(4466)=-51.68 cm(-1). The K-structures of the polyads bear almost no resemblance to the normal asymmetric top patterns, and many local avoided crossings occur between close-lying levels with nominal K-values differing by one or more units. Least squares analysis shows that the coupling parameters change only slightly with vibrational excitation, which has allowed successful predictions of the structures of the higher polyads: A number of weak bands from the v(4)+v(6)=4 and 5 polyads have been identified unambiguously. The state discovered by Scherer et al. [J. Chem. Phys. 85, 6315 (1986)], which appears to interact with the K=1 levels of the 3(3) vibrational state at low J, is identified as the second highest of the five K=1 members of the v(4)+v(6)=4 polyad. After allowing for the Darling-Dennison resonance, the zero-order bending structure can be represented by omega(4)=764.71, omega(6)=772.50, x(44)=0.19, x(66)=-4.23, and x(46)=11.39 cm(-1). The parameters x(46) and K(4466) are both sums of contributions from the vibrational angular momentum and from the anharmonic force field. For x(46) these contributions are 14.12 and -2.73 cm(-1), respectively, while the corresponding values for K(4466) are -28.24 and -23

  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. 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.

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

    NASA Astrophysics Data System (ADS)

    Liu, D.

    2016-11-01

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

  16. Pulsed supersonic molecular-beam coherent anti-Stokes Raman spectroscopy of C2H2

    NASA Technical Reports Server (NTRS)

    Duncan, M. D.; Byer, R. L.; Osterlin, P.

    1981-01-01

    A high-resolution coherent anti-Stokes Raman spectrum of C2H2 in a pulsed molecular beam was obtained and the resolved Q-branch spectrum was used to study the properties of the expansion. Cluster formation limited the minimum observed rotational temperature in the pure-acetylene expansion to 30 K.

  17. 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

  18. A Diels–Alder super diene breaking benzene into C2H2 and C4H4 units

    PubMed Central

    Inagaki, Yusuke; Nakamoto, Masaaki; Sekiguchi, Akira

    2014-01-01

    Cyclic polyene with six carbon atoms (benzene) is very stable, whereas cyclic polyene with four carbon atoms (cyclobutadiene) is extremely unstable. The electron-withdrawing pentafluorophenyl group of a substituted cyclobutadiene lowers the energy of the lowest unoccupied molecular orbital, greatly increasing its reactivity as a diene in Diels–Alder reactions with acetylene, ethylene and even benzene. Here we show that the reaction with benzene occurs cleanly at the relatively low temperature of 120 °C and results in the formal fragmentation of benzene into C2H2 and C4H4 units, via a unique Diels–Alder/retro-Diels–Alder reaction. This is a new example of the rare case where breaking the C–C bond of benzene is possible with no activation by a transition metal. PMID:24398593

  19. 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.

  20. 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.

  1. Primary branching ratios for the low-temperature reaction of state-prepared N2+ with CH4, C2H2, and C2H4.

    PubMed

    Gichuhi, Wilson K; Suits, Arthur G

    2011-06-30

    Product branching ratios (BRs) are reported for ion-molecule reactions of state-prepared nitrogen cation (N(2)(+)) with methane (CH(4)), acetylene (C(2)H(2)). and ethylene (C(2)H(4)) at low temperature using a modified ion imaging apparatus. These reactions are performed in a supersonic nozzle expansion characterized by a rotational temperature of 40 ± 5K. For the N(2)(+) + CH(4) reaction, a BR of 0.83:0.17 is obtained for the dissociative charge-transfer (CT) reaction that gives rise to the formation of CH(3)(+) and CH(2)(+) product ions, respectively. The N(2)(+) + C(2)H(2) ion-molecule reaction proceeds through a nondissociative CT process that results in the sole formation of C(2)H(2)(+) product ions. The reaction of N(2)(+) with C(2)H(4) leads to the formation of C(2)H(3)(+) and C(2)H(2)(+) product ions with a BR of 0.74:0.26, respectively. The reported BR for the N(2)(+) + C(2)H(4) reaction is supportive of a nonresonant dissociative CT mechanism similar to the one that accompanies the N(2)(+) + CH(4) reaction. No dependence of the branching ratios on N(2)(+) rotational level was observed. In addition to providing direct insight into the dynamics of the state-prepared N(2)(+) ion-molecule reactions with the target neutral hydrocarbon molecules, the reported low-temperature BRs are also important for accurate modeling of the nitrogen-dominated upper atmosphere of Saturn's moon, Titan.

  2. 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.

  3. 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.

  4. Triel Bonds, π-Hole-π-Electrons Interactions in Complexes of Boron and Aluminium Trihalides and Trihydrides with Acetylene and Ethylene.

    PubMed

    Grabowski, Sławomir J

    2015-06-19

    MP2/aug-cc-pVTZ calculations were performed on complexes of aluminium and boron trihydrides and trihalides with acetylene and ethylene. These complexes are linked through triel bonds where the triel center (B or Al) is characterized by the Lewis acid properties through its π-hole region while π-electrons of C2H2 or C2H4 molecule play the role of the Lewis base. Some of these interactions possess characteristics of covalent bonds, i.e., the Al-π-electrons links as well as the interaction in the BH3-C2H2 complex. The triel-π-electrons interactions are classified sometimes as the 3c-2e bonds. In the case of boron trihydrides, these interactions are often the preliminary stages of the hydroboration reaction. The Quantum Theory of "Atoms in Molecules" as well as the Natural Bond Orbitals approach are applied here to characterize the π-hole-π-electrons interactions.

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

    PubMed Central

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

    1989-01-01

    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. PMID:2655535

  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.

  9. 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

  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. 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.

  12. 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.

  13. Klebsiella pneumoniae nitrogenase. Mechanism of acetylene reduction and its inhibition by carbon monoxide.

    PubMed Central

    Lowe, D J; Fisher, K; Thorneley, R N

    1990-01-01

    The electron flux through the MoFe-protein of nitrogenase from Klebsiella pneumoniae determines the absolute and relative rates of 2H+ reduction to H2 and acetylene (C2H2) reduction to ethylene (C2H4) at saturating levels of reductant (Na2S2O4) and MgATP. High electron flux, induced by a high Fe-protein (Kp2)/MoFe protein (Kp1) ratio, favours C2H2 reduction. These data can be explained if ethylene, the two-electron reduction product of C2H2, is not released until three electrons have been transferred from Kp2 to Kp1. This explanation is also consistent with a pre-steady-state lag phase for C2H4 formation of 250 ms observed when functioning enzyme is quenched with acid. Electron flux through nitrogenase is inhibited by C2H2 at high protein concentrations. This is because the association rate between Kp1 and oxidized Kp2 is enhanced by C2H2, leading to an increased steady-state concentration of the inhibitory complex Kp2oxKp1C2H2. This effect is not relieved by CO. Thus CO and C2H2 (or C2H4) must be bound at the same time to distinct sites, presumably at Mo or Fe centres, on the enzyme. PMID:2268290

  14. SysZNF: the C2H2 zinc finger gene database.

    PubMed

    Ding, Guohui; Lorenz, Peter; Kreutzer, Michael; Li, Yixue; Thiesen, Hans-Juergen

    2009-01-01

    C2H2 zinc finger (C2H2-ZNF) genes are one of the largest and most complex gene super-families in metazoan genomes, with hundreds of members in the human and mouse genome. The ongoing investigation of this huge gene family requires computational support to catalog genotype phenotype comparisons of C2H2-ZNF genes between related species and finally to extend the worldwide knowledge on the evolution of C2H2-ZNF genes in general. Here, we systematically collected all the C2H2-ZNF genes in the human and mouse genome and constructed a database named SysZNF to deposit available datasets related to these genes. In the database, each C2H2-ZNF gene entry consists of physical location, gene model (including different transcript forms), Affymetrix gene expression probes, protein domain structures, homologs (and synteny between human and mouse), PubMed references as well as links to relevant public databases. The clustered organization of the C2H2-ZNF genes is highlighted. The database can be searched using text strings or sequence information. The data are also available for batch download from the web site. Moreover, the graphical gene model/protein view system, sequence retrieval system and some other tools embedded in SysZNF facilitate the research on the C2H2 type ZNF genes under an integrative view. The database can be accessed from the URL http://epgd.biosino.org/SysZNF.

  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. 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

  17. Full Dimensional Rovibrational Variational Calculations of the S_1 State of C_2H_2

    NASA Astrophysics Data System (ADS)

    Changala, Bryan; Baraban, Joshua H.; Stanton, John F.

    2015-06-01

    Rovibrational variational calculations on global potential energy surfaces are often essential for investigating large amplitude vibrational motion and isomerization between multiple stable conformers, as well as for understanding the spectroscopic signatures of such dynamics. The efficient and accurate representation of high dimensional potential energy surfaces and the diagonalization of large rovibrational Hamiltonians make these calculations a technically non-trivial task. The first excited singlet electronic state of acetylene (C_2H_2) is an ideal model isomerizing system. The S_1 state supports both a trans conformer and a higher energy cis conformer (Tecis-Tetrans ≈ 2700 wn), separated by a planar near-half-linear transition state (TeTS-Tetrans ≈ 5000 wn). The low-energy structure of the trans well is complicated by strong Coriolis and Darling-Dennison interactions between the near-resonant torsion and asymmetric bending modes. The resulting polyad patterns are eventually broken as the internal vibrational energy approaches that of the barrier to isomerization. In this region, qualitatively new spectroscopic patterns emerge, such as rotational K-staggering and vibrational effective frequency dips. We examine these effects with an efficient ab initio variational treatment. Our global potential energy surface is constructed as a hybrid of a high-level reduced dimension surface, which excludes the two rCH bond lengths, and a lower-level full dimensional surface incorporating the effects of rtext{CH} displacement. Diagonalization of the large, sparse Hamiltonian, which contains an exact internal coordinate rovibrational kinetic energy operator, is achieved with an efficient restarted Lanczos algorithm that generates variational energies and wavefunctions. We discuss how our results elucidate the S_1 state's rich variety of spectroscopic features and the insights they provide into the isomerization process.

  18. 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.

  19. 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.

  20. 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.

  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. Electronic dynamics of charge resonance enhanced ionization probed by laser-induced alignment in C2H2

    NASA Astrophysics Data System (ADS)

    Cornaggia, C.

    2016-10-01

    Although charge resonance enhanced ionization (CREI) be an ubiquitous effect in molecules in strong laser fields, the associated electron emission remains difficult to deal with. The main reason relies on the fact that CREI is part of an overall multielectron ionization, where the initial steps of single and dissociative ionization of neutral species dominate the electron spectrum. Using the rescattered electrons, we show that it is possible to address the electron signal from CREI without any contribution from other electron signals. The electrons from CREI are preferentially emitted when the molecular axis is parallel to the laser electric field as expected from its electronic dynamics. Acetylene is chosen for demonstration purpose because single ionization, which is not related to CREI, is more pronounced when the C2H2 molecular axis is perpendicular to the laser electric field.

  3. Involvement of plant C(2)H(2)-type zinc finger transcription factors in stress responses.

    PubMed

    Kiełbowicz-Matuk, Agnieszka

    2012-04-01

    Abiotic and biotic stresses frequently impose constraints on plant distribution and affect agricultural productivity. Various aspects of the multiplicity and the complexity of stress responsive gene networks have been previously studied. Many of individual transcription factors in plants and their family classes that regulate the expression of several genes in responses to environmental stresses have been identified. One such class of transcription regulators is the C(2)H(2) class of zinc finger proteins. Numerous members of the C(2)H(2)-type zinc finger family have been shown to play diverse roles in the plant stress response and the hormone signal transduction. Transcription profiling analyses have demonstrated that the transcript level of many C(2)H(2)-type zinc finger proteins is elevated under different abiotic stress conditions such as low temperature, salt, drought, osmotic stress and oxidative stress. Some C(2)H(2)-type proteins are additionally involved in the biotic stress signaling pathway. Moreover, it has been reported that overexpression of some C(2)H(2)-type zinc finger protein genes resulted in both the activation of some stress-related genes and enhanced tolerance to various stresses. Current genetic studies have focused on possible interactions between different zinc finger transcription factors during stresses to regulate transcription. This review highlights the role of the C(2)H(2) class of the zinc finger proteins in regulating abiotic and biotic stress tolerance in the plants.

  4. 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

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

    NASA Technical Reports Server (NTRS)

    Tannenbaum, Stanley

    1957-01-01

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

  6. 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).

  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. 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

  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.

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

    NASA Astrophysics Data System (ADS)

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

    1981-02-01

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

  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. Spectroscopy and dynamics of the Rydberg states of C2H2 and their relevance to astrophysical photochemistry.

    NASA Astrophysics Data System (ADS)

    Shafizadeh, N.; Fillion, J.-H.; Gauyacq, D.; Couris, S.

    1997-08-01

    In order to understand the role of the Rydberg states in the photodestruction of acetylene in circumstellar envelopes, the authors have investigated the spectroscopy of some of the ungerade and gerade states by resonant multiphoton ionization in a magnetic bottle photoelectron spectrometer. The ungerade ns+nd Rydberg supercomplexes of C2H2 have been investigated by one-colour (3+1) multiphoton ionization, in the energy region 79500 - 87000 cm-1. The highly excited gerade nf Rydberg states have been observed for the first time, by two-colour (3+1') multiphoton ionization. A value for the adiabatic ionization potential, 91956 cm-1, has been obtained from the observed series limit and from earlier high-resolution infrared data on the ground state of the ion. This value is 4 cm-1 higher than the one measured by ZEKE spectroscopy. The apparent broadening of the observed Rydberg features may originate both from Zeeman 'broadening' of the non-penetrating nf complexes and from predissociation. The np Rydberg states, for which observation is fully allowed in the same spectral region, do not appear in the ionization signal at least in the low-n range, most probably because of their very short lifetime. In the high-energy region, spectral congestion, probably involving p-f mixing, occurs.

  13. Spectroscopy and Dynamics of the Rydberg States of C2H2 and their Relevance to Astrophysical Photochemistry

    NASA Astrophysics Data System (ADS)

    Shafizadeh, Niloufar; Fillion, Jean-Hugues; Gauyacq, Dolores; Couris, Stelios

    1997-08-01

    In order to understand the role of the Rydberg states in the photodestruction of acetylene in circumstellar envelopes, we have investigated the spectroscopy of some of the ungerade and gerade states by resonant multiphoton ionization in a magnetic bottle photoelectron spectrometer. The ungerade ns + nd Rydberg supercomplexes of C2H2 have been investigated by one-colour (3 + 1) multiphoton ionization, in the energy region 79 500-87 000 cm-1. Our spectral data show a very different behaviour of the various components of these supercomplexes towards predissociation. The highly excited gerade nf Rydberg states have been observed for the first time, by two-colour (3+1') multiphoton ionization. A value for the adiabatic ionization potential, 91 956 cm-1, has been obtained from the observed series limit and from earlier high-resolution infrared data on the ground state of the ion. This value is 4 cm-1 higher than the one measured by ZEKE spectroscopy. The apparent broadening of the observed Rydberg features may originate both from Zeeman `broadening' of the non-penetrating nf complexes and from predissociation. The np Rydberg states, for which observation is fully allowed in the same spectral region, do not appear in the ionization signal at least in the low-n range, most probably because of their very short lifetime. In the high-energy region, spectral congestion, probably involving p-f mixing, occurs.

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

    PubMed

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

    2015-10-30

    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

  15. 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.

  16. 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

  17. Saturn's latitudinal C 2H 2 and C 2H 6 abundance profiles from Cassini/CIRS and ground-based observations

    NASA Astrophysics Data System (ADS)

    Hesman, Brigette E.; Jennings, Donald E.; Sada, Pedro V.; Bjoraker, Gordon L.; Achterberg, Richard K.; Simon-Miller, Amy A.; Anderson, Carrie M.; Boyle, Robert J.; Nixon, Conor A.; Fletcher, Leigh N.; McCabe, George H.

    2009-07-01

    Hydrocarbons in the upper atmosphere of Saturn are known, from Voyager, ground-based, and early Cassini results, to vary in emission intensity with latitude. Of particular interest is the marked increase in hydrocarbon line intensity near the south pole during southern summer, as the increased line intensity cannot be simply explained by the increased temperatures observed in that region since the variations between C2H2 and C2H6 emission in the south pole region are different. In order to measure the latitudinal variations of hydrocarbons in Saturn's southern hemisphere we have used 3 cm-1 resolution Cassini CIRS data from 2006 and combined this with measurements from the ground in October 2006 at NASA's IRTF using Celeste, an infrared high-resolution cryogenic grating spectrometer. These two data sets have been used to infer the molecular abundances of C2H2 and C2H6 across the southern hemisphere in the 1-10 mbar altitude region. We find that the latitudinal acetylene profile follows the yearly average mean daily insolation except at the southern pole where it peaks in abundance. Near the equator (5° S) the C2H2 abundance at the 1.2 mbar level is (1.6 ± 0.19) ×10-7 and it decreases by a factor of 2.7 from the equator toward the pole. However, at the pole (∼87° S) the C2H2 abundance jumps to (1.8 ± 0.3) ×10-7, approximately the equatorial value. The C2H6 abundance near the equator at the 2 mbar level is (0.7 ± 0.1) ×10-5 and stays approximately constant until mid-latitudes where it increases gradually toward the pole, attaining a value of (1.4 ± 0.4) ×10-5 there. The increase in ethane toward the pole with the corresponding decrease in acetylene is consistent with southern hemisphere meridional winds [Greathouse, T.K., Lacy, J.H., Bézard, B., Moses, J.I., Griffith, C.A., Richter, M.J., 2005. Icarus 177, 18-31]. The localized increase in acetylene at the pole provides evidence that there is dynamical transport of hydrocarbons from the equator to the

  18. Production of Ethane, Ethylene, and Acetylene from Halogenated Hydrocarbons by Methanogenic Bacteria

    PubMed Central

    Belay, Negash; Daniels, Lacy

    1987-01-01

    Several methanogenic bacteria were shown to produce ethane, ethylene, and acetylene when exposed to the halogenated hydrocarbons bromoethane, dibromo- or dichloroethane, and 1,2-dibromoethylene, respectively. They also produced ethylene when exposed to the coenzyme M analog and specific methanogenic inhibitor bromoethanesulfonic acid. The production of these gases from halogenated hydrocarbons has a variety of implications concerning microbial ecology, agriculture, and toxic waste treatment. All halogenated aliphatic compounds tested were inhibitory to methanogens. Methanococcus thermolithotrophicus, Methanococcus deltae, and Methanobacterium thermoautotrophicum ΔH and Marburg were completely inhibited by 7 μM 1,2-dibromoethane and, to various degrees, by 51 to 1,084 μM 1,2-dichloroethane, 1,2-dibromoethylene, 1,2-dichloroethylene, and trichloroethylene. In general, the brominated compounds were more inhibitory. The two Methanococcus species were fully inhibited by 1 μM bromoethanesulfonic acid, whereas both Methanobacterium strains were only partly inhibited by 2,124 μM. Coenzyme M protected cells from bromoethanesulfonic acid but not from any of the other inhibitors. PMID:16347389

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

    PubMed

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

    2006-09-28

    The NCO+C(2)H(2) 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-B3LYP6-31G(d), B3LYP6-311++G(d,p), quadratic configuration interaction with single and double excitations QCISD6-31G(d), and Gaussian-3 levels are performed for the NCO+C(2)H(2) 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-B3LYP6-311++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 P(3) 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 (298-1500 K) and pressures (10-560 Torr) 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 P(2) HCN+HCCO and P

  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. Spectrum sensing of trace C(2)H(2) detection in differential optical absorption spectroscopy technique.

    PubMed

    Chen, Xi; Dong, Xiaopeng

    2014-09-10

    An improved algorithm for trace C(2)H(2) detection is presented in this paper. The trace concentration is accurately calculated by focusing on the absorption spectrum from the frequency domain perspective. The advantage of the absorption spectroscopy frequency domain algorithm is its anti-interference capability. First, the influence of the background noise on the minimum detectable concentration is greatly reduced. Second, the time-consuming preprocess of spectra calibration in the differential optical absorption spectroscopy technique is skipped. Experimental results showed the detection limit of 50 ppm is achieved at a lightpath length of 0.2 m. This algorithm can be used in real-time spectrum analysis with high accuracy.

  2. The rate of the reaction between CN and C2H2 at interstellar temperatures

    NASA Technical Reports Server (NTRS)

    Woon, D. E.; Herbst, E.

    1997-01-01

    The rate coefficient for the important interstellar reaction between CN and C2H2 has been calculated as a function of temperature between 10 and 300 K. The potential surface for this reaction has been determined through ab initio quantum chemical techniques; the potential exhibits no barrier in the entrance channel but does show a small exit channel barrier, which lies below the energy of reactants. Phase-space calculations for the reaction dynamics, which take the exit channel barrier into account, show the same unusual temperature dependence as determined by experiment, in which the rate coefficient at first increases as the temperature is reduced below room temperature and then starts to decrease as the temperature drops below 50-100 K. The agreement between theory and experiment provides strong confirmation that the reaction occurs appreciably at cool interstellar temperatures.

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

    PubMed

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

    2009-05-28

    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 microm range. The C(2)H(2)-CO(2) van der Waals complex is observed around the nu(1) + nu(3) 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, C(2v) geometry. The present overtone data, involving ground state levels with higher J/K states (J < or = 35 and K(a) < or = 20) than previously reported, are combined to 3 microm 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 A(1). 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.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

    Farmanzadeh, Davood; Abdollahi, Tahereh

    2016-11-01

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

  6. 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. 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

  8. Sloping alveolar plateaus of CO2, O2, and intravenously infused C2H2 and CHClF2 in the dog.

    PubMed

    Meyer, M; Mohr, M; Schulz, H; Piiper, J

    1990-08-01

    To investigate the role of the various mechanisms assumed to contribute to the slope of the alveolar plateau, two test gases exhibiting identical solubility but two-fold differing diffusivity, acetylene (C2H2) and chlorodifluoromethane (Freon 22, CHClF2), dissolved in saline were intravenously infused in 10 anesthetized, paralyzed, artificially ventilated dogs (mean body mass, 18 kg). The partial pressures of C2H2, CHClF2, CO2 and O2 during a constant-flow single-breath washout maneuver were recorded by mass spectrometry and analyzed in terms of slope of the alveolar plateau (phase III) and series (Fowler) dead space. The slope of the alveolar plateau (S) was determined as the relative alveolar slope normalized to mixed-expired partial pressure and referred to expired volume (VE), S(V) = delta PE/(PE - PI)/delta VE or expiration time (tE), S(t) = delta PE/(PE - PI)/delta tE (subscripts I, E, and E refer to inspired, instantaneous expired and mixed-expired gas, respectively). The effects of expiratory flow rate (VE), and time of breath-hold (BH) were studied with reference to control conditions (VI = 0.5 L.sec-1, VE = 0.1 L.sec-1, VI = 50% and VE = 75% of volume at FRC, BH = 0 sec). In control conditions, the following significantly different S(V) values (units: L-1), grouped in ascending order, were obtained (means +/- SD): CO2, 0.83 +/- 0.26; C2H2, 0.93 +/- 0.18; CHClF2, 1.00 +/- 0.20; O2, 1.07 +/- 0.29. The mean C2H2/CHClF2 ratio for S(V), 0.94 (SD +/- 0.03), was statistically different from unity. In line with model calculations, the experimental findings suggest that three mechanisms contribute to the sloping alveolar plateaus: 1, continuing gas exchange during expiration; 2, ventilation-perfusion inequality combined with sequential emptying; 3, intrapulmonary diffusion limitation.

  9. Near ultraviolet photolysis of C2H2: A precise determination of D0(HCC - H)

    NASA Astrophysics Data System (ADS)

    Mordaunt, David H.; Ashfold, Michael N. R.

    1994-08-01

    The near ultraviolet photolysis of jet-cooled acetylene molecules has been further investigated using the technique of H atom photofragment translational spectroscopy. Analysis of the rotational structure evident in the total fragment kinetic energy spectrum yields a precise value for the C-H bond dissociation energy: D0(HCC-H)=46 074±8 cm-1 (551.2±0.1kJ mol-1).

  10. 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.

  11. Infrared fingerprints and periodic formation of nanoparticles in Ar/C2H2 plasmas

    NASA Astrophysics Data System (ADS)

    Kovačević, Eva; Stefanović, Ilija; Berndt, Johannes; Winter, Jörg

    2003-03-01

    The formation of dust particles in argon diluted C2H2 plasmas was studied by means of Fourier transform infrared absorption spectroscopy and mass spectroscopy. The detection limit for infrared absorption was significantly improved by the use of a multipass technique. Measuring the intensity of the Rayleigh/Mie scattering of the infrared signal we found a periodicity of dust formation/vanishing (period of about 35 min in our experimental conditions). The fast disappearance of the dust from the plasma region at the end of every period is the evidence of a narrow particle size distribution, as confirmed by secondary electron micrographs of the collected powder. Characteristic infrared absorption features have their origin in absorption within the dust particles. Besides the strong presence of aliphatic hydrocarbons characteristic for amorphous hydrocarbon films, a significant amount of aromatic structures was detected. Heavy positive ions measured by ion-mass spectroscopy originate from polyacetilenic (C2nH2) and aromatic compounds. Time resolved mass spectra gave insight into the plasma response to the dust formation.

  12. 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.

  13. 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.

  14. Fast Response, vertically oriented graphene nanosheet electric double layer capacitors synthesized from C(2)H(2).

    PubMed

    Cai, Minzhen; Outlaw, Ronald A; Quinlan, Ronald A; Premathilake, Dilshan; Butler, Sue M; Miller, John R

    2014-06-24

    The growth and electrical characteristics of vertically oriented graphene nanosheets grown by radio frequency plasma-enhanced chemical vapor deposition from C2H2 feedstock on nickel substrates and used as electrodes in symmetric electric double layer capacitors (EDLC) are presented. The nanosheets exhibited 2.7 times faster growth rate and much greater specific capacitance for a given growth time than CH4 synthesized films. Raman spectra showed that the intensity ratio of the D band to G band versus temperature initially decreased to a minimum value of 0.45 at a growth temperature of 750 °C, but increased rapidly with further temperature increase (1.15 at 850 °C). The AC specific capacitance at 120 Hz of these EDLC devices increased in a linear fashion with growth temperature, up to 265 μF/cm(2) (2 μm high film, 850 °C with 10 min growth). These devices exhibited ultrafast frequency response: the frequency response at -45° phase angle reached over 20 kHz. Consistent with the increase in D band to G band ratio, the morphology of the films became less vertical, less crystalline, and disordered at substrate temperatures of 800 °C and above. This deterioration in morphology resulted in an increase in graphene surface area and defect density, which, in turn, contributed to the increased capacitance, as well as a slight decrease in frequency response. The low equivalent series resistance varied from 0.07 to 0.08 Ω and was attributed to the significant carbon incorporation into the Ni substrate. PMID:24797018

  15. Fast Response, vertically oriented graphene nanosheet electric double layer capacitors synthesized from C(2)H(2).

    PubMed

    Cai, Minzhen; Outlaw, Ronald A; Quinlan, Ronald A; Premathilake, Dilshan; Butler, Sue M; Miller, John R

    2014-06-24

    The growth and electrical characteristics of vertically oriented graphene nanosheets grown by radio frequency plasma-enhanced chemical vapor deposition from C2H2 feedstock on nickel substrates and used as electrodes in symmetric electric double layer capacitors (EDLC) are presented. The nanosheets exhibited 2.7 times faster growth rate and much greater specific capacitance for a given growth time than CH4 synthesized films. Raman spectra showed that the intensity ratio of the D band to G band versus temperature initially decreased to a minimum value of 0.45 at a growth temperature of 750 °C, but increased rapidly with further temperature increase (1.15 at 850 °C). The AC specific capacitance at 120 Hz of these EDLC devices increased in a linear fashion with growth temperature, up to 265 μF/cm(2) (2 μm high film, 850 °C with 10 min growth). These devices exhibited ultrafast frequency response: the frequency response at -45° phase angle reached over 20 kHz. Consistent with the increase in D band to G band ratio, the morphology of the films became less vertical, less crystalline, and disordered at substrate temperatures of 800 °C and above. This deterioration in morphology resulted in an increase in graphene surface area and defect density, which, in turn, contributed to the increased capacitance, as well as a slight decrease in frequency response. The low equivalent series resistance varied from 0.07 to 0.08 Ω and was attributed to the significant carbon incorporation into the Ni substrate.

  16. 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.

  17. Crossed molecular beam study of gas phase reactions relevant to the chemistry of planetary atmospheres: The case of C 2+C 2H 2

    NASA Astrophysics Data System (ADS)

    Leonori, Francesca; Petrucci, Raffaele; Hickson, Kevin M.; Segoloni, Enrico; Balucani, Nadia; Le Picard, Sébastien D.; Foggi, Paolo; Casavecchia, Piergiorgio

    2008-11-01

    The reaction between dicarbon (C 2) and acetylene was recently suggested as a possible competitive reaction in the atmospheres of Titan, Saturn and Uranus by rate constant measurements at very low temperatures [see Canosa, A., Páramo, A., Le Picard, S.D., Sims, I.R., 2007. An experimental study of the reaction kinetics of C 2(X 1Σ g+) with hydrocarbons (CH 4, C 2H 2, C 2H 4, C 2H 6 and C 3H 8) over the temperature range 24-300 K: implications for the atmospheres of Titan and the Giant Planets. Icarus 187, 558-568]. We have investigated the reaction of the two low lying electron states of C 2 and acetylene by the crossed molecular beam (CMB) technique with mass spectrometric detection. C 4H, already identified as a primary product in previous CMB experiments, is confirmed as such, even though the mechanism of formation is inferred to be partly different with respect to the previous study. An experimental setup has been devised to characterize the internal population of C 2 and refine the interpretation of the scattering results. The implications for the modelling of the atmospheres of Giant Planets and Titan, as well as cometary comae and the interstellar medium, are discussed.

  18. 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.

  19. Acetylene on Titan

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  20. 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.

  1. 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).

  2. Azotobacter vinelandii nitrogenases containing altered MoFe proteins with substitutions in the FeMo-cofactor environment: effects on the catalyzed reduction of acetylene and ethylene.

    PubMed

    Fisher, K; Dilworth, M J; Kim, C H; Newton, W E

    2000-03-21

    Altered MoFe proteins of Azotobacter vinelandii Mo-nitrogenase, with amino acid substitutions in the FeMo-cofactor environment, were used to probe interactions among C(2)H(2), C(2)H(4), CO, and H(2). The altered MoFe proteins used were the alpha-195(Asn) or alpha-195(Gln) MoFe proteins, which have either asparagine or glutamine substituting for alpha-histidine-195, and the alpha-191(Lys) MoFe protein, which has lysine substituting for alpha-glutamine-191. On the basis of K(m) determinations, C(2)H(2) was a particularly poor substrate for the nitrogenase containing the alpha-191(Lys) MoFe protein. Using C(2)D(2), a correlation was shown between the stereospecificity of proton addition to give the products, cis- and trans-C(2)D(2)H(2), and the propensity of nitrogenase to produce ethane. The most extensive loss of stereospecificity occurred with nitrogenases containing either the alpha-195(Asn) or the alpha-191(Lys) MoFe proteins, which also exhibited the highest rate of ethane production from C(2)H(2). These data are consistent with the presence of a common ethylenic intermediate on the enzyme, which is responsible for both ethane production and loss of proton-addition stereochemistry. C(2)H(4) was not a substrate of the nitrogenase with the alpha-191(Lys) MoFe protein and was a poor substrate of the nitrogenases incorporating either the wild-type or the alpha-195(Gln) MoFe protein, both of which had a low V(max) and high K(m) (120 kPa). Ethylene was a somewhat better substrate for the nitrogenase with the alpha-195(Asn) MoFe protein, which exhibited a K(m) of 48 kPa and a specific activity for C(2)H(6) formation from C(2)H(4) 10-fold higher than the others. Neither the wild-type nitrogenase nor the nitrogenase containing the alpha-195(Asn) MoFe protein produced cis-C(2)D(2)H(2) when turned over under trans-C(2)D(2)H(2). These results suggest that the C(2)H(4)-reduction site is affected by substitution at residue alpha-195, although whether the effect is related to

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. Identification and expression of C2H2 transcription factor genes in Carica papaya under abiotic and biotic stresses.

    PubMed

    Jiang, Ling; Pan, Lin-jie

    2012-06-01

    C2H2 proteins belong to a group of transcription factors (TFs) existing as a superfamily that plays important roles in defense responses and various other physiological processes in plants. The present study aimed to screen for and identify C2H2 proteins associated with defense responses to abiotic and biotic stresses in Carica papaya L. Data were collected for 47,483 papaya-expressed sequence tags (ESTs). The full-length cDNA nucleotide sequences of 87 C2H2 proteins were predicated by BioEdit. All 91 C2H2 proteins were aligned, and a phylogenetic tree was constructed using DNAman. The expression levels of 42 C2H2 were analyzed under conditions of salt stress by quantitative reverse transcriptase-polymerase chain reaction (qRT-PCR). Methyl jasmonate treatment rapidly upregulated ZF(23.4) and ZF(30,912.1) by 18.6- and 21.7-fold, respectively. ZF(1.3), ZF(138.44), ZF(94.49), ZF(29.160), and ZF(20.206) were found to be downregulated after low temperature treatment at very significant levels (p < 0.01). ZF(23.4), ZF(161.1), and ZF(30,912.1) were upregulated while ZF1.3, ZF(158.1), ZF(249.5), ZF(138.44), ZF(94.49), ZF(29.160), and ZF(20.206) were significantly downregulated by Spermine treatment. ZF(23.4) was upregulated while ZF(1.3), ZF(249.5), ZF(94.94), ZF(29.160), ZF(138.44), and ZF(20.206) were significantly repressed after SA treatment. ZF(23.4) and ZF(30,912.1) were significantly upregulated after sap inoculation with papaya ringspot virus pathogen. ZF(30,912.1) was subcellularly localized in the nucleus by a transgenic fusion of pBS-ZF(30,912.1)-GFP into the protoplast of papaya. The results of the present study showed that ZF(30,912.1) could be an important TF that mediates responses to abiotic and biotic stresses in papaya.

  9. 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.

  10. 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.

  11. 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

  12. A survey of well conserved families of C2H2 zinc-finger genes in Daphnia

    PubMed Central

    2010-01-01

    Background A recent comparative genomic analysis tentatively identified roughly 40 orthologous groups of C2H2 Zinc-finger proteins that are well conserved in "bilaterians" (i.e. worms, flies, and humans). Here we extend that analysis to include a second arthropod genome from the crustacean, Daphnia pulex. Results Most of the 40 orthologous groups of C2H2 zinc-finger proteins are represented by just one or two proteins within each of the previously surveyed species. Likewise, Daphnia were found to possess a similar number of orthologs for all of these small orthology groups. In contrast, the number of Sp/KLF homologs tends to be greater and to vary between species. Like the corresponding mammalian Sp/KLF proteins, most of the Drosophila and Daphnia homologs can be placed into one of three sub-groups: Class I-III. Daphnia were found to have three Class I proteins that roughly correspond to their Drosophila counterparts, dSP1, btd, CG5669, and three Class II proteins that roughly correspond to Luna, CG12029, CG9895. However, Daphnia have four additional KLF-Class II proteins that are most similar to the vertebrate KLF1/2/4 proteins, a subset not found in Drosophila. Two of these four proteins are encoded by genes linked in tandem. Daphnia also have three KLF-Class III members, one more than Drosophila. One of these is a likely Bteb2 homolog, while the other two correspond to Cabot and KLF13, a vertebrate homolog of Cabot. Conclusion Consistent with their likely roles as fundamental determinants of bilaterian form and function, most of the 40 groups of C2H2 zinc-finger proteins are conserved in kind and number in Daphnia. However, the KLF family includes several additional genes that are most similar to genes present in vertebrates but missing in Drosophila. PMID:20433734

  13. A soybean C2H2-type zinc finger gene GmZF1 enhanced cold tolerance in transgenic Arabidopsis.

    PubMed

    Yu, Guo-Hong; Jiang, Lin-Lin; 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.

  14. Collision Reactions between CN and C2H2: Short-Time Fourier Transform Analysis of AIMD Simulation

    NASA Astrophysics Data System (ADS)

    Tamaoki, Mari; Sakura, Daisuke; Yamauchi, Yusuke; Nakai, Hiromi

    2006-09-01

    Collision reactions between the cyano radical (CN) and unsaturated hydrocarbons (C2H2), which occur in the atmosphere of Saturn's moon Titan, were investigated using ab initio molecular dynamics (AIMD) simulations. The simulation results were categorized into three kinds: nonreactive collision, incorporation, and substitution. Short-time Fourier transform analysis of velocity auto-correlation functions obtained by the AIMD simulations was performed to examine the non-equilibrium condition of the vibrational states. Spectrograms, which correspond to the time evolution of power spectra, clarify the relationship between the three reaction channels and the dynamical changes of the vibrational states.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Hydrogen and fluorine migration in photo double ionization of 1,1-difluoroethylene (C2H2F2)

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

    Dissociative and nondissociative ionization of 1,1-C2H2F2 is studied with single photons of energies between 40 to 70 eV by employing the Cold Target Recoil Ion Momentum Spectroscopy (COLTRIMS) method. We present the branching ratio of nondissociative and two-body dissociative ionization channels as a function of photon energy. The yield of nondissociative ionization decreases significantly with higher photon energies. We have observed the migration of hydrogen and fluorine ions in some of the two-body dissociative ionization channels. The small yield of the H2+ + C2F2+ production indicates some interesting mechanisms for the formation of H2 molecules. This work was 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.

  1. 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.

  2. The rate of the reaction between C2H and C2H2 at interstellar temperatures.

    PubMed

    Herbst, E; Woon, D E

    1997-11-01

    The reaction between the radical C2H and the stable hydrocarbon C2H2 is one of the simplest neutral-neutral hydrocarbon reactions in chemical models of dense interstellar clouds and carbon-rich circumstellar shells. Although known to be rapid at temperatures > or = 300 K, the reaction has yet to be studied at lower temperatures. We present here ab initio calculations of the potential surface for this reaction and dynamical calculations to determine its rate at low temperature. Despite a small potential barrier in the exit channel, the calculated rate is large, showing that this reaction and, most probably, more complex analogs contribute to the formation of complex organic molecules in low-temperature sources.

  3. The rate of the reaction between C2H and C2H2 at interstellar temperatures

    NASA Technical Reports Server (NTRS)

    Herbst, E.; Woon, D. E.

    1997-01-01

    The reaction between the radical C2H and the stable hydrocarbon C2H2 is one of the simplest neutral-neutral hydrocarbon reactions in chemical models of dense interstellar clouds and carbon-rich circumstellar shells. Although known to be rapid at temperatures > or = 300 K, the reaction has yet to be studied at lower temperatures. We present here ab initio calculations of the potential surface for this reaction and dynamical calculations to determine its rate at low temperature. Despite a small potential barrier in the exit channel, the calculated rate is large, showing that this reaction and, most probably, more complex analogs contribute to the formation of complex organic molecules in low-temperature sources.

  4. 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.

  5. Photoion-pair formation and photoelectron-induced dissociative attachment in C2H2: D0(HCC-H)

    NASA Astrophysics Data System (ADS)

    Ruscic, B.; Berkowitz, J.

    1990-10-01

    The formation of C2H- is observed in two broad resonance bands when C2H2 is irradiated with vuv light. The higher-energy band has partially resolved structure, approximately linear pressure dependence, and a threshold at 16.335±0.021 eV. It is attributed to photoion-pair formation (C2H-+H+) consequent upon predissociation of one or more Rydberg states. This threshold, together with IP(H) and EA(C2H), gives D0(HCC-H)≤5.706±0.022 eV≡131.6±0.5 kcal/mol, or ΔH0f0 (C2H)≤134.5±0.5 kcal/mol. The lower-energy band has an approximately quadratic pressure dependence and curved step-like structure. It is attributed to photoelectron-induced dissociative attachment mediated by a πg shape resonance. The threshold, at 878.5±2.0 Å, corresponds to a photoelectron energy of 2.715±0.032 eV. This threshold combined with EA(C2H)=2.969±0.010 eV, yields D0(HCC-H)≤5.684±0.033 eV≡131.1±0.7 kcal/mol, or ΔH0f0 (C2H)=134.0±0.7 kcal/mol.

  6. 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

  7. 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 PAGES

    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

  8. Simultaneous Measurement of Nitrogen Fixation Estimated by Acetylene-Ethylene Assay and Nitrate Absorption by Soybeans 1

    PubMed Central

    Wych, Robert D.; Rains, D. William

    1978-01-01

    An apparatus was designed for simultaneous measurement of rates of N2 fixation estimated by C2H2-C2H4 assay (N2[C2H2] fixation) and NO3− absorption by roots of intact, nodulated soybeans (Glycine max [L.] Merr.). The principal design features include: (a) a gas-tight mist chamber in which nodulated roots can be exposed simultaneously to C2H2 in the gas phase and to a liquid phase containing NO3− sprayed in a fine mist; and (b) provision for sampling the gas phase for C2H4 determination, and the liquid phase for NO3− determination. We studied NO3− absorption by soybeans as affected by nodulation, NO3− concentration during assay, and previous N nutrition during growth in nutrient solution culture in controlled environment chambers. It was established that 0.5 mm NO3− nearly saturated the NO3− absorption system of both nodulated and unnodulated soybeans when the concentration dependence of NO3− absorption rate was measured just after flowering began. Nitrate absorption rates were measured after development of N stress in unnodulated plants, and during recovery from N stress in nodulated plants. The results suggested that the lower capacity for NO3− absorption of nodulated plants was a consequence of N stress during the period of nodule growth and development. Nitrogen [C2H2] fixation rates were compared in intact plants assayed in the mist chamber and in excised roots assayed in both the mist chamber and in glass jars. Excised roots had a lower N2[C2H2] fixation rate than intact plants. The decline observed during the first hour after shoot removal was more pronounced for glass jar-assayed excised roots than for mist chamber-assayed excised roots. We discuss the advantages of our method for assessing the capability of a nodulated legume to acquire nitrogen through both N2 fixation and absorption and assimilation of NO3−. PMID:16660534

  9. 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

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

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

    The pressure dependence of the absolute rate constant for the reaction of the hydroxyl radical with acetylene, important in both atmospheric and combustion chemistry, is determined for temperatures between 228 and 413 K. The flash photolysis-resonance fluorescence technique was employed at five temperatures over wide ranges of pressure and acetylene concentrations, with the OH produced by water photolysis and hydroxyl resonance fluorescent photons measured by multiscaling techniques. Results indicate that, except at the lowest temperature, the bimolecular rate constant for the reaction depends strongly on total pressure, with the pressure effect becoming more pronounced with increasing temperature. At limiting high pressures, the rate constant is found to be equal to 6.83 + or - 1.19 x 10 to the -12th exp (-646 + or - 47/T) cu cm/molecule per sec, where T is the temperature. Results thus demonstrate the importance of environmental conditions in theoretical studies of atmospheric and combustion product compositions

  11. Expirograms of O2, CO2 and intravenously infused C2H2 and Freon-22 during panting in dogs.

    PubMed

    Sipinková, I; Hahn, G; Hillebrecht, A; Meyer, M; Piiper, J

    1990-01-01

    To study pulmonary gas transport in panting, expirograms of several inert and respiratory gases were simultaneously measured in panting dogs. The experiments were performed on 5 conscious dogs (mean body weight 34.4 kg) provided with a chronic tracheostomy. Panting at a mean frequency of 312/min (5.2 Hz) was induced by elevated room temperature (mean 28.1 degrees C). Isotonic saline equilibrated with 50% acetylene and 50% Freon-22 was infused intravenously at a constant rate (4 ml/min). Fractional concentrations in the tracheostomy tube were measured by a respiratory mass spectrometer, using a special sampling system designed for quasi-continuous analysis of rapidly changing gas concentrations. Air flow was monitored by an ultrasonic transit-time flowmeter. A tracing of expired gas concentrations versus expired volume showed no alveolar plateau, displaying a steep increase of Freon-22, acetylene and CO2 (decrease of O2) up to the onset of inspiration. The small but statistically highly significant differences between the expirograms of CO2 and O2, and of Freon-22 and acetylene, could be qualitatively explained by ventilation-perfusion inequalities with sequential emptying, by Taylor dispersion and by reversible solution in airway mucosa in the course of the respiratory cycle.

  12. C2H2 zinc finger-SET histone methyltransferase is a plant-specific chromatin modifier

    PubMed Central

    Krichevsky, Alexander; Gutgarts, Helen; Kozlovsky, Stanislav V.; Tzfira, Tzvi; Sutton, Ann; Sternglanz, Rolf; Mandel, Gail; Citovsky, Vitaly

    2007-01-01

    Histone modification represents a universal mechanism for regulation of eukaryotic gene expression underlying diverse biological processes from neuronal gene expression in mammals to control of flowering in plants. In animal cells, these chromatin modifications are effected by well-defined multiprotein complexes containing specific histone-modifying activities. In plants, information about the composition of such co-repressor complexes is just beginning to emerge. Here, we report that two Arabidopsis thaliana factors, a SWIRM domain polyamine oxidase protein, AtSWP1, and a plant-specific C2H2 zinc finger-SET domain protein, AtCZS, interact with each other in plant cells and repress expression of a negative regulator of flowering, FLOWERING LOCUS C (FLC) via an autonomous, vernalization-independent pathway. Loss-of-function of either AtSWP1 or AtCZS results in reduced dimethylation of lysine 9 and lysine 27 of histone H3 and hyperacetylation of histone H4 within the FLC locus, in elevated FLC mRNA levels, and in moderately delayed flowering. Thus, AtSWP1 and AtCZS represent two main components of a co-repressor complex that fine tunes flowering and is unique to plants. PMID:17224141

  13. 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

  14. 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.

  15. 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.

  16. Secondary hydrogen isotope effects on the structure and stability of cation-pi complexes (cation = Li(+), Na(+), K(+) and pi = acetylene, ethylene, benzene).

    PubMed

    Moreno, Diego V; González, Sergio A; Reyes, Andrés

    2010-09-01

    Secondary hydrogen isotope effects on the geometries, electronic wave functions and binding energies of cation-pi complexes (cation = Li(+), Na(+), K(+) and pi = acetylene, ethylene, benzene) are investigated with NEO/HF and NEO/MP2 methods. These methods determine both electronic and nuclear wave functions simultaneously. Our results show that an increase of the hydrogen nuclear mass leads to the elongation of the cation-pi bond distance and the decrease in its binding energy. An explanation to this behavior is given in terms of the changes in the pi-molecule electronic structure and electrostatic potential induced by isotopic substitutions.

  17. 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

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

    PubMed

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

    2015-10-26

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

  19. 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.

  20. 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.

  1. 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.

  2. Distortion of ethyne on coordination to silver acetylide, C2H2ṡṡṡAgCCH, characterised by broadband rotational spectroscopy and ab initio calculations

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

    The rotational spectra of six isotopologues of a complex of ethyne and silver acetylide, C2H2ṡṡṡAgCCH, 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 C2H2ṡṡṡAgCCH 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 107Ag13C13CH and 109Ag13C13CH 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.

  3. 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

  4. 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.

  5. 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

  6. 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

  7. 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

  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. 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.

  10. Phylogenetic study of plant Q-type C2H2 zinc finger proteins and expression analysis of poplar genes in response to osmotic, cold and mechanical stresses.

    PubMed

    Gourcilleau, Delphine; Lenne, Catherine; Armenise, Claudia; Moulia, Bruno; Julien, Jean-Louis; Bronner, Gisèle; Leblanc-Fournier, Nathalie

    2011-04-01

    Plant Q-type C2H2 zinc finger transcription factors play an important role in plant tolerance to various environmental stresses such as drought, cold, osmotic stress, wounding and mechanical loading. To carry out an improved analysis of the specific role of each member of this subfamily in response to mechanical loading in poplar, we identified 16 two-fingered Q-type C2H2-predicted proteins from the poplar Phytozome database and compared their phylogenetic relationships with 152 two-fingered Q-type C2H2 protein sequences belonging to more than 50 species isolated from the NR protein database of NCBI. Phylogenetic analyses of these Q-type C2H2 proteins sequences classified them into two groups G1 and G2, and conserved motif distributions of interest were established. These two groups differed essentially in their signatures at the C-terminus of their two QALGGH DNA-binding domains. Two additional conserved motifs, MALEAL and LVDCHY, were found only in sequences from Group G1 or from Group G2, respectively. Functional significance of these phylogenetic divergences was assessed by studying transcript accumulation of six poplar C2H2 Q-type genes in responses to abiotic stresses; but no group specificity was found in any organ. Further expression analyses focused on PtaZFP1 and PtaZFP2, the two genes strongly induced by mechanical loading in poplars. The results revealed that these two genes were regulated by several signalling molecules including hydrogen peroxide and the phytohormone jasmonate. PMID:21367962

  11. 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.

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

    DOE PAGES

    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

  13. 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)

  14. Success and pitfalls of the Sin-2C2H2-C2Bn-2Hn isolobal analogy: Depth and breadth of the boron connection

    NASA Astrophysics Data System (ADS)

    Zdetsis, Aristides D.

    2009-02-01

    The extent and depth of the so-called boron connection suggested recently by the present author [J. Chem. Phys. 128, 184305 (2008)] for the Sin-2C2H2-C2Bn-2Hn isovalent species [following similar connection of (Sin)2--(BnHn)2- dianions] are further investigated by considering larger species up to n =12 and additional isovalent moieties. Here we consider, using density functional and coupled clusters theory, isovalent Sin-2C2H2 and Gen-2C2H2 clusters, in comparison to the corresponding C2Bn-2Hn carboranes and to each other for n =3-8, 12. Special attention is given to the n =8 species, where the corresponding carborane is highly fluxional, and to n =12, where the "parent structures" of the corresponding (Si12)2- and (B12H12)2- dianions have drastically different symmetries. The structures generated by substitutions on (Si12)2-, as well as (B12H12)2-, are compared and interrelated for both C2B10H12 and Si10C2H12. The carborane generated from the Cs (Si12)2- dianion provides an illustrative example of carborane rearrangements, reverting after geometry optimization to the second lowest C2B10H12 meta isomer of C2v symmetry, 0.12 eV above the lowest energy para isomer. This demonstrates the amphidirectional character of the boron connection. It is found that n =8 is the upper limit of the n range in which the isolobal Sin-2C2H2-C2Bn-2Hn analogy is fully operative not only for the lowest but also for the second and third lowest energy states. For n ≤8 all three pairs of structures are isovalent, isostructural, and isolobal. For large values of n (n >8) the boron connection, although not fully isolobal, is still valid in a broader and more general sense, still providing deeper and broader fundamental understanding and insight for both species. It was also found that the Gen-2C2H2 clusters are not fully homologous (isolobal) neither to the isovalent Sin-2C2H2 clusters nor to the corresponding C2Bn-2Hn carboranes, preferring structures in which the two carbon atoms are

  15. 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.

  16. An XPS investigation of the interaction of CH 4, C 2H 2, C 2H 4 and C 2H 6 with a barium surface

    NASA Astrophysics Data System (ADS)

    Verhoeven, J. A. Th.; Van Doveren, H.

    1982-12-01

    The generation and pumping of hydrocarbon gases by a barium getter layer in electronic vacuum devices has been investigated by characterizing a barium film in an ultra high vacuum equipment by means of XPS before, during and after exposures to respectively CH 4, C 2H 2, C 2H 4 and C 2H 6. The reaction conditions (temperatures and pretreatment of the surface, background pressure and exposure doses) closely resemble those in electronic vacuum devices. The probability that a barium layer will react with CH 4 and C 2H 6 was below the detection limit. C 2H 2 and C 2H 4 give rise to the formation of barium carbide compounds and with a high reaction probability. In addition, the interaction with C 2H 2 reveals the formation of carbon-containing surface complexes. Investigations by means of XPS on the C Is spectral features show the presence of at least two groups of carbon-containing surface complexes, which behave differently in response to moderate heating and to an exposure to water vapour. In cases where oxygen is present at the surface, oxygen-containing (hydro) carbon adsorbates are present too. XPS observations of the behaviour of these surface complexes show similarities with reaction steps in the mechanisms proposed for the hydrogenation of CO in the Fischer-Tropsch synthesis of hydrocarbons. Low-pressure hydrogenation of these adsorbates containing hydrocarbons and oxygen can led to the formation of hydrocarbon gases in electronic vacuum devices.

  17. Microwave Spectra and Geometries of C2H2\\cdots AuI and C2H4\\cdots AuI

    NASA Astrophysics Data System (ADS)

    Stephens, Susanna Louise; Mullaney, John Connor; Sprawling, Matt John; Tew, David Peter; Walker, Nick; Legon, Anthony

    2014-06-01

    A chirped-pulse Fourier transform microwave spectrometer has been used to measure the microwave spectra of both C2H2\\cdots AuI and C2H4\\cdots AuI. These complexes are generated via laser ablation at 532 nm of a gold surface in the presence of CF3I and either C2H2 or C2H4 and argon and are stabilized by a supersonic expansion. Rotational (A0, B0, C0) and centrifugal distortion constants (ΔJ, ΔJK and δJ) of each molecule have been determined as well the nuclear electric quadrupole coupling constants of gold and iodine atoms (χaa(Au}, χbb-χcc(Au), 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 C2H2 or C2H4 subunits are in progress and in conjunction with high level ab initio calculations will allow for accurate determination of the geometry of each molecule.

  18. 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.

  19. 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.

  20. Volumetric Properties of the Mixture 1,1,2,2-Tetrachloroethane C2H2Cl4 + C14H30 Tetradecane (VMSD1111, LB3198_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume B 'Binary Liquid Systems of Nonelectrolytes II' 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 1,1,2,2-Tetrachloroethane C2H2Cl4 + C14H30 Tetradecane (VMSD1111, LB3198_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

  1. Volumetric Properties of the Mixture 1,1,2,2-Tetrachloroethane C2H2Cl4 + C14H30 Tetradecane (VMSD1212, LB3194_V)

    NASA Astrophysics Data System (ADS)

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

    This document is part of Subvolume B 'Binary Liquid Systems of Nonelectrolytes II' 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 1,1,2,2-Tetrachloroethane C2H2Cl4 + C14H30 Tetradecane (VMSD1212, LB3194_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  2. 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

  3. Electron ionization of acetylene

    NASA Astrophysics Data System (ADS)

    King, Simon J.; Price, Stephen D.

    2007-11-01

    Relative partial ionization cross sections and precursor specific relative partial ionization cross sections for fragment ions formed by electron ionization of C2H2 have been measured using time-of-flight mass spectrometry coupled with a 2D ion-ion coincidence technique. We report data for the formation of H+, H2+, C2+, C+/C22+, CH +/C2H22+, CH2+, C2+, and C2H + relative to the formation of C2H2+, as a function of ionizing electron energy from 30-200eV. While excellent agreement is found between our data and one set of previously published absolute partial ionization cross sections, some discrepancies exist between the results presented here and two other recent determinations of these absolute partial ionization cross sections. We attribute these differences to the loss of some translationally energetic fragment ions in these earlier studies. Our relative precursor-specific partial ionization cross sections enable us, for the first time, to quantify the contribution to the yield of each fragment ion from single, double, and triple ionization. Analysis shows that at 50eV double ionization contributes 2% to the total ion yield, increasing to over 10% at an ionizing energy of 100eV. From our ion-ion coincidence data, we have derived branching ratios for charge separating dissociations of the acetylene dication. Comparison of our data to recent ab initio/RRKM calculations suggest that close to the double ionization potential C2H22+ dissociates predominantly on the ground triplet potential energy surface (Σg-3) with a much smaller contribution from dissociation via the lowest singlet potential energy surface (Δg1). Measurements of the kinetic energy released in the fragmentation reactions of C2H22+ have been used to obtain precursor state energies for the formation of product ion pairs, and are shown to be in good agreement with available experimental data and with theory.

  4. 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.

  5. Application of a quantum cascade laser for time-resolved, in situ probing of CH4/H2 and C2H2/H2 gas mixtures during microwave plasma enhanced chemical vapor deposition of diamond.

    PubMed

    Cheesman, A; Smith, J A; Ashfold, M N R; Langford, N; Wright, S; Duxbury, G

    2006-03-01

    First illustrations of the utility of pulsed quantum cascade lasers for in situ probing of the chemistry prevailing in microwave plasma activated hydrocarbon/Ar/H2 gas mixtures used for diamond thin film growth are reported. CH4 and C2H2 molecules, and their interconversion, have been monitored by line-of-sight single pass absorption methods, as a function of process conditions (e.g., choice of input hydrocarbon (CH4 or C2H2), hydrocarbon mole fraction, total gas pressure, and applied microwave power). The observed trends can be rationalized, qualitatively, within the framework of the previously reported modeling of the gas-phase chemistry prevailing in hot filament activated hydrocarbon/H2 gas mixtures (Ashfold et al. Phys. Chem. Chem. Phys. 2001, 3, 3471). Column densities of vibrationally excited C2H2(v5=1) molecules at low input carbon fractions are shown to be far higher than expected on the basis of local thermodynamic equilibrium. The presence of vibrationally excited C2H2 molecules (C2H2(double dagger)) can be attributed to the exothermicity of the C2H3 + H <==> C2H2 + H2 elementary reaction within the overall multistep CH4 --> C2H2 conversion. Diagnostic methods that sample just C2H2(v=0) molecules thus run the risk of underestimating total C2H2 column densities in hydrocarbon/H2 mixtures operated under conditions where the production rate of C2H2(double dagger) molecules exceeds their vibrational relaxation (and thermal equilibration) rates.

  6. 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.

  7. Characterization of the minimum energy paths for the reactions of CH(X 2Π) and 1CH2 with C2H2

    NASA Astrophysics Data System (ADS)

    Walch, Stephen P.

    1995-10-01

    The reactions of CH(2Π) and singlet methylene (1CH2) with acetylene lead to intermediates which may be important in soot formation. CH(2Π)+acetylene leads to CHCHCH (C3H3), CHCCH, CH2CC, and propargyl (CH2CCH). 1CH2+acetylene leads to cyclopropene, allene, and propyne. Except for CHCCH, which involves a barrier of 7.5 kcal/mol with respect to reactants, 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 CHCCH are shown to dimerize with no barrier to give benzene and para-benzyne, respectively. C3H3, CHCCH, and CH2CC can also add to smaller polycyclic aromatic hydrocarbons (PAH), and may be important species in forming larger PAH or fullerenes.

  8. 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.

  9. 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.

  10. A single amino acid substitution beyond the C2H2-zinc finger in Ros derepresses virulence and T-DNA genes in Agrobacterium tumefaciens.

    PubMed

    Archdeacon, J; Bouhouche, N; O'Connell, F; Kado, C I

    2000-06-15

    Ros is a chromosomally-encoded repressor containing a novel C2H2 zinc finger in Agrobacterium tumefaciens. Ros regulates the expression of six virulence genes and an oncogene on the Ti plasmid. Constitutive expression of these genes occurs in the spontaneous mutant 4011R derived from the octopine strain Ach-5, resulting in T-DNA processing in the absence of induction, and in the biosynthesis of cytokinin. Interestingly, the mutation in 4011R is an Arg to Cys conversion at amino acid residue 125 near the C-terminus well outside the zinc finger of Ros. Yet, Ros bearing this mutation is unable to bind to the Ros-box and is unable to complement other ros mutants. PMID:10856653

  11. Photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 in the VUV region

    NASA Technical Reports Server (NTRS)

    Xia, T. J.; Chien, T. S.; Wu, C. Y. Robert; Judge, D. L.

    1991-01-01

    Using synchrotron radiation as a continuum light source, the photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 have been measured from their respective ionization thresholds to 1060 A. The vibrational constants associated with the nu(2) totally symmetric, out-of-plane bending vibration of the ground electronic state of PH3(+) have been obtained. The cross sections and quantum yields for producing neutral products through photoexcitation of these molecules in the given spectral regions have also been determined. In the present work, autoionization processes were found to be less important than dissociation and predissociation processes in NH3, PH3, and C2H4. Several experimental techniques have been employed in order to examine the various possible systematic errors critically.

  12. Root and nodule respiration in relation to acetylene reduction in intact nodulated peas.

    PubMed

    Mahon, J D

    1977-12-01

    Inoculated pea plants (Pisum sativum L.) were grown with N-free nutrients in a controlled environment room and rates of respiratory CO(2) evolution and C(2)H(2) reduction by the intact nodulated roots were determined. Experiments followed changes related to diurnal cycles, light and dark treatments, partial defoliation, aging of plants and NH(4)NO(3) addition. In all experiments, changes in C(2)H(2) reduction were associated with parallel changes in the respiration rate, although in all but the defoliation experiment there was a basal level of respiration which was independent of the rate of C(2)H(2) reduction. In conditions which affected growth or plant size as well as C(2)H(2) reduction, respiration changed by an average of 0.42 mg CO(2) (mumol C(2)H(2) reduced)(-1). However, some treatments decreased C(2)H(2) reduction without greatly changing the growth and in these conditions respiration was decreased by an average of 0.27 mg CO(2) (mumol C(2)H(2) reduced)(-1). While this value may also include some respiration associated with other processes, it is proposed that it more closely estimates respiration directly associated with energy utilization for acetylene reduction; whereas the higher value includes respiration related to maintenance and growth processes as well.

  13. 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

  14. 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.

  15. 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

  16. Infrared spectra of the C2H2-(OCS)2 van der Waals complex: observation of a structure with C2 symmetry.

    PubMed

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

    2011-09-29

    Infrared spectra of the C(2)H(2)-(OCS)(2) trimer are studied by means of direct infrared absorption spectroscopy. The van der Waals complexes are generated in a supersonic slit-jet apparatus and probed using a rapid-scan tunable diode laser in the region of the ν(1) fundamental vibration of the OCS monomer. Two infrared bands are analyzed for the lowest energy isomer of the trimer, which has C(2) symmetry and is experimentally observed here for the first time. A relatively strong band centered at 2068.93 cm(-1) is assigned as the out-of-phase vibrations of the pair of equivalent OCS monomers. This band is blue-shifted relative to the free OCS monomer but with a reduced shift as compared with the analogous vibration of the nonpolar OCS dimer. A weaker red-shifted band observed at 2049.64 cm(-1) establishes the nonplanarity of the OCS dimer subunit within the trimer. Spectra for three isotopologues in addition to the normal form are used to help define an experimental structure, which agrees well with past and present semiempirical calculations.

  17. Underlying theory of a model for the Renner-Teller effect in tetra-atomic molecules: X(2)Πu electronic state of C2H2(+).

    PubMed

    Perić, M; Jerosimić, S; Mitić, M; Milovanović, M; Ranković, R

    2015-05-01

    In the present study, we prove the plausibility of a simple model for the Renner-Teller effect in tetra-atomic molecules with linear equilibrium geometry by ab initio calculations of the electronic energy surfaces and non-adiabatic matrix elements for the X(2)Πu state of C2H2 (+). This phenomenon is considered as a combination of the usual Renner-Teller effect, appearing in triatomic species, and a kind of the Jahn-Teller effect, similar to the original one arising in highly symmetric molecules. Only four parameters (plus the spin-orbit constant, if the spin effects are taken into account), which can be extracted from ab initio calculations carried out at five appropriate (planar) molecular geometries, are sufficient for building up the Hamiltonian matrix whose diagonalization results in the complete low-energy (bending) vibronic spectrum. The main result of the present study is the proof that the diabatization scheme, hidden beneath the apparent simplicity of the model, can safely be carried out, at small-amplitude bending vibrations, without cumbersome computation of non-adiabatic matrix elements at large number of molecular geometries.

  18. 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

  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. 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.

  1. Electron impact induced anion production in acetylene.

    PubMed

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

    2014-02-28

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

  2. 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.

  3. 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.

  4. 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

  5. Tuberculate fruit gene Tu encodes a C2 H2 zinc finger protein that is required for the warty fruit phenotype in cucumber (Cucumis sativus L.).

    PubMed

    Yang, Xuqin; Zhang, Weiwei; He, Huanle; Nie, Jingtao; Bie, Beibei; Zhao, Junlong; Ren, Guoliang; Li, Yue; Zhang, Dabing; Pan, Junsong; Cai, Run

    2014-06-01

    Cucumber fruits that have tubercules and spines (trichomes) are known to possess a warty (Wty) phenotype. In this study, the tuberculate fruit gene Tu was identified by map-based cloning, and was found to encode a transcription factor (TF) with a single C2 H2 zinc finger domain. Tu was identified in all 38 Wty lines examined, and was completely absent from all 56 non-warty (nWty) lines. Cucumber plants transgenic for Tu (TCP) revealed that Tu was required for the Wty fruit phenotype. Subcellular localization showed that the fusion protein GFP-Tu was localized mainly to the nucleus. Based on analyses of semi-quantitative and quantitative reverse transcription polymerase chain reaction (RT-PCR), and mRNA in situ hybridization, we found that Tu was expressed specifically in fruit spine cells during development of fruit tubercules. Moreover, cytokinin (CTK) content measurements and cytological observations in Wty and nWty fruits revealed that the Wty fruit phenotype correlated with high endogenous CTK concentrations. As a result of further analyses on the transcriptomic profile of the nWty fruit epidermis and TCP fruit warts, expression of CTK-associated genes, and hormone content in nWty fruit epidermis, Wty fruit warts and epidermis, and TCP fruit warts and epidermis, we found that Tu probably promoted CTK biosynthesis in fruit warts. Here we show that Tu could not be expressed in the glabrous and tubercule-free mutant line gl that contained Tu, this result that futher confirmed the epistatic effect of the trichome (spine) gene Gl over Tu. Taken together, these data led us to propose a genetic pathway for the Wty fruit trait that could guide future mechanistic studies.

  6. 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

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. Single Photon K-2 and K-1K-1 Double Core Ionization in C2H2n (n=1-3), CO, and N2 as a Potential New Tool for Chemical Analysis

    NASA Astrophysics Data System (ADS)

    Nakano, M.; Penent, F.; Tashiro, M.; Grozdanov, T. P.; Žitnik, M.; Carniato, S.; Selles, P.; Andric, L.; Lablanquie, P.; Palaudoux, J.; Shigemasa, E.; Iwayama, H.; Hikosaka, Y.; Soejima, K.; Suzuki, I. H.; Kouchi, N.; Ito, K.

    2013-04-01

    We have observed single photon double K-shell photoionization in the C2H2n (n=1-3) hydrocarbon sequence and in N2 and CO, using synchrotron radiation and electron coincidence spectroscopy. Our previous observations of the K-2 process in these molecules are extended by the observations of a single photon double photoionization with one core hole created at each of the two neighboring atoms in the molecule (K-1K-1 process). In the C2H2n sequence, the spectroscopy of K-1K-1 states is much more sensitive to the bond length than conventional electron spectroscopy for chemical analysis spectroscopy based on single K-shell ionization. The cross section variation for single photon K-1K-1 double core ionization in the C2H2n sequence and in the isoelectronic C2H2, N2 and CO molecules validates a knock-out mechanism in which a primary ionized 1s photoelectron ejects another 1s electron of the neighbor atom. The specific Auger decay from such states is clearly observed in the CO case.

  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. Theoretical study of the bonding of Sc, Y, and La singly charged and dipositive ions to C2H2, C2H4, and C3H6

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

    The interaction of the Sc and Y singly-charged and dipositive ions with C2H2, C2H4, and C3H6 is studied using electronic structure calculations that include high levels of electron correlation. These results are compared with comparable calculations performed previously for La(+) and La(2+). For C2H2 and C2H4, all three metal ions insert into the C-C pi bond, making a three-membered ring. The optimal structures for the MC3H6(+) ions all involve rearrangement to make a four-membered ring. The strength of the metal-ligand bond for the singly charged ions follows the order La greater than Sc equal to about Y. In contrast, the bonds involving the dipositive ions are electrostatic, so that the binding energy increases as the size of the ion decreases, leading to the trend Sc greater than Y greater than La.

  18. Cyclopolymerization of Acetylene to Benzyne and Naphthalene

    NASA Astrophysics Data System (ADS)

    Hewage, Dilrukshi; Silva, Ruchira; Yang, Dong-Sheng

    2012-06-01

    Reactions of acetylene (C_2H_2) with laser-vaporized La atoms produced La(C_6H_4) and La (C10H_8) in supersonic molecular beams. The organic fragments in these complexes were benzyne and naphthalene. The benzyne species was produced by the La-mediated cyclotrimerization of three acetylene molecules, whereas naphthalene was formed likely by the cyclization of the transient benzyne with two additional acetylene molecules. These cyclized products were identified by mass-analyzed threshold ionization mass spectroscopy, which measured adiabatic ionization energies and several vibrational frequencies. The measured ionization energies were 40875 (5) cm-1 for La(C_6H_4) and 36767 (5) cm-1 for La(C10H_8). The most active vibrational transitions of both complexes were metal-ligand stretching with 326 cm-1 for La(C_6H_4) and 286 cm-1 for La (C10H_8). By combining the spectra with theoretical calculations, the ground electronic states of the neutral complexes were determined to be ^2A_1 (C2v) and ^2A' (C_s) and those of the corresponding ions were ^1A_1 (C2v) and ^1A' (C_s) for La (C_6H_4) and La(C10H_8), respectively.

  19. 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

  20. 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.

  1. On the Radiolysis of Ethylene Ices by Energetic Electrons and Implications to the Extraterrestrial Hydrocarbon Chemistry

    NASA Astrophysics Data System (ADS)

    Zhou, Li; Maity, Surajit; Abplanalp, Matt; Turner, Andrew; Kaiser, Ralf I.

    2014-07-01

    The chemical processing of ethylene ices (C2H4) 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 (CH4), the C2 species acetylene (C2H2), ethane (C2H6), the ethyl radical (C2H5), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C4H8) and n-butane (C4H10). 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.

  2. Measurements of excess O3, CO2, CH4, C2H4, C2H2, HCN, NO, NH3, HCOOH, CH3COOH, HCHO, and CH3H in 1997 Alaskan biomass burning plumes by airborne Fourier transform infrared spectroscopy (AFTIR) [O3 CO2 CH4 C2H4 C2H2 NH3 CH3COOH CH3H

    NASA Astrophysics Data System (ADS)

    Goode, Jon G.; Yokelson, Robert J.; Ward, Darold E.; Susott, Ronald A.; Babbitt, Ronald E.; Davies, Mary Ann; Hao, Wei Min

    2000-09-01

    We used an airborne Fourier transform infrared spectrometer (AFTIR), coupled to a flow-through, air-sampling cell, on a King Air B-90 to make in situ trace gas measurements in isolated smoke plumes from four, large, boreal zone wildfires in interior Alaska during June 1997. AFTIR spectra acquired near the source of the smoke plumes yielded excess mixing ratios for 13 of the most common trace gases: water, carbon dioxide, carbon monoxide, methane, nitric oxide, formaldehyde, acetic acid, formic acid, methanol, ethylene, acetylene, ammonia and hydrogen cyanide. Emission ratios to carbon monoxide for formaldehyde, acetic acid, and methanol were 2.2±0.4%, 1.3±0.4%, and 1.4±0.1%, respectively. For each oxygenated organic compound, a single linear equation fits our emission factors from Alaska, North Carolina, and laboratory fires as a function of modified combustion efficiency (MCE). A linear equation for predicting the NH3/NOx emission ratio as a function of MCE fits our Alaskan AFTIR results and those from many other studies. AFTIR spectra collected in downwind smoke that had aged 2.2±1 hours in the upper, early plume yielded ΔO3/ΔCO ratios of 7.9±2.4% resulting from O3 production rates of ˜50 ppbv h-1. The ΔNH3/ΔCO ratio in another plume decreased to 1/e of its initial value in ˜2.5 hours. A set of average emission ratios and emission factors for fires in Alaskan boreal forests is derived. We estimate that the 1997 Alaskan fires emitted 46±11 Tg of CO2.

  3. Heat of Mixing and Solution of 1,1,2,2-Tetrachloroethane C2H2Cl4 + C6H10O Cyclohexanone (HMSD1111, LB3666_H)

    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 'heat of Mixing and Solution of 1,1,2,2-Tetrachloroethane C2H2Cl4 + C6H10O Cyclohexanone (HMSD1111, LB3666_H)' providing data from direct low-pressure calorimetric measurement of molar excess enthalpy at variable mole fraction and constant temperature.

  4. 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.

  5. Adsorption of Acetylene and Formation of Benzene on Cosmic Dust in Titan's Atmosphere

    NASA Astrophysics Data System (ADS)

    Frankland, Victoria; James, Alexander; Carrillo Sanchez, Juan; Mangan, Thomas; Willacy, Karen; Plane, John

    2016-04-01

    The formation of the haze layers and tholins in Titan's atmosphere is unclear. One potential mechanism is that small precursors, such as acetylene (C2H2), adsorb onto un-ablated cosmic dust particles as they sediment through Titan's atmosphere. The uptake coefficient of C2H2 onto cosmic dust analogues was measured using low temperature dual flow tube apparatus. Synthesized olivines analogues (Mg2-2nFe2nSiO4 where 1 ≥ n ≥ 0) were used to represent the cosmic dust particles based on investigations of cometary dust. The results indicated that the adsorption of C2H2 was independent of the Mg:Fe ratio in the dust analogue with the mean uptake coefficient (at 181 K) as 1.7 × 10-4. In some cases, the uptake experiments were left until the surface had become saturated with C2H2. Here, a small benzene (C6H6) mass trace was detected indicating that cyclotrimerzation of C2H2 into C6H6 was occurring on the surface. Further experiments using ultrahigh vacuum apparatus were used to confirm this observation. The rate of C6H6 (formed through C2H2 cyclotrimerization) desorbing from un-ablated cosmic dust particles sedimenting through Titan's atmosphere was explored using a 1D model. The results revealed that this heterogeneous formation and desorption route was competitive with gaseous C6H6 formation rates suggesting that the dust could be acting as a seed for the formation of complex organic molecules (such as PAHs) and tholins and, through this, the formation of the haze layers.

  6. 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.

  7. 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.

  8. 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

  9. Endorhizal and Exorhizal Acetylene-reducing Activity in a Grass (Spartina alterniflora Loisel.)-Diazotroph Association.

    PubMed

    Boyle, C D; Patriquin, D G

    1980-08-01

    Earlier studies indicated that bacteria responsible for nitrogenase activity of some grasses are located inside the roots. Those studies were conducted with excised roots in which a long, unexplained "lag phase" occurred before initiation of nitrogenase activity. When hydroponically maintained Spartina alterniflora Loisel. was incubated in a two-compartment system with acetylene, ethylene was produced following, at most, a 2-hour lag in both the upper (shoot) and lower (roots + water) phases. Ethylene production in the upper phase not attributable to leaf-associated acetylene-reducing activity or to diffusion of ethylene from around the roots is considered to represent "endorhizal acetylene-reducing activity," the internally produced ethylene diffusing into the upper phase via the lacunae. Ethylene produced in the lower phase is designated "exorhizal acetylene-reducing activity." The endorhizal acetylene-reducing activity, in comparison to exorhizal activity, was relatively insensitive to additions of HgCl(2), NH(4)Cl, or carbon sources to the lower phase. Post-lag acetylene-reducing activity of roots excised from plants growing in soil responded to additions in a manner similar to that of endorhizal acetylene-reducing activity, whereas post-lag acetylene-reducing activity of rhizosphere soil responded in a manner similar to that of exorhizal acetylene-reducing activity. PMID:16661421

  10. Theoretical self-broadening and self-shifting coefficients of 12C2H2 transitions in the 3ν5, (2ν4 + ν5)І and (2ν4 + ν5)ІІ bands

    NASA Astrophysics Data System (ADS)

    Galalou, S.; Aroui, H.

    2013-06-01

    Using a semi-classical model based upon the Robert and Bonamy formalism, self-broadening and self-shifting coefficients of 12C2H2 have been calculated for transitions belonging to the P, Q and R branches of the 3ν5, (2ν4 + ν5)І and (2ν4 + ν5)ІІ cold bands near the 5 μm region. The intermolecular potential used in this work includes, in addition to the overwhelming electrostatic interactions, a Tipping-Herman potential. Such a calculation leads to satisfactory agreement with measurements from literature. For the studied bands, the theoretical results reproduce the experimental rotational dependence of the self-broadening and self-shifting coefficients. The self-broadening coefficients show the predominance of the quadrupole-quadrupole contributions, especially for middle J values.

  11. 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.

  12. 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

  13. Reactions of group 14 metal atoms with acetylene: a matrix isolation infrared spectroscopic and theoretical study.

    PubMed

    Teng, Yun-Lei; Xu, Qiang

    2009-11-01

    Laser-ablated group 14 metal atoms have been codeposited at 4 K with acetylene in excess argon. Products, Ge(C2H2), HGeCCH, Sn(C2H2), Sn2CCH2, HSnCCH, and HPbCCH, have been formed in the present experiments and characterized using infrared spectroscopy on the basis of the results of the isotopic shifts, mixed isotopic splitting patterns, stepwise annealing, the change of reagent concentration and laser energy, and the comparison with theoretical predictions. Density functional theory calculations have been performed on these molecules. The agreement between the experimental and the calculated vibrational frequencies, relative absorption intensities, and isotopic shifts supports the identification of these molecules from the matrix infrared spectra. Plausible reaction mechanisms have been proposed to account for the formation of these molecules.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. 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.

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

    PubMed

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

    1996-10-17

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

  7. 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.

  8. 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 C2H2/CO2 mixtures is about twice that of the high-capacity HOF-3, and its actual separation selectivity for C2H2/C2H4 mixtures containing 1% acetylene is the highest among reported porous materials. Based on first-principles calculations, the extraordinary separation performance of C2H2 for FJU-22 a was attributed to hydrogen-bonding interactions between the C2H2 molecules with the open O donors on the wall, which provide better recognition ability for C2H2 than other functional sites, including open metal sites and amino groups.

  9. 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.

  10. 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.

  11. 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.

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

    DOE PAGES

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

    2015-10-06

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

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  15. 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.

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

    NASA Technical Reports Server (NTRS)

    McLaren, Ian A.; Wrobel, Jacek D.

    1997-01-01

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

  17. 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).

  18. 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.

  19. 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.

  20. 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.

  1. Elimination kinetics of acetylene and Freon 22 in resting and active lungless salamanders.

    PubMed

    Feder, M E; Full, R J; Piiper, J

    1988-05-01

    To quantify diffusion limitation in cutaneous gas exchange, the elimination of two inert gases of different diffusivity, Freon 22 (CHC1F2) and acetylene (C2H2), was measured simultaneously in exclusively skin-breathing lungless salamanders, Desmognathus quadramaculatus. In resting salamanders, elimination of both gases could be described as the sum of three exponential terms. For both the medium and the slow exponential component, the ratio of the respective rate constants (k) for acetylene and Freon averaged 1.77. This value is between the values expected for perfusion limitation (1.00) and diffusion limitation (1.94), indicating combined diffusion and perfusion limitation. In salamanders stimulated to run on a treadmill, the elimination rates and the rate constants increased more for Freon than for acetylene. During spontaneous activity, the increase in elimination of Freon was larger than that of acetylene. These findings suggest an increase in the diffusing capacity of the skin during exercise. Thus the diffusing capacity of salamander skin for gases appears to be variable and to be adjusted to meet the increased O2 requirement during exercise.

  2. Acetylene removal process

    SciTech Connect

    Mc Farland, C.G.

    1987-02-17

    This patent describes a vapor phase process for the preparation of unsaturated hydrocarbon monoolefins in diolefins comprising oxidative dehydrogenation of stream of C/sub 3/ to C/sub 9/ hydrocarbon compounds to produce a product stream comprising 3.5 to 80 mol percent of unsaturated hydrocarbon product and of about or from 0.0001 to 2.5 mol percent acetylenic compound impurity, about or from 0.0005 to 2.5 mol percent carbonyl compounds and 5 to 93 mol percent non-condensable gases. The improvement described here comprises contacting the product stream in vapor phase at a temperature in the range of 250/sup 0/ to 900/sup 0/C. and containing less than 5 mol percent fee oxygen with a solid catalyst for reducing the acetylenic compounds in the product stream. The catalyst consists essentially of a mixture of oxides, carbonates or hydroxides of Fe and Ni, Fe being present as the major metal component and Ni being present in the range of about 0.25 to 20 weight percent based on total catalyst, an alkaline earth metal oxide, carbonate or hydroxide of Mg, Ca, Sr or Ba, and about 0.5 to 30 weight percent of an alkali metal oxide, carbonate or hydroxide of Li, Na, K or Rb determined as metal and based on the other metallic elements, and recovering the stream having the amount of acetylenic compounds therein reduced.

  3. 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.

  4. Comparison of N2 Fixation and Yields in Cajanus cajan between Hydrogenase-Positive and Hydrogenase-Negative Rhizobia by In Situ Acetylene Reduction Assays and Direct 15N Partitioning 1

    PubMed Central

    La Favre, Jeffrey S.; Focht, Dennis D.

    1983-01-01

    Pigeon peas [Cajanus cajan (L.) Millsp.] were grown in soil columns containing 15N-enriched organic matter. Seasonal N2 fixation activity was determined by periodically assaying plants for reduction of C2H2. N2 fixation rose sharply from the first assay period at 51 days after planting to a peak of activity between floral initiation and fruit set. N2 fixation (acetylene reduction) activity dropped concomitantly with pod maturation but recovered after pod harvests. Analysis of 15N content of plant shoots revealed that approximately 91 to 94% of plant N was derived from N2 fixation. The effect of inoculation with hydrogenase-positive and hydrogenase-negative rhizobia was examined. Pigeon peas inoculated with strain P132 (hydrogenase-positive) yielded significantly more total shoot N than other inoculated or uninoculated treatments. However, two other hydrogenase-positive strains did not yield significantly more total shoot N than a hydrogenase-negative strain. The extent of nodulation by inoculum strains compared to indigenous rhizobia was determined by typing nodules according to intrinsic antibiotic resistance of the inoculum strains. The inoculum strains were detected in almost all typed nodules of inoculated plants. Gas samples were taken from soil columns several times during the growth cycle of the plants. H2 was never detected, even in columns containing pigeon peas inoculated with hydrogenase-negative rhizobia. This was attributed to H2 consumption by soil bacteria. Estimation of N2 fixation by acetylene reduction activity was closest to the direct 15N method when ethylene concentrations in the gas headspace (between the column lid and soil surface) were extrapolated to include the soil pore space as opposed solely to measurement in the headspace. There was an 8-fold difference between the two acetylene reduction assay methods of estimation. Based on a planting density of 15,000 plants per hectare, the direct 15N fixation rates ranged from 67 (noninoculated

  5. 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

  6. 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.

  7. Low temperature rate coefficients for reactions of the butadiynyl radical, C4H, with various hydrocarbons. Part II: reactions with alkenes (ethylene, propene, 1-butene), dienes (allene, 1,3-butadiene) and alkynes (acetylene, propyne and 1-butyne).

    PubMed

    Berteloite, Coralie; Le Picard, Sébastien D; Balucani, Nadia; Canosa, André; Sims, Ian R

    2010-04-21

    The kinetics of the reactions of the linear butadiynyl radical, C4H (CCCCH), with a variety of unsaturated hydrocarbons have been studied over the temperature range of 39-300 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, or reaction kinetics in uniform supersonic flow) apparatus combined with the pulsed laser photolysis-laser induced fluorescence technique. The rate coefficients for all the reactions studied are found to all be in excess of 10(-10) cm(3) molecule(-1) s(-1) over the entire temperature range. They can be fitted with the following expressions (valid from 39 K to 300 K, with RMS deviations of the experimental points from the predicted values shown, to which should be added 10% possible systematic error) for reaction of C4H with alkenes: k(C2H4) = (1.95 +/- 0.17) x 10(-10) (T/298 K)(-0.40) exp(9.4 K/T) cm3 molecule(-1) s(-1); k(C3H6) = (3.25 +/- 0.12) x 10(-10) (T/298 K)(-0.84) exp(-48.9 K/T) cm3 molecule(-1) s(-1); k(1-C4H8) = (6.30 +/- 0.35) x 10(-10) (T/298 K)(-0.61) exp(-65.0 K/T) cm3 molecule(-1) s(-1), for reaction of C4H with dienes: k(C3H4) = (3.70 +/- 0.34) x 10(-10) (T/298 K)(-1.18) exp(-91.1 K/T) cm3 molecule(-1) s(-1); k(1,3-C4H6) = (5.37 +/- 0.30) x 10(-10) (T/298 K)(-1.25) exp(-116.8 K/T) cm3 molecule(-1) s(-1), and for reaction of C4H with alkynes: k(C2H2) = (1.82 +/- 0.19) x 10(-10) (T/298 K)(-1.06) exp(-65.9 K/T) cm3 molecule(-1) s(-1); k(C3H4) = (3.20 +/- 0.08) x 10(-10) (T/298 K)(-0.82) exp(-47.5 K/T) cm3 molecule(-1) s(-1); k(1-C4H6) = (3.48 +/- 0.14) x 10(-10) (T/298 K)(-0.65) exp(-58.4 K/T) cm3 molecule(-1) s(-1). Possible reaction mechanisms and product channels are discussed in detail for each of these reactions. Potential implications of these results for models of low temperature chemical environments, in particular cold interstellar clouds and star-forming regions, are considered.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Reactions of yttrium and scandium atoms with acetylene: a matrix isolation infrared spectroscopic and theoretical study.

    PubMed

    Teng, Yun-Lei; Xu, Qiang

    2010-09-01

    Laser-ablated yttrium and scandium metal atoms have been codeposited at 4 K with acetylene in excess argon. Products, Y(C(2)H(2)), HYCCH, HScCCH(-), and HScScCCH(-), have been formed in the present experiments and characterized using infrared spectroscopy on the basis of the results of the isotopic shifts, mixed isotopic splitting patterns, stepwise annealing, the change of reagent concentration and laser energy, and the comparison with theoretical predictions. Density functional theory calculations have been performed on these molecules. The agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts supports the identification of these molecules from the matrix infrared spectra. Plausible reaction mechanisms have been proposed to account for the formation of these molecules.

  17. 29 CFR 1910.102 - Acetylene.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...., 2003). (b) Piped systems. (1) Employers must comply with Chapter 9 (“Acetylene Piping”) of NFPA 51A..., 2006, these employers may comply with the provisions of Chapter 7 (“Acetylene Piping”) of NFPA 51A-2001... (fill) acetylene cylinders comply with the provisions of NFPA 51A-2006 (“Standard for Acetylene...

  18. 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.

  19. Immediate Acetylene Reduction by Excised Grass Roots Not Previously Preincubated at Low Oxygen Tensions 1

    PubMed Central

    van Berkum, Peter; Sloger, Charles

    1979-01-01

    Excised roots of Spartina alterniflora Loisel. and corn reduced acetylene in air without the previously reported period of zero activity lasting 8 to 18 hours. The profiles of acetylene-dependent ethylene accumulation by excised roots and intact plants of S. alterniflora were similar. No significant change in the number of bacteria associated with the roots was detectable during the assay. Most of the nitrogenase activity was detected in the roots and rhizomes of the plants. The salt marsh sediment also was capable of reducing acetylene. Additional damage to roots by washing and cutting increased the rate of acetylene reduction with samples incubated in air. Low concentrations of nitrate significantly inhibited the nitrogenase activity associated with the sediment and excised roots, but not with intact plants. Rates of acetylene reduction by excised corn roots were low. Oxidation and endogenous production of ethylene in the absence of acetylene were negligible. Measurements made with excised grass roots as described probably reflect the occurrence and magnitude of nitrogenase activity associated with the plants in the field. PMID:16661045

  20. 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.

  1. Acetylene removal process

    SciTech Connect

    Mc Farland, C.G.

    1987-04-14

    This patent describes a vapor phase process for the preparation of hydrocarbon monoolefins and diolefins comprising oxidative dehydrogenation of a stream of C/sub 3/ to C/sub 9/ hydrocarbon compounds to produce a product stream comprising, exclusive of any water present, 3.5 to 80 mol percent hydrocarbon monoolefins and diolefins and about from 0.0001 to 2.5 mol percent carbonyl compounds and 5 to 93 mol percent non-condensable gases. The improvement described here comprises contacting the product stream in vapor phase at a temperature in the range of 250/sup 0/ to 900/sup 0/C and containing less than 5 mol percent free oxygen with a solid catalyst for reducing the acetylene compounds in the product stream, the catalyst consisting essentially of zinc ferrite and nickel oxide. The Fe is the major metal component by weight, an alkaline earth metal oxide, carbonate or hydroxide of Mg, Ca, Sr or Ba, and about 0.5 to 30 weight percent of an alkali metal oxide, carbonate or hydroxide, based on the other metallic elements of Li, Na, K or Rh.

  2. 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

  3. 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.

  4. Abscission: The Role of Ethylene, Ethylene Analogues, Carbon Dioxide, and Oxygen

    PubMed Central

    Abeles, F. B.; Gahagan, H. E.

    1968-01-01

    Ethylene was the most effective abscission accelerant examined, with decreasing activity shown by propene, carbon monoxide, acetylene, vinyl fluoride, 1-butene, and 1,3-butadiene. Carbon dioxide inhibited abscission, but its effect was overcome by ethylene. Oxygen was required for abscission as an electron acceptor for respiration and not as a potentiator or activator of the ethylene attachment site. The molecular requirements for abscission were similar to those shown by other workers for other biological processes under the influence of ethylene. PMID:16656908

  5. 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.

  6. 29 CFR 1910.102 - Acetylene.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... acetylene piping systems, see CGA G-1.2-2006, part 3 (“Acetylene piping”) (Compressed Gas Association, Inc., 3rd ed., 2006). (c) Generators and filling cylinders. (1) Employers must ensure that...

  7. Effect of polynuclear hydrocarbons on algal nitrogen fixation (acetylene reduction)

    SciTech Connect

    Bastian, M.V.; Toetz, D.W.

    1985-08-01

    The objective of this research was to determine the effects of polynuclear aromatic hydrocarbons (PAH) on N/sub 2/ fixation by the alga, Anabaena flos-aquea. The reduction of acetylene (C/sub 2/H/sub 2/) to ethylene (C/sub 2/H/sub 4/) was measured as a measure of the capacity of an organism to fix atmospheric N/sub 2/ and reduce it to an assimilable form. The primary advantage of this assay is its speed since chemical exposure and quantitative chromatographic analysis can be completed in a few hours.

  8. 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.

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

    SciTech Connect

    Zubrin, R.M. )

    1992-01-01

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

  10. 29 CFR 1910.102 - Acetylene.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...). (b) Piped systems. (1) Employers must comply with Chapter 9 (“Acetylene Piping”) of NFPA 51A-2006... may comply with the provisions of Chapter 7 (“Acetylene Piping”) of NFPA 51A-2001 (“Standard for... comply with the provisions of NFPA 51A-2006 (“Standard for Acetylene Charging Plants”) (National...

  11. 29 CFR 1910.102 - Acetylene.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...). (b) Piped systems. (1) Employers must comply with Chapter 9 (“Acetylene Piping”) of NFPA 51A-2006... may comply with the provisions of Chapter 7 (“Acetylene Piping”) of NFPA 51A-2001 (“Standard for... comply with the provisions of NFPA 51A-2006 (“Standard for Acetylene Charging Plants”) (National...

  12. 41 CFR 50-204.66 - Acetylene.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 41 Public Contracts and Property Management 1 2010-07-01 2010-07-01 true Acetylene. 50-204.66 Section 50-204.66 Public Contracts and Property Management Other Provisions Relating to Public Contracts...) Plants for the generation of acetylene and the charging (filling) of acetylene cylinders shall...

  13. 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

  14. Absolute frequency measurement of an acetylene stabilized laser using a selected single mode from a femtosecond fiber laser comb.

    PubMed

    Ryu, Han Young; Lee, Sung Hun; Lee, Won Kyu; Moon, Han Seb; Suh, Ho Suhng

    2008-03-01

    We performed an absolute frequency measurement of an acetylene stabilized laser utilizing a femtosecond injection locking technique that can select one component among the fiber laser comb modes. The injection locking scheme has all the fiber configurations. Femtosecond comb lines of 250 MHz spacing based on the fiber femtosecond laser were used for injection locking of a distributed feedback (DFB) laser operating at 1542 nm as a frequency reference. The comb injected DFB laser serves as a selection filter of optical comb modes and an amplifier for amplification of the selected mode. The DFB laser injection locked to the desired comb mode was used to evaluate the frequency stability and absolute frequency measurement of an acetylene stabilized laser. The frequency stability of the acetylene stabilized laser was measured to be 1.1 x 10(-12) for a 1 s averaging time, improving to 6.9 x 10(-14) after 512 s. The absolute frequency of the laser stabilized on the P(16) transition of (13)C(2)H(2) was measured to be 194 369 569 385.7 kHz.

  15. 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.

  16. 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.

  17. Formation of Polyynes C4H2, C6H2, C8H2, and C10H2 from Reactions of C2H, C4H, C6H, and C8H Radicals with C2H2.

    PubMed

    Sun, Yi-Lun; Huang, Wen-Jian; Lee, Shih-Huang

    2015-10-15

    Some of the polyynes (HC2n+2H, 1 ≤ n ≤ 4) are observable in planetary atmospheres, interstellar space, and flames. Polyynes are proposed to play an important role in synthesis of large carbonaceous molecules. We explore the dynamics of reactions of C2nH (n = 1-4) radicals with C2H2 by interrogating time-of-flight spectra and photoionization efficiency spectra of products C2n+2H2. The reactions of n = 2-4 were investigated for the first time. The translational energy release is biased to low energy but extends to the energetic limit of product HC2n+2H + H, corresponding to a fraction of 0.34-0.36 on translational energy. Product C2n+2H2 has a deconvoluted ionization threshold in good agreement with the ionization energy of polyynes. The quantum chemical calculations support the experimental observations. This work verifies that the title reaction is an important source for formation of polyynes that have been observed in interstellar/circumstellar media and combustion processes. PMID:26722787

  18. 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.

  19. 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.

  20. 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.

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

    NASA Astrophysics Data System (ADS)

    Nadeem, Shahid; Dörsch, Peter; Bakken, Lars

    2013-04-01

    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

  2. What is Different Between Borazine-Acetylene and Benzene-Acetylene a Matrix Isolation and Ab-Initio Study.

    NASA Astrophysics Data System (ADS)

    Verma, Kanupriya; Viswanathan, K. S.

    2016-06-01

    Borazine (B_3N_3H_6)-C_2H_2 system was studied experimentally, using matrix isolation infrared spectroscopy and supported by ab-initio computations. B_3N_3H_6, also referred to as inorganic benzene, presents an interesting comparison with C_6H_6. While C_6H_6 has a delocalized π system, B_3N_3H_6 has electron density centered on the nitrogen atoms, while the boron atoms are electron deficient. In addition, B_3N_3H_6 can also serve as a proton donor through N-H group. Similarly, C_2H_2 can act both as a proton donor, using the hydrogen attached to the sp carbon or as a proton acceptor at its π-cloud. At the MP2/aug-cc-pVDZ level of theory, C_6H_6-C_2H_2 system showed three minimaThe. global minimum was a structure where the C_2H_2 was the proton donor to the C_6H_6 π system. The next was a local minimum where the C_6H_6 was the proton donor to C_2H_2 and the third was a π stacked structure. B_3N_3H_6-C_2H_2 also shows three minima at the same level of theory mentioned above. One was a structure where C_2H_2 donates a proton to B_3N_3H_6, approaching it from above the plane of the ring, much like in C_6H_6-C_2H_2. A second near degenerate structure was also located where the C_2H_2 serves as a proton acceptor towards the N-H group of B_3N_3H_6. A similar structure in C_6H_6-C_2H_2 was a local minimum. While in the case of C_6H_6-C_2H_2, the global minimum was the only one observed in the experiments, in the case of B_3N_3H_6-C_2H_2, both near degenerate minima mentioned above were observed in the matrix. B_3N_3H_6-C_2H_2 therefore reveals similarities and differences from the C_6H_6-C_2H_2 system. A π-stacked local minimum was also computationally indicated in the B_3N_3H_6-C_2H_2 system, though it was not observed in our experiments. Our earlier work comparing B_3N_3H_6-H_2O to C_6H_6-H_2O also yielded a similar behavioral pattern. Details of the experimental data and computational results will be presented. References: 1. M. Majumder, B. K. Mishra, N

  3. The Methane-Acetylene Cycle Aerospace Plane: A potential option for inexpensive Earth to orbit transportation

    NASA Astrophysics Data System (ADS)

    Zubrin, Robert M.

    1994-06-01

    Methane, a cheap, soft cryogen with six times the density of hydrogen could be an ideal fuel for use in a hypersonic aerospace plane. However, it does not burn fast enough for efficient scramjet operation and it possesses an inadequate thermal heat sink to cool the aircraft effectively. This paper proposes a concept, termed the Methane-Acetylene Cycle Aerospace Plane (MACASP), that may overcome these difficulties. In the MACASP concept, methane fuel is run out within the wing leading edge in pipes which are allowed to rise in temperature to about 1800 K. Drag heating is used to drive the highly endothermic chemical reaction; 2CH4 = 3H2 + C2H2. The reaction occurs on a millisecond time scale and endows the methane with a heat sink per unit mass comparable to that possessed by liquid hydrogen. The reaction products are fed into a combustion chamber and burned in air, releasing as much energy per unit mass at as rapid a combustion rate as hydrogen. This paper explores the thermodynamics of the MACASP concept and theoretical feasibility is demonstrated. Potential problems and areas of concern are identified. A conceptual point design for a MACASP vehicle is advanced and mission analysis performed comparing the MACASP to a conventional hydrogen aerospace plane. It is shown that the MACASP concept offers significant promise for economical Earth to orbit transportation.

  4. 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

  5. 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.

  6. 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

  7. Electron Stimulated Decomposition of Acetylene as a Precursor for Graphene

    NASA Astrophysics Data System (ADS)

    Kumar, Mahesh; Rothwell, Sara; Cohen, Philip

    2011-03-01

    We report here on the deposition of carbon via C2 H2 dissociation by electron beam irradiation and thermal decomposition. The substrates investigated include sapphire, silicon, ALD deposited Al 2 O3 / Si O2 , and GaN/sapphire. Raman analyses show that on C-plane sapphire both thermal decomposition and electron beam stimulated dissociation of C2 H2 deposit carbon successfully. On other substrates these methods were inactive, showing the decomposition of C2 H2 on sapphire is catalytic. We tested different annealing times and C2 H2 pressures, gauging absorption saturation with RHEED. Samples exposed to 15 min. C2 H2 adsorption during 400 eV electron irradiation and then annealed for 2 hr. to above 600° C in high vacuum showed the greatest proportion of sp2 to sp3 bonding by Raman analysis. The Raman spectra also suggest hydrogen adsorption, which may hinder further sp2 bonding. Annealing samples in a hydrogen atmosphere does not change their Raman spectra, suggesting hydrogen saturation. Partial support from the University of Minnesota Institute for Renewable Energy and the Environment

  8. Yttrium-Assisted C-H and C-C Bond Activation of Ethylene Probed by Mass-Analyzed Threshold Ionization Spectroscopy

    NASA Astrophysics Data System (ADS)

    Kim, Jong Hyun; Yang, Dong-Sheng

    2016-06-01

    The reaction between Y atom and ethylene (CH2=CH2) was performed in a laser-ablation supersonic molecular beam source. Y(C2H2), Y(C2H4), and Y(C4H6) were observed by time-of-flight mass spectrometry and investigated with mass-analyzed threshold ionization (MATI) spectroscopy and theoretical calculations. Y(C2H2) is formed by hydrogen elimination, Y(C2H4) by simple association, and La(C4H6) by C-C bond coupling and dehydrogenation. Both Y(C2H2) and Y(C2H4) have a C2v triangular structure with a C=C double bond in Y(C2H2) and a C-C single bond in Y(C2H4). Y(C4H6) has a five-membered metallacyclic structure (Cs) with Y binding to the two terminal carbon atoms of butene, which is the exactly same as that of Y(C4H6) formed in the Y + 1-butene reaction. For all three complexes, ionization has a small effect on the metal-carbon bond lengths because the rejected electron has basically a Y 5s character. The adiabatic ionization energies are measured to be 45679(5) wn for Y(C2H2), 45603(5) wn for Y(C2H4) and 43475(5) wn for Y(C4H6). The metal-ligand stretching frequencies of the three complexes are also measured from the MATI spectra.

  9. Theoretical study of the bonding of the first-row transition-metal positive ions to ethylene

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

    Ab initio calculations were performed to study the bonding of the first-row transition-metal ions with ethylene. While Sc(+) and Ti(+) insert into the pi bond of ethylene to form a three-membered ring, the ions V(+) through Cu(+) form an electrostatic complex with ethylene. The binding energies are compared with those from experiment and with those of comparable calculations performed previously for the metal-acetylene ion systems.

  10. 46 CFR 154.1735 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Methyl acetylene-propadiene mixture. 154.1735 Section... Operating Requirements § 154.1735 Methyl acetylene-propadiene mixture. (a) The composition of the methyl acetylene-propadiene mixture at loading must be within the following limits or specially approved by...

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

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Methyl acetylene-propadiene mixture. 154.1735 Section... Operating Requirements § 154.1735 Methyl acetylene-propadiene mixture. (a) The composition of the methyl acetylene-propadiene mixture at loading must be within the following limits or specially approved by...

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

    Code of Federal Regulations, 2013 CFR

    2013-10-01

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

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

    Code of Federal Regulations, 2014 CFR

    2014-10-01

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

  14. 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

  15. 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

  16. Influence of and additives on acetylene detonation

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  17. 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.

  18. 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…

  19. Method development for the determination of fluorine in toothpaste via molecular absorption of aluminum mono fluoride using a high-resolution continuum source nitrous oxide/acetylene flame atomic absorption spectrophotometer.

    PubMed

    Ozbek, Nil; Akman, Suleyman

    2012-05-30

    Fluorine was determined via the rotational molecular absorption line of aluminum mono fluoride (AlF) generated in C(2)H(2)/N(2)O flame at 227.4613 nm using a high-resolution continuum source flame atomic absorption spectrophotometer (HR-CS-FAAS). The effects of AlF wavelength, burner height, fuel rate (C(2)H(2)/N(2)O) and amount of Al on the accuracy, precision and sensitivity were investigated and optimized. The Al-F absorption band at 227.4613 nm was found to be the most suitable analytical line with respect to sensitivity and spectral interferences. Maximum sensitivity and a good linearity were obtained in acetylene-nitrous oxide flame at a flow rate of 210 L h(-1) and a burner height of 8mm using 3000 mg L(-1) of Al for 10-1000 mg L(-1)of F. The accuracy and precision of the method were tested by analyzing spiked samples and waste water certified reference material. The results were in good agreement with the certified and spiked amounts as well as the precision of several days during this study was satisfactory (RSD<10%). The limit of detection and characteristic concentration of the method were 5.5 mg L(-1) and 72.8 mg L(-1), respectively. Finally, the fluorine concentrations in several toothpaste samples were determined. The results found and given by the producers were not significantly different. The method was simple, fast, accurate and sensitive.

  20. 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

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

    PubMed Central

    Winship, Lawrence J.; Tjepkema, John D.

    1982-01-01

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

  2. 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.

  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. 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.

  5. Recent Line-Shape and Doppler Thermometry Studies Involving Transitions in the ν1 +ν3 Band of Acetylene

    NASA Astrophysics Data System (ADS)

    Hashemi, Robab; Rozario, Hoimonti; Povey, Chad; Garber, Jolene; Derksen, Mark; Predoi-Cross, Adriana

    2014-06-01

    The line positions for transitions in the ν1 +ν3 band are often used as a frequency standard by the telecom industry and also needed for planetary atmospheric studies. Four relevant studies have been recently carried out in our group and will be discussed briefly below. (1) N2-broadened line widths and N2-pressure induced line shifts have been measured for transitions in the ν1 +ν3 band of acetylene at seven temperatures in the range 213333K 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. This study has been published in Molecular Physics, 110 Issue 21/22 (2012) 2645-2663. (2) Six nitrogen perturbed transitions of acetylene within the ν1 +ν3 absorption band have been recorded using a 3-channel diode laser spectrometer. We have examined C2H2 spectra using a hard collision (Rautian) profile over a range of five temperatures (213 K-333 K). From these fits we have obtained the N2-broadening and narrowing coefficients of C2H2 and examined their temperature dependence. The experimentally measured narrowing coefficients have been used to estimate the nitrogen diffusion coefficients. The broadening coefficients and corresponding temperature dependence exponents have also been compared to that of calculations completed using a classical impact approach on an ab initio potential energy surface. We have observed a good agreement between our theoretical and experimental results. This study was published in Canadian Journal of Physics 91(11) 896-905 (2013). (3) An extension of the previous study was to analyze the room temperature for the same six transitions using the Voigt, Rautian, Galatry, RautianGalatry and Correlated Rautian profiles. For the entire pressure range, we have tested the applicability of these line-shape models. Except for Voigt profile, Dicke narrowing effect has been considered in all mentioned line-shape models. The experimental

  6. High temperature polymer from maleimide-acetylene terminated monomers

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  7. 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.

  8. Addition of ethylene or hydrogen to a main-group metal cluster under mild conditions.

    PubMed

    Vasko, Petra; Wang, Shuai; Tuononen, Heikki M; Power, Philip P

    2015-03-16

    Reaction of the tin cluster Sn8(Ar(Me6))4(Ar(Me6)=C6H2-2,6-(C6H3-2,4,6-Me3)2) with excess ethylene or dihydrogen at 25 °C/1 atmosphere yielded two new clusters that incorporated ethylene or hydrogen. The reaction with ethylene yielded Sn4(Ar(Me6))4(C2H2)5 that contained five ethylene moieties bridging four aryl substituted tin atoms and one tin-tin bond. Reaction with H2 produced a cyclic tin species of formula (Sn(H)Ar(Me6))4, which could also be synthesized by the reaction of {(Ar(Me6))Sn(μ-Cl)}2 with DIBAL-H. These reactions represent the first instances of direct reactions of isolable main-group clusters with ethylene or hydrogen under mild conditions. The products were characterized in the solid state by X-ray diffraction and IR spectroscopy and in solution by multinuclear NMR and UV/Vis spectroscopies. Density functional theory calculations were performed to explain the reactivity of the cluster.

  9. Spectroscopic study of acetylene and hydrogen cyanide

    NASA Astrophysics Data System (ADS)

    Rozario, Hoimonti Immaculata

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

  10. 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...

  11. Acetylenic polymers for hair styling products.

    PubMed

    Martiny, S

    2002-06-01

    This paper looks at the basic requirements of hair styling products from a consumer's perspective before moving onto a very brief outline of the various chemistries available to the formulator. It then discusses the manufacture of vinyl pyrrolidone from acetylene. The properties of polyvinyl pyrrolidone are described, followed by the features and benefits of some vinyl pyrrolidone copolymers and terpolymers. The instrumental analysis of the hold, flexibility, tack and combing properties of polymer films is discussed in some detail, along with the effect of application type on these measurable properties concentrating upon vinyl caprolactam/vinyl pyrrolidone/dimethylaminopropyl methacrylamide acrylates copolymer.

  12. 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

  13. 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.

  14. 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

  15. Enantiopure laterally functionalized alleno-acetylenic macrocycles: synthesis, chiroptical properties, and self-assembly in aqueous media.

    PubMed

    Tzirakis, Manolis D; Alberti, Mariza N; Weissman, Haim; Rybtchinski, Boris; Diederich, François

    2014-12-01

    A family of shape-persistent alleno-acetylenic macrocycles (SPAAMs), peripherally decorated with structurally diverse pendant groups, has been synthesized and characterized in enantiomerically pure form. Their electronic circular dichroism (ECD) spectra feature a strong chiroptical response, which is more than two times higher than for open-chain tetrameric analogues. A water-soluble oligo(ethylene glycol)-appended SPAAM undergoes self-assembly in aqueous solution. Morphology studies by cryogenic transmission electron microscopy (cryo-TEM) revealed the formation of aggregates with fibrous fine structures that correspond to tubular, macrocyclic stacks.

  16. Acetylene-based materials in organic photovoltaics.

    PubMed

    Silvestri, Fabio; Marrocchi, Assunta

    2010-04-08

    Fossil fuel alternatives, such as solar energy, are moving to the forefront in a variety of research fields. Organic photovoltaic systems hold the promise of a lightweight, flexible, cost-effective solar energy conversion platform, which could benefit from simple solution-processing of the active layer. The discovery of semiconductive polyacetylene by Heeger et al. in the late 1970s was a milestone towards the use of organic materials in electronics; the development of efficient protocols for the palladium catalyzed alkynylation reactions and the new conception of steric and conformational advantages of acetylenes have been recently focused the attention on conjugated triple-bond containing systems as a promising class of semiconductors for OPVs applications. We review here the most important and representative (poly)arylacetylenes that have been used in the field. A general introduction to (poly)arylacetylenes, and the most common synthetic approaches directed toward making these materials will be firstly given. After a brief discussion on working principles and critical parameters of OPVs, we will focus on molecular arylacetylenes, (co)polymers containing triple bonds, and metallopolyyne polymers as p-type semiconductor materials. The last section will deal with hybrids in which oligomeric/polymeric structures incorporating acetylenic linkages such as phenylene ethynylenes have been attached onto C(60), and their use as the active materials in photovoltaic devices.

  17. Chemistry of acetylene on platinum (111) and (100) surfaces

    PubMed Central

    Muetterties, E. L.; Tasi, M.-C.; Kelemen, S. R.

    1981-01-01

    An ultra-high vacuum experimental study of acetylene chemisorption on Pt(111) and Pt(100) and of the reaction of hydrogen with the acetylene adsorbate has established distinguishing features of carbon-hydrogen bond breaking and making processes as a function of pressure, temperature, and surface crystallography. The rates for both processes are substantially higher on the Pt(100) surface. Net acetylene-hydrogen processes, in the temperature range of 20°C to ≈130°C, are distinctly different on the two surfaces: on Pt(100) the net reaction is hydrogen exchange (1H-2H exchange) and on Pt(111) the only detectable reaction is hydrogenation. Stereochemical differences in the acetylene adsorbate structure are considered to be a contributing factor to the differences in acetylene chemistry on these two surfaces. Images PMID:16593110

  18. 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

  19. Graphenes in the absence of metals as carbocatalysts for selective acetylene hydrogenation and alkene hydrogenation

    NASA Astrophysics Data System (ADS)

    Primo, Ana; Neatu, Florentina; Florea, Mihaela; Parvulescu, Vasile; Garcia, Hermenegildo

    2014-10-01

    Catalysis makes possible a chemical reaction by increasing the transformation rate. Hydrogenation of carbon-carbon multiple bonds is one of the most important examples of catalytic reactions. Currently, this type of reaction is carried out in petrochemistry at very large scale, using noble metals such as platinum and palladium or first row transition metals such as nickel. Catalysis is dominated by metals and in many cases by precious ones. Here we report that graphene (a single layer of one-atom-thick carbon atoms) can replace metals for hydrogenation of carbon-carbon multiple bonds. Besides alkene hydrogenation, we have shown that graphenes also exhibit high selectivity for the hydrogenation of acetylene in the presence of a large excess of ethylene.

  20. Acetylene: Synergy between theory and experiment

    NASA Astrophysics Data System (ADS)

    Lundberg, James K.; Field, Robert W.; Sherrill, C. David; Seidl, Edward T.; Xie, Yaoming; Schaefer, Henry F., III

    1993-06-01

    Six anomalous vibronic feature states [˜2 cm-1 full-width at half-maximum (FWHM), each consisting of ˜20 partially resolved eigenstates] have been observed in stimulated emission pumping (SEP) spectra of C2D2. Of the two plausible assignments for these features, the one most consistent with spectroscopic observations would imply that the lowest energy cis-bent triplet state of acetylene has T0≤25 820 cm-1, which is inconsistent with previous ab initio predictions. New higher level ab initio quantum mechanical methods have been used to predict the energy difference between X˜ 1Σg+ ground state and the cis-bent ã 3B2 lowest triplet state of acetylene. In conjunction with a triple zeta plus double polarization plus f function (TZ2Pf) basis set, the coupled cluster including single, double, and linearized triple excitations CCSD(T) method yields T0=ΔE(ã 3B2-X˜ 1Σg+)=30 500 cm-1. The true value of T0 for the ã 3B2 state is estimated to be ˜500 cm-1 higher. At the same level of theory the zero-point levels of the lowest triplet state of the trans-bent (ã 3Bu) and vinylidene (ã 3B2) isomers lie at still higher energies. This result conclusively rules out any triplet assignment for the anomalous feature states. The alternative assignment, as highly excited vibrational levels of the X˜ 1Σg+ state, is surprising in view of the Franck-Condon selectivity, dynamical stability, and nonselective relaxation of this special class of ``bright states'' observed in the SEP spectra. Such an assignment would be implausible in the absence of the present ab initio calculations. Previous experimental observations [Lisy and Klemperer, J. Chem. Phys. 72, 3880 (1980) and Wendt, Hippler, and Hunziker, J. Chem. Phys. 70, 4044 (1979)] of acetylene triplet states are discussed and shown to be completely consistent with each other and with the present ab initio ordering of the cis and trans isomeric minima on the T1 potential energy surface: cis ã 3B2 below trans ã 3Bu .

  1. 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+.

  2. Angular and energy distributions of fragment ions in dissociative double photoionization of acetylene molecules in the 31.9-50.0 eV photon energy range

    NASA Astrophysics Data System (ADS)

    Falcinelli, Stefano; Alagia, Michele; Farrar, James M.; Kalogerakis, Konstantinos S.; Pirani, Fernando; Richter, Robert; Schio, Luca; Stranges, Stefano; Rosi, Marzio; Vecchiocattivi, Franco

    2016-09-01

    The two-body dissociation reactions of the dication C2H2+2, initiated via double ionization of acetylene molecules by photons in the energy range 31.9-50.0 eV, have been studied by coupling photoelectron-photoion-photoion coincidence and ion imaging techniques. The angular distributions and kinetic energy of product ions, measured in the 31.9-50.0 eV energy range, exhibit significant differences for the three leading dissociation reactions with respect to a previous investigation carried out at a fixed energy of 39.0 eV, providing thus new information on the dynamical evolution of the system. The analysis of the results indicates that such dissociation reactions occur with a different mechanism. In particular, the symmetric dissociation in two CH+ ions is characterized by different dynamics, and the anisotropy of the angular distribution of ionic products increases with photon energy in a more pronounced way than the other two reactions. Moreover, the kinetic energy distribution of the symmetric dissociation reaction exhibits several components that change with photon energy. The new experimental findings cast light on the microscopic evolution of the system and can provide a laboratory reference for new theoretical calculations on specific features of the multidimensional potential energy surface, namely, the structure, energy and symmetry of dication states, the electronic state of dissociation products, energy barriers and their dependence on the geometry of the intermediate state.

  3. 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.

  4. High pressure chemistry of substituted acetylenes

    SciTech Connect

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

    2011-01-25

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

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

    Code of Federal Regulations, 2012 CFR

    2012-10-01

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

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

    Code of Federal Regulations, 2013 CFR

    2013-10-01

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

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

    Code of Federal Regulations, 2014 CFR

    2014-10-01

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

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

    NASA Astrophysics Data System (ADS)

    Chen, Yanjun; Chen, Jixiang

    2016-11-01

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

  9. The role of tin-promoted Pd/MWNTs via the management of carbonaceous species in selective hydrogenation of high concentration acetylene

    NASA Astrophysics Data System (ADS)

    Esmaeili, Elaheh; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Rashidi, Ali Morad; Rashidzadeh, Mehdi

    2012-12-01

    In the present study, Pd/MWNTs are synthesized using polyol process and modified by tin as a promoter for selective hydrogenation of high concentrated acetylene feedstock. Polyol method results in highly dispersed nanoparticles with a depletion of particle size for tin-promoted Pd catalysts as characterized by TEM. Tin promoter plays a considerable role in hydrogenation of pure acetylene stream. This is attributed to formation of Pd2Sn structural phase, confirmed by XRD and TPR techniques, composed mainly of intermetallic species. Catalytic behavior of tin-promoted Pd catalysts is affected by geometric and electronic factors which are more pronounced in the case of Sn/Pd = 0.25. A discontinuity in Arrhenius plots for the Sn-promoted catalysts is appeared, which seems to be due to a kinetic factor as a result of change in acetylene coverage on Pd metallic ensembles at low and high temperature ranges. Higher selectivity of the catalysts to ethylene is attributed to the presence of more isolated adsorption sites on the catalyst surface originated from both intermetallic compounds confirmed by XPS and the ones formed via the carbonaceous species upon the acetylene hydrogenation reaction.

  10. 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.

  11. 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.

  12. 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

  13. 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%.

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. Ethylene prunes translation.

    PubMed

    Salehin, Mohammad; Estelle, Mark

    2015-10-22

    Ethylene regulates many aspects of plant growth and development. In the presence of ethylene, the C terminus of EIN2 (EIN2C) translocates into the nucleus and activates transcription. Li et al. and Merchante et al. show that EIN2C also regulates translation through an interaction with the 3' UTRs of transcripts. PMID:26496600

  20. 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.

  1. Plant Life without Ethylene.

    PubMed

    Voesenek, Laurentius A C J; Pierik, Ronald; Sasidharan, Rashmi

    2015-12-01

    We propose that the ability to synthesize ethylene was selectively lost in evolution when the ancestors of fully aquatic higher plants lost their terrestrial lifestyle. We suggest that there has been negative selection on ethylene in these submerged species because it might interfere with growth in permanently deluged environments.

  2. 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

  3. 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.

  4. Theoretical determination of the structure of acetylene on Pt(111)

    NASA Astrophysics Data System (ADS)

    Anderson, Alfred B.; Hubbard, Arthur T.

    1980-09-01

    An atom superposition and electron delocalization technique applied to acetylene chemisorption on small cluster models for the Pt(111) surface shows preference for the triangular site as deduced from electron energy loss analyses by Ibach and Lehwald. This confirms the applicability of Badger's and related rules in this instance. Calculations on CCH 3 produce a structure in agreement with a dynamic LEED analysis at 400 K by Kesmodel, Dubois and Somorjai. Structures of CCH 2 and CHCH 2 are calculated and these species are found to be less stable than acetylene and CCH 3, respectively, when chemisorbed on Pt(111).

  5. 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...

  6. 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...

  7. 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...

  8. 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...

  9. 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...

  10. Ethylene, seed germination, and epinasty.

    PubMed

    Stewart, E R; Freebairn, H T

    1969-07-01

    Ethylene activity in lettuce seed (Lactuca satina) germination and tomato (Lycopersicon esculentum) petiole epinasty has been characterized by using heat to inhibit ethylene synthesis. This procedure enabled a separation of the production of ethylene from the effect of ethylene. Ethylene was required in tomato petioles to produce the epinastic response and auxin was found to be active in producing epinasty through a stimulation of ethylene synthesis with the resulting ethylene being responsible for the epinasty. In the same manner, it was shown that gibberellic acid stimulated ethylene synthesis in lettuce seeds. The ethylene produced then in turn stimulated the seeds to germinate. It was hypothesized that ethylene was the intermediate which caused epinasty or seed germination. Auxin and gibberellin primarily induced their response by stimulating ethylene production.

  11. 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.

  12. 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.

  13. 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.

  14. 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... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF LABOR... rulemaking, the Agency is proposing to revise its Acetylene Standard for general industry by updating...

  15. 76 FR 75782 - Revising Standards Referenced in the Acetylene Standard

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-12-05

    ... on November 9, 2009. See 74 FR 57883. The Compressed Gas Association published a new edition of CGA G... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF LABOR... is revising its Acetylene Standard for general industry by updating a reference to a...

  16. 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...

  17. 46 CFR 154.1735 - Methyl acetylene-propadiene mixture.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Methyl acetylene-propadiene mixture. 154.1735 Section 154.1735 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SAFETY STANDARDS FOR SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Special Design...

  18. Acetylene absorption and binding in nonporous crystal lattice

    SciTech Connect

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

    2006-09-01

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

  19. 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.

  20. 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.

  1. Multi-Valued Versus Single-Valued Large-Amplitude Bending-Torsional Coordinate Systems for Simultaneously Treating Trans-Bent and Cis-Bent Acetylene in its S_1 Excited Electronic State

    NASA Astrophysics Data System (ADS)

    Hougen, Jon T.

    2012-06-01

    There are now a large number of papers in the spectroscopic literature which make use of multiple-valued (frequently double-valued) coordinate systems and multiple-groups of the permutation-inversion group to deal with the symmetry properties of large-amplitude motions in molecules of high symmetry. The use of multiple-valued coordinate systems, and the resultant appearance of more minima on the potential surface than would be found on the surface for a single-valued coordinate system, can lead to conceptual discomfort and questions of mathematical legitimacy. In the present talk we show that treatments using multiple-valued coordinate systems simply represent one scheme for applying the appropriate quantum mechanical boundary conditions to Schrödinger's equation defined in a single-valued coordinate system. The demonstration is not general, but rather focusses on the specific example of a non-linear electronic state of C_2H_2 and on the two-fold and eight-fold extended permutation-inversion groups recently introduced to treat simultaneously symmetry questions in trans-bent and cis-bent acetylene. Some discussion of the mathematical convenience lost by insisting on using a single-valued coordinate system will also be presented.

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

    PubMed

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

    2002-10-01

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

  3. 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)

  4. Satellite observations of ethylene

    NASA Astrophysics Data System (ADS)

    Dolan, W.; Payne, V.; Kulawik, S. S.; Bowman, K. W.

    2015-12-01

    Ethylene (C2H4) is a trace gas commonly associated with boreal fire plumes and the petrochemical industry. It has a short lifetime (~1-2 days) in the troposphere due to its reaction with OH. Chemical destruction of ethylene in the atmosphere leads to the production of ozone precursors such as carbon monoxide (CO) and formaldehyde. The Tropospheric Emission Spectrometer (TES) is a Fourier Transform Spectrometer aboard the Aura satellite that measures thermal infrared radiances with high spectral resolution. Trace gas products retrieved routinely from TES spectra include O3, CO, H2O, HDO, CH4, NH3, HCOOH, CH3OH, with OCS and PAN to be included in the next data release. The TES spectra also includes a wealth of untapped information about other trace gasses including ethylene. Ethylene was first observed in TES spectra by Alvarado et al. (2011), though it has yet to be developed into an operational product. Our study focuses on the detection and initial quantitative estimates of ethylene in TES special observations taken in support of the 2008 ARCTAS mission. Initial observations of HCN in the spectra may provide a way to distinguish between fire plume and petrochemical derived ethylene. Results indicate a correlation between ethylene and CO in fresh fire plumes but not in older plumes, consistent with the gas's short lifetime. The approach adopted here to detect ethylene in the TES 2008 ARCTAS special observations can easily be expanded to larger datasets, including those from other thermal infrared sounders as well as to other trace gases.

  5. 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.

  6. Inspecting an ethylene pipe line

    SciTech Connect

    Ramsvig, D.M. ); Duncan, J.; Zillinger, L. )

    1991-07-01

    This paper reports on the Alberta Gas Ethylene Co. (AGEC), completion of intensive internal cleaning and inspection program on their 112-mi ethylene pipe line. AGEC operates two ethylene manufacturing facilities in central Alberta, Canada. The ethylene plants are located 12.4 mi east of Red Deer, Alta., at Joffre, and supply two customers in Joffre. The remaining ethylene is shipped by the 112-mi, 12-in. line to a storage cavern near Edmonton.

  7. Enhanced Photoluminescence in Acetylene-Treated ZnO Nanorods.

    PubMed

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

    2016-12-01

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

  8. 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.

  9. Enhanced Photoluminescence in Acetylene-Treated ZnO Nanorods

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  10. Enhanced Photoluminescence in Acetylene-Treated ZnO Nanorods.

    PubMed

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

    2016-12-01

    Zinc oxide (ZnO) nanorods were manufactured using the aqueous chemical growth (ACG) method, and the effect of thermal acetylene treatment on their morphology, chemical composition, and optical properties was investigated. Changes in the elemental content of the treated rods were found to be different than in previous reports, possibly due to the different defect concentrations in the samples, highlighting the importance of synthesis method selection for the process. Acetylene treatment resulted in a significant improvement of the ultraviolet photoluminescence of the rods. The greatest increase in emission intensity was recorded on ZnO rods treated at the temperature of 825 °C. The findings imply that the changes brought on by the treatment are limited to the surface of the ZnO rods. PMID:27644239

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

    PubMed

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

    2014-12-28

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

  12. 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

  13. 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.

  14. 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

  15. 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.

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

    SciTech Connect

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

    2009-07-01

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

  17. 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

  18. 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

  19. 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.

  20. Limitation of Acetylene Reduction (Nitrogen Fixation) by Photosynthesis in Soybean Having Low Water Potentials 1

    PubMed Central

    Huang, Chi-Ying; Boyer, John S.; Vanderhoef, Larry N.

    1975-01-01

    The role of photosynthesis and transpiration in the desiccation-induced inhibition of acetylene reduction (nitrogen fixation) was investigated in soybean (Glycine max [L.] Merr. var. Beeson) using an apparatus that permitted simultaneous measurements of acetylene reduction, net photosynthesis, and transpiration. The inhibition of acetylene reduction caused by low water potentials and their aftereffects could be reproduced by depriving shoots of atmospheric CO2 even though the soil remained at water potentials that should have favored rapid acetylene reduction. The inhibition of acetylene reduction at low water potentials could be partially reversed by exposing the shoots to high CO2 concentrations. When transpiration was varied independently of photosynthesis and dark respiration in plants having high water potentials, no effects on acetylene reduction could be observed. There was no correlation between transpiration and acetylene reduction in the CO2 experiments. Therefore, the correlation that was observed between transpiration and acetylene reduction during desiccation was fortuitous. We conclude that the inhibition of shoot photosynthesis accounted for the inhibition of nodule acetylene reduction at low water potentials. PMID:16659277

  1. 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

  2. Transmission filter for the extreme ultraviolet spectral region composed of a thin Saran (C2H2Cl2) foil

    NASA Astrophysics Data System (ADS)

    Seely, John F.; Shirey, L.; Kingman, A.

    1989-05-01

    Saran foils of 4000-A thickness have been fabricated and used as transmission filters in the extreme ultraviolet spectral region. The transmittances of the Saran foils were determined for the 20-620-A wavelength region. The foils transmitted radiation with wavelengths between the L absorption edge of chlorine at 61.4 and about 120 A.

  3. 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

  4. 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.

  5. 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.

  6. Assay of the deuterium enrichment of water via acetylene.

    PubMed

    Previs, S F; Hazey, J W; Diraison, F; Beylot, M; David, F; Brunengraber, H

    1996-06-01

    A technique is presented for measuring the 2H enrichment of water in biological samples when this enrichment is greater than 0.2%. The sample is reacted with calcium carbide to form acetylene gas, which is determined by gas chromatography electron impact ionization mass spectrometry. Ion-molecule reactions, resulting in proton abstraction, are minimized by lowering the electron ionization energy from the usual 70 eV to 45 eV. This technique is much more rapid and economical than the classical isotope ratio mass spectrometric assay of the enrichment of hydrogen gas derived from reduction of water.

  7. [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.

  8. 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

  9. Quantification and removal of some contaminating gases from acetylene used to study gas-utilizing enzymes and microorganisms.

    PubMed

    Hyman, M R; Arp, D J

    1987-02-01

    Acetylene generated from various grades of calcium carbide and obtained from commercial- and purified-grade acetylene cylinders was shown to contain high concentrations of various contaminants. Dependent on the source of acetylene, these included, at maximal values, H(2) (0.023%), O(2) (0.779%), N(2) (3.78%), PH(3) (0.06%), CH(4) (0.073%), and acetone (1 to 10%). The concentration of the contaminants in cylinder acetylene was highly dependent on the extent of cylinder discharge. Several conventional methods used to partially purify cylinder acetylene were compared. A small-scale method for extensively purifying acetylene is described. An effect of acetylene quality on acetylene reduction assays conducted with purified nitrogenase from Azotobacter vinelandii was demonstrated.

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

    PubMed Central

    Hyman, Michael R.; Arp, Daniel J.

    1987-01-01

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

  11. 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.

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

    Code of Federal Regulations, 2011 CFR

    2011-10-01

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

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

    Code of Federal Regulations, 2010 CFR

    2010-10-01

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

  14. 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.

  15. Organogermanium Chemistry: Germacyclobutanes and digermane Additions to Acetylenes

    SciTech Connect

    Andrew Michael Chubb

    2003-12-12

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

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. Abiotic reductive dechlorination of chlorinated ethylenes by iron-bearing soil minerals. 2. Green rust.

    PubMed

    Lee, Woojin; Batchelor, Bill

    2002-12-15

    Abiotic reductive dechlorination of chlorinated ethylenes by the sulfate form of green rust (GR(SO4)) was examined in batch reactors. Dechlorination kinetics were described by a modified Langmuir-Hinshelwood model. The rate constant for reductive dechlorination of chlorinated ethylenes at reactive GR(SO4) surfaces was in the range of 0.592 (+/-4.4%) to 1.59 (+/-6.3%) day(-1). The specific reductive capacity of GR(SO4) for target organics was in the range of 9.86 (+/-10.1%) to 18.0 (+/-4.3%) microM/g and sorption coefficient was in the range of 0.53 (+/-2.4%) to 1.22 (+/-4.3%) mM(-1). Surface area-normalized pseudo-first-order initial rate constants for chlorinated ethylenes by GR(SO4) were 3.4 to 8.2 times greater than those by pyrite. Chlorinated ethylenes were mainly transformed to acetylene, and no detectable amounts of chlorinated intermediates were observed. The rate constants for the reductive dechlorination of trichloroethylene (TCE) increased as pH increased (6.8 to 10.1) but were independent of solid concentration and initial TCE concentration. Magnetite and/or maghemite were produced by the oxidation of GR(SO4) by TCE. These findings are relevant to the understanding of the role of abiotic reductive dechlorination during natural attenuation in environments that contain GR(SO4).

  1. 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.

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

    USGS Publications Warehouse

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

    2008-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Oremland, Ronald S.; Voytek, Mary A.

    2008-02-01

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

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

    PubMed

    Oremland, Ronald S; Voytek, Mary A

    2008-02-01

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

  5. 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

  6. Characterization of nitrogen-fixing bacteria from a temperate saltmarsh lagoon, including isolates that produce ethane from acetylene.

    PubMed

    Tibbles, B J; Rawlings, D E

    1994-01-01

    Nitrogen-fixing bacteria were isolated from sediments and water of a saltmarsh lagoon on the west coast of South Africa, and characterized according to factors that regulate nitrogen fixation in the marine environment. The majority of isolates were assigned to the Photobacterium or Vibrio genera on the basis of physiological and biochemical characteristics. One isolate was further assigned to the species Vibrio diazotrophicus. Carbohydrate utilization by each diazotrophic isolate was examined. Abilities of the isolates to utilize a range of mono-, di-, and polysaccharides largely reflected the predicted availability of organic carbon and energy in the lagoon, except that chitin was not utilized. Biochemical tests on the utilization of combined nitrogen showed that one isolate could utilize nitrate, and that this strain was susceptible to full repression of nitrogenase activity by 10mM nitrate. Urease activity was not detected in any of the isolates. In the absence of molybdenum two of the isolates, a Photobacterium spp. and V. diazotrophicus, reduced acetylene to ethylene and ethane, a property frequently associated with the activity of alternative nitrogenases. Addition of 25µM molybdenum inhibited ethane production by V. diazotrophicus, but stimulated ethylene and ethane production by the Photobacterium isolate. Addition of 28µM vanadium did not appear to regulate ethane production by either strain. Assays of nitrogenase activity in sediments from which some isolates were obtained indicated that molybdenum was not limiting nitrogenase activity at naturally-occurring concentrations. Southern hybridizations of the chromosomes of these strains with the anfH and vnfH genes of Azotobacter vinelandii and the nifH gene of Klebsiella pneumoniae indicated the presence of only one nitrogenase in these isolates.

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

    USGS Publications Warehouse

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

    1988-01-01

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

  8. The Coupled Photochemistry of Ammonia and Acetylene: Applications to the Atmospheric Chemistry on Jupiter

    NASA Astrophysics Data System (ADS)

    Keane, Thomas Christopher

    1995-01-01

    The existence of hydrogen cyanide (HCN) in the highly reducing atmosphere of Jupiter was a surprising discovery (Tokunaga et al., 1981). Previous studies that tested the theoretical proposal of Kaye and Strobel (1983a) that the HCN observed on Jupiter is the result of NH _3 photolysis in the presence of C _2H_2 established that acetonitrile (CH_3CN) and acetaldazine (CH _3CH=NN=CHCH_3) are important intermediates in HCN formation (Ferris and Ishikawa, 1988). In this study the rates of formation of these compounds, and of other recently detected intermediates, have been determined in static photolysis experiments at 296 K and at temperatures which are closer to those found in the Jovian atmosphere. Experiments were also performed, using a photochemical flow reactor, that allowed for a better approximation of the mixing ratios of reactant gases (8 times 10^{ -4} for NH_3 and 1 times 10^{-5} for C_2H_2) and the process of advection in the Jovian atmosphere. An overall reaction pathway for HCN formation is proposed. Major intermediates and products found in these laboratory simulations that have not yet been observed on Jupiter are acetonitrile (CH_3CN), acetaldazine (CH_3CH=NN=CHCH _3), acetaldehyde hydrazone (CH_3 CH=NNH_2), N-ethylethylideneimine (CH_3CH=NC_2H _5), ethylamine (C_2H _5NH_2) and methylamine (CH _3NH_2). HCN is formed by the photolysis of NH_3/C _2H_2 mixtures (40:5 torr) at 296 K and at low temperature (208 K, 195 K and 180 K) with the highest quantum efficiency for HCN formation observed at 180 K. In static experiments using a high partial pressure of H_2 the quantum yield for HCN formation decreased three-fold relative to the 296 K photolyses when no H_2 was used. An additional ten-fold decrease in the quantum yield for HCN formation occurred when using the flow system. The quantum yields for acetaldazine and acetaldehyde hydrazone formation were found to vary inversely to that for HCN formation. For those static experiments which best simulate

  9. 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.

  10. 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.

  11. 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

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

    NASA Technical Reports Server (NTRS)

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

    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.

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

    SciTech Connect

    Meyer, M.K.

    1991-12-20

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

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    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.

  16. 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

  17. [Crystalluria in ethylene glycol intoxication].

    PubMed

    Montagnac, Richard; Thouvenin, Maxime; Luxey, Grégoire; Schendel, Adeline; Parent, Xavier

    2014-11-01

    When seen, some habits of calcium oxalate monohydrate crystals (whewellite) are so typical of ethylene glycol intoxication that they may be helpful for its diagnosis when circumstances are not clearly established.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene.

    PubMed

    Taylor, P H; Wehrmeier, A; Sidhu, S S; Lenoir, D; Schramm, K W; Kettrup, A

    2000-06-01

    The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C2 through C8 organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene. PMID:10789968

  3. Vibrational characterization of ethylene adsorption and its thermal evolution on Si(001)-(2 x 1): identification of majority and minority species.

    PubMed

    Kostov, Krassimir L; Nathaniel, Rachel; Mineva, Tzonka; Widdra, Wolf

    2010-08-01

    The vibrational and structural properties of a single-domain Si(001)-(2 x 1) surface upon ethylene adsorption have been studied by density functional cluster calculations and high-resolution electron energy loss spectroscopy. The detailed analysis of the theoretically and the experimentally determined vibrational frequencies reveals two coexisting adsorbate configurations. The majority species consist of ethylene molecules which are di-sigma bonded to the two Si atoms of a single Si-Si dimer. The local symmetry of this adsorption complex is reduced to C(2) for ethylene saturation coverage as determined by surface selection rules for the vibrational excitation process. The symmetry reduction includes the rotation of the C-C bond around the surface normal and the twist of the methylene groups around the C-C axis. Experimentally, 17 ethylene-derived modes are found and assigned for the majority and the minority species based on a comparison with calculated vibrational frequencies. The minority species which can account up to 14% of the total ethylene coverage is spectroscopically identified for the first time. It is assigned to ethylene molecules di-sigma bonded to two adjacent Si-Si dimers (in an end-bridge configuration). One part of the minority species desorbs molecularly at 665 K, about 50 K higher than the majority species, whereas the remaining part dissociates to adsorbed acetylene at temperatures around 630 K. For the latter, a di-sigma end-bridge like bonding configuration is proposed based on a comparison with vibrational data for adsorbed acetylene on Si(100)-(2 x 1).

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. 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.

  9. 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

  10. The Anharmonic Force Field of Ethylene, C2H4, by Means of Accurate Ab Initio Calculations

    NASA Technical Reports Server (NTRS)

    Martin, Jan M. L.; Lee, Timothy J.; Taylor, Peter R.; Francois, Jean-Pierre; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    The quartic force field of ethylene, C2H4, has been calculated ab initio using augmented coupled cluster, CCSD(T), methods and correlation consistent basis sets of spdf quality. For the C-12 isotopomers C2H4, C2H3D, H2CCD2, cis-C2H2D2, trans-C2H2D2, C2HD3, and C2D4, all fundamentals could be reproduced to better than 10 per centimeter, except for three cases of severe Fermi type 1 resonance. The problem with these three bands is identified as a systematic overestimate of the Kiij Fermi resonance constants by a factor of two or more; if this is corrected for, the predicted fundamentals come into excellent agreement with experiment. No such systematic overestimate is seen for Fermi type 2 resonances. Our computed harmonic frequencies suggest a thorough revision of the accepted experimentally derived values. Our computed and empirically corrected re geometry differs substantially from experimentally derived values: both the predicted rz geometry and the ground-state rotational constants are, however, in excellent agreement with experiment, suggesting revision of the older values. Anharmonicity constants agree well with experiment for stretches, but differ substantially for stretch-bend interaction constants, due to equality constraints in the experimental analysis that do not hold. Improved criteria for detecting Fermi and Coriolis resonances are proposed and found to work well, contrary to the established method based on harmonic frequency differences that fails to detect several important resonances for C2H4 and its isotopomers. Surprisingly good results are obtained with a small spd basis at the CCSD(T) level. The well-documented strong basis set effect on the v8 out-of-plane motion is present to a much lesser extent when correlation-optimized polarization functions are used. Complete sets of anharmonic, rovibrational coupling, and centrifugal distortion constants for the isotopomers are available as supplementary material to the paper.

  11. 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

  12. 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

  13. Quantum Dynamics of Vinylidene Photodetachment on an Accurate Global Acetylene-Vinylidene Potential Energy Surface.

    PubMed

    Guo, Lifen; Han, Huixian; Ma, Jianyi; Guo, Hua

    2015-08-01

    Vinylidene is a high-energy isomer of acetylene, and the rearrangement of bonds in the two species serves as a prototype for isomerization reactions. Here, a full-dimensional quantum mechanical study of the vinylidene vibration is carried out on a recently developed global acetylene-vinylidene potential energy surface by simulating the photodetachment dynamics of the vinylidene anion. Several low-lying vibrational levels of the anion were first determined on a new ab initio based potential energy surface, and their photoelectron spectra were obtained within the Condon approximation. The vibrational features of the vinylidene isomer are found to agree well with the experiment in both positions and intensities, validating the global acetylene-vinylidene potential energy surface.

  14. 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.

  15. 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.

  16. 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.

  17. Volatilization of ethylene dibromide from water

    USGS Publications Warehouse

    Rathbun, R.E.; Tai, D.Y.

    1987-01-01

    Overall mass-transfer coefficients for the volatilization of ethylene dibromide from water were measured simultaneously with the oxygen absorption coefficient in a laboratory stirred tank. Coefficients were measured as a function of mixing conditions in the water for two windspeeds. The ethylene dibromide mass-transfer coefficient depended on windspeed; the ethylene dibromide liquid-film coefficient did not, in agreement with theory. A constant relation existed between the liquid-film coefficients for ethylene dibromide and oxygen.

  18. 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.

  19. Synthesis of micro- and nanodiamonds by the method of oxy- acetylene combustion flame

    NASA Astrophysics Data System (ADS)

    Sabitov, S.; Mansurov, B.; Medyanova, B.; Partizan, G.; Koshanova, A.; Merkibayev, Ye; Mansurova, M.; Lesbayev, B.

    2016-08-01

    This work presents the results of experiments on synthesis of micro- and nanodiamonds by the method of oxy-acetylene torch on the surface of pre-deposited copper thin films. The influence of the thickness of the buffer copper film and the concentration ratio of oxygen and acetylene on the structure formation of the deposited samples was investigated during performed experiments. Studies by Raman scattering and scanning electron microscopy showed that the synthesis of micro- and nano-diamonds occurs under certain experimental conditions.

  20. 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.

  1. Application of an oxygen-shielded air-acetylene flame to atomic spectroscopy.

    PubMed

    Stephens, R

    1973-08-01

    A burner has been designed which provides an oxygen-shielded air-acetylene flame for atomic-absorption work. The chemical reducing properties of the oxygen-shielded flame operated under fuel-rich conditions are enhanced by the higher C: O ratio obtainable in the flame and by the higher flame temperature just above the reaction zone. The flame is inherently essentially free from the risk of flashback, and is offered as an alternative to the nitrous oxide-acetylene flame for use with certain types of equipment and for particular applications.

  2. 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

  3. 46 CFR 154.1725 - Ethylene oxide.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Ethylene oxide. 154.1725 Section 154.1725 Shipping COAST....1725 Ethylene oxide. (a) A vessel carrying ethylene oxide must: (1) Have cargo piping, vent piping, and... asbestos, rubber, or cast iron components in the cargo containment system and piping; (6) Not have...

  4. 46 CFR 154.1725 - Ethylene oxide.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Ethylene oxide. 154.1725 Section 154.1725 Shipping COAST....1725 Ethylene oxide. (a) A vessel carrying ethylene oxide must: (1) Have cargo piping, vent piping, and... asbestos, rubber, or cast iron components in the cargo containment system and piping; (6) Not have...

  5. 46 CFR 154.1725 - Ethylene oxide.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Ethylene oxide. 154.1725 Section 154.1725 Shipping COAST....1725 Ethylene oxide. (a) A vessel carrying ethylene oxide must: (1) Have cargo piping, vent piping, and... asbestos, rubber, or cast iron components in the cargo containment system and piping; (6) Not have...

  6. 46 CFR 154.1725 - Ethylene oxide.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Ethylene oxide. 154.1725 Section 154.1725 Shipping COAST....1725 Ethylene oxide. (a) A vessel carrying ethylene oxide must: (1) Have cargo piping, vent piping, and... asbestos, rubber, or cast iron components in the cargo containment system and piping; (6) Not have...

  7. 46 CFR 154.1725 - Ethylene oxide.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Ethylene oxide. 154.1725 Section 154.1725 Shipping COAST....1725 Ethylene oxide. (a) A vessel carrying ethylene oxide must: (1) Have cargo piping, vent piping, and... asbestos, rubber, or cast iron components in the cargo containment system and piping; (6) Not have...

  8. 21 CFR 573.440 - Ethylene dichloride.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive Listing § 573.440 Ethylene dichloride. The food additive ethylene dichloride may be safely used in... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Ethylene dichloride. 573.440 Section 573.440...

  9. 21 CFR 573.440 - Ethylene dichloride.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive Listing § 573.440 Ethylene dichloride. The food additive ethylene dichloride may be safely used in... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Ethylene dichloride. 573.440 Section 573.440...

  10. 21 CFR 573.440 - Ethylene dichloride.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive Listing § 573.440 Ethylene dichloride. The food additive ethylene dichloride may be safely used in... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Ethylene dichloride. 573.440 Section 573.440...

  11. 21 CFR 573.440 - Ethylene dichloride.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive Listing § 573.440 Ethylene dichloride. The food additive ethylene dichloride may be safely used in... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Ethylene dichloride. 573.440 Section 573.440...

  12. 21 CFR 573.440 - Ethylene dichloride.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive Listing § 573.440 Ethylene dichloride. The food additive ethylene dichloride may be safely used in... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Ethylene dichloride. 573.440 Section 573.440...

  13. 21 CFR 173.230 - Ethylene dichloride.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ethylene dichloride. 173.230 Section 173.230 Food... Solvents, Lubricants, Release Agents and Related Substances § 173.230 Ethylene dichloride. A tolerance of 30 parts per million is established for ethylene dichloride in spice oleoresins when present...

  14. 21 CFR 173.230 - Ethylene dichloride.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene dichloride. 173.230 Section 173.230 Food... Solvents, Lubricants, Release Agents and Related Substances § 173.230 Ethylene dichloride. A tolerance of 30 parts per million is established for ethylene dichloride in spice oleoresins when present...

  15. 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...

  16. 21 CFR 173.230 - Ethylene dichloride.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ethylene dichloride. 173.230 Section 173.230 Food... Solvents, Lubricants, Release Agents and Related Substances § 173.230 Ethylene dichloride. A tolerance of 30 parts per million is established for ethylene dichloride in spice oleoresins when present...

  17. 21 CFR 173.230 - Ethylene dichloride.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Ethylene dichloride. 173.230 Section 173.230 Food... Related Substances § 173.230 Ethylene dichloride. A tolerance of 30 parts per million is established for ethylene dichloride in spice oleoresins when present therein as a residue from the extraction of...

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  19. Stimulation of lettuce seed germination by ethylene.

    PubMed

    Abeles, F B; Lonski, J

    1969-02-01

    Ethylene increased the germination of freshly imbibed lettuce (Lactuca sativa L. var. Grand Rapids) seeds. Seeds receiving either red or far-red light or darkness all showed a positive response to the gas. However, ethylene was apparently without effect on dormant seeds, those which failed to germinate after an initial red or far-red treatment. Carbon dioxide, which often acts as a competitive inhibitor of ethylene, failed to clearly reverse ethylene-enhanced seed germination. While light doubled ethylene production from the lettuce seeds, its effect was not mediated by the phytochrome system since both red and far-red light had a similar effect.

  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. 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...

  2. 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…

  3. Technical opportunities for converting natural gas to acetylene-based chemicals

    SciTech Connect

    Cooke, N.E.; Ashraf, F.A.; Divanji, H.

    1987-01-01

    Canada has abundant natural gas and in some provinces such as Quebec, cheap and surplus electricity is also available. A techno-economic study has been carried out which indicates that it is economically attractive to manufacture acetylene via the electric-arc process from natural gas and electricity at the cost of raw materials prevailing at present in the Province of Quebec, Canada.

  4. 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

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

    PubMed

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

    2010-12-28

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

  6. Energy conservation in ethylene production

    SciTech Connect

    Kobayashi, N.

    1983-10-01

    The petrochemical industry is one of the most important industries and is of critical importance to the steel industry, petroleum refining industry and other heavy-and-chemical industries. These heavy-andchemical industries are the basis of the driving and growing force of the Japanese economic progress. And these industries consume a large amount of material and energy. Last year, the Chiba Plant won a commendation for being an excellent energy-controlling plant by the Chief of Resources and Energy Office. It was the first commendation among the many ethylene units. In light of this, the authors have prepared a review of the efforts in the field of saving energy in ethylene unit.

  7. 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

  8. Dimerize ethylene to butene-1

    SciTech Connect

    Commereuc, D.; Andrews, J.; Chauvin, Y.; Gillard, J.; Leonard, J.

    1984-11-01

    Institut Francais du Petrole (IFP) has developed a new process, Alphabutol, to dimerize selectively ethylene to butene-1. The Alphabutol process uses a homogeneous catalyst which means that reactants, products and catalyst are all soluble in the same liquid phase. The new catalytic system used in the Alphabutol process avoids isomerization of butene-1 to butene-2. Therefore, there is no need for product superfractionation.

  9. 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

  10. Ethylene enhances water transport in hypoxic aspen.

    PubMed

    Kamaluddin, Mohammed; Zwiazek, Janusz J

    2002-03-01

    Water transport was examined in solution culture grown seedlings of aspen (Populus tremuloides) after short-term exposures of roots to exogenous ethylene. Ethylene significantly increased stomatal conductance, root hydraulic conductivity (L(p)), and root oxygen uptake in hypoxic seedlings. Aerated roots that were exposed to ethylene also showed enhanced L(p). An ethylene action inhibitor, silver thiosulphate, significantly reversed the enhancement of L(p) by ethylene. A short-term exposure of excised roots to ethylene significantly enhanced the root water flow (Q(v)), measured by pressurizing the roots at 0.3 MPa. The Q(v) values in ethylene-treated roots declined significantly when 50 microM HgCl(2) was added to the root medium and this decline was reversed by the addition of 20 mM 2-mercaptoethanol. The results suggest that the response of Q(v) to ethylene involves mercury-sensitive water channels and that root-absorbed ethylene enhanced water permeation through roots, resulting in an increase in root water transport and stomatal opening in hypoxic seedlings.

  11. 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...

  12. Ethylene Regulates Levels of Ethylene Receptor/CTR1 Signaling Complexes in Arabidopsis thaliana.

    PubMed

    Shakeel, Samina N; Gao, Zhiyong; Amir, Madiha; Chen, Yi-Feng; Rai, Muneeza Iqbal; Haq, Noor Ul; Schaller, G Eric

    2015-05-01

    The plant hormone ethylene is perceived by a five-member family of receptors in Arabidopsis thaliana. The receptors function in conjunction with the Raf-like kinase CTR1 to negatively regulate ethylene signal transduction. CTR1 interacts with multiple members of the receptor family based on co-purification analysis, interacting more strongly with receptors containing a receiver domain. Levels of membrane-associated CTR1 vary in response to ethylene, doing so in a post-transcriptional manner that correlates with ethylene-mediated changes in levels of the ethylene receptors ERS1, ERS2, EIN4, and ETR2. Interactions between CTR1 and the receptor ETR1 protect ETR1 from ethylene-induced turnover. Kinetic and dose-response analyses support a model in which two opposing factors control levels of the ethylene receptor/CTR1 complexes. Ethylene stimulates the production of new complexes largely through transcriptional induction of the receptors. However, ethylene also induces turnover of receptors, such that levels of ethylene receptor/CTR1 complexes decrease at higher ethylene concentrations. Implications of this model for ethylene signaling are discussed.

  13. 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.

  14. Biocatalytic conversion of ethylene to ethylene oxide using an engineered toluene monooxygenase.

    PubMed

    Carlin, D A; Bertolani, S J; Siegel, J B

    2015-02-11

    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.

  15. 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.

  16. 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.

  17. 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.)

  18. Coherent-states dynamics of the H + + C 2H 2 reaction at ELab = 30 eV: A complete electron nuclear dynamics investigation

    NASA Astrophysics Data System (ADS)

    Morales, Jorge A.; Maiti, Buddhadev; Yan, Yunan; Tsereteli, Kakha; Laraque, Jennifer; Addepalli, Srirangam; Myers, Chris

    2005-10-01

    Preliminary results of an exhaustive study of H + + HC tbnd CH at ELab = 30 eV within the electron nuclear dynamics (END) and coherent state dynamics (CSD) theories are herein presented. Current END-CSD method employs frozen Gaussian wave packets in the semiclassical limit of ℏ → 0 for the nuclei and a single-determinantal Thouless coherent state (CS) for the electrons. The simulated 6800 trajectories from 68 independent HC tbnd CH target orientations provide a definite description of all the reactive processes, including H 2 formation and charge transfers. Differential and integral cross-sections are evaluated via a novel CS S-matrix formulation in conjunction with semiclassical techniques. Calculated cross-sections show a good agreement with both experimental and previous END results.

  19. 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.

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

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.; Taylor, Peter R.

    1995-01-01

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

  1. Carbide sludge management in acetylene producing plants by using vacuum filtration.

    PubMed

    Ramasamy, Palanisamy; Periathamby, Agamuthu; Ibrahim, Shaliza

    2002-12-01

    Carbide sludge (10.4-11.5 tonnes day(-1)) is generated from the reaction of calcium carbide (900 kg) and water (6,000 L) in the production of acetylene (2,400 m3), in three selected acetylene manufacturing plants. The sludge (of pH 12.2 and containing Cu, Pb, Fe, Mn, Ni and Zn ions whose concentrations exceed the Department of Environment limits for industrial wastewater) was treated by vacuum filtration as a substitute for the ponding system, which is environmentally less acceptable. A similar system by flocculation was also developed. The filtration system represents an improvement over the ponding method, as shown by a pH of 7 for the clear filtrate; the solid cake, which contains 98% of the metals, can be conveniently disposed at an integrated scheduled waste treatment centre.

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

    DOE PAGES

    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

  3. Theoretical and Experimental Evidence of Hydrogen Migration rather than Isomerization in the Acetylene Dication

    NASA Astrophysics Data System (ADS)

    Liekhus-Schmaltz, Chelsea; Li, Zheng; Petrovic, Vladimir; Martinez, Todd; Bucksbaum, Phil; AMO75113 Collaboration

    2016-05-01

    Theoretical calculations and experimental results in the acetylene dication have long agreed that isomerization after x-ray excitation occurs in the first singlet state, where the carbon-carbon bond lives long enough for isomerization to complete. These same calculations predict that a large barrier to isomerization exists that would cause isomerization to occur in about a picosecond, while there is some evidence for ultrafast isomerization in under 100 fs. However, new ab initio calculations of the acetylene dication reveal that ultrafast isomerization after x-ray excitation is unlikely. In this talk, we present evidence that signatures of hydrogen migration observed in recent time resolved LCLS data are mostly due to hydrogen migration in an excited state which dissociates too quickly for isomerization to complete. This material is based upon work supported by the National Science Foundation under Grant No. PHY-0649578.

  4. Groundwater remediation engineering sparging using acetylene--study on the flow distribution of air.

    PubMed

    Zheng, Yan-Mei; Zhang, Ying; Huang, Guo-Qiang; Jiang, Bin; Li, Xin-Gang

    2005-01-01

    Air sparging (AS) is an emerging method to remove VOCs from saturated soils and groundwater. Air sparging performance highly depends on the air distribution resulting in the aquifer. In order to study gas flow characterization, a two-dimensional experimental chamber was designed and installed. In addition, the method by using acetylene as the tracer to directly image the gas distribution results of AS process has been put forward. Experiments were performed with different injected gas flow rates. The gas flow patterns were found to depend significantly on the injected gas flow rate, and the characterization of gas flow distributions in porous media was very different from the acetylene tracing study. Lower and higher gas flow rates generally yield more irregular in shape and less effective gas distributions.

  5. Control of the nucleation and quality of graphene grown by low-pressure chemical vapor deposition with acetylene

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    Although many studies have reported the chemical vapor deposition (CVD) growth of large-area monolayer graphene from methane, synthesis of graphene using acetylene as the source gas has not been fully explored. In this study, the low-pressure CVD (LPCVD) growth of graphene from acetylene was systematically investigated. We succeeded in regulating the domain size, defects density, layer number and the sheet resistance of graphene by changing the acetylene flow rates. Scanning electron microscopy and Raman spectroscopy were employed to confirm the layer number, uniformity and quality of the graphene films. It is found that a low flow rate of acetylene (0.28 sccm) is required to form high-quality monolayer graphene in our system. On the other hand, the high acetylene flow rate (7 sccm) will induce the growth of the bilayer graphene domains with high defects density. On the basis of selected area electron diffraction (SAED) pattern, the as-grown monolayer graphene domains were analyzed to be polycrystal. We also discussed the relation between the sheet resistacne and defects density in graphene. Our results provide great insights into the understanding of the CVD growth of monolayer and bilayer graphene from acetylene.

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

    SciTech Connect

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

    1996-12-31

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

  7. Phase-vanishing method with acetylene evolution and its utilization in several organic syntheses.

    PubMed

    Matake, Ryosuke; Niwa, Yuki; Matsubara, Hiroshi

    2015-05-15

    A novel quadraphasic phase-vanishing system in which acetylene is evolved from calcium carbide and directly applied in situ to the Sonogashira coupling reaction was developed. This method, which provides a safe, convenient, and one-pot means to utilize gaseous reagents without special equipment, was also applied to a Cu-catalyzed azide-alkyne cycloaddition (CuAAC) reaction and a three-component aldehyde-alkyne-amine (A(3)) coupling reaction with excellent results.

  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. Epigenetic modifier-induced biosynthesis of novel acetylenic sterols from Cladosporium colocasiae.

    PubMed

    Liu, Dong-Ze; Liang, Bo-Wen; Li, Xiao-Fei; Yu, Zhi-Yuan

    2014-09-01

    The addition of an HDAC inhibitor, suberoylanilide hydroxamic acid (SBHA), to the culture medium of Cladosporium colocasiae, dramatically altered its metabolic profiles. Analysis of the culture broth extract led to the isolation of two new acetylenic sterols (1-2). The isolated compounds were further evaluated for their cytotoxic and antibacterial activities. Compound 1 showed activity against Bacillus subtilis, affording a zone of inhibition of 12mm at 100μg/disk. However, none of them showed noticeable growth inhibitory effects.

  10. Genome-Wide Analysis of Ethylene-Responsive Element Binding Factor-Associated Amphiphilic Repression Motif-Containing Transcriptional Regulators in Arabidopsis1[W][OA

    PubMed Central

    Kagale, Sateesh; Links, Matthew G.; Rozwadowski, Kevin

    2010-01-01

    The ethylene-responsive element binding factor-associated amphiphilic repression (EAR) motif is a transcriptional regulatory motif identified in members of the ethylene-responsive element binding factor, C2H2, and auxin/indole-3-acetic acid families of transcriptional regulators. Sequence comparison of the core EAR motif sites from these proteins revealed two distinct conservation patterns: LxLxL and DLNxxP. Proteins containing these motifs play key roles in diverse biological functions by negatively regulating genes involved in developmental, hormonal, and stress signaling pathways. Through a genome-wide bioinformatics analysis, we have identified the complete repertoire of the EAR repressome in Arabidopsis (Arabidopsis thaliana) comprising 219 proteins belonging to 21 different transcriptional regulator families. Approximately 72% of these proteins contain a LxLxL type of EAR motif, 22% contain a DLNxxP type of EAR motif, and the remaining 6% have a motif where LxLxL and DLNxxP are overlapping. Published in vitro and in planta investigations support approximately 40% of these proteins functioning as negative regulators of gene expression. Comparative sequence analysis of EAR motif sites and adjoining regions has identified additional preferred residues and potential posttranslational modification sites that may influence the functionality of the EAR motif. Homology searches against protein databases of poplar (Populus trichocarpa), grapevine (Vitis vinifera), rice (Oryza sativa), and sorghum (Sorghum bicolor) revealed that the EAR motif is conserved across these diverse plant species. This genome-wide analysis represents the most extensive survey of EAR motif-containing proteins in Arabidopsis to date and provides a resource enabling investigations into their biological roles and the mechanism of EAR motif-mediated transcriptional regulation. PMID:20097792

  11. 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)

  12. 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

  13. Soot formation in pyrolysis of acetylene, allene and 1,3-butadiene

    NASA Technical Reports Server (NTRS)

    Frenklach, M.; Durgaprasad, M. B.; Matula, R. A.; Taki, S.

    1983-01-01

    The formation of soot behind reflected shock waves in argon-diluted mixtures of acetylene, allene, and 1,3-butadiene was investigated by monitoring the attenuation of a laser beam in both the visible (632.8 nm) and the infrared (3.39 microns) regions of the spectrum. The experiments utilized temperatures ranging from 1500-3100 K, reflected shock pressures of 0.3-7.0 bar, and total carbon atom concentrations of 2-20 x 10 to the 17th atoms/cu cm. A bell-shaped dependence of soot yield on temperature was observed during the pyrolysis of all three compounds, which was similar to that previously found for toluene. For acetylene, the decrese in total pressure was found to shift the soot bell to higher temperatures with a significant increase in the maximum soot yield. A computer simulation for acetylene pyrolysis suggested that the reactions between C2H3, C4H3, and C4H4 may be those which lead to the formation of aromatic structures. In addition, it was found that soot is formed much faster and in much larger quantities from allene than from 1,3-butadiene.

  14. 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

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

    SciTech Connect

    Han, Huixian; Li, Anyang; Guo, Hua

    2014-12-28

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

  16. 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.

  17. Effects of Ethylene on Auxin Transport 1

    PubMed Central

    Morgan, Page W.; Gausman, Harold W.

    1966-01-01

    The effect of ethylene on the uptake, distribution and polar transport of C14 from indole-3-acetic acid-2-C14 and naphthalene acetic acid-1-C14 in tissue sections was studied. Test species were cotton (Gossypium hirsutum, L.) and cowpea (Vigna sinensis, Endl.). Generally, incubation of tissue or intact plants with ethylene reduced the degree of polar auxin transport. Ethylene inhibited the movement of both auxins in stem tissue and IAA in petiole tissue of cotton. The effect of ethylene on auxin movement in cow-peas was more complex. Ethylene apparently inhibited transport in younger petiole and stem tissue, but stimulated the process to a small but significant degree in basal petiole segments. Ethylene, in some experiments, reduced C14 (auxin) uptake. This reduction was consistently smaller than the inhibition of transport. Effects upon transport were observed when uptake was not different. Differences in uptake declined as the period of incubation with auxin was lengthened, but transport was inhibited for up to 23 hours. It is proposed that ethylene may, through its effect on transport, cause localized shortages and surpluses of auxin which in turn contribute to symptoms now associated with the response of sensitive species to ethylene. PMID:16656230

  18. 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

  19. 49 CFR 173.323 - Ethylene oxide.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... ethylene oxide in non-bulk packagings, silver mercury or any of its alloys or copper may not be used in any... transportation, may come in contact with ethylene oxide liquid or vapor. Copper alloys may be used only where gas... following: (1) In hermetically sealed glass or metal inner packagings suitably cushioned in an outer...

  20. 49 CFR 173.323 - Ethylene oxide.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... ethylene oxide in non-bulk packagings, silver mercury or any of its alloys or copper may not be used in any... transportation, may come in contact with ethylene oxide liquid or vapor. Copper alloys may be used only where gas... following: (1) In hermetically sealed glass or metal inner packagings suitably cushioned in an outer...

  1. 29 CFR 1926.1147 - Ethylene oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 29 Labor 8 2014-07-01 2014-07-01 false Ethylene oxide. 1926.1147 Section 1926.1147 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... Ethylene oxide. Note: The requirements applicable to construction work under this section are identical...

  2. 29 CFR 1915.1047 - Ethylene oxide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 7 2010-07-01 2010-07-01 false Ethylene oxide. 1915.1047 Section 1915.1047 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1047 Ethylene oxide. Note: The requirements applicable to shipyard employment under this...

  3. 29 CFR 1915.1047 - Ethylene oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 29 Labor 7 2014-07-01 2014-07-01 false Ethylene oxide. 1915.1047 Section 1915.1047 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1047 Ethylene oxide. Note: The requirements applicable to shipyard employment under this...

  4. 29 CFR 1915.1047 - Ethylene oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 29 Labor 7 2013-07-01 2013-07-01 false Ethylene oxide. 1915.1047 Section 1915.1047 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1047 Ethylene oxide. Note: The requirements applicable to shipyard employment under this...

  5. 29 CFR 1926.1147 - Ethylene oxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 29 Labor 8 2012-07-01 2012-07-01 false Ethylene oxide. 1926.1147 Section 1926.1147 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... Ethylene oxide. Note: The requirements applicable to construction work under this section are identical...

  6. 29 CFR 1926.1147 - Ethylene oxide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 8 2010-07-01 2010-07-01 false Ethylene oxide. 1926.1147 Section 1926.1147 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... Ethylene oxide. Note: The requirements applicable to construction work under this section are identical...

  7. 29 CFR 1915.1047 - Ethylene oxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 29 Labor 7 2012-07-01 2012-07-01 false Ethylene oxide. 1915.1047 Section 1915.1047 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1047 Ethylene oxide. Note: The requirements applicable to shipyard employment under this...

  8. 29 CFR 1926.1147 - Ethylene oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 29 Labor 8 2013-07-01 2013-07-01 false Ethylene oxide. 1926.1147 Section 1926.1147 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... Ethylene oxide. Note: The requirements applicable to construction work under this section are identical...

  9. 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.

  10. Targeting Plant Ethylene Responses by Controlling Essential Protein-Protein Interactions in the Ethylene Pathway.

    PubMed

    Bisson, Melanie M A; Groth, Georg

    2015-08-01

    The gaseous plant hormone ethylene regulates many processes of high agronomic relevance throughout the life span of plants. A central element in ethylene signaling is the endoplasmic reticulum (ER)-localized membrane protein ethylene insensitive2 (EIN2). Recent studies indicate that in response to ethylene, the extra-membranous C-terminal end of EIN2 is proteolytically processed and translocated from the ER to the nucleus. Here, we report that the conserved nuclear localization signal (NLS) mediating nuclear import of the EIN2 C-terminus provides an important domain for complex formation with ethylene receptor ethylene response1 (ETR1). EIN2 lacking the NLS domain shows strongly reduced affinity for the receptor. Interaction of EIN2 and ETR1 is also blocked by a synthetic peptide of the NLS motif. The corresponding peptide substantially reduces ethylene responses in planta. Our results uncover a novel mechanism and type of inhibitor interfering with ethylene signal transduction and ethylene responses in plants. Disruption of essential protein-protein interactions in the ethylene signaling pathway as shown in our study for the EIN2-ETR1 complex has the potential to guide the development of innovative ethylene antagonists for modern agriculture and horticulture.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. Ethylene-Mediated Acclimations to Flooding Stress.

    PubMed

    Sasidharan, Rashmi; Voesenek, Laurentius A C J

    2015-09-01

    Flooding is detrimental for plants, primarily because of restricted gas exchange underwater, which leads to an energy and carbohydrate deficit. Impeded gas exchange also causes rapid accumulation of the volatile ethylene in all flooded plant cells. Although several internal changes in the plant can signal the flooded status, it is the pervasive and rapid accumulation of ethylene that makes it an early and reliable flooding signal. Not surprisingly, it is a major regulator of several flood-adaptive plant traits. Here, we discuss these major ethylene-mediated traits, their functional relevance, and the recent progress in identifying the molecular and signaling events underlying these traits downstream of ethylene. We also speculate on the role of ethylene in postsubmergence recovery and identify several questions for future investigations.

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

    NASA Astrophysics Data System (ADS)

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

    1996-02-01

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

  17. 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

  18. 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

  19. Expression of ethylene biosynthetic and receptor genes in rose floral tissues during ethylene-enhanced flower opening

    PubMed Central

    Xue, Jingqi; Li, Yunhui; Tan, Hui; Yang, Feng; Ma, Nan; Gao, Junping

    2008-01-01

    Ethylene production, as well as the expression of ethylene biosynthetic (Rh-ACS1–4 and Rh-ACO1) and receptor (Rh-ETR1–5) genes, was determined in five different floral tissues (sepals, petals, stamens, gynoecia, and receptacles) of cut rose (Rosa hybrida cv. Samantha upon treatment with ethylene or the ethylene inhibitor 1-methylcyclopropene (1-MCP). Ethylene-enhanced ethylene production occurred only in gynoecia, petals, and receptacles, with gynoecia showing the greatest enhancement in the early stage of ethylene treatment. However, 1-MCP did not suppress ethylene production in these three tissues. In sepals, ethylene production was highly decreased by ethylene treatment, and increased dramatically by 1-MCP. Ethylene production in stamens remained unchanged after ethylene or 1-MCP treatment. Induction of certain ethylene biosynthetic genes by ethylene in different floral tissues was positively correlated with the ethylene production, and this induction was also not suppressed by 1-MCP. The expression of Rh-ACS2 and Rh-ACS3 was quickly induced by ethylene in gynoecia, but neither Rh-ACS1 nor Rh-ACS4 was induced by ethylene in any of the five tissues. In addition, Rh-ACO1 was induced by ethylene in all floral tissues except sepals. The induced expression of ethylene receptor genes by ethylene was much faster in gynoecia than in petals, and the expression of Rh-ETR3 was strongly suppressed by 1-MCP in all floral tissues. These results indicate that ethylene biosynthesis in gynoecia is regulated developmentally, rather than autocatalytically. The response of rose flowers to ethylene occurs initially in gynoecia, and ethylene may regulate flower opening mainly through the Rh-ETR3 gene in gynoecia. PMID:18535299

  20. Expression of ethylene biosynthetic and receptor genes in rose floral tissues during ethylene-enhanced flower opening.

    PubMed

    Xue, Jingqi; Li, Yunhui; Tan, Hui; Yang, Feng; Ma, Nan; Gao, Junping

    2008-01-01

    Ethylene production, as well as the expression of ethylene biosynthetic (Rh-ACS1-4 and Rh-ACO1) and receptor (Rh-ETR1-5) genes, was determined in five different floral tissues (sepals, petals, stamens, gynoecia, and receptacles) of cut rose (Rosa hybrida cv. Samantha upon treatment with ethylene or the ethylene inhibitor 1-methylcyclopropene (1-MCP). Ethylene-enhanced ethylene production occurred only in gynoecia, petals, and receptacles, with gynoecia showing the greatest enhancement in the early stage of ethylene treatment. However, 1-MCP did not suppress ethylene production in these three tissues. In sepals, ethylene production was highly decreased by ethylene treatment, and increased dramatically by 1-MCP. Ethylene production in stamens remained unchanged after ethylene or 1-MCP treatment. Induction of certain ethylene biosynthetic genes by ethylene in different floral tissues was positively correlated with the ethylene production, and this induction was also not suppressed by 1-MCP. The expression of Rh-ACS2 and Rh-ACS3 was quickly induced by ethylene in gynoecia, but neither Rh-ACS1 nor Rh-ACS4 was induced by ethylene in any of the five tissues. In addition, Rh-ACO1 was induced by ethylene in all floral tissues except sepals. The induced expression of ethylene receptor genes by ethylene was much faster in gynoecia than in petals, and the expression of Rh-ETR3 was strongly suppressed by 1-MCP in all floral tissues. These results indicate that ethylene biosynthesis in gynoecia is regulated developmentally, rather than autocatalytically. The response of rose flowers to ethylene occurs initially in gynoecia, and ethylene may regulate flower opening mainly through the Rh-ETR3 gene in gynoecia.