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Sample records for acetylene intersystem crossing

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

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

    2009-02-24

    We report on an experimental approach that reveals crucial details of the composition of singlet-triplet mixed eigenstates in acetylene. Intersystem crossing in this prototypical polyatomic molecule embodies the mixing of the lowest excited singlet state (S(1)) with 3 triplet states (T(1), T(2), and T(3)). Using high-energy (157-nm) photons from an F(2) laser to record excited-state photoelectron spectra, we have decomposed the mixed eigenstates into their S(1), T(3), T(2), and T(1) constituent parts. One example of the interpretive power that ensues from the selective sensitivity of the experiment to the individual electronic state characters is the discovery and examination of destructive interference between two doorway-mediated intersystem crossing pathways. This observation of an interference effect in nonradiative decay opens up possibilities for rational coherent control over molecular excited state dynamics. PMID:19179288

  2. Internal Conversion vs. Intersystem Crossing – What Drives the Dynamics of Cyclic α,β-Enones?

    Riedle E.

    2013-03-01

    Full Text Available The origin of ultrafast intersystem crossing and its competitiveness with singlet pathways was studied in cyclic α,β-enones by transient absorption, time-resolved photoelectron spectroscopy and ab initio calculations.

  3. Nonadiabatic dynamics with intersystem crossings: A time-dependent density functional theory implementation

    Franco de Carvalho, F. [Centre Européen de Calcul Atomique et Moléculaire, Ecole Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Tavernelli, I. [IBM Research GmbH, Zurich Research Laboratory, 8803 Ruschlikon (Switzerland)

    2015-12-14

    In this work, we derive a method to perform trajectory-based nonadiabatic dynamics that is able to describe both nonadiabatic transitions and intersystem crossing events (transitions between states of different spin-multiplicity) at the same level of theory, namely, time-dependent density functional theory (TDDFT). To this end, we combined our previously developed TDDFT-based trajectory surface hopping scheme with an accurate and efficient algorithm for the calculation of the spin-orbit coupling (SOC) matrix elements. More specifically, we designed two algorithms for the calculation of intersystem crossing transitions, one based on an extended Tully’s surface hopping scheme including SOC and the second based on a Landau-Zener approximation applied to the spin sector of the electronic Hilbert space. This development allows for the design of an efficient on-the-fly nonadiabatic approach that can handle, on an equal footing, nonadiabatic and intersystem crossing transitions. The method is applied to the study of the photophysics of sulfur dioxide (SO{sub 2}) in gas and liquid phases.

  4. Nonadiabatic dynamics with intersystem crossings: A time-dependent density functional theory implementation

    In this work, we derive a method to perform trajectory-based nonadiabatic dynamics that is able to describe both nonadiabatic transitions and intersystem crossing events (transitions between states of different spin-multiplicity) at the same level of theory, namely, time-dependent density functional theory (TDDFT). To this end, we combined our previously developed TDDFT-based trajectory surface hopping scheme with an accurate and efficient algorithm for the calculation of the spin-orbit coupling (SOC) matrix elements. More specifically, we designed two algorithms for the calculation of intersystem crossing transitions, one based on an extended Tully’s surface hopping scheme including SOC and the second based on a Landau-Zener approximation applied to the spin sector of the electronic Hilbert space. This development allows for the design of an efficient on-the-fly nonadiabatic approach that can handle, on an equal footing, nonadiabatic and intersystem crossing transitions. The method is applied to the study of the photophysics of sulfur dioxide (SO2) in gas and liquid phases

  5. Intersystem Crossing Mechanisms and Single Molecule Fluorescence: Terrylene in Anthracene Crystals

    Single molecule spectroscopy requires molecules with low triplet yields and/or short triplet lifetimes. The intersystem crossing (ISC) rate may be dramatically enhanced by the host matrix. Comparing the fluorescence intensity of single terrylene molecules in para-terphenyl, naphthalene, and anthracene crystals, we found a reduction of the saturation intensity by three orders of magnitude in the latter case. The fluorescence autocorrelation function indicates that the bottleneck state is the terrylene triplet. We propose a ping-pong mechanism between host and guest. This intermolecular ISC mechanism, which can open whenever the host triplet lies lower than the guest singlet, was overlooked in previous single molecule investigations

  6. Direct observation of slow intersystem crossing in an aromatic ketone, fluorenone.

    Soep, Benoît; Mestdagh, Jean-Michel; Briant, Marc; Gaveau, Marc-André; Poisson, Lionel

    2016-08-17

    Direct measurements of Single vibronic Level InterSystem Crossing (SLISC) have been performed on the fluorenone molecule in the gas phase, by time resolved photoelectron and photoion spectroscopy. Vibronic transitions above the S1 nπ* origin were excited in the 432-420 nm region and the decay of S1 and growth of T1(3)ππ* could be observed within a 10 ns time domain. The ionization potential is measured as 8.33 ± 0.04 eV. The energy of the first excited triplet state of fluorenone, T1 has been characterized directly at 18 640 ± 250 cm(-1). The internal conversion of S1 to S0 is found to amount to ∼15% of the population decay, thus ISC is the dominant electronic relaxation process. ISC, although favored by the S1(1)nπ*-T1(3)ππ* coupling scheme, is 3 orders of magnitude less efficient than in the similar molecule benzophenone. Thus, the planarity of the fluorenone molecule disfavors the exploration of the configuration space where surface crossings would create high ISC probability, which occurs in benzophenone through surface crossings. The time evolution of S1 fluorenone is well accounted for by the statistical decay of individual levels into a quasi-continuum of T1 vibronic levels. PMID:27485671

  7. Internal conversion and intersystem crossing in α,β-enones: a combination of electronic structure calculations and dynamics simulations.

    Cao, Jun; Xie, Zhi-Zhong

    2016-03-01

    The ab initio electronic structure calculations and CASSCF-based nonadiabatic dynamics simulations have been used to investigate the internal conversion and intersystem crossing process of both trans-acrolein and 2-cyclopentenone in the gas phase. Our calculation results show that relaxation from the Franck-Condon region to an S1 minimum is ultrafast and that the S1 state will dominantly undergo intersystem crossing to triplet states due to the existence of significant barriers to access the S1/S0 intersection points and of energetically close-lying triplet states. The S1/T2/T1 three-state intersection is observed in our dynamics simulations to play an important role in the population of the lowest triplet state, which is consistent with previous suggestions. Although the evolution into triplet states involves a similar path and gives rise to a similar triplet quantum yield for these two molecules, the intersystem crossing rate of 2-cyclopentenone is lower owing to the ring constraint that results in a smaller spin-orbital coupling in the singlet-triplet crossing region. The present theoretical study reproduces the experimental results and gives an explanation about the structural factors that govern the excited-state decay of some types of α,β-enones. PMID:26882275

  8. Ab Initio Multiple Spawning Method for Intersystem Crossing Dynamics: Spin-Forbidden Transitions between (3)B1 and (1)A1 States of GeH2.

    Fedorov, Dmitry A; Pruitt, Spencer R; Keipert, Kristopher; Gordon, Mark S; Varganov, Sergey A

    2016-05-12

    Dynamics at intersystem crossings are fundamental to many processes in chemistry, physics, and biology. The ab initio multiple spawning (AIMS) method was originally developed to describe internal conversion dynamics at conical intersections where derivative coupling is responsible for nonadiabatic transitions between electronic states with the same spin multiplicity. Here, the applicability of the AIMS method is extended to intersystem crossing dynamics in which transitions between electronic states with different spin multiplicities are mediated by relativistic spin-orbit coupling. In the direct AIMS dynamics, the nuclear wave function is expanded in the basis of frozen multidimensional Gaussians propagating on the coupled electronic potential energy surfaces calculated on the fly. The AIMS method for intersystem crossing is used to describe the nonadiabatic transitions between the (3)B1 and (1)A1 states of GeH2. The potential energies and gradients were obtained at the CASSCF(6,6)/6-31G(d) level of theory. The spin-orbit coupling matrix elements were calculated with the configuration interaction method using the two-electron Breit-Pauli Hamiltonian. The excited (3)B1 state lifetime and intersystem crossing rate constants were estimated by fitting the AIMS state population with the first-order kinetics equation for a reversible unimolecular reaction. The obtained rate constants are compared with the values predicted by the statistical nonadiabatic transition state theory with transition probabilities calculated using the Landau-Zener and weak coupling formulas. PMID:27064356

  9. Exciton-photon coupling in organic materials with large intersystem crossing rates and strong excited-state molecular relaxation

    Holmes, R. J.; Forrest, S. R.

    2005-06-01

    We examine the influence of singlet-triplet intersystem crossing (ISC) and excited-state molecular relaxation on strong exciton-photon coupling in optical microcavities filled with small-molecular-weight organic materials. The effect of ISC is considered by comparing coupling effects in the phosphorescent organic platinum(II) octaethylporphyrin to those in the fluorescent free-base porphyrin tetraphenylporphyrin (TPP). The influence of excited-state molecular relaxation is studied by examining coupling to the Soret band of TPP. Both ISC and excited-state molecular relaxation prevent the population of polariton states under nonresonant optical excitation. The interplay between strong coupling and relaxation processes offers a unique opportunity to directly probe fundamental ultrafast excitonic phenomena. The competition between coupling in microcavities and these processes allows for estimation of their relative transition rates.

  10. Singlet and triplet excited states and intersystem crossing in free-base porphyrin: TDDFT and DFT/MRCI study.

    Perun, Serhiy; Tatchen, Jörg; Marian, Christel M

    2008-02-01

    Extensive time-dependent DFT (TDDFT) and DFT/multireference configuration interaction (MRCI) calculations are performed on the singlet and triplet excited states of free-base porphyrin, with emphasis on intersystem crossing processes. The equilibrium geometries, as well as the vertical and adiabatic excitation energies of the lowest singlet and triplet excited states are determined. Single and double proton-transfer reactions in the first excited singlet state are explored. Harmonic vibrational frequencies are calculated at the equilibrium geometries of the ground state and of the lowest singlet and triplet excited states. Furthermore, spin-orbit coupling matrix elements of the lowest singlet and triplet states and their numerical derivatives with respect to nuclear displacements are computed. It is shown that opening of an unprotonated pyrrole ring as well as excited-state single and double proton transfer inside the porphyrin cavity lead to crossings of the potential energy curves of the lowest singlet and triplet excited states. It is also found that displacements along out-of-plane normal modes of the first excited singlet state cause a significant increase of the , , and spin-orbit coupling matrix elements. These phenomena lead to efficient radiationless deactivation of the lowest excited states of free-base porphyrin via intercombination conversion. In particular, the S1-->T1 population transfer is found to proceed at a rate of approximately 10(7) s(-1) in the isolated molecule. PMID:18189251

  11. Absolute cross sections for dissociative electron attachment to acetylene and diacetylene

    May, Olivier; Fedor, Juraj; Ibănescu, Bogdan C.; Allan, Michael

    2008-01-01

    Absolute cross sections for the production of the two astronomy-relevant negative ions H−C≡C⁻ and H−C≡C−C≡C⁻ by dissociative electron attachment to acetylene C₂H₂ and diacetylene C₄H₂ were measured (with a ±25% error bar). Acetylene yielded the C₂H⁻ ion at an electron energy of 2.95  eV with a cross section of 3.6±0.9  pm² and also the C₂⁻ ion at 8.1  eV with a cross section of 4.1±1  pm². Diacetylene yielded the C₄H⁻ ion at 2.5  eV with a cross section of 3.0±0.8  pm² and at 5.25  eVwith a c...

  12. Quantum confinement-tunable intersystem crossing and the triplet state lifetime of cationic porphyrin–CdTe quantum dot nano-assemblies

    Ahmed, Ghada H.

    2015-03-27

    Here, we report a ground-state interaction between the positively charged cationic porphyrin and the negatively charged carboxylate groups of the thiol ligands on the surface of CdTe quantum dots (QDs), leading to the formation of a stable nanoassembly between the two components. Our time-resolved data clearly demonstrate that we can dramatically tune the intersystem crossing (ISC) and the triplet state lifetime of porphyrin by changing the size of the QDs in the nanoassembly.

  13. Photo-assisted intersystem crossing: The predominant triplet formation mechanism in some isolated polycyclic aromatic molecules excited with pulsed lasers

    Naphthalene, anthracene, and phenanthrene are shown to have very long-lived triplet lifetimes when the isolated molecules are excited with nanosecond pulsed lasers resonant with the lowest singlet state. For naphthalene, triplet state populations are created only during the laser pulse, excluding the possibility of normal intersystem crossing at the one photon level, and all molecules have triplet lifetimes greater than hundreds of microseconds, similar to the behavior previously reported for phenylacetylene. Although containing 7-12 thousand cm-1 of vibrational energy, the triplet molecules have ionization thresholds appropriate to vibrationless T1 states. The laser power dependences (slopes of log-log power plots) of the excited singlet and triplet populations are about 0.7 for naphthalene and about 0.5 for anthracene. Kinetic modeling of the power dependences successfully reproduces the experimental results and suggests that the triplet formation mechanism involves an enhanced spin orbit coupling caused by sigma character in states at the 2-photon level. Symmetry Adapted Cluster-Configuration Interaction calculations produced excited state absorption spectra to provide guidance for estimating kinetic rates and the sigma character present in higher electronic states. It is concluded that higher excited state populations are significant when larger molecules are excited with pulsed lasers and need to be taken into account whenever discussing the molecular photodynamics

  14. Photo-assisted intersystem crossing: The predominant triplet formation mechanism in some isolated polycyclic aromatic molecules excited with pulsed lasers

    Johnson, Philip M., E-mail: Philip.johnson@stonybrook.edu [Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400 (United States); Sears, Trevor J. [Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400 (United States); Department of Chemistry, Brookhaven National Laboratory, Upton, New York 11973 (United States)

    2015-07-28

    Naphthalene, anthracene, and phenanthrene are shown to have very long-lived triplet lifetimes when the isolated molecules are excited with nanosecond pulsed lasers resonant with the lowest singlet state. For naphthalene, triplet state populations are created only during the laser pulse, excluding the possibility of normal intersystem crossing at the one photon level, and all molecules have triplet lifetimes greater than hundreds of microseconds, similar to the behavior previously reported for phenylacetylene. Although containing 7–12 thousand cm{sup −1} of vibrational energy, the triplet molecules have ionization thresholds appropriate to vibrationless T{sub 1} states. The laser power dependences (slopes of log-log power plots) of the excited singlet and triplet populations are about 0.7 for naphthalene and about 0.5 for anthracene. Kinetic modeling of the power dependences successfully reproduces the experimental results and suggests that the triplet formation mechanism involves an enhanced spin orbit coupling caused by sigma character in states at the 2-photon level. Symmetry adapted cluster-configuration interaction calculations produced excited state absorption spectra to provide guidance for estimating kinetic rates and the sigma character present in higher electronic states. It is concluded that higher excited state populations are significant when larger molecules are excited with pulsed lasers and need to be taken into account whenever discussing the molecular photodynamics.

  15. Solvent-dependent excited-state hydrogen transfer and intersystem crossing in 2-(2′-hydroxyphenyl)-benzothiazole

    Aly, Shawkat Mohammede

    2015-02-12

    The excited-state intramolecular hydrogen transfer (ESIHT) of 2-(2′-hydroxyphenyl) benzothiazole (HBT) has been investigated in a series of nonpolar, polar aprotic, and polar protic solvents. A variety of state-of-the-art experimental methods were employed, including femto- and nanosecond transient absorption and fluorescence upconversion spectroscopy with broadband capabilities. We show that the dynamics and mechanism of ESIHT of the singlet excited HBT are strongly solvent-dependent. In nonpolar solvents, the data demonstrate that HBT molecules adopt a closed form stabilized by O-H⋯N chelated hydrogen bonds with no twisting angle, and the photoinduced H transfer occurs within 120 fs, leading to the formation of a keto tautomer. In polar solvents, owing to dipole-dipole cross talk and hydrogen bonding interactions, the H transfer process is followed by ultrafast nonradiative deactivation channels, including ultrafast internal conversion (IC) and intersystem crossing (ISC). This is likely to be driven by the twisting motion around the C-C bond between the hydroxyphenyl and thiazole moieties, facilitating the IC back to the enol ground state or to the keto triplet state. In addition, our femtosecond time-resolved fluorescence experiments indicate, for the first time, that the lifetime of the enol form in ACN is approximately 280 fs. This observation indicates that the solvent plays a crucial role in breaking the H bond and deactivating the excited state of the HBT. Interestingly, the broadband transient absorption and fluorescence up-conversion data clearly demonstrate that the intermolecular proton transfer from the excited HBT to the DMSO solvent is about 190 fs, forming the HBT anion excited state.

  16. Isotope effect in dissociative electron attachment cross sections in acetylene

    May, Olivier; Fedor, Juraj; Allan, Michael, E-mail: olivier.may@unifr.c [Department of Chemistry, University of Fribourg, Chemin du Muse 9, 1700 Fribourg (Switzerland)

    2009-11-01

    We present absolute cross section measurement of dissociative electron attachment to C{sub 2}H{sub 2} and C{sub 2}D{sub 2}. The C{sub 2}H{sup -}/ C{sub 2}D{sup -} band at 3 eV shows pronounced isotope effect with the cross section for C{sub 2}H{sub 2} being 14.7 times larger than that for C{sub 2}D{sub 2}. The light fragments H{sup -} and D{sup -} dominate the second dissociative electron attachment band around 8 eV. These bands exhibit much weaker isotope effects which is in agreement with their assignment to Feshbach resonances.

  17. The effect of intersystem crossings in N({sup 2}D) + H{sub 2} collisions

    Galvão, B. R. L., E-mail: brenogalvao@gmail.com; Poveda, L. A. [Centro Federal de Educação Tecnológica de Minas Gerais, CEFET-MG, Av. Amazonas 5253, 30421-169 Belo Horizonte, Minas Gerais (Brazil)

    2015-05-14

    The transitions between quartet and doublet states of the NH{sub 2} molecule are studied for the first time, allowing the evaluation of the N({sup 4}S) + H{sub 2} reactive channel. High level ab initio calculations of the spin-orbit coupling are performed over the whole configurational space of the NH{sub 2} molecule and fitted to a proposed analytic form. Quasiclassical trajectories coupled with the surface hopping method are employed to calculate reaction cross section and rate constants. The reaction is largely affected by the initial rovibrational states of H{sub 2}, while the formation of long-lived complexes enhances the reaction probability.

  18. Quantum confinement-tunable intersystem crossing and the triplet state lifetime of cationic porphyrin-CdTe quantum dot nano-assemblies

    Ahmed, Ghada H.

    2015-01-01

    Here, we report a ground-state interaction between the positively charged cationic porphyrin and the negatively charged carboxylate groups of the thiol ligands on the surface of CdTe quantum dots (QDs), leading to the formation of a stable nanoassembly between the two components. Our time-resolved data clearly demonstrate that we can dramatically tune the intersystem crossing (ISC) and the triplet state lifetime of porphyrin by changing the size of the QDs in the nanoassembly. © 2015 The Royal Society of Chemistry.

  19. A quantum time-dependent wave-packet study of intersystem crossing effects in the O(3P0, 1, 2) + D2(v = 0, j = 0) reaction

    Zhao, Juan

    2013-04-01

    We investigated spin-orbit-induced intersystem crossing effects in the title reaction by the time-dependent wave-packet method combined with an extended split operator scheme. We performed non-adiabatic calculations of the fine-structure-resolved cross section and adiabatic calculations of integral cross section. The calculations are based on the potential energy surfaces of 3A' and the two degenerate 3A'' states [S. Rogers, D. Wang, A. Kuppermann, and S. Walch, J. Phys. Chem. A 104, 2308 (2000)], 10.1021/jp992985g, together with the spin-orbit coupling matrix [B. Maiti and G. C. Schatz, J. Chem. Phys. 119, 12360 (2003)], 10.1063/1.1623481 and singlet 1A' potential energy surface [J. Dobbyn and P. J. Knowles, Faraday Discuss. 110, 247 (1998)]. The results of the O(3P) + D2 are similar to those of the O(3P) + H2 reaction. The product spin state-resolved reaction cross section and the total reaction cross section both show that the adiabatic channel is dominant in all cases, and the non-adiabatic channels have cross sections of several orders of magnitude smaller than the adiabatic channels at high collision energy. Although the cross sections caused by the intersystem crossing effects in the O(3P) + D2 reaction are larger than those in the O(3P) + H2 reaction, the differences in non-adiabaticity between these two reaction systems are quite modest. Based on the results of the O(3P) + H2 reaction, we can predict that the influence of spin-orbit on the total reaction cross sections of the O(3P) + D2 reaction is also insignificant. However, these non-adiabatic effects can be reflected in the presence of some forward-scattering in the angular distribution for the OD product.

  20. Exploring the Mechanism of Ultrafast Intersystem Crossing in Rhenium(I) Carbonyl Bipyridine Halide Complexes: Key Vibrational Modes and Spin-Vibronic Quantum Dynamics.

    Harabuchi, Yu; Eng, Julien; Gindensperger, Etienne; Taketsugu, Tetsuya; Maeda, Satoshi; Daniel, Chantal

    2016-05-10

    The mechanism of ultrafast intersystem crossing in rhenium(I) carbonyl bipyridine halide complexes Re(X)(CO)3(bpy) (X = Cl, Br, I) is studied by exploring the structural deformations when going from Franck-Condon (FC) to critical geometries in the low-lying singlet and triplet excited states and by selecting the key vibrational modes. The luminescent decay observed in [Re(Br)(CO)3(bpy)] is investigated by means of wavepacket propagations based on the multiconfiguration time-dependent Hartree (MCTDH) method. The dominant coordinates underlying the nonradiative decay process are extracted from minima, minimum energy seam of crossing (MESX) and minimum energy conical intersection (MECI) geometries obtained by the seam model function (SMF)/single-component artificial force induced reaction (SC-AFIR) approach. By choosing the normal modes used in MCTDH from the MECI and MESX geometries, not only the degenerate energy points but also the low-energy-gap regions are included. For this purpose a careful vibrational analysis is performed at each critical geometry and analyzed under the light of the pertinent nonadiabatic coupling terms obtained from the linear vibronic coupling (LVC) model augmented by spin-orbit coupling (SOC) in the electronic diabatic representation. PMID:27045949

  1. Enhanced intersystem crossing due to long-range exchange interaction in copper(II) porphyrin-free base porphyrin dimers: HOMO and spacer dependence

    Highlights: • We found a parallel relationship between the two correlation lines of ln Δkisc vs. number of bonds. • Effects of HOMO of the terminal chromophore appear as the intercept of the correlation lines. • Difference of HOMO of the terminal porphyrin does not affect the interaction within the bridge part. • An expression involving both HOMO and spacer dependence for EISC rate was derived. - Abstract: Photodynamics induced by long-range exchange interaction was studied in two series of copper(II) porphyrin – free base porphyrin dimers linked via an aromatic spacer: one has a2u orbital as HOMO in the porphyrin π-system and the other has a1u orbital. Dependence on the HOMO as well as that on the spacer is presented for enhanced intersystem crossing (EISC) occurring in the free base half due to long-range coupling with the copper unpaired electron. Semilogarithmic plots of EISC rates vs. number of bonds show a linear correlation in each series of dimers. It was found that the two correlation lines show the same slope but different intercepts. This clearly indicates that electronic communication within the linkage does not depend on the terminal chromophore, while the terminal π-system affects the magnitude of EISC rates. Separately, a general expression for EISC rate, involving coupling between the terminal and linkage, was derived theoretically

  2. Reversibility of Intersystem Crossing in the {a}1A1(000) and {a}1A1(010) States of Methylene, CH_2

    Le, Anh T.; Sears, Trevor; Hall, Gregory

    2015-06-01

    The lowest energy singlet ( {a}1A1) and triplet ( {X}3B1) electronic states of methylene, CH_2, are only separated by 3150 wn, but differ greatly in chemical reactivity. Overall methylene reaction rates and chemical behavior are therefore strongly dependent on collisionally-mediated singlet-triplet interconversion. Collisions with inert partners tend to depopulate the excited singlet state and populate vibrationally excited triplet levels in CH_2. This process is generally considered as irreversible for large molecules, however, this is not the case for small molecules such as CH_2. An investigation of the decay kinetics of CH_2 in the presence of argon and various amounts of oxygen has been carried out using transient frequency modulation (FM) absorption spectroscopy, to monitor ortho and para rotational levels in both the {a}1A1(000) and {a}1A1(010) states. In the {a}1A1(000) state, all observed rotational levels follow double exponential decay kinetics, a direct consequence of reversible intersystem crossing. The relative amplitude of the slower decay component is an indicator of how quickly the reverse crossing from excited triplet levels becomes significant during the reaction and relaxation of singlet methylene. The para rotational levels show more obvious signs of reversibility than ortho rotational levels. Adding oxygen enhances the visibility of reversibility for both ortho and para levels. However, in the {a}1A1(010) state where the FM signal is 5-10 times smaller than the {a}1A1(000) state, there is no evidence of double exponential decay kinetics. Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886 and DE-SC0012704 with the U.S. Department of Energy and supported by its Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences.

  3. The lowest quartet-state of the ketenyl (HCCO) radical: Collision-induced intersystem crossing and the ν2 vibrational mode

    Graphical abstract: Generation, transformation, deactivation, and loss of the ketenyl radical. Highlights: • ISC rate constants measured for lowest cis-quartet-state HCCO with He, Ar, and Xe. • Ar and Xe induced ISC shown to exhibit an external heavy atom effect. • He observed to be more effective at vibrational deactivation than inducing ISC. • First experimental observation of nu2 mode of cis-quartet-state HCCO at 1785 ± 36 cm−1. - Abstract: We have used time-resolved IR emission spectroscopy to examine collision induced intersystem crossing (CIISC) and deactivation of vibronically excited cis-HCCO(a-tilde4A″), generated following the 193 nm photolysis of ethyl ethynyl ether, by inert gases: He, Ar, and Xe. Observation of vibrationally excited CO(X1Σ+), in experiments quenched with Ar or Xe, suggest rapid CIISC due to a heavy-atom effect. Conversely, experiments quenched with He show transient signal from cis-HCCO(a-tilde4A″), and a distinct absence of CO(X1Σ+), suggesting that CIISC occurs only after cis-HCCO(a-tilde4A″) has been quenched (i.e., CIISC is significantly less efficient with He). Inert gas CIISC rate constants for cis-HCCO(a-tilde4A″) were deduced to be kISCHe=(4.3±0.2)×10−11 cm3molecules-1s-1, kISCAr=(8.1±0.2)×10−11 cm3molecules-1s-1, and kISCXe=(13.0±0.1)×10−11 cm3molecules-1s-1. Additionally, we report the first experimental assignment of 1785 ± 36 cm−1 for the fundamental transition of the ν2 asym-CCO stretch of cis-HCCO(a-tilde4A″), which, compared with ab initio calculations, suggests that cis-HCCO(a-tilde4A″) exhibits positive anharmonicity

  4. Experimental and theoretical studies of the O(3P) + C2H4 reaction dynamics: collision energy dependence of branching ratios and extent of intersystem crossing.

    Fu, Bina; Han, Yong-Chang; Bowman, Joel M; Leonori, Francesca; Balucani, Nadia; Angelucci, Luca; Occhiogrosso, Angela; Petrucci, Raffaele; Casavecchia, Piergiorgio

    2012-12-14

    The reaction of O((3)P) with C(2)H(4), of importance in combustion and atmospheric chemistry, stands out as paradigm reaction involving not only the indicated triplet state potential energy surface (PES) but also an interleaved singlet PES that is coupled to the triplet surface. This reaction poses great challenges for theory and experiment, owing to the ruggedness and high dimensionality of these potentials, as well as the long lifetimes of the collision complexes. Crossed molecular beam (CMB) scattering experiments with soft electron ionization detection are used to disentangle the dynamics of this polyatomic multichannel reaction at a collision energy E(c) of 8.4 kcal∕mol. Five different primary products have been identified and characterized, which correspond to the five exothermic competing channels leading to H + CH(2)CHO, H + CH(3)CO, CH(3) + HCO, CH(2) + H(2)CO, and H(2) + CH(2)CO. These experiments extend our previous CMB work at higher collision energy (E(c) ∼ 13 kcal∕mol) and when the results are combined with the literature branching ratios from kinetics experiments at room temperature (E(c) ∼ 1 kcal∕mol), permit to explore the variation of the branching ratios over a wide range of collision energies. In a synergistic fashion, full-dimensional, QCT surface hopping calculations of the O((3)P) + C(2)H(4) reaction using ab initio PESs for the singlet and triplet states and their coupling, are reported at collision energies corresponding to the CMB and the kinetics ones. Both theory and experiment find almost an equal contribution from the triplet and singlet surfaces to the reaction, as seen from the collision energy dependence of branching ratios of product channels and extent of intersystem crossing (ISC). Further detailed comparisons at the level of angular distributions and translational energy distributions are made between theory and experiment for the three primary radical channel products, H + CH(2)CHO, CH(3) + HCO, and CH(2) + H(2)CO

  5. Intersystem-crossing and phosphorescence rates in fac-Ir{sup III}(ppy){sub 3}: A theoretical study involving multi-reference configuration interaction wavefunctions

    Kleinschmidt, Martin; Marian, Christel M., E-mail: Christel.Marian@hhu.de [Institute of Theoretical and Computational Chemistry, Heinrich-Heine-University Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf (Germany); Wüllen, Christoph van [Fachbereich Chemie and Forschungszentrum OPTIMAS, Technical University of Kaiserslautern, Erwin-Schrödinger-Straße 52, 67663 Kaiserslautern (Germany)

    2015-03-07

    We have employed combined density functional theory and multi-reference configuration interaction methods including spin–orbit coupling (SOC) effects to investigate the photophysics of the green phosphorescent emitter fac-tris-(2-phenylpyridine)iridium (fac-Ir(ppy){sub 3}). A critical evaluation of our quantum chemical approaches shows that a perturbational treatment of SOC is the method of choice for computing the UV/Vis spectrum of this heavy transition metal complex while multi-reference spin–orbit configuration interaction is preferable for calculating the phosphorescence rates. The particular choice of the spin–orbit interaction operator is found to be of minor importance. Intersystem crossing (ISC) rates have been determined by Fourier transformation of the time correlation function of the transition including Dushinsky rotations. In the electronic ground state, fac-Ir(ppy){sub 3} is C{sub 3} symmetric. The calculated UV/Vis spectrum is in excellent agreement with experiment. The effect of SOC is particularly pronounced for the metal-to-ligand charge transfer (MLCT) band in the visible region of the absorption spectrum which does not only extend its spectral onset towards longer wavelengths but also experiences a blue shift of its maximum. Pseudo-Jahn-Teller interaction leads to asymmetric coordinate displacements in the lowest MLCT states. Substantial electronic SOC and a small energy gap make ISC an ultrafast process in fac-Ir(ppy){sub 3}. For the S{sub 1}↝T{sub 1} non-radiative transition, we compute a rate constant of k{sub ISC} = 6.9 × 10{sup 12} s{sup −1} which exceeds the rate constant of radiative decay to the electronic ground state by more than six orders of magnitude, in agreement with the experimental observation of a subpicosecond ISC process and a triplet quantum yield close to unity. As a consequence of the geometric distortion in the T{sub 1} state, the T{sub 1} → S{sub 0} transition densities are localized on one of the

  6. A mid-infrared absorption diagnostic for acetylene detection

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

    2015-08-01

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

  7. A mid-infrared absorption diagnostic for acetylene detection

    KC, Utsav

    2015-05-14

    Acetylene is an important combustion intermediate and plays a critical role in soot formation. Accurate measurements of trace concentrations of acetylene can be very useful in validating hydrocarbon oxidation and soot formation mechanisms. Strongest vibrational band of acetylene near 13.7 μm is probed here to develop a highly sensitive absorption diagnostic. Experiments are carried out behind reflected shock waves to measure absorption cross sections of acetylene near 730 cm−1 over a wide range of temperatures (1000–2200 K) and pressures (1–5 bar). The diagnostic is demonstrated by measuring acetylene formation during the shock-heated pyrolysis and oxidation of propene. © 2015 Springer-Verlag Berlin Heidelberg

  8. Inter-system LOCA risk assessment

    Inter-systems loss-of-coolant accidents (ISLOCAs) have been included in probabilistic risk assessments (PRAs) since WASH-1400. While estimated as being relatively low contributors to core damage frequency, ISLOCAs have been identified as major contributors to risk at nuclear power plants (NPPs). They have the potential to result in core melt and containment bypass, which may lead to the early release of large quantities of fission products. Recent events at several operating reactors have been identified as ISLOCA precursors. The occurrence of these events have raised concerns that the frequency of ISLOCA sequences might be underestimated in current state-of-the-art PRAs. In order to expand the current state-of-the-art, a Nuclear Regulatory Commission research program is being conducted by ED and G Idaho, Inc. at the Idaho National Engineering Laboratory. The objective of the ISLOCA research program is to generate qualitative and quantitative information on the hardware, human factors, and accident consequence issues that dominate nuclear power plant risks for ISLOCA. To meet this objective, the approach being taken includes analysis of all interfaces between the primary reactor coolant system and other, lower pressure systems. This historical experience (primarily, licensee event reports) has provided the basis for determining the scope of the analysis with respect to potential failure mechanisms of the pressure isolation boundary. It is important to note that in the vast majority of these events, the dominant failure was a human error. Because of their significance, human errors are given particular attention in the present analysis

  9. Transition probability of the Al II 2669 intersystem line

    Johnson, B. C.; Smith, P. L.; Parkinson, W. H.

    1986-01-01

    Time-resolved observations of the spin-changing, or 'intersystem' emission at 2669.157 A obtained by the ion storage technique are used to measure the transition probability of the 3s2 1S0 - 3s3p 3P1 exp 0 line in Al II. A laser-generated plasma was used as the source of the metastable Al(+) ions. The A-value result obtained for the intersystem transition is 3.33 + or - 0.23 x 10 to the 3rd/sec at the 90-percent confidence level; this value is used to derive two line-intensity ratios which involve the intersystem line as a function of electron density and temperature.

  10. 12 CFR 611.1130 - Inter-System transfer of funds and equities.

    2010-01-01

    ... 12 Banks and Banking 6 2010-01-01 2010-01-01 false Inter-System transfer of funds and equities. 611.1130 Section 611.1130 Banks and Banking FARM CREDIT ADMINISTRATION FARM CREDIT SYSTEM ORGANIZATION Rules for Inter-System Fund Transfers § 611.1130 Inter-System transfer of funds and equities....

  11. An Integrative, Intersystemic Approach to Supervision of Couple Therapy.

    Betchen, Stephen J.

    1995-01-01

    Offers an integrative model of supervision--the Intersystem Model of couple therapy of the Marriage Council of Philadelphia--that consolidates individual, interactional, and intergenerational therapies, providing a base from which the supervisor of couple therapy can be most effective. A detailed case of supervision is utilized to demonstrate the…

  12. A statistical characterization of the Galileo-to-GPS inter-system bias

    Gioia, Ciro; Borio, Daniele

    2016-06-01

    Global navigation satellite system operates using independent time scales and thus inter-system time offsets have to be determined to enable multi-constellation navigation solutions. GPS/Galileo inter-system bias and drift are evaluated here using different types of receivers: two mass market and two professional receivers. Moreover, three different approaches are considered for the inter-system bias determination: in the first one, the broadcast Galileo to GPS time offset is used to align GPS and Galileo time scales. In the second, the inter-system bias is included in the multi-constellation navigation solution and is estimated using the measurements available. Finally, an enhanced algorithm using constraints on the inter-system bias time evolution is proposed. The inter-system bias estimates obtained with the different approaches are analysed and their stability is experimentally evaluated using the Allan deviation. The impact of the inter-system bias on the position velocity time solution is also considered and the performance of the approaches analysed is evaluated in terms of standard deviation and mean errors for both horizontal and vertical components. From the experiments, it emerges that the inter-system bias is very stable and that the use of constraints, modelling the GPS/Galileo inter-system bias behaviour, significantly improves the performance of multi-constellation navigation.

  13. Acetylene degradation by new isolates of aerobic bacteria and comparison of acetylene hydratase enzymes

    Rosner, Bettina M; Rainey, Frederick A.; Kroppenstedt, Reiner M.; Schink, Bernhard

    1997-01-01

    Aerobic acetylene-degrading bacteria were isolated from soil samples. Two isolates were assigned to the species Rhodococcus opacus, two others to Rhodococcus ruber and Gordona sp. They were compared with known strains of aerobic acetylene-, cyanide-, or nitrile-utilizing bacteria. The acetylene hydratases of R. opacus could be measured in cell-free extracts only in the presence of a strong reductant like titanium(III) citrate. Expression of these enzymes was molybdenum-dependent. Acetylene hy...

  14. Plasma Thermal Conversion of Methane to Acetylene

    This paper describes a re-examination of a known process for the direct plasma thermal conversion of methane to acetylene. Conversion efficiencies (% methane converted) approached 100% and acetylene yields in the 90-95% range with 2-4% solid carbon production were demonstrated. Specificity for acetylene was higher than in prior work. Improvements in conversion efficiency, yield, and specificity were due primarily to improved injector design and reactant mixing, and minimization of temperature gradients and cold boundary layers. At the 60-kilowatt scale cooling by wall heat transfer appears to be sufficient to quench the product stream and prevent further reaction of acetylene resulting in the formation of heavier hydrocarbon products or solid carbon. Significantly increasing the quenching rate by aerodynamic expansion of the products through a converging-diverging nozzle led to a reduction in the yield of ethylene but had little effect on the yield of other hydrocarbon products. While greater product selectivity for acetylene has been demonstrated, the specific energy consumption per unit mass of acetylene produced was not improved upon. A kinetic model that includes the reaction mechanisms resulting in the formation of acetylene and heavier hydrocarbons, through benzene, is described

  15. Acetylene diffusion in Na-Y zeolite

    S Mitra; S Sumitra; A M Umarji; R Mukhopadhyay; S Yashonath; S L Chaplot

    2004-08-01

    Study of diffusivity of acetylene adsorbed in Na-Y zeolite by quasi-elastic neutron scattering (QENS) measurements at temperatures of 300, 325 and 350 K is reported. A model in which the acetylene molecules undergo random-walk diffusion characterized by a Gaussian distribution of jump lengths inside zeolite cages describes the data consistently. The diffusion constant, residence time between jumps and root mean square jump length are determined.

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

    Hu, Tong-Liang

    2015-06-04

    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.

  17. Radical recombinations in acetylene-air flames

    Zeegers, P.J.Th.; Alkemade, C.T.J.

    1965-01-01

    In this paper an analysis is given of the behaviour of excess radical concentrations, H, OH and O as a function of height above the reaction zone in premixed acetylene-air flames at 2–200° to 2400°K and 1 atmosphere pressure. The intensity was measured of the Li resonance line which is related to th

  18. Radiation Polymerization of Acetylene Hydrocarbons. Special Features

    The synthesis and study of the properties of polymers with conjugated bond systems offers new and extremely promising prospects in the chemistry of high molecular compounds. A high degree of de-localization of p-electrons in the macromolecule is characteristic of such polymer systems. The decrease in the energy excited in the triplet state, just like the diminished ionization potential with large conjugated bonds, conditions the semiconductor and specific magnetic properties of such compounds. In addition, polymer systems with conjugated bonds have proved to be extremely effective stabilizers in the thermo- and photo-oxidation destruction of polymers. The radiation polymerization of acetylene derivatives offers one suitable method of obtaining such polymers and is the only one which ensures that the polymers obtained are free of contamination from initiators at low temperatures. The kinetics of the radiation polymerization of ethynyl benzene and other acetylene derivatives have a number of features typical of ion polymerization quite rare in radical polymerization (speed of polymerization linearly proportional to speed of initiation: very low activation energy; no oxygen inhibition). Nevertheless this polymerization is obviously radical. We reached that conclusion on the basis of a study of polymerization initiation for acetylene hydrocarbons by typical radical initiators - benzoyl peroxide and the dinitrile of azoisobutyric acid. They investigated the kinetic features and mechanism of peroxide decomposition in the presence of acetylene hydrocarbons (e.g. ethynyl benzene, deutero-ethynyl benzene and phenylpropyne). The kinetics of radiation co-polymerization of ethynyl benzene with different vinyl monomers and the composition of copolymers in different initial mixtures were also studied. These data and the results of a study of the kinetics of inhibited ethynyl benzene polymerization (benzoquinone initiator) indicate a small reactivity capacity of the ethynyl

  19. Two new acetylenic compounds from Asparagus officinalis.

    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

  20. Acetylene-sensitized radiation crosslinking of polytetrafluoroethylene

    The radiation crosslinking of polytetrafluoroethylene (PTFE) in the presence of acetylene under γ radiation (60Co) at a dose rate of 2 Gy/s up to absorbed doses of 20-60 kGy was studied. The yield of crosslinking was determined from thermomechanical testing data and, on this basis, it was concluded that crosslinking follows the chain mechanism. Radiation-crosslinked PTFE is shown to possess high wear resistance and enhanced radiation stability

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

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

    2015-11-01

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

  2. Synthesis of acetylenic derivatives of hydroxynaphthoquinone

    The acetylene derivatives synthesis 2-hydroxy-1 ,4-naphthoquinones was studied using different reaction conditions: coupling with copper and silver acetylides, Sonogashira reaction with and without CU (I) as cocatalyst. The reaction conditions are optimized for coupling of iodine lawson and ylide phenyl lawsone of iodine with various terminal acetylenes: phenyl acetylene, propargyl alcohol, 1-heptin and 2-methyl-3-butyne-2-ol. Also, reactants such as bromides of hidroxinaphthoquinones were used with protecting groups such as acetate, methoxy, phenyloxy, benzyloxy and tricloroetoxy. The synthesis of 2-hydroxy-3-(3-hydroxy-3-ynyl-1-methylbutane)-1,4-naphthoquinone, 2-methoxy-3-(2-phenylethynyl) -1,4-naphthoquinone and 2-(2-phenylethynyl)-3-(2,2,2-tricloroetoxy)-1,4-naphthoquinone was performed with rates of return of 22%, 57% and 67% respectively. The reaction of the yodolawsona was obtained with 3-chloro-3-methyl-1-butyne in the presence of CuI, CsI and Cs2Co3 obtaining the enol ether: 3,3-dimethyl-2-methyl-2 ,3-dihydronaphto [2 ,3-b]furan-4,9-dione (dehydro-α-dunion), with a rate of return of 58%. This enol ether was used as a reactant for the formation, through a regioselective hydrogenation with PtO2/t-butanol of α-dunion with a yield of 50%. Furthermore, by acid hydrolysis with H2SO4 has been possible to obtain a percentage yield of 75% streptocarpone. Both, α-dunion and streptocarpone, natural products extracted from Streptocarpus dunni shrub, with antiparasitic activity, and which so far had not presented an efficient synthesis. A mechanism is proposed for the reaction of formation of the enol ether where it is presumed the presence of a zwitterion-vinyl carbene as key intermediate of the reaction. All products were characterized by spectroscopy 1H and 13C-NMR, UV-Vis and IR. (author)

  3. Largest Experimental Facility for Acetylene Production in Operation

    2005-01-01

    @@ Scientists from the CAS Institute of Plasma Physics (IPP) completed in early November, 2004, a 2-megawatt experimental facility for acetylene production by coal plasma pyrolysis. The successful operation of the largest installation of the kind in the world confirms a new method for the large-scale industrialization of acetylene production.

  4. 76 FR 75782 - Revising Standards Referenced in the Acetylene Standard

    2011-12-05

    ... organizations (``SDO standards'') (69 FR 68283). A SDO standard referenced in OSHA's Acetylene Standard (29 CFR... of the Compressed Gas Association standard, CGA G-1-2003, in the Acetylene Standard. See 74 FR 40442... appropriate, revoke references to outdated national SDO standards in OSHA rules (see, e.g., 69 FR 68283, 70......

  5. Acetylene-Based Materials in Organic Photovoltaics

    Fabio Silvestri

    2010-04-01

    Full Text Available 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 (polyarylacetylenes that have been used in the field. A general introduction to (polyarylacetylenes, 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, (copolymers containing triple bonds, and metallopolyyne polymers as p-type semiconductor materials. The last section will deal with hybrids in which oligomeric/polymeric structures incorporating acetylenic linkages such as phenylene ethynylenes have been attached onto C60, and their use as the active materials in photovoltaic devices.

  6. Diamond growth in oxygen-acetylene flame

    What was supposed to be a laboratory curiosity in the 80's, in recent years the low pressure process for the production of man-made diamond turned out to be a major target for research and development of many high-tech companies. The main reason for such an interest stems on the possibility of coating many materials with a diamond film possessing the same amazing properties of the bulk natural diamond. Polycrystalline diamond film has been deposited on Mo substrate by using oxygen-acetylene flame of a welding torch. The substrate temperature has been held constant about 700deg C by means of a water cooled mount designed properly. Precision flowmeters have been used to control the flow ratio oxygen/acetylene, a key parameter for the success in diamond growth. Diamond has been detected by X-ray diffraction, a fast foolproof technique for crystal identification. Another method of analysis often used in Raman spectroscopy, which is able to exhibit amorphous structure besides crystalline phase. (author)

  7. Studies on the crystalline acetylene-d2 by thermal neutron powder diffraction technique

    The two crystalline phases of acetylene-d2, C2D2, have been investigated by thermal neutron powder diffraction technique. The crystal structure studies of the orthorhombic low phase at 4.2 K, 77 K and 109 K and of the cubic structure at 150.5 K, as well as investigations on molecular motion and lattice parameter dependence on temperature in the orthorhombic phase along with a report concerning with the orthorhombic-cubic solid phase transition have been published ealier. In the thesis, the reported studies are presented under a main title. A short description of the experimental details is given, and the results and discrepancies of the studies are discussed. (author)

  8. Synthesis and Antifeeding Activity of Acetylene-Containing Tonghaosu Analogs

    CHEN,Li; HU,Tai-Shan; XU,Han-Hong; YIN,Biao-Lin; XIAO,Chun; WU,Yu-Lin

    2004-01-01

    @@ During our continuous efforts towards the search for environmental benign insect antifeedant, we established a concise method for the synthesis of Tonghaosu, a naturally occurring antifeedant.[1] Herein, we report the synthesis and antifeeding activity of 22 new tonghaosu analogs, which contain varied B ring as well as one or two acetylene functionalities. Preliminary bioassay indicates that two acetylene groups containing tonghaosu analogs have better antifeedant activity against large white butterfly (Pieris brassicae L.) than those with one acetylene group. More interestingly,Z-isomers are much more active than their corresponding E-isomers.

  9. Ultrafast Intersystem-Crossing Dynamics and Breakdown of the Kasha-Vavilov's Rule of Naphthalenediimides.

    Yushchenko, Oleksandr; Licari, Giuseppe; Mosquera-Vazquez, Sandra; Sakai, Naomi; Matile, Stefan; Vauthey, Eric

    2015-06-01

    The fluorescence quantum yield of a red naphthalenediimide dye (rNDI) with amino and Br core substituents has been found to decrease by a factor of almost 2 by going from S1 ← S0 to S2 ← S0 excitation. Time-resolved spectroscopic measurements reveal that this deviation from the Kasha-Vavilov's rule is due to an ultrafast, naphthalenediimide (pNDI), ISC is slower, ∼2 ps, and was found to be reversible on a time scale shorter than that of vibrational cooling. The fluorescence and triplet quantum yields of rNDI, thus, can be substantially changed by a simple variation of the excitation wavelength. PMID:26266508

  10. Inhibiting the combustion of air-acetylene mixtures

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

    2016-01-01

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

  11. Ion structure and sequence of ion formation in acetylene flames

    Larionova, I.A.; Fialkov, B.S.; Kalinich, K.YA.; Fialkov, A.B.; Ospanov, B.S.

    1993-06-01

    Results of a study of the ion composition of acetylene-air flames burning at low pressures are reported. Data on ion formation are compared for flames of saturated hydrocarbons, oxygen-containing fuels, and acetylene. It is shown that the characteristics of ion formation in the flame front and directly ahead of it are similar to those observed in flames of other fuels. These characteristics, however, are different in the low-temperature region. 9 refs.

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

    Sajid, M.B.

    2015-04-01

    The mid-infrared wavelength region near 8 mu m contains absorption bands of several molecules such as water vapor, hydrogen peroxide, nitrous oxide, methane and acetylene. A new laser absorption sensor based on the v(4) band of methane and the v(4)+v(5) band of acetylene is reported for interference-free, time-resolved measurements under combustion-relevant conditions. A detailed line-selection procedure was used to identify optimum transitions. Methane and acetylene were measured at the line centers of Q12 (1303.5 cm(-1)) and P23 (1275.5 cm(-1)) transitions, respectively. High-temperature absorption cross sections of methane and acetylene were measured at peaks (on-line) and valleys (off-line) of the selected absorption transitions. The differential absorption strategy was employed to eliminate interference absorption from large hydrocarbons. Experiments were performed behind reflected shock waves over a temperature range of 1200-2200 K, between pressures of 1-4 atm. The diagnostics were then applied to measure the respective species time-history profiles during the shock-heated pyrolysis of n-pentane. (C) 2015 Elsevier Ltd. All rights reserved.

  13. Safety assessment of inter-channel / inter-system digital communications: A defensive measures approach

    Inappropriately designed inter-channel and inter-system digital communications could initiate common cause failure of multiple channels or multiple systems. Defensive measures were introduced in EPRI report TR-1002835 (Guideline for Performing Defense-in-Depth and Diversity Assessments for Digital Upgrades) to assess, on a deterministic basis, the susceptibility of digital systems architectures to common-cause failures. This paper suggests how this approach could be applied to assess inter-channel and inter-system digital communications from a safety standpoint. The first step of the approach is to systematically identify the so called 'influence factors' that one end of the data communication path can have on the other. Potential factors to be considered would typically include data values, data volumes and data rates. The second step of the approach is to characterize the ways possible failures of a given end of the communication path could affect these influence factors (e.g., incorrect data values, excessive data rates, time-outs, incorrect data volumes). The third step is to analyze the designed-in measures taken to guarantee independence of the other end. In addition to classical error detection and correction codes, typical defensive measures are one-way data communication, fixed-rate data communication, fixed-volume data communication, validation of data values. (authors)

  14. Is acetylene essential for carbon dust formation?

    Dhanoa, Harpreet

    2013-01-01

    We have carried out an investigation of the chemical evolution of gas in different carbon-rich circumstellar environments. Previous studies have tended to invoke terrestrial flame chemistries, based on acetylene (C2H2) combustion to model the formation of carbon dust, via Polycyclic Aromatic Hydrocarbons (PAHs). In this work we pay careful attention to the accurate calculation of the molecular photoreaction rate coefficients to ascertain whether there is a universal formation mechanism for carbon dust in strongly irradiated astrophysical environments. A large number of possible chemical channels may exist for the formation of PAHs, so we have concentrated on the viability of the formation of the smallest building block species, C2H2, in a variety of carbon-rich stellar outflows. C2H2 is very sensitive to dissociation by UV radiation. This sensitivity is tested, using models of the time-dependent chemistry. We find that C2H2 formation is sensitive to some of the physical parameters and that in some known sourc...

  15. Measurement of the transition probability of the C III 190.9 nanometer intersystem line

    Kwong, Victor H. S.; Fang, Z.; Gibbons, T. T.; Parkinson, W. H.; Smith, Peter L.

    1993-01-01

    A radio-frequency ion trap has been used to store C(2+) ions created by electron bombardment of CO. The transition probability for the 2s2p 3Po1-2s2 1S0 intersystem line of C m has been measured by recording the radiative decay at 190.9 nm. The measured A-value is 121 +/- 7/s and agrees, within mutual uncertainty limits, with that of Laughlin et al. (1978), but is 20 percent larger than that of Nussbaumer and Storey (1978). The effective collision mixing rate coefficient among the fine structure levels of 3Po and the combined quenching and charge transfer rate coefficients out of the 3Po1 level with the CO source gas have also been measured.

  16. Microgravity Superagglomerates Produced By Silane And Acetylene

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

    2003-01-01

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

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

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

    2015-04-24

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

  18. Donor-Acceptor Chromophores based on Acetylenic Scaffolds and Indenofluorenes

    Christensen, Mikkel Andreas

    The work described in this thesis has been focused on synthesizing donor-acceptor chromophores with conjugated π-bridges. It has also led to the development of an alternative synthetic tool for acetylenic scaffolding. The first chapter focuses on the nitrophenol D-π-A system – A phenol in...

  19. 76 FR 75840 - Revising Standards Referenced in the Acetylene Standard

    2011-12-05

    ... language from outdated standards published by standards developing organizations (``SDO standards'') (69 FR... Association standard, CGA G-1-2003, in the Acetylene Standard. See 74 FR 40442 and 74 FR 40450, respectively... outdated standard; and impose no significant new compliance costs on employers (69 FR 68283, 68285).......

  20. 77 FR 13969 - Revising Standards Referenced in the Acetylene Standard

    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...

  1. Interstitial pneumonitis after acetylene welding: A case report

    Miran Brvar

    2014-02-01

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

  2. Radiation-induced crosslinking of acetylene-impregnated polyesters

    Enhanced crosslinking and reduction in chain scission are found in the amorphous regions of polycrystalline polyesters, when they are irradiated in the presence of acetylene. Increasing the chain length of the alkyl moiety is also found to decrease the extent of damaging main chain scission

  3. Fuzzy logic control for selective hydrogenation of acetylene in ethylene rich streams using visual basic

    Presence of acetylene is technically disadvantageous in the ethylene rich gas streams from steam crackers. Acetylene tends to polymerize and inactivates the transition metal catalysts, forming highly explosive compounds. The acetylene content has to be selectively reduced to less than one part per million for such streams. The acetylene hydrogenation unit requires stringent control parameters and needs specialized process control techniques for its operation. This study is concerned with application of Fuzzy Logic Control to manipulate and control the process plant with higher precision and greater simplicity. The control program has been written in visual Basic and entails all major scenarios of work modes for successful hydrogenation of Acetylene. (author)

  4. Superexcited states on ethylene and acetylene

    Electron energy loss spectra were obtained for C2H2 and C2H4 in the energy loss range from 12 to 50 eV for 1 Kev electrons. Elastic and inelastic cross sections and generalized oscillator strengths for transitions at 13.3, 15.7 and 18.7 eV were obtained. (A.C.A.S.)

  5. Component evaluation for intersystem loss-of-coolant accidents in advanced light water reactors

    Using the methodology outlined in NUREG/CR-5603 this report evaluates (on a probabilistic basis) design rules for components in ALWRs that could be subjected to intersystem loss-of-coolant accidents (ISLOCAs). The methodology is intended for piping elements, flange connections, on-line pumps and valves, and heat exchangers. The NRC has directed that the design rules be evaluated for BWR pressures of 7.04 MPa (1025 psig), PWR pressures of 15.4 MPa (2235 psig), and 177 degrees C (350 degrees F), and has established a goal of 90% probability that system rupture will not occur during an ISLOCA event. The results of the calculations in this report show that components designed for a pressure of 0.4 of the reactor coolant system operating pressure will satisfy the NRC survival goal in most cases. Specific recommendations for component strengths for BWR and PWR applications are made in the report. A peer review panel of nationally recognized experts was selected to review and critique the initial results of this program

  6. Inter-system biases estimation in multi-GNSS relative positioning with GPS and Galileo

    Deprez, Cecile; Warnant, Rene

    2016-04-01

    The recent increase in the number of Global Navigation Satellite Systems (GNSS) opens new perspectives in the field of high precision positioning. Particularly, the European Galileo program has experienced major progress in 2015 with the launch of 6 satellites belonging to the new Full Operational Capability (FOC) generation. Associated with the ongoing GPS modernization, many more frequencies and satellites are now available. Therefore, multi-GNSS relative positioning based on GPS and Galileo overlapping frequencies should entail better accuracy and reliability in position estimations. However, the differences between satellite systems induce inter-system biases (ISBs) inside the multi-GNSS equations of observation. Once these biases estimated and removed from the model, a solution involving a unique pivot satellite for the two considered constellations can be obtained. Such an approach implies that the addition of even one single Galileo satellite to the GPS-only model will strengthen it. The combined use of L1 and L5 from GPS with E1 and E5a from Galileo in zero baseline double differences (ZB DD) based on a unique pivot satellite is employed to resolve ISBs. This model removes all the satellite- and receiver-dependant error sources by differentiating and the zero baseline configuration allows atmospheric and multipath effects elimination. An analysis of the long-term stability of ISBs is conducted on various pairs of receivers over large time spans. The possible influence of temperature variations inside the receivers over ISB values is also investigated. Our study is based on the 5 multi-GNSS receivers (2 Septentrio PolaRx4, 1 Septentrio PolaRxS and 2 Trimble NetR9) installed on the roof of our building in Liege. The estimated ISBs are then used as corrections in the multi-GNSS observation model and the resulting accuracy of multi-GNSS positioning is compared to GPS and Galileo standalone solutions.

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

    The inhibition of purified and membrane-bound hydrogenase from Azotobacter vinelandii by dihydrogen-free acetylene was investigated. The inhibition was a time-dependent process which exhibited first-order kinetics. Both H2 and CO protected against the inhibition by acetylene. K/sub protect(app)/ values of 0.41 and 24 μM were derived for these gases, respectively. Both H2-oxidizing activity and the tritium exchange capacity of the purified enzyme were inhibited at the same rate by acetylene. Removal of acetylene reversed the inhibition for both the purified and the membrane-associated form of the enzyme. The purified hydrogenases from both Rhizobium japonicum and Alcaligenes eutrophus H16 were also inhibited by acetylene in a time-dependent fashion. These findings suggest that acetylene is an active-site-directed, slow-binding, reversible inhibitor of some membrane-bound hydrogenases from aerobic bacteria

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

    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

  9. Acetylene-Accelerated Alcohol Catalytic CVD Growth of Vertically Aligned Single-Walled Carbon Nanotubes

    R. Xiang; Einarsson, E.; Okawa, J.; Miyauchi, Y.; Maruyama, S.

    2008-01-01

    Addition of only 1% of acetylene into ethanol was found to enhance the growth rate of singlewalled carbon nanotubes (SWNTs) by up to ten times. Since acetylene is a byproduct of the thermal decomposition of ethanol, this suggests an alternative fast reaction pathway to the formation of SWNTs from ethanol via byproducts of decomposition. This accelerated growth, however, only occurred in the presence of ethanol, whereas pure acetylene at the same partial pressure resulted in negligible growth ...

  10. Support state modeling for the treatment of intersystem dependence in the probabilistic safety study for Italian ENEL PWR nuclear standard power stations

    The support state model employed in the Progetto Unificato Nucleare (PUN) Probabilistic Safety Study was an effective means for the analysis of intersystem dependencies for modeling and quantifying accident sequences. The model identifies the various plant system interactions and defines the complete spectrum of support system conditions, in such a way as to significantly reduce intersystem dependencies in frontline event trees. The support state model allows for eminent insights into the understanding of plant system dependencies and provides an immediate perception of support system failures that are critical for the safety of the plant. It is a very effective model for an accurate quantification of accident sequence frequencies

  11. The IR acetylene spectrum in HITRAN: update and new results

    The 2000 HITRAN edition, with the updates of 2001, contains improved and new data on the acetylene molecule. The main changes concern the 13.6- and 7.5-μm spectral regions (improved line intensities), and the 5-μm region (previously absent from the database). These changes are reviewed, and the key problem of the validation of line intensities is dealt with. The status of the currently available line parameters is critically examined, and recommendations for future improvements are given

  12. BASF and acetylene. 70 years of reppe chemistry - long-standing reliability and promising future - and now, the only natural gas based clean technology for acetylene production

    Vicari, M. [BASF SE, Ludwigshafen (Germany)

    2013-11-01

    Acetylene is still an attractive intermediate synthesis component because carbon in methane from natural gas comes at a lower price than carbon in naphtha from crude oil or coal. Acetylene can be understood as a product of C-C coupling and functionalization. Beginning in the 1950s, BASF developed the partial oxidation (Pox) process, in addition to the electric arc process dating from the 1930s and the submerged flame process. The originally developed Pox process came along with severe emissions of hydrocarbons to the environment. Nowadays it is extremely important to have a clean, environmentally friendly technology. So in the 1990s a closed water-quench process was developed and built in the United States. The presentation focuses on the ways of making acetylene, the use of acetylene and BASF's closed water-quench process based on natural gas. This process will be presented including some important safety aspects. The process is available for licensing. (orig.)

  13. 46 CFR 56.50-103 - Fixed oxygen-acetylene distribution piping.

    2010-10-01

    ... outlet stations. (c) Acetylene distribution piping and pipe fittings must be seamless steel. Copper..., and other equipment used with acetylene. (d) Oxygen distribution piping and pipe fittings must be seamless steel or copper. (e) When more than two cylinders are connected to a manifold, the supply...

  14. Photophysics of the geminate polaron-pair state in copper phthalocyanine organic photovoltaic blends: evidence for enhanced intersystem crossing.

    Snedden, Edward W; Monkman, Andrew P; Dias, Fernando B

    2013-04-01

    Geminate polaron-pair recombination directly to the triplet state of the small dye molecule copper(II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31H- phthalocyanine (CuPC) and exciton trapping in CuPC domains, combine to reduce the internal quantum efficiency of free polaron formation in the bulk-heterojunction blends of CuPC doped with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as the electron acceptor. PMID:22933249

  15. Data underpinning - Direct observation of intersystem crossing in a Thermally Activated Delayed Florescence copper complex in the solid state

    Bergmann, Larissa; Hedley, Gordon James; Baumann, Thomas; Braese, Stefan; Samuel, Ifor David William

    2015-01-01

    We are grateful to CYNORA GmbH for financial support. This work was supported by the Engineering and Physical Sciences Research Council (grant number EP/J009016/1) and by the European Union Seventh Framework Programme under grant agreement 321305.

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

    We present an extensive study of the stationary points on the acetylene-water (AW) ground-state potential energy surface (PES) aimed in establishing accurate energetics for the two different bonding scenarios that are considered. Those include arrangements in which water acts either as a proton acceptor from one of the acetylene hydrogen atoms or a proton donor to the triple bond. We used a hierarchy of theoretical methods to account for electron correlation [MP2 (second-order Moller-Plesset), MP4 (fourth-order Moller-Plesset), and CCSD(T) (coupled-cluster single double triple)] coupled with a series of increasing size augmented correlation consistent basis sets (aug-cc-pVnZ, n=2,3,4). We furthermore examined the effect of corrections due to basis set superposition error (BSSE). We found that those have a large effect in altering the qualitative features of the PES of the complex. They are responsible for producing a structure of higher (C2v) symmetry for the global minimum. Zero-point energy (ZPE) corrections were found to increase the stability of the C2v arrangement. For the global (water acceptor) minimum of C2v symmetry our best estimates are ΔEe=-2.87 kcal/mol (ΔE0=-2.04 kcal/mol) and a van der Waals distance of Re=2.190 Aa. The water donor arrangement lies 0.3 kcal/mol (0.5 kcal/mol including ZPE corrections) above the global minimum. The barrier for its isomerization to the global minimum is Ee=0.18 kcal/mol; however, inclusion of BSSE- and ZPE-corrections destabilize the water donor arrangement suggesting that it can readily convert to the global minimum. We therefore conclude that there exists only one minimum on the PES in accordance with previous experimental observations. To this end, vibrational averaging and to a lesser extend proper description of intermolecular interactions (BSSE) were found to have a large effect in altering the qualitative features of the ground-state PES of the acetylene-water complex. (c) 2000 American Institute of Physics

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

    Eres, Gyula [ORNL; Wang, Ying [Nagoya University, Japan; Gao, Xingfa [Institute of High Energy Physics, Chinese Academy of Sciences, China; Qian, Hu-Jun [Jilin University, Changchun; Ohta, Yasuhito [Fukui Institute of Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan; Wu, Xiaona [Nagoya University, Japan; Morokuma, Keiji [Fukui Institute of Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan; Irle, Stephan [WPI-Institute of Transformative Bio-Molecules and Department of Chemistry, Nagoya University, Japan

    2014-01-01

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

  18. Research on the intersystem interference between COMPASS and Galileo%COMPASS和Galileo系统间信号干扰研究

    胡媛; 刘卫

    2012-01-01

    随着各国和地区的卫星导航系统建设.我国北斗COMPASS和欧盟Galileo系统间信号干扰已成为广泛关注的焦点。首先建立有效评价卫星导航系统间信号干扰的方法,其次分析COMPASS和Galileo系统的星座构型和信号体制参数,最后对两大系统间的民用信号间干扰进行仿真分析,结果表明COMPASS信号的引入对Galileo造成干扰,但其造成的干扰比Galileo对COMPASS的干扰小。所建立的评价方法和结果可为导航系统的信号体制设计和接收机应用提供理论参考。%With the development of satellite navigation system in many countries and regions, the intersystem interference between Chinese COMPASS and EU's Galileo has become a matter of great concern for the system providers and user communities. First, an effective evaluation method for signal interference among satellite navigation systems is established. Second, the constellation configuration and signal parameters of COMPASS and Galileo are analyzed. Finally, real simulations accounting for the interference effects between Galileo and COMPASS are carried out. All results show that COMPASS introduces intersystem interference to Galileo, but the interference effects are lower than Galileo interfered to COMPASS signals. The evaluation method and results can provide a theoretical reference for signal structure design and receiver apply.

  19. Inclusion of 13C and D in protonated acetylene

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

    2016-04-01

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

  20. Acetylene fuel from atmospheric CO2 on Mars

    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.

  1. Organogermanium Chemistry: Germacyclobutanes and digermane Additions to Acetylenes

    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.

  2. Watching the acetylene vinylidene intramolecular reaction in real time

    Jiang, Y H; Rudenko, A; Madjet, M E; Vendrell, O; Kurka, M; Schnorr, K; Foucar, L; Kübel, M; Herrwerth, O; Lezius, M; Kling, M F; van Tilborg, J; Belkacem, A; Ueda, K; Düsterer, S; Treusch, R; Schröter, C D; Santra, R; Ullrich, J; Moshammer, R

    2014-01-01

    It is a long-standing dream of scientists to capture the ultra-fast dynamics of molecular or chemical reactions in real time and to make a molecular movie. With free-electron lasers delivering extreme ultraviolet (XUV) light at unprecedented intensities, in combination with pump-probe schemes, it is now possible to visualize structural changes on the femtosecond time scale in photo-excited molecules. In hydrocarbons the absorption of a single photon may trigger the migration of a hydrogen atom within the molecule. Here, such a reaction was filmed in acetylene molecules (C2H2) showing a partial migration of one of the protons along the carbon backbone which is consistent with dynamics calculations on ab initio potential energy surfaces. Our approach opens attractive perspectives and potential applications for a large variety of XUV-induced ultra-fast phenomena in molecules relevant to physics, chemistry, and biology.

  3. Acetylene plasma coated surfaces for covalent immobilization of proteins

    A modified plasma enhanced chemical vapor method was used for acetylene plasma polymerization of biocompatible surfaces on a range of substrates. Smooth polymerized surfaces with excellent mechanical properties were achieved suitable for a wide range of biochemical and biomedical applications. Horseradish peroxidase activity analysis showed that the proteins immobilized on the plasma polymerized surfaces maintained their biological function for a much longer period of time compared to untreated surfaces. The plasma polymerized surfaces and the protein immobilization were also analyzed using quartz crystal microbalance with dissipation analysis, spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and tensile strength analysis. The results indicate that the plasma polymerized surfaces provide covalent bonding sites and immobilize a dense monolayer of proteins after incubation in protein containing solution.

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

    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.

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

    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.

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

    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 ...

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

    Gautam, Seema; Sarkar, Abir De

    2016-05-18

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

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

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

    2001-01-01

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

  9. A Convenient Synthesis of Conjugated Acetylenic Ketones by Copper(l)-Catalyzed under Microwave Irradiation

    2001-01-01

    @@ Alkynyl ketones are useful precursors and intermediates in synthetic organic chemistry1 and has evoked considerable interest. A number of methods for the synthesis of conjugated acetylenic ketones involve the reaction a metal acetylide with an acyl chlorides or another carboxylic acid derivative have been developed 2. Recently, the synthesis of α, β-conjugated acetylenic ketones catalyzed by Pd(Ⅱ) or by copper(Ⅰ)pd(Ⅱ) reaction of 1-alkynes and acyl chlorides have been described. The acylation of terminal alkynes by acyl chlorides in the presence of catalytic amounts copper(Ⅰ) salts leading to α, β-conjugated acetylenic ketones has also been reported. However, many of these reactions suffer from lack of high pressure (17 atm), long reaction time (30 h)and require low temperatures (-78℃). Our work involves the synthesis of conjugated acetylenic ketones via the reaction of terminal alkynes with aroyl chlorides in the presence of cuprous iodide under microwave irradiation conditions.

  10. Synthesis of chirals regioisomers from D-mannitol: obtainment of a acetylenic alcohols mixture

    The synthesis of chiral acetylenic regioisomers was described by using an appropriate intermediate such as isopropylidene glycerol, a synthon widely used in the enantioselective syntheses. This intermediate was prepared from D-mannitol. The nine obtained compounds have been characterized by their respective spectral data. The mixture of chiral acetylenic alcohols showed activity against Escherichia coli when tested through the monitoring of CO2 released during microbial respiration by using a conductimetric system. (author)

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

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

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

  12. Investigation of supercapacitors with carbon electrodes obtained from argon-acetylene arc plasma

    Kavaliauskas, Žydrūnas

    2010-01-01

    The dissertation examines topics related to the formation of supercapacitors using plasma technology and their analysis. Plasma spray technology was used to form supercapacitors electrodes. Carbon was deposited on stainless steel surface using the atmospheric pressure argon-acetylene plasma. The deposition of nickel oxide on the surface of carbon electrodes was made using magnetron sputtering method. The influence of acetylene amount to the supercapacitors electrodes and the electrical charac...

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

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

    2015-01-01

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

  14. Effect of surface free energy of acetylene black powder on air electrode performance

    OU Xiuqin; LIU Shuguang; LIANG Guangchuan; LI Ying; ZHI Xiaoke; HAN Bin

    2006-01-01

    The effects of acetylene black powder surface free energy on air electrode electrochemical performance and lifetime were studied. The acetylene black was immersed in 30% H2O2 at room temperature and the changes of functional groups and surface free energy were investigated by X-ray Photoelectron Spectroscopy (XPS) and powder contact angle (CA). The air electrode performance was characterized by the potential polarization curves and the lifetime was measured by constant-current discharge. It shows that, its surface free energy is the lowest when the acetylene black is immersed in H2O2 for 240 h. The polarization potential of the air electrode prepared by the pretreated acetylene black is 0.25 V(vs. Hg/HgO), 0.21 V lower than the air electrode with untreated acetylene black when the working current density is 100 mA·cm-1 . And its lifetime is over 800 h at 80 mA·cm-1 . The pretreatment of acetylene black for proper time by H2O2 is favorable for the stability of the tri-phase reaction interface of air electrode and improvement of its performance.

  15. Mechanism-based inactivation of benzo[a]pyrene hydroxylase by aryl acetylenes and aryl olefins

    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, 3H-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

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

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

    2015-11-25

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

  17. VOLT-AMPERE CHARACTERISTICS OF CIS-POLY (PHENYL ACETYLENE)

    HONG Haiping; ZHOU Shuqin; JIN Xiangfeng; QIAN Renyuan; Anita FURLANI

    1991-01-01

    The volt-ampere (I-V) characteristics of the cis-poly (phenyl acetylene) (PPA) of cis-transoidal structure has been studied in the temperature range of 253-288K. An ITO/ PPA/ Au sandwich configuration was used for the measurements. Under an applied field of less than 105V/ cm it showed ohmic behavior, while the space charge.limited current (SCLC) was observed at applied fields above 5 × 105V/ cm. In the ohmic region a conductivity of 1.37× 10-16S/ cm was obtained at room temperature with an activation energy of 0.5 eV. These data indicate that the conduction is not intrinsic one but is the result of thermal release of trapped carriers. In fact the data in the SCLC region treated according to the theory for a single Gaussian distribution of traps gave a mean trap energy of 0.48 eV with a half-width of 0.4 eV and a total density of trapping states of 5× 1016/ cm3 .

  18. Acetylene-chromene terminated resins as high temperature thermosets

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

    1990-01-01

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

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

    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

  20. Selected properties of GPS and Galileo-IOV receiver intersystem biases in multi-GNSS data processing

    Two overlapping frequencies—L1/E1 and L5/E5a—in GPS and Galileo systems support the creation of mixed double-differences in a tightly combined relative positioning model. On the other hand, a tightly combined model makes it necessary to take into account receiver intersystem bias, which is the difference in receiver hardware delays. This bias is present in both carrier-phase and pseudorange observations. Earlier research showed that using a priori knowledge of earlier-calibrated ISB to correct GNSS observations has significant impact on ambiguity resolution and, therefore, precise positioning results. In previous research concerning ISB estimation conducted by the authors, small oscillations in phase ISB time series were detected. This paper investigates this effect present in the GPS–Galileo-IOV ISB time series. In particular, ISB short-term temporal stability and its dependence on the number of Galileo satellites used in the ISB estimation was examined. In this contribution we investigate the amplitude and frequency of the detected ISB time series oscillations as well as their potential source. The presented results are based on real observational data collected on a zero baseline with the use of different sets of GNSS receivers. (paper)

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

    Kocisek, J.; Lengyel, J.; Farnik, M. [J. Heyrovsky Institute of Physical Chemistry v.v.i., Academy of Sciences of the Czech Republic, Dolejskova 3, 18223 Prague (Czech Republic)

    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

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

    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

  3. A study on methane coupling to acetylene under the microwave plasma

    2010-01-01

    By optimizing the microwave chemistry reactor made of the rectangular waveguide resonator,the methane conversion(the maximum 93.7%),the C2 hydrocarbon yield(the maximum 91.0%) and the acetylene yield(the maximum 88.6%) were all greatly increased under the microwave plasma.Furthermore,for the optimal reactor,the change of the methane conversion and the C2 hydrocarbon yield is little within the range of the pressures in the experiments.The C2 hydrocarbon is mainly made up of acetylene,and the selectivity for acetylene is above 90%.Energy yield and space time yield of acetylene are also high.Optical emission spectroscopy(OES) was adopted for the diagnosis of methane coupling to acetylene under microwave plasma.The excited species(CH,C2,H2,Hα) were detected in the spectra range of 300-750 nm.Based on the products and the excited species,the reaction mechanism of methane coupling under microwave plasma was investigated,using the thermodynamics and kinetics of the chemical reaction.

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

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

    2015-08-21

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

  5. Modeling, simulation, and optimization of a front-end system for acetylene hydrogenation reactors

    Gobbo R.

    2004-01-01

    Full Text Available The modeling, simulation, and dynamic optimization of an industrial reaction system for acetylene hydrogenation are discussed in the present work. The process consists of three adiabatic fixed-bed reactors, in series, with interstage cooling. These reactors are located after the compression and the caustic scrubbing sections of an ethylene plant, characterizing a front-end system; in contrast to the tail-end system where the reactors are placed after the de-ethanizer unit. The acetylene conversion and selectivity profiles for the reactors are optimized, taking into account catalyst deactivation and process constraints. A dynamic optimal temperature profile that maximizes ethylene production and meets product specifications is obtained by controlling the feed and intercoolers temperatures. An industrial acetylene hydrogenation system is used to provide the necessary data to adjust kinetics and transport parameters and to validate the approach.

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

    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.

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

    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

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

    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.

  9. A joint theoretical and experimental study of phenylene-acetylene molecular wires

    Magyar, R J; Gao, Y; Wang, H L; Shreve, A P

    2004-01-01

    The excited state electronic structure of $\\pi$ conjugated phenylene-acetylene oligomers is calculated using time-dependent density functional theory (TD-DFT) approaches. The theoretical fluorescence spectra are analyzed in terms of Frank-Condon active nuclear normal modes and shown to compare well with experiment. Theoretical and experimental results for the optical absorption and emission spectra of these molecules indicate that the conjugation length can be significantly reduced by conformational rotations about the triple-bonded carbon links. This has serious implications on the electronic functionalities of polyphenylene-acetylene based molecular wires and their possible use as charge/energy conduits in nano-assemblies.

  10. Simulations of shock-induced mixing and combustion of an acetylene cloud in a chamber

    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

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

    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.

  12. Synthesis of Fullerene by Pyrolysis of Acetylene in Thermal HF-Plasma

    ZHU Yanjuan; ZHANG Guofu; ZHANG Wei; LIN Tianjin; XIE Hongbo; LIU Qiuxiang; ZHANG Haiyan

    2007-01-01

    Carbon soot containing fullerene was continuously produced in volume by pyrolyzing acetylene in thermal HF-Plasma. The characteristics of the carbon soot and C60 were analyzed by thtransmission electron microscopy, UV/visible, IR and Raman spectroscopy. The results show that the main ingredients of the carbon soot with size of about 25 nm are amorphous carbon, graphite and fullerene. The fullerene yield in carbon soot is about 2.5 g·h-1. Compared with the graphite arc discharge method, the acetylene thermal plasma method is a preferential one for synthesis of fullerene.

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

    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.

  14. 49 CFR 178.59 - Specification 8 steel cylinders with porous fillings for acetylene.

    2010-10-01

    ... cylinders with porous fillings for acetylene. (a) Type and service pressure. A DOT 8 cylinder is a seamless... the cylinders must comply with the following: (1) Standard taper pipe threads are required; (2) Length may not be less than as specified for American Standard pipe threads; tapped to gauge; clean cut,...

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

    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

  16. Short review on the acetylene photochemistry in clusters: photofragment caging and reactivity

    Fárník, Michal; Poterya, Viktoriya; Kočišek, Jaroslav; Fedor, Juraj; Slavíček, P.

    2012-01-01

    Roč. 110, 21-22 (2012), s. 2817-2828. ISSN 0026-8976 R&D Projects: GA ČR GA203/09/0422; GA ČR GAP208/11/0161 Institutional support: RVO:61388955 Keywords : acetylene clusters * photochemistry * molecular beams Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.670, year: 2012

  17. Acetylenic dithiafulvene derived donor-pi-acceptor dyads: synthesis, electrochemistry and non-linear optical properties

    Nielsen, Mogens Brønsted; Petersen, Jan Conrad; Thorup, Niels;

    2005-01-01

    A selection of donor-acceptor chromophores containing the redox-active dithiafulvene unit about acetylenic and aryl scaffolds has been synthesized. The molecules were studied for their optical, redox and structural properties. Moreover, third-order non-linear optical properties were investigated ...

  18. A Convenient Synthesis of Conjugated Acetylenic Ketones by Copper(l)-Catalyzed under Microwave Irradiation

    WANG; JinXian

    2001-01-01

    Alkynyl ketones are useful precursors and intermediates in synthetic organic chemistry1 and has evoked considerable interest. A number of methods for the synthesis of conjugated acetylenic ketones involve the reaction a metal acetylide with an acyl chlorides or another carboxylic acid derivative have been developed 2. Recently, the synthesis of α, β-conjugated acetylenic ketones catalyzed by Pd(Ⅱ) or by copper(Ⅰ)pd(Ⅱ) reaction of 1-alkynes and acyl chlorides have been described. The acylation of terminal alkynes by acyl chlorides in the presence of catalytic amounts copper(Ⅰ) salts leading to α, β-conjugated acetylenic ketones has also been reported. However, many of these reactions suffer from lack of high pressure (17 atm), long reaction time (30 h)and require low temperatures (-78℃). Our work involves the synthesis of conjugated acetylenic ketones via the reaction of terminal alkynes with aroyl chlorides in the presence of cuprous iodide under microwave irradiation conditions.……

  19. Synthesis of trifluoromethylated acetylenes via copper-catalyzed trifluoromethylation of alkynyltrifluoroborates

    Zheng, Huidong

    2012-12-01

    A new method for the synthesis of trifluoromethylated acetylenes is developed which involves the copper-catalyzed trifluoromethylation of alkynyltrifluoroborates with an electrophilic trifluoromethylating reagent. This method offers significant advantages such as efficiency and mild and base-free reaction conditions. A plausible mechanism is proposed. © 2012 Elsevier Ltd. All rights reserved.

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

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

    2013-01-01

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

  1. Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene

    Studt, Felix; Abild-Pedersen, Frank; Bligaard, Thomas; Sørensen, Rasmus Zink; Christensen, Claus H.; Nørskov, Jens Kehlet

    2008-01-01

    The removal of trace acetylene from ethylene is performed industrially by palladium hydrogenation catalysts ( often modified with silver) that avoid the hydrogenation of ethylene to ethane. In an effort to identify catalysts based on less expensive and more available metals, density functional...

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

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

    2016-05-01

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

  3. The Electrooxidation of Tetracycline at Acetylene Black Electrode in the Presence of Sodium Dodecyl Sulfate

    Xue Ping DANG; Cheng Guo HU; Ying Liang WEI; Sheng Shui HU

    2004-01-01

    The electrooxidation of tetracycline (TC) at acetylene black electrode has been studied in the presence of sodium dodecyl sulfate (SDS). Tetracycline (TC) exhibited very sensitive oxidation peak in this system. The peak current was proportional to TC concentration, and the detection limit was 1.2 × 10-8 mol/L. The system was used to the determination of TC in pharmaceuticals.

  4. On the Role of Surface Modifications of Palladium Catalysts in the Selective Hydrogenation of Acetylene

    Studt, Felix; Abild-Pedersen, Frank; Bligaard, Thomas;

    2008-01-01

    Summing Me up: DFT calculations have shown that alloying, subsurface carbon, and hydride formation, all increase the selectivity of Pd catalysts for acetylene hydrogenation by weakening the surface–adsorbate bond. A simple descriptor—the adsorption energy of a methyl group—has been used to quanti...

  5. 49 CFR 173.303 - Charging of cylinders with compressed gas in solution (acetylene).

    2010-10-01

    ... Federal Register citations affecting § 173.303, see the List of CFR Sections Affected which appears in the... 49 Transportation 2 2010-10-01 2010-10-01 false Charging of cylinders with compressed gas in....303 Charging of cylinders with compressed gas in solution (acetylene). (a) Cylinder, filler...

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

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

    2015-02-01

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

  7. Facile synthesis and electrochemical performances of binder-free flexible graphene/acetylene black sandwich film

    Graphene/acetylene black sandwich film was fabricated by a simple vacuum filtration procedure using a stable complex suspension of graphene oxide (GO) and acetylene black followed by a hydroiodic acid (HI) immersion process to fully reduce the GO to graphene sheets. The self-restacking of individual graphene sheets were greatly alleviated and electric conductivity was obviously improved using the acetylene black nanoparticles as both effective spacers to expand the inter-layer interval of the individual graphene sheets during the film assembly course and highly conducting bridges to facilitate the electron/ion transfer between the upper and lower graphene sheets. The flexible graphene/acetylene black film was utilized as supercapacitor electrode without additional conductive additives, binders and current collectors, which achieved an obviously higher specific capacitance (ca. 136.6 F g−1 at 0.5 A g−1) and much better specific capacitance retention at high current densities than that of the pure graphene film electrode, indicating that such a novel sandwich film structure allows for a higher charge storage capability. More importantly, the assembled symmetric supercapacitor device displayed a satisfactory specific capacitance of 59.2 F g−1 at 0.1 A g−1, 47.6 F g−1 at 0.5 A g−1 and 42.8 F g−1 at 1 A g−1, and only negligible 4.05% capacitance degradation have been found after 1000 continuous charge-discharge cycles at 0.5 A g−1, revealing outstanding rate capability, excellent electrochemical reversibility and long-term cyclability. These results proved that such a flexible and highly conductive graphene/acetylene black film can be promising electroactive materials in the development of advanced electrochemical energy storage devices

  8. Study on using acetylene in dual fuel mode with exhaust gas recirculation

    Interest in employing gaseous fuels to internal combustion (IC) engines whether for stationary or mobile automotive applications has gained importance because of the economical, sustainable and environmental technical features associated with their usage. However, the incidence of preignition and knock remains a significant barrier in achieving their optimum performance potential. With the advent of latest technologies, the above barriers are eliminated. One such technique is timed manifold injection (TMI) of the gaseous fuel, which is controlled electronically to precisely monitor the induction of fuel to overcome the preignition problem in the intake. In the present investigation, acetylene was injected in the intake manifold in a single cylinder diesel engine, with a gas flow rate of 240 g/h, start of injection time is 10o aTDC and 90o CA (9.9 ms) duration, operated in dual fuel mode. In order to decrease the NOx emissions from acetylene-diesel engine, cooled EGR was employed. The cylinder pressure, brake thermal efficiency and emissions such as NOx, smoke, CO, HC, CO2 and exhaust gas temperature were studied. Dual fuel operation with acetylene induction coupled with cooled EGR results in lowered NOx emissions and improved part load performance. -- Highlights: → Acetylene was tried in SI engines, but due to backfire further research was hindered as an alternative fuel. → But it is not tried in CI engine. Timed manifold injection was tried in diesel engine in the present work to combat backfire. → Author was successful in running the diesel engine in dual fuel mode. → 21% maximum diesel replacement was achieved. Author is confident that acetylene will be commercialised as a fuel for diesel engine in future.

  9. Influence of soil composition in the determination of chromium by atomic absorption spectrometry with flame air / acetylene

    The Air-acetylene Flame Atomic Absorption determination of chromium is a complex task, being strongly influenced by sample composition and instrumental conditions. The objective of this work was to study the influence of Al, Ca, Fe, K, Mg, and Na on the absorption of chromium in the air-acetylene flame, both separately and combined in solution, when acetylene flow and burner height vary. Dissolutions of the mixtures simulated the composition of four soils from the Quibu River Basin in Havana, Cuba. Chromium absorption first increased and then decreased with increment of acetylene flow for shorter burner heights (∼ 2-4 mm); while a continuous increase was observed for larger heights (> 4 mm). This behavior was the same in the presence and absence of interfering chemical element, mentioned above. On the other hand, the dependence of the magnitude of the interference with acetylene flow and burner height was complex and dependent on the interfering element, particularly at larger heights where the behavior of Al was remarkably different. The interference of the four mixtures of Al, Ca, K, Fe, Mg and Na decreased in comparison to individual interfering effects and was less dependent on acetylene flow and burner height. Finally, a significant reduction of interference on chromium determination in soil samples was achieved by an adequate selection of acetylene flow and burner height

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

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

    1999-08-01

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

  11. Reactivity of free radical intermediates that form spontaneously during molecular chlorine action on acetylene and vinyl monomers at low temperatures

    In this study ESR, UV, VIS and IR spectroscopy, chromatography, calorimetry, and elemental analysis were employed to show the spontaneous formation of free radicals under low-temperature action of molecular chlorine on acetylene monomer p-diethynylbenzene, and vinyl monomer acrylamide. These radicals are able to initiate chain reaction of polymerization of monomers at low temperatures. This reaction results in a completely soluble polymer with a yield of 25 %, while an insoluble cross-linked polymer has been obtained during polymerization of p-diethynylbenzene initiated by other means. For example, under radiolysis by 1000 kGy the soluble fraction of obtained polymer was ∼ 1% while the overall yield was ∼ 10%. p-Diethynylbenzene polymerizes at temperatures close to chlorine melting (170 K). Polymerization of acrylamide takes place in the temperature range of 180-210 K with an yield of polymer ∼ 10%. The low-temperature chlorination of a 20%-solution of acrylamide in glycerol enables a twofold increase of the polymer yield, and a tenfold decrease of the chlorine content in it.

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

    CHEN Longwei; SHEN Jie; SHU Xingsheng; FANG Shidong; ZHANG Lipeng; MENG Yuedong

    2009-01-01

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

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

    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...

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

    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.

  15. spectroscopic temperature measurements and verification of thermodynamic equilibrium in air-acetylene flame

    an attempt was made to use the Boltzmann plot method for the equivalent width of several absorption lines to measure the flame temperature. the equivalent width of iron atom and ion lines has been obtained from atomic absorbance measurements. the data have been used to determine the temperature of air-acetylene flame. the iron lines of interest fall in the range between 253.6 to 376.6 nm for the atom lines (Fe I)and from 249.3 to 271.4 nm for the ion lines (Fe II). the results showed that the flame temperature obtained ranged from 2100 to 2400 k, which are compatible with other spectroscopic measurements made for air acetylene flame. the question is discussed as to what extent thermodynamic equilibrium does exist in the flame.

  16. Modelingof Acetylene Pyrolysis under Steel Vacuum Carburizing Conditions in a Tubular Flow Reactor

    Rainer Reimert

    2007-03-01

    Full Text Available In the present work, the pyrolysis of acetylene was studied under steel vacuumcarburizing conditions in a tubular flow reactor. The pyrolysis temperature ranged from650 °C to 1050 °C. The partial pressure of acetylene in the feed mixture was 10 and 20mbar, respectively, while the rest of the mixture consisted of nitrogen. The total pressureof the mixture was 1.6 bar. A kinetic mechanism which consists of seven species andnine reactions has been used in the commercial computational fluid dynamics (CFDsoftware Fluent. The species transport and reaction model of Fluent was used in thesimulations. A comparison of simulated and experimental results is presented in thispaper.

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

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

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

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

    2009-10-01

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

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

    Y. Miyamoto; Zhang, H.; Rubio, A.

    2012-01-01

    Nanoscale molecular confinement substantially modifies the functionality and electronic properties of encapsulated molecules. Many works have approached this problem from the perspective of quantifying ground-state molecular changes, but little is known about the nonequilibrium dynamics of encapsulated molecular system. In this letter, we report an analysis of the nonequilibrium dynamics of acetylene (C2H2) inside a semiconducting carbon nanotube (CNT). An ultrashort high-intense laser pulse ...

  20. Rotation of a single acetylene molecule on Cu(001) by tunneling electrons in STM

    Shchadilova, Yulia E.; Tikhodeev, Sergei G.; Paulsson, Magnus; Ueba, Hiromu

    2013-01-01

    We study the elementary processes behind one of the pioneering works on STM controlled reactions of single molecules [Stipe et al., Phys. Rev. Lett. 81, 1263 (1998)]. Using the Keldysh-Green function approach for the vibrational generation rate in combination with DFT calculations to obtain realistic parameters we reproduce the experimental rotation rate of an acetylene molecule on a Cu(100) surface as a function of bias voltage and tunneling current. This combined approach allows us to ident...

  1. Dual fuel operation of used transformer oil with acetylene in a DI diesel engine

    Highlights: • Utilisation of Used transformer oil (UTO) as a fuel in a diesel engine. • UTO with acetylene in a diesel engine, on a dual fuel mode technique. • Analysis of combustion characteristics of the diesel engine. • Analysis of performance and emission characteristics of the diesel engine. - Abstract: Used transformer oil (UTO) is a waste oil obtained from power transformers and welding transformers. It possesses considerable heating value and properties similar to diesel fuel. A preliminary investigation on the utilization of the UTO in a single cylinder, four stroke small powered direct injection (DI) diesel engine revealed that at an optimum injection timing of 20°CA the engine exhibited lower nitric oxide (NO) and higher smoke emissions, compared to that of diesel operation. In order to improve the performance and reduce the smoke emission, a dual fuel operation was attempted in the present investigation. Acetylene was inducted as a primary fuel at four different flow rates viz 132 g/h, 198 g/h, 264 g/h and 330 g/h along with the air, to study the combustion, performance and emission behavior of a four-stroke, 4.4 kW diesel engine, while the UTO was injected as pilot fuel with the optimized injection timing. The experimental results were compared with diesel-acetylene dual fuel operation in the same engine. Acetylene aspiration reduced the ignition delay and maximum cylinder pressure by about 3°CA, and 25% respectively at full load in comparison with the sole UTO operation. Higher thermal efficiency and lower exhaust gas were also observed at full load. Smoke was reduced by about 13.7%, in comparison with the UTO operation at full load

  2. 1,3-Dipolar Cycloaddition Reactions of Substituted Benzyl Azides with Acetylenic Compounds

    Sultan T. Abu-Orabi

    2002-02-01

    Full Text Available We review in this article some of our work which has been published over the last fifteen years in the area of 1,3-dipolar cycloaddition reactions of substituted benzyl azides with acetylenic compounds to form the corresponding 1,2-3-triazoles. Several triazole derivatives were transformed into triazolopyridazine and triazolo-1,3,4-oxadiazole derivatives upon their reactions with hydrazine.

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

    Courtney, Amy; Andrusiv, Lubov; Courtney, Michael

    2011-01-01

    This paper describes the development and characterization of modular, oxy-acetylene driven laboratory scale shock tubes. Such tools are needed to produce realistic blast waves in a laboratory setting. The pressure-time profiles measured at 1 MHz using high speed piezoelectric pressure sensors have relevant durations and show a true shock front and exponential decay characteristic of free-field blast waves. Descriptions are included for shock tube diameters of 27 - 79 mm. A range of peak press...

  4. Transition probabilities for the 3s2 3p(2P0)-3s3p2(4P) intersystem lines of Si II

    Calamai, Anthony G.; Smith, Peter L.; Bergeson, S. D.

    1993-01-01

    Intensity ratios of lines of the spin-changing 'intersystem' multiplet of S II (4P yields 2P0) at 234 nm have been used to determine electron densities and temperatures in a variety of astrophysical environments. However, the accuracy of these diagnostic calculations have been limited by uncertainties associated with the available atomic data. We report the first laboratory measurement, using an ion-trapping technique, of the radiative lifetimes of the three metastable levels of the 3s3p2 4P term of Si II. Our results are 104 +/- 16, 406 +/- 33, and 811 +/- 77 micro-s for lifetimes of the J = 1/2, 5/2, and 3/2 levels, respectively. A-values were derived from our lifetimes by use of measured branching fractions. Our A-values, which differ from calculated values by 30 percent or more, should give better agreement between modeled and observed Si II line ratios.

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

    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

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

    Han, Huixian [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); School of Physics, Northwest University, Xi’an, Shaanxi 710069 (China); Li, Anyang; Guo, Hua, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

    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.

  7. Molecular movie for the isomerization of acetylene dication made by time resolved Coulomb imaging

    Li, Zheng; Curchod, Basile; Liekhus-Schmaltz, Chelsea; Vendrell, Oriol; Medvedev, Nikita; Pabst, Stefan; Cryan, James; Osipov, Timur; Bucksbaum, Phil; Martinez, Todd

    2016-01-01

    Experimental evidence has pointed toward the existence of ultrafast proton migration and isomerization as a key process for acetylene and its ions, however the actual mechanism for ultrafast isomerization of the acetylene [HCCH]2+ to vinylidene [H2CC]2+ dication remains nebulous. Theoretical studies show a high potential barrier of over 2 eV [J. Chem. Phys. 123, 134320 (2005)] for the isomerization pathways on the low lying dicationic states, the corresponding isomerization should take picoseconds. However a recent experiment with femtosecond X-ray free electron laser (XFEL) [Nature Commun. 6, 8199 (2015)] suggests signature of isomerization proceeding on a sub-100 femtosecond time scale. We present here a complete theoretical study of the dynamics of acetylene dication from Auger decay induced by X-ray photoionizing the carbon K shell. We find a pathway from high lying dissociative dicationic states, which can lead to the sub-100fs isomerization with assistance of the non-Born-Oppenheimer effect. Moreover, o...

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

    A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S0) 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−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−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

  9. Melamine Modification of Spherical Activated Carbon and Its Effects on Acetylene Hydrochlorination

    HAN Weijie; WANG Xugen; ZHU Mingyuan; ZHANG Haiyang; CHEN Kun; WANG Qinqin; LI Xiaoyan; DAI Bin

    2014-01-01

    Commercial spherical activated carbon (SAC) was modified by impregnation to enhance the catalytic properties of SAC in acetylene hydrochlorination through melamine modification. Different modification conditions for SAC with nitrogen were compared by changing the SAC-Melamine ratios. The effect of carbonization temperature on the modification was also investigated. Surface chemistry and adsorption properties of the modified and unmodified SACs were studied by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), elementary analysis, BET, and temperature-programmed desorption (TPD). Moreover, the catalytic properties of SAC in acetylene hydrochlorination under differently modified conditions were also investigated. Elemental analysis showed that the nitrogen content of the modified SAC was greatly improved. XPS revealed that nitrogen mainly exists in Pyrrole nitrogen and Pyridine nitrogen. TPD showed that desorption of C2H2 was changed by modification. The conversion rate of acetylene was up to 70%under the following reaction conditions:temperature, 150℃;C2H2 hourly space velocity (GHSV), 36 h-1;feed volume ratio V (HCl)/V (C2H2) = 1.15. The catalytic properties of SAC were improved significantly via melamine modification.

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

    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

  11. Evidence for alkali metal induced intermolecular acetylenic hydrogen atom transfer between hydrogen-bonded alkyne complexes in solid argon

    Condensation of acetylene, propyne, and 2-butyne/acetylene mixtures with heavy alkali metal atoms (Na, K, Cs) in an argon matrix at 15 K has led to the appearance of infrared absorptions due to ethylene, propylene, and trans-2-butene, respectively. These results stand in sharp contrast with the products obtained with lithium. Isotopic studies have shown that ethylene formation involved three different acetylene molecules and evidenced a difference in the product yield with hydrogen vs. deuterium as well as a preference for trans- vs. cis-C2H2D2 formation, which is discussed and rationalized by differences in the zero point energies for the different mixed deuterium isotopes of the intermediate vinyl radical. This trend is amplified by methyl substitution. Spectroscopic evidence was found in these experiments for cesium acetylide (Cs+C2H-) and a cesium-acetylene π complex, which are involved in the intermolecular acetylenic hydrogen atom transfer process. 26 references, 3 figures, 2 tables

  12. Structural Control of (1)A(2u)-to-(3)A(2u) Intersystem Crossing in Diplatinum(II,II) Complexes

    Durrell, A. C.; Keller, G. E.; Lam, Y.; Ch.; Sýkora, Jan; Vlček Jr., Antonín; Gray, H. B.

    2012-01-01

    Roč. 134, č. 34 (2012), s. 14201-14207. ISSN 0002-7863 R&D Projects: GA MŠk(CZ) ME10124 Institutional support: RVO:61388955 Keywords : TRIPLET EXCITED-STATE * BINUCLEAR PLATINUM (II) PHOTOCHEMISTRY * ELECTRON-TRANSFER REACTIONS Subject RIV: CG - Electrochemistry Impact factor: 10.677, year: 2012

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

    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.

  14. Ab-initio simulation of the ionization and fragmentation of acetylene by strong femtosecond laser pulses

    The electron and nuclear dynamics of acetylene when interacting with strong short laser pulses has been simulated in the framework of real-space Time Dependent Density Functional Theory (TDDFT) and molecular dynamics. The stretching and dissociation of individual bonds are reported, and are shown to depend on the laser field intensity and orientation relative to the laser polarization. The ionization dynamics, including ionization from individual Kohn-Sham orbitals, is also reported. The orbital ionization dynamics are shown to vary with an increase in the intensity of the laser field

  15. Nitrogen/argon diluted acetylene and ethylene blue flames under infrared CO2 laser irradiation

    Peter V. Pikhitsa

    2011-09-01

    Full Text Available We investigated changes in emission spectra from nitrogen/argon diluted laminar diffusion acetylene and ethylene blue flames irradiated by a powerful cw infrared CO2 laser. The changes in the radical emission bands can be interpreted as an indication of laser-induced decomposition of ethylene (for laser absorbing C2H4 fuel and of laser-absorbing intermediates (for non-absorbing C2H2 fuel. The results indicate that released active hydrogen plays an important role in addition/abstraction reactions without any participation of oxygen.

  16. Nitrogen/argon diluted acetylene and ethylene blue flames under infrared CO2 laser irradiation

    Pikhitsa, Peter V.; Daegyu Kim; Mansoo Choi

    2011-01-01

    We investigated changes in emission spectra from nitrogen/argon diluted laminar diffusion acetylene and ethylene blue flames irradiated by a powerful cw infrared CO2 laser. The changes in the radical emission bands can be interpreted as an indication of laser-induced decomposition of ethylene (for laser absorbing C2H4 fuel) and of laser-absorbing intermediates (for non-absorbing C2H2 fuel). The results indicate that released active hydrogen plays an important role in addition/abstraction reac...

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

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

    2016-06-01

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

  18. Denitrification in Low pH Spodosols and Peats Determined with the Acetylene Inhibition Method

    1980-01-01

    Potential denitrification rates were determined for predominantly acid (pH ≥ 3.6) horizons of forestal, miry, and agricultural soils from 22 locations in southern Finland. The acetylene inhibition method was used with nitrate-amended water-logged soils incubated in an N2 atmosphere containing 2.5 or 5% C2H2. Complete inhibition of the reduction of N2O to N2 was observed in 99.3% of the samples. The denitrification rates varied from 0.12 to 53.8 μg of N·cm-3·day-1. Correlation between denitrif...

  19. Aerosols from oxy-acetylene gas cutting operations on metal plates: a laboratory study

    The decommissioning of radioactively contaminated sites has the potential for creating radioactive and other potentially toxic aerosols. Laboratory studies characterized aerosols from oxy-acetylene cutting of carbon steel and stainless steel, and steel coated with stable Cs, Cd and Sr to simulate fission product contamination. Aerosol characteristics were studied with an electrical aerosol analyzer, a scanning electron microscope, filters, cascade impactors and an HCl impinger trap. Quantification of aerosolized products was by atomic absorption spectroscopy. In general, gas cutting operations produced a multicomponent, multimodal, respirable-sized aerosol

  20. Mechanisms of π-bond oxidation by cytochrome p-450: acetylenes as probes

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

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

    Hsu, Liang-Yan; Rabitz, Herschel

    2012-11-01

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

  2. Cycloisomerization of acetylenic oximes and hydrazones under gold catalysis: Synthesis and cytotoxic evaluation of isoxazoles and pyrazoles

    J C Jeyaveeran; Chandrasekar Praveen; Y Arun; A A M Prince; P T Perumal

    2016-01-01

    The synthesis of substituted isoxazoles and pyrazoles through a general cycloisomerization methodology has been reported. The capability of gold(III) chloride to promote cycloisomerization of both , -acetylenic oximes and , -acetylenic hydrazones is the centrepiece of the strategy. A range of acetylenic precursors were investigated to afford 28 examples of the products with good to excellent chemical yields. Selected compounds were screened for their cytotoxic potential towards COLO320 cancer cell lines. The IC50 values of the tested compounds were in the micromolar range, with the best compound, 5-(6-Methoxy-naphthalen-2-yl)-3-phenyl-isoxazole (3h) displaying an IC50 of 38.9 M. For this compound, the crystal structure in complex with Aurora-A kinase was obtained which revealed details of its binding mode within the active site with a free energy of binding -9.54 kcal/mol.

  3. 2-methyl-3-butyn-2-ol as an acetylene precursor in the Mannich reaction. A new synthesis of suicide inactivators of monoamine oxidase

    A two-step reaction process is reported for the synthesis of 11C, 13C, or 14C-labelled propargylamines in moderate yields. The propargylamines were prepared by a modified Mannich scheme without the use of acetylene. The reaction scheme involved the use of 2-methyl-3-butyn-2-ol followed by KOH-catalyzed elimination of acetone from the acetylenic carbinols

  4. Structure and electrochemical properties of track membranes with a polymer layer obtained by plasma polymerization of acetylene

    The structure and electrochemical properties of poly(ethylene terephthalate) track membrane modified by acetylene plasma were studied. It was found that polymer deposition on the surface of a track membrane by plasma polymerization of acetylene results in the creation of composite membranes that, in the case of formation of a thin semipermeable layer, possess an asymmetry of conductivity in electrolyte solutions – a rectification effect. It is caused by the reduction of the pores diameter due to the plasma polymer that results in changing the pore geometry, and as well due to the existence of an interface between the initial membrane and the polymer layer which have various concentrations of carboxyl groups.

  5. A CATALYST, A PROCESS FOR SELECTIVE HYDROGENATION OF ACETYLENE TO ETHYLENE AND A METHOD FOR THE MANUFACTURE OF THE CATALYST

    2009-01-01

    A catalyst comprising a mixture of metal A selected from the group of Fe, Co and Ni and metal B selected from the group of Zn and Ga, and a support material, wherein the two metals are present in an intermetallic composition; A method for the manufacture of the catalyst; and the use of above...... mentioned catalyst for the selective hydrogenation of acetylene to ethylene in a gas mixture comprising acetylenic impurities and hydrogen and one or more of, ethylene and carbon monoxide. The catalyst has a high selectivity and is based on easily available metal compounds....

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

    Walker, Michael P.

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

  7. π Type Lithium Bond Interaction between Ethylene,Acetylene,or Benzene and Amido-lithium

    YUAN,Kun; LIU,Yanzhi; L(U),Lingling; ZHU,Yuancheng; ZHANG,Ji; ZHANG,dunyan

    2009-01-01

    The optimization geometries and interaction energy corrected by basis set super-position error (BSSE) of the lithium bond complexes between ethylene,acetylene,or benzene and amido-lithium have been calculated at the B3L YP/6-311++G** and MP2/6-311 ++-G** levels.And only one configuration was obtained for each lithium bond system.All the equilibrium geometries were confirmed to be stable state by analytical frequency computations.The calculations showed that all the N(2)-Li(4) bond lengths increased obviously and the red shift of N(2)-Li(4) stretching frequency occurred after complexes formed.The calculated binding energies with BSSE and zero-point vibrational energy corrections of complexes Ⅰ,Ⅱ and Ⅲ are -26.04,-24.86 and -30.02 kJ·mol-1 via an MP2 method,respectively.Natural bond orbital (NBO) theory analysis revealed that the three complexes were all formed with π type lithium bond interaction between ethylene,acetylene,or benzene and amido-lithium.

  8. Experimental and theoretical studies of the reaction between cationic vanadium oxide clusters and acetylene

    YIN Shi; MA YanPing; DU Lin; HE ShengGui; GE MaoFa

    2008-01-01

    The time of flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source and a fast flow reactor was adopted to study the reactivity of cationic vanadium oxide clusters (VmO+n) toward acetylene (C2H2) molecules under gas phase (P, ~ 1.14 kPa), under near room temperature (T, ~ 350 K) conditions. Association products, VmOnC2H+2 (m,n = 2,4; 2,6; 3,7-8; 4,9-11; 5,12-13;6,13-16, and 7,17), are observed. The oxidation of C2H2 by (V2O5)+n, (n = 1-3) is experimentally identified.The reactivity of (V2O5)+n decreases as n increases. Density functional theory (DFT) calculations were carried out to interpret the reaction mechanisms. The DFT results indicate that a terminal oxygen atom from V2O+5 can transfer overall barrierlessly to C2H2 at room temperature, which is in agreement with the experimental observation. Other experimental results such as the observation of V2O6C2H+2 and nonobservation of V2O7,8C2H+2 in the experiments are also well interpreted based on the DFT calculations.The reactivity of vanadium oxide clusters toward acetylene and other hydrocarbons may be considered in identifying molecular level mechanisms for related heterogeneous catalysis.

  9. Rhodium(III)-Catalyzed C-H Activation/Annulation with Vinyl Esters as an Acetylene Equivalent

    Webb, NJ; Marsden, SP; Raw, SA

    2014-01-01

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

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

    Walch, Stephen P.

    1995-01-01

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

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

    Highlights: • Acetylene was decomposed on SBA-15 and Ni-SBA-15 at 650–850 °C. • Carbon spheres and filaments were formed after acetylene decomposition. • PAHs were determined in tar and residues. • Exhaust constituents include CO2, H2, NOx and hydrocarbon species. - Abstract: 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 sp2 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 1104 ppm 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

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

    Chiang, Hung-Lung, E-mail: hlchiang@mail.cmu.edu.tw [Department of Risk Management, China Medical University, Taichung 40402, Taiwan (China); Wu, Trong-Neng [Department of Public Health, China Medical University, Taichung 40402, Taiwan (China); Ho, Yung-Shou [Department of Applied Chemistry and Materials Science, Fooyin University, Kaohsiung 831, Taiwan (China); Zeng, Li-Xuan [Department of Risk Management, China Medical University, Taichung 40402, Taiwan (China)

    2014-07-15

    Highlights: • Acetylene was decomposed on SBA-15 and Ni-SBA-15 at 650–850 °C. • Carbon spheres and filaments were formed after acetylene decomposition. • PAHs were determined in tar and residues. • Exhaust constituents include CO{sub 2}, H{sub 2}, NO{sub x} and hydrocarbon species. - Abstract: 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{sup 2} structure) cm{sup −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), H{sub 2}, and C{sub 2}H{sub 2} 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 1104 ppm 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.

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

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

    2016-01-01

    A novel mid-infrared/near-infrared double resonant absorption setup for studying infrared-inactive vibrational states is presented. A strong vibrational transition in the mid-infrared region is excited using an idler beam from a singly resonant continuous-wave optical parametric oscillator, to populate an intermediate vibrational state. High output power of the optical parametric oscillator and the strength of the mid-infrared transition result in efficient population transfer to the intermediate state, which allows measuring secondary transitions from this state with a high signal-to-noise ratio. A secondary, near-infrared transition from the intermediate state is probed using cavity ring down spectroscopy, which provides high sensitivity in this wavelength region. Due to the narrow linewidths of the excitation sources, the rovibrational lines of the secondary transition are measured with sub-Doppler resolution. The setup is used to access a previously unreported symmetric vibrational state of acetylene, $\

  14. Acetylene black nanoparticle-modified electrode as an electrochemical sensor for rapid determination of rutin

    Acetylene black nanoparticles were homogeneously dispersed into water in the presence of hydrophobic surfactant and then used to modify the surface of a glassy carbon electrode. An examination of the electrochemistry of rutin showed that this modification of the electrodes resulted in a considerable enhancement of the surface, thus remarkably increasing the signal for rutin. As a result, a sensitive and convenient electrochemical method was developed for the determination of rutin. The linear range is from 20 μg L-1 to 5 mg L-1, and the limit of detection is 10 μg L-1. The method was successfully employed to the determination of rutin in traditional Chinese medicines. (author)

  15. Features of photopolymerization of Langmiur-Blodgett thin films of acetylenic acids

    UV-induced polymerization of thin (1-4 monolayers) Langmuir-Blodgett films of acetylenic carboxylic acids with triple bonds in different positions (terminal: 23-tetracosinic acid HC≡C(CH2)21COOH, and internal: 2-docosinic CH3(CH2)18C≡CCOOH) and their lead salts is investigated. It is shown by means of IR spectroscopy that the topochemical reaction proceeds with the participation of carboxylic groups. The differences in the structure of mono- and bilayers are demonstrated. The mechanism of the topochemical reaction depends on the method of film transfer onto the substrate. It is shown by means of UV spectroscopy that short conjugated polyenes (containing 7 to 9 carbon atoms) are formed as the product of polymerization. The mechanism of the formation of these polyene chains is proposed on the basis of the experimental data and semi-empirical calculations.

  16. Features of photopolymerization of Langmiur-Blodgett thin films of acetylenic acids

    Dultsev, F.N., E-mail: fdultsev@thermo.isp.nsc.r [Institute of Semiconductor Physics SB RAS, Novosibisrk, 630090, Lavrentiev Ave., 13 (Russian Federation); Badmaeva, I.A. [Institute of Semiconductor Physics SB RAS, Novosibisrk, 630090, Lavrentiev Ave., 13 (Russian Federation)

    2009-11-02

    UV-induced polymerization of thin (1-4 monolayers) Langmuir-Blodgett films of acetylenic carboxylic acids with triple bonds in different positions (terminal: 23-tetracosinic acid HC{identical_to}C(CH2)21COOH, and internal: 2-docosinic CH3(CH2)18C{identical_to}CCOOH) and their lead salts is investigated. It is shown by means of IR spectroscopy that the topochemical reaction proceeds with the participation of carboxylic groups. The differences in the structure of mono- and bilayers are demonstrated. The mechanism of the topochemical reaction depends on the method of film transfer onto the substrate. It is shown by means of UV spectroscopy that short conjugated polyenes (containing 7 to 9 carbon atoms) are formed as the product of polymerization. The mechanism of the formation of these polyene chains is proposed on the basis of the experimental data and semi-empirical calculations.

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

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

    2016-01-01

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

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

    Yung, E.

    1974-01-01

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

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

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

    2016-01-01

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

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

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

    2016-08-28

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

  1. Effect of the molecule structure of acetylene compound on the kinetics of the electrode reactions of iron in hydrochloric and sulfuric acids

    Electrochemical interaction between acetylene compounds both with and without α-hydrogen and ion in hydrochloric and sulfuric acids was studied by the method of potentiostatic voltammetry using rotating disk electrode and measurements of stationary electrode capacity. Tendency of acetylene compounds towards electrochemical reduction correlates with their capability to be polymerized on iron in acid solutions. The presence of α-hydrogen atom defines the acetylene compound ability for polymerization on iron providing secondary inhibition effect. Compound that does not contain α-hydrogen manifests solely adsorption mechanism of inhibition

  2. Gas and soot products formed in the pyrolysis of acetylene mixed with methanol, ethanol, isopropanol or n-butanol

    The pyrolysis of acetylene-methanol, acetylene-ethanol, acetylene-isopropanol and acetylene-n-butanol mixtures has been studied in a flow reactor in the 975–1475 K temperature range. The purpose of this work is to analyze the effect of each alcohol on soot and gas products coming from the pyrolysis of the mixtures compared to the results observed in the pyrolysis of pure acetylene, taken as a reference. Results show that the presence of alcohols always reduces the formation of soot and that the lower the atomic carbon/oxygen (C/O) ratio in the reacting mixture, the higher the soot reduction achieved, mainly due to the enhancement of oxidation reactions by the presence of O in the fuel mixture. The experimental evolution of gas products at the reactor outlet is interpreted through a detailed gas phase chemical kinetic mechanism, which allows insight into the causes for soot reduction by the presence of the different alcohols. This analysis reveals that including methanol in the reacting mixture favours mainly the formation of CO, preventing most of the carbon coming from the alcohol to take part in soot formation and its precursors. The rest of the alcohols not only decompose into oxidation products but they can also form species that may contribute to soot formation. In particular, ethanol promotes the formation of CO and CH4, which come from competing reactions that prevent PAH formation, but also forms C2H4 that may contribute to soot precursors growth. Isopropanol contributes to disfavour PAH formation because it decomposes into CO and CH4, but it also forms C2 and C3 hydrocarbons that play an important role in PAH formation and growth. N-butanol enhances oxidation reactions to CO and CH4 formation in a lower degree than the rest of the alcohols and tends to decompose into small hydrocarbons, able to contribute to PAH formation and growth. -- Highlights: ► Study of acetylene-alcohol pyrolysis (including methanol, ethanol, isopropanol and n-butanol). ► The

  3. Mechanism of Ziegler-Natta polymerization of acetylene: a nutation NRMR study. Technical report, 22 Jun 82-9 Dec 83

    Clarke, T.C.; Yannoni, C.S.; Katz, T.J.

    1983-12-09

    Using nutation NMR spectroscopy the distance between adjacent /sup 13/C labels was measured in samples of polyacetylene prepared by polymerizing a dilute solution of double /sup 13/C-labelled acetylene in /sup 12/C-acetylene using titanium tetra-n-butoxide plus triethylaluminum as a catalyst. The experiments accord with expectation if the polymerization proceeds by a four-center insertion mechanism rather than by a metallacycle mechanism involving metal-carbenes.

  4. Design and implementation of a stable state control system for acetylene production by coal H-plasma pyrolysis

    To keep the 2 MW equipment for producing acetylene by coal H-plasma pyrolysis running stably and safely, and to improve acetylene yield, an multi-function control system has been designed and implemented. In this system, the time slice division method has been adopted to collect important signals at high speed and in continuous mode for a long time. For improving the stability and the response speed of the control system. Integral Separation Control Arithmetic has been used. Moreover, to meet local user and remote user requirements, the control system has provided fast and visual information by the combination of C/S mode and B/S mode. The control system has shown favorable stability, reliability and usability in many experiments. (authors)

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

    Wierzbowska, Małgorzata; Sobolewski, Andrzej L.

    2016-03-01

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

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

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

    2013-12-15

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

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

    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.

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

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

    2014-06-01

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

  9. The Study of the Adsorption Kinetics of Acetylene and Methanol on Silica Gel by Gravimetry and Global Fitting

    Galíková, Anna; Galík, Aftanas

    Bratislava: Slovak University of Technology , 2004 - (Markoš, J.; Štefuca, V.), s. 64 ISBN 80-227-2052-6. [International Conference of Slovak Society of Chemical Engineering /31./. Tatranské Matliare (SK), 24.05.2004-28.05.2004] R&D Projects: GA ČR GA104/04/2028 Institutional research plan: CEZ:AV0Z4072921 Keywords : adsorption * desorption * acetylene Subject RIV: CI - Industrial Chemistry, Chemical Engineering

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

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

    2013-01-01

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

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

    Takeshi Hikata

    2013-04-01

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

  12. Differences in acetylene chemistry of highly substituted zirconocene and titanocene complexes - thermal stability and linear dimerization of terminal alkynes

    Horáček, Michal; Štěpnička, P.; Kubišta, Jiří; Gyepes, R.; Mach, Karel

    Rende: Centro Editoriale e Librario, 2005 - (Giordano, G.), s. 55-58 ISBN 88-7458-032-0. [Convegno Nazionale Scienza e Tecnologia Delle Zeoliti /7./ joint with Czech-Italian Workshop on Catalysis and Zeolites /1./. Camigliatello Silano (IT), 26.06.2005-30.06.2005] Institutional research plan: CEZ:AV0Z40400503 Keywords : bis(trimethylsilyl)acetylene * zirconocene-BTMSA complexes * catalysis Subject RIV: CF - Physical ; Theoretical Chemistry

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

    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.

  14. Using Acetylene for Selective Catalytic Reduction of NO in Excess Oxygen

    YU Shan-Shan; WANG Xin-Ping; WANG Chong; XU Yan

    2006-01-01

    Acetylene as a reducing agent for selective catalytic reduction of NO (C2H2-SCR) was investigated over a series of metal exchanged HY catalysts, in the reaction system of 0.16% NO, 0.08% C2H2, and 9.95% O2 (volume percent)in He. 75% of NO conversion to N2 with hydrocarbon efficiency about 1.5 was achieved over a Ce-HY catalyst around 300 ℃. The NO removal level was comparable with that of selective catalytic reduction of NOx by C3H6reported in literatures, although only one third of the reducing agent in carbon moles was used in the C2H2-SCR of NO. The protons in zeolite were crucial to the C2H2-SCR of NO, and the performance of HY in the reaction was significantly promoted by cerium incorporation into the zeolite. NO2 was proposed to be the intermediate of NO reduction to N2, and the oxidation of NO to NO2 was rate-determining step of the C2H2-SCR of NO over Ce-HY.The suggestion was well supported by the results of the NO oxidation with O2, and the C2H2 consumption under the conditions in the presence or absence of NO.

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

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

    2016-07-01

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

  16. Diffusion air effects on the soot axial distribution concentration in a premixed acetylene/air flame

    Fassani, Fabio Luis; Santos, Alex Alisson Bandeira; Goldstein Junior, Leonardo [Universidade Estadual de Campinas, SP (Brazil). Faculdade de Engenharia Mecanica. Dept. de Engenharia Termica e de Fluidos]. E-mails: fassani@fem.unicamp.br; absantos@fem.unicamp.br; leonardo@fem.unicamp.br; Ferrari, Carlos Alberto [Universidade Estadual de Campinas, SP (Brazil). Inst. de Fisica. Dept. de Eletronica Quantica]. E-mail: ferrari@ifi.unicamp.br

    2000-07-01

    Soot particles are produced during the high temperature pyrolysis or combustion of hydrocarbons. The emission of soot from a combustor, or from a flame, is determined by the competition between soot formation and its oxidation. Several factors affect these processes, including the type of fuel, the air-to-fuel ratio, flame temperature, pressure, and flow pattern. In this paper, the influence of the induced air diffusion on the soot axial distribution concentration in a premixed acetylene/air flame was studied. The flame was generated in a vertical axis burner in which the fuel - oxidant mixture flow was surrounded by a nitrogen discharge coming from the annular region between the burner tube and an external concentric tube. The nitrogen flow provided a shield that protected the flame from the diffusion of external air, enabling its control. The burner was mounted on a step-motor driven, vertical translation table. The use of several air-to-fuel ratios made possible to establish the sooting characteristics of this flame, by measuring soot concentration along the flame height with a non-intrusive laser light absorption technique. (author)

  17. In situ acetylene reduction activity of Scytonema julianum in Vapor cave (Spain

    Asencio Antonia Dolores

    2011-01-01

    Full Text Available Nitrogen fixation was measured in situ for the first time by acetylene reduction for a greyish mat composed of Scytonema julianum in cave- like environments. Mat-specific rates (129.9-215.7 nmol C2 H4 m-2 s-1 for daytime fixation and 65.1-120.6 nmol C2 H4 m-2 s-1 for nighttime fixation recorded in the Vapor cave differed considerably due to the energy reserves stored during photosynthesis being exhausted and used in the dark phase. The most influential environmental parameter for nitrogen fixation in the Vapor cave is temperature in the daytime and nighttime fixations. Nitrogen fixation by cyanobacteria may contribute considerably to the overall nitrogen cycle in harsh environments such as caves. Nitrogenase activity in Scytonema julianum was roughly 30 times higher than that of Scytonema mirabile, which also grew in cave environments, which is due to the characteristics of each site. The entrance of Vapour cave (Spain faces SE, measures 0.75 x 0.6 m and opens to shafts of a total depth of 80 m. Its dimensions and environmental conditions (relative humidity up to 100%; maximum temperature, 43oC imply that it is isolated from external influences, and that the microclimate differs substantially from that experienced externally. Nitrogen fixation, photon flux density, relative humidity and temperature in the Vapor cave were taken hourly over a 24-hour period in winter.

  18. Molecular Heterogeneous Catalysis: a Single-Site Zeolite-Supported Rhodium Complex for Acetylene Cyclotrimerization

    By anchoring metal complexes to supports, researchers have attempted to combine the high activity and selectivity of molecular homogeneous catalysis with the ease of separation and lack of corrosion of heterogeneous catalysis. However, the intrinsic nonuniformity of supports has limited attempts to make supported catalysts truly uniform. We report the synthesis and performance of such a catalyst, made from (Rh(C2H4)2(CH3COCHCOCH3)) and a crystalline support, dealuminated Y zeolite, giving {Rh(C2H4)2} groups anchored by bonds to two zeolite oxygen ions, with the structure determined by extended X-ray absorption fine structure (EXAFS) spectroscopy and the uniformity of the supported complex demonstrated by 13C NMR spectroscopy. When the ethylene ligands are replaced by acetylene, catalytic cyclotrimerization to benzene ensues. Characterizing the working catalyst, we observed evidence of intermediates in the catalytic cycle by NMR spectroscopy. Calculations at the level of density functional theory confirmed the structure of the as-synthesized supported metal complex determined by EXAFS spectroscopy. With this structure as an anchor, we used the computational results to elucidate the catalytic cycle (including transition states), finding results in agreement with the NMR spectra.

  19. Dissociation of Methanol and Acetylene by slow Highly Charged Ion Collision

    We report here the results of dissociation of multiple charged methanol and acetylene molecules in collision with 1.2 MeV Ar8+ projectiles. We observed a wide range of dissociation products from the TOF spectrum starting from undissociated molecular ions, fragments losing an hydrogen atom due to breakage of C-H and/or O-H bonds, to complete rupture of C-C and C-O skeletons for the respective molecules. From the coincidence map of the fragments, we could separate out the different dissociation channels between carbon and oxygen ionic fragments as well as complete two-body dissociation events. The most striking feature in the breakup of CH3OH is the formation of H2+ and H3+ due to intramolecular rearrangement of the C-H bonds within the methyl group. In dissociative ionization studies of C2H2, we observed a diatom-like behaviour of the C-C charged complex as evidenced from the measured slopes of the coincidence islands for carbon atomic charged fragments and theoretical values determined from the charge and momentum distribution of the correlated particles. The shape and orientation of the islands give further information about the momentum balance in the fragmentation process in two-body dissociation

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

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

    2016-01-01

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

  1. Picosecond phase conjugation in two-photon absorption in poly-di-acetylenes

    Poly-di-acetylenes exhibit a large two-photon absorption at 1064 nm wavelength. Its different effects on phase-conjugate nonlinearity are described in the framework of picosecond experiments. In solutions, gels, and films (optically thin media), third-order susceptibility appears as an increasing intensity dependent function. Phase measurements by nonlinear interferometry with the substrate or with the solvent are compared with predictions of a resonantly driven three level system. Phase-conjugate response exhibits a multi-exponential decay. Polarization symmetries analysis shows a one-dimensional effect. Study under strong static electric field action reveals that we face charged species bound to photoconductive polymer chains. In PTS single crystals (optically thick media), response saturates and cancels at high light intensity. This is well accounted for by propagation equations solved in large two-photon absorption conditions. The effect is exploited in a phase conjugation experiment under external optical pump excitation. We thus demonstrate that enhanced nonlinearity is a two-photon absorption relayed and amplified by mid-gap absorbing species which have been created by this two-photon absorption. We formally face a four-photon absorption described by a positive imaginary seventh-order non-linearity. (author)

  2. SMFs-supported Pd nanocatalysts in selective acetylene hydrogenation:Pore structure-dependent deactivation mechanism

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

    2013-01-01

    In the present study,CNFs,ZnO and Al2O3 were deposited on the SMFs panels to investigate the deactivation mechanism of Pd-based catalysts in selective acetylene hydrogenation reaction.The examined supports were characterized by SEM,NH3-TPD and N2adsorption-desorption isotherms to indicate their intrinsic characteristics.Furthermore,in order to understand the mechanism of deactivation,the resulted green oil was characterized using FTIR and SIM DIS.FTIR results confirmed the presence of more unsaturated constituents and then,more branched hydrocarbons formed upon the reaction over alumina-supported catalyst in comparison with the ones supported on CNFs and ZnO,which in turn,could block the pores mouths.Besides the limited hydrogen transfer,N2 adsorption-desorption isotherms results supported that the lowest pore diameters of Al2O3/SMFs close to the surface led to fast deactivation,compared with the other catalysts,especially at higher temperatures.

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

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

    2016-07-01

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

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

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

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

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

    2003-01-01

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

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

    Courtney, Michael

    2011-01-01

    Instrumentation is needed to produce realistic blast waves in a laboratory setting. This paper describes the development and characterization of oxy-acetylene driven, laboratory scale shock tubes for use in studying blast injury, candidate armor materials, and material properties at blast loading rates. The pressure-time profiles show a true shock front and exponential decay characteristic of blast waves and have relevant durations. The modular design includes shock tube diameters of 27 mm and 41 mm, and a selection of peak pressures from 204 kPa to 920 kPa can be produced by selection of the driver section diameter and placement of the test sample. Characterization studies of several driver/driven section combinations showed consistent results, with peak pressures having 0.8 - 6.9 percent uncertainty in the mean. This shock tube design provides a more realistic blast profile than current air-driven shock tubes. In addition, operation does not require specialized personnel or facilities like most blast-driven...

  7. Analysis of the influence of various effects on frequency shifts of the acetylene saturated absorption lines

    Dong Lei; Zhang Lei; Dou Hai-Peng; Yin Wang-Bao; Jia Suo-Tang

    2008-01-01

    Frequency shifts of the acetylene saturated absorption lines at 1.5μm with temperature,gas pressure and laser power have been investigated in detail.The second-order Doppler effect,the recoil effect,the Zeeman effect,the pressure shift and the power shift are taken into consideration.The magnitudes of those shifts caused by various effects are evaluated.In order to reproduce the stability of 5.7 x 10-14 obtained by Edwards,all necessary conditions are given.The results show that when there is a larger external magnetic field,the Zeeman shift could not be neglected,so that the shield should be employed.And the design of a long cavity is advantageous to reduce the influence of the second-order Doppler effect.The results also show that at least ±2.5°C temperature control for cavity can effectively prevent several effects and improve the frequency stability.

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

    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.

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

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

  10. Acetylene black incorporated layered copper sulfide nanosheets for high-performance supercapacitor

    Highlights: • CuS/AB composites were synthesized by a simple solvothermal route. • Supercapacitor electrode based on CuS/AB was fabricated. • Microstructures and electrochemical properties of the electrodes were evaluated. • CuS/AB electrode exhibited ultrahigh specific capacitance and good cycling stability. - Abstract: Two-dimensional transition metal chalcogenides are attracting increasing attention in energy storage due to their unique structures and electronic properties. CuS has been demonstrated with a metal-like electronic conductivity and a high theoretical capacity. In this work, a facile strategy was reported for one-step synthesis of acetylene black (AB) incorporated layered CuS nanosheet via a simple solvothermal route. X-ray diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy were used to investigate the morphologies and microstructures of the as-prepared materials. Electrochemical data showed that the CuS/AB composites displayed a high specific capacitance of 2981 F/g at 1.0 A/g and retained 64.6% (1924.5 F/g) at a high current density of 20 A/g, indicative of good rate capability. Furthermore, the composites retained approximately 92% of the initial specific capacitance after 600 cycles at a current density of 1.0 A/g, demonstrating good cycling stability. The outstanding electrochemical properties of the CuS/AB composite suggested that it had great potential for practical applications in high-performance supercapacitors and the present synthesis strategy maybe readily extended to the preparation of other composites based on CuS for potential applications in energy storage and conversion devices

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

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

    1999-10-01

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

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

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

    2014-06-01

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

  13. Acetylene black incorporated layered copper sulfide nanosheets for high-performance supercapacitor

    Huang, Ke-Jing, E-mail: kejinghuang11@163.com; Zhang, Ji-Zong; Jia, Yu-Ling; Xing, Ke; Liu, Yan-Ming

    2015-08-25

    Highlights: • CuS/AB composites were synthesized by a simple solvothermal route. • Supercapacitor electrode based on CuS/AB was fabricated. • Microstructures and electrochemical properties of the electrodes were evaluated. • CuS/AB electrode exhibited ultrahigh specific capacitance and good cycling stability. - Abstract: Two-dimensional transition metal chalcogenides are attracting increasing attention in energy storage due to their unique structures and electronic properties. CuS has been demonstrated with a metal-like electronic conductivity and a high theoretical capacity. In this work, a facile strategy was reported for one-step synthesis of acetylene black (AB) incorporated layered CuS nanosheet via a simple solvothermal route. X-ray diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy were used to investigate the morphologies and microstructures of the as-prepared materials. Electrochemical data showed that the CuS/AB composites displayed a high specific capacitance of 2981 F/g at 1.0 A/g and retained 64.6% (1924.5 F/g) at a high current density of 20 A/g, indicative of good rate capability. Furthermore, the composites retained approximately 92% of the initial specific capacitance after 600 cycles at a current density of 1.0 A/g, demonstrating good cycling stability. The outstanding electrochemical properties of the CuS/AB composite suggested that it had great potential for practical applications in high-performance supercapacitors and the present synthesis strategy maybe readily extended to the preparation of other composites based on CuS for potential applications in energy storage and conversion devices.

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

    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.

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

    Kroneck, Peter M H

    2016-03-01

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

  16. Measurement of ethylene and methane production in a temperate forest soil using inhibition of acetylene and carbon monoxide

    XU XingKai; INUBUSHI Kazuyuki

    2008-01-01

    We studied in the laboratory the effects of acetylene (C2H2) concentrations on the accumulation and consumption of ethylene and methane in a temperate pine forest soil, and in situ ethylene and methane production and flush effects of nitrogen sources on both productions in the pine forest stand (Pinus sylvestris L.). The addition of C2H2 at concentrations more than 50 Pa C2H2 in the headspace caused a more than 95% reduction in rates of ethylene and methane consumption in forest soil compared to those with no C2H2. Furthermore, addition of acetylene within a range of 50 to 10, 000 Pa C2H2 induced a similar rate of methane accumulation in forest soil. Hence, it can be concluded that presence of more than 50 Pa C2H2 in the headspace is an effective method to measure methane production in forest soil. The addition of C2H2 at concentrations more than 50 Pa C2H2 induced an increasing concentration of ethylene in the headspace (P≤0.05), indicating the reduction of acetylene to ethylene in forest soil. Using inhibition of 0.5 kPa C2H2 in combination with 5 kPa carbon monoxide that inhibits the reduction of acetylene in a short term, it was observed that there was a larger in situ methane production rate (218±26 μg C m-2 h-1 (μg C per square meter per hour, the same below)) than in situethylene produc-tion rate (92 ± 6 μg C m-2 h-1) in the pine forest soil. The addition of nitrogen sources such as urea, urea plus a nitrification inhibitor dicyandiamide, and potassium nitrate, could induce a 5-fold greater in-crease in rates of in situ ethylene and methane production compared to those in the control, particu-larly in the latter (P≤0.05). The results can promote in situ measurement of ethylene and methane production in forest soils at different sites.

  17. Morphology of carbon nanotubes prepared via chemical vapour deposition technique using acetylene: A small angle neutron scattering investigation

    D Sen; K Dasgupta; J Bahadur; S Mazumder; D Sathiyamoorthy

    2008-11-01

    Small angle neutron scattering (SANS) has been utilized to study the morphology of the multi-walled carbon nanotubes prepared by chemical vapour deposition of acetylene. The effects of various synthesis parameters like temperature, catalyst concentration and catalyst support on the size distribution of the nanotubes are investigated. Distribution of nanotube radii in two length scales has been observed. The number density of the smaller diameter tubes was found more in number compared to the bigger one for all the cases studied. No prominent scaling of the structure factor was observed for the different synthesis conditions.

  18. Temperature dependence of corrosion inhibition of steels used in oil well stimulation using acetylenic compound and halide ion salt mixtures

    Menezes, M.A.M. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica], E-mail: marcom@eq.ufrj.br; Valle, M.L.M. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica. Dept. de Processos Organicos; Dweck, J. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica. Dept. de Processos Inorganicos; Queiroz Neto, J.C. [Petroleo Brasileiro S.A. (CENPES / PETROBRAS), Rio de Janeiro, RJ (Brazil). Centro de Pesquisas

    2007-07-15

    Halogenated salt (HS)-acetylenic compound (AC) mixtures were tested as corrosion inhibitors of 13Cr and 22Cr stainless steel and N80 and P110 carbon steel when exposed to 15 wt.% HCl solutions, at 50 deg C, 80 deg C and 100 deg C. The best corrosion inhibition efficiency is obtained when the concentration of both AC and HS is 1.5 wt. %, which indicates the use of all tested steels in oil well stimulation operated at 50 deg C and the use of 13Cr, N80 and P110 steels in oil well processing temperatures up to 100 deg C. (author)

  19. Nuclear magnetic resonance study of the structure of simple molecules adsorbed on metal surfaces: acetylene on platinum

    We have used NMR to determine the structure of acetylene (HC - CH) adsorbed at room temperature on small platinum particles by studying the 13C-13C, 13C-1H, and 1H-1H dipolar interactions among the nuclei in the adsorbed molecules. We find a model of 77% CCH2 and 23% HCCH to be the only one consistent with all of our data. The C-C bond length of the majority species, CCH2, is determined as 1.44 +- 0.02 A, midway between a single and double bond, suggesting that both carbon atoms bond to the surface. 36 references, 29 figures, 1 table

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

    Malla, Pavani

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

  1. El cieno de acetileno como tratamiento de la tricofitosis de los terneros-(Acetylene mud as tricophytosis treatment in calves.

    Hernández Barreto, Miguel A

    2011-04-01

    Full Text Available ResumenLa tricofitosis es una enfermedad micótica que afecta a numerosas especies animales, incluyendo al hombre. Los tratamientos utilizados para combatir esta entidad son numerosos e incluyen antimicóticos, vacunas y desinfectantes.SummaryTricophytosis is a mycotic disease that affects numerous animal species, including man. The treatments used to combat this entity are numerous and include antimycotics, vaccines and disinfectants. In our work we use acetylene mud paste made from waste carbide (industrial residual as topical treatment in dermatomycoses lesions in calves (group I, study, comparing the results with cooper sulfate dissolution 22% (group II, control.

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

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

    1991-01-01

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

  3. Cross-coupling of propargylated arabinogalactan with 2-bromothiophene.

    Parshina, Lidiya N; Grishchenko, Lyudmila A; Larina, Lyudmila I; Novikova, Lyubov N; Trofimov, Boris A

    2016-10-01

    Novel pharmacologically prospective derivatives of arabinogalactan (a polysaccharide from larch wood) containing acetylenic and thiophene moieties have been obtained in up to 90% yield by cross-coupling of propargylic ethers of arabinogalactan with 2-bromothiophene. The reaction proceeds in the presence of the catalytic system Pd(Ph3P)4/CuBr/LiBr and piperidine in DMSO at 80-85°С. An advantageous feature of the synthesis is that it requires 5-25 times lesser catalytic loading than in common Sonogashira protocols thus making the reaction particularly beneficial to synthesize pharmaceutically-oriented polysaccharides. PMID:27312616

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

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

    2014-12-01

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

  5. Effects of acetylene flow rate and processing temperature on graphene films grown by thermal chemical vapor deposition

    We used thermal chemical vapor deposition (CVD) to synthesize few-layer graphene (FLG) films at a low temperature (600 °C). The FLG films were synthesized on Ni foils using a gaseous mixture of various ratios of H2 to acetylene (C2H2). We investigated that the effects of C2H2 flow on the structural properties of graphene. The quality of low-temperature CVD FLG films was investigated by Raman spectroscopy, field-emission scanning electron microscopy, and high-resolution transmission electron microscopy. The results of Raman spectroscopy revealed that C2H2 flux clearly influences the features of FLG films. To enhance the quality of FLG films grown by low-temperature CVD, the films were grown under various gas flow ratios. The results demonstrated that the common thermal CVD method that uses C2H2 as a supplemental carbon source constitutes a low-cost and easy way to synthesize graphene films at low temperature for graphene-based applications. - Highlights: • We synthesized the graphene on nickel foil by thermal CVD method. • The graphene was successfully synthesized at a low temperature of 600 °C. • The acetylene flows were controlled to enhance the quality of graphene

  6. Experimental investigation of timed manifold injection of acetylene in direct injection diesel engine in dual fuel mode

    The increase in demand and decrease in availability of fossil fuels with more stringent emission norms have led to research in finding an alternative fuel for internal combustion (IC) engines. Among the alternative fuels, gaseous fuels find a great potential. The gaseous fuel taken up for the present study is acetylene, which possesses excellent combustion properties. Preignition is the major problem with this fuel. In the present study, timed manifold injection technique is adopted to induct the fuel into the IC engine. A four-stroke, 4.4 kW diesel engine is selected, with slight modification in intake manifold for holding the gas injector, which is controlled by an electronic control unit (ECU). By using an ECU, an optimized injection timing of 10o after top dead center and 90o crank angle duration are arrived. At this condition, experiments were conducted for the various gas flow rates of 110 g/s, 180 g/s and 240 g/s. The performance was nearer to diesel at full load. Oxides of nitrogen, hydrocarbon and carbon monoxide emission decreased due to lean operation with marginal increase in smoke emission. To conclude, a safe operation of acetylene replacement up to 24% was possible with reduction in emission parameters.

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

    Mackenzie, Rebecca B.; Dewberry, Christopher T.; Leopold, Kenneth R., E-mail: A.C.Legon@bristol.ac.uk, E-mail: david.tew@bristol.ac.uk, E-mail: kleopold@umn.edu [Department of Chemistry, University of Minnesota, 207 Pleasant St., SE, Minneapolis, Minnesota 55455 (United States); Coulston, Emma; Cole, George C. [Department of Chemistry, University of Exeter, Stocker Road, Exeter EX4 4QD (United Kingdom); Legon, Anthony C., E-mail: A.C.Legon@bristol.ac.uk, E-mail: david.tew@bristol.ac.uk, E-mail: kleopold@umn.edu; Tew, David P., E-mail: A.C.Legon@bristol.ac.uk, E-mail: david.tew@bristol.ac.uk, E-mail: kleopold@umn.edu [Department of Chemistry, School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS (United Kingdom)

    2015-09-14

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

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

    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

  9. Denitrification rate determined by nitrate disapperance is higher than determined by nitrous oxide production with acetylene blockage

    Yu, Kewei; Struwe, Sten; Kjøller, Annelise;

    2008-01-01

    A mixed beech and spruce forest soil was incubated under potential denitrification assay (PDA) condition with 10% acetylene (C2H2) in the headspace of soil slurry bottles. Nitrous oxide (N2O) concentration in the headspace, as well as nitrate, nitrite and ammonium concentrations in the soil...... different treatments. Commonly applied PDA measurement likely underestimates the nitrate removal capacity of a system. Incubation time and organic matter/nitrate ratio are the most critical factors to consider using C2H2 inhibition technique to quantify denitrification. By comparing the treatments with and...... slurries were monitored during the incubation. Results show that nitrate disappearance rate was higher than N2O production rate with C2H2 blockage during the incubation. Sum of nitrate, nitrite, and N2O with C2H2 blockage could not recover the original soil nitrate content, showing an N imbalance in such a...

  10. The Breathing Orbital Valence Bond Method in Diffusion Monte Carlo: C-H Bond Dissociation ofAcetylene

    Domin, D.; Braida, Benoit; Lester Jr., William A.

    2008-05-30

    This study explores the use of breathing orbital valence bond (BOVB) trial wave functions for diffusion Monte Carlo (DMC). The approach is applied to the computation of the carbon-hydrogen (C-H) bond dissociation energy (BDE) of acetylene. DMC with BOVB trial wave functions yields a C-H BDE of 132.4 {+-} 0.9 kcal/mol, which is in excellent accord with the recommended experimental value of 132.8 {+-} 0.7 kcal/mol. These values are to be compared with DMC results obtained with single determinant trial wave functions, using Hartree-Fock orbitals (137.5 {+-} 0.5 kcal/mol) and local spin density (LDA) Kohn-Sham orbitals (135.6 {+-} 0.5 kcal/mol).

  11. Two-wavelength interferometer based on sinusoidal phase modulation with an acetylene stabilized laser and a second harmonic generation.

    Kawata, Yoshiyuki; Hyashi, Kyohei; Aoto, Tomohiro

    2015-06-15

    A two-wavelength interferometer (TWI) based on a sinusoidal-phase-modulation method with an acetylene stabilized laser and a second harmonic generation (SHG) was developed. The periodic non-linearity error for the TWI was estimated to be ± 0.1 µm at a dead path of 0.32 m. A long-term measurement showed that the TWI stability was ± 3 × 10(-7) at a dead path of 1.00 m for 12 hours with an ambient pressure variation of 3 hPa under controlled conditions of ambient temperature and humidity. Finally, we confirmed that the TWI has substantially better stability than a single-wavelength interferometer by comparing both interferometers with large temporal and spatial temperature variations. PMID:26193576

  12. Full-dimensional quantum dynamics study of vinylidene-acetylene isomerization: a scheme using the normal mode Hamiltonian.

    Ren, Yinghui; Li, Bin; Bian, Wensheng

    2011-02-14

    Full-dimensional quantum dynamics calculations of vinylidene-acetylene isomerization are performed and the state-specific resonance decay lifetimes of vinylidene(-d(2)) are computed. The theoretical scheme is a combination of several methods: normal coordinates are chosen to describe the nuclear motion of vinylidene, with both the parity and permutation symmetry exploited; phase space optimization in combination with physical considerations is used to generate an efficient discrete variable representation; the reaction coordinate is defined by us according to the three most relevant normal coordinates, along which a kind of optimal complex absorbing potential is imposed; the preconditioned inexact spectral transform method combined with an efficient preconditioner is employed to extract the energies and lifetimes of vinylidene. The overall computation is efficient. The computed energy levels generally agree with experiment well, and several state-specific lifetimes are reported for the first time. PMID:21186383

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

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

    2015-12-01

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

  14. Fabrication and Characterization of Nanocarbon-Based Nanofluids by Using an Oxygen-Acetylene Flame Synthesis System.

    Teng, Tun-Ping; Wang, Wei-Ping; Hsu, Yu-Chun

    2016-12-01

    In this study, an oxygen-acetylene flame synthesis system was developed to fabricate nanocarbon-based nanofluids (NCBNFs) through a one-step synthesis method. Measured in liters per minute (LPM), the flame's fuel flows combined oxygen and acetylene at four ratios: 1.5/2.5 (P1), 1.0/2.5 (P2), 0.5/2.5 (P3), and 0/2.5 (P4). The flow rate of cooling water (base fluid) was fixed at 1.2 LPM to produce different nanocarbon-based materials (NCBMs) and various concentrations of NCBNFs. Tests and analyses were conducted for determining the morphology of NCBMs, NCBM material, optical characteristics, the production rate, suspension performance, average particle size, zeta potential, and other relevant basic characteristics of NCBNFs to understand the characteristics and materials of NCBNFs produced through different process parameters (P1-P4). The results revealed that the NCBMs mainly had flaky and spherical morphologies and the diameters of the spherical NCBMs measured approximately 20-30 nm. X-ray diffraction and Raman spectroscopy revealed that the NCBMs contained graphene oxide (GO) and amorphous carbon (AC) when the oxygen flow rate was lower than 1.0 LPM. In addition, the NCBMs contained reduced GO, crystalline graphite (graphite-2H), and AC when the oxygen flow rate was higher than 1.0 LPM. The process parameters of P1, P2, P3, and P4 resulted in NCBMs produced at concentrations of 0.010, 0.013, 0.040, and 0.023 wt%, respectively, in NCBNFs. All the NCBNFs exhibited non-Newtonian and shear-thinning rheological properties. The P4 ratio showed the highest enhancement rate of thermal conductivity for NCBNFs, at a rate 4.85 % higher than that of water. PMID:27295256

  15. Fabrication and Characterization of Nanocarbon-Based Nanofluids by Using an Oxygen-Acetylene Flame Synthesis System

    Teng, Tun-Ping; Wang, Wei-Ping; Hsu, Yu-Chun

    2016-06-01

    In this study, an oxygen-acetylene flame synthesis system was developed to fabricate nanocarbon-based nanofluids (NCBNFs) through a one-step synthesis method. Measured in liters per minute (LPM), the flame's fuel flows combined oxygen and acetylene at four ratios: 1.5/2.5 (P1), 1.0/2.5 (P2), 0.5/2.5 (P3), and 0/2.5 (P4). The flow rate of cooling water (base fluid) was fixed at 1.2 LPM to produce different nanocarbon-based materials (NCBMs) and various concentrations of NCBNFs. Tests and analyses were conducted for determining the morphology of NCBMs, NCBM material, optical characteristics, the production rate, suspension performance, average particle size, zeta potential, and other relevant basic characteristics of NCBNFs to understand the characteristics and materials of NCBNFs produced through different process parameters (P1-P4). The results revealed that the NCBMs mainly had flaky and spherical morphologies and the diameters of the spherical NCBMs measured approximately 20-30 nm. X-ray diffraction and Raman spectroscopy revealed that the NCBMs contained graphene oxide (GO) and amorphous carbon (AC) when the oxygen flow rate was lower than 1.0 LPM. In addition, the NCBMs contained reduced GO, crystalline graphite (graphite-2H), and AC when the oxygen flow rate was higher than 1.0 LPM. The process parameters of P1, P2, P3, and P4 resulted in NCBMs produced at concentrations of 0.010, 0.013, 0.040, and 0.023 wt%, respectively, in NCBNFs. All the NCBNFs exhibited non-Newtonian and shear-thinning rheological properties. The P4 ratio showed the highest enhancement rate of thermal conductivity for NCBNFs, at a rate 4.85 % higher than that of water.

  16. Synthesis of chirals regioisomers from D-mannitol: obtainment of a acetylenic alcohols mixture; Sintese de regioisomeros quirais a partir de D-manitol: obtencao de uma mistura de alcoois acetilenicos

    Cito, Antonia Maria das Gracas Lopes; Araujo, Bruno Quirino; Lopes, Jose Arimateia Dantas [Universidade Federal do Piaui (UFPI), Teresina, PI(Brazil). Dept. de Quimica; Magalhes, Aderbal Farias; Magalhes, Eva Goncalves [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

    2009-07-01

    The synthesis of chiral acetylenic regioisomers was described by using an appropriate intermediate such as isopropylidene glycerol, a synthon widely used in the enantioselective syntheses. This intermediate was prepared from D-mannitol. The nine obtained compounds have been characterized by their respective spectral data. The mixture of chiral acetylenic alcohols showed activity against Escherichia coli when tested through the monitoring of CO{sub 2} released during microbial respiration by using a conductimetric system. (author)

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

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

    2015-01-01

    A detailed study of the valence state and distribution of the AuCl3/AC catalyst during the acetylene hydrochlorination deactivation process is described and discussed. Temperature-programmed reduction and X-ray photoelectron spectral analysis indicate that the active Au(3+) reduction to metallic Au(0) is one reason for the deactivation of AuCl3/AC catalyst. Transmission electron microscopy characterization demonstrated that the particle size of Au nano-particles increases with increasing reaction time. The results indicated that metallic Au(0) exhibits considerable catalytic activity and that Au nano-particle aggregation may be another reason for the AuCl3/AC catalytic activity in acetylene hydrochlorination. PMID:25994222

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

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

    2016-04-01

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

  19. Measurements of linestrengths, N2-, Ar-, He- and self-broadening coefficients of acetylene in the ν4+ν5 combination band using a cw quantum cascade laser

    Sajid, Muhammad Bilal

    2014-11-01

    Linestrengths, N2-, Ar-, He- and self-broadening coefficients of acetylene have been measured at 296K in the P branch of the ν4+ν5 combination band for 25 rotational transitions. The effect of gas temperature is studied over 296-683K for five transitions to allow the determination of the temperature dependent exponent n for N2- and Ar-broadening coefficients. These measurements were performed using a continuous-wave quantum cascade laser (cw-QCL) operating over 1253-1310cm-1. Spectroscopic parameters were obtained by fitting absorption spectra using Voigt, Galatry and Rautian profiles. Linestrength and broadening results are compared with previous studies available in literature for the ν4+ν5 combination band and other vibrational bands of acetylene. © 2014 Elsevier Ltd.

  20. Effects of acetylene at low concentrations on nitrification, mineralization and microbial biomass nitrogen concentrations in forest soils

    ZHANG TengYu; XU XingKai; LUO XianBao; HAN Lin; WANG YingHong; PAN GenXing

    2009-01-01

    Temperate forest surface soils at the varying distances from main trunks (e.g., Pinus koraiensis and Quercus mongolica) were used to study the effects of acetylene (C2H2) at low concentrations on nitri-fication, mineralization and microbial biomass N concentrations of the soils, and to assess the contri-bution of heterotrophic nitrification to nitrous oxide (N2O) emissions from soils. The use of acetylene at partial pressures within a range from 10 to 100 Pa C2H2 in headspace gas gave a significant decrease in N2O emission at soil moisture of c. 45% water-filled porosity space, and the decrease was almost the same in each soil after exposure of C2H2 at low concentrations. Heterotrophic nitrification could ac-count for 21%-48% of total N2O emission from each soil; the contribution would increase with in-creasing distances from the Pinus koraiensis trunks rather than from the Quercus mongolica trunks.Under the experimental conditions, the use of C2H2 at low concentrations showed no significant influ-ence on soil microbial biomass N, net N mineralization and microbial respiration. However, 100 Pa C2H2in headspace gas could reduce carbon dioxide (CO2) emissions from soils. According to the rapid consumption of 10 Pa C2H2 by forest soils and convenience for laboratory incubations, 50 Pa C2H2 in headspace gas can be used to study the origin of N2O emissions from forest soils under aerobic con-ditions and the key associated driving mechanisms. The N2O and CO2 emissions from the soils at the same distances from the Quercus mongolica trunks were larger than those from the Pinus koraiensis trunks, and both emissions decreased as the distances from trunks increased. The stepwise regression analysis showed that 95% of the variability in soil CO2 emissions could be accounted for by the con-centrations of soil total C and water soluble organic C and soil pH, and that 72% of the variability in soil N2O emissions could be accounted for by the concentrations of soil total N

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

    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

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

    Bin Dai; Qinqin Wang; Feng Yu; Mingyuan Zhu

    2015-01-01

    A detailed study of the valence state and distribution of the AuCl3/AC catalyst during the acetylene hydrochlorination deactivation process is described and discussed. Temperature-programmed reduction and X-ray photoelectron spectral analysis indicate that the active Au3+ reduction to metallic Au0 is one reason for the deactivation of AuCl3/AC catalyst. Transmission electron microscopy characterization demonstrated that the particle size of Au nano-particles increases with increasing reaction...

  3. Three-step laser induced ionization of Ir and Hg atoms in an air-acetylene flame and a gas cell

    The feasibility and the application of three-step excitation and ionization schemes with excimer-pumped, pulsed dye lasers have been studied in the case of Iridium atoms in an air acetylene flame and of Mercury atoms in a gas cell. The detection limits obtained were 0.2 ng/ml in the case of Ir and 107 atoms per cubic centimeter of air

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

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

    2013-01-01

    Acetylene inhibition of N2O reduction in laboratory soil and groundwaterdenitrification assays: evaluation by 15N tracer and 15N site preference ofN2ODaniel Weymann (1), Reinhard Well (2), Dominika Lewicka-Szczebak (2,3), and Rohe Lena (2)(1) Forschungszentrum Juelich, Agrosphere Institute (IBG-3), Juelich, Germany (), (2)Thünen-Institute of Climate-Smart Agriculture, Braunschweig, Germany, (3) University of Wroclaw, PolandThe measurement of denitrification in soils and...

  5. Tuning the Photophysical Properties of anti-B18H22: Efficient Intersystem Crossing between Excited Singlet and Triplet States in New 4,4 '-(HS)(2)-anti-B18H20

    Sauri, V.; Oliva, J. M.; Hnyk, Drahomír; Bould, Jonathan; Braborec, Jakub; Merchan, M.; Kubát, Pavel; Císařová, I.; Lang, Kamil; Londesborough, Michael Geoffrey Stephen

    2013-01-01

    Roč. 52, č. 16 (2013), s. 9266-9274. ISSN 0020-1669 R&D Projects: GA ČR(CZ) GAP207/11/1577; GA ČR GAP208/10/1678 Institutional support: RVO:61388980 ; RVO:61388955 Keywords : CONTAINING CLUSTER CHEMISTRY * 2ND-ORDER PERTURBATION-THEORY * MOLECULAR-OXYGEN Subject RIV: CA - Inorganic Chemistry ; CF - Physical ; Theoretical Chemistry (UFCH-W) Impact factor: 4.794, year: 2013

  6. Mechanism-based inactivation of cytochrome P-450 dependent benzo[a]pyrene hydroxylase activity by acetylenic and olefinic polycyclic arylhydrocarbons

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

  7. Superior mercury-free catalysts for acetylene hydrochlorination to VCM. Achieving high productivities and long catalyst life-time

    Liebens, A.T.; Piccinini, M. [Solvay S.A., Bruxelles (Belgium)

    2013-11-01

    New mercury-free catalytic systems based on the use of ionic liquids (IL) and noble metals (e.g. Pd, Au) have been evaluated for the hydrochlorination reaction of acetylene to produce Vinyl Chloride Monomer (VCM). Two different approaches have been investigated: gas-liquid homogeneous catalytic systems in the presence of molten IL/Metal and heterogeneous gas-solid ones using solid materials. For the latter case, very positive results have been obtained using SILP-type catalysts (SILP: Supported Ionic Liquid Phase) where IL/Metal were deposited onto a solid mesoporous support. Remarkably, both systems display very high Space Time Yield (STY) and breakthrough life-time stability. No deactivation is observed even after 500 h on stream indicating the strong advantages of these new materials compared to most investigated Au/C supported systems. The development of heterogeneous catalysts was preferred as the scale-up of gas-liquid technology implies important CAPEX investments to convert current plants from gas-solid to gas-liquid equipment. (orig.)

  8. Optimization of Acetylene Black Conductive Additive andPolyvinylidene Difluoride Composition for High Power RechargeableLithium-Ion Cells

    Liu, G.; Zheng, H.; Battaglia, V.S.; Simens, A.S.; Minor, A.M.; Song, X.

    2007-07-01

    Fundamental electrochemical methods were applied to study the effect of the acetylene black (AB) and the polyvinylidene difluoride (PVDF) polymer binder on the performance of high-power designed rechargeable lithium ion cells. A systematic study of the AB/PVDF long-range electronic conductivity at different weight ratios is performed using four-probe direct current tests and the results reported. There is a wide range of AB/PVDF ratios that satisfy the long-range electronic conductivity requirement of the lithium-ion cathode electrode; however, a significant cell power performance improvement is observed at small AB/PVDF composition ratios that are far from the long-range conductivity optimum of 1 to 1.25. Electrochemical impedance spectroscopy (EIS) tests indicate that the interfacial impedance decreases significantly with increase in binder content. The hybrid power pulse characterization results agree with the EIS tests and also show improvement for cells with a high PVDF content. The AB to PVDF composition plays a significant role in the interfacial resistance. We believe the higher binder contents lead to a more cohesive conductive carbon particle network that results in better overall all local electronic conductivity on the active material surface and hence reduced charge transfer impedance.

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

    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

  10. Double-slit experiment with a polyatomic molecule: vibrationally resolved C 1s photoelectron spectra of acetylene

    We report the first evidence for double-slit interferences in a polyatomic molecule, which we have observed in the experimental carbon 1s photoelectron spectra of acetylene (or ethyne). The spectra have been measured over the photon energy range of 310-930 eV and show prominent oscillations in the intensity ratios σg(υ)/σu(υ) for the vibrational quantum numbers υ = 0,1 and for the ratios σs(υ 1)/σs(υ = 0) for the symmetry s = g,u. The experimental findings are in very good agreement with ab initio density functional theory (DFT) calculations and are compatible with the Cohen-Fano mechanism of coherent emission from two equivalent atomic centers. This interpretation is supported by the qualitative predictions of a simple model in which the effect of nuclear recoil is taken into account to the lowest order. Our results confirm the delocalized character of the core hole created in the primary photoionization event and demonstrate that intramolecular core-hole coherence can survive the decoherent influence associated with the asymmetric nuclear degrees of freedom which are characteristic of polyatomic molecules. (paper)

  11. Measurements of hydrogen cyanide (HCN and acetylene (C2H2 from the Infrared Atmospheric Sounding Interferometer (IASI

    V. Duflot

    2013-04-01

    Full Text Available Hydrogen cyanide (HCN and acetylene (C2H2 are ubiquitous atmospheric trace gases with medium lifetime, which are frequently used as indicators of combustion sources and as tracers for atmospheric transport and chemistry. Because of their weak infrared absorption, overlapped by the CO2 Q branch near 720 cm−1, nadir sounders have up to now failed to measure these gases routinely. Taking into account CO2 line mixing, we provide for the first time extensive measurements of HCN and C2H2 total columns at Reunion Island (21° S, 55° E and Jungfraujoch (46° N, 8° E in 2009–2010 using observations from the Infrared Atmospheric Sounding Interferometer (IASI. A first order comparison with local ground-based Fourier transform infraRed (FTIR measurements has been carried out allowing tests of seasonal consistency which is reasonably captured, except for HCN at Jungfraujoch. The IASI data shows a greater tendency to high C2H2 values. We also examine a nonspecific biomass burning plume over austral Africa and show that the emission ratios with respect to CO agree with previously reported values.

  12. Measurements of hydrogen cyanide (HCN and acetylene (C2H2 from the Infrared Atmospheric Sounding Interferometer (IASI

    C. Clerbaux

    2012-10-01

    Full Text Available Hydrogen cyanide (HCN and acetylene (C2H2 are ubiquitous atmospheric trace gases with medium lifetime, which are frequently used as indicators of combustion sources and as tracers for atmospheric transport and chemistry. Because of their weak infrared absorption, overlapped by the CO2 Q-branch near 720 cm−1, nadir sounders have up to now failed to measure these gases routinely. Taking into account CO2 line mixing we provide for the first time extensive measurements of HCN and C2H2 total columns at Reunion Island (21° S; 55° E and Jungfraujoch (46° N; 8° E in 2009–2010 using observations from the Infrared Atmospheric Sounding Interferometer (IASI. These are compared with local ground-based Fourier Transform InfraRed (FTIR measurements and we demonstrate that the seasonality is well captured, except for HCN at Jungfraujoch. We also examine a nonspecific biomass burning plume over austral Africa and show that the emission ratios with respect to CO agree with previously reported values.

  13. Direct Observation of Cascade of Photoinduced Ultrafast Intramolecular Charge Transfer Dynamics in Diphenyl Acetylene Derivatives: Via Solvation and Intramolecular Relaxation.

    Karunakaran, Venugopal; Das, Suresh

    2016-07-21

    Interaction of light with electron donor-acceptor π-conjugated systems leading to intramolecular charge transfer (ICT) plays an essential role in transformation of light energy. Here the cascade of photoinduced ICT processes is directly observed by investigating the excited state relaxation dynamics of cyano and mono/di methoxy substituted diphenyl acetylene derivatives using femtosecond pump-probe spectroscopy and nanosecond laser flash photolysis. The femtosecond transient absorption spectra of the chromophores upon ultrafast excitation reveal the dynamics of intermediates involved in transition from initially populated Frank-Condon state to local excited state (LE). It also provides the dynamic details of the transition from the LE to the charge transfer state yielding the formation of the radical ions. Finally, the charge transfer state decays to the triplet state by geminate charge recombination. The latter dynamics are observed in the nanosecond transient absorption spectra. It is found that excited state relaxation pathways are controlled by different stages of solvation and intramolecular relaxation depending on the solvent polarity. The twisted ICT state is more stabilized (978 ps) in acetonitrile than cyclohexane where major components of transient absorption originate from the S1 state. PMID:27347705

  14. NIR bacteriochlorin chromophores accessed by Heck and Sonogashira cross-coupling reactions on a tetrabromobacteriochlorin derivative.

    de Assis, Francisco F; Ferreira, Marco A B; Brocksom, Timothy J; de Oliveira, Kleber T

    2016-01-28

    The synthesis of a new tetrabromobacteriochlorin BCBr4 is reported having the 3,4-dibromo-1H-pyrrole-2-carbaldehyde (10) as the major precursor. The BCBr4 was successfully employed in Pd cross-coupling reactions with methyl acrylate, phenyl acetylene and 4-ethynylanisole. In all three cases, the desired tetra-coupled products were obtained in good to excellent yields, and present a significant red shift in the UV-Vis bands above 800 nm. DFT and TD-DFT theoretical analyses of the NIR bacteriochlorin chromophores were performed in order to evaluate the effect of β substitution on their electronic structures. PMID:26676846

  15. Synthesis, characterization, and stability of Fe-MCM-41 for production of carbon nanotubes by acetylene pyrolysis.

    Amama, Placidus B; Lim, Sangyun; Ciuparu, Dragos; Yang, Yanhui; Pfefferle, Lisa; Haller, Gary L

    2005-02-24

    Fe-substituted MCM-41 molecular sieves with ca. 1, 2, and 3 wt % Fe were synthesized hydrothermally using different sources of colloidal silica (HiSil and Cab-O-Sil) and characterized by ICP, XRD, N2 physisorption, UV-vis, EPR, TPR, and X-ray absorption. Catalysts synthesized from Cab-O-Sil showed higher structural order and stability than those from HiSil. The local environment of Fe in the mesoporous material as studied by UV-vis reveals the dominance of framework Fe in all the as-synthesized Fe-MCM-41 samples. Dislodgement of some Fe species to extraframework location occurs upon calcination, and this effect is more severe for Fe-MCM-41 (2 wt %) and Fe-MCM-41 (3 wt %), as confirmed by EPR and X-ray absorption. These materials have been used as catalytic templates for the production of carbon nanotubes (CNTs) by acetylene pyrolysis at atmospheric pressure. A relationship between the Fe loading in MCM-41 and the carbon species produced during this reaction has been established. Using our optimized conditions for this system, Fe-MCM-41 with ca. 2 wt % Fe showed the best results with particularly high selectivity for single-wall carbon nanotube (SWNT) production. This catalyst was selective for carbon nanotubes with a low amount of amorphous carbon for a narrow range of temperatures from 1073 to 1123 K. To account for the different selectivity of these catalysts for CNTs production, the local environment and chemical state of Fe in the used catalyst was further probed by X-band EPR. PMID:16851270

  16. A DFT study on the mechanisms for the cycloaddition reactions between 1-aza-2-azoniaallene cations and acetylenes.

    Wang, Jing-mei; Li, Zhi-ming; Wang, Quan-rui; Tao, Feng-gang

    2013-01-01

    The mechanisms of cycloaddition reactions between 1-aza-2-azoniaallene cations 1 and acetylenes 2 have been investigated using the global electrophilicity and nucleophilicity of the corresponding reactants as global reactivity indexes defined within the conceptual density functional theory. The reactivity and regioselectivity of these reactions were predicted by analysis of the energies, geometries, and electronic nature of the transition state structures. The theoretical results revealed that the reaction features a tandem process: an ionic 1,3-dipolar cycloaddition to produce the cycloadducts 3 H-pyrazolium salts 3 followed by a [1,2]-shift affording the thermodynamically more stable adducts 4 or 5. The mechanism of the cycloaddition reactions can be described as an asynchronous concerted pathway with reverse electron demand. The model reaction has also been investigated at the QCISD/6-31++G(d,p) and CCSD(T)/6-31++G(d,p)//B3LYP/6-31++G(d,p) levels as well as by the DFT. The polarizable continuum model, at the B3LYP/6-31++G(d,p) level of theory, was used to study solvent effects on all the studied reactions. In solvent dichloromethane, all the initial cycloadducts 3 were obtained via direct ionic process as the result of the solvent effect. The consecutive [1,2]-shift reaction, in which intermediates 3 are rearranged to the five-membered heterocycles 4/5, is proved to be a kinetically controlled reaction, and the regioselectivity can be modulated by varying the migrant. The LOL function and RDG function based on localized electron analysis were used to analysis the covalent bond and noncovalent interactions in order to unravel the mechanism of the title reactions. PMID:22810049

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

    Miller, Laurence G.; 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 sedi...

  18. Solution processed organic light-emitting diodes using the plasma cross-linking technology

    He, Kongduo; Liu, Yang; Gong, Junyi; Zeng, Pan; Kong, Xun; Yang, Xilu; Yang, Cheng; Yu, Yan; Liang, Rongqing; Ou, Qiongrong

    2016-09-01

    Solution processed multilayer organic light-emitting diodes (OLEDs) present challenges, especially regarding dissolution of the first layer during deposition of a second layer. In this work, we first demonstrated a plasma cross-linking technology to produce a solution processed OLED. The surfaces of organic films can be cross-linked after mixed acetylene and Ar plasma treatment for several tens of seconds and resist corrosion of organic solvent. The film thickness and surface morphology of emissive layers (EMLs) with plasma treatment and subsequently spin-rinsed with chlorobenzene are nearly unchanged. The solution processed triple-layer OLED is successfully fabricated and the current efficiency increases 50% than that of the double-layer OLED. Fluorescent characteristics of EMLs are also observed to investigate factors influencing the efficiency of the triple-layer OLED. Plasma cross-linking technology may open up a new pathway towards fabrication of all-solution processed multilayer OLEDs and other soft electronic devices.

  19. Crossing Filaments

    Filippov, Boris

    2011-01-01

    Solar filaments show the position of large scale polarity inversion lines and are used for the reconstruction of large-scale solar magnetic field structure on the basis of H{\\alpha} synoptic charts for the periods when magnetographic measurements were not available. Sometimes crossing filaments are seen in H{\\alpha} filtergrams. We analyze daily H{\\alpha} filtergrams from the archive of Big Bear Solar Observatory for the period of 1999-2003 to find crossing and interacting filaments. A number of examples are presented and filament patterns are compared with photospheric magnetic field distributions. We have found that all crossing filaments reveal quadrupolar magnetic configurations of the photospheric field and presume the presence of null points in the corona.

  20. Reuse of waste sodium hypochlorite solution from the purification of acetylene%乙炔清净次氯酸钠废水的回用

    唐红建; 秦明月

    2013-01-01

    Technologies for the treatment of waste sodium hypochlorite solution from acetylene purification process were introduced .Through adopting such methods as vacuum extraction ,oxida-tion ,flocculation ,precipitation ,and filtration ,acetylene dissolved in the waste sodium hypochlo-rite solution was recovered ;the contained impurities ,such as chlorides ,silicon ,phosphorus ,and magnesium ,were removed ;thus ,the hidden danger existed in the preparation of sodium hypochlo-rite solution was reduced as well as the influences on the production and quality of cement .%介绍了乙炔清净工序产生的次氯酸钠废水的处理技术,通过采用真空萃取、氧化、絮凝、沉淀、过滤等方法,回收了次氯酸钠废水中溶解的乙炔,去除了其中的氯化物、硅、硫、磷、镁等杂质,减少了次氯酸钠配制的安全隐患和对电石渣水泥生产及质量的影响。

  1. X-H···π and X-H···N hydrogen bonds - Acetylene and hydrogen cyanide as proton acceptors

    The hydrogen-bonded systems were considered where acetylene or hydrogen cyanide acts as a proton acceptor and different proton donating molecules are taken into account. The B3LYP/6-311++G(d,p) and MP2/6-311++G(d,p) calculations were performed for the systems considered; for HCN···HF and C2H2···HF complexes various levels of approximation were applied up to CCSD(T)/6-311++G(3df,3pd)//CCSD/6-311++G(3df,3pd). The Quantum Theory of 'Atoms in Molecules' (QTAIM) was also applied. It was found that π-electrons of acetylene might act as the proton accepting centers and the found complex conformations are T-shaped ones. For hydrogen cyanide molecule the nitrogen atom acts as the proton acceptor center but not π-electrons. The characteristics of the bond critical points were also considered for the analyzed interactions and numerous correlations were found between geometrical, energetic and QTAIM parameters. The decomposition of the interaction energy for the systems analyzed was also applied.

  2. Full dimensional Franck-Condon factors for the acetylene A~ 1Au—X~1Σ+g  transition. I. Method for calculating polyatomic linear—bent vibrational intensity factors and evaluation of calculated intensities for the gerade vibrational modes in acetylene

    Franck-Condon vibrational overlap integrals for the A~1Au—X~1Σ+g transition in acetylene have been calculated in full dimension in the harmonic normal mode basis. The calculation uses the method of generating functions first developed for polyatomic Franck-Condon factors by Sharp and Rosenstock [J. Chem. Phys. 41(11), 3453–3463 (1964)], and previously applied to acetylene by Watson [J. Mol. Spectrosc. 207(2), 276–284 (2001)] in a reduced-dimension calculation. Because the transition involves a large change in the equilibrium geometry of the electronic states, two different types of corrections to the coordinate transformation are considered to first order: corrections for axis-switching between the Cartesian molecular frames and corrections for the curvilinear nature of the normal modes at large amplitude. The angular factor in the wave function for the out-of-plane component of the trans bending mode, ν4″, is treated as a rotation, which results in an Eckart constraint on the polar coordinates of the bending modes. To simplify the calculation, the other degenerate bending mode, ν5″, is integrated in the Cartesian basis and later transformed to the constrained polar coordinate basis, restoring the conventional v and l quantum numbers. An updated A~-state harmonic force field obtained recently in the R. W. Field research group is evaluated. The results for transitions involving the gerade vibrational modes are in qualitative agreement with experiment. Calculated results for transitions involving ungerade modes are presented in Paper II of this series [G. B. Park, J. H. Baraban, and R. W. Field, “Full dimensional Franck–Condon factors for the acetylene A~1Au—X~1Σ+g transition. II. Vibrational overlap factors for levels involving excitation in ungerade modes,” J. Chem. Phys. 141, 134305 (2014)

  3. The energy separation between the classical and nonclassical isomers of protonated acetylene - An extensive study in one- and n-particle space saturation

    Lindh, Roland; Rice, Julia E.; Lee, Timothy J.

    1991-01-01

    The energy separation between the classical and nonclassical forms of protonated acetylene has been reinvestigated in light of the recent experimentally deduced lower bound to this value of 6.0 kcal/mol. The objective of the present study is to use state-of-the-art ab initio quantum mechanical methods to establish this energy difference to within chemical accuracy (i.e., about 1 kcal/mol). The one-particle basis sets include up to g-type functions and the electron correlation methods include single and double excitation coupled-cluster (CCSD), the CCSD(T) extension, multireference configuration interaction, and the averaged coupled-pair functional methods. A correction for zero-point vibrational energies has also been included, yielding a best estimate for the energy difference between the classical and nonclassical forms of 3.7 + or - 1.3 kcal/mol.

  4. Comparative study of the monomer grafting: ethylene, acetylene, 1,3-butadiene and estyrene in the matrix of recycled polytetrafluoroethylene (PTFE)

    In this study it is used the recycled polytetrafluoroethylene (PTFE), that with the gamma radiation under inert atmosphere or in presence of air, it is obtained free radicals and a posterior the monomer grafting (ethylene, acetylene, styrene or 1.3 butadiene), obtaining the copolymer polytetrafluoroethylene-g-monomer. It is studied the obtention of the polymer by two methods: by direct way, via grafting, where the polymer is irradiated in presence of monomer, and via grafting when the polymer is irradiated in absence of monomer and under inert or air. The characterization of the copolymer was performed by the techniques of infrared region absorption spectroscopy with Fourier transformation (FTIR), thermogravimetric (TGA) and derivative thermogravimetry (DTG), and percentage of mass grafting (DOG)

  5. Dynamic study of carbon nanotube growth and catalyst morphology evolution during acetylene decomposition on Co/SBA-15 in an environmental TEM

    s Aires, F. J. Cadete Santo; Epicier, T.; Wagner, Jakob Birkedal;

    2012-01-01

    In situ studies of micro- and nano-objects in their characteristic environment have been performed ever since the early days of electron microscopy [1]. Over several decades the in situ observation of the synthesis of filamentous carbon (nanotubes/nanofilaments) during hydrocarbon decomposition has...... been one of the most popular topics [2] for investigation in the environmental transmission electron microscope (ETEM). In this work we study the growth of carbon nanotubes (CNTs) by the decomposition of acetylene on Co nanoparticles inserted into mesoporous silicas (SBA-15) using both conventional...... were reduced in situ in a flow of hydrogen (1 mbar, ~500°C). Electron energy-loss spectra taken before and during reduction showed that the Co oxide nanoparticles were reduced to metallic Co. In situ high resolution TEM images are consistent with cubic Co. A first attempt to study carbon nanotube...

  6. Growth of few-wall carbon nanotubes with narrow diameter distribution over Fe-Mo-MgO catalyst by methane/acetylene catalytic decomposition.

    Labunov, Vladimir A; Basaev, Alexander S; Shulitski, Boris G; Shaman, Yuriy P; Komissarov, Ivan; Prudnikava, Alena L; Tay, Beng Kang; Shakerzadeh, Maziar

    2012-01-01

    Few-wall carbon nanotubes were synthesized by methane/acetylene decomposition over bimetallic Fe-Mo catalyst with MgO (1:8:40) support at the temperature of 900°C. No calcinations and reduction pretreatments were applied to the catalytic powder. The transmission electron microscopy investigation showed that the synthesized carbon nanotubes [CNTs] have high purity and narrow diameter distribution. Raman spectrum showed that the ratio of G to D band line intensities of IG/ID is approximately 10, and the peaks in the low frequency range were attributed to the radial breathing mode corresponding to the nanotubes of small diameters. Thermogravimetric analysis data indicated no amorphous carbon phases. Experiments conducted at higher gas pressures showed the increase of CNT yield up to 83%. Mössbauer spectroscopy, magnetization measurements, X-ray diffraction, high-resolution transmission electron microscopy, and electron diffraction were employed to evaluate the nature of catalyst particles. PMID:22300375

  7. 'Clicking' on the nanoscale: 1,3-dipolar cycloaddition of terminal acetylenes on azide functionalized, nanometric surface templates with nanometer resolution

    Haensch, Claudia; Hoeppener, Stephanie; Schubert, Ulrich S.

    2009-04-01

    Electro-oxidative lithography is used as a tool to create chemical nanostructures on an n-octadecyltrichlorosilane (OTS) monolayer self-assembled on silicon. The use of a bromine precursor molecule, which is exclusively assembled on these chemical templates, can be used to further functionalize the nanostructures by the site-selective generation of azide functions and performing the highly effective 1,3-dipolar cycloaddition reaction with acetylene functionalized molecules. The versatility of this reaction scheme provides the potential to integrate a large variety of functional molecules, to tailor the surface properties of the nanostructures or to anchor molecular building blocks or particles in confined, pre-defined surface areas. The results demonstrated in the present study introduce a conceivable route towards the functionalization of chemically active surface templates with high fidelity and reliability. It is demonstrated that surface features with a lateral resolution of 50 nm functionalized with propargyl alcohol can be fabricated.

  8. 'Clicking' on the nanoscale: 1,3-dipolar cycloaddition of terminal acetylenes on azide functionalized, nanometric surface templates with nanometer resolution

    Electro-oxidative lithography is used as a tool to create chemical nanostructures on an n-octadecyltrichlorosilane (OTS) monolayer self-assembled on silicon. The use of a bromine precursor molecule, which is exclusively assembled on these chemical templates, can be used to further functionalize the nanostructures by the site-selective generation of azide functions and performing the highly effective 1,3-dipolar cycloaddition reaction with acetylene functionalized molecules. The versatility of this reaction scheme provides the potential to integrate a large variety of functional molecules, to tailor the surface properties of the nanostructures or to anchor molecular building blocks or particles in confined, pre-defined surface areas. The results demonstrated in the present study introduce a conceivable route towards the functionalization of chemically active surface templates with high fidelity and reliability. It is demonstrated that surface features with a lateral resolution of 50 nm functionalized with propargyl alcohol can be fabricated.

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

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

    2015-10-30

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

  10. Crossing Borders

    Erik D. Barton, MD, MS, MBA

    2016-01-01

    Full Text Available As emergency physicians, we are privileged to be in a field that crosses more boundaries than any other medical specialty. It is a calling. Our skills are portable and transferable across cultural and geographic disparities. For these reasons, many of us are drawn to sharing our knowledge and training across the globe – towards treating patients in underserved and austere environments abroad. The rapid growth of international and global health educational initiatives across our U.S. residency training programs is a direct result of those undeniable forces. Additionally, inclusion of such rotations becomes a powerful resident recruitment tool as more and more of our trainees are looking for these opportunities during their formative years.

  11. Palladium-catalyzed double cross-coupling of E-vinylic dibromides with PhZnCl and the synthesis of tamoxifen

    Pilli, Ronaldo A.; Robello, Luis Gustavo [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica]. E-mail: pilli@iqm.unicamp.br

    2004-12-01

    (E)-1,2-vinylic dibromides 11a-f were stereoselectively prepared via bromination of acetylenic compounds with pyridinium tribromide in MeOH/CCl{sub 4} at low temperature and double cross-coupled with PhZnCl under Pd(0) catalysis (Negishi protocol) to afford tri- and tetrasubstituted olefins 14a-e. Tamoxifen, a selective estrogen receptor modulator clinically prescribed in breast cancer therapy, was prepared in 7 steps and 30% overall yield from 4-iodophenol (3) as a 2.3:1 mixture of (Z)- and (E)-isomers. (author)

  12. Síntese de regioisômeros quirais a partir de D-manitol: obtenção de uma mistura de álcoois acetilênicos Synthesis of chirals regioisomers from D-mannitol: obtainment of a acetylenic alcohols mixture

    Antônia Maria das Graças Lopes Citó

    2009-01-01

    Full Text Available The synthesis of chiral acetylenic regioisomers was described by using an appropriate intermediate such as isopropylidene glycerol, a synthon widely used in the enantioselective syntheses. This intermediate was prepared from D-mannitol. The nine obtained compounds have been characterized by their respective spectral data. The mixture of chiral acetylenic alcohols showed activity against Escherichia coli when tested through the monitoring of CO2 released during microbial respiration by using a conductimetric system.

  13. Gaseous nitrogen losses from field plots grown with pea (Pisum sativum L.) or spring barley (Hordeum vulgare L.) estimated by 15N mass balance and acetylene inhibition techniques

    Bertelsen, F.; Jensen, E.S.

    1992-01-01

    In a mass balance of N-15-labelled nitrate added to soil grown with pea or barley, denitrification estimates using the acetylene-inhibition technique were compared with unaccounted for N-15. During the growth season of 1989, which was drier than average, N losses due to denitrification estimated by...... the acetylene-inhibition technique were negligible. A substantial amount of fertilizer N was unaccounted for by the N-15 mass balance, especially in the pea plots. The loss took place during the period of grain-filling in which no leaching occurred, and was accompanied by a decrease in N-15 content of...... the plants. Volatilization of ammonia from the aerial parts of the plants is a possible explanation of the observed loss. An estimation of denitrification relying only on the N-15 mass balance would have resulted in an overestimation of denitrification....

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

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

    1991-01-01

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

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

    Nakamura, Yoshiharu

    2010-09-01

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

  16. Effect of Solvent and Acid-Base on Palladium(ll)-catalyzed Dicarbonylation of Terminal Acetylenes: a General, Efficient andStereoselective Synthesis of Maleic Diesters and Maleic Anhydrides

    JIANG, Huan-Feng; LI, JiN-Heng; CHEN, Ming-Cai

    2001-01-01

    The productions of maleic diesters and maleic anhydrises depend on the effect of solvint and acid-bade of solvent and acid-base in palladium-catalyzed dicarbonylation of terminal acetylenes. For primaryand secondary alcohol in benzene.only maleic diesters wereobtained stereospecifically from the sicabonylation ofacetylenes in the presence of PdCl2,and NaHCO3.For tERTIARy alcohols,maleic anhydrides were synthesized selectively.

  17. Border Crossing/Entry Data - Boarder Crossing

    Department of Transportation — Border Crossing/Entry Data provides summary statistics for incoming crossings at the U.S.-Canadian and the U.S.-Mexican border at the port level. Data are available...

  18. Differences of cardiac output measurements by open-circuit acetylene uptake in pulmonary arterial hypertension and chronic thromboembolic pulmonary hypertension: a cohort study

    Schwaiblmair Martin

    2012-03-01

    Full Text Available Abstract Background As differences in gas exchange between pulmonary arterial hypertension (PAH and chronic thromboembolic pulmonary hypertension (CTEPH have been demonstrated, we asked if cardiac output measurements determined by acetylene (C2H2 uptake significantly differed in these diseases when compared to the thermodilution technique. Method Single-breath open-circuit C2H2 uptake, thermodilution, and cardiopulmonary exercise testing were performed in 72 PAH and 32 CTEPH patients. Results In PAH patients the results for cardiac output obtained by the two methods showed an acceptable agreement with a mean difference of -0.16 L/min (95% CI -2.64 to 2.32 L/min. In contrast, the agreement was poorer in the CTEPH group with the difference being -0.56 L/min (95% CI -4.96 to 3.84 L/min. Functional dead space ventilation (44.5 ± 1.6 vs. 32.2 ± 1.4%, p 2 gradient (9.9 ± 0.8 vs. 4.1 ± 0.5 mmHg, p Conclusion Cardiac output evaluation by the C2H2 technique should be interpreted with caution in CTEPH, as ventilation to perfusion mismatching might be more relevant than in PAH.

  19. Determination of halogens via molecules in the air-acetylene flame using high-resolution continuum source absorption spectrometry, Part II: Chlorine

    As continuation of the work on fluorine, the second part of the studies of halogens in the air-acetylene flame attends to the determination of chlorine using high-resolution continuum source absorption spectrometry and molecular absorption. In case of chlorine, the diatomic InCl molecule proved to be a suitable species. For an excess of In in the flame, chlorine is converted to InCl which produces a distinctive band head at 267.24 nm that could be evaluated analytically. The influence of concentrated inorganic acids and metallic matrices on the absorption at this band head was tested. In all cases the signal proved to be unaffected, i.e., no spectral interferences were observed. However, serious chemical interferences were found in the presence of sulfuric and phosphoric acids, which could be partially eliminated by adding Ca in the form of nitrate. Moreover, nitric and hydrofluoric acids as well as Cu and Ga matrices also produced significant chemical interferences. Therefore, the method of standard additions should be used for calibration purposes. Concerning the limit of detection, a value of 3 mg L-1 was achieved for a measurement time of 5 s in the presence of 10,000 mg L-1 In. The calibration curve was linear up to a chlorine concentration of 1800 mg L-1. Three certified reference materials (BCR 151, HISS-1, and PACS-2) were analyzed to test the performance of the new method, yielding good precision and accuracy

  20. Determination of halogens via molecules in the air-acetylene flame using high-resolution continuum source absorption spectrometry: Part I. Fluorine

    The particular capabilities of a high-resolution continuum source absorption spectrometer were exploited to the determination of halogens in an ordinary air-acetylene flame. In the first part of the studies, a simple method was developed, which allows the determination of fluorine by measuring GaF molecular absorption. The molecules are generated in the presence of an excess of Ga in the flame. Under such conditions, all fluorine is converted into GaF, yielding an evaluable signal for the fluorine determination. Molecular bands of GaF were found between 211 and 214 nm; the strongest absorption band head at 211.248 nm was examined in detail to prove its applicability to analytical measurements. To this end, potential chemical and spectral interferences were tested, using various highly concentrated acids and metallic salt solutions. Since no serious interferences were found, the new method proved to be very reliable. As limit of detection, 1 mg L-1 fluorine in the presence of 10 g L-1 Ga was achieved, using a measurement time of five seconds. The linear dynamic range covers more than three orders of magnitude. Accuracy and precision were verified by analysis of a standard reference material (BCR No. 33)

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

    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.

  2. Performance of practical-sized membrane-electrode assemblies using titanium nitride-supported platinum catalysts mixed with acetylene black as the cathode catalyst layer

    Shintani, Haruhiko; Kakinuma, Katsuyoshi; Uchida, Hiroyuki; Watanabe, Masahiro; Uchida, Makoto

    2015-04-01

    The performance of practical-sized membrane-electrode assemblies (MEAs) using titanium nitride-supported platinum (Pt/TiN) as the cathode catalysts was evaluated with the use of a practical single cell designed for microscale combined heat and power (CHP) applications. The performance can be controlled by adding acetylene black (AB), with the behavior being dominated by the percolation law. The electrical resistance of the MEAs drastically decreased for AB contents greater than 37 vol%. The Pt utilization percentage was close to 100% for Pt/TiN with percolated AB networks. It was also found that the percolated AB networks supplied effective gas transport pathways, which were not flooded by generated water, thus enhancing the oxygen mass transport. The practical-sized MEA using Pt/TiN + 47 vol% AB showed 1.5 times greater mass activity and a comparable performance under a practical operating condition for micro-CHP applications, compared with the MEA using a commercial graphitized carbon black-supported platinum catalyst.

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

    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+.

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

    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

  5. Acetylene Black Induced Heterogeneous Growth of Macroporous CoV2O6 Nanosheet for High-Rate Pseudocapacitive Lithium-Ion Battery Anode.

    Zhang, Lei; Zhao, Kangning; Luo, Yanzhu; Dong, Yifan; Xu, Wangwang; Yan, Mengyu; Ren, Wenhao; Zhou, Liang; Qu, Longbing; Mai, Liqiang

    2016-03-23

    Metal vanadates suffer from fast capacity fading in lithium-ion batteries especially at a high rate. Pseudocapacitance, which is associated with surface or near-surface redox reactions, can provide fast charge/discharge capacity free from diffusion-controlled intercalation processes and is able to address the above issue. In this work, we report the synthesis of macroporous CoV2O6 nanosheets through a facile one-pot method via acetylene black induced heterogeneous growth. When applied as lithium-ion battery anode, the macroporous CoV2O6 nanosheets show typical features of pseudocapacitive behavior: (1) currents that are mostly linearly dependent on sweep rate and (2) redox peaks whose potentials do not shift significantly with sweep rate. The macroporous CoV2O6 nanosheets display a high reversible capacity of 702 mAh g(-1) at 200 mA g(-1), excellent cyclability with a capacity retention of 89% (against the second cycle) after 500 cycles at 500 mA g(-1), and high rate capability of 453 mAh g(-1) at 5000 mA g(-1). We believe that the introduction of pseudocapacitive properties in lithium battery is a promising direction for developing electrode materials with high-rate capability. PMID:26938306

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

    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 TiC x 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+

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

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

    2013-04-01

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

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

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

    2016-03-15

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

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

    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.

  10. Secondary Organic Aerosol Formation from Acetylene (C2H2: seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase

    P. J. Ziemann

    2009-03-01

    Full Text Available The lightest Non Methane HydroCarbon (NMHC, i.e., acetylene (C2H2 is found to form secondary organic aerosol (SOA. Contrary to current belief, the number of carbon atoms, n, for a NMHC to act as SOA precursor is lowered to n=2 here. The OH-radical initiated oxidation of C2H2 forms glyoxal (CHOCHO as the highest yield product, and >99% of the SOA from C2H2 is attributed to CHOCHO. SOA formation from C2H2 and CHOCHO was studied in a photochemical and a dark simulation chamber. Further, the experimental conditions were varied with respect to the chemical composition of the seed aerosols, mild acidification with sulphuric acid (SA, 3

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

    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.

  12. Characteristics of Carbon Material Formation on SBA-15 and Ni-SBA-15 Templates by Acetylene Decomposition and Their Bioactivity Effects

    Hsiu-Mei Chiang

    2016-05-01

    Full Text Available Carbon spheres and tubes were formed from acetylene decomposition on SBA-15 and Ni-SBA-15 at 650–850 °C. At 650 °C, the decomposed carbons covered the surface of the support, and no carbon spheres and filament materials were formed. Carbon sphere formation occurred at 750 °C–850 °C; with diameters ranging from 0.8 μm–1.1 μm. For Ni-SBA-15, the diameters of the spheres and filaments were 0.8 μm and 62 nm, respectively, at 650 °C. At 750 °C, the diameter of the ball carbon materials ranged from 0.7 μm–0.8 μm, the diameter of the carbon tubes formed was 120–130 nm, and their pore diameter was 8.0 nm–11 nm. At 850 °C, the diameters of ball carbon materials and carbon tubes were similar to those of the materials at the formation temperature, 750 °C. Si, O and C were the main constituents of SBA-15; Ni-SBA-15 and carbon material formation supports. High-ring PAHs (such as BaP (five rings; IND (six rings; DBA (five rings and B[ghi]P (six rings exist in carbon materials. SBA-15 revealed insignificant cytotoxicity, but Ni-SBA-15 inhibited the proliferation of human lung cancer cells (A549. Less inhibition on cell viability and reactive oxidative species (ROS generation on A549 were determined for carbon material formation on the Ni-SBA-15 compared to the Ni-SBA-15.

  13. Mid-IR Absorption Cross-Section Measurements of Hydrocarbons

    Alrefae, Majed Abdullah

    2013-05-01

    Laser diagnostics are fast-response, non-intrusive and species-specific tools perfectly applicable for studying combustion processes. Quantitative measurements of species concentration and temperature require spectroscopic data to be well-known at combustion-relevant conditions. Absorption cross-section is an important spectroscopic quantity and has direct relation to the species concentration. In this work, the absorption cross-sections of basic hydrocarbons are measured using Fourier Transform Infrared (FTIR) spectrometer, tunable Difference Frequency Generation laser and fixed wavelength helium-neon laser. The studied species are methane, methanol, acetylene, ethylene, ethane, ethanol, propylene, propane, 1-butene, n-butane, n-pentane, n-hexane, and n-heptane. The Fourier Transform Infrared (FTIR) spectrometer is used for the measurements of the absorption cross-sections and the integrated band intensities of the 13 hydrocarbons. The spectral region of the spectra is 2800 – 3400 cm-1 (2.9 – 3.6 μm) and the temperature range is 673 – 1100 K. These valuable data provide huge opportunities to select interference-free wavelengths for measuring time-histories of a specific species in a shock tube or other combustion systems. Such measurements can allow developing/improving chemical kinetics mechanisms by experimentally determining reaction rates. The Difference Frequency Generation (DFG) laser is a narrow line-width, tunable laser in the 3.35 – 3.53 μm wavelength region which contains strong absorption features for most hydrocarbons due to the fundamental C-H vibrating stretch. The absorption cross-sections of propylene are measured at seven different wavelengths using the DFG laser. The temperature range is 296 – 460 K which is reached using a Reflex Cell. The DFG laser is very attractive for kinetic studies in the shock tube because of its fast time response and the potential possibility of making species-specific measurements. The Fixed wavelength

  14. Novel mode of 2-fold interpenetration observed in a primitive cubic network of formula [Ni(1,2-bis(4-pyridyl)acetylene)2(Cr2O7)]n.

    Scott, Hayley S; Bajpai, Alankriti; Chen, Kai-Jie; Pham, Tony; Space, Brian; Perry, John J; Zaworotko, Michael J

    2015-10-14

    A primitive cubic (pcu) network of formula [Ni(1,2-bis(4-pyridyl)acetylene)2(Cr2O7)]n, , has been synthesised and found to exhibit a novel type of inclined 2-fold interpenetration and an isosteric heat of adsorption (Q(st)) of 30.5 kJ mol(-1) towards CO2 at zero loading. Q(st) is relatively high in the broad context but less than that observed in related hybrid ultramicroporous materials, a feature that can be understood after studying pore structure and molecular simulations of CO2 adsorption. PMID:26307270

  15. FEMA DFIRM Cross Sections

    Minnesota Department of Natural Resources — FEMA Cross Sections are required for any Digital Flood Insurance Rate Map database where cross sections are shown on the Flood Insurance Rate Map (FIRM). Normally...

  16. American Red Cross

    ... to Help Sand Fire Evacuees » 90% of the Red Cross Workforce are Volunteers Learn More. Search for ... Volunteer» Digital Advocates» SEARCH FOR OPENINGS Shop the Red Cross Store Be Prepared and Ready to Respond ...

  17. Electron and Positron Scattering with a Few Alkyne Molecules - Theoretical Cross sections

    Patel, U. R.; Joshipura, K. N.; Kothari, H. N.

    2016-05-01

    Electron molecule scattering processes play an important role in the understanding of the electron driven physiochemical phenomena in diverse environments such as biological media, planetary atmospheres, interstellar clouds and plasmas. In modeling and simulating effects induced by electrons traversing through matter, the relevant cross section data are required as an input. An alternative probe, positron has also been used for the similar study of atoms, molecules and matter in bulk. Interaction of positrons with atoms and molecules differs from electron interactions due to opposite sign of charge and absence of exchange potential. In the present paper, our aim is to apply an identical theoretical method1,2 to electrons as well as positrons interacting with alkyne molecules like acetylene (HC ≡ CH), 1- Butyne (HC ≡ C- CH2 CH3) and Propyne (HC ≡ C- CH3) . We have carried out calculations of total scattering cross sections by starting with complex potential approach followed by the solution of the Schrodinger equation using numerical method. Ionization cross sections are deduced as in1,2. Comparisons have been made with available theoretical and experimental results for both electron (e-) and positron (e+) . The study will be extended to alkanes and alkenes.

  18. Pharmacokinetics and pharmacodynamics of orally administered acetylenic tricyclic bis(cyanoenone), a highly potent Nrf2 activator with a reversible covalent mode of action

    The acetylenic tricyclic bis(cyanoenone) TBE-31 is a highly potent cysteine targeting compound with a reversible covalent mode of action; its best-characterized target being Kelch-like ECH-associated protein-1 (Keap1), the cellular sensor for oxidants and electrophiles. TBE-31 reacts with cysteines of Keap1, impairing its ability to target nuclear factor-erythroid 2 p45-related factor 2 (Nrf2) for degradation. Consequently, Nrf2 accumulates and orchestrates cytoprotective gene expression. In this study we investigated the pharmacokinetic and pharmacodynamic properties of TBE-31 in C57BL/6 mice. After a single oral dose of 10 μmol/kg (∼200 nmol/animal), the concentration of TBE-31 in blood exhibited two peaks, at 22.3 nM and at 15.5 nM, 40 min and 4 h after dosing, respectively, as determined by a quantitative stable isotope dilution LC-MS/MS method. The AUC0–24h was 195.5 h/nmol/l, the terminal elimination half-life was 10.2 h, and the kel was 0.068 h−1. To assess the pharmacodynamics of Nrf2 activation by TBE-31, we determined the enzyme activity of its prototypic target, NAD(P)H:quinone oxidoreductase 1 (NQO1) and found it elevated by 2.4- and 1.5-fold in liver and heart, respectively. Continuous feeding for 18 days with diet delivering the same daily doses of TBE-31 under conditions of concurrent treatment with the immunosuppressive agent azathioprine had a similar effect on Nrf2 activation without any indications of toxicity. Together with previous reports showing the cytoprotective effects of TBE-31 in animal models of carcinogenesis, our results demonstrate the high potency, efficacy and suitability for chronic administration of cysteine targeting reversible covalent drugs. - Highlights: • TBE-31 is a cysteine targeting compound with a reversible covalent mode of action. • After a single oral dose, the blood concentration of TBE-31 exhibits two peaks. • Oral TBE-31 is a potent activator of Nrf2-dependent enzymes in multiple organs.

  19. Structural characteristics of copper/hydrogenated amorphous carbon composite films prepared by microwave plasma-assisted deposition processes from methane-argon and acetylene-argon gas mixtures

    Copper/hydrogenated amorphous carbon (Cu/a-C:H) composite films have been deposited on silicon substrates by a hybrid technique combining microwave plasma-assisted chemical vapor deposition and sputter-deposition from methane-argon and acetylene-argon gas mixtures. The major objective of this work was to investigate the effect of the carbon gas precursor on the structural characteristics of Cu/a-C:H composite films deposited at ambient temperature. The major characteristics of CH4-argon and C2H2-argon plasmas were analyzed by Langmuir probe measurements. The composition of films was determined by Rutherford backscattering spectroscopy, energy recoil detection analyses and nuclear reaction analyses. The carbon content in the films was observed to vary in the range 20-77 at.% and 7.5-99 at.% as the CH4 and C2H2 concentrations in the gas phase increased from 10 to 100%, respectively. The atom number ratio H/C in the films was scattered approximately 0.4 whatever the carbon gas precursor used. The crystallographic structure and the size of copper crystallites incorporated in the a-C were determined by X-ray diffraction techniques. The copper crystallite size decreased from 20 nm in pure copper films to less than 5 nm in Cu/a-C:H films containing more than 40 at.% of carbon. Grazing incidence small angle X-ray scattering measurements were performed to investigate the size distribution and distance of copper crystallites as functions of the deposition parameters. The structural characteristics of copper crystallites were dependent on the hydrocarbon gas precursor used. The crystallite size and the width of the size distribution were homogeneous in films deposited from CH4. Copper crystallites with an anisotropic shape were found in films deposited from C2H2. The major radicals formed in the plasma and condensed on the surface of growing films, namely CH and C2H radicals for films produced from CH4 and C2H2, respectively, play probably a crucial role in the growth

  20. Pharmacokinetics and pharmacodynamics of orally administered acetylenic tricyclic bis(cyanoenone), a highly potent Nrf2 activator with a reversible covalent mode of action

    Kostov, Rumen V.; Knatko, Elena V.; McLaughlin, Lesley A.; Henderson, Colin J. [Jacqui Wood Cancer Centre, Division of Cancer Research, Medical Research Institute, University of Dundee, Dundee, DD1 9SY, Scotland (United Kingdom); Zheng, Suqing [Department of Chemistry and Institute of Chemical Biology & Drug Discovery, Stony Brook University, Stony Brook, NY, 11794 (United States); Huang, Jeffrey T.-J. [Jacqui Wood Cancer Centre, Division of Cancer Research, Medical Research Institute, University of Dundee, Dundee, DD1 9SY, Scotland (United Kingdom); Honda, Tadashi [Department of Chemistry and Institute of Chemical Biology & Drug Discovery, Stony Brook University, Stony Brook, NY, 11794 (United States); Dinkova-Kostova, Albena T., E-mail: a.dinkovakostova@dundee.ac.uk [Jacqui Wood Cancer Centre, Division of Cancer Research, Medical Research Institute, University of Dundee, Dundee, DD1 9SY, Scotland (United Kingdom); Department of Medicine, Johns Hopkins University School of Medicine, Baltimore, MD, 21205 (United States); Department of Pharmacology and Molecular Sciences, Johns Hopkins University School of Medicine, Baltimore, MD, 21205 (United States)

    2015-09-25

    The acetylenic tricyclic bis(cyanoenone) TBE-31 is a highly potent cysteine targeting compound with a reversible covalent mode of action; its best-characterized target being Kelch-like ECH-associated protein-1 (Keap1), the cellular sensor for oxidants and electrophiles. TBE-31 reacts with cysteines of Keap1, impairing its ability to target nuclear factor-erythroid 2 p45-related factor 2 (Nrf2) for degradation. Consequently, Nrf2 accumulates and orchestrates cytoprotective gene expression. In this study we investigated the pharmacokinetic and pharmacodynamic properties of TBE-31 in C57BL/6 mice. After a single oral dose of 10 μmol/kg (∼200 nmol/animal), the concentration of TBE-31 in blood exhibited two peaks, at 22.3 nM and at 15.5 nM, 40 min and 4 h after dosing, respectively, as determined by a quantitative stable isotope dilution LC-MS/MS method. The AUC{sub 0–24h} was 195.5 h/nmol/l, the terminal elimination half-life was 10.2 h, and the k{sub el} was 0.068 h{sup −1}. To assess the pharmacodynamics of Nrf2 activation by TBE-31, we determined the enzyme activity of its prototypic target, NAD(P)H:quinone oxidoreductase 1 (NQO1) and found it elevated by 2.4- and 1.5-fold in liver and heart, respectively. Continuous feeding for 18 days with diet delivering the same daily doses of TBE-31 under conditions of concurrent treatment with the immunosuppressive agent azathioprine had a similar effect on Nrf2 activation without any indications of toxicity. Together with previous reports showing the cytoprotective effects of TBE-31 in animal models of carcinogenesis, our results demonstrate the high potency, efficacy and suitability for chronic administration of cysteine targeting reversible covalent drugs. - Highlights: • TBE-31 is a cysteine targeting compound with a reversible covalent mode of action. • After a single oral dose, the blood concentration of TBE-31 exhibits two peaks. • Oral TBE-31 is a potent activator of Nrf2-dependent enzymes in

  1. Health insurance selection in Chile: a cross-sectional and panel analysis.

    Pardo, Cristian; Schott, Whitney

    2014-05-01

    In Chile, workers are mandated to choose either public or private health insurance coverage. Although private insurance premiums depend on health risk, public insurance premiums are solely linked to income. This structure implies that individuals with higher health risks may tend to avoid private insurance, leaving the public insurance system responsible for their care. This article attempts to explore the determinants of health insurance selection (private vs public) by individuals in Chile and to test empirically whether adverse selection indeed exists. We use panel data from Chile's 'Encuesta de Proteccion Social' survey, which allows us to control for a rich set of individual observed and unobserved characteristics using both a cross-sectional analysis and fixed-effect methods. Results suggest that age, sex, job type, income quintile and self-reported health are the most important factors in explaining the type of insurance selected by individuals. Asymmetry in insurance mobility caused by restrictions on pre-existing conditions may explain why specific illnesses have an unambiguous relationship with insurance selection. Empirical evidence tends to indicate that some sorting by health risk and income levels takes place in Chile. In addition, by covering a less healthy population with higher utilization of general health consultations, the public insurance system may be incurring disproportionate expenses. Results suggest that if decreasing segmentation and unequal access to health services are important policy objectives, special emphasis should be placed on asymmetries in the premium structure and inter-system mobility within the health care system. Preliminary analysis of the impact of the 'Garantias Explicitas de Salud' plan (explicit guarantees on health care plan) on insurance selection is also considered. PMID:23558960

  2. Cross currency swap valuation

    Boenkost, Wolfram; Schmidt, Wolfgang M

    2004-01-01

    Cross currency swaps are powerful instruments to transfer assets or liabilities from one currency into another. The market charges for this a liquidity premium, the cross currency basis spread, which should be taken into account by the valuation methodology. We describe and compare two valuation methods for cross currency swaps which are based upon using two different discounting curves. The first method is very popular in practice but inconsistent with single currency swap valuation methods....

  3. Essays on cross listings

    Λουκά, Χριστόδουλος; Louca, Christodoulou

    2006-01-01

    This PhD dissertation consists of three essays on cross listings: a. The Operating Performance of Exchange-Listed American Depositary Receipts. b. Cross Listing, Bonding and Corporate Governance. c. Cross Listing on U.S. Stock Exchanges and the Earnings Management Hypothesis. The questions analyzed in this dissertation arise because of possible frictions in the transition of information from corporations to markets. To overcome informational frictions a company might choose to lis...

  4. Phantom Crossing DGP Gravity

    Hirano, Koichi; Komiya, Zen

    2010-01-01

    We propose a phantom crossing Dvali--Gabadadze--Porrati (DGP) model. In our model, the effective equation of state of the DGP gravity crosses the phantom divide line. We demonstrate crossing of the phantom divide does not occur within the framework of the original DGP model or the DGP model developed by Dvali and Turner. By extending their model, we construct a model that realizes crossing of the phantom divide. DGP models can account for late-time acceleration of the universe without dark en...

  5. Cross-sector Innovation

    Würtz Jessen, Søren; Linnet, Andreas; Tscherning, Rasmus Wiinstedt; Smed, Søren Graakjær; Jensen, Jens F.

    2013-01-01

    The aim of this handbook is to help improve your opportunities for getting started on innovative and business development projects that reach beyond your own sector, commonly known as ’Cross-sector innovation’, or ’Cross innovation’ for short. We believe that there is a need for an easily read in...

  6. Cross Shear Roll Bonding

    Bay, Niels; Bjerregaard, Henrik; Petersen, Søren. B;

    1994-01-01

    The present paper describes an investigation of roll bonding an AlZn alloy to mild steel. Application of cross shear roll bonding, where the two equal sized rolls run with different peripheral speed, is shown to give better bond strength than conventional roll bonding. Improvements of up to 20......-23% in bond strength are found and full bond strength is obtained at a reduction of 50% whereas 65% is required in case of conventional roll bonding. Pseudo cross shear roll bonding, where the cross shear effect is obtained by running two equal sized rolls with different speed, gives the same results....

  7. Facile, soot free approach toward synthesis of carbon nanoropes via chemical vapor deposition of acetylene in the presence of MnFe2O4 coated on stainless steel

    Dhand, Vivek; Bharadwaj, S.; Amareshwari, K.; Himabindu, V.; Rhee, Kyong Yop; Park, Soo-Jin; Hui, David

    2015-12-01

    High density, soot free, novel and a facile approach toward synthesis of carbon nanoropes (CNRs) were successfully carried out in a chemical vapor deposition (CVD) process. Manganese ferrite (MnFe2O4) coated on stainless steel foil (SS 316 grade) was used as a catalyst to initiate the growth of CNR. The coated catalyst was introduced into the CVD and the chamber temperature was set at 700 °C later followed with the release of acetylene (50 sccm) and nitrogen (500 sccm) gas, respectively. Total reaction continued until 30 min. No purification or oxidation process of the soot was involved. Analysis reveals the presence of intermingled CNRs with semi crystalline nature of the sample. The elemental analysis confirms the presence of manganese and iron whereas Raman spectrum shows the characteristic narrow G and D bands. The sample displays a super-paramagnetic behavior and is thermally stable up to 500-550 °C presenting a strong exothermic reaction.

  8. 乙炔法聚氯乙烯生产减少汞排放的“最佳环境实践”%Mercury Emission Control in Acetylene-route PVC Production

    于建国

    2011-01-01

    “最佳环境实践”是国际上普遍推行的旨在减少和控制目标领域和场所环境污染与健康危害的综合管理手段。文中论述了我国乙炔法聚氯乙烯生产中汞使用和排放的“最佳环境实践”,并提出了建议。%World mercury annual consumption is 1,6 kt. China annual mercury consumption in acetylene-route PVC production is 67 ton. Mercury pollution in China is considered to be one of the focal points worldwide. The negotiation committee has been established amon

  9. Crossing simple resonances

    A simple criterion governs the beam distortion and/or loss of protons on a fast resonance crossing. Results from numerical integrations are illustrated for simple sextupole, octupole, and 10-pole resonances

  10. HARP MHI- Cross Seamount

    National Oceanic and Atmospheric Administration, Department of Commerce — PIFSC and Scripps Institution of Oceanography (SIO) conducted passive acoustic monitoring for cetaceans at Cross Seamount in 2005 and 2006 using a High-Frequency...

  11. Cross validation in LULOO

    Sørensen, Paul Haase; Nørgård, Peter Magnus; Hansen, Lars Kai; Larsen, Jan

    1996-01-01

    The leave-one-out cross-validation scheme for generalization assessment of neural network models is computationally expensive due to replicated training sessions. Linear unlearning of examples has recently been suggested as an approach to approximative cross-validation. Here we briefly review the...... linear unlearning scheme, dubbed LULOO, and we illustrate it on a systemidentification example. Further, we address the possibility of extracting confidence information (error bars) from the LULOO ensemble....

  12. Anticrossproducts and cross divisions.

    de Leva, Paolo

    2008-01-01

    This paper defines, in the context of conventional vector algebra, the concept of anticrossproduct and a family of simple operations called cross or vector divisions. It is impossible to solve for a or b the equation axb=c, where a and b are three-dimensional space vectors, and axb is their cross product. However, the problem becomes solvable if some "knowledge about the unknown" (a or b) is available, consisting of one of its components, or the angle it forms with the other operand of the cross product. Independently of the selected reference frame orientation, the known component of a may be parallel to b, or vice versa. The cross divisions provide a compact and insightful symbolic representation of a family of algorithms specifically designed to solve problems of such kind. A generalized algorithm was also defined, incorporating the rules for selecting the appropriate kind of cross division, based on the type of input data. Four examples of practical application were provided, including the computation of the point of application of a force and the angular velocity of a rigid body. The definition and geometrical interpretation of the cross divisions stemmed from the concept of anticrossproduct. The "anticrossproducts of axb" were defined as the infinitely many vectors x(i) such that x(i)xb=axb. PMID:18423647

  13. Cross cultural training

    王容

    2014-01-01

    Under the background of economic globalization, the globalization of human resources management determines the success of enterprise success or failure, in a sense, human resource is the first resource of the enterprise. Cross-cultural training is the core problems in global human resource management, it can let employees quickly familiar with the company's business and job content, understand the enterprise culture and core idea, to play a huge role in promoting enterprise development. Therefore, strengthen enterprise staff training, improve the comprehensive quality of enterprise personnel has become the urgent problems now in the process of enterprise development. Articles in samsung electronics of South Korea, for example, introduces the samsung especial y cross-cultural training content, training method and training effect. And analysis of cross-cultural training impact in the global business team and establish business relationship.

  14. Pullback and pushout crossed polymodules

    Murat Alp; Bijan Davvaz

    2015-02-01

    In this paper, we introduce the concept of pullback and pushout crossed polymodules and we describe the construction of pullback and pushout crossed polymodules. In particular, by using the notion of fundamental relation, we obtain a crossed module from a pullback crossed polymodule.

  15. Cross-Cultural Psychology.

    Triandis, Harry C.; Brislin, Richard W.

    Cross-Cultural psychology refers to the collective efforts of researchers who work among people who live in different societies, with different languages and different forms of government. There are a number of benefits to the study of human behavior which can be accrued by carrying out research in various cultures, largely concerned with better…

  16. Cross cultural usability testing

    Clemmensen, Torkil; Goyal, Shivam

    2005-01-01

    In this paper, we present the results of a pilot study in Denmark of cross cultural effects on Think Aloud usability testing. We provide an overview of previous research on cross cultural usability evaluation with a special focus on the relationship between the evaluator and the test user. This r...... performed, in terms of number of think aloud events and number of usability problems found, when both the evaluators and the test users are local. These results are however limited to the Danish context and need to be investigated in other cultural settings.......In this paper, we present the results of a pilot study in Denmark of cross cultural effects on Think Aloud usability testing. We provide an overview of previous research on cross cultural usability evaluation with a special focus on the relationship between the evaluator and the test user. This...... hereby identify usability problems with the clipart application. Data on the evaluators' and test users' behaviour were recorded and analyzed by coding and summarizing statistics on these behavioural events. The results show that Think Aloud Usability Test of a localized application is most effectively...

  17. Canadian Red Cross.

    Lavender, Colleen

    2008-01-01

    The Canadian Red Cross is guided by its Fundamental Principles--humanity, impartiality, neutrality, independence, voluntary service, unity, and universality--and organized in a traditional geographic hierarchical structure. Among the characteristics that have contributed to its success are a budgeting process that starts at the local level, measurement of program outcomes, and coordinated fundraising activities at the regional level. PMID:18551842

  18. Total Cross Sections

    G. GiacomelliBologna University and INFN

    2014-01-01

    The measurements of the hadron-hadron total cross sections are the first measurements performed when a new hadron accelerator opens up a new energy region; the measurements were made as function of the incoming beam momentum or c.m. energy and have often been repeated with improved accuracy and finer energy spacing.

  19. Cross-Language Experiment

    P. Sovka

    2003-09-01

    Full Text Available The contribution addresses the cross-language experiment. The aimwas to test the possibility of the conversion French phoneme modelsinto Czech ones. This model conversion uses the Hidden Markov Models(HMM classification procedure. The first step consists of theiterative mapping of French models to Czech ones. The mapping is givenby the analysis the confusion matrix. The second step is the Baum-Welchre-estimation resulting in the final models for Czech language. Despiteof the differences between French and Czech languages the finalrecognition score reaches 64% for the phoneme recognition and 74% fordigit recognition. Relatively low recognition accuracy is caused by theinadequate noise model. The experiences gained with the cross-languageexperiment were utilized for the classification of simple human bodymovements. The solution of this problem and results are described inthe second part of this contribution under the title EEG SignalsClassification-Introduction to the Problem.

  20. Cross-commodity hedges

    Energy risk management is the principal topic of this paper. Four major subjects are examined: cross-commodity trading objectives (reduce the risk of an underlying exposure in another commodity); portfolio risk reduction (an Alberta power distributor exposed to high pool prices could protect against high pool prices through a fixed price purchase of Alberta natural gas); tailoring pricing to customer needs (sell power to the gas producer indexed to the price of gas); and (4) reducing insurance costs (rather than purchasing downside protection (puts) individually against oil and gas prices, a producer could purchase a basket option). Since the key issue in cross-commodity transactions is the estimation of correlation, it is important to be prepared to alter correlation assumptions. 1 tab., 2 figs

  1. Cross Disciplinary Biometric Systems

    Liu, Chengjun

    2012-01-01

    Cross disciplinary biometric systems help boost the performance of the conventional systems. Not only is the recognition accuracy significantly improved, but also the robustness of the systems is greatly enhanced in the challenging environments, such as varying illumination conditions. By leveraging the cross disciplinary technologies, face recognition systems, fingerprint recognition systems, iris recognition systems, as well as image search systems all benefit in terms of recognition performance.  Take face recognition for an example, which is not only the most natural way human beings recognize the identity of each other, but also the least privacy-intrusive means because people show their face publicly every day. Face recognition systems display superb performance when they capitalize on the innovative ideas across color science, mathematics, and computer science (e.g., pattern recognition, machine learning, and image processing). The novel ideas lead to the development of new color models and effective ...

  2. Cross-cultural Leadership

    Oana Simona Hudea

    2014-01-01

    The present paper is meant to outline the positive effects that diversity may have on any organisation, subject to the condition that the said diversity be appropriately managed. As the leader is a person who, by power of example, makes other people adopting a similar attitude, the actions of the same oriented towards the fructification of the advantages of a cross-cultural environment, which are depicted in this study, are not only directly, but also indirectly, by synergy, impacting, in a p...

  3. Cross-cultural advertising

    Пурчельянова, Н. Ю.

    2011-01-01

    The essence of successful advertising is to convince people that a product is meant for them. By purchasing it, they will receive some benefit (lifestyle, status, convenience, etc.). However, when an advertising campaign is taken abroad different values as to what enhances status or gives convenience exist. These differences make the original advertising campaign defunct. It is therefore critical to any cross cultural advertising campaign that an understanding of a particular culture is acqui...

  4. Competitive Cross-Subsidization

    Chen, Zhijun; Rey, Patrick

    2013-01-01

    This paper analyzes competitive pricing policies by multiproduct firms facing heterogeneous buying patterns. We show that cross-subsidization arises when firms have comparative advantages on different products but are equally efficient overall: Firms earn a profit from multi-stop shoppers by charging positive margins on their strong products but, as price competition for one-stop shoppers drives total margins down to zero, they price weaker products below cost. Banning below-cost pricing lead...

  5. 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).

    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

  6. Diffractive and rising cross sections

    The energy dependence of the diffractive component of the proton-proton cross section is discussed and its contribution to the rise of the total cross section at high energies is examined. 17 refs., 9 figs

  7. Safe lighting of pedestrian crossings

    Bláha, Zdeněk; Sokanský, Karel; Novák, Tomáš

    2015-01-01

    This paper solves the lighting of pedestrian crossings. This type of lighting helps to improve the safety of pedestrians in this conflict area (means a pedestrian crossing). The research was drawn on the basis of measurements of 87 pedestrian crossings in district Ostrava because the regularities can be better understood. Pedestrian crossings were evaluated on the basis of luminance ratio and statistical data of accident rate. This paper also solves the reflectance of clothes which is also im...

  8. German cross-cultural psychology

    Trommsdorff, Gisela

    1986-01-01

    The present study deals with German-language cross-cultural research in different fields of psychology which attempts to achieve one Or more goals of cross-cultural psychology. First, methodological problems are discussed, followed by a selective presentation of cross-cultural research in personality, clinical, ethological, developmental, and social psychology. The theoretical and methodological advancement of these studies is investigated with respect to four approaches - universals in cross...

  9. On partitions avoiding right crossings

    Yan, Sherry H. F.; Xu, Yuexiao

    2011-01-01

    Recently, Chen et al. derived the generating function for partitions avoiding right nestings and posed the problem of finding the generating function for partitions avoiding right crossings. In this paper, we derive the generating function for partitions avoiding right crossings via an intermediate structure of partial matchings avoiding 2-right crossings and right nestings. We show that there is a bijection between partial matchings avoiding 2-right crossing and right nestings and partitions...

  10. Crossed Molecular Beams and Quasiclassical Trajectory Surface Hopping Studies of the Multichannel Nonadiabatic O((3)P) + Ethylene Reaction at High Collision Energy.

    Balucani, Nadia; Leonori, Francesca; Casavecchia, Piergiorgio; Fu, Bina; Bowman, Joel M

    2015-12-17

    The combustion relevant O((3)P) + C2H4 reaction stands out as a prototypical multichannel nonadiabatic reaction involving both triplet and singlet potential energy surfaces (PESs), which are strongly coupled. Crossed molecular beam (CMB) scattering experiments with universal soft electron ionization mass spectrometric detection have been used to characterize the dynamics of this reaction at the relatively high collision energy Ec of 13.7 kcal/mol, attained by crossing the reactant beams at an angle of 135°. This work is a full report of the data at the highest Ec investigated for this reaction. From laboratory product angular and velocity distribution measurements, angular and translational energy distributions in the center-of-mass system have been obtained for the five observed exothermic competing reaction channels leading to H + CH2CHO, H + CH3CO, CH3 + HCO, CH2 + H2CO, and H2 + CH2CO. The product branching ratios (BRs) have been derived. The elucidation of the reaction dynamics is assisted by synergic full-dimensional quasiclassical trajectory surface-hopping calculations of the reactive differential cross sections on coupled ab initio triplet/singlet PESs. This joint experimental/theoretical study extends and complements our previous combined CMB and theoretical work at the lower collision energy of 8.4 kcal/mol. The theoretically derived BRs and extent of intersystem crossing (ISC) are compared with experimental results. In particular, the predictions of the QCT results for the three main channels (those leading to vinoxy + H, methyl + HCO and methylene + H2CO formation) are compared directly with the experimental data in the laboratory frame. Good overall agreement is noted between theory and experiment, although some small, yet significant shortcomings of the theoretical differential cross section are noted. Both experiment and theory find almost an equal contribution from the triplet and singlet surfaces to the reaction, with a clear tendency of the

  11. [Fast neutron cross section measurements

    This paper discusses the following topics: 14 MeV pulsed neutron facility; detection and measurement system; 238U capture cross sections at 23 and 964 keV using photon neutron sources; capture cross sections of Au-197 at 23 and 964 keV; and yttrium nuclear cross section measurement

  12. Focused crossed Andreev reflection

    Haugen, H.; Brataas, A.; Waintal, X.; Bauer, G. E. W.

    2011-03-01

    We consider non-local transport mediated by Andreev reflection in a two-dimensional electron gas (2DEG) connected to one superconducting and two normal metal terminals. A robust scheme is presented for observing crossed Andreev reflection (CAR) between the normal metal terminals based on electron focusing by weak perpendicular magnetic fields. At slightly elevated temperatures the CAR signature can be easily distinguished from a background of quantum interference fluctuations. The CAR-induced entanglement between electrons can be switched on and off over large distances by the magnetic field.

  13. Cross-cultural Leadership

    Oana Simona Hudea

    2014-05-01

    Full Text Available The present paper is meant to outline the positive effects that diversity may have on any organisation, subject to the condition that the said diversity be appropriately managed. As the leader is a person who, by power of example, makes other people adopting a similar attitude, the actions of the same oriented towards the fructification of the advantages of a cross-cultural environment, which are depicted in this study, are not only directly, but also indirectly, by synergy, impacting, in a positive way, on the organisation.Innovation, performance, competitive advantage and reputation are just some of the outcomes of finding unity in diversity.

  14. Cross-species infections.

    Weiss, R A

    2003-01-01

    Animals have always been a major source of human infectious disease. Some infections like rabies are recognized as primary zoonoses caused in each case by direct animal-to-human transmission, whereas others like measles become independently sustained within the human population so that the causative virus has diverged from its morbillivirus progenitor in ruminants. Recent examples of direct zoonoses are variant Creutzfeldt-Jakob disease arising from bovine spongiform encephalopathy, and the H5N1 avian influenza outbreak in Hong Kong. Recent epidemic diseases of animal origin are the 1918-1919 influenza pandemic, and the acquired immune deficiency syndrome pandemic caused by human immunodeficiency virus. Some retroviruses move into and out of the chromosomal DNA of the host germline, so that they may oscillate between being an avirulent inherited Mendelian trait in one species and an infectious pathogen in another. Cross-species viral and other infections are reviewed historically with respect to the evolution of virulence and the concern about iatrogenic enhancement of cross-species transfer by medical procedures akin to xenotransplantation. PMID:12934941

  15. Cosmetic crossings and Seifert matrices

    Balm, Cheryl; Kalfagianni, Efstratia; Powell, Mark

    2011-01-01

    We study cosmetic crossings in knots of genus one and obtain obstructions to such crossings in terms of knot invariants determined by Seifert matrices. In particular, we prove that for genus one knots the Alexander polynomial and the homology of the double cover branching over the knot provide obstructions to cosmetic crossings. As an application we prove the nugatory crossing conjecture for twisted Whitehead doubles of non-cable knots. We also verify the conjecture for several families of pretzel knots and all genus one knots with up to 12 crossings.

  16. Neutrino Cross section Future

    Gollapinni, Sowjanya

    2016-01-01

    The study of neutrino-nucleus interactions has recently received renewed attention due to their importance in interpreting the neutrino oscillation data. Over the past few years, there has been continuous disagreement between neutrino cross section data and predictions due to lack of accurate nuclear models suitable for modern experiments which use heavier nuclear targets. Also, the current short and long-baseline neutrino oscillation experiments focus in the few GeV region where several distinct neutrino processes come into play resulting in complex nuclear effects. Despite recent efforts, more experimental input is needed to improve nuclear models and reduce neutrino interaction systematics which are currently dominating oscillation searches together with neutrino flux uncertainties. A number of new detector concepts with diverse neutrino beams and nuclear targets are currently being developed to provide necessary inputs required for next generation oscillation experiments. This paper summarizes these effor...

  17. Group cross sections calculations

    Just a few methods have been developped to compute multigroup cross-sections from ENDF data. We have developped an original method in order to get accuracy and to reduce the number of discretization points in the same time; this is why we have tried to use polynomial integration. In this paper, we describe this method: in the first part, we recall some physical hypothesis generally used to solve the linear Boltzmann equation: that is the frame in which the numerical method has been developped. Polynomial methods are really powerfull only if discretization points are suitably chosen. This choice is explained in the next part of this paper. In conclusion, some numerical results are given to illustrate our method

  18. Level crossing analysis of chemically induced dynamic nuclear polarization: Towards a common description of liquid-state and solid-state cases

    Sosnovsky, Denis V.; Jeschke, Gunnar; Matysik, Jörg; Vieth, Hans-Martin; Ivanov, Konstantin L.

    2016-04-01

    Chemically Induced Dynamic Nuclear Polarization (CIDNP) is an efficient method of creating non-equilibrium polarization of nuclear spins by using chemical reactions, which have radical pairs as intermediates. The CIDNP effect originates from (i) electron spin-selective recombination of radical pairs and (ii) the dependence of the inter-system crossing rate in radical pairs on the state of magnetic nuclei. The CIDNP effect can be investigated by using Nuclear Magnetic Resonance (NMR) methods. The gain from CIDNP is then two-fold: it allows one to obtain considerable amplification of NMR signals; in addition, it provides a very useful tool for investigating elusive radicals and radical pairs. While the mechanisms of the CIDNP effect in liquids are well established and understood, detailed analysis of solid-state CIDNP mechanisms still remains challenging; likewise a common theoretical frame for the description of CIDNP in both solids and liquids is missing. Difficulties in understanding the spin dynamics that lead to the CIDNP effect in the solid-state case are caused by the anisotropy of spin interactions, which increase the complexity of spin evolution. In this work, we propose to analyze CIDNP in terms of level crossing phenomena, namely, to attribute features in the CIDNP magnetic field dependence to Level Crossings (LCs) and Level Anti-Crossings (LACs) in a radical pair. This approach allows one to describe liquid-state CIDNP; the same holds for the solid-state case where anisotropic interactions play a significant role in CIDNP formation. In solids, features arise predominantly from LACs, since in most cases anisotropic couplings result in perturbations, which turn LCs into LACs. We have interpreted the CIDNP mechanisms in terms of the LC/LAC concept. This consideration allows one to find analytical expressions for a wide magnetic field range, where several different mechanisms are operative; furthermore, the LAC description gives a way to determine CIDNP sign

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

    Sgouridis, Fotis; Stott, Andrew; Ullah, Sami

    2016-03-01

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

  20. Cross-tools and cross-media effects

    H. Voorveld

    2013-01-01

    Effects of persuasive messages depend on the content of the message itself and on the media or tools that deliver the persuasive messages. Nowadays almost all campaigns make use of multiple media or multiple promotional tools. Therefore, it is important to study so-called cross-media (or cross-tools

  1. (n,2n) cross sections

    Most of the fission products and a few of the actinides in ENDF/B-V do not have (n,2n) cross sections. A complete set of these cross sections is presented in the multigroup structure defined. These were constructed for future use in the DANDE Code System

  2. XCOM: Photon Cross Sections Database

    SRD 8 XCOM: Photon Cross Sections Database (Web, free access)   A web database is provided which can be used to calculate photon cross sections for scattering, photoelectric absorption and pair production, as well as total attenuation coefficients, for any element, compound or mixture (Z <= 100) at energies from 1 keV to 100 GeV.

  3. On crossed product of algebras

    Borowiec, A.; Marcinek, W.

    2000-01-01

    The concept of a crossed tensor product of algebras is studied from a few points of views. Some related constructions are considered. Crossed enveloping algebras and their representations are discussed. Applications to the noncommutative geometry and particle systems with generalized statistics are indicated.

  4. Cross Sections and Lorentz Violation

    Colladay, Don; Kostelecky, Alan

    2001-01-01

    The derivation of cross sections and decay rates in the Lorentz-violating standard-model extension is discussed. General features of the physics are described, and some conceptual and calculational issues are addressed. As an illustrative example, the cross section for the specific process of electron-positron pair annihilation into two photons is obtained.

  5. Internet and Cross Media Productions

    Petersen, Anja Bechmann

    2006-01-01

    Convergence is one of the hot topics in Internet studies. Recently, however, media organizations have turned their focus to cross media communication. Media organizations are interested in optimizing communication across platforms such as TV, radio, websites, mobile telephones and newspapers....... The aim of this article is to examine the roles of the Internet when emphasis is put on cross media rather than convergence. This article proposes not one unidirectional convergent tendency but manifold roles of the Internet in cross media communication. Inside the media organizations, however......, the Internet continues to play a minor role when compared to older media. The content of the cross media concepts and organizations' history are crucial elements in deciding the priority and use of platforms. Methodologically, the article approaches cross media and the roles of the Internet on a micro...

  6. abo-cross: Hydrogen broadening cross-section calculator

    Barklem, P. S.; Anstee, S. D.; O'Mara, B. J.

    2015-07-01

    Line broadening cross sections for the broadening of spectral lines by collisions with neutral hydrogen atoms have been tabulated by Anstee & O'Mara (1995), Barklem & O'Mara (1997) and Barklem, O'Mara & Ross (1998) for s-p, p-s, p-d, d-p, d-f and f-d transitions. abo-cross, written in Fortran, interpolates in these tabulations to make these data more accessible to the end user. This code can be incorporated into existing spectrum synthesis programs or used it in a stand-alone mode to compute line broadening cross sections for specific transitions.

  7. Cross helicity and related dynamo

    Yokoi, Nobumitsu

    2013-01-01

    The turbulent cross helicity is directly related to the coupling coefficients for the mean vorticity in the electromotive force and for the mean magnetic-field strain in the Reynolds stress tensor. This suggests that the cross-helicity effects are important in the cases where global inhomogeneous flow and magnetic-field structures are present. Since such large-scale structures are ubiquitous in geo/astrophysical phenomena, the cross-helicity effect is expected to play an important role in geo/astrophysical flows. In the presence of turbulent cross helicity, the mean vortical motion contributes to the turbulent electromotive force. Magnetic-field generation due to this effect is called the cross-helicity dynamo. Several features of the cross-helicity dynamo are introduced. Unlike the case in the helicity or $\\alpha$ effect, where ${\\bf{J}}$ is aligned with ${\\bf{B}}$ in the turbulent electromotive force, we in general have a finite mean-field Lorentz force ${\\bf{J}} \\times {\\bf{B}}$ in the cross-helicity dynam...

  8. Synthesis of nano-carbon materials by decomposing acetylene using iron supported on sodium chloride as catalyst%NaCl担载Fe催化裂解乙炔制备纳米碳材料

    王存景; 王艳博; 陈改荣

    2011-01-01

    Nano-carbon materials were synthesized by the catalytic decomposition of acetylene at 400 ℃ and 420℃ in a chemical vapor deposition process using iron supported on sodium chloride as catalyst Hie catalyst was examined by X-ray diffraction,scanning electron microscopy and energy dispersive spectroscopy. The results show that the active composition iron was dispersed into nanoparticles with diameters in the range 10-40 nm on the surface of NaCl support successfully. The products were examined by scanning electron microscopy and high resolution transmission electron microscopy. The results show that nano onion-like fullerenes encapsulating Fe cores with diameters in the range 20-50 nm were obtained when the reaction temperature was 400℃ and there were no carbon nanotubes in the product These onion-like fullerenes are composed of concentric graphene layers with an interlayer distance of 0. 348 nm between the layers. When the reaction temperature was 420℃ , carbon nanotubes with a structure of rope were obtained and the graphitization degree of these carbon nanotubes was not high due to the low reaction temperature.%以水溶性NaCl担载Fe作催化剂,于400℃和420C下化学气相沉积法催化裂解乙炔进行了反应.通过X射线衍射仪、扫描电子显微镜和能谱分析仪对催化剂进行了表征,表征结果显示:活性组分Fe被分散成了粒径在10~40nm之间的纳米颗粒;通过扫描电子显微镜和高分辨透射电镜对产物进行了表征,表征结果显示:当裂解温度为400℃时,主要产物为直径在20~50 nm之间,基本具有清晰同心石墨壳层结构的内包铁NOLFs,同心石墨壳层的层间距约为0.348nm,产物中没有碳纳米管出现;当裂解温度为420℃时,主要产物为直径在10 ~40 nm之间结构呈绳结状的碳纳米管,其石墨壳层不是十分规整,石墨化程度较低.

  9. Effects of radio-frequency power on the properties of carbon thin films prepared by thermal chemical vapor deposition enhanced with remote inductively-coupled-plasma using acetylene/nitrogen mixtures

    The effects of radio-frequency (rf) power on the properties of carbon thin films prepared by thermal chemical vapor deposition (CVD) enhanced with remote inductively-coupled-plasma (ICP) are investigated. Acetylene and nitrogen were used as the precursor gases, and rf-powers of ICP were set as 0, 100, 200, 300, and 400 W. The deposition temperature, working pressure, and deposition time were set as 1248 K, 4 kPa, and 2 h, respectively. The residual gases, film thicknesses, microstructures, chemical characteristics, mechanical properties, and electrical properties of carbon thin films were investigated by residual gas analyzer (RGA), field emission scanning electron microscopy, X-ray diffractometer (and Raman scattering spectrometer), X-ray photoelectron spectrometer, nanoindenter, and four point probe, respectively. RGA results reveal that the main species in the gas phase contain H2, C2H, C2H2, HCN (or C2H3), and N2 (or C2H4). Moreover, C2H, C2H2, and C2H4 can be speculated as the main species for carbon thin film deposition. As the rf-power increases from 0 to 400 W, the deposition rate of carbon thin films decreases from 204 to 36.0 nm/h. The crystallinity and ordering degree of carbon thin films increase with increasing rf-power from 0 to 400 W, but the ratio of sp2 carbon sites in carbon thin films decreases from 95 to 75%. The Young's modulus, hardness, and electrical resistivity of carbon thin films increase with increasing rf-power. Furthermore, the effects of rf-power on the deposition rates of carbon thin films prepared by thermal CVD enhanced with remote ICP using C2H2/N2 and CH4/N2 mixtures are compared. - Highlights: • Carbon films are prepared by TCVD enhanced with remote ICP using C2H2/N2 mixtures. • The deposition rate of carbon thin films decreases with increasing the rf-power. • C2H, C2H2, and C2H4 are speculated as the main species for carbon film deposition. • The sp2 sites in carbon thin films decrease with increasing rf-power.

  10. Interfacial Bioorthogonal Cross-Linking

    Zhang, Han; Dicker, Kevin T.; Xu, Xian; Jia, Xinqiao; Fox, Joseph M.

    2014-01-01

    Described herein is interfacial bioorthogonal cross-linking, the use of bioorthogonal chemistry to create and pattern biomaterials through diffusion-controlled gelation at the liquid-gel interface. The basis is a rapid (k 2 284000 M–1 s–1) reaction between strained trans-cyclooctene (TCO) and tetrazine (Tz) derivatives. Syringe delivery of Tz-functionalized hyaluronic acid (HA-Tz) to a bath of bis-TCO cross-linker instantly creates microspheres with a cross-linked shell through which bis-TCO ...

  11. Adverse selection without single crossing

    Schottmüller, Christoph

    2015-01-01

    The single-crossing assumption simplifies the analysis of screening models as local incentive compatibility becomes sufficient for global incentive compatibility. If single crossing is violated, global incentive compatibility constraints have to be taken into account. This paper studies monotone...... solutions in a screening model that allows a one-time violation of single crossing. The results show that local and non-local incentive constraints distort the solution in opposite directions. Therefore, the optimal decision might involve distortions above as well as below the first-best decision...

  12. Opas CrossFit -harjoitteluun

    Knaapi, Matti

    2014-01-01

    CrossFit on laji, joka pyrkii edistämään terveyttä ja kuntoa. CrossFit saleja löytyy mailmalta yli 10 000 kappaletta. CrossFit -harjoittelussa pyritään parantamaan ihmisen kuntoa mahdollisimman laajalla skaalalla kehittämällä mm. voimaa, kestävyyttä, tarkkuutta, tasapainoa ja eri aineenvaihduntareittejä samanaikaisesti. Terveyden ja kunnon kehittämiseen kuuluu kuntoilun lisäksi myös muita osa-alueita. Ruokavalio ja kehonhuolto ovat tärkeitä osa-alueita hyvän kunnon saavuttamiseksi. Ruokav...

  13. Crossing borders via mental bridges

    Keil, Dirk

    influence coopera- tion, coordination and collaboration in administrative cross-border networks. In this connection the project asks after the perception of regional integration seen from the different national backgrounds. The research concentrates on the group of decision makers within the field of public......The project studies cross-border regional integration in Europe drawing on the example of the emerging Danish-German Femern Belt Region. It focuses on cross-border networking within public administration as part of regional integra- tion. My central question is how national-cultural differences...

  14. Cross-National Yardstick Comparisons

    Møller Hansen, Kasper; Leth Olsen, Asmus; Bech, Mickael

    2015-01-01

    Comparing performance between countries is both a theoretically and intuitively useful yardstick for voters. Cross-national comparisons provide voters with heuristics that are less cognitively demanding, less ambiguous, and less uncertain than solely national, absolute performance measurements. We...... test this proposition using a unique, choice experiment embedded in the 2011 Danish National Election Study. This design allows to contrast cross-national comparisons with more traditional national sociotropic and egotropic concerns. The findings suggest that voters are strongly influenced by cross-national...... performance comparisons—even when accounting for classic national sociotropic and egotropic items. Specifically, voters respond strongly to how the prospective wealth of Denmark evolves relative to the neighboring Sweden. Interestingly, voters are more negative in their response to cross-national losses...

  15. Canada and Mexico Border Crossings

    Department of Homeland Security — Border Crossing Ports are points of entry for land modes along the U.S. - Canadian and U.S.- Mexcian borders. The ports of entry are located in 15 states along the...

  16. Measurement of fission cross sections

    A review is presented on the recent progress in the experiment of fission cross section measurement, including recent activity in Japan being carried out under the project of nuclear data measurement. (author)

  17. The definition of cross polarization

    Ludwig, Arthur

    1973-01-01

    There are at least three different definitions of cross polarization used in the literature. The alternative definitions are discussed with respect to several applications, and the definition which corresponds to one standard measurement practice is proposed as the best choice.......There are at least three different definitions of cross polarization used in the literature. The alternative definitions are discussed with respect to several applications, and the definition which corresponds to one standard measurement practice is proposed as the best choice....

  18. Entropy, Duality and Cross Diffusion

    Desvillettes, Laurent; Lepoutre, Thomas; Moussa, Ayman

    2013-01-01

    This paper is devoted to the use of the entropy and duality methods for the existence theory of reaction-cross diffusion systems consisting of two equations, in any dimension of space. Those systems appear in population dynamics when the diffusion rates of individuals of two species depend on the concentration of individuals of the same species (self-diffusion), or of the other species (cross diffusion).

  19. Considerations on Cross Cultural Negotiations

    Valeriu Potecea

    2007-01-01

    Our world is getting smaller and smaller. Continuous improvements in transportation and communication make it easier for companies to become involved in international commerce. With the increase in cross-cultural interaction comes the need for both large and small companies to become versed in successful negotiations with the variety of cultures with which it may be exposed. This report is aimed at educating and assisting the reader in the process of cross-cultural negotiations. This report w...

  20. Cross-Domain Sparse Coding

    Wang, Jim Jing-Yan

    2013-01-01

    Sparse coding has shown its power as an effective data representation method. However, up to now, all the sparse coding approaches are limited within the single domain learning problem. In this paper, we extend the sparse coding to cross domain learning problem, which tries to learn from a source domain to a target domain with significant different distribution. We impose the Maximum Mean Discrepancy (MMD) criterion to reduce the cross-domain distribution difference of sparse codes, and also ...

  1. DIRECT SHIPMENT VS. CROSS DOCKING

    TAMÁS BÁNYAI

    2012-01-01

    The globalization of production and service enterprises increased the complexity of supply chain systems and processes. The complexity of supply problems leaded to the development of new shipment strategies. The optimal design of supply chain is an important success factor of the economical operation of enterprises. Within the frame of this paper the author compare the costs of the direct shipment and the cross docking supply from the point of view of all members of supply chain. Cross dockin...

  2. Cross-correlation laser scattering.

    Kam, Z; Rigler, R

    1982-01-01

    Cross-correlation between two detectors was applied to analyze laser light-scattering fluctuations. Laser scattering from random concentration fluctuations is spatially coherent over small angular areas that are inversely proportional in size to the dimension of the scattering volume. By cross-correlating scattering intensity fluctuations in different angles, the correlation due to relaxation of concentration fluctuations is practically eliminated, and correlations reflecting changes in the s...

  3. The total charm cross section

    R. Vogt

    2007-01-01

    We assess the theoretical uncertainties on the total charm cross section. We discuss the importance of the quark mass, the scale choice and the parton densities on the estimate of the uncertainty. We conclude that due to the small charm quark mass, which amplifies the effect of the other parameters in the calculation, the uncertainty on the total charm cross section is difficult to quantify.

  4. Cross-cultural communication and global economy

    Krutskikh A. V.

    2011-01-01

    The article gives a review of the basic issues related to cross-cultural communication. The author focuses on the origin of cross-cultural diversity and analyses modern approaches to building cross-cultural competence.

  5. Syntheses and studies of acetylenic polymers

    Yiwei, Ding

    1994-03-03

    Based on new diiodo aryl compounds a series of novel soluble polymers, poly(2,5-dialkoxy-1,4-phenyleneethynylene)s (PPE polymers) were synthesized using palladium-catalysis. The molecular weights (MW) range from 8,000 to 40,000. Properties such as absorption, fluorescence, and conductivity were studied. A PPE polymer with butoxy side chain exhibits a weak electrical conductivity ({sigma} = 10{sup {minus}3} S/cm) after doping with AsF{sub 5}. Absorption spectra in THF solution at room temperature (RT) show a maximum at 440 nm. However, absorption spectra of PPE polymers in the film state at (RT) show a maximum at 480 nm. PPE polymer-based light emitting diode (LED) devices have been prepared; greenish light from these LED devices can be observed. Poly(ethynylene-p-arylene-ethynylene-silylene)s were synthesized through the same palladium-catalyzed polymerization; MWs are between 6,000 and 82,000. Absorption and fluorescence were studied. Some of these polymers exhibit thermotropic liquid crystalline properties. In addition, nonlinear optical properties were briefly examined. Poly(silylene-ethynylene) homopolymers as well as alternating copolymers were synthesized through a novel palladium-catalyzed polymerization; MWs range from 56 {times} 10{sup 3} to 5.3 {times} 10{sup 3}. Thermal stability of these was also investigated; char yields range from 56 to 83%. One of these polymers exhibits thermotropic liquid crystalline properties.

  6. Triple Crossing Numb ers of Graphs

    Tanaka Hiroyuki; Teragaito Masakazu

    2016-01-01

    We introduce the triple crossing number, a variation of the crossing number, of a graph, which is the minimal number of crossing points in all drawings of the graph with only triple crossings. It is defined to be zero for planar graphs, and to be infinite for non-planar graphs which do not admit a drawing with only triple crossings. In this paper, we determine the triple crossing numbers for all complete multipartite graphs which include all complete graphs.

  7. Cross-cultural organizational behavior.

    Gelfand, Michele J; Erez, Miriam; Aycan, Zeynep

    2007-01-01

    This article reviews research on cross-cultural organizational behavior (OB). After a brief review of the history of cross-cultural OB, we review research on work motivation, or the factors that energize, direct, and sustain effort across cultures. We next consider the relationship between the individual and the organization, and review research on culture and organizational commitment, psychological contracts, justice, citizenship behavior, and person-environment fit. Thereafter, we consider how individuals manage their interdependence in organizations, and review research on culture and negotiation and disputing, teams, and leadership, followed by research on managing across borders and expatriation. The review shows that developmentally, cross-cultural research in OB is coming of age. Yet we also highlight critical challenges for future research, including moving beyond values to explain cultural differences, attending to levels of analysis issues, incorporating social and organizational context factors into cross-cultural research, taking indigenous perspectives seriously, and moving beyond intracultural comparisons to understand the dynamics of cross-cultural interfaces. PMID:17044797

  8. CHALLENGES IN CROSS CULTURAL ADVERTISING

    Yuni Retnowati

    2015-10-01

    Full Text Available At first, marketing practitioners and academics consider standardized approaches to marketing and advertising strategies in globalization, and then some studies proved that the standardization of advertising across culture is not valid. Therefore, cross cultural advertising takes local culture into account when conveying messages in advertisements. Cross cultural understanding is very important in order to produce successful localized advertising that would reflect the cultural values and norms of intended audience. Challenge in cross cultural advertising is the problem of communicating to people of diverse cultural background. Cross cultural solutions are applied in areas such as language, communication style, images and cultural values. Cross cultural advertising is simply about using common sense and analyzing how the different elements of an advertising campaign are impacted by culture and modifying them to best speak to the target audience. Other challenges are determining between standardization and adaptation of cultural values content of advertising when facing different people from diverse cultures. In academic side, the challenge is preparing students to design advertisements that communicate effectively to diverse cultures.

  9. Uncertainty in Cross Orthogonality Checks

    Matsumura, Yuichi

    Finite element structural dynamic models are typically validated using data obtained from a modal testing. Although it is known that test variability may affect the verification, the test variability is typically ignored in the verification process. This paper describes the sensitivities of cross orthogonality check to the test variability. The cross orthogonality check is one of correlation techniques which is gaining acceptance in the structural dynamics community, because of its improved accuracy over the standard modal assurance criterion. Then an uncertainty index of the cross orthogonality check is proposed based on the fact that the sensitivities are much dependent on sensor placement. The results of some artificially generated test cases are presented to demonstrate the applicability of the proposed approach.

  10. A crossing method for quinoa

    Peterson, Adam; Jacobsen, Sven-Erik; Bonifacio, Alejandro;

    2015-01-01

    As sustainable production of quinoa (Chenopodium quinoa Willd.) increases and its geographic range of cultivation expands, quinoa breeding will allow use of the crop’s wide genetic diversity for cultivar improvement and for adaptation to new agroecosystems and climactic regimes. Such breeding work...... will require a reliable technique for crossing quinoa plants using hand emasculation. The technique described herein focuses on the isolation of small flower clusters produced low on the plant, emasculation of male flowers, and subsequent pairing of the emasculated female parent with a male parent...... successfully used to generate crosses between quinoa cultivars, as well as interspecific crosses between quinoa and Chenopodium berlandieri. This technology will help pave the way for the introduction and sustainable expansion of quinoa on a global scale across a wide range of target environments and diverse...

  11. Cross-Cultural Interpretations of Curricular Contextual Crossings

    Schlein, Candace; Garii, Barbara

    2011-01-01

    Teachers--who are generally representatives of the cultural mainstream--are expected to use global experiences to become culturally enhanced and to bring these enhancements back to their classrooms. In this article, the authors discuss a cross-cultural exploration of investigations into the experiences of Canadian and U.S. educators with…

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

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

    2015-08-01

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

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

    F. Sgouridis

    2015-08-01

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

  14. Effects of radio-frequency power on the properties of carbon thin films prepared by thermal chemical vapor deposition enhanced with remote inductively-coupled-plasma using acetylene/nitrogen mixtures

    Lai, Liang-Hsun; Wu, Kuan-Chang; Shiue, Sham-Tsong, E-mail: stshiue@dragon.nchu.edu.tw

    2014-11-03

    The effects of radio-frequency (rf) power on the properties of carbon thin films prepared by thermal chemical vapor deposition (CVD) enhanced with remote inductively-coupled-plasma (ICP) are investigated. Acetylene and nitrogen were used as the precursor gases, and rf-powers of ICP were set as 0, 100, 200, 300, and 400 W. The deposition temperature, working pressure, and deposition time were set as 1248 K, 4 kPa, and 2 h, respectively. The residual gases, film thicknesses, microstructures, chemical characteristics, mechanical properties, and electrical properties of carbon thin films were investigated by residual gas analyzer (RGA), field emission scanning electron microscopy, X-ray diffractometer (and Raman scattering spectrometer), X-ray photoelectron spectrometer, nanoindenter, and four point probe, respectively. RGA results reveal that the main species in the gas phase contain H{sub 2}, C{sub 2}H, C{sub 2}H{sub 2}, HCN (or C{sub 2}H{sub 3}), and N{sub 2} (or C{sub 2}H{sub 4}). Moreover, C{sub 2}H, C{sub 2}H{sub 2}, and C{sub 2}H{sub 4} can be speculated as the main species for carbon thin film deposition. As the rf-power increases from 0 to 400 W, the deposition rate of carbon thin films decreases from 204 to 36.0 nm/h. The crystallinity and ordering degree of carbon thin films increase with increasing rf-power from 0 to 400 W, but the ratio of sp{sup 2} carbon sites in carbon thin films decreases from 95 to 75%. The Young's modulus, hardness, and electrical resistivity of carbon thin films increase with increasing rf-power. Furthermore, the effects of rf-power on the deposition rates of carbon thin films prepared by thermal CVD enhanced with remote ICP using C{sub 2}H{sub 2}/N{sub 2} and CH{sub 4}/N{sub 2} mixtures are compared. - Highlights: • Carbon films are prepared by TCVD enhanced with remote ICP using C{sub 2}H{sub 2}/N{sub 2} mixtures. • The deposition rate of carbon thin films decreases with increasing the rf-power. • C{sub 2}H, C{sub 2}H

  15. New Approach to Resonance Crossing

    Franchetti, G

    2012-01-01

    Time varying nonlinear oscillatory systems produce phenomena of resonance crossing and trapping of particles in resonance islands. Traditionally such processes have been analyzed in terms of adiabatic conditions. Considering, as an example, a simplified 1-dimensional (1-D) model describing the “electron cloud pinch” during a bunch passage in a particle accelerator, here we present an approach to resonance trapping which does not require any adiabatic condition. Instead we introduce the concept of attraction point and investigate invariance and scaling properties of motion close to the attraction point, considering a single resonance crossing.

  16. Redressing Cross-Dressed Shakespeare

    Martin, Thomas L.; Pesta, Duke

    2003-01-01

    Gender critics obsess over the boy actors who played female roles on the Elizabethan stage. But, in their far-fetched interpretation of Shakespearean drama as a spectacle of cross dressing, these new historicists lose sight of a fundamental principle of theater. Thomas Martin and Duke Pesta argue that with their prurient chatter of "the…

  17. Cross-Cultural HRD. Symposium.

    2002

    The first of three papers from this symposium on cross-cultural human resource development (HRD), "Determinants of Supply of Technical Training Opportunities for Human Capital Development in Kenya" (Moses Waithanji Ngware, Fredrick Muyia Nafukho) reports findings from interviews of technical training institute department heads in Kenya who…

  18. Revolutionizing Cross-sectional Imaging

    Fan, Yifang; Luo, Liangping; Lin, Wentao; Li, Zhiyu; Zhong, Xin; Shi, Changzheng; Newman, Tony; Zhou, Yi; Lv, Changsheng; Fan, Yuzhou

    2014-01-01

    Cross-sectional imaging is so important that, six Nobel Prizes have been awarded to the field of nuclear magnetic resonance alone because it revolutionized clinical diagnosis. The BigBrain project supported by up to 1 billion euro each over a time period of 10 years predicts to "revolutionize our ability to understand internal brain organization" (Evan 2013). If we claim that cross-sectional imaging diagnosis is only semi-quantitative, some may believe because no doctor would ever tell their patient that we can observe the changes of this cross-sectional image next time. If we claim that BigBrain will make no difference in clinical medicine, then few would believe because no doctor would ever tell their patient to scan this part of the image and compare it with that from the BigBrain. If we claim that the BigBrain Project and the Human Brain Project have defects in their key method, one might believe it. But this is true. The key lies in the reconstruction of any cross-sectional image along any axis. Using Ga...

  19. Terahertz radar cross section measurements

    Iwaszczuk, Krzysztof; Heiselberg, Henning; Jepsen, Peter Uhd

    2010-01-01

    We perform angle- and frequency-resolved radar cross section (RCS) measurements on objects at terahertz frequencies. Our RCS measurements are performed on a scale model aircraft of size 5-10 cm in polar and azimuthal configurations, and correspond closely to RCS measurements with conventional radar...

  20. Improved Zero-Crossing Detector

    Dick, G. John; Kuhnle, Paul F.

    1992-01-01

    Improved zero-crossing-detector circuit designed for precisely measuring difference between frequencies of two frequency-standard signal sources. Contains low-bandwidth first-stage amplifier and three limiting amplifiers, each "squares" signal bit more. Crosstalk eliminated and jitter reduced to about 10 to the negative 7th power microseconds.

  1. Cross sections for nuclear astrophysics

    General properties of low-energy cross sections and of reaction rates are presented. We describe different models used in nuclear astrophysics: microscopic models, the potential model, and the R-matrix method. Two important reactions, 7Be(p,γ)8B and 12C(α,γ)16O, are then briefly discussed. (author)

  2. Crossing Thresholds in Academic Reading

    Abbott, Rob

    2013-01-01

    This paper looks at the conceptual thresholds in relation to academic reading which might be crossed by undergraduate English Literature students. It is part of a wider study following 16 students through three years of undergraduate study. It uses theoretical ideas from Bakhtin and Foucault to analyse interviews with English lecturers. It…

  3. Cross-Language Information Retrieval.

    Oard, Douglas W.; Diekema, Anne R.

    1998-01-01

    Reviews research and practice in cross-language information retrieval (CLIR) that seeks to support the process of finding documents written in one natural language with automated systems that can accept queries expressed in other languages. Addresses user needs, document preprocessing, query formulation, matching strategies, sources of translation…

  4. A Crossing Method for Quinoa

    Adam Peterson

    2015-03-01

    Full Text Available As sustainable production of quinoa (Chenopodium quinoa Willd. increases and its geographic range of cultivation expands, quinoa breeding will allow use of the crop’s wide genetic diversity for cultivar improvement and for adaptation to new agroecosystems and climactic regimes. Such breeding work will require a reliable technique for crossing quinoa plants using hand emasculation. The technique described herein focuses on the isolation of small flower clusters produced low on the plant, emasculation of male flowers, and subsequent pairing of the emasculated female parent with a male parent undergoing anthesis. Various traits, such as plant color, seed color, and axil pigmentation can be used to confirm the successful production of F1 plants. The manual hybridization technology provides a significant advantage over pairing plants and relying on chance cross-pollination, and has been successfully used to generate crosses between quinoa cultivars, as well as interspecific crosses between quinoa and Chenopodium berlandieri. This technology will help pave the way for the introduction and sustainable expansion of quinoa on a global scale across a wide range of target environments and diverse farming systems.

  5. Comparative study of the monomer grafting: ethylene, acetylene, 1,3-butadiene and estyrene in the matrix of recycled polytetrafluoroethylene (PTFE); Estudo comparativo da enxertia dos monomeros: etileno, acetileno, 1,3-butadieno e estireno na matriz de politetrafluoroetileno (PTFE) reciclado

    Ikari, Carolina T.; Rosner, Gerhardyne O.; Oliveira, Ana C.F. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Quimica e Meio Ambiente (CQMA); Faculdades Oswaldo Cruz, Sao Paulo, SP (Brazil); Ferreto, Helio F.R.; Lima, Luiz F.C.P.; Lugao, Ademar B., E-mail: hferreto@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Quimica e Meio Ambiente (CQMA); Moreira, Otavio M. [Faculdades Oswaldo Cruz, Sao Paulo, SP (Brazil)

    2009-07-01

    In this study it is used the recycled polytetrafluoroethylene (PTFE), that with the gamma radiation under inert atmosphere or in presence of air, it is obtained free radicals and a posterior the monomer grafting (ethylene, acetylene, styrene or 1.3 butadiene), obtaining the copolymer polytetrafluoroethylene-g-monomer. It is studied the obtention of the polymer by two methods: by direct way, via grafting, where the polymer is irradiated in presence of monomer, and via grafting when the polymer is irradiated in absence of monomer and under inert or air. The characterization of the copolymer was performed by the techniques of infrared region absorption spectroscopy with Fourier transformation (FTIR), thermogravimetric (TGA) and derivative thermogravimetry (DTG), and percentage of mass grafting (DOG)

  6. Crossing Total Occlusions: Navigating Towards Recanalization.

    Sakes, Aimée; Regar, Evelyn; Dankelman, Jenny; Breedveld, Paul

    2016-06-01

    Chronic total occlusions (CTOs) represent the "last frontier" of percutaneous interventions. The main technical challenges lies in crossing the guidewire into the distal true lumen, which is primarily due to three problems: device buckling during initial puncture, inadequate visualization, and the inability to actively navigate through the CTO. To improve the success rate and to identify future research pathways, this study systematically reviews the state-of-the-art of all existing and invented devices for crossing occlusions. The literature search was executed in the databases of Scopus and Espacenet using medical and instrument-related keyword combinations. The search yielded over 840 patents and 69 articles. After scanning for relevancy, 45 patents and 16 articles were included. The identified crossing devices were subdivided based on the determinant for the crossing path through the occlusion, which is either the device (straight and angled crossing), the environment (least resistance, tissue selective, centerline, and subintimal crossing) or the user (directly steered and sensor enhanced crossing). It was found that each crossing path is characterized by specific advantages and disadvantages. For a future crossing device, a combination of crossing paths is suggested were the interventionist is able to exert high forces on the CTO (as seen in the device approach) and actively steer through the CTO (user: directly steered crossing) aided by intravascular imaging (user: sensor enhanced crossing) or an intrinsically safe device following the centerline or path of least resistance (environment: centerline crossing or least resistance crossing) to reach the distal true lumen. PMID:26831298

  7. Collagen cross linking: Current perspectives

    Srinivas K Rao

    2013-01-01

    Full Text Available Keratoconus is a common ectatic disorder occurring in more than 1 in 1,000 individuals. The condition typically starts in adolescence and early adulthood. It is a disease with an uncertain cause and its progression is unpredictable, but in extreme cases, vision deteriorates and can require corneal transplant surgery. Corneal collagen cross-linking (CCL with riboflavin (C3R is a recent treatment option that can enhance the rigidity of the cornea and prevent disease progression. Since its inception, the procedure has evolved with newer instrumentation, surgical techniques, and is also now performed for expanded indications other than keratoconus. With increasing experience, newer guidelines regarding optimization of patient selection, the spectrum of complications and their management, and combination procedures are being described. This article in conjunction with the others in this issue, will try and explore the uses of collagen cross-linking (CXL in its current form.

  8. CULTURE CROSSING IN THE SCHOOL

    María Padrós

    2009-11-01

    Full Text Available The educational centres are a multicultural reality that comprises the coexistenceof different cultural minorities, languages, religions, lifestyles and social codes.The critical pedagogy presents ways of living and learning in this culture crossing overcomingboth the ethnocentric model of racism (assimilation to the culture understood as“superior” as well as the relativist model (with emphasis on the difference and denyingequality, aiming for the idea of equality of differences. In the article are presented waysof crossing cultures and historical backgrounds from a critical, supportive and transformationalapproach among languages, religions and believes. It is stated that the consensusis possible in the framework of the plurality of identities and cultural patterns, andthat egalitarian dialog between cultures in the school promotes not only individualtransformations but also changes in the social relationships.

  9. Crossings in Clustered Level Graphs

    Forster, Michael

    2005-01-01

    Clustered graphs are an enhanced graph model with a recursive clustering of the vertices according to a given nesting relation. This prime technique for expressing coherence of certain parts of the graph is used in many applications, such as biochemical pathways and UML class diagrams. For directed clustered graphs usually level drawings are used, leading to clustered level graphs. In this thesis we analyze the interrelation of clusters and levels and their influence on edge crossings and clu...

  10. Cross-Cultural Knowledge Management

    Giudice, Manlio Del; Peruta, Maria Rosaria Della

    2012-01-01

    Cross-cultural knowledge management, an elusive yet consequential phenomenon, is becoming an increasingly essential factor in organizational practice and policy in the era of globalization. In order to overcome culturally shaped blind spots in conducting research in different settings, this volume highlights how the structuring of roles, interests, and power among different organizational elements, such as teams, departments, and management hierarchies (each comprised of members from different intellectual and professional backgrounds), generates various paradoxes and tensions that bring into

  11. Metonymy and Cross Section Demand

    Evstigneev, Igor V.; Hildenbrand, Werner; Jerison, Michael

    1996-01-01

    Cross section consumer expenditure data are frequently used to make conclusions about consumer demand behavior. Such conclusions, however, can only be justified under certain assumptions, which are often left unstated in the empirical demand literature. An assumption of this type, the metonymy hypothesis, was stated rigorously and then exploited by Hardle, Hildenbrand and Jerison when analyzing the monotonicity property of aggregate demand functions. The purpose of the present paper is to exa...

  12. A Crossing Method for Quinoa

    Adam Peterson; Sven-Erik Jacobsen; Alejandro Bonifacio; Kevin Murphy

    2015-01-01

    As sustainable production of quinoa ( Chenopodium quinoa Willd.) increases and its geographic range of cultivation expands, quinoa breeding will allow use of the crop’s wide genetic diversity for cultivar improvement and for adaptation to new agroecosystems and climactic regimes. Such breeding work will require a reliable technique for crossing quinoa plants using hand emasculation. The technique described herein focuses on the isolation of small flower clusters produced low on the plant, e...

  13. Wind Turbine Radar Cross Section

    David Jenn; Cuong Ton

    2012-01-01

    The radar cross section (RCS) of a wind turbine is a figure of merit for assessing its effect on the performance of electronic systems. In this paper, the fundamental equations for estimating the wind turbine clutter signal in radar and communication systems are presented. Methods of RCS prediction are summarized, citing their advantages and disadvantages. Bistatic and monostatic RCS patterns for two wind turbine configurations, a horizontal axis three-blade design and a vertical axi...

  14. CULTURE CROSSING IN THE SCHOOL

    María Padrós; Itxaso Tellado

    2009-01-01

    The educational centres are a multicultural reality that comprises the coexistenceof different cultural minorities, languages, religions, lifestyles and social codes.The critical pedagogy presents ways of living and learning in this culture crossing overcomingboth the ethnocentric model of racism (assimilation to the culture understood as“superior”) as well as the relativist model (with emphasis on the difference and denyingequality), aiming for the idea of equality of differences. In the art...

  15. New Approach to Resonance Crossing

    Franchetti, G.; Zimmermann, F.

    2012-01-01

    Time varying nonlinear oscillatory systems produce phenomena of resonance crossing and trapping of particles in resonance islands. Traditionally such processes have been analyzed in terms of adiabatic conditions. Considering, as an example, a simplified 1-dimensional (1-D) model describing the “electron cloud pinch” during a bunch passage in a particle accelerator, here we present an approach to resonance trapping which does not require any adiabatic condition. Instead we introduce the concep...

  16. New activation cross section data

    New nuclear cross section libraries (known as USACT92) have been created for activation calculations. A point-wise file was created from merging the previous version of the activation library, the U.S. Nuclear Data Library (ENDF/B-VI), and the European Activation File (EAF-2). 175 and 99 multi-group versions were also created. All the data are available at the National Energy Research Supercomputer Center

  17. CLEF - Cross Language Evaluation Form

    Peters, Carol

    2000-01-01

    A Cross-Language Evaluation Forum (CLEF), an important initiative for the evaluation of multilingual information retrieval systems, is now being launched in Europe. The activity will be sponsored by the DELOS Network of Excellence for Digital Libraries and funded by the Information Societies Technology programme of the European Commission. It will be conducted in collaboration with the US National Institute of Standards and Technology (NIST) and the TREC conference series. We present the agen...

  18. Cross-language information retrieval

    Jure Dimec

    2002-01-01

    The article reviews the motivation behind the development of cross-language information retrieval (CLIR) – a relatively new area of information retrieval in multilingual textual databases, defines its objectives and position among the research disciplines dealing with various aspects of processing electronic texts. A short historical overview is followed by a description of the most important methodologies (document translation and query translation) and language resources used in connection ...

  19. Cross-border innovation cooperation

    Hjaltadóttir, Rannveig Edda; Makkonen, Teemu; Sørensen, Nils Karl

    2014-01-01

    the location of the partners into account. In particular, the discussion is tied to the notion of varying knowledge bases firms utilize in their innovation creation processes. Firm level data from the 2010 Community Innovation Survey in Denmark was used to analyse cross-border innovation cooperation patterns...... of choosing a foreign partner while the decision between foreign partners from different locations is not. The results do however not provide support for the theory of knowledge bases influencing the location of innovation partners....

  20. Electron-Impact Ionization Cross Section Database

    SRD 107 Electron-Impact Ionization Cross Section Database (Web, free access)   This is a database primarily of total ionization cross sections of molecules by electron impact. The database also includes cross sections for a small number of atoms and energy distributions of ejected electrons for H, He, and H2. The cross sections were calculated using the Binary-Encounter-Bethe (BEB) model, which combines the Mott cross section with the high-incident energy behavior of the Bethe cross section. Selected experimental data are included.

  1. Microscopic cross sections: An utopia?

    Hilaire, S. [CEA Bruyeres-le-Chatel, DIF 91 (France); Koning, A.J. [Nuclear Research and Consultancy Group, PO Box 25, 1755 ZG Petten (Netherlands); Goriely, S. [Institut d' Astronomie et d' Astrophysique, Universite Libre de Bruxelles, Campus de la Plaine, CP 226, 1050 Brussels (Belgium)

    2010-07-01

    The increasing need for cross sections far from the valley of stability poses a challenge for nuclear reaction models. So far, predictions of cross sections have relied on more or less phenomenological approaches, depending on parameters adjusted to available experimental data or deduced from systematical relations. While such predictions are expected to be reliable for nuclei not too far from the experimentally known regions, it is clearly preferable to use more fundamental approaches, based on sound physical bases, when dealing with very exotic nuclei. Thanks to the high computer power available today, all major ingredients required to model a nuclear reaction can now be (and have been) microscopically (or semi-microscopically) determined starting from the information provided by a nucleon-nucleon effective interaction. We have implemented all these microscopic ingredients in the TALYS nuclear reaction code, and we are now almost able to perform fully microscopic cross section calculations. The quality of these ingredients and the impact of using them instead of the usually adopted phenomenological parameters will be discussed. (authors)

  2. Crossing Intentions in Participatory Innovation

    Buur, Jacob; Larsen, Henry

    2010-01-01

    In this paper we explore the role of 'crossing intentions' among participants involved in innovation processes with users. We use improvised theatre to investigate what happens in industrial (and other) organizations that embark on participatory activities, and to explore the barriers that hinder...... the surface are experienced as risky to participate in. We examine four examples of such meetings with the intent to disclose conceptual themes that show high potential for developing participatory innovation.......In this paper we explore the role of 'crossing intentions' among participants involved in innovation processes with users. We use improvised theatre to investigate what happens in industrial (and other) organizations that embark on participatory activities, and to explore the barriers that hinder...... such activities. We propose that people who meet each other with different and conflicting intentions relevant to the theme together can create new insight (understood as movement of thought and action) that may become a driver of innovation. However, such meetings in which crossing intentions come to...

  3. Generalized Cross-Gramian for Linear Systems

    Shaker, Hamid Reza

    2012-01-01

    The cross-gramian is a well-known matrix with embedded controllability and observability information. The cross-gramian is related to the Hankel operator and the Hankel singular values of a linear square system and it has several interesting properties. These properties make the cross......-gramian popular in several applications including model reduction, control configuration selection and sensitivity analysis. The ordinary cross-gramian which has been defined in the literature is the solution of a Sylvester equation. This Sylvester equation is not always solvable and therefore for some linear...... square symmetric systems, the ordinary cross-gramian does not exist. To cope with this problem, a new generalized cross-gramian is introduced in this paper. In contrast to the ordinary cross-gramian, the generalized cross-gramian can be easily obtained for general linear systems and therefore can be used...

  4. Navigation in Cross-cultural business relationships

    Andersen, Poul Houman

    2001-01-01

    Cross-cultural business navigation concerns the process of handling the complexity of several interacting cultural spheres of influence......Cross-cultural business navigation concerns the process of handling the complexity of several interacting cultural spheres of influence...

  5. Evaluation of cross section for 103Rh

    A completely new evaluation for the neutron cross sections is presented. The experimental data mainly referred to EXFOR, and the recommended cross sections are compared with ENDF/B-6, BROND-2, JENDL-3.2 and JEF-2

  6. Quadratic and 2-Crossed Modules of Algebras

    Z. Arvasi; E. Ulualan

    2007-01-01

    In this work, we define the quadratic modules for commutative algebras and give relations among 2-crossed modules, crossed squares, quadratic modules and simplicial commutative algebras with Moore complex of length 2.

  7. CBP Customs Rulings Online Search System (CROSS)

    Department of Homeland Security — CROSS is a searchable database of CBP rulings that can be retrieved based on simple or complex search characteristics using keywords and Boolean operators. CROSS...

  8. VARIOUS ASPECTS OF CROSS-CULTURAL COMMUNICATION

    Tsibulya, N.

    2014-01-01

    The author considers the main cultural dimensions and tendencies in cross-cultural communication studies from the 1950s till the present day. Using one’s own experience in carrying out research of non-verbal and prosodic aspects of cross-cultural interaction, the author suggests a system of exercises useful in teaching and learning cross-cultural communication and aimed at formation and developing cross-cultural competence.

  9. Photoproduction total cross section and shower development

    Cornet, F.; García Canal, C. A.; Grau, A.; Pancheri, G.; Sciutto, S. J.

    2015-12-01

    The total photoproduction cross section at ultrahigh energies is obtained using a model based on QCD minijets and soft-gluon resummation and the ansatz that infrared gluons limit the rise of total cross sections. This cross section is introduced into the Monte Carlo system AIRES to simulate extended air showers initiated by cosmic ray photons. The impact of the new photoproduction cross section on common shower observables, especially those related to muon production, is compared with previous results.

  10. Photoproduction total cross section and shower development

    Cornet, F; Grau, A; Pancheri, G; Sciutto, S J

    2015-01-01

    The total photoproduction cross section at ultra-high energies is obtained using a model based on QCD minijets and soft-gluon resummation and the ansatz that infrared gluons limit the rise of total cross sections. This cross section is introduced into the Monte Carlo system AIRES to simulate extended air-showers initiated by cosmic ray photons. The impact of the new photoproduction cross section on common shower observables, especially those related to muon production, is compared with previous results.

  11. Cross-docking: State of the art

    Van Belle, Jan; Valckenaers, Paul; Cattrysse, Dirk

    2012-01-01

    Cross-docking is a logistics strategy in which freight is unloaded from inbound vehicles and (almost) directly loaded into outbound vehicles, with little or no storage in between. This article presents an overview of the cross-docking concept. Guidelines for the successful use and implementation of cross-docking are discussed and several characteristics are described that can be used to distinguish between different cross-dock types. In addition, this article presents an extensive review of t...

  12. Web Based Cross Language Plagiarism Detection

    Kent, Chow Kok; Salim, Naomie

    2009-01-01

    As the Internet help us cross language and cultural border by providing different types of translation tools, cross language plagiarism, also known as translation plagiarism are bound to arise. Especially among the academic works, such issue will definitely affect the student's works including the quality of their assignments and paper works. In this paper, we propose a new approach in detecting cross language plagiarism. Our web based cross language plagiarism detection system is specially t...

  13. Electrospinning formaldehyde cross-linked zein solutions

    In order to develop zein fibers with improved physical properties and solvent resistance, formaldehyde was used as the cross-linking reagent before spinning. The cross-linking reaction was carried out in either acetic acid or ethanolic-HCl where the amount of cross-linking reagent was between 1 and...

  14. Cross-border merger and domestic welfare

    Arijit Mukherjee

    2006-01-01

    We consider the welfare effect of cross-border merger in presence of international R&D competition. Cross-border merger increases domestic welfare if the bargaining power of the foreign firm and the slope of the marginal cost of R&D are sufficiently low. Otherwise, domestic welfare is lower under cross-border merger.

  15. JENDL gas-production cross section file

    The JENDL gas-production cross section file was compiled by taking cross-section data from JENDL-3 and by using the ENDF-5 format. The data were given to 23 nuclei or elements in light nuclei and structural materials. Graphs of the cross sections and brief description on their evaluation methods are given in this report. (author)

  16. [Fast neutron cross section measurements

    In this report, we outline the progress achieved in two distinct under the DOE-sponsored cross section project: the initial results obtained from the pulsed 14 MeV neutron facility, and a cooperative effort with Argonne National Laboratory in the measurement of fast neutron cross sections in yttrium. In the 14 MeV neutron laboratory, this year has seen the maturation of the project into one in which initial scattering measurements are now underway. We have improved the accelerator and ion source in several significant ways, so that neutron intensities have now been proven to be adequate for our series of elastic scattering angular distribution measurements outlined in our initial proposal of two years ago. We have successfully tested all components of the time-of-flight spectrometer and recorded initial neutron spectra from the ring targets that we have obtained for our first angular distribution measurements. Examples of the time-of-flight spectra that have been obtained are given later in this report. At the present time, the accelerator is operating with the highest degree of reliability that we have experienced since installing the pulsing system. Improvements made over the past year have not only increased the available neutron intensity, but also increased our capability to deal with inevitable component failures that require repair or replacement. The measurements carried out in conjunction with Argonne have contributed significantly to the available database on fast neutron interactions in yttrium. Results indicate that the cross section for the 89 Y(n,p)89Sr reaction is substantially higher than represented in ENDF/B-VI

  17. Faunapassager : How animals cross roads

    Lundberg, Adina; Gunnarsson, Fredrik

    2008-01-01

    A fauna passage is a way for animals to cross roads separated from the traffic. In Sweden, there are an unknown number of passages with different functions and appearances. These passages would, with the question “Which fauna passages can be found in Sweden, and how well do they work?” as a base, be compiled in a comparable way. This would be done with a number of questions asked to the different regions of Vägverket. The essay was delimited to only include ecoducts, animal bridges, landscape...

  18. Wind Turbine Radar Cross Section

    David Jenn

    2012-01-01

    Full Text Available The radar cross section (RCS of a wind turbine is a figure of merit for assessing its effect on the performance of electronic systems. In this paper, the fundamental equations for estimating the wind turbine clutter signal in radar and communication systems are presented. Methods of RCS prediction are summarized, citing their advantages and disadvantages. Bistatic and monostatic RCS patterns for two wind turbine configurations, a horizontal axis three-blade design and a vertical axis helical design, are shown. The unique electromagnetic scattering features, the effect of materials, and methods of mitigating wind turbine clutter are also discussed.

  19. Cross-language information retrieval

    Nie, Jian-Yun

    2010-01-01

    Search for information is no longer exclusively limited within the native language of the user, but is more and more extended to other languages. This gives rise to the problem of cross-language information retrieval (CLIR), whose goal is to find relevant information written in a different language to a query. In addition to the problems of monolingual information retrieval (IR), translation is the key problem in CLIR: one should translate either the query or the documents from a language to another. However, this translation problem is not identical to full-text machine translation (MT): the

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

    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

  1. Graphite Nanostructures Produce in the Acetilene, Argon-Acetylene and Argon-Hydrogen-Acetylene Plasmas

    Grigonis A.; Marcinauskas L.; Carnauskas M.; Kaliasas R.

    2012-01-01

    The amorphous carbon films were deposited on silicon-metal substrates by plasma jet chemical vapor deposition (PJCVD) and plasma enchanted CVD (PECVD). PJCVD carbon coatings have been prepared at atmospheric pressure in Ar/ C2H2 and Ar/H2/C2H2 mixtures. The films prepared in Ar/C2H2 plasma are at-tributed to graphite-like carbon films. Addition of the hydrogen decreases growth rate and the surface roughness of the coatings, but coatings have low fraction of oxygen (~5 at.%) The formation of t...

  2. Geosynchronous magnetopause crossings: upstream conditions

    Suvorova, A; Chao, J -K; Thomsen, M; Yang, Y -H

    2011-01-01

    The experimental data on GOES magnetic measurements and plasma measurements on LANL geosynchronous satellites is used for selection of 169 case events containing 638 geosynchronous magnetopause crossings (GMCs) in 1995 to 2001. We study the necessary conditions for the geosynchronous magnetopause crossings using scatter plot of the GMCs in the coordinate space of Psw versus Bz. In such representation the upstream solar wind conditions demonstrate sharp envelope boundary under which no GMCs are occurred. The boundary has two strait horizontal branches where Bz does not influence on the magnetopause location. The first branch is located in the range of Psw=21 nPa for large positive Bz and is associated with an asymptotic regime of the pressure balance. The second branch asymptotically approaches to the range of Psw=4.8 nPa under very strong negative Bz and it is associated with a regime of the Bz influence saturation. We suggest that the saturation is caused by relatively high contribution of the magnetosphere ...

  3. Dentists and cross-infection.

    Naidoo, S

    1997-03-01

    A structured questionnaire was administered to a random sample of general dental practitioners in Natal, South Africa in 1994, to ascertain the precautions they use against cross-infection and to gauge the attitudes and behaviour towards the treatment of HIV-infected individuals. An interview was conducted covering 5 broad topics: demographic details, personal barrier protection, instrument sterilization and disinfection, sharps disposal and incidence of needlestick injuries and the extent of the knowledge, attitude and behaviour of the practitioners toward the treatment of HIV-infected individuals. The key findings were: routine glove wearing, for all patients, was practised by 87 per cent. The most common heat sterilization method was by autoclave (68 per cent), although a dry heat sterilizer and water boiler were used by 22 per cent of the respondents. Of the 18 respondents reporting a needlestick injury in the past 6 months only one sought after-care. 42 per cent of the respondents would continue to treat carriers of HIV in their practices. This survey shows that a significant number of dentists are using unacceptable cross-infection control procedures. Educational efforts should be made to improve their knowledge and to alleviate anxiety of health workers to treat HIV-infected patients. PMID:9461908

  4. SNL RML recommended dosimetry cross section compendium

    Griffin, P.J.; Kelly, J.G.; Luera, T.F. [Sandia National Labs., Albuquerque, NM (United States); VanDenburg, J. [Science and Engineering Associates, Inc., Albuquerque, NM (United States)

    1993-11-01

    A compendium of dosimetry cross sections is presented for use in the characterization of fission reactor spectrum and fluence. The contents of this cross section library are based upon the ENDF/B-VI and IRDF-90 cross section libraries and are recommended as a replacement for the DOSCROS84 multigroup library that is widely used by the dosimetry community. Documentation is provided on the rationale for the choice of the cross sections selected for inclusion in this library and on the uncertainty and variation in cross sections presented by state-of-the-art evaluations.

  5. Vehicle routing with cross-docking

    Wen, Min; Larsen, Jesper; Clausen, Jens; Cordeau, Jean-Francois; Laporte, Gilbert

    2009-01-01

    Over the past decade, cross-docking has emerged as an important material handling technology in transportation. A variation of the well-known Vehicle Routing Problem (VRP), the VRP with Cross-Docking (VRPCD) arises in a number of logistics planning contexts. This paper addresses the VRPCD, where a...... set of homogeneous vehicles are used to transport orders from the suppliers to the corresponding customers via a cross-dock. The orders can be consolidated at the cross-dock but cannot be stored for very long because the cross-dock does not have long-term inventory-holding capabilities. The objective...

  6. Recent fission cross section standards measurements

    Wasson, O.A.

    1985-01-01

    The /sup 235/U(n,f) reaction is the standard by which most neutron induced fission cross sections are determined. Most of these cross sections are derived from relatively easy ratio measurements to /sup 235/U. However, the more difficult /sup 235/U(n,f) cross section measurements require the use of advanced neutron detectors for the determination of the incident neutron fluence. Examples of recent standard cross section measurements are discussed, various neutron detectors are described, and the status of the /sup 235/U(n,f) cross section standard is assessed. 23 refs., 8 figs., 4 tabs.

  7. Recent fission cross section standards measurements

    The 235U(n,f) reaction is the standard by which most neutron induced fission cross sections are determined. Most of these cross sections are derived from relatively easy ratio measurements to 235U. However, the more difficult 235U(n,f) cross section measurements require the use of advanced neutron detectors for the determination of the incident neutron fluence. Examples of recent standard cross section measurements are discussed, various neutron detectors are described, and the status of the 235U(n,f) cross section standard is assessed. 23 refs., 8 figs., 4 tabs

  8. CrossFlow: Cross-Organizational Workflow Management in Dynamic Virtual Enterprises

    Grefen, Paul; Aberer, Karl; Hoffner, Yigal; Ludwig, Heiko

    2000-01-01

    In this report, we present the approach to cross-organizational workflow management of the CrossFlow project. CrossFlow is a European research project aiming at the support of cross-organizational workflows in dynamic virtual enterprises. The cooperation in these virtual enterprises is based on dyna

  9. CrossWork: Software-assisted identification of cross-linked peptides

    Rasmussen, Morten; Refsgaard, Jan; Peng, Li;

    2011-01-01

    Work searches batches of tandem mass-spectrometric data, and identifies cross-linked and non-cross-linked peptides using a standard PC. We tested CrossWork by searching mass-spectrometric datasets of cross-linked complement factor C3 against small (1 protein) and large (1000 proteins) search spaces, and show...

  10. 22 CFR 41.32 - Nonresident alien Mexican border crossing identification cards; combined border crossing...

    2010-04-01

    ... identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. 41.32 Section 41... crossing identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. (a) Combined B-1/B-2 visitor visa and border crossing identification card (B-1/B-2 Visa/BCC)—(1)...

  11. Deionization shocks in cross flows

    Mani, Ali

    2011-11-01

    Recent experimental and theoretical studies have shown that surface conduction in supported electrolytes, such as in micro/nanochannels or porous media, can lead to nonlinear modes of transport and formation of sharp concentration fronts analogous to shock waves in gas dynamics. Propagation of these shocks leaves behind a region of ultra pure fluid, acting to deionize the bulk solution. In this work we present the analysis of salt transport in a porous medium next to a membrane with an electric field applied normal to the interface and cross flow in tangential direction. We show that two distinct boundary layers grow near the membrane: an inner (shocked) region with almost deionized solution dominated by surface conduction, and an outer layer with diffuse dynamics. Under certain conditions both regions collapse into a similarity solution with the same scaling. We will discuss advantages of such systems for desalination and water purification. Research performed in collaboration with Martin Bazant (MIT).

  12. Cross-language information retrieval

    Jure Dimec

    2002-01-01

    Full Text Available The article reviews the motivation behind the development of cross-language information retrieval (CLIR – a relatively new area of information retrieval in multilingual textual databases, defines its objectives and position among the research disciplines dealing with various aspects of processing electronic texts. A short historical overview is followed by a description of the most important methodologies (document translation and query translation and language resources used in connection with them. Regarding the resources, attention is focused on the two- and multilingual ontologies (thesauri,transfer lexicons and similarity thesauri, corpora, their construction and use with the CLIR experiments. The article primarily aims at illustrating the various methodological approaches, while the functioning of particular systems is less prominent. There are no references to the condition of CLIR in Slovenia or to the existence of language resources suitable for processing Slovenian texts in CLIR systems, since this topic calls for a separate review.

  13. [Fast neutron cross section measurements

    In the 14 MeV Neutron Laboratory, we have continued the development of a facility that is now the only one of its kind in operation in the United States. We have refined the klystron bunching system described in last year's report to the point that 1.2 nanosecond pulses have been directly measured. We have tested the pulse shape discrimination capability of our primary NE 213 neutron detector. We have converted the RF sweeper section of the beamline to a frequency of 1 MHz to replace the function of the high voltage pulser described in last year's report which proved to be difficult to maintain and unreliable in its operation. We have also overcome several other significant experimental difficulties, including a major problem with a vacuum leak in the main accelerator column. We have completed additional testing to prove the remainder of the generation and measurement systems, but overcoming some of these experimental difficulties has delayed the start of actual data taking. We are now in a position to begin our first series of ring geometry elastic scattering measurements, and these will be underway before the end of the current contract year. As part of our longer term planning, we are continuing the conceptual analysis of several schemes to improve the intensity of our current pulsed beam. These include the provision of a duoplasmatron ion source and/or the provision of preacceleration bunching. Additional details are given later in this report. A series of measurements were carried out at the Tandem Dynamatron Facility involving the irradiation of a series of yttrium foils and the determination of activation cross sections using absolute counting techniques. The experimental work has been completed, and final analysis of the cross section data will be completed within several months

  14. Background-cross-section-dependent subgroup parameters

    A new set of subgroup parameters was derived that can reproduce the self-shielded cross section against a wide range of background cross sections. The subgroup parameters are expressed with a rational equation which numerator and denominator are expressed as the expansion series of background cross section, so that the background cross section dependence is exactly taken into account in the parameters. The advantage of the new subgroup parameters is that they can reproduce the self-shielded effect not only by group basis but also by subgroup basis. Then an adaptive method is also proposed which uses fitting procedure to evaluate the background-cross-section-dependence of the parameters. One of the simple fitting formula was able to reproduce the self-shielded subgroup cross section by less than 1% error from the precise evaluation. (author)

  15. Vertically stabilized elongated cross-section tokamak

    Sheffield, George V.

    1977-01-01

    This invention provides a vertically stabilized, non-circular (minor) cross-section, toroidal plasma column characterized by an external separatrix. To this end, a specific poloidal coil means is added outside a toroidal plasma column containing an endless plasma current in a tokamak to produce a rectangular cross-section plasma column along the equilibrium axis of the plasma column. By elongating the spacing between the poloidal coil means the plasma cross-section is vertically elongated, while maintaining vertical stability, efficiently to increase the poloidal flux in linear proportion to the plasma cross-section height to achieve a much greater plasma volume than could be achieved with the heretofore known round cross-section plasma columns. Also, vertical stability is enhanced over an elliptical cross-section plasma column, and poloidal magnetic divertors are achieved.

  16. Measurements of neutron capture cross sections

    A review of measurement techniques for the neutron capture cross sections is presented. Sell transmission method, activation method, and prompt gamma-ray detection method are described using examples of capture cross section measurements. The capture cross section of 238U measured by three different prompt gamma-ray detection methods (large liquid scintillator, Moxon-Rae detector, and pulse height weighting method) are compared and their discrepancies are resolved. A method how to derive the covariance is described. (author)

  17. Crossing Statistics of Anisotropic Stochastic Surface

    Nezhadhaghighi, M Ghasemi; Yasseri, T; Allaei, S M Vaez

    2015-01-01

    We use crossing statistics and its generalization to determine the anisotropic direction imposed on a stochastic fields in $(2+1)$Dimension. This approach enables us to examine not only the rotational invariance of morphology but also we can determine the Gaussianity of underlying stochastic field in various dimensions. Theoretical prediction of up-crossing statistics (crossing with positive slope at a given threshold $\\alpha$ of height fluctuation), $\

  18. Cosmetic crossings of genus one knots

    Balm, Cheryl

    2011-01-01

    We show that for genus one knots the Alexander polynomial and the homology of the double cover branching over the knot provide obstructions to cosmetic crossings. As an application we prove the nugatory crossing conjecture for the negatively twisted, positive Whitehead doubles of all knots. We also verify the conjecture for several families of pretzel knots and all genus one knots with up to 10 crossings.

  19. Cross-Cultural Research and Qualitative Inquiry

    Pranee Liamputtong

    2010-01-01

    Cross-cultural research has become important in this postmodern world where many people have been made, and are still, marginalised and vulnerable by others in more powerful positions like colonial researchers. In this paper, I contend that qualitative research is particularly appropriate for cross-cultural research because it allows us to find answers which are more relevant to the research participants. Cross-cultural qualitative research must be situated within some theoretical frameworks....

  20. Compilation of cross-sections. Pt. 2

    A compilation of integrated cross-sections for hadronic reactions is presented. This is an updated version of CERN/HERA 79-1, 79-2, 79-3. It contains all data published up to the beginning of 1982, but some more recent data have also been included. Plots of the cross sections versus incident laboratory momentum are also given. This volume II contains cross-sections for K+ and K- induced reactions. (orig.)

  1. Cross-platform mobile game development

    Pirttiaho, Joonas

    2014-01-01

    The main purpose of this thesis was to find and learn about a framework for cross-platform mobile game development for modern mobile operating systems. The target mobile platforms were Google's Android and Apple's iOS. The thesis was started by finding out different types of solutions for cross-platform application and game development for mobile devices. Different types of solutions should be briefly described and the found solution for cross-platform development should be more extensive...

  2. Cross Sections for Electron Collisions with Methane

    Song, Mi-Young, E-mail: mysong@nfri.re.kr; Yoon, Jung-Sik [Plasma Technology Research Center, National Fusion Research Institute, 814-2 Osikdo-dong, Gunsan, Jeollabuk-do 573-540 (Korea, Republic of); Cho, Hyuck [Department of Physics, Chungnam National University, Daejeon 305-764 (Korea, Republic of); Itikawa, Yukikazu [Institute of Space and Astronautical Science, Sagamihara 252-5210 (Japan); Karwasz, Grzegorz P. [Faculty of Physics, Astronomy and Applied Informatics, University Nicolaus Copernicus, Grudziadzka 5, 87100 Toruń (Poland); Kokoouline, Viatcheslav [Department of Physics, University of Central Florida, Orlando, Florida 32816 (United States); Nakamura, Yoshiharu [6-1-5-201 Miyazaki, Miyamae, Kawasaki 216-0033 (Japan); Tennyson, Jonathan [Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom)

    2015-06-15

    Cross section data are compiled from the literature for electron collisions with methane (CH{sub 4}) molecules. Cross sections are collected and reviewed for total scattering, elastic scattering, momentum transfer, excitations of rotational and vibrational states, dissociation, ionization, and dissociative attachment. The data derived from swarm experiments are also considered. For each of these processes, the recommended values of the cross sections are presented. The literature has been surveyed through early 2014.

  3. The Cross-Cultural Knowledge Sharing Challenge

    Persson, John Stouby

    2013-01-01

    Cross-cultural offshoring in software development challenges effective knowledge sharing. While research has suggested temporarily co-locating participants to address this challenge, few studies are available on what knowledge sharing practices emerge over time when co-locating cross-cultural sof...... period of colocation four facilitators of cross-cultural knowledge sharing were shared office, shared responsibility for tasks and problems, shared prioritization of team spirit, and a champion of social integration....

  4. Piano Crossing - Generating music using computer vision

    Lipanje, Matevž

    2010-01-01

    Piano Crossing is an interactive art installation which transforms the zebra crossing into a working piano keyboard where pedestrians generate music by walking across it. Installation consists of the zeboard - zebra crossing turned keyboard - by adding black stripes to the existing white ones, serving as keys, a digital camera overlooking the zeboard and of a laptop computer with speakers. The computer runs a specially designed software, which recognizes pedestrian's contacts with the keys by...

  5. Teaching NHCE with Cross-Cultural Simulations

    杨非

    2008-01-01

    Cross-cultural communication competence is very important for the students who study English as a second language. In order to teach effectively.the teachers may try to teach with cross-cultural simulations.The au- thor Of the article uses 5 simulations in the course of New Horizon College English.Although the sample size in this research is small,the author shows the ideas that cross-cultural awareness is related to communication competence and teaching with cross-cultural simulations helps understanding.

  6. Ion and electron impact ionization cross sections

    Several current projects are described in which cross sections of interest to radiation physics are being measured. These include total and multiple ionization cross sections for protons on several gases covering a wide energy range, the measurement of cross sections differential in the angle and energy of ejected electrons for several gases including water vapor, and a review of proton ionization data. The work on water vapor has also been extended to electron and neutral hydrogen impact. A brief discussion is also given of some systematics of ionization cross sections. 13 references

  7. Improved Empirical Parametrization of Fragmentation Cross Sections

    Sümmerer, Klaus

    2012-01-01

    A new version is proposed for the universal empirical formula, EPAX, which describes fragmentation cross sections in high-energy heavy-ion reactions. The new version, EPAX 3, can be shown to yield cross sections that are in better agreement with experimental data for the most neutron-rich fragments than the previous version. At the same time, the very good agreement of EPAX 2 with data on the neutron-deficient side has been largely maintained. Comparison with measured cross sections show that the bulk of the data is reproduced within a factor of about 2, for cross sections down to the pico-barn range.

  8. Damage cross section library (DAMSIG77)

    The damage cross sections of various materials are converted to a data format, which can be used as library for the program SAND-II. The materials available in this library are graphite, stainless steel, aluminium, silicium, chromium, iron, nickel, copper, zirconium, molybdenum, tungsten, vanadium and niobium. A number of these materials have more than one cross section set, originating from different evaluations. Cross sections for some activation reactions, commonly used to determine thermal and fast neutron fluences have been included too. Moreover, also some artificial cross sections are introduced in this library which can be used to derive values for some physical quantities which may characterize neutron spectra

  9. Multilevel crossing rates for automated signal classification

    An investigation was made of multilevel crossing rates as a means of time series analysis of random signals. Pattern recognition techniques based on the Mahalanobis distance were implemented as a means of evaluating the discriminating power of level crossings. Measurement of multilevel crossing rates was found to be an easily implementable means for detection of changes in general frequency content. Level crossing analysis was also shown to be applicable for the study of conductivity measurements of two-phase flow of air and water, where knowledge of the relationship between amplitude and frequency was beneficial in characterizing the process

  10. [Fast neutron cross section measurements

    From its inception, the Nuclear Data Project at the University of Michigan has concentrated on two major objectives: (1) to carry out carefully controlled nuclear measurements of the highest possible reliability in support of the national nuclear data program, and (2) to provide an educational opportunity for students with interests in experimental nuclear science. The project has undergone a successful transition from a primary dependence on our photoneutron laboratory to one in which our current research is entirely based on a unique pulsed 14 MeV fast neutron facility. The new experimental facility is unique in its ability to provide nanosecond bursts of 14 MeV neutrons under conditions that are ''clean'' and as scatter-free as possible, and is the only one of its type currently in operation in the United States. It has been designed and put into operation primarily by graduate students, and has met or exceeded all of its important initial performance goals. We have reached the point of its routine operation, and most of the data are now in hand that will serve as the basis for the first two doctoral dissertations to be written by participating graduate students. Our initial results on double differential neutron cross sections will be presented at the May 1993 Fusion Reactor Technology Workshop. We are pleased to report that, after investing several years in equipment assembly and optimization, the project has now entered its ''data production'' phase

  11. Cross-Connections of Chemistry

    Mason, Diana S.

    2002-02-01

    We are in desperate need of qualified chemistry teachers. Are the teachers who have biology, physics, or some psychology degrees qualified to teach chemistry? Have they taken enough chemistry to be prepared to teach outside their degree field? If remediation is necessary, what courses should be required? Attracting pre-service science teachers to the study of pure chemistry is not an easy task when more attractive course offerings are available. Maybe we should concentrate on cross-training in-service teachers by providing appropriate graduate courses to encourage them and bring them into the family. Many teachers with degrees outside the traditional discipline of chemistry have adequate backgrounds in the applications of chemistry. Requiring hours of undergraduate education before they enter the hallowed halls of the chemistry building as graduate students only serves to discourage a large segment of in-service teachers who wish to broaden their perspective. The National Science Education Standards make a compelling argument for connecting and integrating science courses for practicing teachers (3). We are at the crossroads. At a time when we so desperately need qualified chemistry teachers, shouldn't we be more open in our graduate teaching programs, inviting those with degrees in other disciplines to start on a graduate degree without insisting on undergraduate or survey coursework first? Many potential chemical education graduate students have a background in chemistry--it is just known by another name.

  12. Proton and helium stopping cross sections in gaseous hydrocarbon compounds

    Proton and 4He ion stopping powers were measured for various hydrocarbon gases in the energy ranges 60-750 keV and 100-1050 keV, respectively. The statistical and systematical errors are about 1% each. The target compounds, which contain different types of carbon-carbon bonds, were n-alkanes Csub(n)Hsub(2n+2)(n=1-10), 1-alkenes Csub(n)Hsub(2n)(n=2-4), 1-alkynes Csub(n)Hsub(2n-2)(n=5-7), acetylene C2H2 and (1,3)-butadiene C4H6. Thus, this experiment provides a large data base for a Bragg-rule analysis with hydrocarbon compounds. (orig.)

  13. Thermodynamics second law and ω=-1 crossing(s) in interacting holographic dark energy model

    By the assumption that the thermodynamics second law is valid, we study the possibility of ω=-1 crossing in an interacting holographic dark energy model. We show that this crossing is possible provided we choose appropriate parameters for the system

  14. CuO hollow nanosphere-catalyzed cross-coupling of aryl iodides with thiols

    Woo, Hyunje; Mohan, Balaji; Heo, Eunjung; Park, Ji Chan; Song, Hyunjoon; Park, Kang Hyun

    2013-01-01

    New functionalized CuO hollow nanospheres on acetylene black (CuO/AB) and on charcoal (CuO/C) have been found to be effective catalysts for C-S bond formation under microwave irradiation. CuO catalysts showed high catalytic activity with a wide variety of substituents which include electron-rich and electron-poor aryl iodides with thiophenols by the addition of two equivalents of K2CO3 as base in the absence of ligands.

  15. Commutativity and ideals in category crossed products

    Öinert, Per Johan; Lundström, Patrik

    2010-01-01

    In order to simultaneously generalize matrix rings and group graded crossed products, we introduce category crossed products. For such algebras we describe the centre and the commutant of the coefficient ring. We also investigate the connection between on the one hand maximal commutativity of the...

  16. Cross-training policies and team performance

    Slomp, J.; Molleman, E.

    2002-01-01

    Labour flexibility is an important issue in the design and development of teams. By means of an analytical study this paper investigates the impact of cross-training on team performance. Four cross-training policies are distinguished and compared according to their effects on important performance m

  17. The Cross-Referenced Patent Cooperation Treaty

    Mulder, C.A.M.

    2015-01-01

    'The Cross-Referenced Patent Cooperation Treaty' is a book covering the 'Patent Cooperation Treaty (PCT)' and the 'Regulations under the PCT'. The large number of references in the articles and rules makes the PCT difficult to read. The idea behind this book is to add cross-references to the article

  18. The Cross-Referenced Patent Cooperation Treaty

    Mulder, C.A.M.

    2012-01-01

    'The Cross-Referenced Patent Cooperation Treaty' is a book covering the 'Patent Cooperation Treaty (PCT)' and the 'Regulations under the PCT'. The large number of references in the articles and rules makes the PCT difficult to read. The idea behind this book is to add cross-references to the article

  19. The cross-Referenced Patent Cooperation Treaty

    Mulder, C.A.M.

    2014-01-01

    'The Cross-Referenced Patent Cooperation Treaty' is a book covering the 'Patent Cooperation Treaty (PCT)' and the 'Regulations under the PCT'. The large number of references in the articles and rules makes the PCT difficult to read. The idea behind this book is to add cross-references to the article

  20. The Cross-Referenced Patent Cooperation Treaty

    Mulder, C.A.M.

    2013-01-01

    'The Cross-Referenced Patent Cooperation Treaty' is a book covering the 'Patent Cooperation Treaty (PCT)' and the 'Regulations under the PCT'. The large number of references in the articles and rules makes the PCT difficult to read. The idea behind this book is to add cross-references to the article

  1. The Cross-Referenced Patent Cooperation Treaty

    Mulder, C.A.M.

    2009-01-01

    'The Cross-Referenced Patent Cooperation Treaty' is a book covering the 'Patent Cooperation Treaty (PCT)' and the 'Regulations under the PCT'. The large number of references in the articles and rules makes the PCT difficult to read. The idea behind this book is to add cross-references to the article

  2. Water Treatment Technology - Cross-Connections.

    Ross-Harrington, Melinda; Kincaid, G. David

    One of twelve water treatment technology units, this student manual on cross connections provides instructional materials for two competencies. (The twelve units are designed for a continuing education training course for public water supply operators.) The competencies focus on cross connections terminology and control devices. For each…

  3. Study of Politeness in Cross Cultural Communication

    桂仁娜; 姜艳

    2012-01-01

      Politeness is a universal linguistic phenomenon but also relative by nature and subject to culture. The politeness in pragmatic study and its cultural specificity in cross cultural communication are explained. Some tactics in cross communication are also suggested.

  4. Cross-Cultural Psychotherapy and Art

    McNiff, Shaun

    2009-01-01

    This article presents an introduction to cross-cultural psychotherapy, with reference to historical theories of art, symbols and myth, and to the therapist working with the client--both individual and groups. Cross-cultural dimensions of art therapy are delineated with a support for further research and cooperation between cultures, with attention…

  5. Linear Unlearning for Cross-Validation

    Hansen, Lars Kai; Larsen, Jan

    1996-01-01

    The leave-one-out cross-validation scheme for generalization assessment of neural network models is computationally expensive due to replicated training sessions. In this paper we suggest linear unlearning of examples as an approach to approximative cross-validation. Further, we discuss the...... time series prediction benchmark demonstrate the potential of the linear unlearning technique...

  6. Compilation of cross-sections. Pt. 4

    This is the fourth volume in our series of data compilations on integrated cross-sections for weak, electromagnetic, and strong interaction processes. This volume covers data on reactions induced by photons, neutrinos, hyperons, and KL0. It contains all data published up to June 1986. Plots of the cross-sections versus incident laboratory momentum are also given. (orig.)

  7. Compilation of cross-sections. Pt. 1

    A compilation of integral cross-sections for hadronic reactions is presented. This is an updated version of CERN/HERA 79-1, 79-2, 79-3. It contains all data published up to the beginning of 1982, but some more recent data have also been included. Plots of the cross-sections versus incident laboratory momentum are also given. (orig.)

  8. Cross-cultural difference in OSH

    Starren, A.; Drupsteen, L.

    2014-01-01

    In this article we describe cross-cultural aspects in the context of safety management. When working abroad, cross-cultural differences ask for other competencies to enhance safe behaviour than at home due to cultural and language differences. In this wiki some guidance is given on aspects of cultur

  9. Border Crossing Monitoring along the Northern Corridor

    Fitzmaurice, Mike; Hartmann, Olivier

    2013-01-01

    Border-crossing times in East Africa have been identified as a major constraint for smooth trade flows, both for regional trade and for international transit. Delays at borders disrupt efficient trade logistics, impacting on the transport costs and prices, and ultimately on trade competitiveness. In order to improve the efficiency of border crossings in East Africa, the East Africa Communi...

  10. Curriculum Integration and Cross-Cultural Psychology.

    Goldstein, Susan B.

    While many undergraduate disciplines are revising curricula to address issues of diversity more effectively, it is commonly assumed that courses in cross-cultural psychology are less in need of revision due to their inherent multi-cultural focus. The field of cross-cultural psychology, however, is not immune to Eurocentric and androcentric biases.…

  11. Nucleon-XcJ Dissociation Cross Sections

    冯又层; 许晓明; 周代翠

    2002-01-01

    Nucleon-XcJ dissociation cross sections are calculated in a constituent interexchange model in which quark-quark potential is derived from the Buchmüller-Tye quark-anti-quark potential. These new cross sections for dominant reaction channels depend on the centre-of-mass energy of the nucleon and the charmonium.

  12. Test Anxiety: A Cross-Cultural Perspective

    Bodas, Jaee; Ollendick, Thomas H.

    2005-01-01

    The present paper examines test anxiety from a cross-cultural perspective with specific reference to the Indian and American cultures. The construct of test anxiety has been examined in many cultures all over the world. In this review, the importance of understanding and incorporating contextual factors in cross-cultural research is emphasized.…

  13. Fission cross section calculations for Pa isotopes

    Based on the recently measured cross-section values for the neutron-induced fission of 231Pa and our experience gained with other isotopes, new self consistent neutron cross section calculations for n+231Pa have been performed up to 30 MeV. The results are quite different to the existing evaluations, especially above the first chance fission threshold. (authors)

  14. Cross-cultural Knowledge Management

    Dorel Mihai PARASCHIV

    2009-01-01

    Full Text Available The success of international companies in providing high quality products and outstanding services is subject, on the one hand, to the increasing dynamic of the economic environment and on the other hand to the adoption of worldwide quality standards and procedures. As market place is becoming more and more global, products and services offered worldwide by international companies must face the multi-cultural environment challenges. These challenges manifest themselves not only at customer relationship level but also deep inside companies, at employee level. Important support in facing all these challenges has been provided at cognitive level by management system models and at technological level by information cutting edge technologies Business Intelligence & Knowledge Management Business Intelligence is already delivering its promised outcomes at internal business environment and, with the explosive deployment of public data bases, expand its analytical power at national, regional and international level. Quantitative measures of economic environment, wherever available, may be captured and integrated in companies’ routine analysis. As for qualitative data, some effort is still to be done in order to integrate measures of social, political, legal, natural and technological environment in companies’ strategic analysis. An increased difficulty is found in treating cultural differences, common knowledge making the most hidden part of any foreign environment. Managing cultural knowledge is crucial to success in cultivating and maintaining long-term business relationships in multicultural environments. Knowledge Management provides the long needed technological support for cross-cultural management in the tedious task of improving knowledge sharing in multi-national companies and using knowledge effectively in international joint ventures. The paper is approaching the conceptual frameworks of knowledge management and proposes an unified model

  15. Crossing point temperature of coal

    Qi Xuyao; Deming Wang; James A. Milke; Xiaoxing Zhong

    2011-01-01

    A further understanding of the self-heating of coal was obtained by investigating the crossing point temperature (CPT) of different ranks of coal. The tests were carried out using a self-designed experimental system for coal self-heating. 50 g (±0.01 g) of coal particles ranging from 0.18 mm to 0.38 mm in size were put into a pure copper reaction vessel attached to the center of a temperature programmed enclosure. The temperature program increased the temperature at a rate of 0.8 ℃/min. Dry air was permitted to flow into the coal reaction vessel at different rates. The surrounding temperature and the coal temperature were monitored by a temperature logger. The results indicate that CPT is affected by coal rank, moisture, sulfur,and the experimental conditions. Higher ranked coals show higher CPT values. A high moisture content causes a delay phenomenon during the self-heating of the coal. Drying at 40 ℃ decreases the effects of moisture. The reactivity of sulfur components in the coal is low under dry and low-temperature conditions.These components form a film that covers the coal surface and slightly inhibits the self-heating of the coal.The flow rate of dry air, and the heating rate of the surroundings, also affect the self-heating of the coal. The most appropriate experimental conditions for coal samples of a given weight and particle size were determined through contrastive analysis. Based on this analysis we propose that CPTs be determined under the same, or nearly the same conditions, for evaluation of the spontaneous combustion of coal.

  16. The foundations of cross-modal plasticity.

    Rabinowitch, Ithai; Bai, Jihong

    2016-01-01

    Cross-modal plasticity is a striking adaptive feature of the brain, whereby the loss of one sensory modality induces cortical reorganization that leads to enhanced sensory performance in remaining modalities. Much is known about the macroscopic modifications in the brain that underly cross-modal plasticity and the associated changes in sensory performance. In contrast there is relatively scant information about the molecular and cellular underpinnings of this mechanism. We hypothesized that cross-modal plasticity is a fundamental feature of the nervous system. As such, it should be found in organisms with brains that are substantially less complex than our own. Indeed, we discovered a cross-modal plasticity mechanism in the roundworm Caenorhabditis elegans, whose nervous system is composed of only 302 neurons. Taking advantage of the simplicity of the C. elegans nervous system, we were able to comprehensively study cross-modal plasticity from molecule through circuit to behavior. PMID:27195068

  17. Comparative analysis among several cross section sets

    Critical parameters were calculated using the one dimensional multigroup transport theory for several cross section sets. Calculations have been performed for water mixtures of uranium metal, plutonium metal and uranium-thorium oxide, and for metallics systems, to determine the critical dimensions of geometries (sphere and cylinder). For this aim, the following cross section sets were employed: 1) multigroup cross section sets obtained from the GAMTEC-II code; 2) the HANSEN-ROACH cross section sets; 3) cross section sets from the ENDF/B-IV, processed by the NJOY code. Finally, we have also calculated the corresponding critical radius using the one dimensional multigroup transport DTF-IV code. The numerical results agree within a few percent with the critical values obtained in the literature (where the greatest discrepancy occured in the critical dimensions of water mixtures calculated with the values generated by the NJOY code), a very good results in comparison with similar works. (Author)

  18. Robust optimisation of railway crossing geometry

    Wan, Chang; Markine, Valeri; Dollevoet, Rolf

    2016-05-01

    This paper presents a methodology for improving the crossing (frog) geometry through the robust optimisation approach, wherein the variability of the design parameters within a prescribed tolerance is included in the optimisation problem. Here, the crossing geometry is defined by parameterising the B-spline represented cross-sectional shape and the longitudinal height profile of the nose rail. The dynamic performance of the crossing is evaluated considering the variation of wheel profiles and track alignment. A multipoint approximation method (MAM) is applied in solving the optimisation problem of minimising the contact pressure during the wheel-rail contact and constraining the location of wheel transition at the crossing. To clarify the difference between the robust optimisation and the normal deterministic optimisation approaches, the optimisation problems are solved in both approaches. The results show that the deterministic optimum fails under slight change of the design variables; the robust optimum, however, has improved and robust performance.

  19. Photoproton cross section for 17O

    The measurement of the 17O(γ,p)16N reaction from threshold to an excitation energy of 44 MeV is presented. These results have been summed with the previously measured total photoneutron cross section to provide an approximation to the total photoabsorption cross section of 17O. The magnitude of the 17O photoabsorption cross section at the peak of the Giant Dipole Resonance is considerably less than the equivalent value for the photoabsorption cross sections of 16O and 18O. In addition, the integrated total photoabsorption cross section for 17O (up to 40 MeV) exhausts only about 58% of the sum rule; the values for the cases of 16O and 18O are significantly larger than this. The present data along with results from other reaction channels of this nucleus, were used to make spin, parity, and isospin assignments for several states in 17O. 48 refs., 4 tabs., 7 figs

  20. Recommended evaluation procedure for photonuclear cross section

    Lee, Young-Ouk; Chang, Jonghwa; Fukahori, Tokio [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1998-03-01

    In order to generate photonuclear cross section library for the necessary applications, data evaluation is combined with theoretical evaluation, since photonuclear cross sections measured cannot provide all necessary data. This report recommends a procedure consisting of four steps: (1) analysis of experimental data, (2) data evaluation, (3) theoretical evaluation and, if necessary, (4) modification of results. In the stage of analysis, data obtained by different measurements are reprocessed through the analysis of their discrepancies to a representative data set. In the data evaluation, photonuclear absorption cross sections are evaluated via giant dipole resonance and quasi-deutron mechanism. With photoabsorption cross sections from the data evaluation, theoretical evaluation is applied to determine various decay channel cross sections and emission spectra using equilibrium and preequilibrium mechanism. After this, the calculated results are compared with measured data, and in some cases the results are modified to better describe measurements. (author)

  1. Probing the dynamics of polyatomic multichannel elementary reactions by crossed molecular beam experiments with soft electron-ionization mass spectrometric detection.

    Casavecchia, Piergiorgio; Leonori, Francesca; Balucani, Nadia; Petrucci, Raffaele; Capozza, Giovanni; Segoloni, Enrico

    2009-01-01

    In this Perspective we highlight developments in the field of chemical reaction dynamics. Focus is on the advances recently made in the investigation of the dynamics of elementary multichannel radical-molecule and radical-radical reactions, as they have become possible using an improved crossed molecular beam scattering apparatus with universal electron-ionization mass spectrometric detection and time-of-flight analysis. These improvements consist in the implementation of (a) soft ionization detection by tunable low-energy electrons which has permitted us to reduce interfering signals originating from dissociative ionization processes, usually representing a major complication, (b) different beam crossing-angle set-ups which have permitted us to extend the range of collision energies over which a reaction can be studied, from very low (a few kJ mol(-1), as of interest in astrochemistry or planetary atmospheric chemistry) to quite high energies (several tens of kJ mol(-1), as of interest in high temperature combustion systems), and (c) continuous supersonic sources for producing a wide variety of atomic and molecular radical reactant beams. Exploiting these new features it has become possible to tackle the dynamics of a variety of polyatomic multichannel reactions, such as those occurring in many environments ranging from combustion and plasmas to terrestrial/planetary atmospheres and interstellar clouds. By measuring product angular and velocity distributions, after having suppressed or mitigated, when needed, the problem of dissociative ionization of interfering species (reactants, products, background gases) by soft ionization detection, essentially all primary reaction products can be identified, the dynamics of each reaction channel characterized, and the branching ratios determined as a function of collision energy. In general this information, besides being of fundamental relevance, is required for a predictive description of the chemistry of these

  2. Cross polarization caused by perturbed circular cross sections of waveguides and horn antennas

    Lier, Erik

    1987-03-01

    The cross polarization caused by a perturbed cross section of the conical hybrid-mode horn is analyzed. The perturbed cross section is assumed to be slightly elliptical. The theory of Lier and Bergh (1986) for cross polarization in a smooth-walled waveguide supporting the TE11-mode is referred and applied to the HE11 mode as well. Simple analytical formulas which are sufficiently accurate for small ellipticites of the cross-section ellipse are presented. These show that the tolerances on the waveguide diameter are extremely strong, typically on the order of 0.02-0.04 mm in the horn throat for typical horn geometries at 12 GHz.

  3. Piano Crossing – Walking on a Keyboard

    Bojan Kverh

    2010-11-01

    Full Text Available Piano Crossing is an interactive art installation which turns a pedestrian crossing marked with white stripes into a piano keyboard so that pedestrians can generate music by walking over it. Matching tones are created when a pedestrian steps on a particular stripe or key. A digital camera is directed at the crossing from above. A special computer vision application was developed, which maps the stripes of the pedestrian crossing to piano keys and detects by means of an image over which key the center of gravity of each pedestrian is placed at any given moment. Black stripes represent the black piano keys. The application consists of two parts: (1 initialization, where the model of the abstract piano keyboard is mapped to the image of the pedestrian crossing, and (2 the detection of pedestrians at the crossing, so that musical tones can be generated according to their locations. The art installation Piano crossing was presented to the public for the first time during the 51st Jazz Festival in Ljubljana in July 2010.

  4. Photoneutron cross sections for the silicon isotopes

    The photoneutron cross sections for 28Si, 29Si, and 30Si have been measured up to 33 MeV with monoenergetic photons from the annihilation in flight of fast positrons, using neutron multiplicity counting. Average neutron energies were obtained simultaneously with the cross-section data by the ring-ratio technique. The giant dipole resonance for 28Si and 30Si exhibit appreciable fragmentation; that for 29Si does not. The (γ,2n) cross section for 30Si is large; that for 29Si is consistent with zero. The (γ,1n) cross section for 30Si decreases sharply with energy to values near zero as the (γ,2n) cross section grows, then increases to appreciable values as the (γ,2n) cross section diminishes; this extreme behavior, although never seen before, is attributable to the competition between the (γ,n), (γ,2n), and (γ,pn) decay channels. Some properties of the isospin components of the giant resonance are inferred. Other features of the data, including the integrated cross sections, are found to be similar in many respects to corresponding results for the oxygen and magnesium isotopes. The 28Si nucleus is found to be a better core for 29Si and 30Si than might have been expected from previous descriptions of its open-shell character

  5. Histone cross-linking by transglutaminase.

    Kim, Jae-Hong; Nam, Kang Hoon; Kwon, Oh-Seok; Kim, In Gyu; Bustin, Michael; Choy, Hyon E; Park, Sang Chul

    2002-05-24

    Transglutaminases irreversibly catalyze covalent cross-linking of proteins by forming isopeptide bonds between peptide-bound glutamine and lysine residues. Among several transglutaminases, tissue-type transglutaminase (tTGase) is most ubiquitously found in every type of cells and tissues in animals, but its natural substrate has yet to be identified. In an attempt to identify the natural substrate for tTGase, we examined in vitro if core histones were subject to cross-linking by tTGase. We found core histone subunits, H2A and H2B, were specifically cross-linked by tTGase. The cross-linking was between either one or both glutamines at C-terminal end of H2A (-VTIAQ104 GGVLPNTQ112 SVLLPKKTESSKSK-C' end) and the first and/or third lysine from C-terminal end of H2B (-AVESEGK116 AVTKYTSSK125-C' end). The cross-linking occurred only when these subunits were released from nucleosome but not when these were organized in nucleosome. Most interestingly, in chicken erythrocyte the cross-linked H2A-H2B was present in a significant amount. From these results, it can be proposed that tTGase-mediated cross-linking is an another form of core histone modification and it may play a role of chromatin condensation during erythrocyte differentiation. PMID:12054678

  6. Cross-spectrally pure light, cross-spectrally pure fields and statistical similarity in electromagnetic fields

    Chen, Jingjing; Lu, RongSheng; Chen, Feinan; Li, Jia

    2014-08-01

    This paper describes the concept of cross-spectrally pure light, implications of statistical similarity of an optical field on its cross-spectral purity and cross-spectrally pure fields. First, the concept of cross-spectral purity of light is analysed in the space-frequency domain by taking into account the vectorial nature of the radiation, and the conditions and reduction formula are obtained. Then, by utilizing statistical similarity, the relationship between cross-spectral purity and spatial coherence is explored in the electromagnetic field. Last, the conditions for cross-spectrally pure fields are discussed, the polychromatic plane wave and the far field produced by a planar, secondary, stochastic electromagnetic source are studied as examples, and moreover, the relationship between cross-spectral purity and spatial coherence, which we have drawn, is verified during the study.

  7. Transition probability of the Si III 189.2-nm intersystem line

    Kwong, H. S.; Johnson, B. C.; Smith, P. L.; Parkinson, W. H.

    1983-01-01

    Measurement of the lifetime of the metastable 3s3p(3)P(0)1 level of Si(2+) (Si III), which decays by photon emission at 189.2 nm to the 3s2(1)S0 state, is reported. The data were taken from spontaneous emission from metastable Si III stored in an RF ion trap. The Si III ions were produced through electron bombardment of SiH4 and SiF4 at pressures of 1/100,000,000-1/10,000,000 Torr. A photomultiplier was employed to count the photon emissions from the transitions. A total of 11 decay curves were generated for analysis, with Poisson statistics used to set the uncertainties at within 8 pct. Significant systematic effects were controlled, and the lifetime was found to be within 3.6 microsec of 59.9 microsec. The method used is concluded valid for determining the lifetimes of metastable levels of low-Z ions with low charge, and thereby the transition probabilities.

  8. Minimization of Power Deficiency in Electric Power System Taking into Account Intersystem Connections

    O. Alexandrov

    2014-09-01

    Full Text Available The paper considers problems of possible decrease in power consumption for deficient electric power system. A mathematical model for a minimum search of criterion function has been  formulated in the paper. Power deficiency is described as a complicated function for an integrated assessment on electricity delivery and consumption. The criterion function is multicriterial and includes main components for determination of the total power deficiency. The system of restrictions takes into account extreme values of adjustable parameters. 

  9. Corporate Social Responsibility in the Dynamic Information Age of Inter-Systems Connectivity

    Arvind Ashta

    2009-01-01

    The Information Age, with its new technologies, is accompanied by an accelerating shift in work relations, of which this article focuses on connectivity, interdependence and dynamism. Along with this change in relations, new ethical cultures and responsibilities are evolving at different levels: individual, corporate, governmental, NGO, and global. This article zooms in on theoretical developments related to Corporate Social Responsibility to see how they have evolved to adapt to the new mode...

  10. An application of the explicit method for analysing intersystem dependencies in the evaluation of event trees

    A computacional application of the explicit method for analyzing event trees in the context of probabilistic risk assessments is discussed. A detailed analysis of the explicit method is presented, including the train level analysis (TLA) of safety systems and the impact vector method. It is shown that the penalty for not adopting TLA is that in some cases non-conservative results may be reached. The impact vector method can significantly reduce the number of sequences to be considered, and its use has inspired the definition of a dependency matrix, which enables the proper running of a computer code especially developed for analysing event trees. The code has been extensively used in the Angra 1 PRA currently underway. In its present version it gives as output the dominant sequences for each given initiator, properly classiying them in core-degradation classes as specified by the user. (Author)

  11. Remote postradiation immunodeficiency a disorder of endocrine regulation and thymic function. Role of intersystems interactions

    A total of 265 reports on radiation effects on the immune, nervous, and endocrine systems are reviewed. The role of the thymus, hypothalamus, and pituitary in remote manifestations of immunodeficiency in patients with cancer of the head and neck, treated by radiotherapy, is discussed. The pathogenesis of stubborn postradiation disturbances in immunoendocrine homeostasis after local exposure of the thymus and hypothalamus-pituitary at doses of 1-10 Gy, characterized as a syndrome, is analyzed

  12. Degenerated codimension 1 crossings and resolvent estimates

    Duyckaerts, Thomas; Jecko, Thierry

    2008-01-01

    In this article, we analyze the propagation of Wigner measures of a family of solutions to a system of semi-classical pseudodifferential equations presenting eigenvalues crossings on hypersurfaces. We prove the propagation along classical trajectories under a geometric condition which is satisfied for example as soon as the Hamiltonian vector fields are transverse or tangent at finite order to the crossing set. We derive resolvent estimates for semi-classical Schr\\"odinger operator with matrix-valued potential under a geometric condition of the same type on the crossing set and we analyze examples of degenerate situations where one can prove transfers between the modes.

  13. The 42Ca photoneutron cross section

    The measurement of the 42Ca(γ,nsub(t)) is reported here over the energy range 10.5 - 28 MeV. Bremsstrahlung radiation from the 35 MeV Betatron at this University was used to measure a yield curve of photoneutrons, from which the (γ,nsub(t)) cross section was derived. Since proton and neutron emission are the major decay modes of the giant dipole resonance, summing these cross sections approximates the photo-absorption cross section. With this information the theoretical predictions can be checked

  14. Chemical cross-linking of Chlamydia trachomatis

    Birkelund, Svend; Lundemose, AG; Christiansen, Gunna

    1988-01-01

    Purified elementary bodies (EBs) of Chlamydia trachomatis serovar L2 were analyzed by chemical cross-linking with disuccinimidyl selenodipropionate. The effect of the cross-linking was analyzed by immunoblotting sodium dodecyl sulfate-polyacrylamide gel electrophoresis-separated components which...... forms of MOMP without LPS, was observed. A totally different membrane structure must be present in reticulate bodies, since there, MOMP was so heavily cross-linked that it did not enter the polyacrylamide gel and thus became impossible to analyze. Furthermore, the monoclonal antibody, which reacted with...

  15. Compilation of cross-sections. Pt. 3

    A compilation of integrated cross-sections for hadronic reactions is presented. This is an updated version of CERN/HERA 79-1, 79-2, 79-3. It contains all data published up to the beginning of 1982, but some more recent data, particularly those from the CERN Collider, have also been included. Plots of the cross-sections versus incident laboratory momentum are also given. This volume III contains cross-sections for p and anti p induced reactions. (orig.)

  16. Detrended cross-correlation analysis of electroencephalogram

    In the paper we use detrended cross-correlation analysis (DCCA) to study the electroencephalograms of healthy young subjects and healthy old subjects. It is found that the cross-correlation between different leads of a healthy young subject is larger than that of a healthy old subject. It was shown that the cross-correlation relationship decreases with the aging process and the phenomenon can help to diagnose whether the subject's brain function is healthy or not. (interdisciplinary physics and related areas of science and technology)

  17. Screening corrections to the Rutherford cross section

    Differential cross sections for elastic p-Au scattering were measured in the energy range between 0.2 and 0.8 MeV for scattering angles from 300 to 1500 in order to determine corrections to the Rutherford cross section due to the screening of the nuclear charge by the atomic electrons. Furthermore, differential cross sections have been calculated in the weakly screening region using various screening functions. A simple analytical expression has been derived for the representation of both experimental and theoretical results. (orig.)

  18. Transition crossing simulation at the Fermilab Booster

    Yang, X.; Drozhdin, A.I.; Pellico, W.; /Fermilab

    2007-06-01

    The demand in high intensity and low emittance of the beam extracted from the Booster requires a better control over the momentum spread growth and bunch length shortening at transition crossing, in order to prevent beam loss and coupled bunch instability. Since the transition crossing involves both longitudinal and transverse dynamics, the recently modified 3-D STRUCT code provides an opportunity to numerically investigate the different transition crossing schemes in the machine environment, and apply the results of simulation to minimize the beam loss and emittance growth operationally.

  19. Parents' Attitudes and Expectations about Children's Cross-Gender Behavior.

    Sandnabba, N. Kenneth; Ahlberg, Christian

    1999-01-01

    Assessed parents' attitudes toward cross-gender behavior of boys and girls. Responses of 224 white Finnish parents of 5-year olds reveal that cross-gender boys are regarded more negatively than cross-gender girls. Men perceived more societal acceptance of cross-gender boys than did women. It is thought that cross-gender boys were more likely to…

  20. METROBORDER. Cross-border Polycentric Metropolitan Regions

    Walther, Olivier

    Metropolitan regions are generally seen as drivers for territorial development in the national context, as well as drivers for economic, social and cultural development on a European and global scale. Many border regions dispose of specific potentials but also specific barriers for a cross-border...... polycentric metropolitan region. However, cross-border areas appear to be systematically underestimated in their development opportunities so that awareness about specific advantages needs to be improved. This is why this project addresses cross-border metropolitan regions in Europe in relation to the policy...... aim of polycentric development. It aims at identifying criteria, potentials and governance practices based on available ESPON evidence for polycentric cross-border metropolitan regions in Europe and proposing options for development strategies towards a multilevel approach for two case study regions...