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Sample records for absolute reaction cross

  1. Absolute state-selected and state-to-state total cross sections for the Ar sup + ( sup 2 P sub 3/2,1/2 )+CO reactions

    SciTech Connect

    Flesch, G.D.; Nourbakhsh, S.; Ng, C.Y. . Ames Laboratory Iowa State University, Ames, Iowa . Department of Chemistry)

    1991-09-01

    Absolute spin--orbit state-selected total cross sections for the reactions, Ar{sup +}({sup 2}{ital P}{sub 3/2,1/2})+CO{r arrow}CO{sup +}+Ar (reaction (1)), C{sup +}+O+Ar (reaction (2)), O{sup +}+C+Ar (reaction (3)), and ArC{sup +}+O (reaction (4)), have been measured in the center-of-mass collision energy ({ital E}{sub c.m.}) range of 0.04--123.5 eV. Absolute spin--orbit state transition total cross sections for the Ar{sup +}({sup 2}{ital P}{sub 3/2,1/2})+CO reactions at {ital E}{sub c.m.} have also been obtained. The appearance energies (AE) for C{sup +}({ital E}{sub c.m.}=6.6{plus minus}0.4 eV) and O{sup +}({ital E}{sub c.m.}=8.6{plus minus}0.4 eV) are in agreement with the thermochemical thresholds for reactions (2) and (3), respectively. The observed AE for reaction (4) yields a lower bound of 0.5 eV for the ArC{sup +} bond dissociation energy. The kinetic energy dependence of the absolute cross sections and the retarding potential analysis of the product ions support that ArC{sup +}, C{sup +}, and O{sup +} are formed via a charge transfer predissociation mechanism, similar to that proposed to be responsible for the formation of O{sup +} (N{sup +}) and ArO{sup +} (ArN{sup +}) in the collisions of Ar{sup +}({sup 2}{ital P}{sub 3/2,1/2})+O{sub 2}(N{sub 2}).

  2. Absolute partial photoionization cross sections of ozone.

    SciTech Connect

    Berkowitz, J.; Chemistry

    2008-04-01

    Despite the current concerns about ozone, absolute partial photoionization cross sections for this molecule in the vacuum ultraviolet (valence) region have been unavailable. By eclectic re-evaluation of old/new data and plausible assumptions, such cross sections have been assembled to fill this void.

  3. Absolute photoionization cross sections of atomic oxygen

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.; Pareek, P. N.

    1985-01-01

    The absolute values of photoionization cross sections of atomic oxygen were measured from the ionization threshold to 120 A. An auto-ionizing resonance belonging to the 2S2P4(4P)3P(3Do, 3So) transition was observed at 479.43 A and another line at 389.97 A. The experimental data is in excellent agreement with rigorous close-coupling calculations that include electron correlations in both the initial and final states.

  4. Absolute photoionization cross sections of atomic oxygen

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.; Pareek, P. N.

    1982-01-01

    The absolute values of photoionization cross sections of atomic oxygen were measured from the ionization threshold to 120 A. An auto-ionizing resonance belonging to the 2S2P4(4P)3P(3Do, 3So) transition was observed at 479.43 A and another line at 389.97 A. The experimental data is in excellent agreement with rigorous close-coupling calculations that include electron correlations in both the initial and final states.

  5. Absolute photoneutron cross sections of Sm isotopes

    SciTech Connect

    Gheorghe, I.; Glodariu, T.; Utsunomiya, H.; Filipescu, D.; Nyhus, H.-T.; Renstrom, T.; Tesileanu, O.; Shima, T.; Takahisa, K.; Miyamoto, S.

    2015-02-24

    Photoneutron cross sections for seven samarium isotopes, {sup 144}Sm, {sup 147}Sm, {sup 148}Sm, {sup 149}Sm, {sup 150}Sm, {sup 152}Sm and {sup 154}Sm, have been investigated near neutron emission threshold using quasimonochromatic laser-Compton scattering γ-rays produced at the synchrotron radiation facility NewSUBARU. The results are important for nuclear astrophysics calculations and also for probing γ-ray strength functions in the vicinity of neutron threshold. Here we describe the neutron detection system and we discuss the related data analysis and the necessary method improvements for adapting the current experimental method to the working parameters of the future Gamma Beam System of Extreme Light Infrastructure - Nuclear Physics facility.

  6. Absolute photoionization cross-section of the propargyl radical

    SciTech Connect

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

    2012-04-07

    Using synchrotron-generated vacuum-ultraviolet radiation and multiplexed time-resolved photoionization mass spectrometry we have measured the absolute photoionization cross-section for the propargyl (C{sub 3}H{sub 3}) radical, {sigma}{sub propargyl}{sup ion}(E), relative to the known absolute cross-section of the methyl (CH{sub 3}) radical. We generated a stoichiometric 1:1 ratio of C{sub 3}H{sub 3} : CH{sub 3} from 193 nm photolysis of two different C{sub 4}H{sub 6} isomers (1-butyne and 1,3-butadiene). Photolysis of 1-butyne yielded values of {sigma}{sub propargyl}{sup ion}(10.213 eV)=(26.1{+-}4.2) Mb and {sigma}{sub propargyl}{sup ion}(10.413 eV)=(23.4{+-}3.2) Mb, whereas photolysis of 1,3-butadiene yielded values of {sigma}{sub propargyl}{sup ion}(10.213 eV)=(23.6{+-}3.6) Mb and {sigma}{sub propargyl}{sup ion}(10.413 eV)=(25.1{+-}3.5) Mb. These measurements place our relative photoionization cross-section spectrum for propargyl on an absolute scale between 8.6 and 10.5 eV. The cross-section derived from our results is approximately a factor of three larger than previous determinations.

  7. Absolute photoionization cross-section of the methyl radical.

    SciTech Connect

    Taatjes, C. A.; Osborn, D. L.; Selby, T.; Meloni, G.; Fan, H.; Pratt, S. T.; Chemical Sciences and Engineering Division; SNL

    2008-01-01

    The absolute photoionization cross-section of the methyl radical has been measured using two completely independent methods. The CH{sub 3} photoionization cross-section was determined relative to that of acetone and methyl vinyl ketone at photon energies of 10.2 and 11.0 eV by using a pulsed laser-photolysis/time-resolved synchrotron photoionization mass spectrometry method. The time-resolved depletion of the acetone or methyl vinyl ketone precursor and the production of methyl radicals following 193 nm photolysis are monitored simultaneously by using time-resolved synchrotron photoionization mass spectrometry. Comparison of the initial methyl signal with the decrease in precursor signal, in combination with previously measured absolute photoionization cross-sections of the precursors, yields the absolute photoionization cross-section of the methyl radical; {sigma}{sub CH}(10.2 eV) = (5.7 {+-} 0.9) x 10{sup -18} cm{sup 2} and {sigma}{sub CH{sub 3}}(11.0 eV) = (6.0 {+-} 2.0) x 10{sup -18} cm{sup 2}. The photoionization cross-section for vinyl radical determined by photolysis of methyl vinyl ketone is in good agreement with previous measurements. The methyl radical photoionization cross-section was also independently measured relative to that of the iodine atom by comparison of ionization signals from CH{sub 3} and I fragments following 266 nm photolysis of methyl iodide in a molecular-beam ion-imaging apparatus. These measurements gave a cross-section of (5.4 {+-} 2.0) x 10{sup -18} cm{sup 2} at 10.460 eV, (5.5 {+-} 2.0) x 10{sup -18} cm{sup 2} at 10.466 eV, and (4.9 {+-} 2.0) x 10{sup -18} cm{sup 2} at 10.471 eV. The measurements allow relative photoionization efficiency spectra of methyl radical to be placed on an absolute scale and will facilitate quantitative measurements of methyl concentrations by photoionization mass spectrometry.

  8. Absolute doubly differential bremsstrahlung cross sections from rare gas atoms

    NASA Astrophysics Data System (ADS)

    Portillo, Salvador

    The absolute doubly differential bremsstrahlung cross section has been measured for 28 and 50 keV electrons incident on the rare gases Xe, Kr, Ar and Ne. The cross sections are differential with respect to energy and photon emission. A SiLi solid state detector measured data at 90° with respect to the beam line. A thorough analysis of the experimental systematic error yielded a high degree of confidence in the experimental data. The absolute bremsstrahlung doubly differential cross sections provided for a rigorous test of the normal bremsstrahlung theory, tabulated by Kissel, Quarles and Pratt1 (KQP) and of the SA theory2 that includes the contribution from polarization bremsstrahlung. To test the theories a comparison of the overall magnitude of the cross section as well as comparison of the photon energy dependence was carried out. The KQP theoretical values underestimated the magnitude of the cross section for all targets and for both energies. The SA values were in excellent agreement with the 28 keV data. For the 50keV data the fit was also very good. However, there were energy regions where there was a small discrepancy between the theory and the data. This suggests that the Polarization Bremsstrahlung (PB) mechanism does contribute to the overall spectrum and is detectable in this parameter space. 1Kissel, L., Quarles, C. A., Pratt, R. H., Atom. Data Nucl. Data Tables 28, 381 (1983). 2Avdonina N. B., Pratt, R. H., J. Phys. B: At. Mol. Opt. Phys. 32 4261 (1999).

  9. Absolute photoionization cross sections of the ions Ca+ Ni+

    NASA Astrophysics Data System (ADS)

    Hansen, J. E.; Kjeldsen, H.; Folkmann, F.; Martins, M.; West, J. B.

    2007-01-01

    Absolute measurements of the photoionization cross sections of the singly charged ions in the sequence Ca to Ni are presented, focussing on the 3p → 3d resonance region. Major differences are found in both spectral structure and cross section as the 3d shell is filled progressively. The behaviour of the total oscillator strength is studied as well as its relation to the collapse of the 3d orbital. The 3p53d 1P term is found to have an influence on the spectra even when further 3d electrons are added and this dependence combined with the effect of Hund's rule leads to a considerable simplification in the structure of the absorption spectra before the half-filled 3d shell, while from the half-filled 3d shell Hund's rule is the main simplifying effect.

  10. Measurement of the absolute and differential cross sections for 7Li(γ, n0)6Li

    SciTech Connect

    W.A. Wurtz, R.E. Pywell, B.E. Norum, S. Kucuker, B.D. Sawatzky, H.R. Weller, M.W. Ahmed, S. Stave

    2011-10-01

    We have measured the cross section of the photoneutron reaction channel {sup 7}Li+{gamma}{yields}{sup 6}Li(g.s.)+n where the progeny nucleus is the ground state of {sup 6}Li. We obtained the absolute cross section at photon energies 10, 11, 12, 13, 15, 20, 25, 30, and 35 MeV and also the dependence of the cross section on polar angle for all but the highest photon energy. For the energies 10 to 15 MeV we were able to use linearly polarized photons to obtain the dependence of the cross section on the photon polarization.

  11. Estimation of absolute protein quantities of unlabeled samples by selected reaction monitoring mass spectrometry.

    PubMed

    Ludwig, Christina; Claassen, Manfred; Schmidt, Alexander; Aebersold, Ruedi

    2012-03-01

    For many research questions in modern molecular and systems biology, information about absolute protein quantities is imperative. This information includes, for example, kinetic modeling of processes, protein turnover determinations, stoichiometric investigations of protein complexes, or quantitative comparisons of different proteins within one sample or across samples. To date, the vast majority of proteomic studies are limited to providing relative quantitative comparisons of protein levels between limited numbers of samples. Here we describe and demonstrate the utility of a targeting MS technique for the estimation of absolute protein abundance in unlabeled and nonfractionated cell lysates. The method is based on selected reaction monitoring (SRM) mass spectrometry and the "best flyer" hypothesis, which assumes that the specific MS signal intensity of the most intense tryptic peptides per protein is approximately constant throughout a whole proteome. SRM-targeted best flyer peptides were selected for each protein from the peptide precursor ion signal intensities from directed MS data. The most intense transitions per peptide were selected from full MS/MS scans of crude synthetic analogs. We used Monte Carlo cross-validation to systematically investigate the accuracy of the technique as a function of the number of measured best flyer peptides and the number of SRM transitions per peptide. We found that a linear model based on the two most intense transitions of the three best flying peptides per proteins (TopPep3/TopTra2) generated optimal results with a cross-correlated mean fold error of 1.8 and a squared Pearson coefficient R(2) of 0.88. Applying the optimized model to lysates of the microbe Leptospira interrogans, we detected significant protein abundance changes of 39 target proteins upon antibiotic treatment, which correlate well with literature values. The described method is generally applicable and exploits the inherent performance advantages of SRM

  12. Absolute np and pp Cross Section Determinations Aimed At Improving The Standard For Cross Section Measurements

    SciTech Connect

    Laptev, A. B.; Haight, R. C.; Tovesson, F.; Arndt, R. A.; Briscoe, W. J.; Paris, M. W.; Strakovsky, I. I.; Workman, R. L.

    2011-06-01

    Purpose of present research is a keeping improvement of the standard for cross section measurements of neutron-induced reactions. The cross sections for np and pp scattering below 1 GeV are determined based on partial-wave analyses (PWAs) of nucleon-nucleon scattering data. These cross sections are compared with the most recent ENDF/B-VII.0 and JENDL-4.0 data files, and the Nijmegen PWA. Also a comparison of evaluated data with recent experimental data was made to check a quality of evaluation. Excellent agreement was found between the new experimental data and our PWA predictions.

  13. Absolute np and pp cross section determinations aimed at improving the standard for cross section measurements

    SciTech Connect

    Laptev, Alexander B; Haight, Robert C; Tovesson, Fredrik; Arndt, Richard A; Briscoe, William J; Paris, Mark W; Strakovsky, Igor I; Workman, Ron L

    2010-01-01

    Purpose of present research is a keeping improvement of the standard for cross section measurements of neutron-induced reactions. The cross sections for np and pp scattering below 1000 MeV are determined based on partial-wave analyses (PW As) of nucleon-nucleon scattering data. These cross sections are compared with the most recent ENDF/B-V11.0 and JENDL-4.0 data files, and the Nijmegen PWA. Also a comparison of evaluated data with recent experimental data was made to check a quality of evaluation. Excellent agreement was found between the new experimental data and our PWA predictions.

  14. Beam Elements with Trapezoidal Cross Section Deformation Modes Based on the Absolute Nodal Coordinate Formulation

    NASA Astrophysics Data System (ADS)

    Matikainen, Marko K.; Dmitrochenko, Oleg; Mikkola, Aki

    2010-09-01

    In this study, higher order beam elements are developed based on the absolute nodal coordinate formulation. The absolute nodal coordinate formulation is a finite element procedure that was recently proposed for flexible multibody applications. Many different elements based on the absolute nodal coordinate formulation are introduced, but still the beam elements are not able to describe the trapezoidal cross section mode. This leads to the locking phenomena, and therefore, the beam elements based on the absolute nodal coordinate formulation with three dimensional elasticity converge to an inexact solution. In order to avoid the locking phenomena, the trapezoidal cross section deformation mode is included in the beam elements based on the absolute nodal coordinate with additional degrees of freedom. The proper description for the trapezoidal cross section deformation is important for the continuum beam elements based on three-dimensional elasticity where the material model is often based on general continuum mechanics.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  17. Absolute UV absorption cross sections of dimethyl substituted Criegee intermediate (CH3)2COO

    NASA Astrophysics Data System (ADS)

    Chang, Yuan-Pin; Chang, Chun-Hung; Takahashi, Kaito; Lin, Jim-Min, Jr.

    2016-06-01

    The absolute absorption cross sections of (CH3)2COO under a jet-cooled condition were measured via laser depletion to be (1.32 ± 0.10) × 10-17 cm2 molecule-1 at 308 nm and (9.6 ± 0.8) × 10-18 cm2 molecule-1 at 352 nm. The peak UV cross section is estimated to be (1.75 ± 0.14) × 10-17 cm2 molecule-1 at 330 nm, according to the UV spectrum of (CH3)2COO (Huang et al., 2015) scaled to the absolute cross section at 308 nm.

  18. Principles and procedures for determining absolute differential electron-molecule (atom) scattering cross sections

    NASA Technical Reports Server (NTRS)

    Nickel, J. C.; Zetner, P. W.; Shen, G.; Trajmar, S.

    1989-01-01

    Procedures and calibration techniques for measuring the absolute elastic and inelastic differential cross sections (DCS) for electron impact on molecular (atomic) species are described and illustrated by examples. The elastic DCS for the molecule under study is first determined by calibration against helium using the relative flow technique. The second step involves the production of energy-loss spectra for the instrument response function, the unfolding of overlapping inelastic structures and the normalization of inelastic intensities to the elastic cross sections. It is concluded that this method of determining absolute differential electron-molecule (atom) scattering cross sections is generally applicable and provides reliable results.

  19. Absolute electron-impact total ionization cross sections of chlorofluoromethanes

    NASA Astrophysics Data System (ADS)

    Martínez, Roberto; Sierra, Borja; Redondo, Carolina; Rayo, María N. Sánchez; Castaño, Fernando

    2004-12-01

    An experimental study is reported on the electron-impact total ionization cross sections (TICSs) of CCl4, CCl3F, CCl2F2, and CClF3 molecules. The kinetic energy of the colliding electrons was in the 10-85 eV range. TICSs were obtained as the sum of the partial ionization cross sections of all fragment ions, measured and identified in a linear double focusing time-of-flight mass spectrometer. The resulting TICS profiles—as a function of the electron-impact energy—have been compared both with those computed by ab initio and (semi)empirical methods and with the available experimental data. The computational methods used include the binary-encounter-Bethe (BEB) modified to include atoms with principal quantum numbers n⩾3, the Deutsch and Märk (DM) formalism, and the modified additivity rule (MAR). It is concluded that both modified BEB and DM methods fit the experimental TICS for (CF4), CClF3, CCl2F2, CCl3F, and CCl4 to a high accuracy, in contrast with the poor accord of the MAR method. A discussion on the factors influencing the discrepancies of the fittings is presented.

  20. Cross-coupling reaction with lithium methyltriolborate.

    PubMed

    Yamamoto, Yasunori; Ikizakura, Kazuya; Ito, Hajime; Miyaura, Norio

    2012-12-28

    We newly developed lithium methyltriolborate as an air-stable white solid that is convenient to handle. The good performance of this triolborate for metal-catalyzed bond-forming reactions was demonstrated in palladium-catalyzed cross-coupling reactions with haloarenes. Cross-coupling reaction of [MeB(OCH₂)₃CCH₃]Li with aryl halides occurred in the presence of Pd(OAc)₂/RuPhos complex in refluxing MeOH/H₂O and the absence of bases.

  1. Absolute cross section for photoionization of Mn+ in the 3p region

    NASA Astrophysics Data System (ADS)

    Kjeldsen, H.; Folkmann, F.; Kristensen, B.; West, J. B.; Hansen, J. E.

    2004-03-01

    The absolute cross section for photoionization of Mn+ has been measured using the merged-beam technique, focusing on the region of the 'giant' 3p rarr 3d resonance. The main discrepancy between theory and earlier experiments has been removed. However, more extensive relativistic calculations are required for a rigorous comparison with theory.

  2. Measurement of the absolute differential cross section for np elastic scattering at 194 MeV

    SciTech Connect

    Sarsour, M.; Peterson, T.; Planinic, M.; Vigdor, S. E.; Allgower, C.; Hossbach, T.; Jacobs, W. W.; Klyachko, A. V.; Rinckel, T.; Stephenson, E. J.; Wissink, S. W.; Zhou, Y.; Bergenwall, B.; Blomgren, J.; Johansson, C.; Klug, J.; Nadel-Turonski, P.; Nilsson, L.; Olsson, N.; Pomp, S.

    2006-10-15

    A tagged medium-energy neutron beam was used in a precise measurement of the absolute differential cross section for np backscattering. The results resolve significant discrepancies within the np database concerning the angular dependence in this regime. The experiment has determined the absolute normalization with {+-}1.5% uncertainty, suitable to verify constraints of supposedly comparable precision that arise from the rest of the database in partial wave analyses. The analysis procedures, especially those associated with the evaluation of systematic errors in the experiment, are described in detail so that systematic uncertainties may be included in a reasonable way in subsequent partial wave analysis fits incorporating the present results.

  3. Absolute differential cross sections for electron capture and loss by kilo-electron-volt hydrogen atoms

    NASA Technical Reports Server (NTRS)

    Smith, G. J.; Johnson, L. K.; Gao, R. S.; Smith, K. A.; Stebbings, R. F.

    1991-01-01

    This paper reports measurements of absolute differential cross sections for electron capture and loss for fast hydrogen atoms incident on H2, N2, O2, Ar, and He. Cross sections have been determined in the 2.0- to 5.0-keV energy range over the laboratory angular range 0.02-2 deg, with an angular, resolution of 0.02 deg. The high angular resolution allows observation of the structure at small angles in some of the cross sections. Comparison of the present results with those of other authors generally shows very good agreement.

  4. Measurements of absolute absorption cross sections of ozone in the 185- to 254-nm wavelength region and the temperature dependence

    NASA Technical Reports Server (NTRS)

    Yoshino, K.; Esmond, J. R.; Freeman, D. E.; Parkinson, W. H.

    1993-01-01

    Laboratory measurements of the relative absorption cross sections of ozone at temperatures 195, 228, and 295 K have been made throughout the 185 to 254 nm wavelength region. The absolute absorption cross sections at the same temperatures have been measured at several discrete wavelengths in the 185 to 250 nm region. The absolute cross sections of ozone have been used to put the relative cross sections on a firm absolute basis throughout the 185 to 255 nm region. These recalibrated cross sections are slightly lower than those of Molina and Molina (1986), but the differences are within a few percent and would not be significant in atmospheric applications.

  5. Absolute rate of the reaction of hydrogen atoms with ozone from 219-360 K

    NASA Technical Reports Server (NTRS)

    Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

    1978-01-01

    Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence technique. The results can be expressed in Arrhenius form by K = (1.33 plus or minus 0.32)x10 to the minus 10 power exp (-449 plus or minus 58/T) cu cm/molecule/s (two standard deviations). The present work is compared to two previous determinations and is discussed theoretically.

  6. Absolute absorption cross sections of ozone in the 185- to 350-nm wavelength range

    NASA Technical Reports Server (NTRS)

    Molina, L. T.; Molina, M. J.

    1986-01-01

    The absorption cross sections of ozone have been measured in the wavelength range 185-350 nm and in the temperature range 225-298 K. The absolute ozone concentrations were established by measuring the pressure of pure gaseous samples in the 0.08to 300-torr range, and the UV spectra were recorded under conditions where less than 1 percent of the sample decomposed. The temperature dependence is significant for wavelengths longer than about 280 nm. The absorption cross-section values around 210 nm were found to be about 10 percent larger than the previously accepted values.

  7. Absolute measurement of the 242Pu neutron-capture cross section

    NASA Astrophysics Data System (ADS)

    Buckner, M. Q.; Wu, C. Y.; Henderson, R. A.; Bucher, B.; Chyzh, A.; Bredeweg, T. A.; Baramsai, B.; Couture, A.; Jandel, M.; Mosby, S.; O'Donnell, J. M.; Ullmann, J. L.; Dance Collaboration

    2016-04-01

    The absolute neutron-capture cross section of 242Pu was measured at the Los Alamos Neutron Science Center using the Detector for Advanced Neutron-Capture Experiments array along with a compact parallel-plate avalanche counter for fission-fragment detection. The first direct measurement of the 242Pu(n ,γ ) cross section was made over the incident neutron energy range from thermal to ≈6 keV, and the absolute scale of the (n ,γ ) cross section was set according to the known 239Pu(n ,f ) resonance at En ,R=7.83 eV. This was accomplished by adding a small quantity of 239Pu to the 242Pu sample. The relative scale of the cross section, with a range of four orders of magnitude, was determined for incident neutron energies from thermal to ≈40 keV. Our data, in general, are in agreement with previous measurements and those reported in ENDF/B-VII.1; the 242Pu(n ,γ ) cross section at the En ,R=2.68 eV resonance is within 2.4 % of the evaluated value. However, discrepancies exist at higher energies; our data are ≈30 % lower than the evaluated data at En≈1 keV and are approximately 2 σ away from the previous measurement at En≈20 keV.

  8. Miniature high-throughput chemosensing of yield, ee, and absolute configuration from crude reaction mixtures

    PubMed Central

    Bentley, Keith W.; Zhang, Peng; Wolf, Christian

    2016-01-01

    High-throughput experimentation (HTE) has emerged as a widely used technology that accelerates discovery and optimization processes with parallel small-scale reaction setups. A high-throughput screening (HTS) method capable of comprehensive analysis of crude asymmetric reaction mixtures (eliminating product derivatization or isolation) would provide transformative impact by matching the pace of HTE. We report how spontaneous in situ construction of stereodynamic metal probes from readily available, inexpensive starting materials can be applied to chiroptical chemosensing of the total amount, enantiomeric excess (ee), and absolute configuration of a wide variety of amines, diamines, amino alcohols, amino acids, carboxylic acids, α-hydroxy acids, and diols. This advance and HTS potential are highlighted with the analysis of 1 mg of crude reaction mixtures of a catalytic asymmetric reaction. This operationally simple assay uses a robust mix-and-measure protocol, is amenable to microscale platforms and automation, and provides critical time efficiency and sustainability advantages over traditional serial methods. PMID:26933684

  9. Absolute X-ray emission cross section measurements of Fe K transitions

    NASA Astrophysics Data System (ADS)

    Hell, Natalie; Brown, Gregory V.; Beiersdorfer, Peter; Boyce, Kevin R.; Grinberg, Victoria; Kelley, Richard L.; Kilbourne, Caroline; Leutenegger, Maurice A.; Porter, Frederick Scott; Wilms, Jörn

    2016-06-01

    We have measured the absolute X-ray emission cross sections of K-shell transitions in highly charged L- and K-shell Fe ions using the LLNL EBIT-I electron beam ion trap and the NASA GSFC EBIT Calorimeter Spectrometer (ECS). The cross sections are determined by using the ECS to simultaneously record the spectrum of the bound-bound K-shell transitions and the emission from radiative recombination from trapped Fe ions. The measured spectrum is then brought to an absolute scale by normalizing the measured flux in the radiative recombination features to their theoretical cross sections, which are well known. Once the spectrum is brought to an absolute scale, the cross sections of the K-shell transitions are determined. These measurements are made possible by the ECS, which consists of a 32 channel array, with 14 channels optimized for detecting high energy photons (hν > 10 keV) and 18 channels optimized for detecting low energy photons (hν < 10 keV). The ECS has a large collection area, relatively high energy resolution, and a large bandpass; all properties necessary for this measurement technique to be successful. These data will be used to benchmark cross sections in the atomic reference data bases underlying the plasma modeling codes used to analyze astrophysical spectra, especially those measured by the Soft X-ray Spectrometer calorimeter instrument recently launched on the Hitomi X-ray Observatory.This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344, and supported by NASA grants to LLNL and NASA/GSFC and by ESA under contract No. 4000114313/15/NL/CB.

  10. Absolute absorption cross-section measurements of ozone in the wavelength region 238-335 nm and the temperature dependence

    NASA Technical Reports Server (NTRS)

    Yoshino, K.; Freeman, D. E.; Esmond, J. R.; Parkinson, W. H.

    1988-01-01

    The absolute absorption cross-section of ozone has been experimentally determined at the temperatures 195, 228, and 295 K at several discrete wavelengths in the 238-335-nm region. The present results for ozone at 295 K are found to be in agreement with those of Hearn (1961). Absolute cross-section measurements of ozone at 195 K have confirmed previous (Freeman et al., 1984) relative cross-section measurements throughout the 240-335-nm region.

  11. Absolute measurement of the 242Pu neutron-capture cross section

    DOE PAGES

    Buckner, M. Q.; Wu, C. Y.; Henderson, R. A.; Bucher, B.; Chyzh, A.; Bredeweg, T. A.; Baramsai, B.; Couture, A.; Jandel, M.; Mosby, S.; et al

    2016-04-21

    Here, the absolute neutron-capture cross section of 242Pu was measured at the Los Alamos Neutron Science Center using the Detector for Advanced Neutron-Capture Experiments array along with a compact parallel-plate avalanche counter for fission-fragment detection. The first direct measurement of the 242Pu(n,γ) cross section was made over the incident neutron energy range from thermal to ≈ 6 keV, and the absolute scale of the (n,γ) cross section was set according to the known 239Pu(n,f) resonance at En,R = 7.83 eV. This was accomplished by adding a small quantity of 239Pu to the 242Pu sample. The relative scale of the crossmore » section, with a range of four orders of magnitude, was determined for incident neutron energies from thermal to ≈ 40 keV. Our data, in general, are in agreement with previous measurements and those reported in ENDF/B-VII.1; the 242Pu(n,γ) cross section at the En,R = 2.68 eV resonance is within 2.4% of the evaluated value. However, discrepancies exist at higher energies; our data are ≈30% lower than the evaluated data at En ≈ 1 keV and are approximately 2σ away from the previous measurement at En ≈ 20 keV.« less

  12. Absolute photoabsorption cross sections of Sr I from the 5s ionization threshold to the 5p threshold

    NASA Astrophysics Data System (ADS)

    Chu, C. C.; Fung, H. S.; Wu, H. H.; Yih, T. S.

    1998-09-01

    We have measured the absolute photoabsorption cross sections of Sr I from its 5s ionization threshold up to the 0953-4075/31/17/010/img1 thresholds. The spectrum includes the Sr I 0953-4075/31/17/010/img2, 0953-4075/31/17/010/img3, 0953-4075/31/17/010/img4 and 0953-4075/31/17/010/img5 doubly excited series which converge to the 0953-4075/31/17/010/img6 or 0953-4075/31/17/010/img1 series limits. Synchrotron radiation, from the 1 m Seya-Namioka beam line of the Synchrotron Radiation Research Center at Hsin-Chu, Taiwan, was used as the background continuum. The absolute column density was determined by measuring simultaneously the temperature distribution profiles and the total pressure in a heatpipe. Absolute cross sections were obtained using the Beer-Lambert law. The measured absolute cross section for the 5s ionization threshold was 0953-4075/31/17/010/img8. At the most significant autoionizing resonance, 0953-4075/31/17/010/img9 around 0953-4075/31/17/010/img10, the absolute cross section was measured as 0953-4075/31/17/010/img11. The absolute cross sections presented here are larger than those based on saturated vapour-pressure data, and less than those based on the f-value measurements. All the absolute cross sections in this work are compared with both recent experiments and

  13. Absolute cross sections for molecular photoabsorption, partial photoionization, and ionic photofragmentation process

    SciTech Connect

    Gallagher, J.W.; Brion, C.E.; Samson, J.A.R.; Langhoff, P.W.

    1988-01-01

    A compilation is provided of absolute total photoabsorption and partial-channel photoionization cross sections for the valence shells of selected molecules, including diatomics (H2, N2, O2, CO, NO) and triatomics (CO2, N2O), simple hydrides (H2O, NH3, CH4), hydrogen halides (HF, HCl, HBr, HI), sulfur compounds (H2S, CS2, OCS, SO2, SF6),and chlorine compounds (Cl2, CCl4). The partial-channel cross sections presented refer to production of the individual electronic states of molecular ions and also to production of parent and specific fragment ions, as functions of incident photon energy, typically from approximately 20 to 100 eV. Photoelectron anisotropy factors, which together with electronic partial cross sections provide cross sections differential in photon energy and in ejection angle, are also reported. There is generally good agreement between cross sections measured by the physically distinct optical and dipole electron-impact methods. The cross sections and anisotropy factors also compare favorably with selection ab initio and model potential (X-alpha) calculations which provide a basis for interpretation of the measurements.

  14. Separation of Betti Reaction Product Enantiomers: Absolute Configuration and Inhibition of Botulinum Neurotoxin A

    PubMed Central

    2011-01-01

    The racemic product of the Betti reaction of 5-chloro-8-hydroxyquinoline, benzaldehyde, and 2-aminopyridine was separated by chiral HPLC to determine which enantiomer inhibited botulinum neurotoxin serotype A. When the enantiomers unexpectedly proved to have comparable activity, the absolute structures of (+)-(R)-1 and (−)-(S)-1 were determined by comparison of calculated and observed circular dichroism spectra. Molecular modeling studies were undertaken in an effort to understand the observed bioactivity and revealed different ensembles of binding modes, with roughly equal binding energies, for the two enantiomers. PMID:22102940

  15. Absolute vacuum ultraviolet photoabsorption cross section studies of atomic and molecular species: Techniques and observational data

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

    Absorption of a high energy photon (greater than 6 eV) by an isolated molecule results in the formation of highly excited quasi-discrete or continuum states which evolve through a wide range of direct and indirect photochemical processes. These are: photoionization and autoionization, photodissociation and predissociation, and fluorescence. The ultimate goal is to understand the dynamics of the excitation and decay processes and to quantitatively measure the absolute partial cross sections for all processes which occur in photoabsorption. Typical experimental techniques and the status of observational results of particular interest to solar system observations are presented.

  16. Measurement of the absolute cross section for multiphoton ionization of atomic hydrogen at 248 nm

    SciTech Connect

    Kyrala, G.A.; Nichols, T.D.

    1990-01-01

    We present measurements of the absolute rates for multiphoton ionization of the ground state from atomic hydrogen by a linearly polarized, subpicosecond KrF laser pulse at a wavelength of 248 nm. A laser crossed atomic beam technique is used. The irradiance was varied from 3{times}10{sup 12} w/cm{sup 2} to 2{times}10{sup 14} w/cm{sup 2} and three above threshold ionization peaks were observed. The measured rate for total electron production is less than predicted by the numerical and perturbation calculations, but significantly higher than calculated by the Reiss and Keldysh methods. 21 refs., 7 figs.

  17. The Kings Cross fire: psychological reactions.

    PubMed

    Turner, S W; Thompson, J; Rosser, R M

    1995-07-01

    The psychological reactions of 50 survivors of the King's Cross fire, which hit London's underground railway system on the 18th day of November 1987, are described. Results are presented for the Impact of Event scale, the General Health Questionnaire (28-item version), the Eysenck Personality Questionnaire and a King's Cross Event Schedule. These are investigated in relation to (a) validity measures, (b) relationships between exposure and personality, and (c) spontaneous de-briefing. Two thirds of the sample had significant levels of psychological distress (meeting the "caseness" criterion on the GHQ). Both personality (neuroticism and L-scale) and degree of trauma exposure were related to subsequent reaction. Spontaneous debriefing was associated with subjective benefit. Transportation disasters present particular problems in relation to research and service delivery. PMID:7582607

  18. Saturation Dynamics Measures Absolute Cross Section and Generates Contrast within a Neuron.

    PubMed

    Kumar, Suraj; Singh, Aditya; Singh, Vijay R; George, Jude B; Balaji, J

    2016-09-20

    The intensity required to optically saturate a chromophore is a molecular property that is determined by its absorption cross section (σ) and the excited state lifetime. We present an analytical description of such a system and show that fluorescence around the onset of saturation is characterized by product of absorption cross section and lifetime. Using this approach we formulate a generalized method for measuring the multiphoton cross section of fluorophores and use it to obtain the absolute three-photon cross-section spectra of tryptophan. We find that the tryptophan three-photon cross section ranges from 0.28 S.I. units (m(6)s(2)photon(-2)) at 870 nm to 20 S.I. units at 740 nm. Further, we show that the product of molecular rate of excitation and de-excitation, denoted as β, serves as a vital contrasting agent for imaging local environment. Our contrast parameter, β, is related to fraction of the population present in the excited state and is independent of the fluorophore concentration. We show that β-imaging can be carried out in a regular two-photon microscope setup through a series of intensity scans. Using enhanced green fluorescent protein (EGFP) fluorescence from the brain slices of Thy-1 EGFP transgenic mice, we show that there is an inherent, concentration independent, variation in contrast across the soma and the dendrite.

  19. Saturation Dynamics Measures Absolute Cross Section and Generates Contrast within a Neuron.

    PubMed

    Kumar, Suraj; Singh, Aditya; Singh, Vijay R; George, Jude B; Balaji, J

    2016-09-20

    The intensity required to optically saturate a chromophore is a molecular property that is determined by its absorption cross section (σ) and the excited state lifetime. We present an analytical description of such a system and show that fluorescence around the onset of saturation is characterized by product of absorption cross section and lifetime. Using this approach we formulate a generalized method for measuring the multiphoton cross section of fluorophores and use it to obtain the absolute three-photon cross-section spectra of tryptophan. We find that the tryptophan three-photon cross section ranges from 0.28 S.I. units (m(6)s(2)photon(-2)) at 870 nm to 20 S.I. units at 740 nm. Further, we show that the product of molecular rate of excitation and de-excitation, denoted as β, serves as a vital contrasting agent for imaging local environment. Our contrast parameter, β, is related to fraction of the population present in the excited state and is independent of the fluorophore concentration. We show that β-imaging can be carried out in a regular two-photon microscope setup through a series of intensity scans. Using enhanced green fluorescent protein (EGFP) fluorescence from the brain slices of Thy-1 EGFP transgenic mice, we show that there is an inherent, concentration independent, variation in contrast across the soma and the dendrite. PMID:27653491

  20. Absolute photoionization cross sections of furanic fuels: 2-ethylfuran, 2-acetylfuran and furfural.

    PubMed

    Smith, Audrey R; Meloni, Giovanni

    2015-11-01

    Absolute photoionization cross sections of the molecules 2-ethylfuran, 2-acetylfuran and furfural, including partial ionization cross sections for the dissociative ionized fragments, are measured for the first time. These measurements are important because they allow fuel quantification via photoionization mass spectrometry and the development of quantitative kinetic modeling for the complex combustion of potential fuels. The experiments are carried out using synchrotron photoionization mass spectrometry with an orthogonal time-of-flight spectrometer used for mass analysis at the Advanced Light Source of Lawrence Berkeley National Laboratory. The CBS-QB3 calculations of adiabatic ionization energies and appearance energies agree well with the experimental results. Several bond dissociation energies are also derived and presented.

  1. Partial (gamma)-Ray Cross Sections for the Reaction 239Pu(n,2n(gamma)i) and the 239Pu(n,2n) Cross Section

    SciTech Connect

    Beacker, J.A.; Bernstein, L.A.; Younes, W.; McNabb, D.P.; Garrett, P.E.; Archer, D.; McGrath, C.A.; Stoyer, M.A.; Chen, H.; Ormand, W.E.; Nelson, R.O.; Chadwick, M.B.; Johns, G.D.; Drake, D.; Young, P.G.; Devlin, M.; Fotiades, N.; Wilburn, W.S.

    2001-09-14

    Absolute partial {gamma}-ray cross sections for production of discrete {gamma} rays in the {sup 239}Pu(n,2n{gamma}i){sup 238}Pu reaction have been measured. The experiments were performed at LANSCE/WNR on the 60R flight line. Reaction {gamma}-rays were measured using the large-scale Compton-suppressed array of Ge detectors, GEANIE. The motivation for this experiment, an overview of the partial {gamma}-ray cross-section measurement, and an introduction to the main experimental issues will be presented. The energy resolution of the Ge detectors allowed identification of reaction {gamma} rays above the background of sample radioactivity and fission {gamma} rays. The use of planar Ge detectors with their reduced sensitivity to neutron interactions and improved line shape was also important to the success of this experiment. Absolute partial {gamma}-ray cross sections are presented for the 6{sub 1}{sup +} {yields} 4{sub 1}{sup +} member of the ground state rotational band in {sup 238}Pu, together with miscellaneous other {gamma}-ray partial cross sections. The n,2n reaction cross section shape and magnitude as a function of neutron energy was extracted from these partial cross sections using nuclear modeling (enhanced Hauser-Feshbach) to relate partial {gamma}-ray cross sections to the n,2n cross section. The critical nuclear modeling issue is the ratio of a partial cross section to the reaction channel cross section, and not the prediction of the absolute magnitude.

  2. Photodissociation of acetaldehyde and the absolute photoionization cross section of HCO.

    SciTech Connect

    Shubert, V. A.; Pratt, S. T.

    2010-01-01

    Photodissociation of acetaldehyde (CH{sub 3}CHO) at 266 nm produced CH{sub 3} and HCO radicals, and single-photon vacuum ultraviolet ionization was used to record velocity map ion images of both CH{sub 3}{sup +} and HCO{sup +}. Comparison of the translational energy distributions from both species indicates that secondary fragmentation of HCO is negligible for 266 nm photodissociation. Thus, the relative photoion signals for CH{sub 3}{sup +} and HCO{sup +} in the mass spectrometer, combined with the recently measured absolute photoionization cross section of CH{sub 3}, allowed the determination of the absolute photoionization cross section of HCO ({sigma}(HCO) = 4.8 {+-} {sub 1.5}{sup 2.0}, 5.9 {+-} {sub 1.6}{sup 2.2}, and 3.7 {+-} {sub 1.2}{sup 1.6} Mb at 10.257, 10.304, and 10.379 eV, respectively). The observed values are quite small but consistent with the similarly small value at threshold for the isoelectronic species NO. This behavior is discussed in terms of the character of the HOMO in both molecules.

  3. Absolute partial and total cross sections for electron-impact ionization of argon from threshold to 1000 eV

    NASA Astrophysics Data System (ADS)

    Straub, H. C.; Renault, P.; Lindsay, B. G.; Smith, K. A.; Stebbings, R. F.

    1995-08-01

    Absolute partial cross sections from threshold to 1000 eV are reported for the production of Arn+ (n=1-4) by electron-impact ionization of argon. The total cross sections, obtained from an appropriately weighted sum of the partial cross sections, are also reported. These results are obtained with an apparatus incorporating a time-of-flight mass spectrometer with position-sensitive detection of the product ions. The simple apparatus design embodies recent developments in pressure measurement and particle detection and is believed to yield more reliable results than those previously reported. For singly charged ions, the overall uncertainty in the absolute cross section values reported here is +/-3.5%. Previous measurements of absolute partial and total cross sections are reviewed and compared with the present results.

  4. Cross coupling reactions of polyfluoroarenes via C-F activation.

    PubMed

    Sun, Alex D; Love, Jennifer A

    2010-11-21

    This Perspective provides an overview of transition metal-catalyzed cross coupling reactions of polyfluoroarenes. When appropriate, stoichiometric C-F activation and subsequent reaction are briefly covered.

  5. The Br+HO 2 reaction revisited: Absolute determination of the rate constant at 298 K

    NASA Astrophysics Data System (ADS)

    Laverdet, G.; Le Bras, G.; Mellouki, A.; Poulet, G.

    1990-09-01

    The absolute determination of the rate constant for the reaction Br+HO 2→HBr+O 2 has been done at 298 K using the discharge-flor EPR method. The value k1 = (1.5±0.2) × 10 -12 cm 3 molecule -1 s -1 was obtained. Previous indirect measurements of k1 from a discharge-flow, LIF/mass spectrometric study of the Br/H 2CO/O 2 system have been reinterpreted, leading to values for k1 ranging from 1.0 × 10 -12 to 2.2 × 10 -12 cm 3 molecule -1 s -1 at 298 K. These results are discussed and compared with other literature values.

  6. Metal-Catalyzed Cross-Coupling Reactions for Indoles

    NASA Astrophysics Data System (ADS)

    Li, Jie Jack; Gribble, Gordon W.

    Metal-catalyzed cross-coupling reactions for indoles are reviewed. Palladium-catalyzed cross-coupling reactions are the most widely explored and applied of all metal-catalyzed cross-coupling reactions. Applications of Kumada coupling, Negishi coupling, Suzuki coupling, Stille coupling, Sonogashira reaction, the Heck reaction, carbonylation, and C-N bond formation reactions in indoles are summarized. In addition, other transition metal-catalyzed cross-coupling reactions using copper, rhodium, iron, and nickel in indole synthesis are also discussed.

  7. ^241Am(n,γ) absolute cross sections measured with DANCE

    NASA Astrophysics Data System (ADS)

    Jandel, M.; Bredeweg, T. A.; Fowler, M. M.; Bond, E. M.; Chadwick, M. B.; Clement, R. R.; Couture, A.; O'Donnell, J. M.; Reifarth, R.; Rundberg, R. S.; Ullmann, J. L.; Vieira, D. J.; Wilhelmy, J. B.; Wouters, J. M.; Agvaanluvsan, U.; Macri, R. A.; Sheets, S. A.; Wu, C. Y.; Becker, J. A.

    2007-10-01

    ^241Am is present in plutonium due to the beta decay of ^241Pu (t1/2=14.38 years). As such ^241Am can be used as a detector for nuclear forensics. A precise measurement of ^241Am(n,γ) cross section is thus needed for this application. The measurement is also of interest for advanced reactor design as part of the Global Nuclear Energy Partnership (GNEP). The Detector for Advanced Neutron Capture Experiments (DANCE) at Los Alamos National Laboratory (LANL) was used for neutron capture cross section measurement on ^241Am. The high granularity of DANCE (160 BaF2 detectors in a 4π geometry) enables the efficient detection of prompt gamma-rays following a neutron capture. DANCE is located on the 20.26 m neutron flight path 14(FP14) at the Manuel Lujan Jr. Neutron Scattering Center at the Los Alamos Neutron Science Center (LANSCE). The absolute ^241Am(n,γ) cross sections were obtained in the range of neutron energies from 0.02 eV to 320 keV. The results will be compared to existing evaluations in detail.

  8. Absolute angle-differential vibrational excitation cross sections for electron collisions with diacetylene

    SciTech Connect

    Allan, M.; May, O.; Fedor, J.; Ibanescu, B. C.; Andric, L.

    2011-05-15

    Absolute vibrational excitation cross sections were measured for diacetylene (1,3-butadiyne). The selectivity of vibrational excitation reveals detailed information about the shape resonances. Excitation of the C{identical_to}C stretch and of double quanta of the C-H bend vibrations reveals a {sup 2}{Pi}{sub u} resonance at 1 eV (autodetachment width {approx}30 meV) and a {sup 2}{Pi}{sub g} resonance at 6.2 eV (autodetachment width 1-2 eV). There is a strong preference for excitation of even quanta of the bending vibration. Excitation of the C-H stretch vibration reveals {sigma}* resonances at 4.3, 6.8, and 9.8 eV, with autodetachment widths of {approx}2 eV. Detailed information about resonances permits conclusions about the mechanism of the dissociative electron attachment.

  9. Systematic determination of absolute absorption cross-section of individual carbon nanotubes

    PubMed Central

    Liu, Kaihui; Hong, Xiaoping; Choi, Sangkook; Jin, Chenhao; Capaz, Rodrigo B.; Kim, Jihoon; Wang, Wenlong; Bai, Xuedong; Louie, Steven G.; Wang, Enge; Wang, Feng

    2014-01-01

    Optical absorption is the most fundamental optical property characterizing light–matter interactions in materials and can be most readily compared with theoretical predictions. However, determination of optical absorption cross-section of individual nanostructures is experimentally challenging due to the small extinction signal using conventional transmission measurements. Recently, dramatic increase of optical contrast from individual carbon nanotubes has been successfully achieved with a polarization-based homodyne microscope, where the scattered light wave from the nanostructure interferes with the optimized reference signal (the reflected/transmitted light). Here we demonstrate high-sensitivity absorption spectroscopy for individual single-walled carbon nanotubes by combining the polarization-based homodyne technique with broadband supercontinuum excitation in transmission configuration. To our knowledge, this is the first time that high-throughput and quantitative determination of nanotube absorption cross-section over broad spectral range at the single-tube level was performed for more than 50 individual chirality-defined single-walled nanotubes. Our data reveal chirality-dependent behaviors of exciton resonances in carbon nanotubes, where the exciton oscillator strength exhibits a universal scaling law with the nanotube diameter and the transition order. The exciton linewidth (characterizing the exciton lifetime) varies strongly in different nanotubes, and on average it increases linearly with the transition energy. In addition, we establish an empirical formula by extrapolating our data to predict the absorption cross-section spectrum for any given nanotube. The quantitative information of absorption cross-section in a broad spectral range and all nanotube species not only provides new insight into the unique photophysics in one-dimensional carbon nanotubes, but also enables absolute determination of optical quantum efficiencies in important

  10. Systematic determination of absolute absorption cross-section of individual carbon nanotubes.

    PubMed

    Liu, Kaihui; Hong, Xiaoping; Choi, Sangkook; Jin, Chenhao; Capaz, Rodrigo B; Kim, Jihoon; Wang, Wenlong; Bai, Xuedong; Louie, Steven G; Wang, Enge; Wang, Feng

    2014-05-27

    Optical absorption is the most fundamental optical property characterizing light-matter interactions in materials and can be most readily compared with theoretical predictions. However, determination of optical absorption cross-section of individual nanostructures is experimentally challenging due to the small extinction signal using conventional transmission measurements. Recently, dramatic increase of optical contrast from individual carbon nanotubes has been successfully achieved with a polarization-based homodyne microscope, where the scattered light wave from the nanostructure interferes with the optimized reference signal (the reflected/transmitted light). Here we demonstrate high-sensitivity absorption spectroscopy for individual single-walled carbon nanotubes by combining the polarization-based homodyne technique with broadband supercontinuum excitation in transmission configuration. To our knowledge, this is the first time that high-throughput and quantitative determination of nanotube absorption cross-section over broad spectral range at the single-tube level was performed for more than 50 individual chirality-defined single-walled nanotubes. Our data reveal chirality-dependent behaviors of exciton resonances in carbon nanotubes, where the exciton oscillator strength exhibits a universal scaling law with the nanotube diameter and the transition order. The exciton linewidth (characterizing the exciton lifetime) varies strongly in different nanotubes, and on average it increases linearly with the transition energy. In addition, we establish an empirical formula by extrapolating our data to predict the absorption cross-section spectrum for any given nanotube. The quantitative information of absorption cross-section in a broad spectral range and all nanotube species not only provides new insight into the unique photophysics in one-dimensional carbon nanotubes, but also enables absolute determination of optical quantum efficiencies in important

  11. Direct and Absolute Quantification of over 1800 Yeast Proteins via Selected Reaction Monitoring*

    PubMed Central

    Lawless, Craig; Holman, Stephen W.; Brownridge, Philip; Lanthaler, Karin; Harman, Victoria M.; Watkins, Rachel; Hammond, Dean E.; Miller, Rebecca L.; Sims, Paul F. G.; Grant, Christopher M.; Eyers, Claire E.; Beynon, Robert J.

    2016-01-01

    Defining intracellular protein concentration is critical in molecular systems biology. Although strategies for determining relative protein changes are available, defining robust absolute values in copies per cell has proven significantly more challenging. Here we present a reference data set quantifying over 1800 Saccharomyces cerevisiae proteins by direct means using protein-specific stable-isotope labeled internal standards and selected reaction monitoring (SRM) mass spectrometry, far exceeding any previous study. This was achieved by careful design of over 100 QconCAT recombinant proteins as standards, defining 1167 proteins in terms of copies per cell and upper limits on a further 668, with robust CVs routinely less than 20%. The selected reaction monitoring-derived proteome is compared with existing quantitative data sets, highlighting the disparities between methodologies. Coupled with a quantification of the transcriptome by RNA-seq taken from the same cells, these data support revised estimates of several fundamental molecular parameters: a total protein count of ∼100 million molecules-per-cell, a median of ∼1000 proteins-per-transcript, and a linear model of protein translation explaining 70% of the variance in translation rate. This work contributes a “gold-standard” reference yeast proteome (including 532 values based on high quality, dual peptide quantification) that can be widely used in systems models and for other comparative studies. PMID:26750110

  12. Absolute cross section for low-energy-electron damage to condensed macromolecules: A case study of DNA

    NASA Astrophysics Data System (ADS)

    Rezaee, Mohammad; Cloutier, Pierre; Bass, Andrew D.; Michaud, Marc; Hunting, Darel J.; Sanche, Léon

    2012-09-01

    Cross sections (CSs) for the interaction of low-energy electrons (LEE) with condensed macromolecules are essential parameters for accurate modeling of radiation-induced molecular decomposition and chemical synthesis. Electron irradiation of dry nanometer-scale macromolecular solid films has often been employed to measure CSs and other quantitative parameters for LEE interactions. Since such films have thicknesses comparable with electron thermalization distances, energy deposition varies throughout the film. Moreover, charge accumulation occurring inside the films shields a proportion of the macromolecules from electron irradiation. Such effects complicate the quantitative comparison of the CSs obtained in films of different thicknesses and limit the applicability of such measurements. Here, we develop a simple mathematical model, termed the molecular survival model, that employs a CS for a particular damage process together with an attenuation length related to the total CS, to investigate how a measured CS might be expected to vary with experimental conditions. As a case study, we measure the absolute CS for the formation of DNA strand breaks (SBs) by electron irradiation at 10 and 100 eV of lyophilized plasmid DNA films with thicknesses between 10 and 30 nm. The measurements are shown to depend strongly on the thickness and charging condition of the nanometer-scale films. Such behaviors are in accord with the model and support its validity. Via this analysis, the CS obtained for SB damage is nearly independent of film thickness and charging effects. In principle, this model can be adapted to provide absolute CSs for electron-induced damage or reactions occurring in other molecular solids across a wider range of experimental conditions.

  13. Absolute elastic differential electron scattering cross sections for He - A proposed calibration standard from 5 to 200 eV

    NASA Technical Reports Server (NTRS)

    Register, D. F.; Trajmar, S.; Srivastava, S. K.

    1980-01-01

    Absolute differential, integral, and momentum-transfer cross sections for electrons elastically scattered from helium are reported for the impact energy range of 5 to 200 eV. Angular distributions for elastically scattered electrons are measured in a crossed-beam geometry using a collimated, differentially pumped atomic-beam source which requires no effective-path-length correction. Below the first inelastic threshold the angular distributions were placed on an absolute scale by use of a phase-shift analysis. Above this threshold, the angular distributions from 10 to 140 deg were fitted using the phase-shift technique, and the resulting integral cross sections were normalized to a semiempirically derived integral elastic cross section. Depending on the impact energy, the data are estimated to be accurate to within 5 to 9%.

  14. Absolute triple-differential cross sections for ionization-excitation of helium

    SciTech Connect

    Bartschat, K.; Bray, I.; Fursa, D. V.; Stelbovics, A. T.

    2007-08-15

    Triple-differential cross sections (TDCSs) for electron-impact ionization of He(1s{sup 2}){sup 1}S leading to He{sup +}(1s) are calculated using the highly accurate convergent close-coupling (CCC) method for incident projectile energies of 268.6 and 112.6 eV, with at least one of the outgoing electrons having an energy of 44 eV. These results are used to obtain absolute TDCSs from the recent experimental data [Bellm et al., Phys. Rev. A 75, 042704 (2007)] for TDCS ratios of ionization with no excitation to ionization with excitation resulting in He{sup +}(n=2,3,4). The TDCSs can be used as comparison benchmarks in future studies, and already allow us to test the accuracy of the TDCSs obtained from the hybrid distorted-wave+R-matrix (close-coupling) model, which was fairly successful in predicting the ratios, using CCC for n=1 and experimental results for n=2,3,4.

  15. Absolute cross sections for dissociative electron attachment to HCN and DCN

    SciTech Connect

    May, O.; Kubala, D.; Allan, M.

    2010-07-15

    Absolute partial cross sections for the formation of CN{sup -} in dissociative electron attachment to HCN and DCN have been measured using a time-of-flight ion spectrometer combined with a trochoidal electron monochromator to be 940pm{sup 2} for CN{sup -}/HCN and 340pm{sup 2} for CN{sup -}/DCN at peaks of the bands due to the {sup 2{Pi}}-shape resonance. The dissociative electron attachment bands were then recorded under higher resolution, 60 meV, with a trochoidal monochromator plus quadrupole mass filter combination and found to have a nearly vertical onset at the threshold energy and to peak at 1.85 eV. Broad structure was observed on the bands, assigned to formation of vibrationally excited CN{sup -}, from which the branching ratios could be determined to be 1,0.49, and 0.22 for the formation of CN{sup -} in the v=0,1, and 2 states, respectively. The results are compared to the recent multidimensional ab initio calculations of Chourou and Orel [Phys. Rev. A 80, 032709 (2009)].

  16. Supplementary absolute differential cross sections for the excitation of atomic hydrogen's n=3 and 4 levels by electron impact

    SciTech Connect

    Sweeney, Christopher J.; Shyn, Tong W.; Grafe, Alan

    2004-05-01

    We have conducted measurements of absolute differential cross sections for the excitation of hydrogen atoms to their n=3(3S+3P+3D) and 4(4S+4P+4D+4F) levels. A modulated, crossed-beam method was employed, and the impact energies were 40 and 60 eV. Comparison of our results with those of others is quite favorable.

  17. ScaRaB: first results of absolute and cross calibration

    NASA Astrophysics Data System (ADS)

    Trémas, Thierry L.; Aznay, Ouahid; Chomette, Olivier

    2015-10-01

    ScaRaB (SCAnner for RAdiation Budget) is the name of three radiometers whose two first flight models have been launched in 1994 and 1997. The instruments were mounted on-board Russian satellites, METEOR and RESURS. On October 12th 2011, a last model has been launched from the Indian site of Sriharikota. ScaRaB is a passenger of MEGHA-TROPIQUES, an Indo-French joint Satellite Mission for studying the water cycle and energy exchanges in the tropics. ScaRaB is composed of four parallel and independent channels. Channel-2 and channel-3 are considered as the main ones. Channel-1 is dedicated to measure solar radiance (0.5 to 0.7 μm) while channel-4 (10 to 13 μm) is an infrared window. The absolute calibration of ScaRab is assured by internal calibration sources (black bodies and a lamp for channel-1). However, during the commissioning phase, the lamp used for the absolute calibration of channel-1 revealed to be inaccurate. We propose here an alternative calibration method based on terrestrial targets. Due to the spectral range of channel-1, only calibration over desert sites (temporal monitoring) and clouds (cross band) is suitable. Desert sites have been widely used for sensor calibration since they have a stable spectral response over time. Because of their high reflectances, the atmospheric effect on the upward radiance is relatively minimal. In addition, they are spatially uniform. Their temporal instability without atmospheric correction has been determined to be less than 1-2% over a year. Very-high-altitude (10 km) bright clouds are good validation targets in the visible and near-infrared spectra because of their high spectrally consistent reflectance. If the clouds are very high, there is no need to correct aerosol scattering and water vapor absorption as both aerosol and water vapor are distributed near the surface. Only Rayleigh scattering and ozone absorption need to be considered. This method has been found to give a 4% uncertainty. Radiometric cross

  18. Absolute quantification of genetically modified MON810 maize (Zea mays L.) by digital polymerase chain reaction.

    PubMed

    Corbisier, Philippe; Bhat, Somanath; Partis, Lina; Xie, Vicki Rui Dan; Emslie, Kerry R

    2010-03-01

    Quantitative analysis of genetically modified (GM) foods requires estimation of the amount of the transgenic event relative to an endogenous gene. Regulatory authorities in the European Union (EU) have defined the labelling threshold for GM food on the copy number ratio between the transgenic event and an endogenous gene. Real-time polymerase chain reaction (PCR) is currently being used for quantification of GM organisms (GMOs). Limitations in real-time PCR applications to detect very low number of DNA targets has led to new developments such as the digital PCR (dPCR) which allows accurate measurement of DNA copies without the need for a reference calibrator. In this paper, the amount of maize MON810 and hmg copies present in a DNA extract from seed powders certified for their mass content and for their copy number ratio was measured by dPCR. The ratio of these absolute copy numbers determined by dPCR was found to be identical to the ratios measured by real-time quantitative PCR (qPCR) using a plasmid DNA calibrator. These results indicate that both methods could be applied to determine the copy number ratio in MON810. The reported values were in agreement with estimations from a model elaborated to convert mass fractions into copy number fractions in MON810 varieties. This model was challenged on two MON810 varieties used for the production of MON810 certified reference materials (CRMs) which differ in the parental origin of the introduced GM trait. We conclude that dPCR has a high metrological quality and can be used for certifying GM CRMs in terms of DNA copy number ratio.

  19. Absolute Rayleigh scattering cross sections of gases and freons of stratospheric interest in the visible and ultraviolet regions

    NASA Technical Reports Server (NTRS)

    SHARDANAND; Rao, A. D. P.

    1977-01-01

    The laboratory measurements of absolute Rayleigh scattering cross sections as a function wavelength are reported for gas molecules He, Ne, Ar, N2, H2, O2, CO2, CH4 and for vapors of most commonly used freons CCl2F2, CBrF3, CF4, and CHClf2. These cross sections are determined from the measurements of photon scattering at an angle of 54 deg 44 min which yield the absolute values independent of the value of normal depolarization ratios. The present results show that in the spectral range 6943-3638A deg, the values of the Rayleigh scattering cross section can be extrapolated from one wavelength to the other using 1/lambda (4) law without knowing the values of the polarizabilities. However, such an extrapolation can not be done in the region of shorter wavelengths.

  20. Measurement of the absolute Raman cross section of the optical phonon in silicon

    NASA Astrophysics Data System (ADS)

    Aggarwal, R. L.; Farrar, L. W.; Saikin, S. K.; Aspuru-Guzik, A.; Stopa, M.; Polla, D. L.

    2011-04-01

    The absolute Raman cross section σ of the first-order 519 cm -1 optical phonon in silicon was measured using a small temperature-controlled blackbody for the signal calibration of the Raman system. Measurements were made with a 25-mil thick (001) silicon sample located in the focal plane of a 20-mm effective focal length (EFL) lens using 785-, 1064-, and 1535-nm CW pump lasers for the excitation of Raman scattering. The pump beam was polarized along the [100] axis of the silicon sample. Values of 1.0±0.2×10 -27, 3.6±0.7×10 -28, and 1.1±0.2×10 -29 cm 2 were determined for σ for 785-, 1064-, and 1535-nm excitation, respectively. The corresponding values of the Raman scattering efficiency S are 4.0±0.8×10 -6, 1.4±0.3×10 -6, and 4.4±0.8×10 -8 cm -1 sr -1.The values of the Raman polarizability |d| for 785-, 1064-, and 1535-nm excitation are 4.4±0.4×10 -15, 5.1±0.5×10 -15, and 1.9±0.2×10 -15 cm 2, respectively. The values of 4.4±0.4×10 -15 and 5.1±0.5×10 -15 cm 2 for |d| for 785- and 1064-nm excitation, respectively, are 1.3 and 2.0 times larger than the values of 3.5×10 -15 and 2.5×10 -15 cm 2 calculated by Wendel. The Raman polarizability |d| computed using the density functional theory in the long-wavelength limit is consistent with the general trend of the measured data and Wendel's model.

  1. Validation of absolute axial neutron flux distribution calculations with MCNP with 197Au(n,γ)198Au reaction rate distribution measurements at the JSI TRIGA Mark II reactor.

    PubMed

    Radulović, Vladimir; Štancar, Žiga; Snoj, Luka; Trkov, Andrej

    2014-02-01

    The calculation of axial neutron flux distributions with the MCNP code at the JSI TRIGA Mark II reactor has been validated with experimental measurements of the (197)Au(n,γ)(198)Au reaction rate. The calculated absolute reaction rate values, scaled according to the reactor power and corrected for the flux redistribution effect, are in good agreement with the experimental results. The effect of different cross-section libraries on the calculations has been investigated and shown to be minor. PMID:24316530

  2. Absolute Rate Constants for the Reaction of OH with [|#11#|]Cyclopentane and Cycloheptane from 230-350 K

    NASA Astrophysics Data System (ADS)

    Dransfield, T. J.; Gennaco, M. M.; Huang, Y.; Hannun, R. A.

    2011-12-01

    We report absolute measurements of the rate constants of the reaction of hydroxyl radical (OH) with cyclopentane and cycloheptane in 6-8 Torr of nitrogen from 230-350 K using Harvard's High Pressure Flow System. Ethane's reactivity was simultaneously measured as a test of experimental performance. Hydroxyl concentrations were measured using Laser-Induced Fluorescence, and alkane concentrations were measured using Fourier-Transform Infrared Spectroscopy. Recent work on this flow system has suggested that cyclohexane has a significantly higher activation energy to reaction with OH than does cyclo-octane, a result which is not suggested by our understanding of hydrocarbon reactivity nor predicted by structure-activity relationships. This work examines the temperature dependent rates for two other similarly-sized cycloalkanes to determine whether they behave as cyclohexane or as cyclooctane. While several previous experiments have studied the reaction with cyclopentane, there is significant scatter in the room temperature rates, and only four absolute rate measurements are available at non-ambient temperatures. There are only two absolute rate measurements available for the reaction with cycloheptane; only one of these reports a temperature dependence, and that study is limited to temperatures above 298 K. Thus, this work significantly expands the available data set for both reactions. The data for the reactions of OH with ethane, cyclopentane, cyclohexane, and cycloheptane are all modeled using a simple Arrhenius fit, and also with a modified Arrhenius equation based on transition state theory, ignoring tunneling. Results from the latter fit indicate that the activation barriers for both title reactions are greater than that of OH + cyclo-octane. The measured activation energy for OH + cyclopentane actually exceeds that of OH + cyclohexane.

  3. Precision Cross Section Measurement for the ^241Am(γ,n) Reaction at HIγS

    NASA Astrophysics Data System (ADS)

    Tonchev, A.; Hutcheson, A.; Howell, C. R.; Kwan, E.; Rusev, G.; Tornow, W.; Hammond, S.; Karwowski, H. J.; Huibregtse, C.; Kelley, J. H.; Vieira, D. L.; Wilhelmy, J. B.; Stoyer, M. A.

    2008-10-01

    The photodisintegration cross section on radioactive ^241Am target has been measured for the first time using monoenergetic γ-ray beams from the HIγS facility. Induced activity from ^240Am produced via the (γ,n) reaction was measured by the activation technique using high resolution HPGe detectors. The (γ,n) cross section was determined both by measuring the absolute γ-flux and by comparison to the ^197Au(γ,n) cross section used as a standard. In the following, we report new data for the excitation function of the ^241Am(γ,n ) reaction from near threshold to 16 MeV incident γ-ray energy and we compare the data with statistical nuclear-model calculations performed with the GNASH, EMPIRE, and TALYS codes.

  4. Absolute Photoionization Cross Sections for Br2+ in the 4 p --> 4d and 3d --> 4p Energy Regions

    NASA Astrophysics Data System (ADS)

    Aguilar, A.; Juarez, A. M.; Bilodeau, R. C.; Esteves, D. A.; Hardy, D. A.; Red, E. C.

    2011-05-01

    Absolute single photoionization cross-section measurements are reported for Br2+ in the 31 eV to 46 eV and 64 eV to 72 eV photon energy ranges. The first energy range includes the low-lying 2P3 / 2 , 1 / 2 and 2D5 / 2 , 3 / 2 metastable state thresholds and extends for 10 eV above the 4S3 / 2 ground state threshold. Strong photoexcitation-autoionization resonances due to 4p --> nd transitions are seen in the cross-section spectrum and identified based on a quantum-defect analysis of the series. The systematic behavior of the quantum defect parameter of some of the Rydberg series observed in the Br2+ spectrum as well as in previously measured Se+ spectrum, are analyzed as a function of the nuclear charge. The 64 eV to 72 eV energy range contains discrete structure that arises from 3d --> np excitations. The R-matrix photoionization cross section calculations of Cummings and O'Sullivan, PRA, 54 (1996) are compared to our absolute cross section measurements in this energy range. Absolute single photoionization cross-section measurements are reported for Br2+ in the 31 eV to 46 eV and 64 eV to 72 eV photon energy ranges. The first energy range includes the low-lying 2P3 / 2 , 1 / 2 and 2D5 / 2 , 3 / 2 metastable state thresholds and extends for 10 eV above the 4S3 / 2 ground state threshold. Strong photoexcitation-autoionization resonances due to 4p --> nd transitions are seen in the cross-section spectrum and identified based on a quantum-defect analysis of the series. The systematic behavior of the quantum defect parameter of some of the Rydberg series observed in the Br2+ spectrum as well as in previously measured Se+ spectrum, are analyzed as a function of the nuclear charge. The 64 eV to 72 eV energy range contains discrete structure that arises from 3d --> np excitations. The R-matrix photoionization cross section calculations of Cummings and O'Sullivan, PRA, 54 (1996) are compared to our absolute cross section measurements in this energy range. This work is

  5. Absolute Rb one-color two-photon ionization cross-section measurement near a quantum interference

    SciTech Connect

    Takekoshi, T.; Brooke, G.M.; Patterson, B.M.; Knize, R.J.

    2004-05-01

    We observe destructive interference in the ground-state Rb two-photon ionization cross section when the single photon energy is tuned between the 5S{yields}5P and 5S{yields}6P transition energies. The minimum cross section is 5.9(1.5)x10{sup -52} cm{sup 4} s and it occurs at a wavelength of 441.0(3) nm (in vacuo). Relative measurements of these cross sections are made at various wavelengths by counting ions produced when magneto-optically trapped Rb atoms are exposed to light from a tunable pulsed laser. This relative curve is calibrated to an absolute cross-section measurement at 532 nm using the trap loss method. A simple calculation agrees reasonably with our results.

  6. Absolute cross sections for vibrational excitations of cytosine by low energy electron impact

    NASA Astrophysics Data System (ADS)

    Michaud, M.; Bazin, M.; Sanche, L.

    2012-09-01

    The absolute cross sections (CSs) for vibrational excitations of cytosine by electron impact between 0.5 and 18 eV were measured by electron-energy loss (EEL) spectroscopy of the molecule deposited at monolayer coverage on an inert Ar substrate. The vibrational energies compare to those that have been reported from IR spectroscopy of cytosine isolated in Ar matrix, IR and Raman spectra of polycrystalline cytosine, and ab initio calculation. The CSs for the various H bending modes at 142 and 160 meV are both rising from their energy threshold up to 1.7 and 2.1 × 10-17 cm2 at about 4 eV, respectively, and then decrease moderately while maintaining some intensity at 18 eV. The latter trend is displayed as well for the CS assigned to the NH2 scissor along with bending of all H at 179 meV. This overall behavior in electron-molecule collision is attributed to direct processes such as the dipole, quadrupole, and polarization contributions, etc. of the interaction of the incident electron with a molecule. The CSs for the ring deformation at 61 meV, the ring deformation with N-H symmetric wag at 77 meV, and the ring deformations with symmetric bending of all H at 119 meV exhibit common enhancement maxima at 1.5, 3.5, and 5.5 eV followed by a broad hump at about 12 eV, which are superimposed on the contribution due to the direct processes. At 3.5 eV, the CS values for the 61-, 77-, and 119-meV modes reach 4.0, 3.0, and 4.5 × 10-17 cm2, respectively. The CS for the C-C and C-O stretches at 202 meV, which dominates in the intermediate EEL region, rises sharply until 1.5 eV, reaches its maximum of 5.7 × 10-17 cm2 at 3.5 eV and then decreases toward 18 eV. The present vibrational enhancements, correspond to the features found around 1.5 and 4.5 eV in electron transmission spectroscopy (ETS) and those lying within 1.5-2.1 eV, 5.2-6.8 eV, and 9.5-10.9 eV range in dissociative electron attachment (DEA) experiments with cytosine in gas phase. While the ETS features are ascribed

  7. Absolute cross sections for vibrational excitations of cytosine by low energy electron impact.

    PubMed

    Michaud, M; Bazin, M; Sanche, L

    2012-09-21

    The absolute cross sections (CSs) for vibrational excitations of cytosine by electron impact between 0.5 and 18 eV were measured by electron-energy loss (EEL) spectroscopy of the molecule deposited at monolayer coverage on an inert Ar substrate. The vibrational energies compare to those that have been reported from IR spectroscopy of cytosine isolated in Ar matrix, IR and Raman spectra of polycrystalline cytosine, and ab initio calculation. The CSs for the various H bending modes at 142 and 160 meV are both rising from their energy threshold up to 1.7 and 2.1 × 10(-17) cm(2) at about 4 eV, respectively, and then decrease moderately while maintaining some intensity at 18 eV. The latter trend is displayed as well for the CS assigned to the NH(2) scissor along with bending of all H at 179 meV. This overall behavior in electron-molecule collision is attributed to direct processes such as the dipole, quadrupole, and polarization contributions, etc. of the interaction of the incident electron with a molecule. The CSs for the ring deformation at 61 meV, the ring deformation with N-H symmetric wag at 77 meV, and the ring deformations with symmetric bending of all H at 119 meV exhibit common enhancement maxima at 1.5, 3.5, and 5.5 eV followed by a broad hump at about 12 eV, which are superimposed on the contribution due to the direct processes. At 3.5 eV, the CS values for the 61-, 77-, and 119-meV modes reach 4.0, 3.0, and 4.5 × 10(-17) cm(2), respectively. The CS for the C-C and C-O stretches at 202 meV, which dominates in the intermediate EEL region, rises sharply until 1.5 eV, reaches its maximum of 5.7 × 10(-17) cm(2) at 3.5 eV and then decreases toward 18 eV. The present vibrational enhancements, correspond to the features found around 1.5 and 4.5 eV in electron transmission spectroscopy (ETS) and those lying within 1.5-2.1 eV, 5.2-6.8 eV, and 9.5-10.9 eV range in dissociative electron attachment (DEA) experiments with cytosine in gas phase. While the ETS features

  8. General Constraints on Cross Sections Deduced from Surrogate Reactions

    SciTech Connect

    Younes, W

    2003-08-14

    Cross sections that cannot be measured in the laboratory, e.g. because the target lifetime is too short, can be inferred indirectly from a different reaction forming the same compound system, but with a more accessible beam/target combination (the ''surrogate-reaction'' technique). The reactions share the same compound system and a common decay mechanism, but they involve different formation processes. Therefore, an implicit constraint is imposed on the inferred cross section deduced from the measured surrogate-reaction data, through the common decay mechanism. In this paper, the mathematical consequences of this implicit constraint are investigated. General formulas are derived from upper and lower bounds on the inferred cross section, estimated from surrogate data in a procedure which does not require any modeling of the common decay process. As an example, the formulas developed here are applied to the case of the {sup 235}U(n,f) cross section, deduced from {sup 234}U(t,pf) surrogate data. The calculated bounds are not very tight in this particular case. However, by introducing a few qualitative assumptions about the physics of the fission process, meaningful bounds on the deduced cross section are obtained. Upper and lower limits for the cross-section ratio of the (n,f) reaction on the {sup 235}U isomer at E{sub x} = 77 eV relative to the (n,f) reaction on the ground state are also calculated. The generalization of this technique to other surrogate reactions is discussed.

  9. Absolute cross sections for the dissociation of hydrogen cluster ions in high-energy collisions with helium atoms

    SciTech Connect

    Eden, S.; Tabet, J.; Samraoui, K.; Louc, S.; Farizon, B.; Farizon, M.; Ouaskit, S.; Maerk, T. D.

    2006-02-15

    Absolute dissociation cross sections are reported for H{sub n}{sup +} clusters of varied mass (n=3,5,...,35) following collisions with He atoms at 60 keV/amu. Initial results have been published previously for a smaller range of cluster sizes [Ouaskit et al., Phys. Rev. A 49, 1484 (1994)]. The present extended study includes further experimental results, reducing the statistical errors associated with the absolute cross sections. The previously suggested quasilinear dependence of the H{sub n}{sup +} dissociation cross sections upon n is developed with reference to expected series of geometrical shells of H{sub 2} molecules surrounding a H{sub 3}{sup +} core. Recent calculations identify n=9 as corresponding to the first closed H{sub 2} shell [e.g., Stich et al., J. Chem. Phys. 107, 9482 (1997)]. Recurrence of the distinct characteristics observed in the dissociation-cross-section dependence upon cluster size around n=9 provides the basis for the presently proposed subsequent closed shells at n=15, 21, 27, and 33, in agreement with the calculations of Nagashima et al. [J. Phys. Chem. 96, 4294 (1992)].

  10. Gold-catalyzed homogeneous oxidative cross-coupling reactions.

    PubMed

    Zhang, Guozhu; Peng, Yu; Cui, Li; Zhang, Liming

    2009-01-01

    Oxidizing gold? A gold(I)/gold(III) catalytic cycle is essential for the first oxidative cross-coupling reaction in gold catalysis. By using Selectfluor for gold(I) oxidation, this chemistry reveals the synthetic potential of incorporating gold(I)/gold(III) catalytic cycles into contemporary gold chemistry and promises a new area of gold research by merging powerful gold catalysis and oxidative metal-catalyzed cross-coupling reactions.

  11. Modelling of reaction cross sections and prompt neutron emission

    NASA Astrophysics Data System (ADS)

    Hambsch, F.-J.; Tudora, A.; Oberstedt, S.

    2010-10-01

    Accurate nuclear data concerning reaction cross sections and the emission of prompt fission neutrons (i.e. multiplicity and spectra) as well as other fission fragment data are of great importance for reactor physics design, especially for the new Generation IV nuclear energy systems. During the past years for several actinides (238U(n, f) and 237Np(n, f)) both the reaction cross sections and prompt neutron multiplicities and spectra have been calculated within the frame of the EFNUDAT project.

  12. Configurationally Stable, Enantioenriched Organometallic Nucleophiles in Stereospecific Pd-Catalyzed Cross-Coupling Reactions: An Alternative Approach to Asymmetric Synthesis

    PubMed Central

    Wang, Chao-Yuan; Derosaa, Joseph

    2015-01-01

    Several research groups have recently developed methods to employ configurationally stable, enantioenriched organometallic nucleophiles in stereospecific Pd-catalyzed cross-coupling reactions. By establishing the absolute configuration of a chiral alkyltin or alkylboron nucleophile prior to its use in cross-coupling reactions, new stereogenic centers may be rapidly and reliably generated with preservation of the known initial stereochemistry. While this area of research is still in its infancy, such stereospecific cross-coupling reactions may emerge as simple, general methods to access diverse, optically active products from common enantioenriched organometallic building blocks. This minireview highlights recent progress towards the development of general, stereospecific Pd-catalyzed cross-coupling reactions using configurationally stable organometallic nucleophiles. PMID:26388985

  13. Absolute elastic differential electron scattering cross sections in the intermediate energy region. III - SF6 and UF6

    NASA Technical Reports Server (NTRS)

    Srivastava, S. K.; Trajmar, S.; Chutjian, A.; Williams, W.

    1976-01-01

    A recently developed technique has been used to measure the ratios of elastic differential electron scattering cross sections (DCS) for SF6 and UF6 to those of He at electron impact energies of 5, 10, 15, 20, 30, 40, 50, 60, and 75 eV and at scattering angles of 20 to 135 deg. In order to obtain the absolute values of DCS from these ratios, He DCS of McConkey and Preston have been employed in the 20 to 90 deg range. At angles in the 90 to 135 deg range the recently determined cross sections of Srivastava and Trajmar have been utilized. From these DCS, elastic integral and momentum transfer cross sections have been obtained.

  14. The recent absolute total np and pp cross section determinations: quality of data description and prediction of experimental observables

    SciTech Connect

    Laptev, Alexander B; Haight, Robert C; Arndt, Richard A; Briscoe, William J; Paris, Mark W; Strakovsky, Igor I; Workman, Ron L

    2010-01-01

    The absolute total cross sections for np and pp scattering below 1000 MeV are determined based on partial-wave analyses (PWAs) of nucleon-nucleon scattering data. These cross sections are compared with the most recent ENDF/B-VII.0 and JENDL-3.3 data files, and the Nijmegen PWA. Systematic deviations from the ENDF/B-VII.0 and JENDL-3.3 evaluations are found to exist in the low-energy region. Comparison of the np evaluation with the result of most recent np total and differential cross section measurements will be discussed. Results of those measurements were not used in the evaluation database. A comparison was done to check a quality of evaluation and its capabilities to predict experimental observables. Excellent agreement was found between the new experimental data and our PWA predictions.

  15. Absolute rate parameters for the reaction of ground state atomic oxygen with carbonyl sulfide

    NASA Technical Reports Server (NTRS)

    Klemm, R. B.; Stief, L. J.

    1974-01-01

    The rate parameters for the reaction of O(3P) with carbonyl sulfide, O(3P) + OCS yields CO + SO, have been determined directly by monitoring O(3P) using the flash photolysis-resonance fluorescence technique. The value for reaction rate was measured over a temperature range of 263-502 K and the data were fitted to an Arrhenius expression with good linearity. A comparison of the present results with those from previous studies of this reaction is also presented.

  16. Metal-tag labeling coupled with multiple reaction monitoring-mass spectrometry for absolute quantitation of proteins.

    PubMed

    Wang, Xueying; Wang, Xin; Qin, Weijie; Lin, Hongjun; Wang, Jifeng; Wei, Junying; Zhang, Yangjun; Qian, Xiaohong

    2013-09-21

    Mass spectrometry-based quantitative proteomics, consisting of relative and absolute parts, has been used to discover and validate proteins with key functions related to physiological and pathological processes. Currently, stable isotope dilution-multiple reaction monitoring-mass spectrometry (SID-MRM-MS) is the most commonly used method for the absolute determination of proteins in a biological sample. A prerequisite for this method is obtaining internal standards with isotope labels. Although many approaches have been developed for the labeling and preparation of internal peptides, expensive stable isotope labeling coupled with SID-MRM-MS has limited the application and development of an absolute quantitative method. Recently, a low-cost strategy using metal-tag labeling and MS has been developed for relative quantification of peptides or proteins. The introduction of labeling using metal tags has the merits of allowing multiple labeling and enlarging the mass shift to overcome the overlap of adjacent isotope clusters. However, most papers described MRM-MS for protein absolute quantification based on the metal in its peptides labelled with metal by inductively coupled plasma mass spectrometry (ICP MS) but not on its peptides labelled with metal. In this work, a novel approach based on metal-tag labeling coupled with MRM-MS was established for the absolute quantification of peptides or proteins. The principle of the method is that a bifunctional chelator, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid bearing an N-hydroxysuccinimide ester (DOTA-NHS ester), is used to modify the N-termini of signature peptides from a target protein, and the modified peptides then chelate a certain metal, such as thulium, to form metal-tagged peptides (Tm-DOTA-P). Internal peptides are chemically synthesized and labeled with another metal, such as terbium (Tb-DOTA-P), as the internal standard. Both the Tb-DOTA- and Tm-DOTA-labeled peptides in samples can be analysed via

  17. Absolute elastic differential electron scattering cross sections in the intermediate energy region. IV - CO

    NASA Technical Reports Server (NTRS)

    Tanaka, H.; Srivastava, S. K.; Chutjian, A.

    1978-01-01

    Using a crossed electron beam-molecular beam scattering geometry and a relative-flow technique, ratios of elastic differential cross sections of CO to those of He have been measured at electron impact energies of 3, 5, 7.5, 9.9, 15, 20, 30, 50, 75, and 100 eV. At each energy, an angular range of 15 to 130 deg has been covered. These ratios have been multiplied by previously known He elastic differential cross sections to obtain elastic differential cross sections for CO. Since pure rotational excitations were not resolved, the elastic differential cross sections are a sum of elastic and pure rotational excitations at room temperature. From a knowledge of differential cross sections (DCS), integral and momentum transfer cross sections have been calculated. Both the DCS and integral cross sections are compared at 50, 75, and 100 eV to a recent two-potential theory of e-molecule scattering. Present results show that the isoelectronic molecules CO and N2 have very similar magnitudes and shapes of their differential cross sections.

  18. Absolute rate constant of the reaction between chlorine /2P/ atoms and hydrogen peroxide from 298 to 424 K

    NASA Technical Reports Server (NTRS)

    Keyser, L. F.

    1980-01-01

    The absolute rate constant of the reaction between chlorine (2P) atoms and hydrogen peroxide was determined from 298 to 424 K, using the discharge flow resonance fluorescence technique. Pseudo-first-order conditions were used with hydrogen peroxide in large excess. A fast flow-sampling procedure limited hydrogen peroxide decomposition to less than 5% over the temperature range studied. At 298 K, the rate constant is (4.1 plus or minus 0.2) x 10 to the minus 13th cu cm/molecule-sec.

  19. The reaction H + C4H2 - Absolute rate constant measurement and implication for atmospheric modeling of Titan

    NASA Technical Reports Server (NTRS)

    Nava, D. F.; Mitchell, M. B.; Stief, L. J.

    1986-01-01

    The absolute rate constant for the reaction H + C4H2 has been measured over the temperature (T) interval 210-423 K, using the technique of flash photolysis-resonance fluorescence. At each of the five temperatures employed, the results were independent of variations in C4H2 concentration, total pressure of Ar or N2, and flash intensity (i.e., the initial H concentration). The rate constant, k, was found to be equal to 1.39 x 10 to the -10th exp (-1184/T) cu cm/s, with an error of one standard deviation. The Arrhenius parameters at the high pressure limit determined here for the H + C4H2 reaction are consistent with those for the corresponding reactions of H with C2H2 and C3H4. Implications of the kinetic carbon chemistry results, particularly those at low temperature, are considered for models of the atmospheric carbon chemistry of Titan. The rate of this reaction, relative to that of the analogous, but slower, reaction of H + C2H2, appears to make H + C4H2 a very feasible reaction pathway for effective conversion of H atoms to molecular hydrogen in the stratosphere of Titan.

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

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

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

  1. Absolute Charge Transfer and Fragmentation Cross Sections in He{sup 2+}-C{sub 60} Collisions

    SciTech Connect

    Rentenier, A.; Moretto-Capelle, P.; Bordenave-Montesquieu, D.; Bordenave-Montesquieu, A.; Ruiz, L. F.; Diaz-Tendero, S.; Alcami, M.; Martin, F.; Zarour, B.; Hanssen, J.; Hervieux, P.-A.; Politis, M. F.

    2008-05-09

    We have determined absolute charge transfer and fragmentation cross sections in He{sup 2+}+C{sub 60} collisions in the impact-energy range 0.1-250 keV by using a combined experimental and theoretical approach. We have found that the cross sections for the formation of He{sup +} and He{sup 0} are comparable in magnitude, which cannot be explained by the sole contribution of pure single and double electron capture but also by contribution of transfer-ionization processes that are important even at low impact energies. The results show that multifragmentation is important only at impact energies larger than 40 keV; at lower energies, sequential C{sub 2} evaporation is the dominant process.

  2. Absolute rate of the reaction of bromine atoms with ozone from 200-360 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Lee, J. H.; Payne, W. A.; Stief, L. J.

    1978-01-01

    The rate constant for the reaction Br + O3 yields BrO + O2 was measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at lambda 165nm.O3 was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3, total pressure and limited variations in flash intensity. The measured rate constants obeyed the Arrhenius expression, where the error quoted is two standard deviations. Results are compared with previous determinations which employed the discharge flow-mass spectrometric technique.

  3. Absolute rate of the reaction of bromine atoms with ozone from 200 to 360 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Lee, J. H.; Payne, W. A.; Stief, L. J.

    1978-01-01

    The rate constant for the reaction Br + O3 yields BrO + O2 has been measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at a wavelength of 165 nm. O3 concentration was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3 concentration, total pressure (Ar), and limited variations in flash intensity (i.e., initial Br concentration). The measured rate constants obey the Arrhenius expression, k = (7.74 plus or minus 0.50) x 10 to the -12th exp(-603 plus or minus 16/T) cu cm/molecule/sec, where the error quoted is two standard deviations.

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

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

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

  5. Cross-ligation and exchange reactions catalyzed by hairpin ribozymes.

    PubMed Central

    Komatsu, Y; Koizumi, M; Sekiguchi, A; Ohtsuka, E

    1993-01-01

    The negative strand of the satellite RNA of tobacco ringspot virus (sTobRV(-)) contains a hairpin catalytic domain that shows self-cleavage and self-ligation activities in the presence of magnesium ions. We describe here that the minimal catalytic domain can catalyze a cross-ligation reaction between two kinds of substrates in trans. The cross-ligated product increased when the reaction temperature was decreased during the reaction from 37 degrees C to 4 degrees C. A two-stranded hairpin ribozyme, divided into two fragments between G45 and U46 in a hairpin loop, showed higher ligation activity than the nondivided ribozyme. The two stranded ribozyme also catalyzed an exchange reaction of the 3'-portion of the cleavage site. Images PMID:8441626

  6. Pd-catalyzed cross-coupling reactions of alkyl halides.

    PubMed

    Kambe, Nobuaki; Iwasaki, Takanori; Terao, Jun

    2011-10-01

    Cross-coupling reactions have become indispensable tools for creating carbon-carbon (or heteroatom) bonds in organic synthesis. Like in other important transition metal catalyzed reactions, such as metathesis, addition, and polymerization, unsaturated compounds are usually employed as substrates for cross-coupling reactions. However during the past decade, a great deal of effort has been devoted to the use of alkyl halides as saturated compounds in cross-coupling reactions, which has resulted in significant progress in this undeveloped area by introducing new effective ligands. Many useful catalytic systems are now available for synthetic transformations based on C(sp(3))-C(sp(3)), C(sp(3))-C(sp(2)) and C(sp(3))-C(sp) bond formation as complementary methods to conventional C(sp(2))-C(sp(2)), C(sp(2))-C(sp) and C(sp)-C(sp) coupling. This tutorial review summarizes recent advances in cross-coupling reactions of alkyl halides and pseudohalides catalyzed by a palladium complex.

  7. Measurement of the absolute vμ-CCQE cross section at the SciBooNE experiment

    SciTech Connect

    Aunion, Jose Luis Alcaraz

    2010-07-01

    This thesis presents the measurement of the charged current quasi-elastic (CCQE) neutrino-nucleon cross section at neutrino energies around 1 GeV. This measurement has two main physical motivations. On one hand, the neutrino-nucleon interactions at few GeV is a region where existing old data are sparse and with low statistics. The current measurement populates low energy regions with higher statistics and precision than previous experiments. On the other hand, the CCQE interaction is the most useful interaction in neutrino oscillation experiments. The CCQE channel is used to measure the initial and final neutrino fluxes in order to determine the neutrino fraction that disappeared. The neutrino oscillation experiments work at low neutrino energies, so precise measurement of CCQE interactions are essential for flux measurements. The main goal of this thesis is to measure the CCQE absolute neutrino cross section from the SciBooNE data. The SciBar Booster Neutrino Experiment (SciBooNE) is a neutrino and anti-neutrino scattering off experiment. The neutrino energy spectrum works at energies around 1 GeV. SciBooNE was running from June 8th 2007 to August 18th 2008. In that period, the experiment collected a total of 2.65 x 1020 protons on target (POT). This thesis has used full data collection in neutrino mode 0.99 x 1020 POT. A CCQE selection cut has been performed, achieving around 70% pure CCQE sample. A fit method has been exclusively developed to determine the absolute CCQE cross section, presenting results in a neutrino energy range from 0.2 to 2 GeV. The results are compatible with the NEUT predictions. The SciBooNE measurement has been compared with both Carbon (MiniBoonE) and deuterium (ANL and BNL) target experiments, showing a good agreement in both cases.

  8. Organoaluminum-mediated direct cross-coupling reactions.

    PubMed

    Minami, Hiroki; Saito, Tatsuo; Wang, Chao; Uchiyama, Masanobu

    2015-04-01

    We present a direct cross-coupling reaction between arylaluminum compounds (ArAlMe2 ⋅LiCl) and organic halides RX (R=aryl, alkenyl, alkynyl; X=I, Br, and Cl) without any external catalyst. The reaction takes place smoothly, simply upon heating, thereby enabling the efficient and chemo-/stereoselective formation of biaryl, alkene, and alkyne coupling products with broad functional group compatibility.

  9. Measurement of the absolute differential cross section of proton–proton elastic scattering at small angles

    DOE PAGES

    Mchedlishvili, D.; Chiladze, D.; Dymov, S.; Bagdasarian, Z.; Barsov, S.; Gebel, R.; Gou, B.; Hartmann, M.; Kacharava, A.; Keshelashvili, I.; et al

    2016-02-03

    The differential cross section for proton-proton elastic scattering has been measured at a beam kinetic energy of 1.0 GeV and in 200 MeV steps from 1.6 to 2.8 GeV for centre-of-mass angles in the range from 12°-16° to 25°-30°, depending on the energy. A precision in the overall normalisation of typically 3% was achieved by studying the energy losses of the circulating beam of the COSY storage ring as it passed repeatedly through the windowless hydrogen target of the ANKE magnetic spectrometer. It is shown that the data have a significant impact upon the results of a partial wave analysis.more » Furthermore, after extrapolating the differential cross sections to the forward direction, the results are broadly compatible with the predictions of forward dispersion relations.« less

  10. Cross sections and reaction rates of relevance to aeronomy

    SciTech Connect

    Fox, J.L. )

    1991-01-01

    Experimental and theoretical data relevant to models and measurements of the chemical and thermal structures and luminosity of the thermospheres of the earth and planets published during the last four years are surveyed. Among chemical processes, attention is given to ion-molecule reactions, dissociative recombination of molecular ions, and reactions between neutral species. Both reactions between ground state species and species in excited states are considered, including energy transfer and quenching. Measured and calculated cross sections for interactions of solar radiation with atmospheric species, such as photoabsorption, photoionization, and photodissociation and related processes are surveyed.

  11. Absolute rate constants for the reaction of atomic hydrogen with ketene from 298 to 500 K

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

    Rate constants for the reaction of atomic hydrogen with ketene have been measured at room temperature by two techniques, flash photolysis-resonance fluorescence and discharge flow-resonance fluorescence. The measured values are (6.19 + or - 1.68) x 10 to the -14th and (7.3 + or - 1.3) x 10 to the -14th cu cm/molecule/s, respectively. In addition, rate constants as a function of temperature have been measured over the range 298-500 K using the FP-RF technique. The results are best represented by the Arrhenius expression k = (1.88 + or - 1.12) x 10 to the -11th exp(-1725 + or - 190/T) cu cm/molecule/s, where the indicated errors are at the two standard deviation level.

  12. A new method for measuring absolute total electron-impact cross sections with forward scattering corrections

    SciTech Connect

    Ma, C.; Liescheski, P.B.; Bonham, R.A. )

    1989-12-01

    In this article we describe an experimental technique to measure the total electron-impact cross section by measurement of the attenuation of an electron beam passing through a gas at constant pressure with the unwanted forward scattering contribution removed. The technique is based on the different spatial propagation properties of scattered and unscattered electrons. The correction is accomplished by measuring the electron beam attenuation dependence on both the target gas pressure (number density) and transmission length. Two extended forms of the Beer--Lambert law which approximately include the contributions for forward scattering and for forward scattering plus multiple scattering from the gas outside the electron beam were developed. It is argued that the dependence of the forward scattering on the path length through the gas is approximately independent of the model used to describe it. The proposed methods were used to determine the total cross section and forward scattering contribution from argon (Ar) with 300-eV electrons. Our results are compared with those in the literature and the predictions of theory and experiment for the forward scattering and multiple scattering contributions. In addition, Monte Carlo simulations were performed as a further test of the method.

  13. Absolute Raman cross-sections of some explosives: Trend to UV

    NASA Astrophysics Data System (ADS)

    Nagli, L.; Gaft, M.; Fleger, Y.; Rosenbluh, M.

    2008-07-01

    The Raman cross-section dependence on excitation energy in spectral range 620-248 nm have been investigated for UN, TATP, RDX, TNT, and PETN explosives. For all investigated explosive materials, significant pre-resonance enhancement in the UV spectral range has been revealed. Normalized Raman scattering signals are 100-200 times stronger with UV excitation at 248 nm compared to visible excitation at 532 nm. Thus the gated Raman technique with UV excitation has significant advantages compared to IR-VIS excitation for the remote detection of explosives. Certain of the observed Raman lines exhibit deviations from classical λ-4 dependence of Raman cross-section and may totally disappear with UV excitation. The possible explanation for this may be that numerous electronic transitions contribute to the molecular polarizability. These contributions could be of opposite sign and lead to partial cancellation of certain transitions. Another possible reason could be that this is a result of the stronger UV absorption that reduces the sampling volume and therefore the number of scatterers that produce the Raman signal.

  14. Decarboxylative Alkyl-Alkyl Cross-Coupling Reactions.

    PubMed

    Konev, Mikhail O; Jarvo, Elizabeth R

    2016-09-12

    Alkyl with alkyl: A significant development in alkyl-alkyl cross-coupling reactions, namely the nickel-catalyzed decarboxylative Negishi coupling of N-hydroxyphthalimide esters, was recently reported by Baran and co-workers. This method enables the synthesis of various highly functionalized compounds, including natural product derivatives.

  15. Organocatalytic and enantioselective Michael reaction between α-nitroesters and nitroalkenes. Syn/anti-selectivity control using catalysts with the same absolute backbone chirality.

    PubMed

    Martínez, Jose I; Uria, Uxue; Muñiz, Maria; Reyes, Efraím; Carrillo, Luisa; Vicario, Jose L

    2015-01-01

    The asymmetric and catalytic Michael reaction between α-nitroesters and nitroalkenes has been studied in the presence of two bifunctional catalysts both containing the same absolute chirality at the carbon backbone. The reaction performed in similar conditions allows us to control the syn or anti selectivity of the Michael adduct obtaining good yields and high enantiocontrol in all cases.

  16. Using DNA origami nanostructures to determine absolute cross sections for UV photon-induced DNA strand breakage.

    PubMed

    Vogel, Stefanie; Rackwitz, Jenny; Schürman, Robin; Prinz, Julia; Milosavljević, Aleksandar R; Réfrégiers, Matthieu; Giuliani, Alexandre; Bald, Ilko

    2015-11-19

    We have characterized ultraviolet (UV) photon-induced DNA strand break processes by determination of absolute cross sections for photoabsorption and for sequence-specific DNA single strand breakage induced by photons in an energy range from 6.50 to 8.94 eV. These represent the lowest-energy photons able to induce DNA strand breaks. Oligonucleotide targets are immobilized on a UV transparent substrate in controlled quantities through attachment to DNA origami templates. Photon-induced dissociation of single DNA strands is visualized and quantified using atomic force microscopy. The obtained quantum yields for strand breakage vary between 0.06 and 0.5, indicating highly efficient DNA strand breakage by UV photons, which is clearly dependent on the photon energy. Above the ionization threshold strand breakage becomes clearly the dominant form of DNA radiation damage, which is then also dependent on the nucleotide sequence.

  17. Absolute vibrational cross sections for 1-19 eV electron scattering from condensed tetrahydrofuran (THF)

    NASA Astrophysics Data System (ADS)

    Lemelin, V.; Bass, A. D.; Cloutier, P.; Sanche, L.

    2016-02-01

    Absolute cross sections (CSs) for vibrational excitation by 1-19 eV electrons impacting on condensed tetrahydrofuran (THF) were measured with a high-resolution electron energy loss spectrometer. Experiments were performed under ultra-high vacuum (3 × 10-11 Torr) at a temperature of about 20 K. The magnitudes of the vibrational CSs lie within the 10-17 cm2 range. Features observed near 4.5, 9.5, and 12.5 eV in the incident energy dependence of the CSs were compared to the results of theoretical calculations and other experiments on gas and solid-phase THF. These three resonances are attributed to the formation of shape or core-excited shape resonances. Another maximum observed around 2.5 eV is not found in the calculations but has been observed in gas-phase studies; it is attributed to the formation of a shape resonance.

  18. New approach to analyzing and evaluating cross sections for partial photoneutron reactions

    SciTech Connect

    Varlamov, V. V. Ishkhanov, B. S.; Orlin, V. N.

    2012-11-15

    The presence of substantial systematic discrepancies between the results of different experiments devoted to determining cross sections for partial photoneutron reactions-first of all, ({gamma}, n), ({gamma}, 2n), and ({gamma}, 3n) reactions-is a strong motivation for studying the reliability and authenticity of these data and for developing methods for taking into account and removing the discrepancies in question. In order to solve the first problem, we introduce objective absolute criteria involving transitional photoneutron-multiplicity functions F{sub 1}, F{sub 2}, F{sub 3}, Horizontal-Ellipsis ; by definition, their values cannot exceed 1.0, 0.5, 0.33, Horizontal-Ellipsis , respectively. With the aim of solving the second problem, we propose a new experimental-theoretical approach. In this approach, reaction cross sections are evaluated by simultaneously employing experimental data on the cross section for the total photoneutron yield, {sigma}{sup expt}({gamma}, xn) = {sigma}{sup expt}({gamma}, n) + 2{sigma}{sup expt}({gamma}, 2n) + 3{sigma}{sup expt}({gamma}, 3n) + Horizontal-Ellipsis , which are free from drawbacks plaguing experimental methods for sorting neutrons in multiplicity, and the results obtained by calculating the functions F{sub theor}{sup 1}, F{sub theor}{sup 2}, F{sub theor}{sup 3}, Horizontal-Ellipsis on the basis of the modern model of photonuclear reactions. The reliability and authenticity of data on the cross sections for ({gamma}, n), ({gamma}, 2n), and ({gamma}, 3n) partial reactions-{sigma}{sup eval}({gamma}, in) = F{sub i}{sup theor}{sigma}{sup expt}({gamma}, xn)-were evaluated for the {sup 90}Zr, {sup 115}In, {sup 112,114,116,117,118,119,120,122,124}Sn, {sup 159}Tb, and {sup 197}Au nuclei.

  19. Recent advances in crossed-beam studies of bimolecular reactions.

    PubMed

    Liu, Kopin

    2006-10-01

    A critical overview of the recent progress in crossed-beam reactive scattering is presented. This review is not intended to be an exhaustive nor a comprehensive one, but rather a critical assessment of what we have been learning about bimolecular reaction dynamics using crossed molecular beams since year 2000. Particular emphasis is placed on the information content encoded in the product angular distribution-the trait of a typical molecular beam scattering experiment-and how the information can help in answering fundamental questions about chemical reactivity. We will start with simple reactions by highlighting a few benchmark three-atom reactions, and then move on progressively to the more complex chemical systems and with more sophisticated types of measurements. Understanding what cause the experimental observations is more than computationally simulating the results. The give and take between experiment and theory in unraveling the physical picture of the underlying dynamics is illustrated throughout this review.

  20. Absolute quantification of mRNA using real-time reverse transcription polymerase chain reaction assays.

    PubMed

    Bustin, S A

    2000-10-01

    The reverse transcription polymerase chain reaction (RT-PCR) is the most sensitive method for the detection of low-abundance mRNA, often obtained from limited tissue samples. However, it is a complex technique, there are substantial problems associated with its true sensitivity, reproducibility and specificity and, as a quantitative method, it suffers from the problems inherent in PCR. The recent introduction of fluorescence-based kinetic RT-PCR procedures significantly simplifies the process of producing reproducible quantification of mRNAs and promises to overcome these limitations. Nevertheless, their successful application depends on a clear understanding of the practical problems, and careful experimental design, application and validation remain essential for accurate quantitative measurements of transcription. This review discusses the technical aspects involved, contrasts conventional and kinetic RT-PCR methods for quantitating gene expression and compares the different kinetic RT-PCR systems. It illustrates the usefulness of these assays by demonstrating the significantly different levels of transcription between individuals of the housekeeping gene family, glyceraldehyde-3-phosphate-dehydrogenase (GAPDH).

  1. Alpha Induced Reaction Cross Section Calculations of Tantalum Nucleus

    NASA Astrophysics Data System (ADS)

    Tel, E.; Ugur, F. A.; Gokce, A. A.

    2013-04-01

    The fusion energy is attractive as an energy source because the fusion will not produce CO2 or SO2 and so fusion will not contribute to environmental problems, such as particulate pollution and excessive CO2 in the atmosphere. The fusion reaction does not produce radioactive nuclides and it is not self-sustaining, as is a fission reaction when a critical mass of fissionable material is assembled. Since the fusion reaction is easily and quickly quenched the primary sources of heat to drive such an accident are heat from radioactive decay and heat from chemical reactions. Both the magnitude and time dependence of the generation of heat from radioactive decay can be controlled by proper selection and design of materials. Tantalum is one of the candidate materials for the first wall of fusion reactors and for component parts of irradiation chambers. Accurate experimental cross-section data of alpha induced reactions on Tantalum are also of great importance for thermonuclear reaction rate determinations since the models used in the study of stellar nucleosynthesis are strongly dependent on these rates (Santos et al. in J Phys G 26:301, 2000). In this study, neutron-production cross sections for target nuclei 181Ta have been investigated up to 100 MeV alpha energy. The excitation functions for (α, xn) reactions (x = 1, 2, 3) have been calculated by pre-equilibrium reaction mechanism. And also neutron emission spectra for 181Ta (α, xn) reactions at 26.8 and 45.2 MeV have been calculated. The mean free path multiplier parameters has been investigated. The pre-equilibrium results have been calculated by using the hybrid model, the geometry dependent hybrid (GDH) model. Calculation results have been also compared with the available measurements in literature.

  2. Absolute Photoionization Cross Section with an Ultra-high Energy Resolution for Ne in the Region of 1s Rydberg States

    SciTech Connect

    Kato, M.; Morishita, Y.; Suzuki, I. H.; Saito, N.; Oura, M.; Yamaoka, H.; Okada, K.; Matsudo, T.; Gejo, T.

    2007-01-19

    The high-resolution absolute photoabsorption cross section with an absolute photon energy scale for Ne in the energy region of 864-872 eV (1s-1np Rydberg states) has been measured using a multi-electrode ionization chamber and monochromatized synchrotron radiation. The natural lifetime width of Ne 1s-13p resonance state has been obtained to be 252 {+-} 5 meV. The Ne+ (1s-1) ionization potential is determined to be 870.16 {+-} 0.04 eV by using the Rydberg formula. These absolute values are supposed to be more reliable than those previously reported.

  3. Absolute hydrogen depth profiling using the resonant 1H(15N, αγ)12C nuclear reaction

    NASA Astrophysics Data System (ADS)

    Reinhardt, Tobias P.; Akhmadaliev, Shavkat; Bemmerer, Daniel; Stöckel, Klaus; Wagner, Louis

    2016-08-01

    Resonant nuclear reactions are a powerful tool for the determination of the amount and profile of hydrogen in thin layers of material. Usually, this tool requires the use of a standard of well-known composition. The present work, by contrast, deals with standard-less hydrogen depth profiling. This approach requires precise nuclear data, e.g. on the widely used 1 H(15 N, αγ)12 C reaction, resonant at 6.4 MeV 15 N beam energy. Here, the strongly anisotropic angular distribution of the emitted γ -rays from this resonance has been re-measured, resolving a previous discrepancy. Coefficients of (0.38 ± 0.04) and (0.80 ± 0.04) have been deduced for the second and fourth order Legendre polynomials, respectively. In addition, the resonance strength has been re-evaluated to (25.0 ± 1.5) eV, 10% higher than previously reported. A simple working formula for the hydrogen concentration is given for cases with known γ -ray detection efficiency. Finally, the absolute approach is illustrated using two examples.

  4. Model-based evaluation of microbial mass fractions: effect of absolute anaerobic reaction time on microbial mass fractions.

    PubMed

    Tunçal, Tolga

    2010-04-14

    Although enhanced biological phosphorus removal processes (EBPR) are popular methods for nutrient control, unstable treatment performances of full-scale systems are still not well understood. In this study, the interaction between electron acceptors present at the start of the anaerobic phase of an EBPR system and the amount of organic acids generated from simple substrate (rbsCOD) was investigated in a full-scale wastewater treatment plant. Quantification of microbial groups including phosphorus-accumulating microorganisms (PAOs), denitrifying PAOs (DPAOs), glycogen-accumulating microorganisms (GAOs) and ordinary heterotrophic microorganisms (OHOs) was based on a modified dynamic model. The intracellular phosphorus content of PAOs was also determined by the execution of mass balances for the biological stages of the plant. The EBPR activities observed in the plant and in batch tests (under idealized conditions) were compared with each other statistically as well. Modelling efforts indicated that the use of absolute anaerobic reaction (eta1) instead of nominal anaerobic reaction time (eta), to estimate the amount of available substrate for PAOs, significantly improved model accuracy. Another interesting result of the study was the differences in EBPR characteristics observed in idealized and real conditions. PMID:20480829

  5. Absolute total electron scattering cross sections for N/sub 2/ between 0. 5 and 50 eV

    SciTech Connect

    Kennerly, R.E.

    1980-06-01

    Absolute total electron scattering cross sections for N/sub 2/ from 0.5 to 50 eV have been measured with an estimated uncertainty of +- 3% using a transmission time-of-flight method previously described. The results are compared to previous experimental results and to recent calculations. The positions of the /sup 2/Pi/sub g/ resonance peaks were determined with much greater accuracy ( +- 15 meV) than in previous transmission measurements. The structure reported by Golden (1966) below the /sup 2/Pi/sub g/ resonance was clearly not present, indicating that, if real, these features are not a property of the N/sub 2/ ground vibronic state. The shape resonance predicted at 11 eV by Dill and Dehmer (1977) was not seen, perhaps because it was too weakly manifested in the total cross section. A weak broad band centered at 25 eV may be interpreted as being due to a sigma/sub u/ shape resonance as predicted by Dehmer, Siegel, Welch, and Dill.

  6. Cross-coupling/cyclization reactions of two different allenic moieties.

    PubMed

    Alcaide, Benito; Almendros, Pedro; Martínez del Campo, Teresa

    2010-05-25

    The allene moiety represents an excellent building block for allene cross-coupling cyclization reactions, affording heterocyclic skeletons in a single step. This strategy is of particular interest when two different allene derivatives are involved in a series of metal-catalyzed cross-coupling heterocyclization processes. This Concept article is focused on the Pd-catalyzed union of two different allenic moieties, with cyclization of at least one of them by intramolecular cyclometalation. These new, versatile, and highly effective transformations are complex multistep processes leading to potential privileged structures that could find wide applications in related medicinal chemistry.

  7. Enhanced Olefin Cross Metathesis Reactions: The Copper Iodide Effect

    PubMed Central

    Voigtritter, Karl; Ghorai, Subir

    2011-01-01

    Copper iodide has been shown to be an effective co-catalyst for the olefin cross metathesis reaction. In particular, it has both a catalyst stabilizing effect due to iodide ion, as well as copper(I)-based phosphine-scavenging properties that apply to use of the Grubbs-2 catalyst. A variety of Michael acceptors and olefinic partners can be cross-coupled under mild conditions in refluxing diethyl ether that avoid chlorinated solvents. This effect has also been applied to chemistry in water at room temperature using the new surfactant TPGS-750-M. PMID:21528868

  8. Easy Absolute Values? Absolutely

    ERIC Educational Resources Information Center

    Taylor, Sharon E.; Mittag, Kathleen Cage

    2015-01-01

    The authors teach a problem-solving course for preservice middle-grades education majors that includes concepts dealing with absolute-value computations, equations, and inequalities. Many of these students like mathematics and plan to teach it, so they are adept at symbolic manipulations. Getting them to think differently about a concept that they…

  9. Crossed-beam studies of the dynamics of radical reactions

    SciTech Connect

    Liu, K.

    1993-12-01

    The objective of this program is to characterize the detailed dynamics of elementary radical reactions and to provide a better understanding of radical reactivity in general. The radical beam is typically generated by a laser photolysis method. After colliding with the reacting molecule in a crossed-beam apparatus, the reaction product state distribution is interrogated by laser spectroscopic techniques. Several radicals of combustion significance, such as O, CH, OH, CN and NCO have been successfully generated and their collisional behavior at the state-to-state integral cross section level of detail has been studied in this manner. During the past year, the detection system has been converted from LIF to REMPI schemes, and the emphasis of this program shifted to investigate the product angular distributions. Both inelastic and reactive processes have been studied.

  10. Amplitude equations for reaction-diffusion systems with cross diffusion

    NASA Astrophysics Data System (ADS)

    Zemskov, Evgeny P.; Vanag, Vladimir K.; Epstein, Irving R.

    2011-09-01

    Using Taylor series expansion, multiscaling, and further expansion in powers of a small parameter, we develop general amplitude equations for two-variable reaction-diffusion systems with cross-diffusion terms in the cases of Hopf and Turing instabilities. We apply this analysis to the Oregonator and Brusselator models and find that inhibitor cross diffusion induced by the activator and activator cross diffusion induced by the inhibitor have opposite effects in the two models as a result of the different structure of their community matrices. Our analysis facilitates finding regions of supercritical and subcritical bifurcations, as well as wave and antiwave domains and domains of turbulent waves in the case of Hopf instability.

  11. Amplitude equations for reaction-diffusion systems with cross diffusion.

    PubMed

    Zemskov, Evgeny P; Vanag, Vladimir K; Epstein, Irving R

    2011-09-01

    Using Taylor series expansion, multiscaling, and further expansion in powers of a small parameter, we develop general amplitude equations for two-variable reaction-diffusion systems with cross-diffusion terms in the cases of Hopf and Turing instabilities. We apply this analysis to the Oregonator and Brusselator models and find that inhibitor cross diffusion induced by the activator and activator cross diffusion induced by the inhibitor have opposite effects in the two models as a result of the different structure of their community matrices. Our analysis facilitates finding regions of supercritical and subcritical bifurcations, as well as wave and antiwave domains and domains of turbulent waves in the case of Hopf instability. PMID:22060484

  12. Crossed molecular beam studies of atmospheric chemical reaction dynamics

    SciTech Connect

    Zhang, Jingsong

    1993-04-01

    The dynamics of several elementary chemical reactions that are important in atmospheric chemistry are investigated. The reactive scattering of ground state chlorine or bromine atoms with ozone molecules and ground state chlorine atoms with nitrogen dioxide molecules is studied using a crossed molecular beams apparatus with a rotatable mass spectrometer detector. The Cl + O{sub 3} {yields} ClO + O{sub 2} reaction has been studied at four collision energies ranging from 6 kcal/mole to 32 kcal/mole. The derived product center-of-mass angular and translational energy distributions show that the reaction has a direct reaction mechanism and that there is a strong repulsion on the exit channel. The ClO product is sideways and forward scattered with respect to the Cl atom, and the translational energy release is large. The Cl atom is most likely to attack the terminal oxygen atom of the ozone molecule. The Br + O{sub 3} {yields} ClO + O{sub 2} reaction has been studied at five collision energies ranging from 5 kcal/mole to 26 kcal/mole. The derived product center-of-mass angular and translational energy distributions are quite similar to those in the Cl + O{sub 3} reaction. The Br + O{sub 3} reaction has a direct reaction mechanism similar to that of the Cl + O{sub 3} reaction. The electronic structure of the ozone molecule seems to play the central role in determining the reaction mechanism in atomic radical reactions with the ozone molecule. The Cl + NO{sub 2} {yields} ClO + NO reaction has been studied at three collision energies ranging from 10.6 kcal/mole to 22.4 kcal/mole. The center-of-mass angular distribution has some forward-backward symmetry, and the product translational energy release is quite large. The reaction proceeds through a short-lived complex whose lifetime is less than one rotational period. The experimental results seem to show that the Cl atom mainly attacks the oxygen atom instead of the nitrogen atom of the NO{sub 2} molecule.

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

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

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

  14. Absolute absorption cross sections of ozone at 300 K, 228 K and 195 K in the wavelength region 185-240 nm

    NASA Technical Reports Server (NTRS)

    Yoshino, K.; Parkinson, W. H.; Freeman, D. E.

    1992-01-01

    An account is given of progress of work on absorption cross section measurements of ozone at 300 K, 228 K and 195 K in the wavelength region 185-240 nm. In this wavelength region, the penetration of solar radiation into the Earth's atmosphere is controlled by O2 and O3. The transmitted radiation is available to dissociate trace species such as halocarbons and nitrous oxide. We have recently measured absolute absorption cross sections of O3 in the wavelength region 240-350 nm (Freeman et al., 1985; Yoshino et al., 1988). We apply these proven techniques to the determination of the absorption cross section of O3 at 300 K, 228 K and 195 K throughout the wavelength region 185-240 nm. A paper titled 'Absolute Absorption Cross Section Measurements of Ozone in the Wavelength Region 185-254 nm and the Temperature Dependence' has been submitted for publication in the Journal of Geophysical Research.

  15. Measurement of Absolute Excitation Cross Sections in Highly-Charged Ions Using Electron Energy Loss and Merged Beams

    NASA Technical Reports Server (NTRS)

    Chutjian, A.; Smith, Steven J.; Lozano, J.

    2002-01-01

    There is increasing emphasis during this decade on understanding energy balance and phenomena observed in high electron temperature plasmas. The UV spectral return from FUSE, the X-ray spectral return from the HETG on Chandra and the LETGS 011 XMM-Newton are just beginning. Line emissions are almost entirely from highly-charged ions (HCIs) of C, N, 0, Ne, Mg, S, Si, Ca, and Fe. The Constellation-X mission will provide X-ray spectroscopy up to photon energies of 0.12 nm (10 keV) where primary line emitters will be HCIs. A variety of atomic parameters are required to model the stellar and solar plasma. These include cross sections for excitation, ionization, charge-exchange, X-ray emission, direct and indirect recombination, lifetimes and branching ratios, and dependences on l, m mixing by external E and B fields. In almost all cases the atomic quantities are calculated, and few comparisons to experiment have been carried out. Collision strengths and Einstein A-values are required to convert the observed spectral intensities to electron temperatures and densities in the stellar plasma. The JPL electron energy-loss and merged beam approach has been used to measure absolute collision strengths in a number of ions, with critical comparison made to the best available theories.

  16. [Interferon alpha antibodies show no cross reactions with typical autoantibodies].

    PubMed

    Görg, S; Klouche, M; Wilhelm, D; Kirchner, H

    1993-04-01

    Patients treated with natural human interferon alpha develop anti-interferon antibodies (IFN-AB) only in very rare cases. By contrast, patients with autoimmune disorders are able to generate high-titered IFN-AB against endogenous interferon alpha. One explanation for the development of auto-IFN-AB could be cross-reactivity with typical autoimmune antigens. We investigated the cross-reactivity of 3 high-titered IgG IFN-AB of female autoimmune patients (aged 32, 36, 74 years; two severe cases of SLE, one case of autoimmune thyroiditis) as well as 25 low-titered natural IgM IFN-AB of healthy blood donors (aged 19-48 years). Typical autoimmune antigens including dsDNA, ENA, as well as natural interferon beta and recombinant interferon gamma are not able to inhibit binding of IFN-AB to interferon alpha in an ELISA test system. Preincubation of sera containing either dsDNA antibodies (dsDNA-AB) (24 patients), thyroid peroxidase (TPO-AB) (9 patients) or thyroglobulin (TG-AB) (12 patients) with interferon alpha resulted in no change in the respective autoantibody titer. These data suggest that there is no cross-reactivity between IFN-alpha-AB and dsDNA-AB, TPO-AB or TG-AB. Thus, an explanation for the occurrence of IFN-AB in autoimmune disorders cannot be found in a cross-reaction between interferon alpha with typical autoimmune antigens.

  17. Iron Cross Reaction Control Flight Simulator - test in hangar

    NASA Technical Reports Server (NTRS)

    1956-01-01

    In the mid-1950s -- after the X-1 had exceeded the speed of sound, the D-558-II had doubled that speed, and the X-2 had flown to a speed of Mach 3.2 (3.2 times the speed of sound) -- the problem of maintaining control of a vehicle at the low dynamic pressures found at high altitudes became real. As the development of larger rocket engines than those used in the X-1, X-2, and D-558-II became a virtual certainty, travel to near-orbital and orbital velocities lay on the horizon. It became natural to investigate alternative means to control an aircraft for low dynamic pressures where aerodynamic controls would be inadequate (even absent for orbital flight outside the atmosphere). Consequently, the High-Speed Flight Station (HSFS--predecessor of the NASA Dryden Flight Research Center) began pioneering work on simulating and then flying with reaction controls in the last years of the National Advisory Committee for Aeronautics (NACA) and the first years of its successor, the National Aeronautics and Space Administration (NASA). The HSFS began a two-phase study. One phase involved a fixed-base effort with an analog computer to solve the equations of motion needed for simulation; the other used a mechanical simulator in which the 'pilot' actually experienced the motions produced by the reaction-control jets. The 'pilot' operated the simulator through a single control stick that -- unusually for the time -- controlled three axes with one device. The stick controlled pitch by fore and aft movements, roll by lateral movements, and yaw through thumb movements. The simulator, shown in the video clip, was known as the 'Iron Cross.' It simulated the X-1B, which was equipped with reaction controls. Although the X-1B flew three missions with reaction controls, it developed fatigue cracks in a propellant tank and had to be retired from flight status. Subsequently, an F-104 equipped with reaction controls flew at relatively low dynamic pressures. Between the simulation studies with

  18. Advanced modeling of reaction cross sections for light nuclei

    SciTech Connect

    Resler, D.A.

    1991-01-01

    The shell model/R-matrix technique of calculating nuclear reaction cross sections for light projectiles incident on light nuclei is discussed, particularly in the application of the technique to thermonuclear reactions. Details are presented on the computational methods for the shell model which display how easily the calculations can be performed. Results of the shell model/R-matrix technique are discussed as are some of the problems encountered in picking an appropriate nucleon-nucleon interaction for the large model spaces which must be used for current problems. The status of our work on developing an effective nucleon-nucleon interaction for use in large-basis shell model calculations is presented. This new interaction is based on a combination of global constraints and microscopic nuclear data. 23 refs., 6 figs., 2 tabs.

  19. Assessment of experimental d-PIGE γ-ray production cross sections for 12C, 14N and 16O and comparison with absolute thick target yields

    NASA Astrophysics Data System (ADS)

    Csedreki, L.; Halász, Z.; Kiss, Á. Z.

    2016-08-01

    Measured differential cross sections for deuteron induced γ-ray emission from the reactions 12C(d,pγ)13C, (Eγ = 3089 keV), 14N(d,pγ)15N (Eγ = 8310 keV) and 16O(d,pγ)17O (Eγ = 871 keV) available in the literature were assessed. In order to cross check the assessed γ-ray production cross section data, thick target γ-yields calculated from the differential cross sections were compared with available measured thick target yields. Recommended differential cross section data for each reaction were deduced for particle induced γ-ray emission (PIGE) applications.

  20. Absolute measurement of the photoionization cross section of atomic hydrogen with a shock tube for the extreme ultraviolet. [for astrophysical applications

    NASA Technical Reports Server (NTRS)

    Palenius, H. P.; Kohl, J. L.; Parkinson, W. H.

    1976-01-01

    The paper reports an experiment which is part of a program to measure the absolute values of the atomic photoionization cross sections of astrophysically abundant elements, particularly in stars and planetary atmospheres. An aerodynamic pressure-driven shock tube constructed from stainless steel with a quadratic cross section was used to measure the photoionization cross section of H I at 19 wavelength points from 910 to 609 A with experimental uncertainties between 7 and 20%. The shock tube was used to produce fully dissociated hydrogen and neon mixtures for the photoabsorption measurements.

  1. Cross-flow electrochemical reactor cells, cross-flow reactors, and use of cross-flow reactors for oxidation reactions

    DOEpatents

    Balachandran, Uthamalingam; Poeppel, Roger B.; Kleefisch, Mark S.; Kobylinski, Thaddeus P.; Udovich, Carl A.

    1994-01-01

    This invention discloses cross-flow electrochemical reactor cells containing oxygen permeable materials which have both electron conductivity and oxygen ion conductivity, cross-flow reactors, and electrochemical processes using cross-flow reactor cells having oxygen permeable monolithic cores to control and facilitate transport of oxygen from an oxygen-containing gas stream to oxidation reactions of organic compounds in another gas stream. These cross-flow electrochemical reactors comprise a hollow ceramic blade positioned across a gas stream flow or a stack of crossed hollow ceramic blades containing a channel or channels for flow of gas streams. Each channel has at least one channel wall disposed between a channel and a portion of an outer surface of the ceramic blade, or a common wall with adjacent blades in a stack comprising a gas-impervious mixed metal oxide material of a perovskite structure having electron conductivity and oxygen ion conductivity. The invention includes reactors comprising first and second zones seprated by gas-impervious mixed metal oxide material material having electron conductivity and oxygen ion conductivity. Prefered gas-impervious materials comprise at least one mixed metal oxide having a perovskite structure or perovskite-like structure. The invention includes, also, oxidation processes controlled by using these electrochemical reactors, and these reactions do not require an external source of electrical potential or any external electric circuit for oxidation to proceed.

  2. Study of Exotic Nuclear Structures via Total Reaction Cross Sections

    NASA Astrophysics Data System (ADS)

    Takechi, Maya

    2009-10-01

    Nuclear radius is one of the most basic physical quantities to study unknown exotic nuclei. A number of radii for unstable nuclei were studied through measurements of interaction cross sections (σI) at high energies, using the Glauber-type calculation (Optical-Limit approximation (OLA) of Glauber theory) to investigate halo and skin structures of exotic nuclei. On the other hand, it was indicated that reaction cross sections (σR) at intermediate energies (from several tens to hundreds of MeV/nucleon) were more sensitive to dilute nucleon density distribution owing to large nucleon-nucleon total cross sections (σNN) compared to high-energy region. Recently, we developed a new method to deduce nucleon density distributions from the energy dependences of σ R, through the precise measurements of σ R for various nuclei and some modifications of Glauber-type calculation. Using this method, we studied nucleon density distributions of light nuclei by measuring σ R for those nuclei at HIMAC (Heavy ion Medical Accelerator in CHIBA), NIRS (National Institute of Radiological Sciences). And very recently, we deduced nuclear radii of neutron-rich Ne isotopes (^28-32Ne) which are in the island-of-inversion region by measuring σI using BigRIPS at RIBF (RI Beam Factory) to study nuclear structures of those isotopes using our method. In this workshop, results of nucleon density distributions obtained at HIMAC and results of the studies of Ne isotopes at RIBF will be introduced and discussed.

  3. Measured Absolute Cross Section of Charge Transfer in H + H2+ at Low Energy: Signature of vi = 2 and Trajectory Effects

    NASA Astrophysics Data System (ADS)

    Strom, R. A.; Bacani, K. G.; Chi, R. M.; Heczko, S. L.; Singh, B. N.; Tobar, J. A.; Vassantachart, A. K.; Andrianarijaona, V. M.; Seely, D. G.; Havener, C. C.

    2015-04-01

    Measurements of absolute cross sections of charge transfer (CT) in H + H2+--> H+ + H2 were conducted at the merged-beam apparatus at Oak Ridge National Laboratory (ORNL) in Oak Ridge, Tennessee, which can reliably create and access collision energies as low as 0.1 eV/u. The measured absolute cross section shows evidence of trajectory effects at low energy. Also, the comparison to state-to-state calculations (PRA 67 022708 (2003) suggests a strong contribution from vi = 2 of the H2+that are produced by the electron cyclotron resonance ion source. The data analysis will be presented here. Research supported by the NASA Solar & Heliospheric Physics Program NNH07ZDA001N, the Office of Fusion Energy Sciences and the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy, the National Science Foundation through Grant No. PHY-1068877.

  4. Calculation of the Reaction Cross Section for Several Actinides

    SciTech Connect

    Hambsch, Franz-Josef; Oberstedt, Stephan; Vladuca, Gheorghita; Tudora, Anabella; Filipescu, Dan

    2005-05-24

    New, self-consistent, neutron-induced reaction cross-section calculations for 235,238U, 237Np, and 231,232,233Pa have been performed. The statistical model code STATIS was extended to take into account the multi-modality of the fission process. The three most dominant fission modes, the two asymmetric standard I (S1) and standard II (S2) modes, and the symmetric superlong (SL) mode have been taken into account. De-convoluted fission cross sections for these modes in 235,238U(n,f) and 237Np(n,f) based on experimental branching ratios, were calculated for the first time up to the second chance fission threshold. For 235U(n,f) and 233Pa(n,f), the calculations being made up to 50 MeV and 20 MeV incident neutron energy, respectively, higher fission chances have been considered. This implied the need for additional calculations for the neighbouring isotopes.As a side product also mass yield distributions could be calculated at energies hitherto not accessible by experiment. Experimental validation of the predictions is being envisaged.

  5. Absolute cascade-free cross-sections for the 2S to 2P transition in Zn(+) using electron-energy-loss and merged-beams methods

    NASA Technical Reports Server (NTRS)

    Smith, Steven J.; Man, K.-F.; Chutjian, A.; Mawhorter, R. J.; Williams, I. D.

    1991-01-01

    Absolute cascade-free excitation cross-sections in an ion have been measured for the resonance 2S to 2P transition in Zn(+) using electron-energy-loss and merged electron-ion beams methods. Measurements were carried out at electron energies of below threshold to 6 times threshold. Comparisons are made with 2-, 5-, and 15-state close-coupling and distorted-wave theories. There is good agreement between experiment and the 15-state close-coupling cross-sections over the energy range of the calculations.

  6. OH reaction rate constants and UV absorption cross-sections of unsaturated esters

    NASA Astrophysics Data System (ADS)

    Teruel, M. A.; Lane, S. I.; Mellouki, A.; Solignac, G.; Le Bras, G.

    Absolute rate coefficients have been determined for the gas-phase reactions of hydroxyl radicals with methyl acrylate ( k1), methyl methacrylate ( k2) and ethyl acrylate ( k3). Experiments were performed using two different techniques, the relative rate method and the pulsed laser photolysis-laser induced fluorescence technique. The kinetic data obtained were used to derive the following Arrhenius expressions in the temperature range 253-374 K (in units of cm 3 molecule -1 s -1): k1=(2.0±0.8)×10exp[(553±51)/T], k2=(2.5±0.8)×10exp[(821±55)/T], k3=(2.3±0.8)×10exp[(580±65)/T]. At 298 K, the reaction rate constants obtained by the two methods were in good agreement. In addition, the UV absorption spectra for the three unsaturated esters have been determined at (298±2) K and the absorption cross-sections in the wavelength region 215-298 nm were reported. The results are presented, discussed and used to estimate the atmospheric lifetimes for the studied esters.

  7. Prospective Teachers' Reactions to "Right-or-Wrong" Tasks: The Case of Derivatives of Absolute Value Functions

    ERIC Educational Resources Information Center

    Tsamir, Pessia; Rasslan, Shaker; Dreyfus, Tommy

    2006-01-01

    This paper illustrates the role of a "Thinking-about-Derivatives" task in identifying learners' derivative conceptions and for promoting their critical thinking about derivatives of absolute value functions. The task included three parts: "Define" the derivative of a function f(x) at x = x[subscript 0], "Solve-if-Possible" the derivative of f(x) =…

  8. STUDY OF THE REACTION DYNAMICS OF Li + HF, HCl BY THE CROSSED MOLECULAR BEAMS METHOD

    SciTech Connect

    Becker, Christopher H.; Casavecchia, Piergiorgio; Tiedemann, Peter W.; Valentini, James J.; Lee, Yuan T.

    1980-05-01

    }) are evaluated by integrating the product distributions in the c.m. frame and using small angle nonreactive scattering of Li as an absolute calibrant. Values of {sigma}{sub R} are: for LiF formation {sigma}{sub R} ~ 0.8 {Angstrom}{sup 2} and 0.94 {Angstrom}{sup 2} at E{sub c} = 3 and 8.7 kcal/mole, while for LiCl formation {sigma}{sub R} = 27 {Angstrom}{sup 2} and 42 {Angstrom}{sup 2} at E{sub c} = 2.9 and 9.2 kcal/mole, with estimated absolute and relative uncertainties of a factor of 2, and 30%, respectively. Average opacities for reaction have been estimated from the reaction cross sections and the extent of rotational excitation of products to be about 0.1 for reaction (I) and 1 for reaction (II), for L values allowed to react. These results are discussed in some detail with regard to the kinematic constraints, reaction dynamics and potential energy surfaces for these two reactions, and related experimental and theoretical work are noted. In addition, angular distributions of nonreactive scattering of Li off HF and HCl are measured at 4 different E{sub c} each. Rainbow structure is observed at low E{sub c} and the angular distributions are fit by a spherically symmetric piecewise analytic potential. The resulting values of the potential's well depth ({epsilon}) and minimum position (r{sub m} ) are: for Li + HF {epsilon} = 0.46 kcal/mole and r{sub m} = 4.34 {Angstrom} and for Li + HCl {epsilon} = 0.32 kcal/mole and r{sub m} = 4.7 {Angstrom}. These results differ significantly from some earlier estimates based on the measurements of integral scattering cross sections.

  9. Silicon-based cross-coupling reaction: an environmentally benign version.

    PubMed

    Nakao, Yoshiaki; Hiyama, Tamejiro

    2011-10-01

    Much attention has been paid to the cross-coupling reaction of organosilicon compounds due to their stability, non-toxicity, and natural abundance of silicon. In addition, the silicon-based cross-coupling has many advantages over other cross-coupling protocols. Successful examples of the silicon-based cross-coupling reaction are reviewed, focusing especially on the advances made in the last decade. Having had a number of highly effective palladium catalysts developed mainly for other cross-coupling reactions, the development of the silicon-based protocol owes heavily to the design of organosilicon reagents which effectively undergo transmetalation, a key elemental step of the silicon-based cross-coupling reaction. This tutorial review thus classifies various organosilicon reagents depending on substituents on silicon and surveys their cross-coupling reactions with various electrophiles.

  10. Modeled Neutron Induced Nuclear Reaction Cross Sections for Radiochemistry in the region of Iriduim and Gold

    SciTech Connect

    Hoffman, R D; Dietrich, F S; Kelley, K; Escher, J; Bauer, R; Mustafa, M

    2008-02-26

    We have developed a set of modeled nuclear reaction cross sections for use in radiochemical diagnostics. Systematics for the input parameters required by the Hauser-Feshbach statistical model were developed and used to calculate neutron induced nuclear reaction cross sections for targets ranging from osmium (Z = 76) to gold (Z = 79). Of particular interest are the cross sections on Ir and Au including reactions on isomeric targets.

  11. Glauber model for {alpha}-nucleus total reaction cross section

    SciTech Connect

    Chauhan, Deeksha; Khan, Z. A.

    2009-11-15

    The Coulomb-modified Glauber model is employed to calculate the total reaction cross section ({sigma}{sub R}) for {alpha} particles from {sup 9}Be, {sup 12}C, {sup 16}O, {sup 28}Si, {sup 40}Ca, {sup 58,60}Ni, {sup 112,116,120,124}Sn, and {sup 208}Pb at 117.2, 163.9, and 192.4 MeV and from the lighter nuclei also at 69.6 MeV. Our main focus in this work is to assess the suitability of semiphenomenological parametrization of the NN amplitude (SPNN), used recently [Deeksha Chauhan and Z. A. Khan, Eur. Phys. J. A 41, 179 (2009)], in the analysis of {sigma}{sub R} at the energies under consideration. Using the realistic form factors for the colliding nuclei, it is found that the SPNN works reasonably well and we have quite a satisfactory account of the {sigma}{sub R} data in all the cases. Moreover, our analysis suggests that the SPNN could be taken as fairly stable to describe simultaneously the elastic angular distribution and the {sigma}{sub R} for a wide range of target nuclei in the relatively low-energy region.

  12. Absolute vibrational excitation cross sections for slow-electron (1-18 eV) scattering in solid H2O

    NASA Astrophysics Data System (ADS)

    Michaud, M.; Sanche, L.

    1987-11-01

    High-resolution vibrational electron-energy-loss spectra of amorphous ice films condensed at 14 K are reported for the incident-energy range 1-18 eV. Absolute electron scattering cross sections for elastic collisions, individual vibrational excitations, and the sum of electronic transitions are obtained by performing a two-stream multiple-scattering analysis of the spectra. The various features found in the energy-dependent cross sections are discussed, whenever possible, by comparison with data and mechanisms (e.g., transient anion formation) well established in the gas phase. Quantum-interference effects introduced implicitly in the cross sections by the classical analysis are discussed within the first Born approximation for electron-multiple-site scattering.

  13. Absolute rate of the reaction of Cl(p-2) with molecular hydrogen from 200 - 500 K

    NASA Technical Reports Server (NTRS)

    Whytock, D. A.; Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

    1976-01-01

    Rate constants for the reaction of atomic chlorine with hydrogen are measured from 200 - 500 K using the flash photolysis-resonance fluorescence technique. The results are compared with previous work and are discussed with particular reference to the equilibrium constant for the reaction and to relative rate data for chlorine atom reactions. Theoretical calculations, using the BEBO method with tunneling, give excellent agreement with experiment.

  14. Tracing multiple scattering patterns in absolute (e,2e) cross sections for H{sub 2} and He over a 4{pi} solid angle

    SciTech Connect

    Ren, X.; Senftleben, A.; Pflueger, T.; Dorn, A.; Ullrich, J.; Colgan, J.; Pindzola, M. S.; Al-Hagan, O.; Madison, D. H.; Bray, I.; Fursa, D. V.

    2010-09-15

    Absolutely normalized (e,2e) measurements for H{sub 2} and He covering the full solid angle of one ejected electron are presented for 16 eV sum energy of both final state continuum electrons. For both targets rich cross-section structures in addition to the binary and recoil lobes are identified and studied as a function of the fixed electron's emission angle and the energy sharing among both electrons. For H{sub 2} their behavior is consistent with multiple scattering of the projectile as discussed before [Al-Hagan et al., Nature Phys. 5, 59 (2009)]. For He the binary and recoil lobes are significantly larger than for H{sub 2} and partly cover the multiple scattering structures. To highlight these patterns we propose a alternative representation of the triply differential cross section. Nonperturbative calculations are in good agreement with the He results and show discrepancies for H{sub 2} in the recoil peak region. For H{sub 2} a perturbative approach reasonably reproduces the cross-section shape but deviates in absolute magnitude.

  15. Benchmark experiment for electron-impact ionization of argon: Absolute triple-differential cross sections via three-dimensional electron emission images

    SciTech Connect

    Ren Xueguang; Senftleben, Arne; Pflueger, Thomas; Dorn, Alexander; Ullrich, Joachim; Bartschat, Klaus

    2011-05-15

    Single ionization of argon by 195-eV electron impact is studied in an experiment, where the absolute triple-differential cross sections are presented as three-dimensional electron emission images for a series of kinematic conditions. Thereby a comprehensive set of experimental data for electron-impact ionization of a many-electron system is produced to provide a benchmark for comparison with theoretical predictions. Theoretical models using a hybrid first-order and second-order distorted-wave Born plus R-matrix approach are employed to compare their predictions with the experimental data. While the relative shape of the calculated cross section is generally in reasonable agreement with experiment, the magnitude appears to be the most significant problem with the theoretical treatment for the conditions studied in the present work. This suggests that the most significant challenge in the further development of theory for this process may lie in the reproduction of the absolute scale rather than the angular dependence of the cross section.

  16. A comparison of total reaction cross section models used in particle and heavy ion transport codes

    NASA Astrophysics Data System (ADS)

    Sihver, Lembit; Lantz, M.; Takechi, M.; Kohama, A.; Ferrari, A.; Cerutti, F.; Sato, T.

    To be able to calculate the nucleon-nucleus and nucleus-nucleus total reaction cross sections with precision is very important for studies of basic nuclear properties, e.g. nuclear structure. This is also of importance for particle and heavy ion transport calculations because, in all particle and heavy ion transport codes, the probability function that a projectile particle will collide within a certain distance x in the matter depends on the total reaction cross sections. Furthermore, the total reaction cross sections will also scale the calculated partial fragmentation cross sections. It is therefore crucial that accurate total reaction cross section models are used in the transport calculations. In this paper, different models for calculating nucleon-nucleus and nucleus-nucleus total reaction cross sections are compared and discussed.

  17. Dissociative recombination of CH{sub 5}{sup +} and CD{sub 5}{sup +}: Measurement of the product branching fractions and the absolute cross sections, and the breakup dynamics in the CH{sub 3}+H+H product channel

    SciTech Connect

    Kaminska, Magdalena; Zhaunerchyk, Vitali; Vigren, Erik; Danielsson, Mathias; Hamberg, Mathias; Geppert, Wolf D.; Larsson, Mats; Rosen, Stefan; Thomas, Richard D.; Semaniak, Jacek

    2010-06-15

    The dissociative recombination (DR) of CH{sub 5}{sup +} and CD{sub 5}{sup +} has been studied at the heavy-ion storage ring CRYRING. The fragmentation dynamics of the dominant reaction channel CH{sub 3}+H+H has been investigated using an imaging detector. The results indicate that a two-step process via the production of a CH{sub 4} intermediate, which has sufficient energy to fragment further to CH{sub 3}+H, may play an important role. Discrepancies between the present and earlier results obtained from storage ring measurements with those from flowing afterglow experiments are addressed. Newly measured branching fractions in the DR of CD{sub 5}{sup +} show an excellent agreement with branching fractions previously measured for CH{sub 5}{sup +}, and the absolute DR cross sections have been also measured over an interaction energy range between {approx}0 and 0.1 eV for both isotopologs.

  18. Absolute partial electron impact ionization cross sections of Xe from threshold up to 180 eV

    SciTech Connect

    Stephan, K.; Maerk, T.D.

    1984-10-01

    Partial electron ionization cross section ratios and functions of Xe were determined in the low energy regime (< or =180 eV) using a refined mass spectrometric technique. The experimental results are compared with previous measurements and calculations.

  19. Solid-state track recorder dosimetry device to measure absolute reaction rates and neutron fluence as a function of time

    DOEpatents

    Gold, Raymond; Roberts, James H.

    1989-01-01

    A solid state track recording type dosimeter is disclosed to measure the time dependence of the absolute fission rates of nuclides or neutron fluence over a period of time. In a primary species an inner recording drum is rotatably contained within an exterior housing drum that defines a series of collimating slit apertures overlying windows defined in the stationary drum through which radiation can enter. Film type solid state track recorders are positioned circumferentially about the surface of the internal recording drum to record such radiation or its secondary products during relative rotation of the two elements. In another species both the recording element and the aperture element assume the configuration of adjacent disks. Based on slit size of apertures and relative rotational velocity of the inner drum, radiation parameters within a test area may be measured as a function of time and spectra deduced therefrom.

  20. Absolute fragmentation cross sections in atom-molecule collisions: Scaling laws for non-statistical fragmentation of polycyclic aromatic hydrocarbon molecules

    SciTech Connect

    Chen, T.; Gatchell, M.; Stockett, M. H.; Alexander, J. D.; Schmidt, H. T.; Cederquist, H.; Zettergren, H.; Zhang, Y.; Rousseau, P.; Maclot, S.; Delaunay, R.; Adoui, L.; Domaracka, A.; Huber, B. A.

    2014-06-14

    We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH{sup +}) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections (including statistical fragmentation) for 110 eV PAH/PAH{sup +} + He collisions, and show that they compare well with experimental results. We demonstrate that non-statistical fragmentation becomes dominant for large PAHs and that it yields highly reactive fragments forming strong covalent bonds with atoms (H and N) and molecules (C{sub 6}H{sub 5}). Thus nonstatistical fragmentation may be an effective initial step in the formation of, e.g., Polycyclic Aromatic Nitrogen Heterocycles (PANHs). This relates to recent discussions on the evolution of PAHNs in space and the reactivities of defect graphene structures.

  1. Absolute cross sections for near-threshold electron-impact excitation of the 2s 2S-->2p 2P transition in C3+

    NASA Astrophysics Data System (ADS)

    Bannister, M. E.; Chung, Y.-S.; Djurić, N.; Wallbank, B.; Woitke, O.; Zhou, S.; Dunn, G. H.; Smith, A. C.

    1998-01-01

    Absolute total cross sections for electron-impact excitation of the 2s 2S-->2p 2P transition in C3+ were measured from 7.35 eV to 8.45 eV using the merged electron-ion-beams energy-loss technique. The results settle the discrepancy between two previous experiments using the crossed-beams fluorescence method, being in very good agreement with the older results [P. O. Taylor, D. Gregory, G. H. Dunn, R. A. Phaneuf, and D. H. Crandall, Phys. Rev. Lett. 39, 1256 (1977)] but less so with the more recent ones [D. W. Savin, L. D. Gardner, D. B. Reisenfeld, A. R. Young, and J. L. Kohl, Phys. Rev. A 51, 2162 (1995)]. The present measurements are also in good agreement with unitarized Coulomb-Born and close-coupling calculations.

  2. Secondary alkyl halides in transition-metal-catalyzed cross-coupling reactions.

    PubMed

    Rudolph, Alena; Lautens, Mark

    2009-01-01

    Enormous effort has gone into the development of metal-catalyzed cross-coupling reactions with alkyl halides as electrophilic coupling partners. Whereas a wide array of primary alkyl halides can now be used effectively in cross-coupling reactions, the synthetic potential of secondary alkyl halides is just beginning to be revealed. This Minireview summarizes selected examples of the use of secondary alkyl halides as electrophiles in cross-coupling reactions. Emphasis is placed on the transition metals employed, the mechanistic pathways involved, and implications in terms of the stereochemical outcome of reactions.

  3. A Macroscopic Reaction: Direct Covalent Bond Formation between Materials Using a Suzuki-Miyaura Cross-Coupling Reaction

    PubMed Central

    Sekine, Tomoko; Kakuta, Takahiro; Nakamura, Takashi; Kobayashi, Yuichiro; Takashima, Yoshinori; Harada, Akira

    2014-01-01

    Cross-coupling reactions are important to form C–C covalent bonds using metal catalysts. Although many different cross-coupling reactions have been developed and applied to synthesize complex molecules or polymers (macromolecules), if cross-coupling reactions are realized in the macroscopic real world, the scope of materials should be dramatically broadened. Here, Suzuki-Miyaura coupling reactions are realized between macroscopic objects. When acrylamide gel modified with an iodophenyl group (I-gel) reacts with a gel possessing a phenylboronic group (PB-gel) using a palladium catalyst, the gels bond to form a single object. This concept can also be adapted for bonding between soft and hard materials. I-gel or PB-gel selectively bonds to the glass substrates whose surfaces are modified with an electrophile or nucleophile, respectively. PMID:25231557

  4. Dynamics of alkali ions-neutral molecules reactions: Radio frequency-guided beam experimental cross-sections and direct quasiclassical trajectory studies

    SciTech Connect

    Aguilar, J.; Andres, J. de; Lucas, J. M.; Alberti, M.; Huarte-Larranaga, F.; Bassi, D.; Aguilar, A.

    2012-11-27

    Different reactive processes taking place in collisions between alkali ions and neutral i-C{sub 3}H{sub 7}Cl molecules in the low (center of mass frame) energy range have been studied using an octopole radiofrequency guided-ion-beam apparatus developed in our laboratory. Cross-section energy dependences for all these reactions have been obtained in absolute units. Ab initio electronic structure calculations for those colliding systems evolving on the ground single potential surface have given relevant information on the main topological features of the surfaces. For some of the reactions a dynamic study by 'on the fly' trajectories has complemented the available experimental and electronic structure information.

  5. A novel double-focusing time-of-flight mass spectrometer for absolute recoil ion cross sections measurements.

    PubMed

    Sigaud, L; de Jesus, V L B; Ferreira, Natalia; Montenegro, E C

    2016-08-01

    In this work, the inclusion of an Einzel-like lens inside the time-of-flight drift tube of a standard mass spectrometer coupled to a gas cell-to study ionization of atoms and molecules by electron impact-is described. Both this lens and a conical collimator are responsible for further focalization of the ions and charged molecular fragments inside the spectrometer, allowing a much better resolution at the time-of-flight spectra, leading to a separation of a single mass-to-charge unit up to 100 a.m.u. The procedure to obtain the overall absolute efficiency of the spectrometer and micro-channel plate detector is also discussed. PMID:27587105

  6. A novel double-focusing time-of-flight mass spectrometer for absolute recoil ion cross sections measurements.

    PubMed

    Sigaud, L; de Jesus, V L B; Ferreira, Natalia; Montenegro, E C

    2016-08-01

    In this work, the inclusion of an Einzel-like lens inside the time-of-flight drift tube of a standard mass spectrometer coupled to a gas cell-to study ionization of atoms and molecules by electron impact-is described. Both this lens and a conical collimator are responsible for further focalization of the ions and charged molecular fragments inside the spectrometer, allowing a much better resolution at the time-of-flight spectra, leading to a separation of a single mass-to-charge unit up to 100 a.m.u. The procedure to obtain the overall absolute efficiency of the spectrometer and micro-channel plate detector is also discussed.

  7. A novel double-focusing time-of-flight mass spectrometer for absolute recoil ion cross sections measurements

    NASA Astrophysics Data System (ADS)

    Sigaud, L.; de Jesus, V. L. B.; Ferreira, Natalia; Montenegro, E. C.

    2016-08-01

    In this work, the inclusion of an Einzel-like lens inside the time-of-flight drift tube of a standard mass spectrometer coupled to a gas cell—to study ionization of atoms and molecules by electron impact—is described. Both this lens and a conical collimator are responsible for further focalization of the ions and charged molecular fragments inside the spectrometer, allowing a much better resolution at the time-of-flight spectra, leading to a separation of a single mass-to-charge unit up to 100 a.m.u. The procedure to obtain the overall absolute efficiency of the spectrometer and micro-channel plate detector is also discussed.

  8. Absolute rate of the reaction of O/3-P/ with hydrogen sulfide over the temperature range 263 to 495 K

    NASA Technical Reports Server (NTRS)

    Whytock, D. A.; Timmons, R. B.; Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

    1976-01-01

    The technique of flash photolysis coupled with time resolved detection of O via resonance fluorescence has been used to obtain rate constants for the reaction of O(3-P) with H2S at temperatures from 263 to 495 K and at pressures in the range 10-400 torr. Under conditions where secondary reactions are avoided, the measured rate constants for the primary step obey the Arrhenius equation k = (7.24 plus or minus 1.07) x 10 to the -12th exp(-3300 plus or minus 100/1.987 T) cu cm/molecules/s. Experiments with D2S show that the reaction exhibits a primary isotope effect, in support of a hydrogen abstraction mechanism.

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

    NASA Technical Reports Server (NTRS)

    Brunning, J.; Stief, L. J.

    1985-01-01

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

  10. Nonadiabatic calculations of ultraviolet absorption cross section of sulfur monoxide: Isotopic effects on the photodissociation reaction

    SciTech Connect

    Danielache, Sebastian O.; Tomoya, Suzuki; Nanbu, Shinkoh; Kondorsky, Alexey; Tokue, Ikuo

    2014-01-28

    Ultraviolet absorption cross sections of the main and substituted sulfur monoxide (SO) isotopologues were calculated using R-Matrix expansion technique. Energies, transition dipole moments, and nonadiabatic coupling matrix elements were calculated at MRCI/AV6Z level. The calculated absorption cross section of {sup 32}S{sup 16}O was compared with experimental spectrum; the spectral feature and the absolute value of photoabsorption cross sections are in good agreement. Our calculation predicts a long lived photoexcited SO* species which causes large non-mass dependent isotopic effects depending on the excitation energy in the ultraviolet region.

  11. Cu-catalyzed cross-coupling reactions of epoxides with organoboron compounds.

    PubMed

    Lu, Xiao-Yu; Yang, Chu-Ting; Liu, Jing-Hui; Zhang, Zheng-Qi; Lu, Xi; Lou, Xin; Xiao, Bin; Fu, Yao

    2015-02-11

    A copper-catalyzed cross-coupling reaction of epoxides with arylboronates is described. This reaction is not limited to aromatic epoxides, because aliphatic epoxides are also suitable substrates. In addition, N-sulfonyl aziridines can be successfully converted into the products. This reaction provides convenient access to β-phenethyl alcohols, which are valuable synthetic intermediates. PMID:25564373

  12. Absorption and scattering of light by Pt, Pd, Ag, and Au nanodisks: absolute cross sections and branching ratios.

    PubMed

    Langhammer, Christoph; Kasemo, Bengt; Zorić, Igor

    2007-05-21

    Localized surface plasmons (LSPs) of metallic nanoparticles decay either radiatively or via an electron-hole pair cascade. In this work, the authors have experimentally and theoretically explored the branching ratio of the radiative and nonradiative LSP decay channels for nanodisks of Ag, Au, Pt, and Pd, with diameters D ranging from 38 to 530 nm and height h=20 nm, supported on a fused silica substrate. The branching ratio for the two plasmon decay channels was obtained by measuring the absorption and scattering cross sections as a function of photon energy. The former was obtained from measured extinction and scattering coefficients, using an integrating sphere detector combined with particle density measurements obtained from scanning electron microscopy images of the nanoparticles. Partly angle-resolved measurements of the scattered light allowed the authors to clearly identify contributions from dipolar and higher plasmonic modes to the extinction, scattering, and absorption cross sections. Based on these experiments they find that absorption dominates the total scattering cross section in all the examined cases for small metallic nanodisks (D<100 nm). For D>100 nm absorption still dominates for Pt and Pd nanodisks, while scattering dominates for Au and Ag. A theoretical approach, where the metal disks are approximated as oblate spheroids, is used to account for the trends in the measured cross sections. The field problem is solved in the electrostatic limit. The spheroid is treated as an induced dipole for which the dipolar polarizability is calculated based on spheroid geometry and the (bulk) dielectric response function of the metal the spheroid consists of and the dielectric medium surrounding it. One might expect this model to be inappropriate for disks with D>100 nm since effects due to the retardation of the incoming field across the metallic nanodisk and contributions from higher plasmonic modes are neglected. However, this model describes quite well

  13. Absolute rate of the reaction of atomic hydrogen with ethylene from 198 to 320 K at high pressure

    NASA Technical Reports Server (NTRS)

    Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

    1978-01-01

    The rate constant for the H+C2H4 reaction has been measured as a function of temperature. Experiments were performed with high pressures of Ar heat bath gas at seven temperatures from 198 to 320 K with the flash photolysis-resonance fluorescence (FP-RF) technique. Pressures were chosen so as to isolate the addition rate constant k1. The results are well represented by an Arrhenius expression. The results are compared with other studies and are theoretically discussed.

  14. Total and partial cross sections of the 112Sn(α ,γ ) 116Te reaction measured via in-beam γ -ray spectroscopy

    NASA Astrophysics Data System (ADS)

    Netterdon, L.; Mayer, J.; Scholz, P.; Zilges, A.

    2015-03-01

    Background: The nucleosynthesis of the neutron-deficient p nuclei remains an open question in nuclear astrophysics. Beside uncertainties on the astrophysical side, the nuclear-physics input parameters entering Hauser-Feshbach calculations for the nucleosynthesis of the p nuclei must be put on a firm basis. Purpose: An extended database of experimental data is needed to address uncertainties of the nuclear-physics input parameters for Hauser-Feshbach calculations. Especially α + nucleus optical model potentials at low energies are not well known. The in-beam technique with an array of high-purity germanium (HPGe) detectors was successfully applied to the measurement of absolute cross sections of an (α ,γ ) reaction on a heavy nucleus at sub-Coulomb energies. Method: The total and partial cross-section values were measured by means of in-beam γ -ray spectroscopy. For this purpose, the absolute reaction yield was measured using the HPGe detector array HORUS at the FN tandem accelerator at the University of Cologne. Total and partial cross sections were measured at four different α -particle energies from Eα=10.5 MeV to Eα=12 MeV . Results: The measured total cross-section values are in excellent agreement with previous results obtained with the activation technique, which proves the validity of the applied method. With the present measurement, the discrepancy between two older data sets is removed. The experimental data was compared to Hauser-Feshbach calculations using the nuclear reaction code talys. With a modification of the semi-microscopic α + nucleus optical model potential OMP 3, the measured cross-section values are reproduced well. Moreover, partial cross sections could be measured for the first time for an (α ,γ ) reaction. Conclusions: A modified version of the semimicroscopic α + nucleus optical model potential OMP3, as well as modified proton and γ widths, are needed in order to obtain a good agreement between experimental data and theory. It

  15. Adult Reactions to Children's Cross-Gender Verbal Behavior.

    ERIC Educational Resources Information Center

    Bell, Nancy J.

    1981-01-01

    Reactions of 82 elementary school teachers and 107 college students were obtained to a tape of a child's voice labeled male or female, exhibiting stereotypically masculine or feminine verbal behavior. (Author/CM)

  16. An improved method for absolute quantification of mRNA using multiplex polymerase chain reaction: determination of renin and angiotensinogen mRNA levels in various tissues.

    PubMed

    Dostal, D E; Rothblum, K N; Baker, K M

    1994-12-01

    We have developed a multiplex, competitive, reverse-transcriptase polymerase chain reaction (RT-PCR) method which measures absolute levels of renin, angiotensinogen, and the housekeeping transcript elongation factor-1 alpha (EF-1 alpha) mRNA. Sample RNA was simultaneously titrated with serial dilutions of renin, angiotensinogen, and EF-1 alpha competitor RNAs which flanked the endogenous concentrations of target transcripts. The samples were coreverse transcribed in the presence of random primers and resulting first-strand cDNA was coamplified for 10-15 cycles with [32P]-dCTP and primers for renin angiotensinogen, after which EF-1 alpha primers were added. Amplified DNA was separated by electrophoresis on polyacrylamide gel and radioactivity in the bands was quantified by direct radioanalytical scanning. Three conditions were necessary to obtain absolute quantification of renin and angiotensinogen mRNA levels: (a) exogenous competitor RNA was used to control for tube-to-tube variability in the efficiencies of reverse transcription and amplification; (b) Sample RNA was titrated with flanking concentrations of competitor RNA to correct for intraassay differences in the efficiency of amplification due to concentration differences between competitor and target templates; and (c) a housekeeping transcript EF-1 alpha was used to control for tube-to-tube differences in RNA loading and/or degradation. We show that the multiplex RT-PCR method is precise and accurate over approximately three logs of transcript concentration and sensitive to less than 5 and 0.5 fg for renin and angiotensinogen mRNA, respectively. This method will be useful for absolute quantification of target mRNAs, especially when the amount of sample RNA is limited or unknown and/or the gene expression is low. PMID:7887470

  17. Measurement of Absolute Excitation Cross Sections in Highly-Charged Ions Using Electron Energy Loss and Merged Beams

    NASA Astrophysics Data System (ADS)

    Chutjian, A.; Smith, Steven J.; Lozano, J. A.

    2002-11-01

    There is increasing emphasis within this decade on understanding energy balance and new phenomena observed in high electron temperature plasmas. The UV spectral return from FUSE, and the X-ray spectral return from the HETG on Chandra and the LETGS on XMM-Newton are just beginning. The line emissions are almost entirely from highly-charged ions (HCIs) of C, N, O, Ne, Mg, S, Si, Ca, and Fe. In addition, the Constellation-X mission, currently in the planning stages, will provide high-throughput X-ray spectroscopy up to photon energies of 0.12 nm (10 keV), where the primary line emitters will again be the HCIs. This array of space instruments is providing an overwhelming return of HCI spectral data from a variety of astrophysical objects. Collision strengths and Einstein A-values are required to convert the observed spectral intensities to electron temperatures and densities in the stellar plasma [1]. The JPL electron energy-loss and merged-beams approach [2] has been used to measure absolute collision strengths in a number of ions, with critical comparisons to the best available theories. Experimental methods will be reviewed, and results presented on experimental comparisons to R-Matrix and Breit-Pauli theoretical results in C3+[3], O2+[4], O5+[5], S2+[6], and Fe9+ [7]. Work is planned for comparisons in Mgq+, and higher charge states Fe(10-15)+. J. Lozano thanks the National Research Council for a fellowship though the NASA- NRC program. This work was carried out at the Jet Propulsion Laboratory, California Institute of Technology, and was supported under contract with the National Aeronautics and Space Administration.

  18. Mechanistic insights into nickamine-catalyzed alkyl-alkyl cross-coupling reactions.

    PubMed

    Breitenfeld, Jan; Hu, Xile

    2014-01-01

    Within the last decades the transition metal-catalyzed cross-coupling of non-activated alkyl halides has significantly progressed. Within the context of alkyl-alkyl cross-coupling, first row transition metals spanning from iron, over cobalt, nickel, to copper have been successfully applied to catalyze this difficult reaction. The mechanistic understanding of these reactions is still in its infancy. Herein we outline our latest mechanistic studies that explain the efficiency of nickel, in particular nickamine-catalyzed alkyl-alkyl cross-coupling reactions.

  19. Tables of Nuclear Cross Sections and Reaction Rates: AN Addendum to the Paper ``ASTROPHYSICAL Reaction Rates from Statistical Model Calculations'' ()

    NASA Astrophysics Data System (ADS)

    Rauscher, Thomas; Thielemann, Friedrich-Karl

    2001-09-01

    In a previous publication (ATOMIC DATAAND NUCLEAR DATA TABLES75, 1 (2000)), we gave seven-parameter analytical fits to theoretical reaction rates derived from nuclear cross sections calculated in the statistical model (Hauser-Feshbach formalism) for targets with 10<=Z<=83 (Ne to Bi) and for a mass range reaching the neutron and proton driplines. Reactions considered were (n,γ), (n,p), (n,α), (p,γ), (p,α), (α,γ), and their inverse reactions. Here, we present the theoretical nuclear cross sections and astrophysical reaction rates from which those rate fits were derived, and we provide these data as on-line electronic files. Corresponding to the fitted rates, two complete data sets are provided, one of which includes a phenomenological treatment of shell quenching for neutron-rich nuclei.

  20. Comprehensive panel of real-time TaqMan polymerase chain reaction assays for detection and absolute quantification of filoviruses, arenaviruses, and New World hantaviruses.

    PubMed

    Trombley, Adrienne R; Wachter, Leslie; Garrison, Jeffrey; Buckley-Beason, Valerie A; Jahrling, Jordan; Hensley, Lisa E; Schoepp, Randal J; Norwood, David A; Goba, Augustine; Fair, Joseph N; Kulesh, David A

    2010-05-01

    Viral hemorrhagic fever is caused by a diverse group of single-stranded, negative-sense or positive-sense RNA viruses belonging to the families Filoviridae (Ebola and Marburg), Arenaviridae (Lassa, Junin, Machupo, Sabia, and Guanarito), and Bunyaviridae (hantavirus). Disease characteristics in these families mark each with the potential to be used as a biological threat agent. Because other diseases have similar clinical symptoms, specific laboratory diagnostic tests are necessary to provide the differential diagnosis during outbreaks and for instituting acceptable quarantine procedures. We designed 48 TaqMan-based polymerase chain reaction (PCR) assays for specific and absolute quantitative detection of multiple hemorrhagic fever viruses. Forty-six assays were determined to be virus-specific, and two were designated as pan assays for Marburg virus. The limit of detection for the assays ranged from 10 to 0.001 plaque-forming units (PFU)/PCR. Although these real-time hemorrhagic fever virus assays are qualitative (presence of target), they are also quantitative (measure a single DNA/RNA target sequence in an unknown sample and express the final results as an absolute value (e.g., viral load, PFUs, or copies/mL) on the basis of concentration of standard samples and can be used in viral load, vaccine, and antiviral drug studies.

  1. Total reaction cross sections in CEM and MCNP6 at intermediate energies

    SciTech Connect

    Kerby, Leslie M.; Mashnik, Stepan G.

    2015-05-14

    Accurate total reaction cross section models are important to achieving reliable predictions from spallation and transport codes. The latest version of the Cascade Exciton Model (CEM) as incorporated in the code CEM03.03, and the Monte Carlo N-Particle transport code (MCNP6), both developed at Los Alamos National Laboratory (LANL), each use such cross sections. Having accurate total reaction cross section models in the intermediate energy region (50 MeV to 5 GeV) is very important for different applications, including analysis of space environments, use in medical physics, and accelerator design, to name just a few. The current inverse cross sections used in the preequilibrium and evaporation stages of CEM are based on the Dostrovsky et al. model, published in 1959. Better cross section models are now available. Implementing better cross section models in CEM and MCNP6 should yield improved predictions for particle spectra and total production cross sections, among other results.

  2. Fe-Catalyzed Cross-Dehydrogenative Coupling Reactions.

    PubMed

    Lv, Leiyang; Li, Zhiping

    2016-08-01

    Cross-dehydrogenative coupling (CDC), which enables the formation of carbon-carbon (C-C) and C-heteroatom bonds from the direct coupling of two C-H bonds or C-H/X-H bonds, represents a new state of the art in the field of organic chemistry. Iron, a prominent metal, has already shown its versatile application in chemical synthesis. This review attempts to provide a comprehensive understanding of the evolution of cross-dehydrogenative coupling via iron catalysis, as well as its application in synthetic chemistry. PMID:27573390

  3. Absolute rate constant of the reaction OH + H2O2 yields HO2 + H2O from 245 to 423 K

    NASA Technical Reports Server (NTRS)

    Keyser, L. F.

    1980-01-01

    The absolute rate constant of the reaction between the hydroxyl radical and hydrogen peroxide was measured by using the discharge-flow resonance fluorescence technique at total pressure between 1 and 4 torr. At 298 K the result is (1.64 + or - 0.32) x 10 to the -12th cu cm/molecule s. The observed rate constant is independent of pressure, surface-to-volume ratio, the addition of vibrational quenchers, and the source of OH. The temperature dependence has also been determined between 245 and 423 K; the resulting Arrhenius expression is k cu cm/molecule s is equal to (2.51 + or - 0.6) x 10 to the -12th exp(-126 + or - 76/T).

  4. Studies on serological cross-reaction in sequential flavivirus infections.

    PubMed

    Makino, Y; Tadano, M; Saito, M; Maneekarn, N; Sittisombut, N; Sirisanthana, V; Poneprasert, B; Fukunaga, T

    1994-01-01

    Acute- and convalescent-phase sera from patients with dengue (DEN) hemorrhagic fever (DHF) and Japanese encephalitis (JE) that contained pre-existing flavivirus antibodies were tested for cross-reacting antibodies to DEN, JE and yellow fever (YF) viruses by a neutralization (N) test. A fourfold or greater rise in N antibody titer in the convalescent-phase was considered significant. Of 39 DHF cases, obtained at Chiang Mai University Hospital, Thailand, 15 (38.5%) showed a rise in DEN antibody titer, while another 15 (38.5%) showed a significant rise in both DEN and JE N antibody titers. On the other hand, eight (61.5%) of 13 JE cases obtained at the same Hospital, showed a significant rise in JE antibody titer, while two (15.4%) showed a significant rise in both DEN and JE antibody titers. Sucrose gradient centrifugation and fractionation of these two cross-reactive JE sera revealed that IgM class antibody was specific for JE, while IgG class antibody was cross-reactive. Of three JE cases with pre-existing YF antibody obtained in Okinawa, Japan, two showed a significant rise in YF and JE antibodies. Both IgM and IgG class antibodies to YF virus were elevated. These results indicate that the cross-reactivity among flaviviruses in different subgroups (complexes), was observed quite often, even by the N test, in sequential flavivirus infection.

  5. Partial gamma-ray cross section measurements in 109Ag(n, x n y p gamma) reactions

    SciTech Connect

    Fotiadis, Nikolaos; Devlin, Matthew James; Nelson, Ronald Owen; Carroll, James

    2015-06-02

    We report on absolute partial cross sections for production of discrete γ-rays using 109Ag(n, xnypγ) reactions with x ≤ 7 and y ≤ 1 in a total of 12 reaction channels. The data were taken using the GEANIE spectrometer comprised of 20 high-purity Ge detectors with 20 BGO escape-suppression shields. The broad-spectrum pulsed neutron beam of the Los Alamos Neutron Science Center’s (LANSCE) WNR facility provided neutrons in the energy range from 0.2 to 300 MeV. The time-of- flight technique was used to determine the incident neutron energies. Partial γ-ray cross sections have been measured for a total of 109 transitions and for neutron energies 0.8 MeV< En<300 MeV. An estimate of the population of isomers in the (n, n'), (n, 2n) and (n, 3n) channels was made.

  6. Actinide cross sections from the reaction of sup 13 C with sup 254 Es sup g

    SciTech Connect

    Moody, K.J.; Lougheed, R.W.; Dougan, R.J.; Hulet, E.K.; Wild, J.F.; Summerer, K.; Hahn, R.L.; Aarle, J.v.; Bethune, G.R. )

    1990-01-01

    We have measured cross sections for the formation of actinide transfer products in the reaction of 72-MeV {sup 13}C projectiles with {sup 254}Es{sup {ital g}} targets. The pattern of nuclide yields is similar to those observed in the reactions of heavier ions with {sup 254}Es{sup {ital g}}. We have constructed the primary element yields from these results and show that the total cross section for transfer reactions is 58 mb. The total reaction cross section is about 300 mb. Lawrencium isotopes are formed with larger cross sections than are consistent with the trends of the transfer-product distributions; we explain this in terms of massive transfer, and model the lawrencium yields with an evaporation code.

  7. Thiyl radical reaction with thymine: absolute rate constant for hydrogen abstraction and comparison to benzylic C-H bonds.

    PubMed

    Nauser, Thomas; Schöneich, Christian

    2003-09-01

    Free radical damage of DNA is a well-known process affecting biological tissue under conditions of oxidative stress. Thiols can repair DNA-derived radicals. However, the product thiyl radicals may also cause biological damage. To obtain quantitative information on the potential reactivity with DNA components, we measured the rate constant for hydrogen abstraction by cysteamine thiyl radicals from thymine C5-CH(3), k = (1.2 +/- 0.8) x 10(4) M(-1) s(-1), and thymidine-5'-monophosphate, k = (0.9 +/- 0.6) x 10(4) M(-1) s(-1). Hence, the hydrogen abstraction from C5-CH(3) occurs with rate constants similar to the hydrogen abstraction from the carbohydrate moieties. Especially at low oxygen concentration such as that found in skeletal muscle, such hydrogen abstraction processes by thiyl radicals may well compete against other dioxygen-dependent reactions. The rate constants for hydrogen abstraction at thymine C5-CH(3) were compared to those with benzylic substrates, toluenesulfonic acid, and benzyl alcohol.

  8. Kinetics of reaction of peroxynitrite with selenium- and sulfur-containing compounds: Absolute rate constants and assessment of biological significance.

    PubMed

    Storkey, Corin; Pattison, David I; Ignasiak, Marta T; Schiesser, Carl H; Davies, Michael J

    2015-12-01

    Peroxynitrite (the physiological mixture of ONOOH and its anion, ONOO(-)) is a powerful biologically-relevant oxidant capable of oxidizing and damaging a range of important targets including sulfides, thiols, lipids, proteins, carbohydrates and nucleic acids. Excessive production of peroxynitrite is associated with several human pathologies including cardiovascular disease, ischemic-reperfusion injury, circulatory shock, inflammation and neurodegeneration. This study demonstrates that low-molecular-mass selenols (RSeH), selenides (RSeR') and to a lesser extent diselenides (RSeSeR') react with peroxynitrite with high rate constants. Low molecular mass selenols react particularly rapidly with peroxynitrite, with second order rate constants k2 in the range 5.1 × 10(5)-1.9 × 10(6)M(-1)s(-1), and 250-830 fold faster than the corresponding thiols (RSH) and many other endogenous biological targets. Reactions of peroxynitrite with selenides, including selenosugars are approximately 15-fold faster than their sulfur homologs with k2 approximately 2.5 × 10(3)M(-1)s(-1). The rate constants for diselenides and sulfides were slower with k2 0.72-1.3 × 10(3)M(-1)s(-1) and approximately 2.1 × 10(2)M(-1)s(-1) respectively. These studies demonstrate that both endogenous and exogenous selenium-containing compounds may modulate peroxynitrite-mediated damage at sites of acute and chronic inflammation, with this being of particular relevance at extracellular sites where the thiol pool is limited.

  9. Recyclable polystyrene-supported siloxane-transfer agent for palladium-catalyzed cross-coupling reactions.

    PubMed

    Nguyen, Minh H; Smith, Amos B

    2014-04-01

    The rational design, synthesis, and validation of a significantly improved insoluble polymer-supported siloxane-transfer agent has been achieved that permits efficient palladium-catalyzed cross-coupling reactions. The cross-linked polystyrene support facilitates product purification with excellent siloxane recycling. Drawbacks of a previous polymer-supported siloxane-transfer agent, relating to reaction efficiency and polymer stability after repeated cycles, have been addressed.

  10. Advances in metal-catalyzed cross-coupling reactions of halogenated quinazolinones and their quinazoline derivatives.

    PubMed

    Mphahlele, Malose Jack; Maluleka, Marole Maria

    2014-10-29

    Halogenated quinazolinones and quinazolines are versatile synthetic intermediates for the metal-catalyzed carbon-carbon bond formation reactions such as the Kumada, Stille, Negishi, Sonogashira, Suzuki-Miyaura and Heck cross-coupling reactions or carbon-heteroatom bond formation via the Buchwald-Hartwig cross-coupling to yield novel polysubstituted derivatives. This review presents an overview of the application of these methods on halogenated quinazolin-4-ones and their quinazolines to generate novel polysubstituted derivatives.

  11. Heavy actinide cross sections in the /sup 238/U + /sup 248/Cm reaction

    SciTech Connect

    Kratz, J V; Bruechle, W; Gaeggeler, H

    1981-01-01

    Cross sections for the production of Cf, Es, Fm, and Md isotopes in the reactions of 7.4 MeV/u /sup 238/U-ions with /sup 248/Cm targets are presented and discussed. Cross sections for the formation of heavy actinides in the reactions of 7.5 MeV/u /sup 136/Xe and /sup 238/U-projectiles with /sup 238/U-targets are presented for comparison. (WHK)

  12. Recyclable Polystyrene-Supported Siloxane-Transfer Agent for Palladium-Catalyzed Cross-Coupling Reactions

    PubMed Central

    2015-01-01

    The rational design, synthesis, and validation of a significantly improved insoluble polymer-supported siloxane-transfer agent has been achieved that permits efficient palladium-catalyzed cross-coupling reactions. The cross-linked polystyrene support facilitates product purification with excellent siloxane recycling. Drawbacks of a previous polymer-supported siloxane-transfer agent, relating to reaction efficiency and polymer stability after repeated cycles, have been addressed. PMID:24661113

  13. Energy and Mass-Number Dependence of Hadron-Nucleus Total Reaction Cross Sections

    NASA Astrophysics Data System (ADS)

    Kohama, Akihisa; Iida, Kei; Oyamatsu, Kazuhiro

    2016-09-01

    We thoroughly investigate how proton-nucleus total reaction cross sections depend on the target mass number A and the proton incident energy. In doing so, we systematically analyze nuclear reaction data that are sensitive to nuclear size, namely, proton-nucleus total reaction cross sections and differential elastic cross sections, using a phenomenological black-sphere approximation of nuclei that we are developing. In this framework, the radius of the black sphere is found to be a useful length scale that simultaneously accounts for the observed proton-nucleus total reaction cross section and first diffraction peak in the proton elastic differential cross section. This framework, which is shown here to be applicable to antiprotons, is expected to be applicable to any kind of projectile that is strongly attenuated in the nucleus. On the basis of a cross-section formula constructed within this framework, we find that a less familiar A1/6 dependence plays a crucial role in describing the energy dependence of proton-nucleus total reaction cross sections.

  14. Computation of charged current neutrino-Te reactions cross sections

    NASA Astrophysics Data System (ADS)

    Tsakstara, V.; Kosmas, T. S.; Sinatkas, J.

    2016-08-01

    Neutrino-nucleus reactions, involving both neutral current (NC) and charged current (CC) interactions are important probes in modern neutrino physics searches. In the present work, we study the concrete CC reactions 130 Te(vℓ,ℓ-)130 I and 130 Te(ṽℓ,ℓ+)130Sb which are of current experimental interest for the CUORE and COBRA experiments operating at Gran Sasso underground laboratory in Italy. The nuclear wave functions for the required initial and final nuclear states are derived by employing the proton-neutron (p-n) quasi-particle random phase approximation (QRPA) which has been previously tested in our neutral-current v-nucleus studies for Te isotopes.

  15. Computation of charged current neutrino-Te reactions cross sections

    NASA Astrophysics Data System (ADS)

    Tsakstara, V.; Kosmas, T. S.; Sinatkas, J.

    2016-08-01

    Neutrino-nucleus reactions, involving both neutral current (NC) and charged current (CC) interactions are important probes in modern neutrino physics searches. In the present work, we study the concrete CC reactions 130 Te(vℓ,ℓ‑)130 I and 130 Te(ṽℓ,ℓ+)130Sb which are of current experimental interest for the CUORE and COBRA experiments operating at Gran Sasso underground laboratory in Italy. The nuclear wave functions for the required initial and final nuclear states are derived by employing the proton-neutron (p-n) quasi-particle random phase approximation (QRPA) which has been previously tested in our neutral-current v-nucleus studies for Te isotopes.

  16. Semiclassical calculations of observable cross sections in breakup reactions

    SciTech Connect

    Marta, H. D.; Canto, L. F.; Donangelo, R.

    2008-09-15

    We develop a semiclassical procedure to calculate breakup reaction products' angular and energy distributions in the laboratory frame of reference. The effects of the Coulomb and nuclear interaction potentials on the classical trajectories, as well as bound-bound, bound-continuum, and continuum-continuum couplings, are included. As an example we consider the {sup 8}B+{sup 58}Ni system at E{sub lab}=26 MeV and find very good agreement with the available experimental data.

  17. Serological cross-reactions between toxoplasma and hammondia.

    PubMed

    Weiland, G; Rommel, M; von Seyerl, F

    1979-07-01

    Toxoplasma and Hammondia infected mice, dogs, rabbits, and pigs were tested for Toxoplasma antibodies by means of 5 serological methods. All Toxoplasma infected animals showed Toxoplasma-specific antibodies. Only sera of Hammondia infected mice and dogs showed positive serological reactions with Toxoplasma antigen in the SFT, CFT, and ELISA. IFAT and IHA, however, proved to be Toxoplasma-specific. The influence of Hammondia infections on the Toxoplasma serology is discussed.

  18. Polymer-supported siloxane transfer agents for Pd-catalyzed cross-coupling reactions.

    PubMed

    Nguyen, Minh H; Smith, Amos B

    2013-08-16

    The design, synthesis, and validation of a ring-opening metathesis polymerization (ROMP) polymer supporting siloxane transfer agents have been achieved that permit efficient palladium-catalyzed cross-coupling reactions. The solubility properties of the polymer facilitate not only product purification but also polymer recycling without significant loss of cross-coupling activity.

  19. A Multigroup Reaction Cross-Section Collapsing Code and Library of 154-Group Fission-Product Cross Sections.

    1983-03-23

    Version 01/02 The code reads multigroup cross sections from a compatible data file and collapses user-selected reaction cross sections to any few-group structure using one of a variety of user neutron flux spectrum options given below: Option Flux description 1 Built-in function including Maxwellian, fission, fusion and slowing-down regions and requiring user-specified parameters and energy-region boundaries. 2 Set of log-log flux-energy interpolation points read from input cross-section data file. 3 Set of log-log flux-energy interpolationmore » points read from user-supplied card input. 4 - 6 Histogram flux values read from user-supplied card input in arbitrary group structure in units of flux-per unit-energy, flux-per-unit lethargy, or integral group flux. LAFPX-E may be used to collapse any set of multigroup reaction cross sections furnished in the required format. However, the code was developed for, and is furnished with, a library of 154-group fission-product cross sections processed from ENDF/B-IV with a typical light water reactor (LWR) flux spectrum and temperature. Four-group radiative capture cross sections produced for LWR calculations are tabulated in the code documentation and are incorporated in the EPRI-CINDER data library, RSIC Code Package CCC-309.« less

  20. Absolute cross sections and branching ratios for the radiative decay of doubly excited helium determined by photon-induced fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Mickat, S.; Schartner, K.-H.; Kammer, Sv; Schill, R.; Werner, L.; Klumpp, S.; Ehresmann, A.; Schmoranzer, H.; Sukhorukov, V. L.

    2005-08-01

    The decay of doubly excited helium states below the N = 2 threshold, cascading radiatively over three steps, were investigated using the photon-induced fluorescence spectroscopy (PIFS) at BESSY II. Absolute cross sections as the product of the resonance excitation cross section of the doubly excited states and their fluorescence rate to decay into the singly excited 1sms(1S) and 1smd(1D) states were measured. The experiments showed that the (sp,2n+)(1P) states decay predominantly into the 1sns(1S) states, whereas the (pd,2n)(1P) states prefer to decay into the 1snd(1D) states. For the (sp,2n-)(1P) states with n = 4, 5 and 6 we observed a broad and complex decay pattern. In addition the angular distribution of the fluorescence radiation was measured. The results are in good agreement with theoretical predictions. Furthermore, the weakening of the LS coupling scheme and the mixing between singlet and triplet states in helium was confirmed by observation of the 1s6d(3D0,1,2) → 1s2p(3P0,1,2) transition on a doubly excited singlet state.

  1. Ionic liquid acceleration of solid-phase suzuki-miyaura cross-coupling reactions.

    PubMed

    Revell, Jefferson D; Ganesan, A

    2002-09-01

    [reaction: see text] Room-temperature ionic liquids promote various transition metal-catalyzed reactions in the solution phase. Here, for the first time, we show that these effects are translatable to solid-phase reactions. The Suzuki-Miyaura cross-coupling of 4-iodophenol immobilized on polystyrene-Wang resin with various arylboronic acids was significantly accelerated by the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)(-)]).

  2. Carbon-carbon cross coupling reactions in ionic liquids catalysed by palladium metal nanoparticles.

    PubMed

    Prechtl, Martin H G; Scholten, Jackson D; Dupont, Jairton

    2010-05-12

    A brief summary of selected pioneering and mechanistic contributions in the field of carbon-carbon cross-coupling reactions with palladium nanoparticles (Pd-NPs) in ionic liquids (ILs) is presented. Five exemplary model systems using the Pd-NPs/ILs approach are presented: Heck, Suzuki, Stille, Sonogashira and Ullmann reactions which all have in common the use of ionic liquids as reaction media and the use of palladium nanoparticles as reservoir for the catalytically active palladium species.

  3. Capture cross sections for the near symmetric {sup 124}Sn+{sup 96}Zr reaction

    SciTech Connect

    Vinodkumar, A. M.; Loveland, W.; Sprunger, P. H.; Peterson, D.; Liang, J. F.; Shapira, D.; Varner, R. L.; Gross, C. J.; Kolata, J. J.

    2006-12-15

    Capture-fission cross sections were measured for the near symmetric reaction between the massive nuclei {sup 124}Sn and {sup 96}Zr for center of mass energies from 195 to 265 MeV. Coincident fission fragments were detected and separated from elastic and deep inelastic scattering products by angle/energy/mass conditions. The measured capture cross sections agree quite well with calculations using the dinuclear system (DNS) model. The DNS model also predicts the fusion cross section for this reaction with a fusion barrier height of 208.0 MeV. The deduced extra push energy, corresponding to this barrier height, differs from that deduced from evaporation residue measurements.

  4. Production Cross Sections for Synthesis of Nuclides with Z = 118 IN Large Mass Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Wang, Nan; Jin, Xin; Yang, Shuang; Zhao, En-Guang

    The production cross sections for the synthesis of superheavy nuclei with charge number 118 are studied with the di-nuclear system model with dynamical potential surface (DNS-DyPES model). The dynamical potential energy surface (PES) and the fusion probabilities for 48Ca bombarding Cf nuclei reactions are studied. By multiplying the capture cross section, fusion probability and survival probability, the evaporation residue(ER) cross sections for superheavy nuclei with Z = 118 are obtained. And the excitation functions for the reactions with a mixture target of Cf isotopes are also shown.

  5. Catalysts for cross-coupling reactions with non-activated alkyl halides.

    PubMed

    Frisch, Anja C; Beller, Matthias

    2005-01-21

    Despite the problems inherent to metal-catalyzed cross-coupling reactions with alkyl halides, these reactions have become increasingly important during the last few years. Detailed mechanistic investigations have led to a variety of novel procedures for the selective cross-coupling of non-activated alkyl halides bearing beta hydrogen atoms with a variety of organometallic nucleophiles under mild reaction conditions. This Minireview highlights selected examples of metal-catalyzed coupling methods and is intended to encourage chemists to exploit the potential of these approaches in organic synthesis.

  6. Silicon-based cross-coupling reactions in the total synthesis of natural products.

    PubMed

    Denmark, Scott E; Liu, Jack H-C

    2010-04-12

    Unlike other variants of transition-metal-catalyzed cross-coupling reactions, those based on organosilicon donors have not been used extensively in natural product synthesis. However, recent advances such as: 1) the development of mild reaction conditions, 2) the expansion of substrate scope, 3) the development of methods to stereoselectively and efficiently introduce the silicon-containing moiety, 4) the development of a large number of sequential processes, and 5) the advent of bifunctional bis(silyl) linchpin reagents, signify the coming of age of silicon-based cross-coupling reactions. The following case studies illustrate how silicon-based cross-coupling reactions play a strategic role in constructing carbon-carbon bonds in selected target molecules.

  7. Radiative thermal neutron-capture cross sections for the 180W(n ,γ ) reaction and determination of the neutron-separation energy

    NASA Astrophysics Data System (ADS)

    Hurst, A. M.; Firestone, R. B.; Szentmiklósi, L.; Sleaford, B. W.; Basunia, M. S.; Belgya, T.; Escher, J. E.; Krtička, M.; Révay, Zs.; Summers, N. C.

    2015-09-01

    Prompt thermal neutron-capture partial γ -ray production cross sections were measured for the first time for the 180W(n ,γ ) reaction using a cold guided-neutron beam at the Budapest Research Reactor. Absolute 181Wγ -ray cross sections were internally standardized using well-known comparator γ -ray cross sections belonging to the other tungsten isotopes present in the 11.35% enriched 180W sample. Transitions were assigned to levels in 181W based largely upon information available in the literature. The total radiative thermal neutron-capture cross section σ0 was determined from the sum of direct prompt γ -ray cross sections populating the ground state and a modeled contribution accounting for ground-state feeding from the quasicontinuum. In this work, we find σ0=21.67 (77 ) b. A new measurement of the cross section for the 5 /2- metastable isomer at 365.6 keV, σ5 /2-(181Wm,14.6 μ s ) =19.96 (55 ) b, is also determined. Additionally, primary γ rays, observed for the first time in the 180W(n ,γ ) reaction, provide the most precise determination for the 181W neutron-separation energy, Sn=6669.02 (16 ) keV.

  8. Cross-diffusion-driven instability for reaction-diffusion systems: analysis and simulations.

    PubMed

    Madzvamuse, Anotida; Ndakwo, Hussaini S; Barreira, Raquel

    2015-03-01

    By introducing linear cross-diffusion for a two-component reaction-diffusion system with activator-depleted reaction kinetics (Gierer and Meinhardt, Kybernetik 12:30-39, 1972; Prigogine and Lefever, J Chem Phys 48:1695-1700, 1968; Schnakenberg, J Theor Biol 81:389-400, 1979), we derive cross-diffusion-driven instability conditions and show that they are a generalisation of the classical diffusion-driven instability conditions in the absence of cross-diffusion. Our most revealing result is that, in contrast to the classical reaction-diffusion systems without cross-diffusion, it is no longer necessary to enforce that one of the species diffuse much faster than the other. Furthermore, it is no longer necessary to have an activator-inhibitor mechanism as premises for pattern formation, activator-activator, inhibitor-inhibitor reaction kinetics as well as short-range inhibition and long-range activation all have the potential of giving rise to cross-diffusion-driven instability. To support our theoretical findings, we compute cross-diffusion induced parameter spaces and demonstrate similarities and differences to those obtained using standard reaction-diffusion theory. Finite element numerical simulations on planary square domains are presented to back-up theoretical predictions. For the numerical simulations presented, we choose parameter values from and outside the classical Turing diffusively-driven instability space; outside, these are chosen to belong to cross-diffusively-driven instability parameter spaces. Our numerical experiments validate our theoretical predictions that parameter spaces induced by cross-diffusion in both the [Formula: see text] and [Formula: see text] components of the reaction-diffusion system are substantially larger and different from those without cross-diffusion. Furthermore, the parameter spaces without cross-diffusion are sub-spaces of the cross-diffusion induced parameter spaces. Our results allow experimentalists to have a wider range

  9. Microwave-assisted C-C bond forming cross-coupling reactions: an overview.

    PubMed

    Mehta, Vaibhav P; Van der Eycken, Erik V

    2011-10-01

    Among the fundamental transformations in the field of synthetic organic chemistry, transition-metal-catalyzed reactions provide some of the most attractive methodologies for the formation of C-C and C-heteroatom bonds. As a result, the application of these reactions has increased tremendously during the past decades and cross-coupling reactions became a standard tool for synthetic organic chemists. Furthermore, a tremendous upsurge in the development of new catalysts and ligands, as well as an increased understanding of the mechanisms, has contributed substantially to recent advances in the field. Traditionally, organic reactions are carried out by conductive heating with an external heat source (for example, an oil bath). However, the application of microwave irradiation is a steadily gaining field as an alternative heating mode since its dawn at the end of the last century. This tutorial review focuses on some of the recent developments in the field of cross-coupling reactions assisted by microwave irradiation.

  10. Absolute Summ

    NASA Astrophysics Data System (ADS)

    Phillips, Alfred, Jr.

    Summ means the entirety of the multiverse. It seems clear, from the inflation theories of A. Guth and others, that the creation of many universes is plausible. We argue that Absolute cosmological ideas, not unlike those of I. Newton, may be consistent with dynamic multiverse creations. As suggested in W. Heisenberg's uncertainty principle, and with the Anthropic Principle defended by S. Hawking, et al., human consciousness, buttressed by findings of neuroscience, may have to be considered in our models. Predictability, as A. Einstein realized with Invariants and General Relativity, may be required for new ideas to be part of physics. We present here a two postulate model geared to an Absolute Summ. The seedbed of this work is part of Akhnaton's philosophy (see S. Freud, Moses and Monotheism). Most important, however, is that the structure of human consciousness, manifest in Kenya's Rift Valley 200,000 years ago as Homo sapiens, who were the culmination of the six million year co-creation process of Hominins and Nature in Africa, allows us to do the physics that we do. .

  11. Exploration of new C-O electrophiles in cross-coupling reactions.

    PubMed

    Yu, Da-Gang; Li, Bi-Jie; Shi, Zhang-Jie

    2010-12-21

    Since their development in the 1970s, cross-coupling reactions catalyzed by transition metals have become one of the most important tools for constructing both carbon-carbon and carbon-heteroatom bonds. Traditionally, organohalides were widely studied and broadly used as the electrophile, both in the laboratory and in industry. Unfortunately, the high cost, environmental toxicity, and sluggish preparation often associated with aryl halides can make them undesirable for the large-scale syntheses of industrial applications. However, with the further development of catalytic systems, and particularly of the ligands contained therein, a variety of electrophiles have now been successfully applied to cross-coupling reactions. Oxygen-based electrophiles have attracted much attention due to their ready availability from phenol and carbonyl compounds. Initially, aryl and alkenyl triflates were used in cross-coupling reactions due to their high reactivity; however, low moisture stability and high cost hampered their application. Later, with the development of highly efficient catalytic systems, the less reactive sulfonates and phosphates were successfully employed in cross-coupling reactions. Although they have higher stability and can be easily prepared, low atom economy remains an obstacle to their broader utility. Our group has worked to directly apply the abundant and readily available oxygen-containing compounds, such as phenols, alcohols, ethers, and carbonyl compounds, to cross-coupling reactions. In this Account, we describe our recent efforts in transition-metal-catalyzed cross-coupling reactions of new O-based electrophiles via C-O bond activation. We began by developing the methylation of aryl methyl ethers and benzyl methyl ethers via Ni-catalyzed selective C-O bond cleavage. With the refined Ni-based catalytic system, we further applied aryl/alkenyl carboxylates and carbamates to Suzuki-Miyaura, Negishi, and Kumada-Tamao-Corriu reactions to construct various

  12. Calculation of cross sections for binary reactions between heavy ion projectiles and heavy actinide targets

    SciTech Connect

    Hoffman, D.C.; Hoffman, M.M.

    1990-11-01

    The computer program, described in this report, is identified as PWAVED5. It was developed to calculate cross sections for nucleon transfer reactions in low energy heavy ion bombardments. The objective was to calculate cross sections that agree with experimental results for ions of different charge and mass and to develop a predictive capability. It was undertaken because previous heavy ion calculations, for which programs were readily available, appeared to focus primarily on reactions resulting in compound nucleus formation and were not particularly applicable to calculations of binary reaction cross sections at low interaction energies. There are to principal areas in which this computation differs from several other partial wave calculations of heavy-ion reaction cross sections. First, this program is designed specifically to calculate cross sections for nucleon exchange interactions and to exclude interactions that are expected to result in fusion of the two nuclei. A second major difference in this calculation is the use of a statistical distribution to assign the total interaction cross section to individual final mass states.

  13. SET-Induced Biaryl Cross-Coupling: An SRN1 Reaction

    PubMed Central

    2015-01-01

    The SET-induced biaryl cross-coupling reaction is established as the first example of a Grignard SRN1 reaction. The reaction is examined within the mechanistic framework of dissociative electron transfer in the presence of a Lewis acid. DFT calculations show that the reaction proceeds through a radical intermediate in the form of an Mg ion-radical cage, which eludes detection in trapping experiments by reacting quickly to form an MgPh2 radical anion intermediate. A new mechanism is proposed. PMID:24564385

  14. Reaction Mechanism of Oxygen Atoms with Unsaturated Hydrocarbons by the Crossed-Molecular-Beams Method

    DOE R&D Accomplishments Database

    Buss, R. J.; Baseman, R. J.; Guozhong, H.; Lee, Y. T.

    1982-04-01

    From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

  15. Atom-efficient metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles.

    PubMed

    Pérez, I; Sestelo, J P; Sarandeses, L A

    2001-05-01

    The novel metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles is described. Triorganoindium compounds (R(3)In) containing alkyl, vinyl, aryl, and alkynyl groups are efficiently prepared from the corresponding lithium or magnesium organometallics by reaction with indium trichloride. The cross-coupling reaction of R(3)In with aryl halides and pseudohalides (iodide 2, bromide 5, and triflate 4), vinyl triflates, benzyl bromides, and acid chlorides proceeds under palladium catalysis in excellent yields and with high chemoselectivity. Indium organometallics also react with aryl chlorides as under nickel catalysis. In the cross-coupling reaction the triorganoindium compounds transfer, in a clear example of atom economy, all three of the organic groups attached to the metal, as shown by the necessity of using only 34 mol % of indium. The feasibility of using R(3)In in reactions with different electrophiles, along with the high yields and chemoselectivities obtained, reveals indium organometallics to be useful alternatives to other organometallics in cross-coupling reactions.

  16. Reactions of nitroxides 15. Cinnamates bearing a nitroxyl moiety synthesized using a Mizoroki–Heck cross-coupling reaction

    PubMed Central

    Huras, Bogumiła

    2015-01-01

    Summary Cinnamic acid derivatives bearing a nitroxyl moiety (2,2,6,6-tetramethyl-1-oxyl-4-piperidyl 3-E-aryl acrylates) were synthesized in 30–100% yield using a Mizoroki–Heck cross-coupling reaction between 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl and iodobenzene derivatives in the presence of palladium(II) acetate coordinated with a tri(o-tolyl)phosphine ligand immobilized in a polyurea matrix. PMID:26199672

  17. Absolute rate constant and O(3P) yield for the O(1D)+N2O reaction in the temperature range 227 K to 719 K

    NASA Astrophysics Data System (ADS)

    Vranckx, S.; Peeters, J.; Carl, S. A.

    2008-10-01

    The absolute rate constant for the reaction that is the major source of stratospheric NOx, O(1D)+N2O → products, has been determined in the temperature range 227 K to 719 K, and, in the temperature range 248 K to 600 K, the fraction of the reaction that yields O(3P). Both the rate constants and product yields were determined using a recently-developed chemiluminescence technique for monitoring O(1D) that allows for higher precision determinations for both rate constants, and, particularly, O(3P) yields, than do other methods. We found the rate constant, kR1, to be essentially independent of temperature between 400 K and 227 K, having a value of (1.37±0.11)×10-10 cm3 s-1, and for temperatures greater than 450 K a marked decrease in rate constant was observed, with a rate constant of only (0.94±0.11)×10-10 cm3 s-1 at 719 K. The rate constants determined over the 227 K 400 K range show very low scatter and are significantly greater, by 20% at room temperature and 15% at 227 K, than the current recommended values. The fraction of O(3P) produced in this reaction was determined to be 0.002±0.002 at 250 K rising steadily to 0.010±0.004 at 600 K, thus the channel producing O(3P) can be entirely neglected in atmospheric kinetic modeling calculations. A further result of this study is an expression of the relative quantum yields as a function of temperature for the chemiluminescence reactions (kCL1)C2H + O(1D) → CH(A) + CO and (kCL2)C2H + O(3P) → CH(A) + CO, both followed by CH(A) → CH(X) + hν, as kCL1(T)/kCL2(T)=(32.8T-3050)/(6.29T+398).

  18. Absolute rate constant and O(3P) yield for the O(1D)+N2O reaction in the temperature range 227 K to 719 K

    NASA Astrophysics Data System (ADS)

    Vranckx, S.; Peeters, J.; Carl, S. A.

    2008-05-01

    We have determined, in the temperature range 227 K to 719 K, the absolute rate constant for the reaction O(1D)+N2O → products and, in the temperature range 248 K to 600 K, the fraction of the reaction that yields O(3P). Both the rate constants and product yields were determined using a recently-developed chemiluminescence technique for monitoring O(1D) that allows for higher precision determinations for both rate constants, and, particularly, O(3P) yields, than do other methods. We found the rate constant, kR1, to be essentially independent of temperature between 400 K and 227 K, having a value of (1.37±0.09)×10-10 cm3 s-1. For temperatures greater than 450 K a marked decrease in value was observed, with a rate constant of only (0.94±0.11)×10-10 cm3 s-1 at 719 K. The rate constants determined over the 227 K-400 K range show very low scatter and are significantly greater, by 20% at room temperature and by 15% at 227 K, than the current recommended values. The fraction of O(3P) produced in this reaction was determined to be 0.002±0.002 at 250 K rising steadily to 0.010±0.004 at 600 K, thus the channel producing O(3P) can be entirely neglected in atmospheric kinetic modeling calculations. A further result of this study is an expression of the relative quantum yields as a function of temperature for the chemiluminescence reactions (kCL1) C2H+O(1D) → CH(A)+CO and (kCL2) C2H+O(3P) → CH(A)+CO, both followed by CH(A) → CH(X)+hν, as kCL1(T)/kCL2(T)=(32.8T-3050)/(6.29T+398).

  19. Cross-linked polymersomes as nanoreactors for controlled and stabilized single and cascade enzymatic reactions.

    PubMed

    Gräfe, David; Gaitzsch, Jens; Appelhans, Dietmar; Voit, Brigitte

    2014-09-21

    Polymeric vesicles or polymersomes are one of the supramolecular entities at the leading edge of synthetic biology. These small compartments have shown to be feasible candidates as nanoreactors, especially for enzymatic reactions. Once cross-linked and equipped with a pH sensitive material, the reaction can be switched off (pH 8) and on (pH 6) in accordance with the increased permeability of the polymersome membranes under acidic conditions. Thus cross-linked and pH sensitive polymersomes provide a basis for pH controlled enzymatic reactions where no integrated transmembrane protein is needed for regulating the uptake and release of educts and products in the polymersome lumen. This pH-tunable working tool was further used to investigate their use in sequential enzymatic reactions (glucose oxidase and myoglobin) where enzymes are loaded in one common polymersome or in two different polymersomes. Crossing membranes and overcoming the space distance between polymersomes were shown successfully, meaning that educts and products can be exchanged between enzyme compartments for successful enzymatic cascade reactions. Moreover the stabilizing effect of polymersomes is also observable by single enzymatic reactions as well as a sequence. This study is directed to establish robust and controllable polymersome nanoreactors for enzymatic reactions, describing a switch between an off (pH 8) and on (pH 6) state of polymersome membrane permeability with no transmembrane protein needed for transmembrane exchange.

  20. High resolution absolute absorption cross sections of the B ̃(1)A'-X ̃(1)A' transition of the CH2OO biradical.

    PubMed

    Foreman, Elizabeth S; Kapnas, Kara M; Jou, YiTien; Kalinowski, Jarosław; Feng, David; Gerber, R Benny; Murray, Craig

    2015-12-28

    Carbonyl oxides, or Criegee intermediates, are formed from the gas phase ozonolysis of alkenes and play a pivotal role in night-time and urban area atmospheric chemistry. Significant discrepancies exist among measurements of the strong B ̃(1)A'-X ̃(1)A' electronic transition of the simplest Criegee intermediate, CH2OO in the visible/near-UV. We report room temperature spectra of the B ̃(1)A'-X ̃(1)A' electronic absorption band of CH2OO acquired at higher resolution using both single-pass broadband absorption and cavity ring-down spectroscopy. The new absorption spectra confirm the vibrational structure on the red edge of the band that is absent from ionization depletion measurements. The absolute absorption cross sections over the 362-470 nm range are in good agreement with those reported by Ting et al. Broadband absorption spectra recorded over the temperature range of 276-357 K were identical within their mutual uncertainties, confirming that the vibrational structure is not due to hot bands.

  1. Suzuki-miyaura cross-coupling in acylation reactions, scope and recent developments.

    PubMed

    Blangetti, Marco; Rosso, Heléna; Prandi, Cristina; Deagostino, Annamaria; Venturello, Paolo

    2013-01-17

    Since the first report and due to its handiness and wide scope, the Suzuki-Miyaura (SM) cross coupling reaction has become a routine methodology in many laboratories worldwide. With respect to other common transition metal catalyzed cross couplings, the SM reaction has been so far less exploited as a tool to introduce an acyl function into a specific substrate. In this review, the various approaches found in the literature will be considered, starting from the direct SM acylative coupling to the recent developments of cross coupling between boronates and acyl chlorides or anhydrides. Special attention will be dedicated to the use of masked acyl boronates, alkoxy styryl and alkoxy dienyl boronates as coupling partners. A final section will be then focused on the acyl SM reaction as key synthetic step in the framework of natural products synthesis.

  2. Palladium-catalyzed cross-coupling reactions of 4a,8a-azaboranaphthalene.

    PubMed

    Sun, Feiye; Lv, Lily; Huang, Min; Zhou, Zhaohui; Fang, Xiangdong

    2014-10-01

    A concise and effective three-step synthesis of 4a,8a-azaboranaphthalene (ABN) has been developed in gram scale. Electrophilic aromatic substitution reactions of ABN provide excellent functional-group-tolerant cross-coupling partners in various Pd-catalyzed cross-coupling reactions (e.g., Sonogashira, Suzuki-Miyaura, or Heck reaction). Photophysical, electrochemical, and DFT calculations all suggest a narrowed HOMO-LUMO gap with extended π-conjugation characters in the cross-coupled molecules. The ABN moiety as a new fluorophore has a distinct and selective fluorescence response toward Zn(II) and Cd(II) ions, demonstrating great potential for the ABN structural motif in fluorescent chemosensors.

  3. Divergent dendrimer synthesis via the Passerini three-component reaction and olefin cross-metathesis.

    PubMed

    Kreye, Oliver; Kugele, Dennis; Faust, Lorenz; Meier, Michael A R

    2014-02-01

    The combination of the Passerini reaction and olefin cross-metathesis is shown to be a very useful approach for the divergent synthesis of dendrimers. Castor oil-derived platform chemicals, such as 10-undecenoic acid and 10-undecenal, are reacted in a Passerini reaction with an unsaturated isocyanide to obtain a core unit having three terminal double bonds. Subsequent olefin cross-metathesis with tert-butyl acrylate, followed by hydrogenation of the double bonds and hydrolysis of the tert-butyl ester, leads to an active core unit bearing three carboxylic acid groups as reactive sites. Iterative steps of the Passerini reaction with 10-undecenal and 10-isocyanodec-1-ene for branching, and olefin cross-metathesis with tert-butyl acrylate, followed by hydrogenation and hydrolysis allow the synthesis of a third-generation dendrimer. All steps of the synthesis are carefully characterized by NMR, GPC, MS, and IR. PMID:24356926

  4. PRECO-D2: program for calculating preequilibrium and direct reaction double differential cross sections

    SciTech Connect

    Kalbach, C.

    1985-02-01

    The code PRECO-D2 uses the exciton model for preequilibrium nuclear reactions to describe the emission of particles with mass numbers of 1 to 4 from an equilibrating composite nucleus. A distinction is made between open and closed configurations in this system and between the multi-step direct (MSD) and multi-step compound (MSC) components of the preequilibrium cross section. Additional MSD components are calculated semi-empirically to account for direct nucleon transfer reactions and direct knockout processes involving cluster degrees of freedom. Evaporation from the equilibrated composite nucleus is included in the full MSC cross section. Output of energy differential and double differential cross sections is provided for the first particle emitted from the composite system. Multiple particle emission is not considered. This report describes the reaction models used in writing PRECO-D2 and explains the organization and utilization of the code. 21 refs.

  5. Suzuki-miyaura cross-coupling in acylation reactions, scope and recent developments.

    PubMed

    Blangetti, Marco; Rosso, Heléna; Prandi, Cristina; Deagostino, Annamaria; Venturello, Paolo

    2013-01-01

    Since the first report and due to its handiness and wide scope, the Suzuki-Miyaura (SM) cross coupling reaction has become a routine methodology in many laboratories worldwide. With respect to other common transition metal catalyzed cross couplings, the SM reaction has been so far less exploited as a tool to introduce an acyl function into a specific substrate. In this review, the various approaches found in the literature will be considered, starting from the direct SM acylative coupling to the recent developments of cross coupling between boronates and acyl chlorides or anhydrides. Special attention will be dedicated to the use of masked acyl boronates, alkoxy styryl and alkoxy dienyl boronates as coupling partners. A final section will be then focused on the acyl SM reaction as key synthetic step in the framework of natural products synthesis. PMID:23344208

  6. Divergent dendrimer synthesis via the Passerini three-component reaction and olefin cross-metathesis.

    PubMed

    Kreye, Oliver; Kugele, Dennis; Faust, Lorenz; Meier, Michael A R

    2014-02-01

    The combination of the Passerini reaction and olefin cross-metathesis is shown to be a very useful approach for the divergent synthesis of dendrimers. Castor oil-derived platform chemicals, such as 10-undecenoic acid and 10-undecenal, are reacted in a Passerini reaction with an unsaturated isocyanide to obtain a core unit having three terminal double bonds. Subsequent olefin cross-metathesis with tert-butyl acrylate, followed by hydrogenation of the double bonds and hydrolysis of the tert-butyl ester, leads to an active core unit bearing three carboxylic acid groups as reactive sites. Iterative steps of the Passerini reaction with 10-undecenal and 10-isocyanodec-1-ene for branching, and olefin cross-metathesis with tert-butyl acrylate, followed by hydrogenation and hydrolysis allow the synthesis of a third-generation dendrimer. All steps of the synthesis are carefully characterized by NMR, GPC, MS, and IR.

  7. Effect of finite range of the NN force and NN cross section on reaction cross section for neutron rich nuclei

    SciTech Connect

    Ismail, M.; Ellithi, A.Y.; Abou-Shady, H.

    2005-02-01

    The reaction cross section ({sigma}{sub R}) is calculated using the optical limit of the Glauber theory. A density-dependent effective nucleon-nucleon (NN) cross section {sigma}{sub NN} is considered. Finite and zero range NN interactions are studied. The effect of finite range and an appropriate local density can increase {sigma}{sub R} up to 20% compared to the zero range at constant density (0.16 fm{sup -3}), while a zero range calculation with free NN cross section increases {sigma}{sub R} up to 13%. These factors affect the values of the rms radii for neutron rich nuclei extracted from {sigma}{sub R}.

  8. A new compilation of experimental nuclear data for total reaction cross sections

    NASA Astrophysics Data System (ADS)

    Lantz, Mattias; Sihver, L.

    The nucleon-nucleus and nucleus-nucleus total reaction cross sections are of importance in many different fields, both for a better theoretical understanding as well as for a number of applications, including space radiation dosimetry. We have performed a comprehensive literature study in order to find all available experimental data on total reaction cross sections, σR , and interaction cross sections, σI , for neutrons, protons, and all stable and exotic heavy ions. Excluded from the data base are measurements where the cross sections have been derived through model-dependent calculations from other kinds of measurements. The objective of the study is to identify where more measurements are needed in view of different applications, and to make the data easily available for model developers and experimentalists. We will present some examples from the study, which is in the stage of quality control of all the gathered data.

  9. Effects of cross diffusion on Turing bifurcations in two-species reaction-transport systems

    NASA Astrophysics Data System (ADS)

    Kumar, Niraj; Horsthemke, Werner

    2011-03-01

    We study the Turing bifurcation in general two-species reaction-transport systems, where particle dispersal is governed by diffusion, including cross diffusion. By performing a linear stability analysis, we find conditions for the Turing instability and compare the results with the standard Turing conditions. We apply our results to two model systems, the Lengyel-Epstein model and the Brusselator, and find strong effects of cross diffusion on the Turing bifurcation.

  10. Effects of cross diffusion on Turing bifurcations in two-species reaction-transport systems.

    PubMed

    Kumar, Niraj; Horsthemke, Werner

    2011-03-01

    We study the Turing bifurcation in general two-species reaction-transport systems, where particle dispersal is governed by diffusion, including cross diffusion. By performing a linear stability analysis, we find conditions for the Turing instability and compare the results with the standard Turing conditions. We apply our results to two model systems, the Lengyel-Epstein model and the Brusselator, and find strong effects of cross diffusion on the Turing bifurcation. PMID:21517556

  11. Aqueous microwave-assisted cross-coupling reactions applied to unprotected nucleosides.

    PubMed

    Hervé, Gwénaëlle; Len, Christophe

    2015-01-01

    Metal catalyzed cross-coupling reactions have been the preferred tools to access to modified nucleosides (on the C5-position of pyrimidines and on the C7- or C8-positions of purines). Our objective is to focus this mini-review on the Suzuki-Miyaura and on the Heck cross-couplings of nucleosides using microwave irradiations which is an alternative technology compatible with green chemistry and sustainable development.

  12. Aqueous microwaves assisted cross-coupling reactions applied to unprotected nucleosides.

    NASA Astrophysics Data System (ADS)

    Len, Christophe; Hervé, Gwénaelle

    2015-02-01

    Nucleoside analogues have attracted much attention due to their potential biological activities. Amongst all synthetic nucleosides, C5-modified pyrimidines and C7- or C8-modified purines have mostly been prepared using palladium cross-coupling reactions and then studied as antitumoral and antiviral agents. Our objective is to focus this review on the Suzuki-Miyaura and on the Heck cross-couplings of nucleosides using microwave irradiations which are an alternative technology compatible with green chemistry and sustainable development.

  13. Investigation of immunofluorescence cross-reactions against Trichinella spiralis by western blot (immunoblot) analysis.

    PubMed Central

    Robert, F; Weil, B; Kassis, N; Dupouy-Camet, J

    1996-01-01

    Immunofluorescence cross-reactions in Trichinella spiralis serodiagnosis are sometimes difficult to identify. We compared the results of an indirect immunofluorescence assay and the profiles obtained by Western blot (immunoblot) analysis for three groups of patients: 10 T. spiralis-infected patients, 10 patients with autoimmune diseases, and 7 patients with parasitic diseases other than trichinellosis. The degree of immunofluorescence cross-reaction was variable. Western blotting allowed us to differentiate Trichinella infection from other parasitic diseases. In 3 of 10 serum samples from patients with autoimmune diseases, bands which had the same sizes as Trichinella bands were observed, and they could correspond to shared epitopes such as heat shock proteins. PMID:8877138

  14. Deformation effect on total reaction cross sections for neutron-rich Ne isotopes

    SciTech Connect

    Minomo, Kosho; Sumi, Takenori; Ogata, Kazuyuki; Shimizu, Yoshifumi R.; Yahiro, Masanobu; Kimura, Masaaki

    2011-09-15

    The isotope dependence of measured reaction cross sections in the scattering of {sup 28-32}Ne isotopes from a {sup 12}C target at 240 MeV/nucleon is analyzed by the double-folding model with the Melbourne g matrix. The density of the projectile is calculated by the mean-field model with the deformed Woods-Saxon potential. The deformation is evaluated by antisymmetrized molecular dynamics. The deformation of the projectile enhances calculated reaction cross sections to the measured values.

  15. Stereospecific nickel-catalyzed cross-coupling reactions of benzylic ethers and esters.

    PubMed

    Tollefson, Emily J; Hanna, Luke E; Jarvo, Elizabeth R

    2015-08-18

    This Account presents the development of a suite of stereospecific alkyl-alkyl cross-coupling reactions employing nickel catalysts. Our reactions complement related nickel-catalyzed stereoconvergent cross-coupling reactions from a stereochemical and mechanistic perspective. Most reactions of alkyl electrophiles with low-valent nickel complexes proceed through alkyl radicals and thus are stereoablative; the correct enantioselective catalyst can favor the formation of one enantiomer. Our reactions, in contrast, are stereospecific. Enantioenriched ethers and esters are cleanly converted to cross-coupled products with high stereochemical fidelity. While mechanistic details are still to be refined, our results are consistent with a polar, two-electron oxidative addition that avoids the formation of radical intermediates. This reactivity is unusual for a first-row transition metal. The cross-coupling reactions engage a range of benzylic ethers and esters, including methyl ethers, tetrahydropyrans, tetrahydrofurans, esters, and lactones. Coordination of the arene substituent to the nickel catalyst accelerates the reactions. Arenes with low aromatic stabilization energies, such as naphthalene, benzothiophene, and furan, serve as the best ligands and provide the highest reactivity. Traceless directing groups that accelerate reactions of sluggish substrates are described, providing partial compensation for arene coordination. Kumada, Negishi, and Suzuki reactions provide incorporation of a broad range of transmetalating agents. In Kumada coupling reactions, a full complement of Grigard reagents, including methyl, n-alkyl, and aryl Grignard reagents, are employed. In reactions employing methylmagnesium iodide, ligation of the nickel catalyst by rac-BINAP or DPEphos provides the highest yield and stereospecificity. For all other Grignard reagents, Ni(dppe)Cl2 has emerged as the best catalyst. Negishi cross-coupling reactions employing dimethylzinc are reported as a strategy to

  16. Stereospecific nickel-catalyzed cross-coupling reactions of benzylic ethers and esters.

    PubMed

    Tollefson, Emily J; Hanna, Luke E; Jarvo, Elizabeth R

    2015-08-18

    This Account presents the development of a suite of stereospecific alkyl-alkyl cross-coupling reactions employing nickel catalysts. Our reactions complement related nickel-catalyzed stereoconvergent cross-coupling reactions from a stereochemical and mechanistic perspective. Most reactions of alkyl electrophiles with low-valent nickel complexes proceed through alkyl radicals and thus are stereoablative; the correct enantioselective catalyst can favor the formation of one enantiomer. Our reactions, in contrast, are stereospecific. Enantioenriched ethers and esters are cleanly converted to cross-coupled products with high stereochemical fidelity. While mechanistic details are still to be refined, our results are consistent with a polar, two-electron oxidative addition that avoids the formation of radical intermediates. This reactivity is unusual for a first-row transition metal. The cross-coupling reactions engage a range of benzylic ethers and esters, including methyl ethers, tetrahydropyrans, tetrahydrofurans, esters, and lactones. Coordination of the arene substituent to the nickel catalyst accelerates the reactions. Arenes with low aromatic stabilization energies, such as naphthalene, benzothiophene, and furan, serve as the best ligands and provide the highest reactivity. Traceless directing groups that accelerate reactions of sluggish substrates are described, providing partial compensation for arene coordination. Kumada, Negishi, and Suzuki reactions provide incorporation of a broad range of transmetalating agents. In Kumada coupling reactions, a full complement of Grigard reagents, including methyl, n-alkyl, and aryl Grignard reagents, are employed. In reactions employing methylmagnesium iodide, ligation of the nickel catalyst by rac-BINAP or DPEphos provides the highest yield and stereospecificity. For all other Grignard reagents, Ni(dppe)Cl2 has emerged as the best catalyst. Negishi cross-coupling reactions employing dimethylzinc are reported as a strategy to

  17. Stereospecific Nickel-Catalyzed Cross-Coupling Reactions of Benzylic Ethers and Esters

    PubMed Central

    2015-01-01

    Conspectus This Account presents the development of a suite of stereospecific alkyl–alkyl cross-coupling reactions employing nickel catalysts. Our reactions complement related nickel-catalyzed stereoconvergent cross-coupling reactions from a stereochemical and mechanistic perspective. Most reactions of alkyl electrophiles with low-valent nickel complexes proceed through alkyl radicals and thus are stereoablative; the correct enantioselective catalyst can favor the formation of one enantiomer. Our reactions, in contrast, are stereospecific. Enantioenriched ethers and esters are cleanly converted to cross-coupled products with high stereochemical fidelity. While mechanistic details are still to be refined, our results are consistent with a polar, two-electron oxidative addition that avoids the formation of radical intermediates. This reactivity is unusual for a first-row transition metal. The cross-coupling reactions engage a range of benzylic ethers and esters, including methyl ethers, tetrahydropyrans, tetrahydrofurans, esters, and lactones. Coordination of the arene substituent to the nickel catalyst accelerates the reactions. Arenes with low aromatic stabilization energies, such as naphthalene, benzothiophene, and furan, serve as the best ligands and provide the highest reactivity. Traceless directing groups that accelerate reactions of sluggish substrates are described, providing partial compensation for arene coordination. Kumada, Negishi, and Suzuki reactions provide incorporation of a broad range of transmetalating agents. In Kumada coupling reactions, a full complement of Grigard reagents, including methyl, n-alkyl, and aryl Grignard reagents, are employed. In reactions employing methylmagnesium iodide, ligation of the nickel catalyst by rac-BINAP or DPEphos provides the highest yield and stereospecificity. For all other Grignard reagents, Ni(dppe)Cl2 has emerged as the best catalyst. Negishi cross-coupling reactions employing dimethylzinc are reported as

  18. Absolute rate coefficients over extended temperature ranges and mechanisms of the CF(X(2)Pi) reactions with F(2), Cl(2) and O(2).

    PubMed

    Vetters, B; Dils, B; Nguyen, T L; Vereecken, L; Carl, S A; Peeters, J

    2009-06-01

    The absolute rate coefficients of the reactions of the carbyne-radical CF(X(2)Pi, nu = 0) with O(2), F(2) and Cl(2) have been measured over extended temperature ranges, using pulsed-laser photodissociation-laser-induced fluorescence (PLP-LIF) techniques. The CF(X(2)Pi) radicals were generated by KrF excimer laser 2-photon photolysis of CF(2)Br(2) at 248 nm and the real-time exponential decays of CF(X(2)Pi, nu = 0) at varying coreactant concentrations, in large excess, were monitored by LIF (A(2)Sigma(+), nu' = 1 <-- X(2)Pi, nu'' = 0 transition). The experimental bimolecular rate coefficients of the CF(X(2)Pi) reactions with F(2) and Cl(2) can be described by simple Arrhenius expressions: k(F2)(295-408 K) = (1.5 +/- 0.2) x 10(-11) exp[-(370 +/- 40)K/T] cm(3) molecule(-1) s(-1); and k(Cl2)(295-392 K) = (6.1 +/- 2.1) x 10(-12) exp[+(280 +/- 120)K/T]. The k(F2)(T) and k(Cl2)(T) results can be rationalized in terms of direct halogen-atom abstraction reactions in which the radical character of CF dominates; a quantum chemical CBS-Q//BHandHLYP/6-311G(d,p) study confirms that the ground state reactants CF(X(2)Pi) + F(2)(X(1)Sigma) connect directly with the ground-state products CF(2)(X(1)A(1)) + F((2)P) via a nearly barrierless F-atom abstraction route. The rate coefficient of CF(X(2)Pi) + O(2) can be represented by a two-term Arrhenius expression: k(O2)(258-780 K) = 1.1 x 10(-11) exp(-850 K/T) + 2.3 x 10(-13) exp(500 K/T), with a standard deviation of 5%. The first term dominates at higher temperatures T and the second at lower T where a negative temperature dependence is observed (<290 K). Quantum chemical computations at the CBS-QB3 and CCSD(T)/aug-cc-pVDZ levels of theory show that the k(O2)(T) behaviour is consistent with a change of the dominant rate-determining mechanism from a carbyne-type insertion into the O-O bond at high T to a radical-radical combination at low T.

  19. Studies of combustion reactions at the state-resolved differential cross section level

    SciTech Connect

    Houston, P.L.; Suits, A.G.; Bontuyan, L.S.; Whitaker, B.J.

    1993-12-01

    State-resolved differential reaction cross sections provide perhaps the most detailed information about the mechanism of a chemical reaction, but heretofore they have been extremely difficult to measure. This program explores a new technique for obtaining differential cross sections with product state resolution. The three-dimensional velocity distribution of state-selected reaction products is determined by ionizing the appropriate product, waiting for a delay while it recoils along the trajectory imparted by the reaction, and finally projecting the spatial distribution of ions onto a two dimensional screen using a pulsed electric field. Knowledge of the arrival time allows the ion position to be converted to a velocity, and the density of velocity projections can be inverted mathematically to provide the three-dimensional velocity distribution for the selected product. The main apparatus has been constructed and tested using photodissociations. The authors report here the first test results using crossed beams to investigate collisions between Ar and NO. Future research will both develop further the new technique and employ it to investigate methyl radical, formyl radical, and hydrogen atom reactions which are important in combustion processes. The authors intend specifically to characterize the reactions of CH{sub 3} with H{sub 2} and H{sub 2}CO; of HCO with O{sub 2}; and of H with CH{sub 4}, CO{sub 2}, and O{sub 2}.

  20. Towards rotationally state-resolved differential cross sections for the hydrogen exchange reaction

    SciTech Connect

    Vrakking, M.J.J.

    1992-11-01

    The hydrogen exchange reaction H + H{sub 2} {yields} H{sub 2} + H (and its isotopic variants) plays a pivotal role in chemical reaction dynamics. It is the only chemical reaction for which fully converged quantum scattering calculations have been carried out using a potential energy surface which is considered to be chemically accurate. To improve our ability to test the theory, a `perfect experiment`, measuring differential cross sections with complete specification of the reactant and product states, is called for. In this thesis, the design of an experiment is described that aims at achieving this goal for the D + H{sub 2} reaction. A crossed molecular beam arrangement is used, in which a photolytic D atom beam is crossed by a pulsed beam of H{sub 2} molecules. DH molecules formed in the D + H{sub 2} reaction are state-specifically ionized using Doppler-free (2+1) Resonance-Enhanced Multi-Photon Ionization (REMPI) and detected using a Position-sensitive microchannel plate detector. This detection technique has an unprecedented single shot detection sensitivity of 6.8 10{sup 3} molecules/cc. This thesis does not contain experimental results for the D + H{sub 2} reaction yet, but progress that has been made towards achieving this goal is reported. In addition, results are reported for a study of the Rydberg spectroscopy of the water molecule.

  1. Towards rotationally state-resolved differential cross sections for the hydrogen exchange reaction

    SciTech Connect

    Vrakking, M.J.J.

    1992-11-01

    The hydrogen exchange reaction H + H[sub 2] [yields] H[sub 2] + H (and its isotopic variants) plays a pivotal role in chemical reaction dynamics. It is the only chemical reaction for which fully converged quantum scattering calculations have been carried out using a potential energy surface which is considered to be chemically accurate. To improve our ability to test the theory, a 'perfect experiment', measuring differential cross sections with complete specification of the reactant and product states, is called for. In this thesis, the design of an experiment is described that aims at achieving this goal for the D + H[sub 2] reaction. A crossed molecular beam arrangement is used, in which a photolytic D atom beam is crossed by a pulsed beam of H[sub 2] molecules. DH molecules formed in the D + H[sub 2] reaction are state-specifically ionized using Doppler-free (2+1) Resonance-Enhanced Multi-Photon Ionization (REMPI) and detected using a Position-sensitive microchannel plate detector. This detection technique has an unprecedented single shot detection sensitivity of 6.8 10[sup 3] molecules/cc. This thesis does not contain experimental results for the D + H[sub 2] reaction yet, but progress that has been made towards achieving this goal is reported. In addition, results are reported for a study of the Rydberg spectroscopy of the water molecule.

  2. Total reaction cross sections in CEM and MCNP6 at intermediate energies

    DOE PAGES

    Kerby, Leslie M.; Mashnik, Stepan G.

    2015-05-14

    Accurate total reaction cross section models are important to achieving reliable predictions from spallation and transport codes. The latest version of the Cascade Exciton Model (CEM) as incorporated in the code CEM03.03, and the Monte Carlo N-Particle transport code (MCNP6), both developed at Los Alamos National Laboratory (LANL), each use such cross sections. Having accurate total reaction cross section models in the intermediate energy region (50 MeV to 5 GeV) is very important for different applications, including analysis of space environments, use in medical physics, and accelerator design, to name just a few. The current inverse cross sections used inmore » the preequilibrium and evaporation stages of CEM are based on the Dostrovsky et al. model, published in 1959. Better cross section models are now available. Implementing better cross section models in CEM and MCNP6 should yield improved predictions for particle spectra and total production cross sections, among other results.« less

  3. Fusion-Evaporation Cross Sections in Reactions Leading to Production of Super-Heavy Nuclei

    SciTech Connect

    Siwek-Wilczynska, K.; Skwira-Chalot, I.; Wilczynski, J.

    2006-08-14

    Fusion-evaporation cross sections were calculated for the 48Ca+204-208Pb and 50Ti+206,208Pb reactions and compared with the existing experimental data of the Dubna and GSI groups. The survival probabilities of the compound Z 102 and Z = 104 nuclei formed in these reactions were calculated using a Monte Carlo program based on the conventional Bohr-Wheeler theory of fission and statistical model of particle evaporation with Reisdorf-Ignatyuk prescription for the level densities and Strutinsky shell corrections of Moeller et al. 'Empirical' magnitudes of the dynamical hindrance of fusion have been deduced for these reactions.

  4. Selective syntheses of [7]-[12]cycloparaphenylenes using orthogonal Suzuki-Miyaura cross-coupling reactions.

    PubMed

    Darzi, Evan R; Sisto, Thomas J; Jasti, Ramesh

    2012-08-01

    The divergent, selective syntheses of [7]-[12]cycloparaphenylenes have been accomplished utilizing sequential, orthogonal Suzuki-Miyaura cross-coupling reactions from two late-stage intermediates. Quantum yields decrease dramatically as cycloparaphenylene size decreases, highlighting the unique photophysical behavior of the smaller cycloparaphenylenes. PMID:22804729

  5. Towards Efficient and Wide-Scope Metal-Catalyzed Alkyl-Alkyl Cross-Coupling Reactions.

    PubMed

    Cárdenas

    1999-10-18

    The simplest organic fragment, C(sp(3))-C(sp(3)), is unfortunately the most difficult to prepare by metal-catalyzed cross-coupling reactions (shown schematically) in the presence of functional groups. Recent advances show, however, that alkane moieties can be built within functionalized molecules by a careful choice of catalysts and conditions.

  6. Symmetrical bisquinolones via metal-catalyzed cross-coupling and homocoupling reactions.

    PubMed

    Hashim, Jamshed; Glasnov, Toma N; Kremsner, Jennifer M; Kappe, C Oliver

    2006-02-17

    Functionalized 4,4'-bisquinolones can be efficiently synthesized by microwave-assisted palladium(0)-catalyzed one-pot borylation/Suzuki cross-coupling reactions or via nickel(0)-mediated homocouplings of 4-chloroquinolin-2(1H)-one precursors. Both methods are also applicable to other types of symmetrical biaryls.

  7. Determining Cross Sections for Reactions on Unstable Nuclei: A Consideration of Indirect Approaches

    SciTech Connect

    Escher, J; Dietrich, F S

    2005-05-24

    An indirect method for determining cross sections for reactions proceeding through a compound nucleus is presented. The appropriate theoretical framework for applications of this method is reviewed and theoretical and experimental challenges that need to be addressed in applications of the method are outlined. Two approximations are considered and their advantages and limitations are discussed.

  8. Determining Cross Sections for Reactions on Unstable Nuclei: A Consideration of Indirect Approaches

    SciTech Connect

    Escher, J.; Dietrich, F.S.

    2005-10-14

    An indirect method for determining cross sections for reactions proceeding through a compound nucleus is presented. The appropriate theoretical framework for applications of this method is reviewed and theoretical and experimental challenges that need to be addressed in applications of the method are outlined. Two approximations are considered and their advantages and limitations are discussed.

  9. Iron-Catalyzed Stereoselective Cross-Coupling Reactions of Stereodefined Enol Carbamates with Grignard Reagents.

    PubMed

    Rivera, Ana Cristina Parra; Still, Raymond; Frantz, Doug E

    2016-06-01

    A practical and highly stereoselective iron-catalyzed cross-coupling reaction of stereodefined enol carbamates and Grignard reagents to yield tri- and tetrasubstituted acrylates is reported. A facile method for the stereoselective generation of these enol carbamates has also been developed. PMID:27088754

  10. MICROWAVE-ACCELERATED SUZUKI CROSS-COUPLING REACTION IN POLYETHYLENE GLYCOL (PEG)

    EPA Science Inventory

    Polyethylene glycol (PEG) is found to be an inexpensive and nontoxic reaction medium for the microwave-assisted Suzuki cross-coupling of arylboronic acids with aryl halides. This environmentally friendly microwave protocol offers the ease of operation and enables the recyclabilit...

  11. More than bystanders: the effect of olefins on transition-metal-catalyzed cross-coupling reactions.

    PubMed

    Johnson, Jeffrey B; Rovis, Tomislav

    2008-01-01

    Olefins and alkynes are ubiquitous in transition-metal catalysis, whether introduced by the substrate, the catalyst, or as an additive. Whereas the impact of metals and ligands is relatively well understood, the effects of olefins in these reactions are generally underappreciated, even though numerous examples of olefins influencing the outcome of a reaction, through increased activity, stability, or selectivity, have been reported. This Review provides an overview of the interaction of olefins with transition metals and documents examples of olefins influencing the outcome of catalytic reactions, in particular cross-coupling reactions. It should thus provide a basis for the improved understanding and further utilization of olefin and alkyne effects in transition-metal-catalyzed reactions.

  12. Activation cross sections of proton induced nuclear reactions on palladium up to 80MeV.

    PubMed

    Tárkányi, F; Ditrói, F; Takács, S; Csikai, J; Hermanne, A; Uddin, M S; Baba, M

    2016-08-01

    Activation cross sections of proton induced nuclear reactions on palladium were measured up to 80MeV by using the stacked foil irradiation technique and gamma ray spectrometry. The beam intensity, the incident energy and the energy degradation were controlled by a method based on flux constancy via normalization to the excitation functions of monitor reactions measured in parallel. Excitation functions for direct and cumulative cross-sections were measured for the production of (104m,104g,105g,106m,110m)Ag, (100,101)Pd, (99m,99g,100,101m,101g,102m,102g,105)Rh and (103,97)Ru radioisotopes. The cross section data were compared with the theoretical predictions of TENDL-2014 and -2015 libraries. For practical applications thick target yields were derived from the measured excitation functions. Application in the field of medical radionuclide production is shortly discussed. PMID:27235887

  13. Stereospecific Nickel-Catalyzed Cross-Coupling Reactions of Benzylic Ethers with Isotopically-Labeled Grignard Reagents

    PubMed Central

    2015-01-01

    In this manuscript we highlight the potential of stereospecific nickel-catalyzed cross-coupling reactions for applications in the pharmaceutical industry. Using an inexpensive and sustainable nickel catalyst, we report a gram-scale Kumada cross-coupling reaction. Reactions are highly stereospecific and proceed with inversion at the benzylic position. We also expand the scope of our reaction to incorporate isotopically labeled substituents. PMID:27458328

  14. A Study on 19F( n,α) Reaction Cross Section

    NASA Astrophysics Data System (ADS)

    Uğur, F. A.; Tel, E.; Gökçe, A. A.

    2013-06-01

    In this study, cross sections of neutron induced reactions have been investigated for fluorine target nucleus. The calculations have been made on the excitation functions of 19F ( n,α), 19F( n,xα) reactions. Fluorine (F) and its molten salt compounds (LiF) can serve as a coolant which can be used at high temperatures without reaching a high vapor pressure and also the molten salt compounds are also a good neutron moderator. In these calculations, the pre-equilibrium and equilibrium effects have been investigated. The pre-equilibrium calculations involve the full exciton model and the cascade exciton model. The equilibrium effects are calculated according to the Weisskopf-Ewing model. Also in the present work, reaction cross sections have calculated by using evaluated empirical formulas developed by Tel et al. at 14-15 MeV energy. The obtained results have been discussed and compared with the available experimental data.

  15. Production cross sections for heavy-ion fragmentation reactions on a liquid deuterium target at intermediate energies

    SciTech Connect

    Roeder, B. T.; Kemper, K. W.; Aoi, N.; Motobayashi, T.; Takeuchi, S.; Bazin, D.; Mueller, W. F.; Yoneda, K.; Bowen, M.; Campbell, C. M.; Cook, J. M.; Dinca, D.-C.; Gade, A.; Glasmacher, T.; Terry, J. R.; Zwahlen, H.; Iwasaki, H.; Sakurai, H.; Suzuki, H.; Kanno, S.

    2006-09-15

    The inclusive cross sections for 38 different reaction products produced in the interaction of {sup 48}Ca, {sup 40}S, and {sup 42}S beams around 100 MeV/nucleon with a liquid deuterium target are reported. The cross sections for the {sup 48}Ca +{sup 2}H products are compared to those with {sup 48}Ca incident on the commonly used fragmentation targets {sup 9}Be and {sup 181}Ta and also to global calculations for fragmentation reaction cross sections based on the EPAX parameterization. The sizes of the measured reaction cross sections for the deuterium target were comparable to those of the cross sections measured on the heavier targets, indicating that nucleon removal from a deuterium target can be carried out for single- and multiple-nucleon knockout reaction studies. It was also found that the charge exchange cross sections were large enough that it should be possible to obtain nuclear structure information from these reactions.

  16. Cross-linked polymersomes as nanoreactors for controlled and stabilized single and cascade enzymatic reactions

    NASA Astrophysics Data System (ADS)

    Gräfe, David; Gaitzsch, Jens; Appelhans, Dietmar; Voit, Brigitte

    2014-08-01

    Polymeric vesicles or polymersomes are one of the supramolecular entities at the leading edge of synthetic biology. These small compartments have shown to be feasible candidates as nanoreactors, especially for enzymatic reactions. Once cross-linked and equipped with a pH sensitive material, the reaction can be switched off (pH 8) and on (pH 6) in accordance with the increased permeability of the polymersome membranes under acidic conditions. Thus cross-linked and pH sensitive polymersomes provide a basis for pH controlled enzymatic reactions where no integrated transmembrane protein is needed for regulating the uptake and release of educts and products in the polymersome lumen. This pH-tunable working tool was further used to investigate their use in sequential enzymatic reactions (glucose oxidase and myoglobin) where enzymes are loaded in one common polymersome or in two different polymersomes. Crossing membranes and overcoming the space distance between polymersomes were shown successfully, meaning that educts and products can be exchanged between enzyme compartments for successful enzymatic cascade reactions. Moreover the stabilizing effect of polymersomes is also observable by single enzymatic reactions as well as a sequence. This study is directed to establish robust and controllable polymersome nanoreactors for enzymatic reactions, describing a switch between an off (pH 8) and on (pH 6) state of polymersome membrane permeability with no transmembrane protein needed for transmembrane exchange.Polymeric vesicles or polymersomes are one of the supramolecular entities at the leading edge of synthetic biology. These small compartments have shown to be feasible candidates as nanoreactors, especially for enzymatic reactions. Once cross-linked and equipped with a pH sensitive material, the reaction can be switched off (pH 8) and on (pH 6) in accordance with the increased permeability of the polymersome membranes under acidic conditions. Thus cross-linked and p

  17. The absolute yield, angular distribution and resonance widths of the 6.13, 6.92 and 7.12 MeV photons from the 340.5 keV resonance of the 19F(p,αγ) 16O reaction

    NASA Astrophysics Data System (ADS)

    Croft, S.

    1991-10-01

    Although the low lying resonances in the 19F(p,αγ) 16O reaction have been studied by many investigators in the past, only a few absolute determinations of the gamma-ray yield and branching ratios have been made. This is somewhat surprising in view of the widespread use of this reaction for the quantitative microanalysis of fluorine concentration profiles in the near surface regions of materials and for the calibration of gamma-ray detectors. In this work we report an absolute measurement of the yield, angular distribution and resonance widths of the 6.13, 6.92 and 7.12 MeV photons from the 340.5 keV resonance of the 19F(p,αγ) 16O reaction. Photons were produced by bombarding a semithick target of CaF 2 with protons from the Harwell 6 MV Van de Graaff accelerator. A 113 cm 3 HPGe spectrometer, with an energy resolution of 6.8 keV at 6129 keV, was used as the photon detector. This detector had previously been calibrated absolutely using a combination of radionuclide and thermal neutron capture gamma-ray sources at the neutron facility Badger, adjacent to the Harwell reactor DIDO. Measurements were made at seven angles in the range 0° - 150° permitting both differential and integral cross-sections to be derived. Geometrical correction factors were calculated using the Monte Carlo code EGS-4. A value for the reaction width was determined from the excitation curve. With conventional notation the principal results are as follows: γ1 : γ2 : γ3 = 0.9701:0.0033:0.0266; ΓCM = (2.08±0.13) keV; and Y( γ1) = (8.72±0.37)×10 4 6129 keV γμC -1as.

  18. Experience in using the covariances of some ENDF/B-V dosimetry cross sections: proposed improvements and addition of cross-reaction covariances

    SciTech Connect

    Fu, C.Y.; Hetrick, D.M.

    1982-01-01

    Recent ratio data, with carefully evaluated covariances, were combined with eleven of the ENDF/B-V dosimetry cross sections using the generalized least-squares method. The purpose was to improve these evaluated cross sections and covariances, as well as to generate values for the cross-reaction covariances. The results represent improved cross sections as well as realistic and usable covariances. The latter are necessary for meaningful intergral-differential comparisons and for spectrum unfolding.

  19. Determination of Resonance Parameters and their Covariances from Neutron Induced Reaction Cross Section Data

    SciTech Connect

    Schillebeeckx, P.; Becker, B.; Danon, Y.; Guber, K.; Harada, H.; Heyse, J.; Junghans, A.R.; Kopecky, S.; Massimi, C.; Moxon, M.C.; Otuka, N.; Sirakov, I.; Volev, K.

    2012-12-15

    Cross section data in the resolved and unresolved resonance region are represented by nuclear reaction formalisms using parameters which are determined by fitting them to experimental data. Therefore, the quality of evaluated cross sections in the resonance region strongly depends on the experimental data used in the adjustment process and an assessment of the experimental covariance data is of primary importance in determining the accuracy of evaluated cross section data. In this contribution, uncertainty components of experimental observables resulting from total and reaction cross section experiments are quantified by identifying the metrological parameters involved in the measurement, data reduction and analysis process. In addition, different methods that can be applied to propagate the covariance of the experimental observables (i.e. transmission and reaction yields) to the covariance of the resonance parameters are discussed and compared. The methods being discussed are: conventional uncertainty propagation, Monte Carlo sampling and marginalization. It is demonstrated that the final covariance matrix of the resonance parameters not only strongly depends on the type of experimental observables used in the adjustment process, the experimental conditions and the characteristics of the resonance structure, but also on the method that is used to propagate the covariances. Finally, a special data reduction concept and format is presented, which offers the possibility to store the full covariance information of experimental data in the EXFOR library and provides the information required to perform a full covariance evaluation.

  20. Calculation of nuclear reaction cross sections on excited nuclei with the coupled-channels method

    SciTech Connect

    Kawano, T.; Talou, P.; Lynn, J. E.; Chadwick, M. B.; Madland, D. G.

    2009-08-15

    We calculate nuclear cross sections on excited nuclei in the fast neutron energy range. We partition the whole process into two contributions: the direct reaction part and the compound nuclear reactions. A coupled-channels method is used for calculating the direct transition of the nucleus from the initial excited state, which is a member of the ground-state rotational band, to the final ground and excited low-lying levels. This process is strongly affected by the channel coupling. The compound nuclear reactions on the excited state are calculated with the statistical Hauser-Feshbach model, with the transmission coefficients obtained from the coupled-channels calculation. The calculations are performed for a strongly deformed nucleus {sup 169}Tm, and selected cross sections for the ground and first excited states are compared. The calculation is also made for actinides to investigate possible modification to the fission cross section when the target is excited. It is shown that both the level coupling for the entrance channel, and the different target spin, change the fission cross section.

  1. Fusion cross sections for {sup 6,7}Li + {sup 24}Mg reactions at energies below and above the barrier

    SciTech Connect

    Ray, M.; Mukherjee, A.; Pradhan, M. K.; Kshetri, Ritesh; Sarkar, M. Saha; Dasmahapatra, B.

    2008-12-15

    Measurement of fusion cross sections for the {sup 6,7}Li + {sup 24}Mg reactions by the characteristic {gamma}-ray method has been done at energies from below to well above the respective Coulomb barriers. The fusion cross sections obtained from these {gamma}-ray cross sections for the two systems are found to agree well with the total reaction cross sections at low energies. The relatively large difference between total cross sections and measured fusion cross sections at higher energies is consistent with the fact that other channels, in particular breakup, open up with an increase of bombarding energy. The breakup channel, however, appears not to have any influence on fusion cross sections. The critical angular momenta (l{sub cr}) deduced from the fusion cross sections are found to have an energy dependence similar to other Li-induced reactions.

  2. Enzyme sequence similarity improves the reaction alignment method for cross-species pathway comparison

    SciTech Connect

    Ovacik, Meric A.; Androulakis, Ioannis P.

    2013-09-15

    Pathway-based information has become an important source of information for both establishing evolutionary relationships and understanding the mode of action of a chemical or pharmaceutical among species. Cross-species comparison of pathways can address two broad questions: comparison in order to inform evolutionary relationships and to extrapolate species differences used in a number of different applications including drug and toxicity testing. Cross-species comparison of metabolic pathways is complex as there are multiple features of a pathway that can be modeled and compared. Among the various methods that have been proposed, reaction alignment has emerged as the most successful at predicting phylogenetic relationships based on NCBI taxonomy. We propose an improvement of the reaction alignment method by accounting for sequence similarity in addition to reaction alignment method. Using nine species, including human and some model organisms and test species, we evaluate the standard and improved comparison methods by analyzing glycolysis and citrate cycle pathways conservation. In addition, we demonstrate how organism comparison can be conducted by accounting for the cumulative information retrieved from nine pathways in central metabolism as well as a more complete study involving 36 pathways common in all nine species. Our results indicate that reaction alignment with enzyme sequence similarity results in a more accurate representation of pathway specific cross-species similarities and differences based on NCBI taxonomy.

  3. Crossed-beam DC slice imaging of fluorine atom reactions with linear alkanes

    SciTech Connect

    Shi, Yuanyuan; Kamasah, Alexander; Joalland, Baptiste; Suits, Arthur G.

    2015-05-14

    We report the reaction dynamics of F atom with selected alkanes studied by crossed beam scattering with DC slice ion imaging. The target alkanes are propane, n-butane, and n-pentane. The product alkyl radicals are probed by 157 nm single photon ionization following reaction at a collision energy of ∼10 kcal mol{sup −1}. The analyzed data are compared with the corresponding theoretical studies. Reduced translational energy distributions for each system show similar trends with little of the reaction exoergicity appearing in translation. However, the pentane reaction shows a somewhat smaller fraction of available energy in translation than the other two, suggesting greater energy channeled into pentyl internal degrees of freedom. The center-of-mass angular distributions all show backscattering as well as sharp forward scattering that decreases in relative intensity with the size of the molecule. Possible reasons for these trends are discussed.

  4. Dynamics of CN+alkane reactions by crossed-beam dc slice imaging

    SciTech Connect

    Huang Cunshun; Li Wen; Estillore, Armando D.; Suits, Arthur G.

    2008-08-21

    The hydrogen atom abstraction reactions of CN (X {sup 2}{sigma}{sup +}) with alkanes have been studied using the crossed molecular beam technique with dc slice ion imaging at collision energies of 7.5 and 10.8 kcal/mol. The product alkyl radical images were obtained via single photon ionization at 157 nm for the reactions of CN (X {sup 2}{sigma}{sup +}) with n-butane, n-pentane, n-hexane, and cyclohexane. From analysis of the images, we obtained the center-of-mass frame product angular distributions and translational energy distributions directly. The results indicate that the products are largely backscattered and that most of the available energy ({approx}80%-85%) goes to the internal energy of the products. The reaction dynamics is discussed in light of recent kinetics data, theoretical calculations, and results for related halogen and oxygen atom reactions.

  5. Differentiating of cross-reactions in patients with latex allergy with the use of ISAC test

    PubMed Central

    Chełmińska, Marta; Różyło, Anna; Kołakowska, Agata; Jassem, Ewa

    2016-01-01

    Introduction Differentiating between cross-reactivity and double sensitization is still a challenging issue in allergology. Aim To differentiate cross-reactions accompanying latex allergy with the use of the ISAC test. Material and methods Thirty-nine patients reporting immediate allergic reactions to latex were enrolled into the study (group A). The control group was comprised of 41 patients with allergic diseases not associated with latex (group B) and 20 healthy individuals (group C). Their history was recorded and skin prick tests were performed with latex, airborne and food allergens. Specific IgE against food allergens, latex (k82) and recombined latex allergens were determined. ImmunoCAP ISAC test was performed with 103 molecules. Results Sensitization to latex was found by means of skin tests in 16 cases and sIgE against latex was revealed in 12 cases (including 10 positive in both SPT and sIgE). In the ISAC test antibodies against recombined latex allergens were found in 8 patients with rHev b 6 as the most common. All the patients positive for rHev b 1, 5, 6, 8 had allergy or asymptomatic sensitization to food allergens cross-reacting with latex. Some reactions could not have been differentiated due to the lack of allergens in the ISAC test. Others, not related to latex-fruits syndrome were explained by cross-reactivity with other profilins or PR-10 proteins. Conclusions ImmunoCAP ISAC test could be useful in differentiating between cross-reactions and double sensitizations. However, in the case of latex its advantages are limited due to a small panel of allergens. PMID:27279821

  6. Cross Sections Calculations of ( d, t) Nuclear Reactions up to 50 MeV

    NASA Astrophysics Data System (ADS)

    Tel, E.; Yiğit, M.; Tanır, G.

    2013-04-01

    In nuclear fusion reactions two light atomic nuclei fuse together to form a heavier nucleus. Fusion power is the power generated by nuclear fusion processes. In contrast with fission power, the fusion reaction processes does not produce radioactive nuclides. The fusion will not produce CO2 or SO2. So the fusion energy will not contribute to environmental problems such as particulate pollution and excessive CO2 in the atmosphere. Fusion powered electricity generation was initially believed to be readily achievable, as fission power had been. However, the extreme requirements for continuous reactions and plasma containment led to projections being extended by several decades. In 2010, more than 60 years after the first attempts, commercial power production is still believed to be unlikely before 2050. Although there have been significant research and development studies on the inertial and magnetic fusion reactor technology, there is still a long way to go to penetrate commercial fusion reactors to the energy market. In the fusion reactor, tritium self-sufficiency must be maintained for a commercial power plant. Therefore, for self-sustaining (D-T) fusion driver tritium breeding ratio should be greater than 1.05. Working out the systematics of ( d, t) nuclear reaction cross sections is of great importance for the definition of the excitation function character for the given reaction taking place on various nuclei at different energies. Since the experimental data of charged particle induced reactions are scarce, self-consistent calculation and analyses using nuclear theoretical models are very important. In this study, ( d, t) cross sections for target nuclei 19F, 50Cr, 54Fe, 58Ni, 75As, 89Y, 90Zr, 107Ag, 127I, 197Au and 238U have been investigated up to 50 MeV deuteron energy. The excitation functions for ( d, t) reactions have been calculated by pre-equilibrium reaction mechanism. Calculation results have been also compared with the available measurements in

  7. Effective Absorption Cross-Sections in Porphyridium cruentum: Implications for Energy Transfer between Phycobilisomes and Photosystem II Reaction Centers.

    PubMed

    Ley, A C

    1984-02-01

    Effective absorption cross-sections for O(2) production by Porphyridium cruentum were measured at 546 and 596 nanometers. Although all photosystem II reaction centers are energetically coupled to phycobilisomes, any single phycobilisome acts as antenna for several photosystem II reaction centers. The cross-section measured in state I was 50% larger than that measured in state II.

  8. Turing space in reaction-diffusion systems with density-dependent cross diffusion

    NASA Astrophysics Data System (ADS)

    Zemskov, E. P.; Kassner, K.; Hauser, M. J. B.; Horsthemke, W.

    2013-03-01

    Reaction-diffusion systems with cross-diffusion terms that depend linearly on density are studied via linear stability analysis and weakly nonlinear analysis. We obtain and analyze the conditions for the Turing instability and derive a universal form of these conditions. We discuss the features of the pattern-forming regions in parameter space for a cross activator-inhibitor system, the Brusselator model, and for a pure activator-inhibitor system, the two-variable Oregonator model. The supercritical or subcritical character of the Turing bifurcation for the Brusselator is determined by deriving an amplitude equation for patterns near the instability threshold.

  9. Transfer cross sections from reactions with /sup 254/Es as a target

    SciTech Connect

    Schadel, M.; Bruechle, W.; Bruegger, M.; Gaggeler, H.; Moody, K.J.; Schardt, D.; Suemmerer, K.; Hulet, E.K.; Dougan, A.D.; Dougan, R.J.

    1986-04-01

    We report radiochemically determined cross sections for the heaviest known actinides produced in transfer reactions of /sup 16,18/O and /sup 22/Ne with /sup 254/Es as a target. A comparison with data for similar transfers from /sup 248/Cm targets is made. Transfer cross sections are extrapolated for the production of the unknown, neutron-rich isotopes of elements 101 through 105, and the unique potential of /sup 254/Es as a target to make these exotic nuclei accessible is demonstrated.

  10. Measurement of inelastic cross sections in relativistic deuteron-on-lead reactions

    SciTech Connect

    Zamani, M.; Stoulos, S.; Fragopoulou, M.; Krivopustov, M.

    2010-10-15

    The inelastic cross section of deuterons hitting a lead target has been determined by the beam attenuation technique. A spallation neutron source based on a lead target was irradiated with 1.6- and 2.5-GeV deuterons. Solid-state nuclear track detectors as well as the activation method were used to obtain the neutron and proton distribution along the surface of the source. The attenuation coefficient was estimated by fitting the experimental data and taking into account the buildup effect and the beam attenuation. Using the attenuation coefficient, the interaction length and then the inelastic cross section of deuterons on lead reaction were determined.

  11. Reengineering the optical absorption cross-section of photosynthetic reaction centers.

    PubMed

    Dutta, Palash K; Lin, Su; Loskutov, Andrey; Levenberg, Symon; Jun, Daniel; Saer, Rafael; Beatty, J Thomas; Liu, Yan; Yan, Hao; Woodbury, Neal W

    2014-03-26

    Engineered cysteine residues near the primary electron donor (P) of the reaction center from the purple photosynthetic bacterium Rhodobacter sphaeroides were covalently conjugated to each of several dye molecules in order to explore the geometric design and spectral requirements for energy transfer between an artificial antenna system and the reaction center. An average of 2.5 fluorescent dye molecules were attached at specific locations near P. The enhanced absorbance cross-section afforded by conjugation of Alexa Fluor 660 dyes resulted in a 2.2-fold increase in the formation of reaction center charge-separated state upon intensity-limited excitation at 650 nm. The effective increase in absorbance cross-section resulting from the conjugation of two other dyes, Alexa Fluor 647 and Alexa Fluor 750, was also investigated. The key parameters that dictate the efficiency of dye-to-reaction center energy transfer and subsequent charge separation were examined using both steady-state and time-resolved fluorescence spectroscopy as well as transient absorbance spectroscopy techniques. An understanding of these parameters is an important first step toward developing more complex model light-harvesting systems integrated with reaction centers. PMID:24568563

  12. Experimental Study of the Cross Sections of {alpha}-Particle Induced Reactions on 209Bi

    SciTech Connect

    Hermanne, A.; Tarkanyi, F.; Takacs, S.; Szucs, Z.

    2005-05-24

    Alpha particle induced reactions for generation of 211At used in therapeutic nuclear medicine and possible contaminants were investigated with the stacked foil activation technique on natural bismuth targets up to E{alpha}=39 MeV. Excitation functions for the reactions 209Bi({alpha},2n)211At, 209Bi({alpha},3n)210At, 209Bi({alpha},x) 210Po obtained from direct alpha emission measurements and gamma spectra from decay products are compared with earlier literature values. Thick target yields have been deduced from the experimental cross sections.

  13. Acid–base bifunctional shell cross-linked micelle nanoreactor for one-pot tandem reaction

    DOE PAGES

    Lee, Li -Chen; Lu, Jie; Weck, Marcus; Jones, Christopher W.

    2015-12-29

    Shell cross-linked micelles (SCMs) containing acid sites in the shell and base sites in the core are prepared from amphiphilic poly(2-oxazoline) triblock copolymers. The materials are utilized as two-chamber nanoreactors for a prototypical acid-base bifunctional tandem deacetalization-nitroaldol reaction. Furthermore, the acid and base sites are localized in different regions of the micelle, allowing the two steps in the reaction sequence to largely proceed in separate compartments, akin to the compartmentalization that occurs in biological systems.

  14. N-tosylhydrazones: versatile reagents for metal-catalyzed and metal-free cross-coupling reactions.

    PubMed

    Shao, Zhihui; Zhang, Hongbin

    2012-01-21

    Transition metal-catalyzed cross-coupling reactions have been established as one of the most powerful tools for the construction of C-C and C-X bonds. In this context, the development of novel metal-catalyzed cross-coupling processes that do not require stoichiometric organometallic reagents is particularly attractive. Recently, N-tosylhydrazones have emerged as a new type of versatile coupling partners for transition metal-catalyzed cross-coupling reactions as well as metal-free cross-coupling reactions, and have attracted increasing attention. This tutorial review summarizes recent important developments in this area with N-tosylhydrazones as versatile coupling partners.

  15. Empirical formula on (n,(3)He) reaction cross sections at 14.6MeV neutrons.

    PubMed

    Yiğit, Mustafa

    2015-11-01

    The systematic behavior of the cross sections of (n,(3)He) nuclear reactions has been studied by various researches at neutron energy of 14.6MeV. A new empirical formula based on the Q-value dependence of the cross sections of the investigated reaction has been proposed. The cross sections obtained from the new formula are compared with the other proposed formulae results and the experimental data. It seems that the present formula based on the Q-value dependence provides the good description for cross sections of neutron-induced (n,(3)He) nuclear reactions at 14.6MeV.

  16. The effect of halo nuclear density on reaction cross-section for light ion collision

    NASA Astrophysics Data System (ADS)

    Hassan, M. A. M.; Nour El-Din, M. S. M.; Ellithi, A.; Ismail, E.; Hosny, H.

    2015-08-01

    In the framework of the optical limit approximation (OLA), the reaction cross-section for halo nucleus — stable nucleus collision at intermediate energy, has been studied. The projectile nuclei are taken to be one-neutron halo (1NHP) and two-neutron halo (2NHP). The calculations are carried out for Gaussian-Gaussian (GG), Gaussian-Oscillator (GO), and Gaussian-2S (G2S) densities for each considered projectile. As a target, the stable nuclei in the range 4-28 of the mass number are used. An analytic expression of the phase shift function has been derived. The zero range approximation is considered in the calculations. Also, the in-medium effect is studied. The obtained results are analyzed and compared with the geometrical reaction cross-section and the available experimental data.

  17. Thermal neutron radiative capture cross-section of 186W(n, γ)187W reaction

    NASA Astrophysics Data System (ADS)

    Tan, V. H.; Son, P. N.

    2016-06-01

    The thermal neutron radiative capture cross section for 186W(n, γ)187W reaction was measured by the activation method using the filtered neutron beam at the Dalat research reactor. An optimal composition of Si and Bi, in single crystal form, has been used as neutron filters to create the high-purity filtered neutron beam with Cadmium ratio of Rcd = 420 and peak energy En = 0.025 eV. The induced activities in the irradiated samples were measured by a high resolution HPGe digital gamma-ray spectrometer. The present result of cross section has been determined relatively to the reference value of the standard reaction 197Au(n, γ)198Au. The necessary correction factors for gamma-ray true coincidence summing, and thermal neutron self-shielding effects were taken into account in this experiment by Monte Carlo simulations.

  18. Cross-Coupling Reactions of Aromatic and Heteroaromatic Silanolates with Aromatic and Heteroaromatic Halides

    PubMed Central

    Denmark, Scott E.; Smith, Russell C.; Chang, Wen-Tau T.; Muhuhi, Joseck M.

    2009-01-01

    The alkali-metal salts (potassium and sodium) of a large number of aryl- and heteroarylsilanols undergo efficient cross coupling with a wide range of aromatic bromides and chlorides under mild conditions to form polysubstituted biaryls. The critical feature for the success of these coupling reactions and their considerable scope is the use of bis(tri-tert-butylphosphine)palladium. Under the optimized conditions, electron-rich, electron-poor, and sterically hindered arylsilanolates afford cross-coupling products in good yields. Many functional groups are compatible with the coupling conditions such as esters, ketones, acetals, ethers, silyl ethers, and dimethylamino groups. Two particularly challenging substrates, (2-benzofuranyl)dimethylsilanolate and (2,6-dichlorophenyl)dimethylsilanolate prepared as their sodium salts showed excellent activity in the coupling reactions, in the former case also with aromatic chlorides. General methods for the efficient synthesis of a wide range of aromatic silanols are also described. PMID:19199785

  19. Influence of projectile neutron number on cross section in cold fusion reactions

    SciTech Connect

    Dragojevic, Irena; Dragojevic, I.; Gregorich, K.E.; Dullmann, Ch.E.; Folden III, C.M.; Garcia, M.A.; Gates, J.M.; Nelson, S.L.; Sudowe, R.; Nitsche, H.

    2007-09-01

    Elements 107-112 [1,2] have been discovered in reactions between {sup 208}Pb or {sup 209}Bi targets and projectiles ranging from {sup 54}Cr through {sup 70}Zn. In such reactions, the compound nucleus can be formed at excitation energies as low as {approx}12 MeV, thus this type of reaction has been referred to as 'cold fusion'. The study of cold fusion reactions is an indispensable approach to gaining a better understanding of heavy element formation and decay. A theoretical model that successfully predicts not only the magnitudes of cold fusion cross sections, but also the shapes of excitation functions and the cross section ratios between various reaction pairs was recently developed by Swiatecki, Siwek-Wilczynska, and Wilczynski [3,4]. This theoretical model, also referred to as Fusion by Diffusion, has been the guide in all of our cold fusion studies. One particularly interesting aspect of this model is the large predicted difference in cross sections between projectiles differing by two neutrons. The projectile pair where this difference is predicted to be largest is {sup 48}Ti and {sup 50}Ti. To test and extend this model, {sup 208}Pb({sup 48}Ti,n){sup 255}Rf and {sup 208}Pb({sup 50}Ti,n){sup 257}Rf excitation functions were recently measured at the Lawrence Berkeley National Laboratory's (LBNL) 88-Inch Cyclotron utilizing the Berkeley Gas-filled Separator (BGS). The {sup 50}Ti reaction was carried out with thin lead targets ({approx}100 {micro}g/cm{sup 2}), and the {sup 48}Ti reaction with both thin and thick targets ({approx}470 {micro}g/cm{sup 2}). In addition to this reaction pair, reactions with projectile pairs {sup 52}Cr and {sup 54}Cr [5], {sup 56}Fe and {sup 58}Fe [6], and {sup 62}Ni [7] and {sup 64}Ni [8] will be discussed and compared to the Fusion by Diffusion predictions. The model predictions show a very good agreement with the data.

  20. Palladium- and nickel-catalyzed Kumada cross-coupling reactions of gem-difluoroalkenes and monofluoroalkenes with Grignard reagents.

    PubMed

    Dai, Wenpeng; Xiao, Juan; Jin, Guanyi; Wu, Jingjing; Cao, Song

    2014-11-01

    A novel Kumada-Tamao-Corriu cross-coupling reaction of gem-di- or monofluoroalkenes with Grignard reagents, with or without β-hydrogen atoms, in the presence of a catalytic amount of palladium- or nickel-based catalysts has been developed. The reaction is performed under mild conditions (room temperature or reflux in diethyl ether for 1-2 h) and leads to di-cross- or mono-cross-coupled products in good to high yields. PMID:25327183

  1. Elastic scattering and total reaction cross section of {sup 6}He+{sup 120}Sn

    SciTech Connect

    Faria, P. N. de; Lichtenthaeler, R.; Pires, K. C. C.; Lepine-Szily, A.; Guimaraes, V.; Mendes, D. R. Jr.; Barioni, A.; Morcelle, V.; Morais, M. C.; Camargo, O. Jr.; Alcantara Nunez, J.; Moro, A. M.; Arazi, A.; Rodriguez-Gallardo, M.; Assuncao, M.

    2010-04-15

    The elastic scattering of {sup 6}He on {sup 120}Sn has been measured at four energies above the Coulomb barrier using the {sup 6}He beam produced at the RIBRAS (Radioactive Ion Beams in Brasil) facility. The elastic angular distributions have been analyzed with the optical model and three- and four-body continuum-discretized coupled-channels calculations. The total reaction cross sections have been derived and compared with other systems of similar masses.

  2. New insights into the mechanism of iron-catalyzed cross-coupling reactions.

    PubMed

    Bekhradnia, Ahmadreza; Norrby, Per-Ola

    2015-03-01

    The mechanism of the iron-catalyzed cross-coupling of alkyl halides with aryl Grignard reagents is studied by a combination of GC monitoring and DFT calculation. Herein, we investigate two possible reaction pathways, the regular oxidative addition (OA) pathway and the atom transfer (AT) pathway that might occur in the rate-limiting step. The computational studies revealed that the AT pathway requires less energy than the regular OA pathway. PMID:25649755

  3. Cross sections for the ^98Mo(d,p) reaction for ^99Tc^m production

    NASA Astrophysics Data System (ADS)

    Chodash, P.; Angell, C. T.; Benitez, J.; Czesumska, A.; Norman, E. B.; Shugart, H.; Swanberg, E.; Yang, H.; Pedretti, M.

    2010-11-01

    There is currently a global shortage of ^99Tc^m, one of the most widely used medical isotopes. To alleviate this shortage, alternative methods for producing ^99Mo, the parent isotope, are being evaluated. One possible technique is the use of a cyclotron to produce ^99Mo via the ^98Mo(d,p) reaction. Existing data for this reaction only covers the energy range from 0.8 to 13 MeV.ootnotetextZ. Randa and K. Svoboda, J. Inorg. Nucl. Chem. 39 (1977) 2121 This work extends cross section data up to 65 MeV in order to better evaluate cyclotron production of ^99Mo. The stacked foil activation technique was used to measure the cross sections. Targets consisted of alternate layers of natural molybdenum and aluminum metal foils. The aluminum was used as an energy degrader, recoil catcher, and for the determination of the beam current. Cross sections for the ^98Mo(d,p) reaction were determined from 10 MeV to 65 MeV using LBNL's 88-Inch Cyclotron. ^99Mo production was determined by observing the 739.5 keV gamma ray using a high purity germanium detector. Results of the experiment will be presented.

  4. Nucleus-nucleus total reaction cross sections, and the nuclear interaction radius

    SciTech Connect

    Abu-Ibrahim, Badawy

    2011-04-15

    We study the nucleus-nucleus total reaction cross sections for stable nuclei, in the energy region from 30A MeV to about 1A GeV, and find them to be in proportion to ({radical}({sigma}{sub pp}{sup tot}Z{sub 1}{sup 2/3}+{sigma}{sub pn}{sup tot}N{sub 1}{sup 2/3})+{radical}({sigma}{sub pp}{sup tot}Z{sub 2}{sup 2/3}+{sigma}{sub pn}{sup tot}N{sub 2}{sup 2/3})) {sup 2} in the mass range 8 to 100. Also, we find a parameter-free relation that enables us to predict a total reaction cross section for any nucleus-nucleus within 10% uncertainty at most, using the experimental value of the total reaction cross section of a given nucleus-nucleus. The power of the relation is demonstrated by several examples. The energy dependence of the nuclear interaction radius is deduced; it is found to be almost constant in the energy range from about 200A MeV to about 1A GeV; in this energy range and for nuclei with N=Z, R{sub I}(A)=(1.14{+-}0.02)A{sup 1/3} fm.

  5. Bayesian Evaluation Including Covariance Matrices of Neutron-induced Reaction Cross Sections of {sup 181}Ta

    SciTech Connect

    Leeb, H. Schnabel, G.; Srdinko, Th.; Wildpaner, V.

    2015-01-15

    A new evaluation of neutron-induced reactions on {sup 181}Ta using a consistent procedure based on Bayesian statistics is presented. Starting point of the evaluation is the description of nuclear reactions via nuclear models implemented in TALYS 1.4. A retrieval of experimental data was performed and covariance matrices of the experiments were generated from an extensive study of the corresponding literature. All reaction channels required for a transport file up to 200 MeV have been considered and the covariance matrices of cross section uncertainties for the most important channels are determined. The evaluation has been performed in one step including all available experimental data. A comparison of the evaluated cross sections and spectra with experimental data and available evaluations is performed. In general the evaluated cross section reflect our best knowledge and give a fair description of the observables. However, there are few deviations from expectation which clearly indicate the impact of the prior and the need to account for model defects. Using the results of the evaluation a complete ENDF-file similarly to those of the TENDL library is generated.

  6. Neutrino-Induced Neutral-Current Reaction Cross Sections for r-PROCESS Nuclei

    NASA Astrophysics Data System (ADS)

    Langanke, K.; Kolbe, E.

    2002-11-01

    Neutrino-induced reactions play an important role during and after the r-process, if the latter occurs in an environment with extreme neutrino fluxes such as the neutrino-driven wind model or neutron star mergers. Recently we have evaluated the charged-current neutrino-nucleus cross sections relevant for r-process simulations. We extend our approach here to the neutral-current cross sections. Our tabulation considers neutron-rich nuclei with neutron numbers N=41-135 and charge numbers Z=21-82 and lists total as well as partial neutron spallation cross sections. The calculations have been performed within the random phase approximation considering multipole transitions with J<=3 and both parities. The supernova neutrino spectrum is described by a Fermi-Dirac distribution with various temperature parameters between T=2.8 MeV and T=10 MeV and with the degeneracy parameters α=0 and α=3.

  7. Preparation of cross-linked maize (Zea mays L.) starch in different reaction media.

    PubMed

    Hong, Jung Sun; Gomand, Sara V; Delcour, Jan A

    2015-06-25

    Granular normal maize starch was reacted with sodium trimetaphosphate in deionized water ( [Formula: see text] ), aqueous sodium sulfate solution ( [Formula: see text] ), aqueous ethanol (MSethanol) or aqueous acetone (MSacetone) under otherwise identical reaction conditions. Analysis of the resultant starches by Rapid Visco Analysis (RVA) showed that the starch was cross-linked to a higher degree in aqueous ethanol or aqueous acetone than in water or sodium sulfate solution, and with minimal starch leaching. While MSacetone and MSethanol had incorporated similar levels of phosphorous, RVA analysis and microscopic analysis showed that MSacetone granules were more effectively stabilized by cross-linking than MSethanol granules. Cross-linking in aqueous acetone is believed to either contain the greater numbers of distarch monophosphate (versus monostarch monophosphate), or occur more intensively at the granule outer layers than that in aqueous ethanol and, at the same time, to account for the greater granular strength of MSethanol than that of MSacetone. PMID:25839824

  8. Code System to Calculate Nuclear Reaction Cross Sections by Evaporation Model.

    2000-11-27

    Version: 00 Both STAPRE and STAPREF are included in this package. STAPRE calculates energy-averaged cross sections for nuclear reactions with emission of particles and gamma rays and fission. The models employed are the evaporation model with inclusion of pre-equilibrium decay and a gamma-ray cascade model. Angular momentum and parity conservation are accounted for. Major improvement in the 1976 STAPRE program relates to level density approach, implemented in subroutine ZSTDE. Generalized superfluid model is incorporated, boltzman-gasmore » modeling of intrinsic state density and semi-empirical modeling of a few-quasiparticle effects in total level density at equilibrium and saddle deformations of actinide nuclei. In addition to the activation cross sections, particle and gamma-ray production spectra are calculated. Isomeric state populations and production cross sections for gamma rays from low excited levels are obtained, too. For fission a single or a double humped barrier may be chosen.« less

  9. Further Exploration of the 33S(α,p)36Cl Reaction Cross Section

    NASA Astrophysics Data System (ADS)

    Skulski, Michael; Anderson, Tyler; Beard, Mary; Collon, Philippe; Lu, Wenting; Ostdiek, Karen

    2015-10-01

    Short-lived radionuclides (SLRs) are extant from the Early Solar System (ESS) and useful for dating products of ESS processes. The SLR 36Cl was potentially produced by solar energetic particles incident on gas and dust in the protoplanetary disk. Measurement of the cross section of the reaction 33S(α,p)36Cl, which contributes significantly to the abundance of 36Cl, is an important input in solar irradiation models regarding the determination of elemental abundances, and is thus of great interest. In a previous measurement performed by Bowers et al. (2013), the cross section of this reaction was studied using a combination of activation of a 4He gas cell and analyzing the produced 36Cl via Accelerator Mass Spectrometry (AMS) over an energy range of 0.7 - 2.42 MeV/A. The result of this measurement was a significantly higher yield of 36Cl than predicted by Hauser-Feshbach cross section calculations. In light of the paper by Mohr (2013), the same activation was repeated at the University of Notre Dame at intermediate energies to study the cross section further, using the same combination of activation and AMS. The results of this measurement will be presented.

  10. Estimation of (n,f) Cross-Sections by Measuring Reaction Probability Ratios

    SciTech Connect

    Plettner, C; Ai, H; Beausang, C W; Bernstein, L A; Ahle, L; Amro, H; Babilon, M; Burke, J T; Caggiano, J A; Casten, R F; Church, J A; Cooper, J R; Crider, B; Gurdal, G; Heinz, A; McCutchan, E A; Moody, K; Punyon, J A; Qian, J; Ressler, J J; Schiller, A; Williams, E; Younes, W

    2005-04-21

    Neutron-induced reaction cross-sections on unstable nuclei are inherently difficult to measure due to target activity and the low intensity of neutron beams. In an alternative approach, named the 'surrogate' technique, one measures the decay probability of the same compound nucleus produced using a stable beam on a stable target to estimate the neutron-induced reaction cross-section. As an extension of the surrogate method, in this paper they introduce a new technique of measuring the fission probabilities of two different compound nuclei as a ratio, which has the advantage of removing most of the systematic uncertainties. This method was benchmarked in this report by measuring the probability of deuteron-induced fission events in coincidence with protons, and forming the ratio P({sup 236}U(d,pf))/P({sup 238}U(d,pf)), which serves as a surrogate for the known cross-section ratio of {sup 236}U(n,f)/{sup 238}U(n,f). IN addition, the P({sup 238}U(d,d{prime}f))/P({sup 236}U(d,d{prime}f)) ratio as a surrogate for the {sup 237}U(n,f)/{sup 235}U(n,f) cross-section ratio was measured for the first time in an unprecedented range of excitation energies.

  11. Synthesis of marine polyacetylenes callyberynes A-C by transition-metal-catalyzed cross-coupling reactions to sp centers.

    PubMed

    López, Susana; Fernandez-Trillo, Francisco; Midón, Pilar; Castedo, Luis; Saa, Carlos

    2006-03-31

    Efficient total syntheses of the sponge-derived hydrocarbon polyacetylenes callyberynes A-C have been achieved using metal-catalyzed cross-coupling reactions of highly unsaturated 1,3-diyne fragments as the key steps, namely: Cadiot-Chodkiewicz reaction under Alami's optimized conditions (sp-sp), sequential Sonogashira reaction of a cis,cis-divinyl dihalide (sp2-sp), and Kumada-Corriu reaction of an unactivated alkyl iodide (sp3-sp). This last approach constitutes the first application of a metal-catalyzed sp3-sp Kumada-Corriu cross-coupling reaction to the synthesis of a natural product.

  12. Synthesis of hindered biphenyls by sequential non-transition metal-catalyzed reaction/palladium-catalyzed cross-couplings.

    PubMed

    He, Ping; Dong, Cheng-Guo; Hu, Qiao-Sheng

    2008-03-17

    The sequential reaction of 1,2-dihalobenzenes with aryl lithiums followed by palladium-catalyzed cross-coupling reactions with Grignard reagents and arylboronic acids is described. This sequential reaction provides a convenient and expeditious access to tri-ortho substituted biaryl derivatives.

  13. Tandem reactions initiated by copper-catalyzed cross-coupling: a new strategy towards heterocycle synthesis.

    PubMed

    Liu, Yunyun; Wan, Jie-Ping

    2011-10-21

    Copper-catalyzed cross-coupling reactions which lead to the formation of C-N, C-O, C-S and C-C bonds have been recognized as one of the most useful strategies in synthetic organic chemistry. During past decades, important breakthroughs in the study of Cu-catalyzed coupling processes demonstrated that Cu-catalyzed reactions are broadly applicable to a variety of research fields related to organic synthesis. Representatively, employing these coupling transformations as key steps, a large number of tandem reactions have been developed for the construction of various heterocyclic compounds. These tactics share the advantages of high atom economics of tandem reactions as well as the broad tolerance of Cu-catalyst systems. Therefore, Cu-catalyzed C-X (X = N, O, S, C) coupling transformation-initiated tandem reactions were quickly recognized as a strategy with great potential for synthesizing heterocyclic compounds and gained worldwide attention. In this review, recent research progress in heterocycle syntheses using tandem reactions initiated by copper-catalyzed coupling transformations, including C-N, C-O, C-S as well as C-C coupling processes are summarized. PMID:21879127

  14. Cross-coupling reactions as valuable tool for the preparation of PET radiotracers.

    PubMed

    Pretze, Marc; Grosse-Gehling, Philipp; Mamat, Constantin

    2011-01-26

    The increasing application of positron emission tomography (PET) in nuclear medicine has stimulated the extensive development of a multitude of new radiotracers and novel radiolabeling procedures with the most prominent short-lived positron emitters carbon-11 and fluorine-18. Radiolabeling with these radionuclides represents a remarkable challenge. Special attention has to be paid to synthesis time and specific labeling techniques due to the short physical half life of the respective radionuclides ¹¹C (t(½) = 20.4 min) and ¹⁸F (t½) = 109.8 min). In the past, numerous transition metal-catalyzed reactions were employed in organic chemistry, even though only a handful of these coupling reactions were adopted in radiochemical practice. Thus, the implementation of modern synthesis methods like cross-coupling reactions offers the possibility to develop a wide variety of novel radiotracers. The introduction of catalysts based on transition metal complexes bears a high potential for rapid, efficient, highly selective and functional group-tolerating incorporation of carbon-11 and fluorine-18 into target molecules. This review deals with design, application and improvement of transition metal-mediated carbon-carbon as well as carbon-heteroatom cross-coupling reactions as a labeling feature with the focus on the preparation of radiolabeled compounds for molecular imaging.

  15. A case of levocetirizine-induced fixed drug eruption and cross-reaction with piperazine derivatives

    PubMed Central

    Kim, Mi-Yeong; Jo, Eun-Jung; Chang, Yoon-Seok; Cho, Sang-Heon; Min, Kyung-Up

    2013-01-01

    Fixed drug eruption is an uncommon adverse drug reaction caused by delayed cell-mediated hypersensitivity. Levocetirizine is an active (R)-enatiomer of cetirizine and there have been a few reports of fixed drug eruption related to these antihistamines. We experienced a case of levocetirizine-induced fixed drug eruption and cross-reaction with other piperazine derivatives confirmed by patch test. A 73-year-old female patient presented with recurrent generalized itching, cutaneous bullae formation, rash and multiple pigmentation at fixed sites after taking drugs for common cold. She took bepotastine besilate (Talion®) and levocetirizine (Xyzal®) as antihistamine. She took acetaminophen, pseudoephedrine 60 mg / triprolidine 2.5 mg (Actifed®), dihydrocodeinebitartrate 5 mg / di-methylephedrine hydrochloride 17.5 mg / chlorpheniramine maleate 1.5 mg / guaifenesin 50 mg (Codening®) and aluminium hydroxide 200 mg / magnesium carbonate 120 mg (Antad®) at the same time. Patch test was done with suspected drugs and the result was positive with levocetirizine. We additionally performed patch test for other antihistamines such as cetirizine, hydroxyzine, fexofenadine and loratadine. Piperazine derivatives (cetirizine and hydroxyzine) were positive, but piperidine derivatives (fexofenadine and loratadine) were negative to patch test. There was no adverse drug reaction when she was challenged with fexofenadine. We report a case of levocetirizine-induced fixed drug eruption confirmed by patch test. Cross-reactions were only observed in the piperazine derivatives and piperidine antihistamine was tolerant to the patient. PMID:24260733

  16. A case of levocetirizine-induced fixed drug eruption and cross-reaction with piperazine derivatives.

    PubMed

    Kim, Mi-Yeong; Jo, Eun-Jung; Chang, Yoon-Seok; Cho, Sang-Heon; Min, Kyung-Up; Kim, Sae-Hoon

    2013-10-01

    Fixed drug eruption is an uncommon adverse drug reaction caused by delayed cell-mediated hypersensitivity. Levocetirizine is an active (R)-enatiomer of cetirizine and there have been a few reports of fixed drug eruption related to these antihistamines. We experienced a case of levocetirizine-induced fixed drug eruption and cross-reaction with other piperazine derivatives confirmed by patch test. A 73-year-old female patient presented with recurrent generalized itching, cutaneous bullae formation, rash and multiple pigmentation at fixed sites after taking drugs for common cold. She took bepotastine besilate (Talion®) and levocetirizine (Xyzal®) as antihistamine. She took acetaminophen, pseudoephedrine 60 mg / triprolidine 2.5 mg (Actifed®), dihydrocodeinebitartrate 5 mg / di-methylephedrine hydrochloride 17.5 mg / chlorpheniramine maleate 1.5 mg / guaifenesin 50 mg (Codening®) and aluminium hydroxide 200 mg / magnesium carbonate 120 mg (Antad®) at the same time. Patch test was done with suspected drugs and the result was positive with levocetirizine. We additionally performed patch test for other antihistamines such as cetirizine, hydroxyzine, fexofenadine and loratadine. Piperazine derivatives (cetirizine and hydroxyzine) were positive, but piperidine derivatives (fexofenadine and loratadine) were negative to patch test. There was no adverse drug reaction when she was challenged with fexofenadine. We report a case of levocetirizine-induced fixed drug eruption confirmed by patch test. Cross-reactions were only observed in the piperazine derivatives and piperidine antihistamine was tolerant to the patient. PMID:24260733

  17. Direct measurement of the 22Ne(p,γ)23Na reaction cross section at LUNA

    NASA Astrophysics Data System (ADS)

    Ferraro, Federico; LUNA Collaboration

    2016-06-01

    The 22Ne(p, γ)23Na reaction takes part in the NeNa cycle of hydrogen burning, influencing the production of the elements between 20Ne and 27Al in red giant stars, asymptotic giant stars and classical novae. The 22Ne(p,γ)27Na reaction rate is very uncertain because of a large number of tentative resonances in the Gamow window, where only upper limits were quoted in literature. A direct measurement of the 22Ne(p, γ)23Na reaction cross section has been carried out at LUNA using a windowless differential-pumping gas target with two high- purity germanium (HPGe) detectors. A new measurement with a 4π bismuth germanate (BGO) summing detector is ongoing. During the HPGe phase of the experiment the strengths of the resonances at 156.2 keV, 189.5 keV and 259.7 keV have been directly measured for the first time and their contribution to the reaction rate has been calculated. The decay scheme of the newly discovered resonances has been established as well and some improved upper limits on the unobserved resonances have been put. The BGO detector with its 70% γ-detection efficiency allows to measure the cross section at lower energy. In order to further investigate the resonances at 71 keV and 105 keV and the direct-capture component, the data taking is ongoing.

  18. Activation cross sections for reactions induced by 14 MeV neutrons on natural tantalum

    SciTech Connect

    Luo Junhua; Tuo Fei; Kong Xiangzhong

    2009-05-15

    Cross sections for (n,2n), (n,p), (n,n{sup '}{alpha}), (n,t), (n,d{sup '}), and (n,{alpha}) reactions have been measured on tantalum isotopes at the neutron energies of 13.5 to 14.7 MeV using the activation technique. Data are reported for the following reactions: {sup 181}Ta(n,2n){sup 180}Ta{sup g}, {sup 181}Ta(n,p){sup 181}Hf, {sup 181}Ta(n,n{sup '}{alpha}){sup 177}Lu{sup m}, {sup 181}Ta(n,t){sup 179}Hf{sup m2}, {sup 181}Ta(n,d{sup '}){sup 180}Hf{sup m}, and {sup 181}Ta(n,{alpha}){sup 178}Lu{sup m}. The neutron fluences were determined using the monitor reaction {sup 27}Al(n,{alpha}){sup 24}Na. Results were discussed and compared with the previous works.

  19. Crossed molecular beam study of the reaction O([sup 3][ital P])+allene

    SciTech Connect

    Schmoltner, A.M.; Huang, S.Y.; Brudzynski, R.J.; Chu, P.M.; Lee, Y.T. )

    1993-08-01

    The reaction between ground state ([sup 3][ital P]) oxygen atoms and allene was studied under single collision conditions using the crossed molecular beams method. Product angular distributions and the translational energy distribution were determined for each channel. Two major reaction channels could be identified unambiguously: the formation of carbon monoxide and ethylene following oxygen atom attack on the central carbon atom, and the formation of allenyloxy (formyl--vinyl) radical and hydrogen atom following oxygen atom attack on the terminal carbon atom. In addition, at least one other reaction channel, which could be identified as the production of vinyl and formyl radicals, occurs. This channel involves the decomposition of acrolein which is formed by the addition of oxygen to the terminal carbon atom, followed by 1,2-hydrogen migration.

  20. Estimating Reaction Cross Sections from Measured (Gamma)-Ray Yields: The 238U(n,2n) and 239Pu(n,2n) Cross Sections

    SciTech Connect

    Younes, W

    2002-11-18

    A procedure is presented to deduce the reaction-channel cross section from measured partial {gamma}-ray cross sections. In its simplest form, the procedure consists in adding complementary measured and calculated contributions to produce the channel cross section. A matrix formalism is introduced to provide a rigorous framework for this approach. The formalism is illustrated using a fictitious product nucleus with a simple level scheme, and a general algorithm is presented to process any level scheme. In order to circumvent the cumbersome algebra that can arise in the matrix formalism, a more intuitive graphical procedure is introduced to obtain the same reaction cross-section estimate. The features and limitations of the method are discussed, and the technique is applied to extract the {sup 235}U (n,2n) and {sup 239}Pu(n,2n) cross sections from experimental partial {gamma}-ray cross sections, coupled with (enhanced) Hauser-Feshbach calculations.

  1. Cross sections of proton- and neutron-induced reactions by the Liège intranuclear cascade model

    NASA Astrophysics Data System (ADS)

    Chen, Jian; Dong, Tiekuang; Ren, Zhongzhou

    2016-06-01

    The purpose of the paper is mainly to test the validity of the Liège intranuclear cascade (INCL) model in calculating the cross sections of proton-induced reactions for cosmogenic nuclei using the newly compiled database of proton cross sections. The model calculations of 3He display the rising tendency of cross sections with the increase of energy, in accordance with the experimental data. Meanwhile, the differences between the theoretical results and experimental data of production cross sections (10Be and 26Al) are generally within a factor of 3, meaning that the INCL model works quite well for the proton-induced reactions. Based on the good agreement, we predict the production cross sections of 26Al from reactions n + 27Al, n + 28Si, and n + 40Ca and those of 10Be from reactions n + 16O and n + 28Si. The results also show a good agreement with a posteriori excitation functions.

  2. Well-defined N-heterocyclic carbenes-palladium(II) precatalysts for cross-coupling reactions.

    PubMed

    Marion, Nicolas; Nolan, Steven P

    2008-11-18

    Metal-catalyzed cross-coupling reactions, notably those permitting C-C bond formation, have witnessed a meteoritic development and are now routinely employed as a powerful synthetic tool both in academia and in industry. In this context, palladium is arguably the most studied transition metal, and tertiary phosphines occupy a preponderant place as ancillary ligands. Seriously challenging this situation, the use of N-heterocyclic carbenes (NHCs) as alternative ligands in palladium-catalyzed cross-coupling reactions is rapidly gaining in popularity. These two-electron donor ligands combine strong sigma-donating properties with a shielding steric pattern that allows for both stabilization of the metal center and enhancement of its catalytic activity. As a result, the number of well-defined NHC-containing palladium(II) complexes is growing, and their use in coupling reactions is witnessing increasing interest. In this Account, we highlight the advantages of this family of palladium complexes and review their synthesis and applications in cross-coupling chemistry. They generally exhibit high stability, allowing for indefinite storage and easy handling. The use of well-defined complexes permits a strict control of the Pd/ligand ratio (optimally 1/1), avoiding the use of excess costly ligand that usually requires end-game removal. Furthermore, it partly removes the "black box" character often associated with cross-coupling chemistry and catalyst formation. In the present Account, four main classes of NHC-containing palladium(II) complexes will be presented: palladium dimers with bridging halogens, palladacycles, palladium acetates and acetylacetonates, and finally pi-allyl complexes. These additional ligands are best described as a protecting shell that will be discarded going from the palladium(II) precatalyst to the palladium(0) true catalyst. The synthesis of all these precatalysts generally requires simple and short synthetic procedures. Their catalytic activity in

  3. Fast and Sequence-Specific Palladium-Mediated Cross-Coupling Reaction Identified from Phage Display

    PubMed Central

    2015-01-01

    Fast and specific bioorthogonal reactions are highly desirable because they provide efficient tracking of biomolecules that are present in low abundance and/or involved in fast dynamic process in living systems. Toward this end, classic strategy involves the optimization of substrate structures and reaction conditions in test tubes, testing their compatibility with biological systems, devising synthetic biology schemes to introduce the modified substrates into living cells or organisms, and finally validating the superior kinetics for enhanced capacity in tracking biomolecules in vivo—a lengthy process often mired by unexpected results. Here, we report a streamlined approach in which the “microenvironment” of a bioorthogonal chemical reporter is exploited directly in biological systems via phage-assisted interrogation of reactivity (PAIR) to optimize not only reaction kinetics but also specificity. Using the PAIR strategy, we identified a short alkyne-containing peptide sequence showing fast kinetics (k2 = 13 000 ± 2000 M–1 s–1) in a palladium-mediated cross-coupling reaction. Site-directed mutagenesis studies suggested that the residues surrounding the alkyne moiety facilitate the assembly of a key palladium–alkyne intermediate along the reaction pathway. When this peptide sequence was inserted into the extracellular domain of epidermal growth factor receptor (EGFR), this reactive sequence directed the specific labeling of EGFR in live mammalian cells. PMID:25025771

  4. [Reflections about allergic and crossed reactions to sulphonamides and drugs with radical-sulphonamide].

    PubMed

    Montes Montes, José; Alfonso Barrón, Enrique; Cruz Leyva, Jazmín del Alva; Flores Flores, José

    2004-01-01

    In the daily pharmacological therapy, some compounds may cause eventually allergic hypersensitivity reactions generating adverse effects. The objective of this study and its reflections has been to recommend caution, being prudent when expressing an opinion on risks and benefits of drugs themselves or some of their radicals that may contain because this attitude might produce a unsuitable concern. Drugs hypersensitivity (an unexpected pharmacological effect) may resemble a true allergic reaction but without the implication of IgE immunoglobulin. Such reactions are result of effector systems drug activation, leading to direct proallergic or proinflammatory chemical mediators release from mast cells, basophils and eosinophils. Sulphonamides are an illustrative example because they possess a chemical core resembling that from other kind of drugs -furosemide, some COXIB and others- besides its haptenic capability (even though they have different chemical structure). Selective COX 2 inhibitors are considered an accepted symptomatic therapy in rheumatic diseases as well as some other conditions where pain and inflammation are present; based on its generalized use in such conditions, authors decided to perform this investigation in the allergy clinics of Hospital General de México and Hospital Español de México, looking for cases of true allergic, crossed or hypersensitivity reactions related to one COXIB that includes a sulphamidic radical in its chemical structure. No clinical significance was found concerning the above mentioned reactions and the antiinflammatory-analgesic compound (celecoxib).

  5. Fast and sequence-specific palladium-mediated cross-coupling reaction identified from phage display.

    PubMed

    Lim, Reyna K V; Li, Nan; Ramil, Carlo P; Lin, Qing

    2014-09-19

    Fast and specific bioorthogonal reactions are highly desirable because they provide efficient tracking of biomolecules that are present in low abundance and/or involved in fast dynamic process in living systems. Toward this end, classic strategy involves the optimization of substrate structures and reaction conditions in test tubes, testing their compatibility with biological systems, devising synthetic biology schemes to introduce the modified substrates into living cells or organisms, and finally validating the superior kinetics for enhanced capacity in tracking biomolecules in vivo--a lengthy process often mired by unexpected results. Here, we report a streamlined approach in which the "microenvironment" of a bioorthogonal chemical reporter is exploited directly in biological systems via phage-assisted interrogation of reactivity (PAIR) to optimize not only reaction kinetics but also specificity. Using the PAIR strategy, we identified a short alkyne-containing peptide sequence showing fast kinetics (k2=13,000±2000 M(-1) s(-1)) in a palladium-mediated cross-coupling reaction. Site-directed mutagenesis studies suggested that the residues surrounding the alkyne moiety facilitate the assembly of a key palladium-alkyne intermediate along the reaction pathway. When this peptide sequence was inserted into the extracellular domain of epidermal growth factor receptor (EGFR), this reactive sequence directed the specific labeling of EGFR in live mammalian cells. PMID:25025771

  6. Exploring Regioselective Bond Cleavage and Cross-Coupling Reactions using a Low-Valent Nickel Complex.

    PubMed

    Desnoyer, Addison N; Friese, Florian W; Chiu, Weiling; Drover, Marcus W; Patrick, Brian O; Love, Jennifer A

    2016-03-14

    Recently, esters have received much attention as transmetalation partners for cross-coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}2(μ-η(2):η(2)-C6H6)] (dtbpe=1,2-bis(di-tert-butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η(2)-carbonyl complexes. In contrast, acetylthioesters underwent rapid Cacyl-S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross-coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an η(2)-carbonyl complex, phenyl esters were found to predominantly undergo Caryl-O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2-naphthyl acetate was also found to undergo clean Caryl-O bond cleavage, and although stoichiometric cross-coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive.

  7. Computational study of gold-catalyzed homo- and cross-coupling reactions.

    PubMed

    Nieto Faza, Olalla; Silva López, Carlos

    2013-05-17

    The role of gold as the organizing metal in homo- and cross-coupling reactions is explored in this paper combining DFT calculations with QTAIM, NBO, and the energetic span model analysis. For the gold(III) complex 7, a key intermediate in the experimental oxidative coupling scheme by Zhang et al., we describe the mechanisms corresponding to a cross-coupling after transmetalation with boron compounds and to a homocoupling after transmetalation with the original gold(I) complex 6, a new example of dual role of this metal in homogeneous catalysis. We predict for the first path a two-step transmetalation with a low energy rate-limiting step characterized by a four-center transition structure, where fluorine plays an essential role, followed by a reductive elimination where the C-C bond formation is coupled to the departure of fluorine from the gold center. The homocoupling path follows a similar mechanism, with a two-step transmetalation with interesting changes in bonding around the Au(I) center and a rate-limiting reductive elimination. Our findings on the competition between mechanisms, and the effect of ligands and solvent, agree with the experimental results and provide new insights into the mechanism of gold-catalyzed cross-coupling reactions. PMID:23597253

  8. Recurrent acute hemolytic transfusion reactions by antibodies against Doa antigens, not detected by cross-matching.

    PubMed

    Baumgarten, Ruben; van Gelder, Warry; van Wintershoven, Joyce; Maaskant-Van Wijk, Petra A; Beckers, Erik A M

    2006-02-01

    An 81-year-old male patient suffered from recurrent acute hemolytic transfusion reactions after transfusion with phenotyped cross-match-negative red blood cells (RBCs). Extensive posttransfusion workup eventually revealed Dombrock (a) (Do(a)) antibodies. Because commercially available cell panels do not allow for identification of anti-Do(a) and owing to the lack of Do(a) typing serum samples, selection of matched units of RBCs is dependent on negative cross-match results. In this case, selection of Do(a-) units by cross-matching failed, indicating that serologic methods were not reliable. A polymerase chain reaction with sequence-specific priming assay was used to detect DOA and DOB alleles, which encode Do(a) and Do(b) antigens, respectively. The patient was confirmed to be DOB/DOB by DNA sequencing. Furthermore, the involved mismatched units in each of the three hemolytic episodes were shown to be Do(a+). In the presenting case, DNA typing appeared to be superior to serologic methods in selecting matched RBC units in the presence of anti-Do(a). PMID:16441602

  9. Exploring Regioselective Bond Cleavage and Cross-Coupling Reactions using a Low-Valent Nickel Complex.

    PubMed

    Desnoyer, Addison N; Friese, Florian W; Chiu, Weiling; Drover, Marcus W; Patrick, Brian O; Love, Jennifer A

    2016-03-14

    Recently, esters have received much attention as transmetalation partners for cross-coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}2(μ-η(2):η(2)-C6H6)] (dtbpe=1,2-bis(di-tert-butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η(2)-carbonyl complexes. In contrast, acetylthioesters underwent rapid Cacyl-S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross-coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an η(2)-carbonyl complex, phenyl esters were found to predominantly undergo Caryl-O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2-naphthyl acetate was also found to undergo clean Caryl-O bond cleavage, and although stoichiometric cross-coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive. PMID:26879766

  10. Measurement of alpha-induced reaction cross sections on erbium isotopes for γ process studies

    SciTech Connect

    Kiss, G. G.; Szücs, T.; Török, Zs.; Fülöp, Zs.; Gyürky, Gy.; Halász, Z.; Somorjai, E.; Rauscher, T.

    2014-05-02

    The cross sections of the {sup 162}Er(α,γ){sup 166}Yb and {sup 162,164,166}Er(α,n){sup 165,167,169}Yb reactions have been measured at MTA Atomki. The radiative alpha capture reaction cross section was measured between E{sub c.m.} = 11.21 MeV and E{sub c.m.} = 16.09 MeV just above the astrophysically relevant energy region (which lies between 7.8 and 11.48 MeV at T{sub 9} = 3 GK). The {sup 162}Er(α,n){sup 165}Yb, {sup 164}Er(α,n){sup 167}Yb and {sup 166}Er(α,n){sup 169}Yb reactions were studied between E{sub c.m.} = 12.19 and 16.09 MeV, E{sub c.m.} = 13.17 and 16.59 MeV and E{sub c.m.} = 12.68 and 17.08 MeV, respectively. The aim of this work is to provide experimental data for modeling the γ process which is thought to be responsible for the production of the proton-rich isotopes heavier than iron.

  11. Teaching Absolute Value Meaningfully

    ERIC Educational Resources Information Center

    Wade, Angela

    2012-01-01

    What is the meaning of absolute value? And why do teachers teach students how to solve absolute value equations? Absolute value is a concept introduced in first-year algebra and then reinforced in later courses. Various authors have suggested instructional methods for teaching absolute value to high school students (Wei 2005; Stallings-Roberts…

  12. Development of Chiral Bis-hydrazone Ligands for the Enantioselective Cross-Coupling Reactions of Aryldimethylsilanolates

    PubMed Central

    2015-01-01

    A palladium-catalyzed, enantioselective, aryl–aryl cross-coupling reaction using 1-naphthyldimethylsilanolates and chiral bis-hydrazone ligands has been developed. A family of glyoxal bis-hydrazone ligands containing various 2,5-diarylpyrrolidine groups was prepared to evaluate the influence of ligand structure on the rate and enantioselectivity of the cross-coupling. New synthetic routes to the 1-amino-2,5-diarylpyrrolidines were developed to enable the structure/reactivity–selectivity studies. Role reversal experiments of aryldimethylsilanolates and aryl bromides result in biaryl products with the same configuration and similar enantioselectivities implying that reductive elimination is the stereodetermining step. The origin of stereoselectivity is rationalized through computational modeling of diarylpalldium(II) complex which occurs through a conrotatory motion for the two aryl groups undergoing C–C bond formation. PMID:25494058

  13. Experimental cross-sections for proton-induced nuclear reactions on natMo

    NASA Astrophysics Data System (ADS)

    Červenák, Jaroslav; Lebeda, Ondřej

    2016-08-01

    In the framework of the Co-ordinated Research Project of the IAEA, we measured in detail cross-sections of the nuclear reactions natMo(p,x)93gTc, 93mTc, 93m+gTc, 94gTc, 94mTc, 95gTc, 95mTc, 96m+gTc, 97mTc, 99mTc, 90Mo, 93mMo, 99Mo, 88gNb, 88mNb, 89gNb, 89mNb, 90m+gNb, 90m+gNbcum, 91mNb, 92mNb, 95gNb, 95mNb, 95m+gNb, 96Nb, 97m+gNb, 88m+gZrcum and 89m+gZrcum in the energy range of 6.9-35.8 MeV. The data for formation of 97mTc, 88gNb, 88mNb and 89mNb are reported for the first time. The obtained results were compared to the prediction of the nuclear reaction model code TALYS adopted from the TENDL-2015 library and to the previously published cross-sections. The thick target yields for all the radionuclides were calculated from the measured data. We suggest recommended cross-sections and thick target yields for the 100Mo(p,2n)99mTc, 100Mo(p,x)99Mo and natMo(p,x)96m+gTc nuclear reactions deduced from the selected experimental data.

  14. Measurement of the ^241Am(n,2n) Reaction Cross Section with the Activation Technique

    NASA Astrophysics Data System (ADS)

    Tonchev, A.; Crowell, A.; Fallin, B.; Howell, C.; Hutcheson, A.; Tornow, W.; Kelley, J.; Angell, C.; Karwowski, H.; Pedroni, R.; Becker, J.; Dashdorj, D.; Macri, R.; Wilhelmy, J.; Bond, E.; Fitzpatrick, J.; Slemmons, A.; Vieira, D.

    2006-10-01

    High-precision measurements of the ^241Am(n,2n)^240Am reaction have been performed with neutron energies from 8.8 to 14.0 MeV. The monoenergetic neutron beams were produced via the ^2H(d,n)^3He reaction using the 10 MV Tandem accelerator at TUNL. The radioactive targets consisted of 1mg highly-enriched ^241Am sandwiched between four different thin monitor foils. They were irradiated with a neutron flux of 3x10^7 n cm-2 s-1. After each irradiation the induced activity in the targets and monitors was measured off-line with 60% HPGe detectors. Our preliminary neutron induced cross sections will be compared with recent literature results and statistical model calculations using the GNASH and EMPIRE codes.

  15. Mixed-ligand catalysts: a powerful tool in transition-metal- catalyzed cross-coupling reactions.

    PubMed

    Fan, Yuting; Cong, Mei; Peng, Ling

    2014-03-01

    Transition-metal-catalyzed cross-coupling reactions have fundamentally revolutionized organic synthesis, empowering the otherwise difficult to achieve products with rapid and convenient accesses alongside excellent yields. Within these reactions, ligands often play a critical role in specifically and effectively advocating the corresponding catalysis. Consequently, a myriad of ligands have been created and applied to make a fine tuning of electronic and steric effect of catalysts, remarkably promoting catalytic efficiency and applicability. The "mixed-ligand" concept has recently emerged; by combining and capitalizing on the superiority of each individual ligand already available, an expedient way can be achieved to reach a larger extent of catalytic diversity and efficacy. Given the availability of a wealth of ligands, it is reasonable to have great expectations for the original application of mixed-ligand catalytic systems and their important value in organic synthesis.

  16. 232Th(n,{gamma})233Th Thermal Reaction Cross-Section Measurement

    SciTech Connect

    Maidana, Nora L.; Vanin, Vito R.; Pascholati, Paulo R.; Helene, Otaviano; Castro, Ruy M.; Dias, Mauro S.; Koskinas, Marina F.

    2005-05-24

    The 232Th(n,{gamma})233Th thermal neutron-capture reaction cross section was measured using targets of {approx} 1.5 mg of high-purity metallic thorium irradiated in the IPEN IEA-R1m 5 MW pool research reactor. The 197Au(n,{gamma})198Au reaction was used to monitor the thermal and epithermal neutron fluxes in the irradiation position, which was found using the Westcott formalism. The residual gamma-ray activity was followed with an HPGe detector. The detector efficiency curve was fitted by the least-squares method applying covariance analysis to all uncertainties involved. The experimental result is {sigma}0 =7.20{+-}0.20 b, in agreement with previous published values.

  17. Activation cross sections for reactions induced by 14 MeV neutrons on natural ruthenium

    NASA Astrophysics Data System (ADS)

    Luo, Junhua; Liu, Gang; Tuo, Fei; Kong, Xiangzhong; Liu, Rong; Jiang, Li; Lou, Benchao

    2007-11-01

    Cross sections for (n,2n), (n,p), (n,α), and (n,d*)1 reactions have been measured on ruthenium isotopes at the neutron energies of 13.5 to 14.8 MeV using the activation technique in combination with high-resolution gamma-ray spectroscopy. Data are reported for the following reactions: Ru104(n,2n)Ru103, Ru98(n,2n)Ru97, Ru96(n,2n)Ru95, Ru96(n,p)Tc96g, Ru96(n,p)Tc96m, Ru104(n,p)Tc104, Ru102(n,p)Tc102m, Ru104(n,α)Mo101, Ru102(n,α)Mo99, Ru96(n,α)Mo93m, and Ru96(n,d*)Tc95m. Results were discussed and compared with the previous works.

  18. Control analysis of systems with reaction blocks that 'cross-talk'.

    PubMed

    Ainscow, E K; Brand, M D

    1998-09-01

    Practical application of metabolic control analysis has been facilitated by use of the top-down approach, which divides a metabolic system into a small number of reaction blocks, linked by a few key intermediates. Previous papers have stressed that communication between blocks should be only through the explicit intermediates, 'cross-talk' between reaction blocks invalidated the approach. Here we show how the restriction is a result of the use of inhibitors of the blocks, and can be overcome if other system modulations are used. We also show a way to treat the related problem of enzymes that appear in more than one block such as the analysis of glycolytic substrate cycles into ATP consuming and net flux activities.

  19. A General Palladium-Catalyzed Hiyama Cross-Coupling Reaction of Aryl and Heteroaryl Chlorides.

    PubMed

    Yuen, On Ying; So, Chau Ming; Man, Ho Wing; Kwong, Fuk Yee

    2016-05-01

    A general palladium-catalyzed Hiyama cross-coupling reaction of aryl and heteroaryl chlorides with aryl and heteroaryl trialkoxysilanes by a Pd(OAc)2 /L2 catalytic system is presented. A newly developed water addition protocol can dramatically improve the product yields. The conjugation of the Pd/L2 system and the water addition protocol can efficiently catalyze a broad range of electron-rich, -neutral, -deficient, and sterically hindered aryl chlorides and heteroaryl chlorides with excellent yields within three hours and the catalyst loading can be down to 0.05 mol % Pd for the first time. Hiyama coupling of heteroaryl chlorides with heteroaryl silanes is also reported for the first time. The reaction can be easily scaled up 200 times (100 mmol) without any degasification and purification of reactants; this facilitates the practical application in routine synthesis.

  20. Differential cross sections and spin density matrix elements for the reaction gamma p -> p omega

    SciTech Connect

    M. Williams, D. Applegate, M. Bellis, C.A. Meyer

    2009-12-01

    High-statistics differential cross sections and spin density matrix elements for the reaction gamma p -> p omega have been measured using the CLAS at Jefferson Lab for center-of-mass (CM) energies from threshold up to 2.84 GeV. Results are reported in 112 10-MeV wide CM energy bins, each subdivided into cos(theta_CM) bins of width 0.1. These are the most precise and extensive omega photoproduction measurements to date. A number of prominent structures are clearly present in the data. Many of these have not previously been observed due to limited statistics in earlier measurements.

  1. Reaction dynamics of phenyl radicals in extreme environments: a crossed molecular beam study.

    PubMed

    Gu, Xibin; Kaiser, Ralf I

    2009-02-17

    Polycyclic aromatic hydrocarbons (PAHs)organic compounds that consist of fused benzene ringsand their hydrogen-deficient precursors have attracted extensive interest from combustion scientists, organic chemists, astronomers, and planetary scientists. On Earth, PAHs are toxic combustion products and a source of air pollution. In the interstellar medium, research suggests that PAHs play a role in unidentified infrared emission bands, diffuse interstellar bands, and the synthesis of precursor molecules to life. To build clean combustion devices and to understand the astrochemical evolution of the interstellar medium, it will be critical to understand the elementary reaction mechanisms under single collision conditions by which these molecules form in the gas phase. Until recently, this work had been hampered by the difficulty in preparing a large concentration of phenyl radicals, but the phenyl radical represents one of the most important radical species to trigger PAH formation in high-temperature environments. However, we have developed a method for producing these radical species and have undertaken a systematic experimental investigation. In this Account, we report on the chemical dynamics of the phenyl radical (C(6)H(5)) reactions with the unsaturated hydrocarbons acetylene (C(2)H(2)), ethylene (C(2)H(4)), methylacetylene (CH(3)CCH), allene (H(2)CCCH(2)), propylene (CH(3)CHCH(2)), and benzene (C(6)H(6)) utilizing the crossed molecular beams approach. For nonsymmetric reactants such as methylacetylene and propylene, steric effects and the larger cones of acceptance drive the addition of the phenyl radical to the nonsubstituted carbon atom of the hydrocarbon reactant. Reaction intermediates decomposed via atomic hydrogen loss pathways. In the phenyl-propylene system, the longer lifetime of the reaction intermediate yielded a more efficient energy randomization compared with the phenyl-methylacetylene system. Therefore, two reaction channels were open: hydrogen

  2. Measurement of absolute total cross sections for the scattering of electrons by He, H/sub 2/, CH/sub 4/ and CCl/sub n/F/sub m/

    SciTech Connect

    Jones, R.K.

    1985-01-01

    Absolute total electron scattering sections (elastic plus inelastic, integrated over all angles) were measured for helium, molecular hydrogen, methane, tetrachloromethane, trichlorofluoromethane, dichlorodifluoromethane, chlorotrifluoromethane and tetrafluoromethane for incident electron energies from below 1 eV to 50 eV. The electron transmission spectrometer employed consisted of a broad spectrum pulsed electron source in line with a gas sample cell and electron detector. The electron energy was derived from the measured electron time of flight from the source to the detector. The total cross section was determined, using Beer's law, from the attenuation of the electron beam as it passed through a sample cell. Thorough theoretical studies have been reported for helium and the simpler molecules. For these systems, comparisons are made between the above results and reported absolute cross section measurements and calculations with careful consideration given to possible causes of the differences observed between recent measurements. For the more complicated molecules there are few reported calculations or measurements of the total cross sections. In these cases the low energy resonances associated with electron capture processes are not adequately described by available theoretical studies, so molecular orbital calculations and complementary experimental results are employed to explain the observed structure.

  3. Cross Sections for Neutron-induced Reactions on Actinide Targets Extracted from Surrogate Experiments: A Status Report

    SciTech Connect

    Escher, J E; Burke, J T; Dietrich, F S; Lesher, S R; Scielzo, N D; Thompson, I J; Younes, W

    2009-10-01

    The Surrogate nuclear reactions method, an indirect approach for determining cross sections for compound-nuclear reactions involving difficult-to-measure targets, is reviewed. Focusing on cross sections for neutron-induced reactions on actinides, we review the successes of past and present applications of the method and assess its uncertainties and limitations. The approximations used in the analyses of most experiments work reasonably well for (n,f) cross sections for neutron energies above 1-2 MeV, but lead to discrepancies for low-energy (n,f) reactions, as well as for (n,{gamma}) applications. Correcting for some of the effects neglected in the approximate analyses leads to improved (n,f) results. We outline steps that will further improve the accuracy and reliability of the Surrogate method and extend its applicability to reactions that cannot be approached with the present implementation of the method.

  4. Absolute cross sections for one electron capture into excited projectile states in collisions between He 2+ (15-150 keV) and Li atoms

    NASA Astrophysics Data System (ADS)

    Kadota, K.; Dijkkamp, D.; Van Der Woude, R.; Yan, Pan Guang; De Heer, F. J.

    1982-03-01

    We have studied the He 2+-Li collision system at laboratory energies between 15 and 150 keV using optical methods. From the measured emission cross sections we derive state-selective capture cross sections for n = 2,3,4 and n ⩾ 5 states of the He + ions. Our data are consistent with theoretical predictions of Bransden and Ermolaev. The total capture cross sections as evaluated from our emission cross section data, agree very well with the results of McCullough et al. obtained from projectile charge detection measurements. Near 15 keV our emission cross sections for 30.4 nm and 25.6 nm are much larger than those measured previously by Barrett and Leventhal at slightly lower energies.

  5. Measurement of Cross-sections of Yttrium (n,xn) Threshold Reactions by Means of Gamma Spectroscopy

    NASA Astrophysics Data System (ADS)

    Chudoba, P.; Kilim, S.; Wagner, V.; Vrzalova, J.; Svoboda, O.; Majerle, M.; Stefanik, M.; Suchopar, M.; Kugler, A.; Bielewicz, M.; Strugalska-Gola, E.; Szuta, M.; Hervas, D.; Herman, T.; Geier, B.

    Neutron activation and gamma spectrometry are usable also for the determination of cross-sections of different neutron reactions. We have studied the cross-section of yttrium (n,xn) threshold reactions using quasi mono-energetic neutron source based on the reaction on 7Li target at Nuclear Physics Institute of ASCR in Rez. Yttrium (n,xn) threshold reactions are suitable candidates for fast neutron field measurement by activation detectors. Fast neutron field monitoring is necessary already today at a wide range of accelerator facilities and will gain on importance in future fast reactors of generation IV, accelerator transmutation systems or fusion reactors. The knowledge of the cross-sections is crucial for such purpose. Unfortunately, the cross-section is sufficiently known only for 89Y(n,2n)88Y reaction. For higher orders of reactions there are almost no experimental data. Special attention was paid to the 89Y(n,3n)87Y reaction. The nuclei are produced, both in the ground state with half-life 79.8 hours and in the isomeric state with half-life 13.38 hours. The isomer decays mainly through the gamma transition to the ground state, the beta decay of the excited state is negligible within our accuracy. The cross-sections of both 87Y productions were analyzed.

  6. Activation of "inert" alkenyl/aryl C-O bond and its application in cross-coupling reactions.

    PubMed

    Li, Bi-Jie; Yu, Da-Gang; Sun, Chang-Liang; Shi, Zhang-Jie

    2011-02-01

    Enol and phenol functionalities are very common in organic molecules. Utilization of these materials is very appealing in organic synthesis because they are important alternatives to organohalides in cross-coupling reactions. In this review, we summarize the transition-metal-catalyzed cross-coupling of enol- and phenol-based electrophiles, including phosphates, sulfonates, ethers, carboxylates, and phenolates.

  7. Investigation of activation cross-section data of proton induced nuclear reactions on rhenium.

    PubMed

    Ditrói, F; Tárkányi, F; Takács, S; Hermanne, A; Yamazaki, H; Baba, M; Mohammadi, A; Ignatyuk, A V

    2013-07-01

    In the frame of systematic investigations of activation cross-section data for different applications the excitation functions of (nat)Re(p,x)(185)Os, (183m)Os, (183g)Os, (182)Os, (181m)Os, (186g)Re, (184m)Re, (184g)Re, (183)Re, (182m)Re, (182g)Re and (181g)Re reactions were measured up to 70MeV. The data for the (nat)Re(p,x) (183m)Os, (183g)Os, (182)Os, (181g)Os,(186g)Re, (184m)Re,(182m)Re, (182g)Re, and (181)Re reactions are reported for the first time. The activation method, the stacked foil irradiation technique and γ-spectroscopy for activity detection were used. The experimental data were compared with predictions of three theoretical codes. From the measured cross-section thick target integral yields were also calculated and presented.

  8. An efficient copper-catalyzed cross-coupling reaction of alkyl-triflates with alkyl-Grignard reagents

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A highly efficient method for the formation of C-C covalent bonds by cross-coupling reaction between alkyl-triflates and alkyl-Grignard reagents catalyzed by copper catalyst, Li2CuCl4, is described. The reaction works with most primary triflates in diethyl ether at low temperature within 0.5-3 h an...

  9. Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265-400 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Whytock, D. A.; Lee, J. H.; Payne, W. A.; Stief, L. J.

    1977-01-01

    Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant.

  10. Lewis acid catalysis of photochemical reactions. 7. Photodimerization and cross-cycloaddition of cinnamic esters

    SciTech Connect

    Lewis, F.D.; Quillen, S.L.; Hale, P.D.; Oxman, J.D.

    1988-02-17

    The effects of Lewis acid complexation upon the molecular structure, solid-state photodimerization, and solution dimerization and cross-cycloaddition of cinnamic esters have been investigated. Comparison of crystal structures for free and SnCl/sub 4/-complexed ethyl cinnamate indicates that the enone double bonds are lengthened, the single bonds are shortened, and the enone conformation changes from s-cis to s-trans upon complexation. These changes are consistent with calculated changes in ..pi.. bonding and net charges. Solid-state photodimerization of free and complexed cinnamic esters and related molecules yield syn head-to-tail (..cap alpha..-truxillate) dimers. In most cases the Lewis acid complexes dimerize more efficiently and stereoselectively than the free esters. Photodimerization and cross-cycloaddition of methyl cinnamate in dilute solution is also catalyzed by Lewis acids. The mechanism of these reactions involves electronic excitation of a ground-state ester (dimerization) or simple olefin (cross cycloaddition). The catalytic effect of Lewis acids is attributed to an increase in excited-state lifetime and reactivity.

  11. Partial-wave analysis of n +241Am reaction cross sections in the resonance region

    NASA Astrophysics Data System (ADS)

    Noguere, G.; Bouland, O.; Kopecky, S.; Lampoudis, C.; Schillebeeckx, P.; Plompen, A.; Gunsing, F.; Sage, C.; Sirakov, I.

    2015-07-01

    Cross sections for neutron-induced reactions of 241Am in the resonance region have been evaluated. Results of time-of-flight cross section experiments carried out at the GELINA, LANSCE, ORELA and Saclay facilities have been combined with optical model calculations to derive consistent cross sections from the thermal energy region up to the continuum region. Resolved resonance parameters were derived from a resonance shape analysis of transmissions, capture yields, and fission yields in the energy region up to 150 eV using the refit code. From a statistical analysis of these parameters, a neutron strength function (104S0=1.01 ±0.12 ), mean level spacing (D0=0.60 ±0.01 eV) and average radiation width (<Γγ 0>=43.3 ±1.1 meV) for s -wave resonances were obtained. Neutron strength functions for higher partial waves (l >0 ) together with channel and effective scattering radii were deduced from calculations based on a complex mean-field optical model potential, applying an equivalent hard-sphere scattering radius approximation.

  12. CuBr catalyzed C-N cross coupling reaction of purines and diaryliodonium salts to 9-arylpurines.

    PubMed

    Niu, Hong-Ying; Xia, Chao; Qu, Gui-Rong; Zhang, Qian; Jiang, Yi; Mao, Run-Ze; Li, De-Yang; Guo, Hai-Ming

    2011-07-21

    CuBr was found to be an efficient catalyst for the C-N cross coupling reaction of purine and diaryliodonium salts. 9-Arylpurines were synthesized in excellent yields with short reaction times (2.5 h). The method represents an alternative to the synthesis of 9-arylpurines via Cu(II) catalyzed C-N coupling reaction with arylboronic acids as arylating agents. PMID:21660365

  13. Organo-Iodine(III)-Catalyzed Oxidative Phenol-Arene and Phenol-Phenol Cross-Coupling Reaction.

    PubMed

    Morimoto, Koji; Sakamoto, Kazuma; Ohshika, Takao; Dohi, Toshifumi; Kita, Yasuyuki

    2016-03-01

    The direct oxidative coupling reaction has been an attractive tool for environmentally benign chemistry. Reported herein is that the hypervalent iodine catalyzed oxidative metal-free cross-coupling reaction of phenols can be achieved using Oxone as a terminal oxidant in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP). This method features a high efficiency and regioselectivity, as well as functional-group tolerance under very mild reaction conditions without using metal catalysts. PMID:26879796

  14. Capture Cross Sections for the Near Symmetric 124Sn + 96Zr Reaction

    SciTech Connect

    Vinodkumar, A. M.; Loveland, Walter; Sprunger, Peter H; Peterson, Don; Liang, Junjien; Shapira, Dan; Varner Jr, Robert L; Gross, Carl J; Kolata, Jim J

    2006-12-01

    Capture-fission cross sections were measured for the near symmetric reaction between the massive nuclei {sup 124}Sn and {sup 96}Zr for center of mass energies from 195 to 265 MeV. Coincident fission fragments were detected and separated from elastic and deep inelastic scattering products by angle/energy/mass conditions. The measured capture cross sections agree quite well with calculations using the dinuclear system (DNS) model. The DNS model also predicts the fusion cross section for this reaction with a fusion barrier height of 208.0 MeV. The deduced extra push energy, corresponding to this barrier height, differs from that deduced from evaporation residue measurements.

  15. Capture Cross Sections for the Near Symmetric 124Sn+96Zr Reaction

    SciTech Connect

    Vinodkumar, A. M.; Loveland, Walter; Sprunger, Peter H; Peterson, Don; Liang, J Felix; Shapira, Dan; Varner Jr, Robert L; Gross, Carl J; Kolata, Jim J

    2006-12-01

    Capture-fission cross sections were measured for the near symmetric reaction between the massive nuclei 124Sn and 96Zr for center of mass energies from 195 to 265 MeV. Coincident fission fragments were detected and separated from elastic and deep inelastic scattering products by angle/energy/mass conditions. The measured capture cross sections agree quite well with calculations using the dinuclear system (DNS) model. The DNS model also predicts the fusion cross section for this reaction with a fusion barrier height of 208.0 MeV. The deduced extra push energy, corresponding to this barrier height, differs from that deduced from evaporation residue measurements.

  16. Palladium-catalyzed C-H functionalization of acyldiazomethane and tandem cross-coupling reactions.

    PubMed

    Ye, Fei; Qu, Shuanglin; Zhou, Lei; Peng, Cheng; Wang, Chengpeng; Cheng, Jiajia; Hossain, Mohammad Lokman; Liu, Yizhou; Zhang, Yan; Wang, Zhi-Xiang; Wang, Jianbo

    2015-04-01

    Palladium-catalyzed C-H functionalization of acyldiazomethanes with aryl iodides has been developed. This reaction is featured by the retention of the diazo functionality in the transformation, thus constituting a novel method for the introduction of diazo functionality to organic molecules. Consistent with the experimental results, the density functional theory (DFT) calculation indicates that the formation of Pd-carbene species in the catalytic cycle through dinitrogen extrusion from the palladium ethyl diazoacetate (Pd-EDA) complex is less favorable. The reaction instead proceeds through Ag2CO3 assisted deprotonation and subsequently reductive elimination to afford the products with diazo functionality remained. This C-H functionalization transformation can be further combined with the recently evolved palladium-catalyzed cross-coupling reaction of diazo compounds with aryl iodides to develop a tandem coupling process for the synthesis of α,α-diaryl esters. DFT calculation supports the involvement of Pd-carbene as reactive intermediate in the catalytic cycle, which goes through facile carbene migratory insertion with a low energy barrier (3.8 kcal/mol). PMID:25794590

  17. Palladium-catalyzed C-H functionalization of acyldiazomethane and tandem cross-coupling reactions.

    PubMed

    Ye, Fei; Qu, Shuanglin; Zhou, Lei; Peng, Cheng; Wang, Chengpeng; Cheng, Jiajia; Hossain, Mohammad Lokman; Liu, Yizhou; Zhang, Yan; Wang, Zhi-Xiang; Wang, Jianbo

    2015-04-01

    Palladium-catalyzed C-H functionalization of acyldiazomethanes with aryl iodides has been developed. This reaction is featured by the retention of the diazo functionality in the transformation, thus constituting a novel method for the introduction of diazo functionality to organic molecules. Consistent with the experimental results, the density functional theory (DFT) calculation indicates that the formation of Pd-carbene species in the catalytic cycle through dinitrogen extrusion from the palladium ethyl diazoacetate (Pd-EDA) complex is less favorable. The reaction instead proceeds through Ag2CO3 assisted deprotonation and subsequently reductive elimination to afford the products with diazo functionality remained. This C-H functionalization transformation can be further combined with the recently evolved palladium-catalyzed cross-coupling reaction of diazo compounds with aryl iodides to develop a tandem coupling process for the synthesis of α,α-diaryl esters. DFT calculation supports the involvement of Pd-carbene as reactive intermediate in the catalytic cycle, which goes through facile carbene migratory insertion with a low energy barrier (3.8 kcal/mol).

  18. Reaction dynamics of Cl + butanol isomers by crossed-beam sliced ion imaging.

    PubMed

    Estillore, Armando D; Visger-Kiefer, Laura M; Suits, Arthur G

    2012-01-01

    Butanol is now prominent among the prototype renewable biofuels. We have studied oxidation of a variety of butanol isomers under single collision conditions using chlorine atom as the oxidizing agent to gain detailed insight into the energetics and dynamics of these reactions. The interaction of chlorine atom radicals with butanol isomers: n-butanol, iso-butanol, sec-butanol, and tert-butanol have been studied by crossed-beam dc slice ion imaging techniques. The hydroxybutyl radicals generated from the H-abstraction processes were probed by single photon ionization using an F2 excimer laser. After background subtraction and density-to-flux correction of the raw images, translational energy distribution and product angular distributions were generated. At low collision energy, the hydroxyalkyl products are backscattered with respect to the alcohol beam and the scattering shifts to the forward direction as the collision energy is increased. The translational energy distributions are reminiscent to that of Cl + pentane reactions we studied earlier, i.e. a sharp forward peak -80% of the collision energy appears at the high collision energy. Isomer-specific details of the reactions will be discussed.

  19. Absolute cross sections for near-threshold electron-impact excitation of the 2s{sup 2}S{r_arrow}2p{sup 2}P transition in C{sup 3+}

    SciTech Connect

    Bannister, M.E.; Chung, Y.; Djuric, N.; Wallbank, B.; Woitke, O.; Zhou, S.; Dunn, G.H.; Smith, A.C.

    1998-01-01

    Absolute total cross sections for electron-impact excitation of the 2s{sup 2}S{r_arrow}2p{sup 2}P transition in C{sup 3+} were measured from 7.35 eV to 8.45 eV using the merged electron-ion-beams energy-loss technique. The results settle the discrepancy between two previous experiments using the crossed-beams fluorescence method, being in very good agreement with the older results [P. O. Taylor, D. Gregory, G. H. Dunn, R. A. Phaneuf, and D. H. Crandall, Phys. Rev. Lett. {bold 39}, 1256 (1977)] but less so with the more recent ones [D. W. Savin, L. D. Gardner, D. B. Reisenfeld, A. R. Young, and J. L. Kohl, Phys. Rev. A {bold 51}, 2162 (1995)]. The present measurements are also in good agreement with unitarized Coulomb-Born and close-coupling calculations. {copyright} {ital 1998} {ital The American Physical Society}

  20. Vibrational state-resolved differential cross sections for the D + H sub 2 yields DH + H reaction

    SciTech Connect

    Continetti, R.E.

    1989-11-01

    In this thesis, crossed-molecular-beams studies of the reaction D + H{sub 2} {yields} DH + H at collision energies of 0.53 and 1.01 eV are reported. Chapter 1 provides a survey of important experimental and theoretical studies on the dynamics of the hydrogen exchange reaction. Chapter 2 discusses the development of the excimer-laser photolysis D atom beam source that was used in these studies and preliminary experiments on the D + H{sub 2} reaction. In Chapter 3, the differential cross section measurements are presented and compared to recent theoretical predictions. The measured differential cross sections for rotationally excited DH products showed significant deviations from recent quantum scattering calculations, in the first detailed comparison of experimental and theoretical differential cross sections. These results indicate that further work on the H{sub 3} potential energy surface, particularly the bending potential, is in order.

  1. Cross section measurements of deuteron induced nuclear reactions on natural titanium up to 34 MeV.

    PubMed

    Duchemin, C; Guertin, A; Haddad, F; Michel, N; Métivier, V

    2015-09-01

    Experimental cross sections for deuteron induced nuclear reactions on natural titanium were measured, using the stacked-foil technique and gamma spectrometry, up to 34 MeV with beams provided by the ARRONAX cyclotron. The experimental cross section values were monitored using the (nat)Ti(d,x)(48)V reaction, recommended by the IAEA. The excitation functions for (nat)Ti(d,x)(44m,46,47,48)Sc are presented and compared with the existing ones and with the TALYS 1.6 code calculations using default models. Our experimental values are in good agreement with data found in the literature. TALYS 1.6 is not able to give a good estimation of the production cross sections investigated in this work. These production cross sections of scandium isotopes fit with the new Coordinated Research Project (CRP) launched by the International Atomic Energy Agency (IAEA) to expand the database of monitor reactions. PMID:26103622

  2. Revised Production Rates for Na-22 and Mn-54 in Meteorites Using Cross Sections Measured for Neutron-induced Reactions

    NASA Technical Reports Server (NTRS)

    Sisterson, J. M.; Kim, K. J.; Reedy, R. C.

    2004-01-01

    The interactions of galactic cosmic rays (GCR) with extraterrestrial bodies produce small amounts of radionuclides and stable isotopes. The production rates of many relatively short-lived radionuclides, including 2.6-year Na-22 and 312-day Mn-54, have been measured in several meteorites collected very soon after they fell. Theoretical models used to calculate production rates for comparison with the measured values rely on input data containing good cross section measurements for all relevant reactions. Most GCR particles are protons, but secondary neutrons make most cosmogenic nuclides. Calculated production rates using only cross sections for proton-induced reactions do not agree well with measurements. One possible explanation is that the contribution to the production rate from reactions initiated by secondary neutrons produced in primary GCR interactions should be included explicitly. This, however, is difficult to do because so few of the relevant cross sections for neutron-induced reactions have been measured.

  3. New data on cross sections for partial and total photoneutron reactions on the isotopes {sup 91,94}Zr

    SciTech Connect

    Varlamov, V. V.; Makarov, M. A.; Peskov, N. N.; Stepanov, M. E.

    2015-07-15

    Experimental data on {sup 91,94}Zr photodisintegration that were obtained in a beam of quasimonoenergetic annihilation photons by the method of neutron multiplicity sorting are analyzed. It is found that the cross sections for the (γ, 1n), (γ, 2n), and (γ, 3n) reactions on both isotopes do not meet the objective data-reliability criteria formulated earlier. Within the experimental–theoretical method for evaluating partial-reaction cross sections that satisfy these criteria, new data on the cross sections for the aforementioned partial reactions, as well as for the (γ, sn) = (γ, 1n) + (γ, 2n) + (γ, 3n) +... total photoneutron reaction, are obtained for the isotopes {sup 91,94}Zr.

  4. Measurement and calculation of absolute single- and double-charge-exchange cross sections for O6 + ions at 1.17 and 2.33 keV/u impacting He and H2

    NASA Astrophysics Data System (ADS)

    Machacek, J. R.; Mahapatra, D. P.; Schultz, D. R.; Ralchenko, Yu.; Chutjian, A.; Simcic, J.; Mawhorter, R. J.

    2014-11-01

    Absolute single- and double-charge-exchange cross sections for the astrophysically prominent O6 + ion with the atomic and molecular targets He and H2 are reported. These collisions give rise to x-ray emissions in the interplanetary medium, planetary atmospheres, and comets as they approach the sun. Measurements have been carried out using the Caltech Jet Propulsion Laboratory electron cyclotron resonance ion source with O6 + at energies of 1.17 and 2.33 keV/u characteristic of the slow and fast components of the solar wind. Absolute charge-exchange (CE) data are derived from knowledge of the target gas pressure, target path length, incident ion current, and charge-exchanged ion currents. These data are compared with results obtained using the n -electron classical trajectory Monte Carlo method. The radiative and Auger evolution of ion populations following one- and two-electron transfers is calculated with the time-dependent collisional-radiative code nomad using atomic data from the flexible atomic code. Calculated CE emission spectra for 100 Å <λ <1400 Å are reported as well and compared with experimental sublevel spectra and cross sections.

  5. First experimental determination of the absolute gas-phase rate coefficient for the reaction of OH with 4-hydroxy-2-butanone (4H2B) at 294 K by vapor pressure measurements of 4H2B.

    PubMed

    El Dib, Gisèle; Sleiman, Chantal; Canosa, André; Travers, Daniel; Courbe, Jonathan; Sawaya, Terufat; Mokbel, Ilham; Chakir, Abdelkhaleq

    2013-01-10

    The reaction of the OH radicals with 4-hydroxy-2-butanone was investigated in the gas phase using an absolute rate method at room temperature and over the pressure range 10-330 Torr in He and air as diluent gases. The rate coefficients were measured using pulsed laser photolysis (PLP) of H(2)O(2) to produce OH and laser induced fluorescence (LIF) to measure the OH temporal profile. An average value of (4.8 ± 1.2) × 10(-12) cm(3) molecule(-1) s(-1) was obtained. The OH quantum yield following the 266 nm pulsed laser photolysis of 4-hydroxy-2-butanone was measured for the first time and found to be about 0.3%. The investigated kinetic study required accurate measurements of the vapor pressure of 4-hydroxy-2-butanone, which was measured using a static apparatus. The vapor pressure was found to range from 0.056 to 7.11 Torr between 254 and 323 K. This work provides the first absolute rate coefficients for the reaction of 4-hydroxy-2-butanone with OH and the first experimental saturated vapor pressures of the studied compound below 311 K. The obtained results are compared to those of the literature and the effects of the experimental conditions on the reactivity are examined. The calculated tropospheric lifetime obtained in this work suggests that once emitted into the atmosphere, 4H2B may contribute to the photochemical pollution in a local or regional scale.

  6. Eosinophil count - absolute

    MedlinePlus

    Eosinophils; Absolute eosinophil count ... the white blood cell count to give the absolute eosinophil count. ... than 500 cells per microliter (cells/mcL). Normal value ranges may vary slightly among different laboratories. Talk ...

  7. Extracting nuclear sizes of medium to heavy nuclei from total reaction cross sections

    NASA Astrophysics Data System (ADS)

    Horiuchi, W.; Hatakeyama, S.; Ebata, S.; Suzuki, Y.

    2016-04-01

    Background: Proton and neutron radii are fundamental quantities of atomic nuclei. To study the sizes of short-lived unstable nuclei, there is a need for an alternative to electron scattering. Purpose: The recent paper by Horiuchi et al. [Phys. Rev. C 89, 011601(R) (2014)], 10.1103/PhysRevC.89.011601 proposed a possible way of extracting the matter and neutron-skin thickness of light- to medium-mass nuclei using total reaction cross section, σR. The analysis is extended to medium to heavy nuclei up to lead isotopes with due attention to Coulomb breakup contributions as well as density distributions improved by paring correlation. Methods: We formulate a quantitative calculation of σR based on the Glauber model including the Coulomb breakup. To substantiate the treatment of the Coulomb breakup, we also evaluate the Coulomb breakup cross section due to the electric dipole field in a canonical-basis-time-dependent-Hartree-Fock-Bogoliubov theory in the three-dimensional coordinate space. Results: We analyze σR's of 103 nuclei with Z =20 , 28, 40, 50, 70, and 82 incident on light targets, H,21, 4He, and 12C. Three kinds of Skyrme interactions are tested to generate those wave functions. To discuss possible uncertainty due to the Coulomb breakup, we examine its dependence on the target, the incident energy, and the Skyrme interaction. The proton is a most promising target for extracting the nuclear sizes as the Coulomb excitation can safely be neglected. We find that the so-called reaction radius, aR=√{σR/π } , for the proton target is very well approximated by a linear function of two variables, the matter radius and the skin thickness, in which three constants depend only on the incident energy. We quantify the accuracy of σR measurements needed to extract the nuclear sizes. Conclusions: The proton is the best target because, once the incident energy is set, its aR is very accurately determined by only the matter radius and neutron-skin thickness. If σR's at

  8. Cross section of reaction 181Ta(p,nγ) 181W and the influence of the spin cut-off parameter on the cross section

    NASA Astrophysics Data System (ADS)

    Zhang, Jun-Jie; Hu, Bi-Tao

    2011-12-01

    In this work, the program Cindy was modified to calculate the formation cross section of each energy level of residual nucleus 181W resulting from the reaction 181Ta(p,nγ) 181W. The concerned cross sections calculated at proton energy Ep = 4.5-8.5 MeV agreed well with experimental results. The influence of the spin cut-off parameter in the energy level density model on the cross section was studied. The obtained results show that the influence of spin cut-off is obvious for lower energy levels.

  9. Study of the cross-reaction between rabbit anti-bovine serum albumin antibodies and equine serum albumin

    PubMed Central

    Rangel, H.

    1965-01-01

    Cross-reactions between bovine serum albumin and equine serum albumin were studied using heterologous soluble complexes and specifically purified cross-reacting antibody. Experiments with soluble complexes showed that homologous antigen can displace heterologous antigen specifically bound to antibody but heterologous antigen cannot displace homologous antigen. On gel precipitation tests a specific precipitation resulted when heterologous soluble complex reacted with homologous antigen. By using equine serum albumin conjugated to polyaminopolystyrene the cross-reacting antibodies from anti-bovine serum albumin imune sera could be isolated. These are divalent 7S, γ-globulin antibodies. A figure of cross-reaction was obtained when these purified antibodies were tested by double diffusion in agar with bovine and equine serum albumins. The results obtained both with soluble complexes and with purified antibody support the view that cross-reacting antibody is more avid for the homologous than for the heterologous antigen. ImagesFIG. 3FIG. 4FIG. 5 PMID:14245318

  10. Study for Nuclear Structures of 22-35Na Isotopes via Measurements of Reaction Cross Sections

    NASA Astrophysics Data System (ADS)

    Suzuki, Shinji

    2014-09-01

    T. Ohtsubo, M. Nagashima, T. Ogura, Y. Shimbara (Grad. Sch. of Sc., Niigata Univ.), M.Takechi, H. Geissel, M. Winkler (GSI), D. Nishimura, T. Sumikama (Dept. of Phys., Tokyo Univ. of Sc.), M. Fukuda, M. Mihara, H. Uenishi (Dept. of Phys., Osaka Univ.), T. Kuboki, T. Suzuki, T. Yamaguchi, H. Furuki, C. S. Lee, K. Sato (Dept. of Phys., Saitama Univ.), A. Ozawa, H. Ohnishi, T. Moriguchi, S. Fukuda, Y. Ishibashi, D. Nagae, R. Nishikiori, T. Niwa (Inst. of Phys., Univ. of Tsukuba), N. Aoi (RCNP), Rui-Jiu Chen, N. Inabe, D. Kameda, T. Kubo, M. Lantz, T. Ohnishi, K. Okumura, H. Sakurai, H. Suzuki, H. Takeda, S. Takeuchi, K. Tanaka, Y. Yanagisawa (RIKEN), De-Qing Fang, Yu-Gang Ma (SINAP), T. Izumikawa (RI Ctr., Niigata Univ.), and S. Momota (Fac. of Engn., Kochi Univ. of Tech.) Reaction cross sections (σR) for 22-35Na isotopes have been measured at around 240 MeV/nucleon. The σR for 22-35Na were measured for the first time. Enhancement in cross sections is clearly observed from the systematics for stable nuclei, for isotopes with large mass numbers. These enhancement can be mainly ascribed to the nuclear deformation. We will discuss the nuclear structure (neutron skin, nuclear shell structure) for neutron-excess Na isotopes. T. Ohtsubo, M. Nagashima, T. Ogura, Y. Shimbara (Grad. Sch. of Sc., Niigata Univ.), M.Takechi, H. Geissel, M. Winkler (GSI), D. Nishimura, T. Sumikama (Dept. of Phys., Tokyo Univ. of Sc.), M. Fukuda, M. Mihara, H. Uenishi (Dept. of Phys., Osaka Univ.), T. Kuboki, T. Suzuki, T. Yamaguchi, H. Furuki, C. S. Lee, K. Sato (Dept. of Phys., Saitama Univ.), A. Ozawa, H. Ohnishi, T. Moriguchi, S. Fukuda, Y. Ishibashi, D. Nagae, R. Nishikiori, T. Niwa (Inst. of Phys., Univ. of Tsukuba), N. Aoi (RCNP), Rui-Jiu Chen, N. Inabe, D. Kameda, T. Kubo, M. Lantz, T. Ohnishi, K. Okumura, H. Sakurai, H. Suzuki, H. Takeda, S. Takeuchi, K. Tanaka, Y. Yanagisawa (RIKEN), De-Qing Fang, Yu-Gang Ma (SINAP), T. Izumikawa (RI Ctr., Niigata Univ.), and S. Momota (Fac. of Engn

  11. Calculated cross sections for neutron induced reactions on sup 19 F and uncertainties of parameters

    SciTech Connect

    Zhao, Z.X. . Inst. of Atomic Energy); Fu, C.Y.; Larson, D.C. )

    1990-09-01

    Nuclear model codes were used to calculate cross sections for neutron-induced reactions on {sup 19}F for incident energies from 2 to 20 MeV. The model parameters in the codes were adjusted to best reproduce experimental data and are given in this report. The calculated results are compared to measured data and the evaluated values of ENDF/B-V. The covariance matrix for several of the most sensitive model parameters is given based on the scatter of measured data around the theoretical curves and the long-range correlation error of measured data. The results of these calculations form the basis for the new ENDF/B-VI fluorine evaluation. 44 refs., 64 figs., 14 tabs.

  12. Differential cross sections and spin density matrix elements for the reaction γp→pω

    NASA Astrophysics Data System (ADS)

    Williams, M.; Applegate, D.; Bellis, M.; Meyer, C. A.; Adhikari, K. P.; Anghinolfi, M.; Baghdasaryan, H.; Ball, J.; Battaglieri, M.; Bedlinskiy, I.; Berman, B. L.; Biselli, A. S.; Bookwalter, C.; Briscoe, W. J.; Brooks, W. K.; Burkert, V. D.; Careccia, S. L.; Carman, D. S.; Cole, P. L.; Collins, P.; Crede, V.; D'Angelo, A.; Daniel, A.; Vita, R. De; Sanctis, E. De; Deur, A.; Dey, B.; Dhamija, S.; Dickson, R.; Djalali, C.; Dodge, G. E.; Doughty, D.; Dugger, M.; Dupre, R.; Alaoui, A. El; Elouadrhiri, L.; Eugenio, P.; Fedotov, G.; Fegan, S.; Fradi, A.; Gabrielyan, M. Y.; Garçon, M.; Gevorgyan, N.; Gilfoyle, G. P.; Giovanetti, K. L.; Girod, F. X.; Gohn, W.; Golovatch, E.; Gothe, R. W.; Griffioen, K. A.; Guidal, M.; Guo, L.; Hafidi, K.; Hakobyan, H.; Hanretty, C.; Hassall, N.; Hicks, K.; Holtrop, M.; Ilieva, Y.; Ireland, D. G.; Ishkhanov, B. S.; Isupov, E. L.; Jawalkar, S. S.; Jo, H. S.; Johnstone, J. R.; Joo, K.; Keller, D.; Khandaker, M.; Khetarpal, P.; Kim, W.; Klein, A.; Klein, F. J.; Krahn, Z.; Kubarovsky, V.; Kuleshov, S. V.; Kuznetsov, V.; Livingston, K.; Lu, H. Y.; Mayer, M.; McAndrew, J.; McCracken, M. E.; McKinnon, B.; Mikhailov, K.; Mirazita, M.; Mokeev, V.; Moreno, B.; Moriya, K.; Morrison, B.; Moutarde, H.; Munevar, E.; Nadel-Turonski, P.; Nepali, C. S.; Niccolai, S.; Niculescu, G.; Niculescu, I.; Niroula, M. R.; Niyazov, R. A.; Osipenko, M.; Ostrovidov, A. I.; Paris, M.; Park, K.; Park, S.; Pasyuk, E.; Pereira, S. Anefalos; Perrin, Y.; Pisano, S.; Pogorelko, O.; Pozdniakov, S.; Price, J. W.; Procureur, S.; Protopopescu, D.; Raue, B. A.; Ricco, G.; Ripani, M.; Ritchie, B. G.; Rosner, G.; Rossi, P.; Sabatié, F.; Saini, M. S.; Salamanca, J.; Salgado, C.; Schott, D.; Schumacher, R. A.; Seraydaryan, H.; Sharabian, Y. G.; Smith, E. S.; Sober, D. I.; Sokhan, D.; Stepanyan, S. S.; Stoler, P.; Strakovsky, I. I.; Strauch, S.; Taiuti, M.; Tedeschi, D. J.; Tkachenko, S.; Ungaro, M.; Vineyard, M. F.; Voutier, E.; Watts, D. P.; Weinstein, L. B.; Weygand, D. P.; Wood, M. H.; Zhang, J.; Zhao, B.

    2009-12-01

    High-statistics differential cross sections and spin-density matrix elements for the reaction γp→pω have been measured using the CEBAF large acceptance spectrometer (CLAS) at Jefferson Lab for center-of-mass (c.m.) energies from threshold up to 2.84 GeV. Results are reported in 11210-MeV wide c.m. energy bins, each subdivided into cosθc.m.ω bins of width 0.1. These are the most precise and extensive ω photoproduction measurements to date. A number of prominent structures are clearly present in the data. Many of these have not previously been observed due to limited statistics in earlier measurements.

  13. Reaction cross-section calculations using new experimental and theoretical level structure data for deformed nuclei

    SciTech Connect

    Hoff, R.W.; Gardner, D.G.; Gardner, M.A.

    1984-10-05

    A technique for modeling quasiparticle excitation energies and rotational parameters in odd-odd deformed nuclei has been used to construct sets of discrete states with energy 0 to 1.5 MeV in /sup 176/Lu and /sup 236/Np. These data were used as part of the input for calculation of isomer production cross-section ratios in the /sup 175/Lu(n,..gamma..)/sup 176/Lu and /sup 237/Np(n,2n)/sup 236/Np reactions. In order to achieve agreement with experiment, it has been found necessary to include in the modeled set many rotational bands (35 to 95), which are comprised of hundreds of levels with their gamma-ray branching ratios. It is essential that enough bands be included to produce a representative selection of K quantum numbers in the de-excitation cascade. 20 refs., 3 figs., 3 tabs.

  14. Stereospecific cross-coupling reactions of aryl-substituted tetrahydrofurans, tetrahydropyrans, and lactones.

    PubMed

    Tollefson, Emily J; Dawson, David D; Osborne, Charlotte A; Jarvo, Elizabeth R

    2014-10-22

    The stereospecific ring-opening of O-heterocycles to provide acyclic alcohols and carboxylic acids with controlled formation of a new C-C bond is reported. These reactions provide new methods for synthesis of acyclic polyketide analogs with complex stereochemical arrays. Stereoselective synthesis of the cyclic template is utilized to control relative configuration; subsequent stereospecific nickel-catalyzed ring-opening affords the acyclic product. Aryl-substituted tetrahydrofurans and tetrahydropyrans undergo nickel-catalyzed Kumada-type coupling with a range of Grignard reagents to furnish acyclic alcohols with high diastereoselectivity. Enantioenriched lactones undergo Negishi-type cross-coupling with dimethylzinc to afford enantioenriched carboxylic acids. Application in a two-step enantioselective synthesis of an anti-dyslipidemia agent is demonstrated. PMID:25308512

  15. Activation cross sections of proton induced nuclear reactions on gold up to 65MeV.

    PubMed

    Ditrói, F; Tárkányi, F; Takács, S; Hermanne, A

    2016-07-01

    Activation cross sections of proton induced reactions on gold for production of (197m,197g,195m,195g, 193m,193g,192)Hg, (196m,196g(cum),195g(cum),194,191(cum))Au, (191(cum))Pt and (192)Ir were measured up to 65MeV proton energy, some of them for the first time. The new data are in acceptably good agreement with the recently published earlier experimental data in the overlapping energy region. The experimental data are compared with the predictions of the TALYS 1.6 (results in TENDL-2015 on-line library) and EMPIRE 3.2 code. PMID:27156194

  16. A full-dimensional model of ozone forming reaction: the absolute value of the recombination rate coefficient, its pressure and temperature dependencies.

    PubMed

    Teplukhin, Alexander; Babikov, Dmitri

    2016-07-28

    Rigorous calculations of scattering resonances in ozone are carried out for a broad range of rotational excitations. The accurate potential energy surface of Dawes is adopted, and a new efficient method for calculations of ro-vibrational energies, wave functions and resonance lifetimes is employed (which uses hyper-spherical coordinates, the sequential diagonalization/truncation approach, grid optimization and complex absorbing potential). A detailed analysis is carried out to characterize distributions of resonance energies and lifetimes, their rotational/vibrational content and their positions with respect to the centrifugal barrier. Emphasis is on the contribution of these resonances to the recombination process that forms ozone. It is found that major contributions come from localized resonances at energies near the top of the barrier. Delocalized resonances at higher energies should also be taken into account, while very narrow resonances at low energies (trapped far behind the centrifugal barrier) should be treated as bound states. The absolute value of the recombination rate coefficient, its pressure and temperature dependencies are obtained using the energy-transfer model developed in the earlier work. Good agreement with experimental data is obtained if one follows the suggestion of Troe, who argued that the energy transfer mechanism of recombination is responsible only for 55% of the recombination rate (with the remaining 45% coming from the competing chaperon mechanism). PMID:27364351

  17. A full-dimensional model of ozone forming reaction: the absolute value of the recombination rate coefficient, its pressure and temperature dependencies.

    PubMed

    Teplukhin, Alexander; Babikov, Dmitri

    2016-07-28

    Rigorous calculations of scattering resonances in ozone are carried out for a broad range of rotational excitations. The accurate potential energy surface of Dawes is adopted, and a new efficient method for calculations of ro-vibrational energies, wave functions and resonance lifetimes is employed (which uses hyper-spherical coordinates, the sequential diagonalization/truncation approach, grid optimization and complex absorbing potential). A detailed analysis is carried out to characterize distributions of resonance energies and lifetimes, their rotational/vibrational content and their positions with respect to the centrifugal barrier. Emphasis is on the contribution of these resonances to the recombination process that forms ozone. It is found that major contributions come from localized resonances at energies near the top of the barrier. Delocalized resonances at higher energies should also be taken into account, while very narrow resonances at low energies (trapped far behind the centrifugal barrier) should be treated as bound states. The absolute value of the recombination rate coefficient, its pressure and temperature dependencies are obtained using the energy-transfer model developed in the earlier work. Good agreement with experimental data is obtained if one follows the suggestion of Troe, who argued that the energy transfer mechanism of recombination is responsible only for 55% of the recombination rate (with the remaining 45% coming from the competing chaperon mechanism).

  18. Diazo compounds and N-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions.

    PubMed

    Xiao, Qing; Zhang, Yan; Wang, Jianbo

    2013-02-19

    Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, with essentially no overlap or integration. Thus, an intriguing question has emerged: can cross-coupling and metal carbene transformations be merged into a single reaction cycle? Such a combination could facilitate the development of novel carbon-carbon bond-forming methodologies. Although this concept was first explored about 10 years ago, rapid developments inthis area have been achieved recently. Palladium catalysts can be used to couple diazo compounds with a wide variety of organic halides. Under oxidative coupling conditions, diazo compounds can also react with arylboronic acids and terminal alkynes. Both of these coupling reactions form carbon-carbon double bonds. As the key step in these catalytic processes, Pd carbene migratory insertion plays a vital role in merging the elementary steps of Pd intermediates, leading to novel carbon-carbon bond formations. Because the diazo substrates can be generated in situ from N-tosylhydrazones in the presence of base, the N-tosylhydrazones can be used as reaction partners, making this type of cross-coupling reaction practical in organic synthesis. N-Tosylhydrazones are easily derived from the corresponding aldehydes or ketones. The Pd-catalyzed cross-coupling of N-tosylhydrazones is considered a complementary reaction to the classic Shapiro reaction for converting carbonyl functionalities into carbon-carbon double bonds. It can also serve as an alternative approach for the Pd-catalyzed cross-coupling of carbonyl compounds, which is usually achieved via triflates. The combination of carbene formation and cross-coupling in a single catalytic cycle is not limited to Pd-catalyzed reactions. Recent studies of Cu-, Rh-, Ni-, and Co-catalyzed cross-coupling reactions with diazo

  19. Experimental Cross Sections for Reactions of Heavy Ions and 208Pb, 209Bi, 238U, and 248Cm Targets

    SciTech Connect

    Patin, Joshua B.

    2002-05-24

    The study of the reactions between heavy ions and {sup 208}Pb, {sup 209}Bi, {sup 238}U, and {sup 248} Cm targets was performed to look at the differences between the cross sections of hot and cold fusion reactions. Experimental cross sections were compared with predictions from statistical computer codes to evaluate the effectiveness of the computer code in predicting production cross sections. Hot fusion reactions were studied with the MG system, catcher foil techniques and the Berkeley Gas-filled Separator (BGS). 3n- and 4n-exit channel production cross sections were obtained for the {sup 238}U({sup 18}O,xn){sup 256-x}Fm, {sup 238}U({sup 22}Ne,xn){sup 260-x}No, and {sup 248}Cm({sup 15}N,xn){sup 263-x}Lr reactions and are similar to previous experimental results. The experimental cross sections were accurately modeled by the predictions of the HIVAP code using the Reisdorf and Schaedel parameters and are consistent with the existing systematics of 4n exit channel reaction products. Cold fusion reactions were examined using the BGS. The {sup 208}Pb({sup 48}Ca,xn){sup 256-x}No, {sup 208}Pb({sup 50}Ti,xn){sup 258-x}Rf, {sup 208}Pb({sup 51}V,xn){sup 259-x}Db, {sup 209}Bi({sup 50}Ti,xn){sup 259-x}Db, and {sup 209}Bi({sup 51}V,xn){sup 260-x}Sg reactions were studied. The experimental production cross sections are in agreement with the results observed in previous experiments. It was necessary to slightly alter the Reisdorf and Schaedel parameters for use in the HIVAP code in order to more accurately model the experimental data. The cold fusion experimental results are in agreement with current 1n- and 2n-exit channel systematics.

  20. The antigens contributing to the serological cross-reactions of Proteus antisera with Klebsiella representatives.

    PubMed

    Palusiak, Agata

    2015-03-01

    Proteus sp. and Klebsiella sp. mainly cause infections of the urinary and respiratory tracts or wounds in humans. The representatives of both genera produce virulence factors like lipopolysaccharide (LPS) or outer membrane proteins (OMPs) having much in common in the structures and/or functions. To check how far this similarity is revealed in the serological cross-reactivity, the bacterial masses of 24 tested Klebsiella sp. strains were tested in ELISA with polyclonal rabbit antisera specific to the representatives of 79 Proteus O serogroups. The strongest reacting systems were selected to Western blot, where the majority of Klebsiella masses reacted in a way characteristic for electrophoretic patterns of proteins. The strongest reactions were obtained for proteins of near 67 and 40 kDa and 12.5 kDa. Mass spectrometry analysis of the proteins samples of one Proteus sp. and one Klebsiella sp. strain showed the GroEL like protein of a sequence GI number 2980926 to be similar for both strains. In Western blot some Klebsiella sp. masses reacted similarly to the homologous Proteus LPSs. The LPS contribution in the observed reactions of the high molecular-mass LPS species was confirmed for Klebsiella oxytoca 0.062.

  1. Cross-reactions in the HLA system revealed by red blood cells expressing HLA determinants, with particular reference to cross-reaction between HLA-A2 and B17.

    PubMed

    Nordhagen, R

    1983-01-01

    Sera with cytotoxic and haemagglutinating activity towards HLA-A2/28 were also shown to react with red blood cells (RBC) expressing the HLA-B17 antigen determinant. Absorption procedures with white blood cells (WBC) indicated that this was due to an HLA-A2/B17 cross-reaction. Absorption experiments with some other sera which previously had shown cytotoxic and haemagglutinating activity towards different HLA specificities, revealed broad cross-reaction related to HLA-B locus antigens.

  2. Development of a measurement system for the determination of (n , γ) cross-sections using multi-nucleon transfer reactions

    NASA Astrophysics Data System (ADS)

    Makii, H.; Ota, S.; Ishii, T.; Wakabayashi, Y.; Furutaka, K.; Nishio, K.; Nishinaka, I.; Chiba, S.; Igashira, M.; Czeszumska, A.

    2015-10-01

    We have installed a new experimental apparatus to measure γ-rays from highly excited states populated by the multi-nucleon transfer reactions with heavy-ion projectiles to determine the (n, γ) cross-sections by means of the surrogate reaction method. An apparatus consists of two anti-Compton LaBr3(Ce) spectrometers to measure the γ-rays and a Si ΔE-E detector system to detect outgoing projectile-like particles. Reactions of 153-MeV 18O beams with 155Gd and 157Gd targets were used to study the performance of apparatus. By using the LaBr3(Ce) scintillators with relatively large volume (101.6 mm in diameter and 127 mm in length), we have successfully measured γ-rays from the compound nuclei, which have excitation energy above neutron separation energy, populated by 155Gd(18O, 16O)157Gd and 157Gd(18O, 16O)159Gd two-neutron transfer reactions. To measure in-beam γ-rays through heavy-ion-induced transfer reaction, it is important to assign the reaction channel clearly, since the cross-sections of the transfer reactions are much smaller than those of competing reactions such as Coulomb excitation and fusion reactions. The Si ΔE-E detector system was used to separate outgoing particles. The present study has demonstrated high capability of apparatus to measure the de-excitation γ-rays in the compound nuclei produced by the multi-nucleon transfer reactions for determination of the (n, γ) cross-sections by using the surrogate reaction method.

  3. Cross section limits for the Cm248(Mg25,4n-5n)Hs268,269 reactions

    NASA Astrophysics Data System (ADS)

    Dvorak, J.; Brüchle, W.; Düllmann, Ch. E.; Dvorakova, Z.; Eberhardt, K.; Eichler, R.; Jäger, E.; Nagame, Y.; Qin, Z.; Schädel, M.; Schausten, B.; Schimpf, E.; Schuber, R.; Semchenkov, A.; Thörle, P.; Türler, A.; Wegrzecki, M.; Yakushev, A.

    2009-03-01

    We report on an attempt to produce and detect Hs268 and Hs269 in the nuclear fusion reaction Mg25+Cm248 using the gas phase chemistry apparatus COMPACT. No decay chains attributable to the decay of hassium isotopes were observed during the course of this experiment. From the nonobservation of Hs269 we derive a cross section limit of 0.4 pb (63% confidence limit) for the reaction Cm248(Mg25,4n)Hs269 at a center-of-target beam energy of 140 MeV. The evaluated cross section limit for the Cm248(Mg25,5n)Hs268 reaction depends on the assumed half-life of unknown Hs268. Current systematics of the half-lives for even-even Hs isotopes suggests a value of 0.5 s, resulting in a cross section limit of 1.3 pb.

  4. Chemoselective chromium(II)-catalyzed cross-coupling reactions of dichlorinated heteroaromatics with functionalized aryl grignard reagents.

    PubMed

    Steib, Andreas K; Kuzmina, Olesya M; Fernandez, Sarah; Malhotra, Sushant; Knochel, Paul

    2015-01-26

    Chromium(II) chloride catalyzes the chemoselective cross-coupling reaction of dichloropyridines with a range of functionalized (hetero)aromatic Grignard reagents at room temperature. Functional groups, such as esters and acetals, are well tolerated in this transformation. Previously challenging substrates, quinolines and isoquinolines, participate in the selective Cr-catalyzed cross-coupling in cyclopentyl methyl ether (CPME) as the solvent. The effective purging of Cr salts is demonstrated by using various solid supports. PMID:25470669

  5. Transition-metal-catalyzed Suzuki-Miyaura cross-coupling reactions: a remarkable advance from palladium to nickel catalysts.

    PubMed

    Han, Fu-She

    2013-06-21

    In the transition-metal-catalyzed cross-coupling reactions, the use of the first row transition metals as catalysts is much more appealing than the precious metals owing to the apparent advantages such as cheapness and earth abundance. Within the last two decades, particularly the last five years, explosive interests have been focused on the nickel-catalyzed Suzuki-Miyaura reactions. This has greatly advanced the chemistry of transition-metal-catalyzed cross-coupling reactions. Most notably, a broad range of aryl electrophiles such as phenols, aryl ethers, esters, carbonates, carbamates, sulfamates, phosphates, phosphoramides, phosphonium salts, and fluorides, as well as various alkyl electrophiles, which are conventionally challenging, by applying palladium catalysts can now be coupled efficiently with boron reagents in the presence of nickel catalysts. In this review, we would like to summarize the progress in this reaction.

  6. The D(+) + H2 reaction: differential and integral cross sections at low energy and rate constants at low temperature.

    PubMed

    González-Lezana, Tomás; Scribano, Yohann; Honvault, Pascal

    2014-08-21

    The D(+) + H2 reaction is investigated by means of a time independent quantum mechanical (TIQM) and statistical quantum mechanical (SQM) methods. Differential cross sections and product rotational distributions obtained with these two theoretical approaches for collision energies between 1 meV and 0.1 eV are compared to analyze the dynamics of the process. The agreement observed between the TIQM differential cross sections and the SQM predictions as the energy increases revealed the role played by the complex-forming mechanism. The importance of a good description of the asymptotic regions is also investigated by calculating rate constants for the title reaction at low temperature. PMID:24802076

  7. Quantum state-to-state cross sections for atom-diatom reactions: A Chebyshev real wave-packet approach

    SciTech Connect

    Lin Shiying; Guo Hua

    2006-08-15

    We describe the implementation of a quantum mechanical method to calculate state-to-state differential cross sections for atom-diatom reactive scattering processes. The key ingredient of this approach is the efficient and accurate propagation of a real scattering wave packet in the Chebyshev order domain, from which the S-matrix elements can be extracted. This approach is implemented with Open MP and applied to compute differential and integral cross sections for the direct H+H{sub 2} abstraction reaction and the more challenging N({sup 2}D)+H{sub 2} insertion reaction.

  8. Absolute quantification of the alleles in somatic point mutations by bioluminometric methods based on competitive polymerase chain reaction in the presence of a locked nucleic acid blocker or an allele-specific primer.

    PubMed

    Iliadi, Alexandra; Petropoulou, Margarita; Ioannou, Penelope C; Christopoulos, Theodore K; Anagnostopoulos, Nikolaos I; Kanavakis, Emmanuel; Traeger-Synodinos, Jan

    2011-09-01

    In somatic (acquired) point mutations, the challenge is to quantify minute amounts of the mutant allele in the presence of a large excess of the normal allele that differs only in a single base pair. We report two bioluminometric methods that enable absolute quantification of the alleles. The first method exploits the ability of a locked nucleic acid (LNA) oligonucleotide to bind to and inhibit effectively the polymerase chain reaction (PCR) amplification of the normal allele while the amplification of the mutant allele remains unaffected. The second method employs allele-specific PCR primers, thereby allowing the amplification of the corresponding allele only. DNA internal standards (competitors) are added to the PCR mixture to compensate for any sample-to-sample variation in the amplification efficiency. The amplification products from the two alleles and the internal standards are quantified by a microtiter well-based bioluminometric hybridization assay using the photoprotein aequorin as a reporter. The methods allow absolute quantification of less than 300 copies of the mutant allele even in samples containing less than 1% of the mutant allele.

  9. Rapid formation of triarylphosphines by microwave-assisted transition metal-catalyzed C-p cross-coupling reactions.

    PubMed

    Stadler, Alexander; Kappe, C Oliver

    2002-10-01

    Rapid, direct transition metal-catalyzed C-P(III) cross-coupling reactions were performed by microwave dielectric heating, employing diphenylphosphine and aryl halides/triflates as substrates. Depending on the specific aryl halide/triflate precursor, the highest yields were obtained utilizing heterogeneous or homogeneous Pd or Ni catalysts in DMF or NMP in the presence of KOAc or DABCO as a base. [reaction: see text

  10. 252Cf spectrum-averaged cross section for the 63Cu(n, p)63Ni reaction

    NASA Astrophysics Data System (ADS)

    Imamura, M.; Shibata, T.; Shibata, S.; Ohkubo, T.; Satoh, S.; Nogawa, N.

    1999-01-01

    The 63Ni produced by the 63Cu(n, p)63Ni reaction provides a unique measure to estimate the fast-neutron fluence of the Hiroshima/Nagasaki atomic bomb. In the similarity of the fission neutron spectrum of 252Cf to that of 235U, we have measured activation cross sections of the 63Cu(n, p)63Ni reaction averaged for the 252Cf fission spectrum.

  11. Highly Stereospecific Cross-Coupling Reactions of Anomeric Stannanes for the Synthesis of C-Aryl Glycosides.

    PubMed

    Zhu, Feng; Rourke, Michael J; Yang, Tianyi; Rodriguez, Jacob; Walczak, Maciej A

    2016-09-21

    We demonstrate that configurationally stable anomeric stannanes undergo a stereospecific cross-coupling reaction with aromatic halides in the presence of a palladium catalyst with exceptionally high levels of stereocontrol. In addition to a broad substrate scope (>40 examples), this reaction eliminates critical problems inherent to nucleophilic displacement methods and is applicable to (hetero)aromatics, peptides, pharmaceuticals, common monosaccharides, and saccharides containing free hydroxyl groups. PMID:27612008

  12. 87Y(n,γ) and 89,90Zr(n,γ) cross sections from a surrogate reaction approach

    NASA Astrophysics Data System (ADS)

    Ota, Shuya; Burke, J. T.; Casperson, R. J.; Escher, J. E.; Hughes, R. O.; Ressler, J. J.; Scielzo, N. D.; Thompson, I.; Austin, R. A. E.; McCleskey, E.; McCleskey, M.; Saastamoinen, A.; Ross, T.

    2015-05-01

    The surrogate reaction approach is an indirect method for determining nuclear reaction cross sections which cannot be measured directly or predicted reliably. While recent studies demonstrated the validity of the surrogate reaction approach for studying fission cross sections for short-lived actinides, its applicability for radiative neutron capture reactions ((n,γ)) is still under investigation. We studied the γ decay of excited 88Y and 90,91Zr nuclei produced by 89Y(p,d), 91Zr(p,d), and 92Zr(p,d) reactions, respectively, in order to infer the 87Y(n,γ) and 89, 90Zr(n,γ) cross sections. The experiments were carried out at the K150 Cyclotron facility at Texas A&M University with a 28.5-MeV proton beam. The reaction deuterons were measured at forward angles of 25-60° with the array of three segmented Micron S2 silicon detectors. The compound nuclei with energies up to a few MeV above the neutron separation thresholds were populated. The coincident γ-rays were measured with the array of five Compton-suppressed HPGe clover detectors.

  13. Absolute cross section for loss of supercoiled topology induced by 10 eV electrons in highly uniform /DNA/1,3-diaminopropane films deposited on highly ordered pyrolitic graphite

    NASA Astrophysics Data System (ADS)

    Boulanouar, Omar; Fromm, Michel; Bass, Andrew D.; Cloutier, Pierre; Sanche, Léon

    2013-08-01

    It was recently shown that the affinity of doubly charged, 1-3 diaminopropane (Dap2+) for DNA permits the growth on highly ordered pyrolitic graphite (HOPG) substrates, of plasmid DNA films, of known uniform thickness [O. Boulanouar, A. Khatyr, G. Herlem, F. Palmino, L. Sanche, and M. Fromm, J. Phys. Chem. C 115, 21291-21298 (2011)]. Post-irradiation analysis by electrophoresis of such targets confirms that electron impact at 10 eV produces a maximum in the yield of single strand breaks that can be associated with the formation of a DNA- transient anion. Using a well-adapted deterministic survival model for the variation of electron damage with fluence and film thickness, we have determined an absolute cross section for strand-break damage by 10 eV electrons and inelastic scattering attenuation length in DNA-Dap complex films.

  14. Absolute cross section for loss of supercoiled topology induced by 10 eV electrons in highly uniform /DNA/1,3-diaminopropane films deposited on highly ordered pyrolitic graphite

    SciTech Connect

    Boulanouar, Omar; Fromm, Michel; Bass, Andrew D.; Cloutier, Pierre; Sanche, Léon

    2013-08-07

    It was recently shown that the affinity of doubly charged, 1-3 diaminopropane (Dap{sup 2+}) for DNA permits the growth on highly ordered pyrolitic graphite (HOPG) substrates, of plasmid DNA films, of known uniform thickness [O. Boulanouar, A. Khatyr, G. Herlem, F. Palmino, L. Sanche, and M. Fromm, J. Phys. Chem. C 115, 21291–21298 (2011)]. Post-irradiation analysis by electrophoresis of such targets confirms that electron impact at 10 eV produces a maximum in the yield of single strand breaks that can be associated with the formation of a DNA{sup −} transient anion. Using a well-adapted deterministic survival model for the variation of electron damage with fluence and film thickness, we have determined an absolute cross section for strand-break damage by 10 eV electrons and inelastic scattering attenuation length in DNA-Dap complex films.

  15. Absolute nuclear material assay

    DOEpatents

    Prasad, Manoj K.; Snyderman, Neal J.; Rowland, Mark S.

    2012-05-15

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

  16. Absolute nuclear material assay

    DOEpatents

    Prasad, Manoj K.; Snyderman, Neal J.; Rowland, Mark S.

    2010-07-13

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

  17. Estimation of the reaction times in tasks of varying difficulty from the phase coherence of the auditory steady-state response using the least absolute shrinkage and selection operator analysis.

    PubMed

    Yokota, Yusuke; Igarashi, Yasuhiko; Okada, Masato; Naruse, Yasushi

    2015-01-01

    Quantitative estimation of the workload in the brain is an important factor for helping to predict the behavior of humans. The reaction time when performing a difficult task is longer than that when performing an easy task. Thus, the reaction time reflects the workload in the brain. In this study, we employed an N-back task in order to regulate the degree of difficulty of the tasks, and then estimated the reaction times from the brain activity. The brain activity that we used to estimate the reaction time was the auditory steady-state response (ASSR) evoked by a 40-Hz click sound. Fifteen healthy participants participated in the present study and magnetoencephalogram (MEG) responses were recorded using a 148-channel magnetometer system. The least absolute shrinkage and selection operator (LASSO), which is a type of sparse modeling, was employed to estimate the reaction times from the ASSR recorded by MEG. The LASSO showed higher estimation accuracy than the least squares method. This result indicates that LASSO overcame the over-fitting to the learning data. Furthermore, the LASSO selected channels in not only the parietal region, but also in the frontal and occipital regions. Since the ASSR is evoked by auditory stimuli, it is usually large in the parietal region. However, since LASSO also selected channels in regions outside the parietal region, this suggests that workload-related neural activity occurs in many brain regions. In the real world, it is more practical to use a wearable electroencephalography device with a limited number of channels than to use MEG. Therefore, determining which brain areas should be measured is essential. The channels selected by the sparse modeling method are informative for determining which brain areas to measure. PMID:26737821

  18. Measurement of absolute cross sections for excitation of the 2s(2) S-1 -> 2s2p P-1 degrees transition in O+4

    NASA Technical Reports Server (NTRS)

    Smith, S. J.; Djuric, N.; Lozano, J. A.; Berrington, K. A.; Chutjian, A.

    2005-01-01

    Experimental cross sections are reported for the 1s(2)2s(2) S-1 -> 1s(2)2s2p P-1(o) transition in O+4 located at 19.689 eV. Use is made of the electron energy-loss method, using a merged electron-ion beam geometry. The center-of-mass interaction energies for the measurements in the S-1 -> P-1(o) transition are in the range 18 eV ( below the threshold) to 30 eV. Data are compared with other previous electron energy-loss measurements and with results of a 26 term R-matrix calculation that includes fine structure explicitly via the Breit-Pauli Hamiltonian. Clear resonance enhancement is observed in all experimental and theoretical results near the threshold for this S-1 -> P-1(o) transition.

  19. Electron photoemission from charged films: absolute cross section for trapping 0-5 eV electrons in condensed CO2.

    PubMed

    Michaud, M; Hébert, E M; Cloutier, P; Sanche, L

    2007-01-14

    The electron trapping or attachment cross section of carbon dioxide (CO2) condensed as thin films on a spacer of Ar is obtained using a simple model for electron trapping in a molecular film and then charge releasing from the same film by photon absorption. The measurements are presented for different electron exposures and impact energies, film thicknesses, and probing photon energies. The cross section for trapping an electron of incident energy between 0 and 5 eV reveals three different attachment processes characterized by a maximum at about 0.75 eV, a structured feature around 2.25 eV, and a shoulder around 3.75 eV. From the measurement of their dependence with the probing photon energy, the two lowest processes produce traps having a vertical electron binding energy of approximately 3.5 eV, whereas the highest one yields a slightly higher value of approximately 3.7 eV. The 0.75 eV maximum corresponds to the formation of vibrational Feshbach resonances in (CO2)n- anion clusters. The 2.25 eV feature is attributed to the formation of a vibrationally excited 2Piu anion in (CO2)n- clusters, followed by fast decay into its vibrational ground state without undergoing autodetachment. Finally, 3.75 eV shoulder is assigned to the well-known dissociative electron attachment process from 2Piu anion state producing the O- anion in the gas phase and the (CO2)nO- anions in clusters.

  20. Preparation of 2-BF3-substituted 1,3-dienes and their Diels-Alder/cross-coupling reactions.

    PubMed

    De, Subhasis; Welker, Mark E

    2005-06-01

    [reaction: see text] 2-BF3-substituted 1,3-butadienes with potassium and tetrabutylammonium counterions have been prepared in gram quantities from chloroprene via a simple synthetic procedure. The potassium salt of this new main group element substituted diene has been characterized by 1H, 13C, 11B, and 19F NMR. Diels-Alder reactions of these dienes with ethyl acrylate and methyl vinyl ketone are reported, as well as subsequent Pd-catalyzed cross-coupling reactions of those Diels-Alder adducts. PMID:15932228

  1. Cross Section of OH Radical Overtone Transition near 7028 cm(-1) and Measurement of the Rate Constant of the Reaction of OH with HO2 Radicals.

    PubMed

    Assaf, Emmanuel; Fittschen, Christa

    2016-09-15

    The absorption cross section of an overtone transition of OH radicals at 7028.831 cm(-1) has been measured using an improved experimental setup coupling laser photolysis to three individual time-resolved detection techniques. Time-resolved relative OH radical profiles were measured by laser-induced fluorescence (LIF), and their absolute profiles have been obtained by cw-cavity ring-down spectroscopy (cw-CRDS). HO2 radicals were quantified simultaneously at the well-characterized absorption line at 6638.21 cm(-1) by a second cw-CRDS absorption path. Initial OH concentrations and thus their absorption cross sections have been deduced from experiments of 248 nm photolysis of H2O2: OH and HO2 profiles have been fitted to a simple kinetic model using well-known rate constants. The rate constant of the reaction between OH and HO2 radicals turned out to be sensitive to the deduction of the initial OH concentration and has been revisited in this work: OH decays have been observed in the presence of varying excess HO2 concentrations. A rate constant of (1.02 ± 0.06) × 10(-10) cm(3) s(-1) has been obtained, in good agreement with previous measurements and recent recommendations. An absorption cross section of σOH = (1.54 ± 0.1) × 10(-19) cm(2) at a total pressure of 50 Torr helium has been obtained from consistent fitting of OH and HO2 profiles in a large range of concentrations.

  2. Cross Section of OH Radical Overtone Transition near 7028 cm(-1) and Measurement of the Rate Constant of the Reaction of OH with HO2 Radicals.

    PubMed

    Assaf, Emmanuel; Fittschen, Christa

    2016-09-15

    The absorption cross section of an overtone transition of OH radicals at 7028.831 cm(-1) has been measured using an improved experimental setup coupling laser photolysis to three individual time-resolved detection techniques. Time-resolved relative OH radical profiles were measured by laser-induced fluorescence (LIF), and their absolute profiles have been obtained by cw-cavity ring-down spectroscopy (cw-CRDS). HO2 radicals were quantified simultaneously at the well-characterized absorption line at 6638.21 cm(-1) by a second cw-CRDS absorption path. Initial OH concentrations and thus their absorption cross sections have been deduced from experiments of 248 nm photolysis of H2O2: OH and HO2 profiles have been fitted to a simple kinetic model using well-known rate constants. The rate constant of the reaction between OH and HO2 radicals turned out to be sensitive to the deduction of the initial OH concentration and has been revisited in this work: OH decays have been observed in the presence of varying excess HO2 concentrations. A rate constant of (1.02 ± 0.06) × 10(-10) cm(3) s(-1) has been obtained, in good agreement with previous measurements and recent recommendations. An absorption cross section of σOH = (1.54 ± 0.1) × 10(-19) cm(2) at a total pressure of 50 Torr helium has been obtained from consistent fitting of OH and HO2 profiles in a large range of concentrations. PMID:27556141

  3. Ordered Mesoporous Polymers for Biomass Conversions and Cross-Coupling Reactions.

    PubMed

    Liu, Fujian; Wu, Qin; Liu, Chen; Qi, Chenze; Huang, Kuan; Zheng, Anmin; Dai, Sheng

    2016-09-01

    Amino group-functionalized, ordered mesoporous polymers (OMP-NH2 ) were prepared using a solvent-free synthesis by grinding mixtures of solid raw precursors (aminophenol, terephthaldehyde), using block copolymer templates, and curing at 140-180 °C. OMP-NH2 was functionalized with acidic sites and incorporated with palladium, giving multifunctional solid catalysts with large Brunauer-Emmett-Teller (BET) surface areas, abundant and ordered mesopores, good thermal stabilities, controllable concentrations, and good dispersion of active centers. The resultant solid catalysts showed excellent catalytic activities and good reusability in biomass conversions and cross-coupling reactions-much superior to those of various reported solid catalysts such as Amberlyst 15, SBA-15-SO3 H, and Pd/C and comparable to those of homogeneous catalysts such as heteropoly acid, HCl, and palladium acetate. A facile green approach was developed for the synthesis of ordered mesoporous polymeric solid catalysts with excellent activities for conversion of low-cost feedstocks into useful chemicals and clean biofuels. PMID:27529676

  4. Hemispheric disconnection syndrome with a "crossed avoiding" reaction in a case of Marchiafava-Bignami disease.

    PubMed Central

    Lechevalier, B; Andersson, J C; Morin, P

    1977-01-01

    A clinicopathological study is presented of a case of Marchiafava-Bignami disease with a hemispheric disconnection syndrome, an association that does not appear to have been reported previously. Gross and microscopic examination of the brain revealed necrosis of the corpus callosum (sparing a small area in front of the splenium) and of the anterior commissure, cortical and subcortical infarction of the right lingual gyrus, diffuse cortical lesions of the laminar sclerosis type, and lacunae in the basal ganglia and the pons. The patient was unable to grasp objects presented to the right visual half-field with the left hand, or to respond to contralateral somaesthetic stimuli with either of the upper limbs. This motor inhibition, with the associated extended posture, is described as a "crossed avoiding reaction", and attributed to the inability of one hemisphere to respond to visual or somaesthetic stimuli projected to the other hemisphere. Clinicopathological correlations and visuomotor coordination mechanisms are discussed in the light of previous clinical and experimental studies. Anomia to pictures projected tachistoscopically to the left visual field, disturbances in the transfer of somaesthetic information, left sided ideomotor apraxia with agraphia, right sided dyscopia, and ideational apraxia especially marked in the right visual field were observed. Images PMID:894319

  5. Iron-Catalyzed Enantioselective Cross-Coupling Reactions of α-Chloroesters with Aryl Grignard Reagents.

    PubMed

    Jin, Masayoshi; Adak, Laksmikanta; Nakamura, Masaharu

    2015-06-10

    The first iron-catalyzed enantioselective cross-coupling reaction between an organometallic compound and an organic electrophile is reported. Synthetically versatile racemic α-chloro- and α-bromoalkanoates were coupled with aryl Grignard reagents in the presence of catalytic amounts of an iron salt and a chiral bisphosphine ligand, giving the products in high yields with acceptable and synthetically useful enantioselectivities (er up to 91:9). The produced α-arylalkanoates were readily converted to the corresponding α-arylalkanoic acids with high optical enrichment (er up to >99:1) via simple deprotections/recrystallizations. The results of radical probe experiments are consistent with a mechanism that involves the formation of an alkyl radical intermediate, which undergoes subsequent enantioconvergent arylation in an intermolecular manner. The developed asymmetric coupling offers not only facile and practical access to various chiral α-arylalkanoic acid derivatives, which are of significant pharmaceutical importance, but also a basis of controlling enantioselectivity in an iron-catalyzed organometallic transformation. PMID:25955413

  6. Influence of the geminal biscyclopropyl group in the reactions of trimethylenemethane: Reversible intersystem crossing

    SciTech Connect

    Paul, G.C.; Gajewski, J.J.

    1996-02-23

    The azo compound precursor to Berson`s trimethylenemethane (TMM) biradical system, 2-methylene-1,3-cyclopentanediyl, was substituted with two cyclopropyl groups on the exomethylene. Generation of the TMM species by pyrolysis, direct photolysis, and benzophenone-sensitized photolysis resulted in formation of both cyclopropane ring-opened monomer and cyclopropane ring-unopened dimers whose ratio depended directly on temperature and extent of dilution. The ground state appears to be triplet on the basis of ESR spectrometry. The results contrast with previous work showing that monocyclopropyl substitution on Berson`s TMM species gives both ring-opened monomer and ring-unopened dimers upon pyrolysis and gives mostly ring-unopened dimer upon direct photolysis at 0-20 {degrees}C in what appear to be concentration-independent reactions. The observations with the biscyclopropyl-substituted species are consistent with steric effects retarding dimerization of the triplet allowing reversible intersystem crossing back to singlet and perhaps with reduction in the singlet-triplet gap as well. 1 tab., 1 fig.

  7. Quantum state-resolved differential cross sections for complex-forming chemical reactions: Asymmetry is the rule, symmetry the exception

    SciTech Connect

    Larrégaray, Pascal Bonnet, Laurent

    2015-10-14

    We argue that statistical theories are generally unable to accurately predict state-resolved differential cross sections for triatomic bimolecular reactions studied in beam experiments, even in the idealized limit where the dynamics are fully chaotic. The basic reason is that quenching of interferences between partial waves is less efficient than intuitively expected, especially around the poles.

  8. Non-cross-linked polystyrene-supported 2-imidazolidinone chiral auxiliary: synthesis and application in asymmetric alkylation reactions

    PubMed Central

    Nguyen, Quynh Pham Bao

    2013-01-01

    Summary Asymmetric alkylation reactions using non-cross-linked polystyrene (NCPS)-supported 2-imidazolidinone chiral auxiliaries were successfully investigated with excellent diastereocontrol (>99% de). The recovery and the recycling of this soluble polymer-supported chiral auxiliary were achieved in order to produce highly optical pure carboxylic acids. PMID:24204423

  9. Revised Calculations of the Production Rates for Co Isotopes in Meteorites Using New Cross Sections for Neutron-induced Reactions

    NASA Technical Reports Server (NTRS)

    Sisterson, J. M.; Brooks, F. D.; Buffler, A.; Allie, M. S.; Herbert, M. S.; Nchodu, M. R.; Makupula, S.; Ullmann, J.; Reedy, R. C.; Jones, D. T. L.

    2002-01-01

    New cross section measurements for reactions induced by neutrons with energies greater than 70 MeV are used to calculate the production rates for cobalt isotopes in meteorites and these new calculations are compared to previous estimates. Additional information is contained in the original extended abstract.

  10. Enantioselective synthesis of benzofurans and benzoxazines via an olefin cross-metathesis-intramolecular oxo-Michael reaction.

    PubMed

    Zhang, Jun-Wei; Cai, Quan; Gu, Qing; Shi, Xiao-Xin; You, Shu-Li

    2013-09-11

    Chiral phosphoric acid and Hoveyda-Grubbs II were found to catalyze an olefin cross-metathesis-intramolecular oxo-Michael cascade reaction of the ortho-allylphenols and enones to provide a variety of benzofuran and benzoxazine derivatives in moderate to good yields and enantioselectivity. PMID:23884172

  11. Enantioselective synthesis of benzofurans and benzoxazines via an olefin cross-metathesis-intramolecular oxo-Michael reaction.

    PubMed

    Zhang, Jun-Wei; Cai, Quan; Gu, Qing; Shi, Xiao-Xin; You, Shu-Li

    2013-09-11

    Chiral phosphoric acid and Hoveyda-Grubbs II were found to catalyze an olefin cross-metathesis-intramolecular oxo-Michael cascade reaction of the ortho-allylphenols and enones to provide a variety of benzofuran and benzoxazine derivatives in moderate to good yields and enantioselectivity.

  12. New efficient ligand for sub-mol % copper-catalyzed C-N cross-coupling reactions running under air.

    PubMed

    Larsson, Per-Fredrik; Astvik, Peter; Norrby, Per-Ola

    2012-01-01

    A new efficient ligand, N,N''-dimethyldiethylene triamine (DMDETA), has been synthesized and evaluated for sub-mol % copper-catalyzed C-N cross-coupling reactions. The efficiency of the ligand was determined by kinetic methods. DMDETA proved to display efficiency similar to DMEDA and, in addition, the resulting catalyst was tolerant to air. PMID:23209530

  13. New efficient ligand for sub-mol % copper-catalyzed C–N cross-coupling reactions running under air

    PubMed Central

    Larsson, Per-Fredrik; Astvik, Peter

    2012-01-01

    Summary A new efficient ligand, N,N’’-dimethyldiethylene triamine (DMDETA), has been synthesized and evaluated for sub-mol % copper-catalyzed C–N cross-coupling reactions. The efficiency of the ligand was determined by kinetic methods. DMDETA proved to display efficiency similar to DMEDA and, in addition, the resulting catalyst was tolerant to air. PMID:23209530

  14. Measurement of Absolute Cross Sections for Excitation of the 2s^2 ^1S - 2s2p ^1P^o Transition in O^4+

    NASA Astrophysics Data System (ADS)

    Smith, Steven J.; Berrington, K. A.

    2005-05-01

    Experimental electron excitation cross sections are reported for the 2s^2 1S - 2s2p^ 1P^o transitions in O^4+ located at 19.689 eV. The JPL electron-cyclotron resonance ion source is utilized [1], along with the electron energy loss method, in a merged electron-ion beams geometry[2]. The center-of-mass interaction energies for the measurements are in the range 18 eV (below threshold) to 30 eV. Data are compared with results of a 26-term R-matrix calculation that includes fine structure explicitly via the Breit-Pauli Hamiltonian [3]. There is good agreement with theoretical results and with previous electron energy-loss measurements [3]. Clear resonance enhancement is observed in both experiment and theoretical results near threshold for this ^1S - ^1P^o transition. J. Lozano and N. Djuric acknowledge support through the NASA-NRC program. This work was carried out at JPL/Caltech and was supported by NASA. [1] J. B. Greenwood, S. J. Smith, A.Chutjian, and E. Pollack, Phys. Rev. A 59 1348, (1999). [2] A. Chutjian, Physica Scripta T110, 203 (2004). [3] M. Bannister et al., Int.J. Mass Spectrometry 192, 39 (1999).

  15. (65)Cu isomeric cross sections for (n,α) reaction using approximately 14MeV neutrons.

    PubMed

    Durusoy, Ayşe; Reyhancan, Iskender Atilla; Akçalı, Özgür

    2015-05-01

    In this paper, activation cross-section measurements for the (65)Cu(n,α)(62m)Co (T1/2=13.86min.) reaction at six different neutron energies ranging from 13.6 and 14.9MeV are presented. The fast neutrons were produced via (3)H(d, n)(4)He reactions from an SAMES T-400 neutron generator. An activation technique was used to measure induced gamma activities. A high-resolution gamma-ray spectrometer with a high-purity germanium (HpGe) detector was used to acquire the data. The measured cross section data were corrected for gamma-ray attenuations, pulse pile-up effects, dead time, variations in neutron flux, and contributions from scattered low-energy neutrons. The measured cross sections were compared with statistical model calculations (TALYS 1.6 code), the experimental data available in the literature and the data obtained from TENDL.

  16. Calculation and analysis of cross-sections for p+184W reactions up to 200 MeV

    NASA Astrophysics Data System (ADS)

    Sun, Jian-Ping; Zhang, Zheng-Jun; Han, Yin-Lu

    2015-08-01

    A set of optimal proton optical potential parameters for p+ 184W reactions are obtained at incident proton energy up to 250 MeV. Based on these parameters, the reaction cross-sections, elastic scattering angular distributions, energy spectra and double differential cross sections of proton-induced reactions on 184W are calculated and analyzed by using theoretical models which integrate the optical model, distorted Born wave approximation theory, intra-nuclear cascade model, exciton model, Hauser-Feshbach theory and evaporation model. The calculated results are compared with existing experimental data and good agreement is achieved. Supported by National Basic Research Program of China, Technology Research of Accelerator Driven Sub-critical System for Nuclear Waste Transmutation (2007CB209903) and Strategic Priority Research Program of Chinese Academy of Sciences, Thorium Molten Salt Reactor Nuclear Energy System (XDA02010100)

  17. Influence of the neutron numbers of projectile and target on the evaporation residue cross sections in hot fusion reactions

    NASA Astrophysics Data System (ADS)

    Zhu, Long; Su, Jun; Zhang, Feng-Shou

    2016-06-01

    Within the framework of a dinuclear system model, the influence of projectile and target neutron number on capture cross section, fusion probability, and survival probability for the reactions S,3634+238U and 48Ca+Pu 239 ,240 ,242 ,244 are investigated. The calculated excitation functions are in good agreement with the experimental data. To synthesize more unknown neutron-deficient isotopes of already-known superheavy elements, the possibility of using lighter calcium isotopes to induce hot fusion reactions is investigated and the maximal evaporation residual cross sections for Ca 44 ,46 ,48 -induced hot fusion reactions to produce unknown neutron-deficient superheavy nuclei with Z =112 -116 are predicted.

  18. Production cross section of At radionuclides from 7Li+natPb and 9Be+natTl reactions

    NASA Astrophysics Data System (ADS)

    Maiti, Moumita; Lahiri, Susanta

    2011-12-01

    Earlier we reported theoretical studies on the probable production of astatine radionuclides from 6,7Li- and 9Be-induced reactions on natural lead and thallium targets, respectively. The production of astatine radionuclides were investigated experimentally with two heavy-ion-induced reactions: 9Be + natTl and 7Li + natPb. Formation cross sections of the evaporation residues, 207,208,209,210At, produced in the (HI,xn) channel, were measured by the stacked-foil technique followed by off-line γ spectrometry at low incident energies (<50 MeV). Measured excitation functions were interpreted in terms of a compound nuclear reaction mechanism using Weisskopf-Ewing and Hauser-Feshbach models. Measured cross-section values are lower than the respective theoretical predictions.

  19. Cross sections of the O{sup +}+H{sub 2}{yields}OH{sup +}+H ion-molecule reaction and isotopic variants (D{sub 2}, HD): Quasiclassical trajectory study and comparison with experiments

    SciTech Connect

    Martinez, Rodrigo; Sierra, Jose Daniel; Gonzalez, Miguel

    2005-11-01

    A dynamics study [cross section and microscopic mechanism versus collision energy (E{sub T})] of the reaction O{sup +}+H{sub 2}{yields}OH{sup +}+H, which plays an important role in Earth's ionosphere and interstellar chemistry, was conducted using the quasiclassical trajectory method, employing an analytical potential energy surface (PES) recently derived by our group [R. Martinez et al., J. Chem. Phys. 120, 4705 (2004)]. Experimental excitation functions for the title reaction, as well as its isotopic variants with D{sub 2} and HD, were near-quantitatively reproduced in the calculations in the very broad collision energy range explored (E{sub T}=0.01-6.0 eV). Intramolecular and intermolecular isotopic effects were also examined, yielding data in good agreement with experimental results. The reaction occurs via two microscopic mechanisms (direct and nondirect abstraction). The results were satisfactorily interpreted based on the reaction probability and the maximum impact parameter dependences with E{sub T}, and considering the influence of the collinear [OHH]{sup +} absolute minimum of the PES on the evolution from reactants to products. The agreement between theory and experiment suggests that the reaction mainly occurs through the lowest energy PES and nonadiabatic processes are not very important in the wide collision energy range analyzed. Hence, the PES used to describe this reaction is suitable for both kinetics and dynamics studies.

  20. Measurement of 235U(n,n'γ) and 235U(n,2nγ) reaction cross sections

    NASA Astrophysics Data System (ADS)

    Kerveno, M.; Thiry, J. C.; Bacquias, A.; Borcea, C.; Dessagne, P.; Drohé, J. C.; Goriely, S.; Hilaire, S.; Jericha, E.; Karam, H.; Negret, A.; Pavlik, A.; Plompen, A. J. M.; Romain, P.; Rouki, C.; Rudolf, G.; Stanoiu, M.

    2013-02-01

    The design of generation IV nuclear reactors and the studies of new fuel cycles require knowledge of the cross sections of various nuclear reactions. Our research is focused on (n,xnγ) reactions occurring in these new reactors. The aim is to measure unknown cross sections and to reduce the uncertainty on present data for reactions and isotopes of interest for transmutation or advanced reactors. The present work studies the 235U(n,n'γ) and 235U(n,2nγ) reactions in the fast neutron energy domain (up to 20 MeV). The experiments were performed with the Geel electron linear accelerator GELINA, which delivers a pulsed white neutron beam. The time characteristics enable measuring neutron energies with the time-of-flight (TOF) technique. The neutron induced reactions [in this case inelastic scattering and (n,2n) reactions] are identified by on-line prompt γ spectroscopy with an experimental setup including four high-purity germanium (HPGe) detectors. A fission ionization chamber is used to monitor the incident neutron flux. The experimental setup and analysis methods are presented and the model calculations performed with the TALYS-1.2 code are discussed.

  1. Vascular peroxidase-1 is rapidly secreted, circulates in plasma, and supports dityrosine cross-linking reactions.

    PubMed

    Cheng, Guangjie; Li, Hong; Cao, Zehong; Qiu, Xiaoyun; McCormick, Sally; Thannickal, Victor J; Nauseef, William M

    2011-10-01

    Members of the peroxidase-cyclooxygenase superfamily catalyze biochemical reactions essential to a broad spectrum of biological processes, including host defense, thyroid hormone biosynthesis, and modification of extracellular matrix, as well as contributing to the pathogenesis of chronic inflammatory diseases. We recently identified a novel member of this family, vascular peroxidase-1 (VPO1), that is highly expressed in the human cardiovascular system. Its biosynthesis and enzymatic properties are largely unknown. Here, we report that VPO1 was rapidly and efficiently secreted into the extracellular space when the gene was stably expressed in human embryonic kidney (HEK) cells. Secreted VPO1 is a monomer with complex N-linked oligosaccharides and exhibits peroxidase activity. Biosynthesis of endogenous VPO1 by cultured human umbilical vein endothelial cells (HUVECs) shares features exhibited by heterologous expression of recombinant VPO1 (rVPO1) in HEK cells. The proinflammatory agents lipopolysaccharide and tumor necrosis factor-α induce expression of VPO1 mRNA and protein in HUVECs. Furthermore, murine and bovine sera and human plasma contain enzymatically active VPO1. rVPO1 exhibits spectral and enzymatic properties characteristic of the peroxidase-cyclooxygenase family, except with regard to its heat stability. rVPO1 catalyzes tyrosyl radical formation and promotes dityrosine cross-linking. Taken together, these data demonstrate that VPO1 is a glycosylated heme peroxidase that is actively secreted into circulating plasma by vascular endothelial cells and shares several features with other members of the peroxidase-cyclooxygenase family, including the catalysis of dityrosine formation. PMID:21798344

  2. Cross-reactions between engineered xylose and galactose pathways in recombinant Saccharomyces cerevisiae

    PubMed Central

    2010-01-01

    Background Overexpression of the PGM2 gene encoding phosphoglucomutase (Pgm2p) has been shown to improve galactose utilization both under aerobic and under anaerobic conditions. Similarly, xylose utilization has been improved by overexpression of genes encoding xylulokinase (XK), enzymes from the non-oxidative pentose phosphate pathway (non-ox PPP) and deletion of the endogenous aldose reductase GRE3 gene in engineered Saccharomyces cerevisiae strains carrying either fungal or bacterial xylose pathways. In the present study, we investigated how the combination of these traits affect xylose and galactose utilization in the presence or absence of glucose in S. cerevisiae strains engineered with the xylose reductase (XR)-xylitol dehydrogenase (XDH) pathway. Results In the absence of PGM2 overexpression, the combined overexpression of XK, the non-ox PPP and deletion of the GRE3 gene significantly delayed aerobic growth on galactose, whereas no difference was observed between the control strain and the xylose-engineered strain when the PGM2 gene was overexpressed. Under anaerobic conditions, the overexpression of the PGM2 gene increased the ethanol yield and the xylose consumption rate in medium containing xylose as the only carbon source. The possibility of Pgm2p acting as a xylose isomerase (XI) could be excluded by measuring the XI activity in both strains. The additional copy of the PGM2 gene also resulted in a shorter fermentation time during the co-consumption of galactose and xylose. However, the effect was lost upon addition of glucose to the growth medium. Conclusions PGM2 overexpression was shown to benefit xylose and galactose fermentation, alone and in combination. In contrast, galactose fermentation was impaired in the engineered xylose-utilizing strain harbouring extra copies of the non-ox PPP genes and a deletion of the GRE3 gene, unless PGM2 was overexpressed. These cross-reactions are of particular relevance for the fermentation of mixed sugars from

  3. Activation evaluation and isotopic effects in the (n, p) reaction cross section on A-180 target nuclei

    SciTech Connect

    Avrigeanu, M.; Forrest, R. A.; Roman, F. L.; Avrigeanu, V.

    2006-07-01

    The fast-neutron nuclear data for the stable isotopes of tungsten, tantalum and hafnium, which are important in nuclear technology applications, have been consistently analyzed by means of the nuclear model computer codes TALYS, EMPIRE-II and STAPRE-H. The latter code uses a unique parameter set. The long-lived Hf isomers, which could be produced after a few reactions on W and Ta in the first-wall material of fusion power plants, need special consideration. The analysis, making use of global as well as local parameters within different model assumptions, aims to increase the predictive power of the models, which is of interest to basic as well as applied questions. This work suggests a physical reason for some of the discrepancies between experimental and calculated cross sections for (n, p) and (n, {alpha}) reactions on {sup 181}Ta. Thus, the rather similar Q-values for the (n, p) reaction on the {sup 179}Hf, {sup 181}Ta, and {sup 183}W odd-A target nuclei, also with similar asymmetry-parameter values, support the comparable cross sections which are predicted by all three computer code calculations at variance with the lower measured cross sections of the {sup 181}Ta(n, p) {sup 181}Hf reaction. (authors)

  4. Nonsymmetrical 3,4-dithienylmaleimides by cross-coupling reactions with indium organometallics: synthesis and photochemical studies.

    PubMed

    Mosquera, Angeles; Férnandez, M Isabel; Canle Lopez, Moisés; Pérez Sestelo, José; Sarandeses, Luis A

    2014-10-27

    The synthesis and photochemical study of novel nonsymmetrical 1,2-dithienylethenes (DTEs) with a maleimide bridge have been carried out. The synthetic approach to the DTEs was based on successive selective palladium-catalyzed cross-coupling reactions of 5-susbtituted-2-methyl-3-thiophenyl indium reagents with 3,4-dichloromaleimides. The required organoindium reagents were prepared from 2-methyl-3,5-dibromothiophene by a selective (C-5) coupling reaction with triorganoindium compounds (R3 In) and subsequent metal-halogen exchange. The coupling reactions usually gave good yields and have a high atom economy with substoichiometric amounts of R3 In. The results of photochemical studies show that these novel dithienylmaleimides undergo a photocyclization reaction upon irradiation in the UV region and a photocycloreversion after excitation in the visible region, thus they can be used as photochemical switches. ON-OFF operations can be repeated in successive cycles without appreciable loss of effectiveness in the process.

  5. Cross section measurements of the B10(d,n0)C11 reaction below 160 keV

    NASA Astrophysics Data System (ADS)

    Stave, S.; Ahmed, M. W.; Antolak, A. J.; Blackston, M. A.; Crowell, A. S.; Doyle, B. L.; Henshaw, S. S.; Howell, C. R.; Kingsberry, P.; Perdue, B. A.; Rossi, P.; Prior, R. M.; Spraker, M. C.; Weller, H. R.

    2008-05-01

    New data were taken at the Triangle Universities Nuclear Laboratory to investigate the plausibility of using low energy deuterons and the B10(d,n)C11 reaction as a portable source of 6.3 MeV neutrons. Analysis of the data at and below incident deuteron energies of 160 keV indicates an n0 neutron cross section that is lower than previous estimates by at least three orders of magnitude. In separate runs, deuterons with two different energies (160 and 140 keV) were stopped in a B10 target. The resulting n0 neutrons of approximately 6.3 MeV were detected at angles between 0° and 150°. The angle integrated yields were used to determine the astrophysical S factor for this reaction assuming a constant value for the S factor below 160 keV. The cross sections reported between 130 and 160 keV were calculated using the extracted value of the S factor. The measured n0 cross section is several orders of magnitude smaller than previous results, thus eliminating B10(d,n)C11 as a portable source of intense neutrons with low energy deuteron beams on the order of tens of microamps. In order to gain insight into the reaction dynamics at these low energies the cross section results have been compared with results from calculations using the distorted wave Born approximation (DWBA) and a detailed Hauser-Feshbach calculation performed by the authors. The angular distribution is consistent with the Hauser-Feshbach calculation suggesting a statistical compound nucleus reaction rather than a direct reaction.

  6. Gamow-Teller unit cross sections for (t,{sup 3}He) and ({sup 3}He,t) reactions

    SciTech Connect

    Perdikakis, G.; Austin, Sam M.; Galaviz, D.; Tur, C.; Zegers, R. G. T.; Deaven, J. M.; Guess, C. J.; Hitt, G. W.; Meharchand, R.; Bazin, D.; Grinyer, G. F.; Caesar, C.; Herlitzius, C.; Gade, A.; Howard, M. E.; Smith, E. E.; Noji, S.; Sakai, H.; Shimbara, Y.

    2011-05-15

    The proportionality between differential cross sections at vanishing linear momentum transfer and Gamow-Teller transition strength, expressed in terms of the unit cross section ({sigma}{sub GT}), was studied as a function of target mass number for (t,{sup 3}He) and ({sup 3}He,t) reactions at 115A MeV and 140A MeV, respectively. Existing ({sup 3}He,t) and (t,{sup 3}He) data on targets with mass number 12{<=}A{<=}120 were complemented with new and reevaluated (t,{sup 3}He) data on proton, deuteron, {sup 6}Li, and {sup 12}C targets. It was found that in spite of the small difference in beam energies between the two probes, the unit cross sections have a nearly identical and simple dependence on target mass number A, for A{>=}12: {sigma}{sub GT}=109/A{sup 0.65}. The factorization of the unit cross sections in terms of a kinematical factor, a distortion factor, and the strength of the effective spin-isospin transfer nucleus-nucleus interaction was investigated. Simple phenomenological functions depending on mass number A were extracted for the latter two. By comparison with plane and distorted-wave Born approximation calculations, it was found that the use of a short-range approximation for knock-on exchange contributions to the transition amplitude results in overestimated cross sections for reactions involving the composite ({sup 3}He,t) and (t,{sup 3}He) probes.

  7. Modeled Neutron and Charged-Particle Induced Nuclear Reaction Cross Sections for Radiochemistry in the Region of Yttrium, Zirconium, Niobium, and Molybdenum

    SciTech Connect

    Hoffman, R D; Kelley, K; Dietrich, F S; Bauer, R; Mustafa, M G

    2006-06-13

    We have developed a set of modeled nuclear reaction cross sections for use in radiochemical diagnostics. Systematics for the input parameters required by the Hauser-Feshbach statistical model were developed and used to calculate neutron, proton, and deuteron induced nuclear reaction cross sections for targets ranging from strontium (Z = 38) to rhodium (Z = 45).

  8. Energy dependence of fusion evaporation-residue cross sections in the sup 28 Si+ sup 28 Si reaction

    SciTech Connect

    Vineyard, M.F.; Bauer, J.S.; Gosdin, C.H.; Trotter, R.S. ); Kovar, D.G.; Beck, C.; Henderson, D.J.; Janssens, R.V.F.; Wilkins, B.D.; Rosner, G.; Chowdhury, P.; Ikezoe, H.; Kuhn, W. ); Kolata, J.J.; Hinnefeld, J.D. ); Maguire, C.F. ); Mateja, J.F. ); Prosser, F.W. ); Stephans, G.S.F. )

    1990-03-01

    Velocity distributions of mass-identified evaporation residues produced in the {sup 28}Si+{sup 28}Si reaction have been measured at bombarding energies of 174, 215, 240, 309, 397, and 452 MeV using time-of-flight techniques. These distributions were used to identify evaporation residues and to separate the complete-fusion and incomplete-fusion components. Angular distributions and total cross sections were extracted at all six bombarding energies. The complete-fusion evaporation-residue cross sections and the deduced critical angular momenta are compared with lower energy data and the predictions of existing models.

  9. Ionic Conduction in Lithium Ion Battery Composite Electrode Governs Cross-sectional Reaction Distribution

    PubMed Central

    Orikasa, Yuki; Gogyo, Yuma; Yamashige, Hisao; Katayama, Misaki; Chen, Kezheng; Mori, Takuya; Yamamoto, Kentaro; Masese, Titus; Inada, Yasuhiro; Ohta, Toshiaki; Siroma, Zyun; Kato, Shiro; Kinoshita, Hajime; Arai, Hajime; Ogumi, Zempachi; Uchimoto, Yoshiharu

    2016-01-01

    Composite electrodes containing active materials, carbon and binder are widely used in lithium-ion batteries. Since the electrode reaction occurs preferentially in regions with lower resistance, reaction distribution can be happened within composite electrodes. We investigate the relationship between the reaction distribution with depth direction and electronic/ionic conductivity in composite electrodes with changing electrode porosities. Two dimensional X-ray absorption spectroscopy shows that the reaction distribution is happened in lower porosity electrodes. Our developed 6-probe method can measure electronic/ionic conductivity in composite electrodes. The ionic conductivity is decreased for lower porosity electrodes, which governs the reaction distribution of composite electrodes and their performances. PMID:27193448

  10. The effect of external magnetic fields on the catalytic activity of Pd nanoparticles in Suzuki cross-coupling reactions.

    PubMed

    Gao, Lei; Wang, Changlai; Li, Ren; Li, Ran; Chen, Qianwang

    2016-04-21

    Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the adsorption system, which is beneficial to the reaction. From the analysis of the partial density states, it could be seen that the 2p orbital of the carbon atom in bromobenzene and the 4d orbital of the Pd atom overlap more closely in the presence of MFs, which is beneficial for the electron transfer from the Pd substrate to the bromobenzene molecule. This study is helpful in understanding the interaction between MFs and catalysts and regulating the process of catalytic reactions via MFs. PMID:27043428

  11. Absolute biological needs.

    PubMed

    McLeod, Stephen

    2014-07-01

    Absolute needs (as against instrumental needs) are independent of the ends, goals and purposes of personal agents. Against the view that the only needs are instrumental needs, David Wiggins and Garrett Thomson have defended absolute needs on the grounds that the verb 'need' has instrumental and absolute senses. While remaining neutral about it, this article does not adopt that approach. Instead, it suggests that there are absolute biological needs. The absolute nature of these needs is defended by appeal to: their objectivity (as against mind-dependence); the universality of the phenomenon of needing across the plant and animal kingdoms; the impossibility that biological needs depend wholly upon the exercise of the abilities characteristic of personal agency; the contention that the possession of biological needs is prior to the possession of the abilities characteristic of personal agency. Finally, three philosophical usages of 'normative' are distinguished. On two of these, to describe a phenomenon or claim as 'normative' is to describe it as value-dependent. A description of a phenomenon or claim as 'normative' in the third sense does not entail such value-dependency, though it leaves open the possibility that value depends upon the phenomenon or upon the truth of the claim. It is argued that while survival needs (or claims about them) may well be normative in this third sense, they are normative in neither of the first two. Thus, the idea of absolute need is not inherently normative in either of the first two senses. PMID:23586876

  12. Absolute biological needs.

    PubMed

    McLeod, Stephen

    2014-07-01

    Absolute needs (as against instrumental needs) are independent of the ends, goals and purposes of personal agents. Against the view that the only needs are instrumental needs, David Wiggins and Garrett Thomson have defended absolute needs on the grounds that the verb 'need' has instrumental and absolute senses. While remaining neutral about it, this article does not adopt that approach. Instead, it suggests that there are absolute biological needs. The absolute nature of these needs is defended by appeal to: their objectivity (as against mind-dependence); the universality of the phenomenon of needing across the plant and animal kingdoms; the impossibility that biological needs depend wholly upon the exercise of the abilities characteristic of personal agency; the contention that the possession of biological needs is prior to the possession of the abilities characteristic of personal agency. Finally, three philosophical usages of 'normative' are distinguished. On two of these, to describe a phenomenon or claim as 'normative' is to describe it as value-dependent. A description of a phenomenon or claim as 'normative' in the third sense does not entail such value-dependency, though it leaves open the possibility that value depends upon the phenomenon or upon the truth of the claim. It is argued that while survival needs (or claims about them) may well be normative in this third sense, they are normative in neither of the first two. Thus, the idea of absolute need is not inherently normative in either of the first two senses.

  13. Practical Iron- and Cobalt-Catalyzed Cross-Coupling Reactions between N-Heterocyclic Halides and Aryl or Heteroaryl Magnesium Reagents.

    PubMed

    Kuzmina, Olesya M; Steib, Andreas K; Fernandez, Sarah; Boudot, Willy; Markiewicz, John T; Knochel, Paul

    2015-05-26

    The reaction scope of iron- and cobalt-catalyzed cross-coupling reactions in the presence of isoquinoline (quinoline) in the solvent mixture tBuOMe/THF has been further investigated. Various 2-halogenated pyridine, pyrimidine, and triazine derivatives were arylated under these mild conditions in excellent yields. The presence of isoquinoline allows us to perform Fe-catalyzed cross-coupling reactions between 6-chloroquinoline and aryl magnesium reagents. Furthermore, it was found that the use of 10% N,N-dimethylquinoline-8-amine increases the yields of some Co-catalyzed cross-coupling reactions with chloropyridines bearing electron-withdrawing substituents. PMID:25899175

  14. Experimental differential cross sections, level densities, and spin cutoffs as a testing ground for nuclear reaction codes

    NASA Astrophysics Data System (ADS)

    Voinov, A. V.; Grimes, S. M.; Brune, C. R.; Bürger, A.; Görgen, A.; Guttormsen, M.; Larsen, A. C.; Massey, T. N.; Siem, S.

    2013-11-01

    Proton double-differential cross sections from 59Co(α,p)62Ni, 57Fe(α,p)60Co, 56Fe(7Li,p)62Ni, and 55Mn(6Li,p)60Co reactions have been measured with 21-MeV α and 15-MeV lithium beams. Cross sections have been compared against calculations with the empire reaction code. Different input level density models have been tested. It was found that the Gilbert and Cameron [A. Gilbert and A. G. W. Cameron, Can. J. Phys.0008-420410.1139/p65-139 43, 1446 (1965)] level density model is best to reproduce experimental data. Level densities and spin cutoff parameters for 62Ni and 60Co above the excitation energy range of discrete levels (in continuum) have been obtained with a Monte Carlo technique. Excitation energy dependencies were found to be inconsistent with the Fermi-gas model.

  15. Production cross-sections of radionuclides from α-induced reactions on natural copper up to 50MeV.

    PubMed

    Usman, Ahmed Rufai; Khandaker, Mayeen Uddin; Haba, Hiromitsu; Otuka, Naohiko; Murakami, Masashi; Komori, Yukiko

    2016-08-01

    The excitation functions were measured for the (nat)Cu(α,x)(66,67)Ga,(65)Zn,(57,58,60)Co reactions in the energy range of 16.5 -50MeV. A conventional stacked-foil activation technique combined with HPGe γ-ray spectrometry was employed to determine cross-sections. The measured cross-sections were critically compared with relevant previous experimental data and also with the evaluated data in the TENDL-2014 library. Present results confirmed some of the previous experimental data, whereas only a partial agreement was found with the evaluated data. The measured data are useful for reducing the existing discrepancies in the literature, to improve the nuclear reaction model codes, and to enrich the experimental database towards various applications.

  16. Differential cross section measurements for the 6Li(n,t)alpha reaction in the few MeV region

    SciTech Connect

    Devlin, Matthew J; Taddeucci, Terence N; Hale, Gerald M; Haight, Robert C; O' Donnell, Johhn M

    2008-01-01

    New measured differential cross sections of tritons and alpha particles following the {sup 6}Li(n,t){alpha} reaction are reported for incident neutron energies between 0.2 and approximately 20 MeV. The neutrons were produced by spallation at the WNR facility at the Los Alamos Neutron Science CEnter (LANSCE), with the incident neutron energy determined by the time-of-flight method. Four E-{Delta}E telescopes were used at eight laboratory angles. These data have been incorporated into a prior R-matrix fit for the compound {sup 7}Li system, and result in an (n,t) reaction cross section that is 4% to 10% higher than previous evaluations in the 1-3 MeV incident neutron energy region.

  17. Production cross-sections of radionuclides from α-induced reactions on natural copper up to 50MeV.

    PubMed

    Usman, Ahmed Rufai; Khandaker, Mayeen Uddin; Haba, Hiromitsu; Otuka, Naohiko; Murakami, Masashi; Komori, Yukiko

    2016-08-01

    The excitation functions were measured for the (nat)Cu(α,x)(66,67)Ga,(65)Zn,(57,58,60)Co reactions in the energy range of 16.5 -50MeV. A conventional stacked-foil activation technique combined with HPGe γ-ray spectrometry was employed to determine cross-sections. The measured cross-sections were critically compared with relevant previous experimental data and also with the evaluated data in the TENDL-2014 library. Present results confirmed some of the previous experimental data, whereas only a partial agreement was found with the evaluated data. The measured data are useful for reducing the existing discrepancies in the literature, to improve the nuclear reaction model codes, and to enrich the experimental database towards various applications. PMID:27227905

  18. Experimental differential cross sections, level densities, and spin cutoffs as a testing ground for nuclear reaction codes

    DOE PAGES

    Voinov, Alexander V.; Grimes, Steven M.; Brune, Carl R.; Burger, Alexander; Gorgen, Andreas; Guttormsen, Magne; Larsen, Ann -Cecilie; Massey, Thomas N.; Siem, Sunniva

    2013-11-08

    Proton double-differential cross sections from 59Co(α,p)62Ni, 57Fe(α,p)60Co, 56Fe(7Li,p)62Ni, and 55Mn(6Li,p)60Co reactions have been measured with 21-MeV α and 15-MeV lithium beams. Cross sections have been compared against calculations with the empire reaction code. Different input level density models have been tested. It was found that the Gilbert and Cameron [A. Gilbert and A. G. W. Cameron, Can. J. Phys. 43, 1446 (1965)] level density model is best to reproduce experimental data. Level densities and spin cutoff parameters for 62Ni and 60Co above the excitation energy range of discrete levels (in continuum) have been obtained with a Monte Carlo technique. Furthermore,more » excitation energy dependencies were found to be inconsistent with the Fermi-gas model.« less

  19. Nitrimines as reagents for metal-free formal C(sp(2) )-C(sp(2) ) cross-coupling reactions.

    PubMed

    Angeles-Dunham, Veronica V; Nickerson, David M; Ray, Devin M; Mattson, Anita E

    2014-12-22

    Nitrimines are employed as powerful reagents for metal-free formal C(sp(2) )-C(sp(2) ) cross-coupling reactions. The new chemical process is tolerant of a wide array of nitrimine and heterocyclic coupling partners giving rise to the corresponding di- or trisubstituted alkenes, typically in high yield and with high stereoselectivity. This method is ideal for the metal-free construction of heterocycle-containing drug targets, such as phenprocoumon. PMID:25365926

  20. Iodine-Catalyzed Cross Dehydrogenative Coupling Reaction: A Regioselective Sulfenylation of Imidazoheterocycles Using Dimethyl Sulfoxide as an Oxidant.

    PubMed

    Siddaraju, Yogesh; Prabhu, Kandikere Ramaiah

    2016-09-01

    A regioselective formation of C-S bonds has been achieved using a cross dehydrogenative coupling (CDC) protocol using iodine as a catalyst and dimethyl sulfoxide as an oxidant under green chemistry conditions. This strategy employs the reaction of easily available heterocyclic thiols or thiones with imidazoheterocycles. This protocol provides an efficient, mild, and inexpensive method for sulfenylation of imidazoheterocycles with a diverse range of heterocyclic thiols and heterocyclic thiones. PMID:27490357

  1. A divergent approach to the synthesis of simplexides and congeners via a late-stage olefin cross-metathesis reaction.

    PubMed

    Li, Jiakun; Li, Wei; Yu, Biao

    2013-08-14

    Simplexides constitute a unique group of immunosuppressive glycolipids that demonstrate antiproliferative activities against activated T-cell lymphocytes via a unique non-cytotoxic inhibition. To investigate the structure-activity relationship of the varied long-chain secondary alcohols on simplexides, we developed an efficient and divergent route to the synthesis of simplexides and congeners, taking advantage of a late-stage olefin cross-metathesis reaction.

  2. Suzuki-Miyaura cross-coupling reaction on copper-trans-A(2)B corroles with excellent functional group tolerance.

    PubMed

    König, Michael; Reith, Lorenz Michael; Monkowius, Uwe; Knör, Günther; Bretterbauer, Klaus; Schoefberger, Wolfgang

    2011-06-10

    The palladium-catalyzed Suzuki-Miyaura cross-coupling reaction has been investigated on meso-substituted trans-A(2)B-corrole using tailored Pd-catalyst systems.We present the first examples of Suzuki-Miyaura cross-coupling reactions on meso-substituted trans-A(2)B-corrole derivatives with neutral, sterically hindered, inactivated and heteroaromatic boronic acids and esters, alkenylboronic acids, as well as quickly deboronating aryl boronic acids and benzo-condensated five membered heterocyclic boronic acids. In addition, we established a high-yield procedure for the Suzuki-Miyaura cross-coupling reaction of corroles with neutral boronic acids.Due to the lability of the free-base corrole macrocycles, functionalization of the corrole periphery was performed with the corresponding Cu-metallated species. meso-Substituted trans-A(2)B-corrole can hence be regarded as highly versatile platform towards more sophisticated corrole systems.X-ray structure analysis of a functionalized meso-substituted trans-A(2)B copper corrole exhibited the typical features of such a Cu-complex: short N-Cu distances and a saddled corrole configuration.Moreover, we observed a sensitivity of the formal oxidation state of the coordinated copper ions towards Suzuki-Miyaura cross-coupling reaction conditions, where the central copper(III) ion approaches the characteristic features of a copper(II) species. This redox behaviour was examined by UV/vis absorption spectra, nuclear magnetic resonance (NMR) experiments and time-dependent density functional theoretical calculations. PMID:21760646

  3. Two G3 feline rotavirus strains lacking cross-neutralization reactions represent distinct subtypes of serotype G3.

    PubMed

    Mochizuki, M; Nakagomi, O

    1994-01-01

    Two feline rotavirus strains, FRV-1 and FRV64, that have been shown to lack cross-neutralization reactions despite the sharing of serotype G3 were examined by plaque-reduction neutralization assays in relation to other G3 strains originating from cats, dogs, humans and monkeys. While FRV-1 and human G3 strains constituted one subtype (G3A), FRV64, canine strains and simian strains constituted another subtype (G3B). PMID:8078427

  4. Melamine and melamine-formaldehyde polymers as ligands for palladium and application to Suzuki-Miyaura cross-coupling reactions in sustainable solvents.

    PubMed

    Edwards, Grant A; Trafford, Mitchell A; Hamilton, Alaina E; Buxton, Audrey M; Bardeaux, Matthew C; Chalker, Justin M

    2014-03-01

    The Suzuki-Miyaura cross-coupling reaction is a foundation stone of modern organic synthesis, as evidenced by its widespread use in the preparation of pharmaceuticals, agrochemicals, polymers, and other functional materials. With the prevalence of this venerable reaction in industrial synthesis, it is prudent to ensure its application adheres to the tenets of green chemistry. The introduction of cross-coupling catalysts that are active in sustainable solvents is therefore an important endeavor. In this report, a melamine-palladium complex is introduced as a versatile catalyst for the Suzuki-Miyaura cross-coupling reaction. This catalyst is soluble and active in both water and the renewable organic solvent ethyl lactate. The melamine-palladium catalyst can also be cross-linked by reaction with formaldehyde to generate an insoluble polymeric catalyst that can be recovered after the cross-coupling. The melamine-palladium system is inexpensive, easy to handle, bench-stable, and effective in catalysis in the presence of a variety of impurities (high cross-coupling yields were obtained in reactions run in unfiltered river water to illustrate this final point). Additionally, investigations reported herein revealed an intriguing relationship between catalytic efficiency and the base employed in the cross-coupling reaction. Implications for the mechanism of transmetalation in aqueous Suzuki-Miyaura cross-coupling reaction are discussed.

  5. Measurement of activation cross-sections for high-energy neutron-induced reactions of Bi and Pb

    NASA Astrophysics Data System (ADS)

    Zaman, Muhammad; Kim, Guinyun; Kim, Kwangsoo; Naik, Haladhara; Shahid, Muhammad; Lee, Manwoo

    2015-08-01

    The cross-sections for 209Bi(n, 4n)206Bi, 209Bi(n, 5n)205Bi, natPb(n, xn)204mPb, natPb(n, xn)203Pb, natPb(n, xn)202mPb,natPb(n, xn)201Pb, natPb(n, xn)200Pb, natPb(n, αxn)203Hg and natPb(n, p xn)202Tl reactions were determined at the Korean Institute of Radiological and Medical Sciences (KIRAMS), Korea in the neutron energy range of 15.2 to 37.2 MeV. The above cross-sections were obtained by using the activation and off-line γ-ray spectrometric technique. The quasi-monoenergetic neutron used for the above reactions are based on the 9Be(p, n) reaction. Simulations of the spectral flux from the Be target were done using the MCNPX program. The cross-sections were estimated with the TALYS 1.6 code using the default parameter. The data from the present work and literature were compared with the data from the EAF-2010 and the TENDL-2013 libraries, and calculated values of TALYS 1.6 code. It shows that appropriate level density model, the γ-ray strength function, and the spin cut-off parameter are needed to obtain a good agreement between experimental data and theoretical values from TALYS 1.6 code.

  6. Integral cross section measurement of the U 235 ( n , n ' ) U 235 m reaction in a pulsed reactor

    DOE PAGES

    Bélier, G.; Bond, E. M.; Vieira, D. J.; Authier, N.; Becker, J. A.; Hyneck, D.; Jacquet, X.; Jansen, Y.; Legendre, J.; Macri, R.; et al

    2015-04-08

    The integral measurement of the neutron inelastic cross section leading to the 26-minute half-life 235mU isomer in a fission-like neutron spectrum is presented. The experiment has been performed at a pulsed reactor, where the internal conversion decay of the isomer was measured using a dedicated electron detector after activation. The sample preparation, efficiency measurement, irradiation, radiochemistry purification, and isomer decay measurement will be presented. We determined the integral cross section for the ²³⁵U(n,n')235mU reaction to be 1.00±0.13b. This result supports an evaluation performed with TALYS-1.4 code with respect to the isomer excitation as well as the total neutron inelastic scatteringmore » cross section.« less

  7. Absolute cross sections with polarization effects in Ne{sup {asterisk}}(2p{sup 5}3p)+He collisions: A detailed comparison between theory and experiment

    SciTech Connect

    Bahrim, C. |; Kucal, H.; Masnou-Seeuws, F.

    1997-08-01

    Quantal calculations are presented for intramultiplet mixing collisions of Ne{sup {asterisk}}(2p{sup 5}3p) with He({sup 1}S{sub 0}) in the 60{endash}1250 meV collision energy range. The coupled equations are solved in a diabatic representation where the coupling terms are obtained using the model potential calculations of Hennecart and Masnou-Seeuws [J. Phys. B {bold 18}, 657 (1985)] for the interaction of the Ne{sup {asterisk}} outer electron with the two cores and values fitted on the spectroscopic data of Dabrowski and Herzberg [Mol. Spectrosc. {bold 73}, 183 (1978)] for the core-core interaction. An extensive comparison with the experimental data of the Eindhoven group is presented for absolute polarized cross sections and anisotropy parameters. Very good agreement is obtained with thermal energy data of Manders {ital et al.} [Phys. Rev. A {bold 39}, 4467 (1989)], while the systematic 30{endash}40{percent} discrepancy with superthermal data of Boom {ital et al.} [Phys. Rev. A {bold 49}, 4660 (1994)] might be attributed to a calibration problem in the experiment rather than to an inaccuracy in the long-range potentials. {copyright} {ital 1997} {ital The American Physical Society}

  8. Inclusive proton spectra and total reaction cross sections for proton-nucleus scattering at 800 MeV

    SciTech Connect

    McGill, J.A.

    1981-08-01

    Current applications of multiple scattering theory to describe the elastic scattering of medium energy protons from nuclei have been shown to be quite successful in reproducing the experimental cross sections. These calculations use the impulse approximation, wherein the scattering from individual nucleons in the nucleus is described by the scattering amplitude for a free nucleon. Such an approximation restricts the inelastic channels to those initiated by nucleon-nucleon scattering. As a first step in determining the nature of p + nucleus scattering at 800 MeV, both total reaction cross sections and (p,p') inclusive cross sections were measured and compared to the free p + p cross sections for hydrogen, deuterium, calcium 40, carbon 12, and lead 208. It is concluded that as much as 85% of all reactions in a nucleus proceed from interactions with a single nucleon in the nucleus, and that the impulse approximation is a good starting point for a microscopic description of p + nucleus interactions at 800 MeV.

  9. (p,α) Reaction Cross Sections Calculations of Fe and Ni Target Nuclei Using New Developed Semi-empirical Formula

    NASA Astrophysics Data System (ADS)

    Tel, E.; Akca, S.; Kara, A.; Yiğit, M.; Aydın, A.

    2013-10-01

    Iron (Fe) and nickel (Ni) are important fusion structural materials in reactor technology. The gas production in the metallic structure arising from many different types of nuclear reactions has been a significant damage mechanism in structural components of fusion reactors. The hydrogen and its isotopes at high temperatures leave out of the metallic lattice but the alpha (α) particles that remain in the lattice generate helium (He) gas bubbles. In other words, the α particles can cause serious changes in the physical and mechanical properties of the fusion structural materials. In this study, the excitation functions of 54,57Fe(p,α) and 58,60,61,64Ni(p,α) reactions have been investigated in the incident proton energy range of 10-40 MeV to estimate the radiation damage effects on fusion structural materials used in the construction of the first walls and core of the reactor. The calculations of (p,α) reaction cross sections on 54,57Fe and 58,60,61,64Ni have been made by using PCROSS code and CEM95 code. The full exciton and cascade exciton model (CEM95) for pre-equilibrium calculations and Weisskopf-Ewing model for equilibrium calculations are used. Besides, the semi-empirical cross section formula with new coefficient obtained by Tel et al. (Pramana J Phys 74:931-943, 2010) has been applied for (p,α) reactions at 17.9 MeV proton incident energy.

  10. Copper-catalyzed alkyl-alkyl cross-coupling reactions using hydrocarbon additives: efficiency of catalyst and roles of additives.

    PubMed

    Iwasaki, Takanori; Imanishi, Reiko; Shimizu, Ryohei; Kuniyasu, Hitoshi; Terao, Jun; Kambe, Nobuaki

    2014-09-19

    Cross-coupling of alkyl halides with alkyl Grignard reagents proceeds with extremely high TONs of up to 1230000 using a Cu/unsaturated hydrocarbon catalytic system. Alkyl fluorides, chlorides, bromides, and tosylates are all suitable electrophiles, and a TOF as high as 31200 h(-1) was attained using an alkyl iodide. Side reactions of this catalytic system, i.e., reduction, dehydrohalogenation (elimination), and the homocoupling of alkyl halides, occur in the absence of additives. It appears that the reaction involves the β-hydrogen elimination of alkylcopper intermediates, giving rise to olefins and Cu-H species, and that this process triggers both side reactions and the degradation of the Cu catalyst. The formed Cu-H promotes the reduction of alkyl halides to give alkanes and Cu-X or the generation of Cu(0), probably by disproportionation, which can oxidatively add to alkyl halides to yield olefins and, in some cases, homocoupling products. Unsaturated hydrocarbon additives such as 1,3-butadiene and phenylpropyne play important roles in achieving highly efficient cross-coupling by suppressing β-hydrogen elimination, which inhibits both the degradation of the Cu catalyst and undesirable side reactions.

  11. Copper-catalyzed alkyl-alkyl cross-coupling reactions using hydrocarbon additives: efficiency of catalyst and roles of additives.

    PubMed

    Iwasaki, Takanori; Imanishi, Reiko; Shimizu, Ryohei; Kuniyasu, Hitoshi; Terao, Jun; Kambe, Nobuaki

    2014-09-19

    Cross-coupling of alkyl halides with alkyl Grignard reagents proceeds with extremely high TONs of up to 1230000 using a Cu/unsaturated hydrocarbon catalytic system. Alkyl fluorides, chlorides, bromides, and tosylates are all suitable electrophiles, and a TOF as high as 31200 h(-1) was attained using an alkyl iodide. Side reactions of this catalytic system, i.e., reduction, dehydrohalogenation (elimination), and the homocoupling of alkyl halides, occur in the absence of additives. It appears that the reaction involves the β-hydrogen elimination of alkylcopper intermediates, giving rise to olefins and Cu-H species, and that this process triggers both side reactions and the degradation of the Cu catalyst. The formed Cu-H promotes the reduction of alkyl halides to give alkanes and Cu-X or the generation of Cu(0), probably by disproportionation, which can oxidatively add to alkyl halides to yield olefins and, in some cases, homocoupling products. Unsaturated hydrocarbon additives such as 1,3-butadiene and phenylpropyne play important roles in achieving highly efficient cross-coupling by suppressing β-hydrogen elimination, which inhibits both the degradation of the Cu catalyst and undesirable side reactions. PMID:25010426

  12. Pd(II)-Catalyzed C–H Activation/C–C Cross-Coupling Reactions: Versatility and Practicality

    PubMed Central

    Chen, Xiao; Engle, Keary M.; Wang, Dong-Hui; Yu, Jin-Quan

    2009-01-01

    In the past decade, palladium-catalyzed C–H activation/C–C bond forming reactions have emerged as promising new catalytic transformations; however, development in this field is still at an early stage compared to the state of the art in cross-coupling reactions using aryl and alkyl halides. This Review begins with a brief introduction of four extensively investigated modes of catalysis for forming C–C bonds from C–H bonds: Pd(II)/Pd(0), Pd(II)/Pd(IV), Pd(0)/Pd(II)/Pd(IV) and Pd(0)/Pd(II) catalysis. More detailed discussion is then directed towards the recent development of Pd(II)-catalyzed coupling of C–H bonds with organometallic reagents through a Pd(II)/Pd(0) catalytic cycle. Despite much progress made to date, improving the versatility and practicality of this new reaction remains a tremendous challenge. PMID:19557755

  13. A crossed beams and ab initio investigation on the formation of cyanodiacetylene in the reaction of cyano radicals with diacetylene.

    PubMed

    Zhang, Fangtong; Kim, Seol; Kaiser, Ralf I; Jamal, Adeel; Mebel, Alexander M

    2009-06-21

    The crossed molecular beams reaction of ground state cyano radicals (CN) with diacetylene (HCCCCH) was studied in the laboratory under single collision conditions. Combining the derived center-of-mass translational energy and angular distributions with novel electronic structure calculations, we show that the linear cyanodiacetylene molecule (HCCCCCN) is the sole reaction product. Our study provided no substantiation of two alternative products which have been suggested previously: cyanoacetylene (HCCCN), speculated to be synthesized via the exchange of the ethynyl by the cyano group, and the 1,3-butadiynyl radical (HCCCC), thought to be formed via hydrogen abstraction. The unambiguous identification of cyanodiacetylene formed in an exoergic, barrierless bimolecular reaction of the cyano radical with diacetylene strongly suggests that cyanodiacetylene can be also synthesized via this process in the interstellar medium (cold molecular clouds) and in hydrocarbon-rich atmospheres of planets and their moons such as Titan.

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

    NASA Astrophysics Data System (ADS)

    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.

  15. Quantitative standards for absolute linguistic universals.

    PubMed

    Piantadosi, Steven T; Gibson, Edward

    2014-01-01

    Absolute linguistic universals are often justified by cross-linguistic analysis: If all observed languages exhibit a property, the property is taken to be a likely universal, perhaps specified in the cognitive or linguistic systems of language learners and users. In many cases, these patterns are then taken to motivate linguistic theory. Here, we show that cross-linguistic analysis will very rarely be able to statistically justify absolute, inviolable patterns in language. We formalize two statistical methods--frequentist and Bayesian--and show that in both it is possible to find strict linguistic universals, but that the numbers of independent languages necessary to do so is generally unachievable. This suggests that methods other than typological statistics are necessary to establish absolute properties of human language, and thus that many of the purported universals in linguistics have not received sufficient empirical justification.

  16. The absolute path command

    2012-05-11

    The ap command traveres all symlinks in a given file, directory, or executable name to identify the final absolute path. It can print just the final path, each intermediate link along with the symlink chan, and the permissions and ownership of each directory component in the final path. It has functionality similar to "which", except that it shows the final path instead of the first path. It is also similar to "pwd", but it canmore » provide the absolute path to a relative directory from the current working directory.« less

  17. The absolute path command

    SciTech Connect

    Moody, A.

    2012-05-11

    The ap command traveres all symlinks in a given file, directory, or executable name to identify the final absolute path. It can print just the final path, each intermediate link along with the symlink chan, and the permissions and ownership of each directory component in the final path. It has functionality similar to "which", except that it shows the final path instead of the first path. It is also similar to "pwd", but it can provide the absolute path to a relative directory from the current working directory.

  18. Validation of Cross Sections with Criticality Experiment and Reaction Rates: the Neptunium Case

    NASA Astrophysics Data System (ADS)

    Leong, L. S.; Tassan-Got, L.; Audouin, L.; Berthier, B.; Le Naour, C.; Stéphan, C.; Paradela, C.; Tarrío, D.; Duran, I.

    2014-04-01

    The 237Np neutron-induced fission cross section has been recently measured in a large energy range (from eV to GeV) at the n_TOF facility at CERN. When compared to previous measurements the n_TOF fission cross section appears to be higher by 5-7% beyond the fission threshold. To check the relevance of the n_TOF data, we considered a criticality experiment performed at Los Alamos with a 6 kg sphere of 237Np, surrounded by uranium highly enriched in 235U so as to approach criticality with fast neutrons. The multiplication factor keff of the calculation is in better agreement with the experiment when we replace the ENDF/B-VII.0 evaluation of the 237Np fission cross section by the n_TOF data. We also explored the hypothesis of deficiencies of the inelastic cross section in 235U which has been invoked by some authors to explain the deviation of 750 pcm. The large modification needed to reduce the deviation seems to be incompatible with existing inelastic cross section measurements. Also we show that the νbar of 237Np can hardly be incriminated because of the high accuracy of the existing data. Fission rate ratios or averaged fission cross sections measured in several fast neutron fields seem to give contradictory results on the validation of the 237Np cross section but at least one of the benchmark experiments, where the active deposits have been well calibrated for the number of atoms, favors the n_TOF data set. These outcomes support the hypothesis of a higher fission cross section of 237Np.

  19. Differential cross sections measurement of 31P(p,pγ1)31P reaction for PIGE applications

    NASA Astrophysics Data System (ADS)

    Jokar, A.; Kakuee, O.; Lamehi-Rachti, M.

    2016-09-01

    Differential cross sections of proton induced gamma-ray emission from the 31P(p,pγ1)31P (Eγ = 1266 keV) nuclear reaction were measured in the proton energy range of 1886-3007 keV at the laboratory angle of 90°. For these measurements a thin Zn3P2 target evaporated onto a self-supporting C film was used. The gamma-rays and backscattered protons were detected simultaneously. An HPGe detector placed at an angle of 90° with respect to the beam direction was employed to collect gamma-rays while an ion implanted Si detector placed at a scattering angle of 165° was used to detect backscattered protons. Simultaneous collection of gamma-rays and RBS spectra is a great advantage of this approach which makes differential cross-section measurements independent on the collected beam charge. The obtained cross-sections were compared with the previously only measured data in the literature. The validity of the measured differential cross sections was verified through a thick target benchmarking experiment. The overall systematic uncertainty of cross section values was estimated to be better than ±9%.

  20. Facile fabrication of core cross-linked micelles by RAFT polymerization and enzyme-mediated reaction.

    PubMed

    Wu, Yukun; Lai, Quanyong; Lai, Shuqi; Wu, Jing; Wang, Wei; Yuan, Zhi

    2014-06-01

    Polymeric micelles formed in aqueous solution by assembly of amphiphilic block copolymers have been extensively investigated due to their great potential as drug carriers. However, the stability of polymeric assembly is still one of the major challenges in delivering drugs to tissues and cells. Here, we report a facile route to fabricate core cross-linked (CCL) micelles using an enzymatic polymerization as the cross-linking method. We present synthesis of poly(ethylene glycol)-block-poly(N-isopropyl acrylamide-co-N-(4-hydroxyphenethyl) acrylamide) diblock copolymer PEG-b-P(NIPAAm-co-NHPAAm) via reversible addition-fragmentation chain transfer (RAFT) polymerization. The diblock copolymer was then self-assembled into non-cross-linked (NCL) micelles upon heating above the lower critical solution temperature (LCST), and subsequently cross-linked using horseradish peroxidase (HRP) and hydrogen peroxide (H2O2) as enzyme and oxidant. The characterization of the diblock copolymer and micelles were studied by NMR, DLS, UV-vis, and fluorescence spectroscopy. The fluorescence study reveals that the cross-linking process endows the micelles with much lower critical micelle concentration (CMC). In addition, the drug release study shows that the CCL micelles have lower release amount of doxorubicin (DOX) than the NCL micelles due to the enhanced stability of the CCL micelles by core cross-linking process. PMID:24768266

  1. Triazole-based monophosphine ligands for palladium-catalyzed cross-coupling reactions of aryl chlorides.

    PubMed

    Dai, Qian; Gao, Wenzhong; Liu, Duan; Kapes, Lea M; Zhang, Xumu

    2006-05-12

    A variety of triazole-based monophosphines (ClickPhos) have been prepared via efficient 1,3-dipolar cycloaddition of readily available azides and acetylenes. Their palladium complexes provided excellent yields in the amination reactions and Suzuki-Miyaura coupling reactions of unactivated aryl chlorides. Ligand 7i, which has a 2,6-dimethoxybenzene moiety, provided good results in Suzuki-Miyaura reaction to form hindered biaryls. A CAChe model for the Pd/7i complex shows that the likelihood of a Pd-arene interaction might be a rationale for its high catalytic reactivity.

  2. Energy-loss cross sections for inclusive charge-exchange reactions at intermediate energies

    NASA Technical Reports Server (NTRS)

    Cucinotta, Francis A.; Townsend, Lawrence W.; Dubey, Rajendra R.

    1993-01-01

    Charge-exchange reactions for scattering to the continuum are considered in a high-energy multiple scattering model. Calculations for (p,n) and (He-3,H-3) reactions are made and compared with experimental results for C-12, O-16, and Al-27 targets. Coherent effects are shown to lead to an important role for inelastic multiple scattering terms when light projectiles are considered.

  3. Sulfur reactions and cryptic cross-linkages to oxygen, iron, and carbon cyclin

    NASA Astrophysics Data System (ADS)

    Druschel, G.; Kafantaris, F. C. A.; Fike, D. A.; Schmitt-Kopplin, P.; Dvorski, S.; Oduro, H.

    2014-12-01

    Sulfur speciation in any setting is controlled by a complex series of redox reactions, polymerization, and complexation reactions that are affected by both biotic and abiotic processes. Additionally there are several crossroads of reactions with oxygen, carbon, and iron in which polysulfide molecules serve as a key reaction component that affects not only sulfur speciation, but the speciation, solubility, and bioavailability of these elements as well. Utilizing a combination of analytical approaches including electrochemistry, spectroscopy, mass spectrometry, and chromatography, we have started to unravel the interconnections between sulfur and other key elements, and how microorganisms may be either direct or indirect contributors to these chemical and mineralogical signatures. In microbial mats, we have observed microbial production of significant hydrogen peroxide under UV-stressed conditions. This peroxide interaction with hydrogen sulfide changes the kinetics and the pathways of abiotic sulfur reactions, potentially affecting the overall bioavailability and isotopic fractionations for specific reactions via a change in the linkage between oxygen and sulfur cycling. In systems containing significant iron, we have observed the production of an electroactive form of ferrous iron and sulfide (FeS(aq)) that is of a size that can be described between a dissolved molecular cluster and a small nanoparticle. This FeS(aq) can be a significant fraction of the dissolved iron or sulfide in a system, and is a key part of both the solubility of iron and sulfur and the pathways potentially important for pyritization reactions. In systems where we investigate the links between sulfur and carbon, laboratory and field experiments indicate a wide range of large and more reduced organic compounds are highly reactive towards polysulfide. Utilizing Fourier-transform ion cyclotron resonance mass spectrometry in conjunction with electrochemistry and chromatography, we are seeing a

  4. The effect of external magnetic fields on the catalytic activity of Pd nanoparticles in Suzuki cross-coupling reactions

    NASA Astrophysics Data System (ADS)

    Gao, Lei; Wang, Changlai; Li, Ren; Li, Ran; Chen, Qianwang

    2016-04-01

    Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the adsorption system, which is beneficial to the reaction. From the analysis of the partial density states, it could be seen that the 2p orbital of the carbon atom in bromobenzene and the 4d orbital of the Pd atom overlap more closely in the presence of MFs, which is beneficial for the electron transfer from the Pd substrate to the bromobenzene molecule. This study is helpful in understanding the interaction between MFs and catalysts and regulating the process of catalytic reactions via MFs.Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the

  5. Cationic Pd(II)-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies

    PubMed Central

    Nishikata, Takashi; Abela, Alexander R; Huang, Shenlin

    2016-01-01

    Summary Cationic palladium(II) complexes have been found to be highly reactive towards aromatic C–H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN)4](BF4)2 or a nitrile-free cationic palladium(II) complex generated in situ from the reaction of Pd(OAc)2 and HBF4, effectively catalyzes C–H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C–H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1) C–H activation to generate a cationic palladacycle; (2) reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3) regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II) complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied. PMID:27340491

  6. Solvent-free cross-dehydrogenative coupling reactions under high speed ball-milling conditions applied to the synthesis of functionalized tetrahydroisoquinolines.

    PubMed

    Su, Weike; Yu, Jingbo; Li, Zhenhua; Jiang, Zhijiang

    2011-11-01

    Solvent-free reaction using a high-speed ball milling technique has been first applied to cross-dehydrogenative coupling (CDC) reactions between tetrahydroisoquinolines and three types of pronucleophiles such as nitroalkanes, alkynes, and indoles. All coupling products were obtained in good yields at short reaction times (no more than 40 min). When alkynes and indoles were used as pronucleophile, the reactions can be catalyzed efficiently by recoverable copper balls without any additional metal catalyst. PMID:21961457

  7. Transglutaminase cross-linking effect on sensory characteristics and antioxidant activities of Maillard reaction products from soybean protein hydrolysates.

    PubMed

    Song, Na; Tan, Chen; Huang, Meigui; Liu, Ping; Eric, Karangwa; Zhang, Xiaoming; Xia, Shuqin; Jia, Chengsheng

    2013-01-01

    To improve the yield of Maillard peptides, a microbial transglutaminase (MTGase) was used to increase the content of 1000-5000Da peptides in soybean protein hydrolysates by using a cross-linking reaction. The sensory characteristics and antioxidant activities of corresponding Maillard Reaction Products (MSPC) was then evaluated. After cross-linking treatment the content of 1000-5000Da peptides in protein hydrolysates and the yield of Maillard peptides increased by 21.19% and 8.71%, respectively, which contributed to the improved mouthfulness of MSPC. The bitter amino acids were significantly decreased and the umami acids were markedly increased in MSPC. Volatile compounds identified by GC-MS analysis showed that the content of the important meaty flavour compounds (such as 2-methyl-3-furanthiol, bis(2-methyl-3-furyl)disulfide) of MSPC were dramatically higher than that of MRPs from uncross-linking peptides. Combined with sensory evaluation, it was confirmed that MTGase cross-linking improved the flavour Characteristics and did not affect the antioxidant activity of MSPC.

  8. Comparison of ankle kinematics and ground reaction forces between prospectively injured and uninjured collegiate cross country runners.

    PubMed

    Kuhman, Daniel J; Paquette, Max R; Peel, Shelby A; Melcher, Daniel A

    2016-06-01

    Biomechanical comparative studies on running-related injuries have included either currently or retrospectively injured runners. The purpose of this study was to prospectively compare ankle joint and ground reaction force variables between collegiate runners who developed injuries during the cross country season and those who did not. Running gait analyses using a motion capture system and force platform were conducted on 19 collegiate runners prior to the start of their cross country season. Ten runners sustained running-related injuries and 9 remained healthy during the course of the season. Strike index, peak loading rate of the vertical ground reaction force, dorsiflexion range of motion (ROM), eversion ROM, peak eversion angle, peak eversion velocity, and eversion duration from the start of the season were compared between injury groups. Ankle eversion ROM and peak eversion velocity were greater in uninjured runners while peak eversion angle was greater in injured runners. Greater ankle eversion ROM and eversion velocity with lower peak eversion angle may be beneficial in reducing injury risk in collegiate runners. The current data may only be applicable to collegiate cross country runners with similar training and racing schedules and threshold magnitudes of ankle kinematic variables to predict injury risk are still unknown.

  9. Comparison of ankle kinematics and ground reaction forces between prospectively injured and uninjured collegiate cross country runners.

    PubMed

    Kuhman, Daniel J; Paquette, Max R; Peel, Shelby A; Melcher, Daniel A

    2016-06-01

    Biomechanical comparative studies on running-related injuries have included either currently or retrospectively injured runners. The purpose of this study was to prospectively compare ankle joint and ground reaction force variables between collegiate runners who developed injuries during the cross country season and those who did not. Running gait analyses using a motion capture system and force platform were conducted on 19 collegiate runners prior to the start of their cross country season. Ten runners sustained running-related injuries and 9 remained healthy during the course of the season. Strike index, peak loading rate of the vertical ground reaction force, dorsiflexion range of motion (ROM), eversion ROM, peak eversion angle, peak eversion velocity, and eversion duration from the start of the season were compared between injury groups. Ankle eversion ROM and peak eversion velocity were greater in uninjured runners while peak eversion angle was greater in injured runners. Greater ankle eversion ROM and eversion velocity with lower peak eversion angle may be beneficial in reducing injury risk in collegiate runners. The current data may only be applicable to collegiate cross country runners with similar training and racing schedules and threshold magnitudes of ankle kinematic variables to predict injury risk are still unknown. PMID:26827155

  10. Cross section systematics for the lightest Bi and Po nuclei produced in complete fusion reactions with heavy ions

    SciTech Connect

    Andreyev, A.N.; Ackermann, D.; Muenzenberg, G.; Antalic, S.; Saro, S.; Streicher, B.; Darby, I.G.; Page, R.D.; Wiseman, D.R.; Franchoo, S.; Hessberger, F.P.; Kuusiniemi, P.; Lommel, B.; Kindler, B.; Mann, R.; Sulignano, B.; Hofmann, S.; Huyse, M.; Vel, K. van de; Duppen, P. van

    2005-07-01

    The production of the very neutron-deficient nuclides {sup 184-192}Bi and {sup 186-192}Po in the vicinity of the neutron midshell at N = 104 has been studied by using heavy-ion-induced complete fusion reactions in a series of experiments at the velocity filter SHIP. The cross sections for the xn and pxn evaporation channels of the {sup 46}Ti+{sup 144}Sm{yields}{sup 190}Po*,{sup 98}Mo+{sup 92}Mo{yields}{sup 190}Po*,{sup 50,52}Cr+{sup 142}Nd{yields}{sup 192,194}Po*, and {sup 94,95}Mo+{sup 93}Nb{yields}{sup 187,188}Bi* reactions were measured. The results obtained, together with the previously known cross section data for the heavier Bi and Po nuclides, are compared with the results of statistical model calculations carried out with the HIVAP code. It is shown that a satisfactory description of the experimental data requires a significant (up to 35%) reduction of the theoretical fission barriers. The optimal reactions for production of the lightest Bi and Po isotopes are discussed.

  11. Effects of Molecular Oxygen, Solvent, and Light on Iridium-Photoredox/Nickel Dual-Catalyzed Cross-Coupling Reactions.

    PubMed

    Oderinde, Martins S; Varela-Alvarez, Adrian; Aquila, Brian; Robbins, Daniel W; Johannes, Jeffrey W

    2015-08-01

    In order to achieve reproducibility during iridium-photoredox and nickel dual-catalyzed sp(3)-sp(2) carbon-carbon bond-forming reactions, we investigated the role that molecular oxygen (O2), solvent and light-source (CF lamp or blue LED) play in a variety of Ir-photoredox mediated transformations. The presence of O2 was discovered to be important for catalyst activation when air-stable Ni(II) precatalysts were used in DMF under CF lamp irradiation; however, O2 was not required for catalysis when conducted with Ni(COD)2 in the same reaction system. O2 is believed to promote rapid reduction of the Ni(II) precatalyst by Ir(II) to Ni(0). In addition to O2, the effects that solvent and light-source have on the dual-catalyzed decarboxylative cross-coupling reactions will be discussed. These findings have enabled us to develop a more robust dual-catalyzed decarboxylative cross-coupling protocol.

  12. Projectile influence on production cross section for ^48Ca-, ^50Ti-, and ^54Cr- induced fusion-evaporation reactions

    NASA Astrophysics Data System (ADS)

    Mayorov, D. A.; Werke, T. A.; Alfonso, M. C.; Bennett, M. E.; Folden, C. M., III

    2013-04-01

    Evaporation residue excitation functions for ^48Ca, ^50Ti + ^159Tb and ^48Ca, ^54Cr + ^162 Dy were measured at Texas A&M University using the vacuum spectrometer MARS. The produced residues are weakly deformed nuclei near the N = 126 shell closure. However, the production cross sections are insensitive to the associated shell stabilization to the fission barrier, an observation previously reported in literature. The ratio of maximum production cross sections between the ^48Ca/^50Ti and ^48Ca/^54Cr reactions is 47 and 7100, respectively. These substantial differences can be reproduced in theoretical calculations by inclusion of collective enhancements during de-excitation of the compound nucleus. The competition between quasifission and complete fusion further contributes to the observed separation in the excitation functions. Model-dependent estimates of the compound nucleus formation probability, PCN, yield ratios of PCN(^48Ca + ^159 Tb) / PCN(^50Ti + ^159 Tb) 2.5 and PCN(^48Ca + ^162Dy) / PCN(^54Cr + ^162Dy) 5. Heavy-ion fusion reactions with ^48Ca, ^50Ti, and ^54Cr projectiles are of interest due to modern-day efforts to synthesize superheavy elements 119 and 120 in warm fusion reactions with projectiles having Z 20.

  13. Fission cross section calculations for 209Bi target nucleus based on fission reaction models in high energy regions

    NASA Astrophysics Data System (ADS)

    Kaplan, Abdullah; Capali, Veli; Ozdogan, Hasan

    2015-07-01

    Implementation of projects of new generation nuclear power plants requires the solving of material science and technological issues in developing of reactor materials. Melts of heavy metals (Pb, Bi and Pb-Bi) due to their nuclear and thermophysical properties, are the candidate coolants for fast reactors and accelerator-driven systems (ADS). In this study, α, γ, p, n and 3He induced fission cross section calculations for 209Bi target nucleus at high-energy regions for (α,f), (γ,f), (p,f), (n,f) and (3He,f) reactions have been investigated using different fission reaction models. Mamdouh Table, Sierk, Rotating Liquid Drop and Fission Path models of theoretical fission barriers of TALYS 1.6 code have been used for the fission cross section calculations. The calculated results have been compared with the experimental data taken from the EXFOR database. TALYS 1.6 Sierk model calculations exhibit generally good agreement with the experimental measurements for all reactions used in this study.

  14. An efficient nonclassical quadrature for the calculation of nonresonant nuclear fusion reaction rate coefficients from cross section data

    NASA Astrophysics Data System (ADS)

    Shizgal, Bernie D.

    2016-08-01

    Nonclassical quadratures based on a new set of half-range polynomials, Tn(x) , orthogonal with respect to w(x) =e - x - b /√{ x } for x ∈ [ 0 , ∞) are employed in the efficient calculation of the nuclear fusion reaction rate coefficients from cross section data. The parameter b = B /√{kB T } in the weight function is temperature dependent and B is the Gamow factor. The polynomials Tn(x) satisfy a three term recurrence relation defined by two sets of recurrence coefficients, αn and βn. These recurrence coefficients define in turn the tridiagonal Jacobi matrix whose eigenvalues are the quadrature points and the weights are calculated from the first components of the eigenfunctions. For nonresonant nuclear reactions for which the astrophysical function can be expressed as a lower order polynomial in the relative energy, the convergence of the thermal average of the reactive cross section with this nonclassical quadrature is extremely rapid requiring in many cases 2-4 quadrature points. The results are compared with other libraries of nuclear reaction rate coefficient data reported in the literature.

  15. Kinetic studies of the BrO + ClO cross-reaction over the range T = 246-314 K.

    PubMed

    Ferracci, Valerio; Rowley, David M

    2014-01-21

    The kinetics of the atmospherically important gas phase radical reaction between BrO and ClO have been studied over the temperature range T = 246-314 K by means of laser flash photolysis coupled with UV absorption spectroscopy. Charge-coupled-device (CCD) detection allowed simultaneous monitoring of both free radicals and the OClO product using 'differential' spectroscopy, which minimised interference from underlying UV absorbing species. In this way, the total rate coefficient for BrO + ClO → products (1) was measured, along with that for the OClO producing channel of this process BrO + ClO → OClO + Br (1c). These reaction rate coefficients are described by the Arrhenius expressions: k1/cm(3) molecule(-1) s(-1) = (2.5 ± 2.2) × 10(-12) exp[(630 ± 240)/T] and k(1c)/cm(3) molecule(-1) s(-1) = (4.6 ± 3.0) × 10(-12) exp[(280 ± 180)/T], where errors are 2σ, statistical only. An extensive sensitivity analysis was performed to quantify the potential additional systematic uncertainties in this work arising from uncertainties in secondary chemistry, absorption cross-sections and precursor concentrations. This analysis identified the reactions of initial and secondarily generated bromine atoms (specifically Br + O3 and Br + Cl2O) as particularly important, along with the reversible combination of ClO with OClO forming Cl2O3. Potential uncertainty in this latter process was used to define the lowest temperature of the present study. Results from this work indicate larger absolute values for k1 and k(1c) than those reported in previous studies, but a weaker negative temperature dependence for k(1c) than previously observed, resulting in a branching ratio for with a positive temperature dependence, in disagreement with previous studies. is the principal source of OClO in the polar stratosphere and is commonly used in atmospheric models as an indicator of stratospheric bromine chemistry. Thus these measurements might lead to a reinterpretation of modelled

  16. Cross-metathesis reaction of α- and β-vinyl C-glycosides with alkenes.

    PubMed

    Šnajdr, Ivan; Parkan, Kamil; Hessler, Filip; Kotora, Martin

    2015-01-01

    Cross-metathesis of α- and β-vinyl C-deoxyribosides and α-vinyl C-galactoside with various terminal alkenes under different conditions was studied. The cross-metathesis of the former proceeded with good yields of the corresponding products in ClCH2CH2Cl the latter required the presence of CuI in CH2Cl2 to achieve good yields of the products. A simple method for the preparation of α- and β-vinyl C-deoxyribosides was also developed. In addition, feasibility of deprotection and further transformations were briefly explored. PMID:26425194

  17. Method of Cross-Linking Aerogels Using a One-Pot Reaction Scheme

    NASA Technical Reports Server (NTRS)

    Meador, Ann B.; Capadona, Lynn A.

    2008-01-01

    A document discusses a new, simplified method for cross-linking silica and other oxide aerogels, with a polymeric material to increase strength of such materials without adversely affecting porosity or low density. This innovation introduces the polymer precursor into the sol before gelation either as an agent, which co-reacts with the oxide gel, or as soluble polymer precursors, which do not interact with the oxide gel in any way. Subsequent exposure to heat, light, catalyst or other method of promoting polymerization causes cross-linking without any additional infiltration steps.

  18. Cross-Cultural Differences in Children's Emotional Reactions to a Disappointing Situation

    ERIC Educational Resources Information Center

    Garrett-Peters, Patricia T.; Fox, Nathan A.

    2007-01-01

    Cross-cultural differences in emotional expressions following disappointment were examined in 59 Chinese American (CA) and 58 European American (EA) children. Children aged four or seven participated in a disappointing gift situation. Dimensions of expressive behaviors following disappointment were coded and included positive, negative, social…

  19. Exact quantum cross sections for a three dimensional angle dependent model for three body reactions.

    NASA Technical Reports Server (NTRS)

    Baer, M.; Kouri, D. J.

    1971-01-01

    Exact quantum mechanical reactive cross sections are reported for a three dimensional angle dependent model surface. The surface simulates an atom-heteronuclear diatom system A + BC leading to AB + C where atom B is much heavier than A or C. The molecules BC and AB are taken to be rotating vibrators which can dissociate. Results for two angle dependent potentials are given.

  20. Comparison Between Zero-Range and Finite-Range Calculations of Total Reaction Cross Sections for Halo Nuclei

    NASA Astrophysics Data System (ADS)

    Al-Thoyaib, S. S.

    2008-03-01

    Total cross-sections of the halo nuclei in both the zero- and the finite-ranges are calculated at energy range of 25--800 MeV/n, by using the carbon nuclei as a probe. The calculations are based on the Optical Limit Approximation (OLA) of the Glauber theory and are done for Li, Be and B isotopes using the finite and the zero range interactions. We found that the total cross-sections depend slightly on the nuclear density. On the other hand, there is a discrepancy between the calculated results of both ranges in the surface region of the reaction probability. The theoretical results for the zero- and the finite-range are compared with experimental data. We found that the zero-range predictions are consistent with experimental data more than the finite-range.

  1. Applications of and alternatives to pi-electron-deficient azine organometallics in metal catalyzed cross-coupling reactions.

    PubMed

    Campeau, Louis-Charles; Fagnou, Keith

    2007-07-01

    While the use of pi-deficient azine halides in palladium catalyzed cross-coupling reactions is common, the use of pi-electron deficient azine organometallics has been less intensively examined. In recent years, important advances have been made that are beginning to address this deficiency and need. The purpose of this tutorial review is to highlight and discuss the innovations that facilitate the synthesis of azine-containing biaryls with a focus on the pyridine structural motif. Given the number of important compounds which exhibit azine-heterobiaryls and the wide use of cross-coupling methods in their synthesis, this review should be of interest among synthetic organic chemists and organometallic chemists alike.

  2. How the projectile neutron number influences the evaporation cross section in complete fusion reactions with heavy ions

    SciTech Connect

    Wang Chengbin; Zhang Jinjuan; Ren, Z. Z.; Shen, C. W.

    2010-11-15

    The influence of the projectile neutron number on the evaporation residue cross sections for the reactions {sup 208}Pb({sup 52,54}Cr,n,2n){sup 258-261}Sg and {sup 208}Pb({sup 48,50}Ti,n,2n){sup 254-257}Rf has been studied within the framework of a fusion-fission statistical model. The results obtained with the kewpie2 code are compared with recent experimental data. The excitation functions represent the experimental results well both in the maximum value and the lactation of the peak. The calculations show that the projectile neutron number greatly influences both the capture cross section and the fusion probability.

  3. Aqueous two-phase system patterning of detection antibody solutions for cross-reaction-free multiplex ELISA

    NASA Astrophysics Data System (ADS)

    Frampton, John P.; White, Joshua B.; Simon, Arlyne B.; Tsuei, Michael; Paczesny, Sophie; Takayama, Shuichi

    2014-05-01

    Accurate disease diagnosis, patient stratification and biomarker validation require the analysis of multiple biomarkers. This paper describes cross-reactivity-free multiplexing of enzyme-linked immunosorbent assays (ELISAs) using aqueous two-phase systems (ATPSs) to confine detection antibodies at specific locations in fully aqueous environments. Antibody cross-reactions are eliminated because the detection antibody solutions are co-localized only to corresponding surface-immobilized capture antibody spots. This multiplexing technique is validated using plasma samples from allogeneic bone marrow recipients. Patients with acute graft versus host disease (GVHD), a common and serious condition associated with allogeneic bone marrow transplantation, display higher mean concentrations for four multiplexed biomarkers (HGF, elafin, ST2 and TNFR1) relative to healthy donors and transplant patients without GVHD. The antibody co-localization capability of this technology is particularly useful when using inherently cross-reactive reagents such as polyclonal antibodies, although monoclonal antibody cross-reactivity can also be reduced. Because ATPS-ELISA adapts readily available antibody reagents, plate materials and detection instruments, it should be easily transferable into other research and clinical settings.

  4. Aqueous two-phase system patterning of detection antibody solutions for cross-reaction-free multiplex ELISA

    PubMed Central

    Frampton, John P.; White, Joshua B.; Simon, Arlyne B.; Tsuei, Michael; Paczesny, Sophie; Takayama, Shuichi

    2014-01-01

    Accurate disease diagnosis, patient stratification and biomarker validation require the analysis of multiple biomarkers. This paper describes cross-reactivity-free multiplexing of enzyme-linked immunosorbent assays (ELISAs) using aqueous two-phase systems (ATPSs) to confine detection antibodies at specific locations in fully aqueous environments. Antibody cross-reactions are eliminated because the detection antibody solutions are co-localized only to corresponding surface-immobilized capture antibody spots. This multiplexing technique is validated using plasma samples from allogeneic bone marrow recipients. Patients with acute graft versus host disease (GVHD), a common and serious condition associated with allogeneic bone marrow transplantation, display higher mean concentrations for four multiplexed biomarkers (HGF, elafin, ST2 and TNFR1) relative to healthy donors and transplant patients without GVHD. The antibody co-localization capability of this technology is particularly useful when using inherently cross-reactive reagents such as polyclonal antibodies, although monoclonal antibody cross-reactivity can also be reduced. Because ATPS-ELISA adapts readily available antibody reagents, plate materials and detection instruments, it should be easily transferable into other research and clinical settings. PMID:24786974

  5. Evaporation residue cross sections for the {sup 100}Mo + {sup 116}Cd reaction -- energy dissipation in hot nuclei

    SciTech Connect

    Back, B.B.; Blumenthal, D.J.; Davids, C.N.

    1995-08-01

    In this experiment we tried to measure the evaporation residue cross section over a wide range of beam energies for the {sup 100}Mo + {sup 116}Cd reaction using the FMA. However, because of longer-than-estimated runs needed at each beam energy, and the difficulty of bending evaporation residues at the higher energies in the FMA, data were taken only at beam energies of E{sub beam} = 460, 490, and 521 MeV, which correspond to excitation energies of E{sub exc} = 62, 78, and 95 MeV, respectively. By comparing to results for the {sup 32}S + {sup 184}W reactions measured recently, we expect to demonstrate a strong entrance channel effect related to the hindrance of complete fusion in near-symmetric heavy systems (a fusion hindrance factor of the order 7-10 is expected on the basis of the Extra-Push Model). The data are being analyzed.

  6. A new cross-section measurement of reactions induced by 3He particles on a carbon target

    NASA Astrophysics Data System (ADS)

    Pichard, A.; Mrázek, J.; Assié, M.; Hass, M.; Honusek, M.; Lhersonneau, G.; de Oliveira Santos, F.; Saint-Laurent, M.-G.; Šimečková, E.

    2011-06-01

    The production of intense beams of light radioactive nuclei can be achieved at the SPIRAL2 facility using intense stable beams accelerated by the driver accelerator and impinging on light targets. The isotope 14O is identified to be of high interest for future experiments. The excitation function of the production reaction 12C(3He, n)14O was measured between 7 and 35MeV. Results are compared with literature data. As an additional result, we report the first cross-section measurement for the 12C(3He, α + n)10C reaction. Based on this new result, the potential in-target 14O yield at SPIRAL2 was estimated: 2.4×1011 pps, for 1mA of 3He at 35MeV. This is a factor 140 higher than the in-target yield at SPIRAL1.

  7. Synthesis of meta-Terphenyl-2,2''-diols by Anodic C-C Cross-Coupling Reactions.

    PubMed

    Lips, Sebastian; Wiebe, Anton; Elsler, Bernd; Schollmeyer, Dieter; Dyballa, Katrin M; Franke, Robert; Waldvogel, Siegfried R

    2016-08-26

    The anodic C-C cross-coupling reaction is a versatile synthetic approach to symmetric and non-symmetric biphenols and arylated phenols. We herein present a metal-free electrosynthetic method that provides access to symmetric and non-symmetric meta-terphenyl-2,2''-diols in good yields and high selectivity. Symmetric derivatives can be obtained by direct electrolysis in an undivided cell. The synthesis of non-symmetric meta-terphenyl-2,2''-diols required two electrochemical steps. The reactions are easy to conduct and scalable. The method also features a broad substrate scope, and a large variety of functional groups are tolerated. The target molecules may serve as [OCO](3-) pincer ligands. PMID:27490451

  8. Elastic scattering and total reaction cross section for the {sup 6}He+{sup 58}Ni system

    SciTech Connect

    Morcelle, V.; Lichtenthäler, R.; Lépine-Szily, A.; Guimarães, V.; Gasques, L.; Scarduelli, V.; Condori, R. Pampa; Leistenschneider, E.; Mendes Jr, D. R.; Faria, P. N. de; Pires, K. C. C.; Barioni, A.; Morais, M. C.; Shorto, J. M. B.; Zamora, J. C.

    2014-11-11

    Elastic scattering measurements of {sup 6}He + {sup 58}Ni system have been performed at the laboratory energy of 21.7 MeV. The {sup 6}He secondary beam was produced by a transfer reaction {sup 9}Be ({sup 7}Li, {sup 6}He) and impinged on {sup 58}Ni and {sup 197}Au targets, using the Radioactive Ion Beam (RIB) facility, RIBRAS, installed in the Pelletron Laboratory of the Institute of Physics of the University of São Paulo, Brazil. The elastic angular distribution was obtained in the angular range from 15° to 80° in the center of mass frame. Optical model calculations have been performed using a hybrid potential to fit the experimental data. The total reaction cross section was derived.

  9. Long-lived excited states of zwitterionic copper(I) complexes for photoinduced cross-dehydrogenative coupling reactions.

    PubMed

    Wang, Bin; Shelar, Deepak Prakash; Han, Xian-Zhu; Li, Ting-Ting; Guan, Xiangguo; Lu, Wei; Liu, Kun; Chen, Yong; Fu, Wen-Fu; Che, Chi-Ming

    2015-01-12

    Four heteroleptic copper(I) complexes containing phenanthroline and monoanionic nido-carborane-diphosphine ligands have been prepared and structurally characterized by various spectroscopic techniques and X-ray diffraction. These complexes exhibit intense absorptions in the visible range and excited-state lifetimes on the microsecond scale. Their application in visible-light-induced cross-dehydrogenative coupling reactions was investigated. Preliminary studies showed that one of the four copper(I) complexes is an efficient catalyst for photoinduced oxidative C-H functionalization using oxygen as oxidant. Furthermore, α-functionalized tertiary amines were obtained in good-to-excellent yields by light irradiation (λ>420 nm) of a mixture of our Cu(I) complex, tertiary amines, and a variety of nucleophiles (nitroalkane, acetone, or indoles) under aerobic conditions. Electron paramagnetic resonance measurements provided evidence for the formation of superoxide radical anions (O2(-⋅)) rather than singlet oxygen ((1)O2) during these photocatalytic reactions. PMID:25413572

  10. PIGE related differential cross-section measurements of the 25Mg(p,p‧γ)25Mg reaction

    NASA Astrophysics Data System (ADS)

    Preketes-Sigalas, K.; Lagoyannis, A.; Axiotis, M.; Becker, H. W.; Foteinou, V.; Harissopulos, S.; Kokkoris, M.; Provatas, G.

    2016-11-01

    The differential cross sections of the 25Mg(p,p‧γ)25Mg reaction, critical for the quantitative determination of magnesium in complex matrices using the PIGE technique, were measured at two (2) angles, 55° and 90°, and at proton energies from 2420 to 4550 keV, by detecting the 390, 585 and 975 keV γ-rays emitted. The experimental setup consisted of two 100% relative efficiency HPGe detectors. The results are compared to those already present in literature and an attempt is made to explain the existing discrepancies. The obtained results from the present work are validated via thick-target measurements.

  11. Tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds

    PubMed Central

    Miró, Javier; Sánchez-Roselló, María; Sanz, Álvaro; Rabasa, Fernando

    2015-01-01

    Summary A new tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR) has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM–IMDAR protocols. PMID:26425205

  12. Tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds.

    PubMed

    Miró, Javier; Sánchez-Roselló, María; Sanz, Álvaro; Rabasa, Fernando; Del Pozo, Carlos; Fustero, Santos

    2015-01-01

    A new tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR) has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM-IMDAR protocols. PMID:26425205

  13. Differential cross sections for the reactions γp→pη and γp→pη'

    DOE PAGES

    Williams, M.; Krahn, Z.; Applegate, D.; Bellis, M.; Meyer, C. A.; Adhikari, K. P.; Anghinolfi, M.; Baghdasaryan, H.; Ball, J.; Battaglieri, M.; et al

    2009-10-29

    In high-statistics differential cross sections for the reactions γ p -> p η and γ p -> p η' the CLAS at Jefferson Lab was used to measure the center-of-mass energies from near threshold up to 2.84 GeV. The eta-prime results are the most precise to date and provide the largest energy and angular coverage. The eta measurements extend the energy range of the world's large-angle results by approximately 300 MeV. These new data, in particular the η' measurements, are likely to help constrain the analyses being performed to search for new baryon resonance states.

  14. Comparison of 3D Classical Trajectory and Transition-State Theory Reaction Cross Sections

    DOE R&D Accomplishments Database

    Koeppl, G. W.; Karplus, Martin

    1970-10-01

    Although there is excellent agreement for a system such as H+H{sub 2} --> H{sub 2}+H, in which both the potential and the particle masses are symmetric, significant deviations occur for more asymmetric reactions. A detailed analysis show that the calculated differences are from the violation of two assumptions of transition-state theory.

  15. Approaches to prepare perfluoroalkyl and pentafluorophenyl copper couples for cross-coupling reactions with organohalogen compounds.

    PubMed

    Kremlev, Mikhail M; Mushta, Aleksej I; Tyrra, Wieland; Yagupolskii, Yurii L; Naumann, Dieter; Schäfer, Mathias

    2015-12-01

    The reactions of iodoperfluoroalkanes CnF2n+1I (n = 2, 3, 4) and n-BuLi at low temperatures give NMR spectroscopic evidence for LiCnF2n+1 which were converted into LiCu(CnF2n+1)2 derivatives upon treatment with 0.5 mol copper(i) bromide, CuBr. An alternative route to obtain perfluoroorgano copper couples, Cu(Rf)2Ag (Rf = n-C3F7, n-C4F9, C6F5) was achieved from the reactions of the corresponding perfluoroorgano silver(i) reagents, AgRf, and elemental copper through redox transmetallations. The composition of the resulting reactive intermediates was investigated by means of (19)F NMR spectroscopy and ESI mass spectrometry. Perfluoro-n-propyl and perfluoro-n-butyl copper-silver reagents prepared by the oxidative transmetallation route exhibited good properties in C-C bond formation reactions with acid chlorides even under moderate conditions. Substitution of bromine directly bound to aromatics for perfluoroalkyl groups was achieved at elevated temperatures, while success in halide substitution reactions using lithium copper couples remained poor. PMID:26488228

  16. Cross-checking of Large Evaluated and Experimental Nuclear Reaction Databases

    SciTech Connect

    Zeydina, O.; Koning, A.J.; Soppera, N.; Raffanel, D.; Bossant, M.; Dupont, E.; Beauzamy, B.

    2014-06-15

    Automated methods are presented for the verification of large experimental and evaluated nuclear reaction databases (e.g. EXFOR, JEFF, TENDL). These methods allow an assessment of the overall consistency of the data and detect aberrant values in both evaluated and experimental databases.

  17. Reexamination of cross sections of the 100Mo(p,2n)99mTc reaction

    NASA Astrophysics Data System (ADS)

    Takács, S.; Hermanne, A.; Ditrói, F.; Tárkányi, F.; Aikawa, M.

    2015-03-01

    The nuclear medicine community has been expressing concerns world wide regarding shortages of 99mTc supply based on fission production of 99Mo from highly enriched uranium (HEU) to prepare 99Mo/99mTc generators. As an alternative to reactor produced 99Mo/99mTc generator technology, the direct production of 99mTc on accelerators is considered. There are a number of methods of using accelerators to produce 99mTc and/or 99Mo. Direct production of 99mTc on highly enriched 100Mo target using cyclotrons is interesting for energies up to 20 MeV, so as to minimize the impurities from additional open reaction channels. To estimate the quality of the accelerator produced 99mTc all the possible reaction routes should be mapped which could be potentially involved in this technology. However, a well defined excitation function for the 100Mo(p,2n)99mTc primary reaction is needed, in order to achieve acceptable good results in assessing the quality of the accelerator-produced 99mTc by theoretical calculations. Most of the available experimental cross section data series for the 100Mo(p,2n)99mTc reaction have the same general shape while their amplitudes are different. A large difference more than a factor of two may, indeed, be observed between the lowest and the highest datasets values. The aim of this study was therefore to get a new evaluation for the 100Mo(p,2n)99mTc cross section, through three independent experiments, aiming at a more confident estimation about the amplitude of the excitation function.

  18. Computational study of the Sonogashira cross-coupling reaction in the gas phase and in dichloromethane solution.

    PubMed

    Sikk, Lauri; Tammiku-Taul, Jaana; Burk, Peeter; Kotschy, András

    2012-07-01

    The Sonogashira cross-couplig reaction, consisting of oxidative addition, cis-trans isomerization, transmetalation, and reductive elimination, was computationally modeled using the DFT B3LYP/cc-pVDZ method for reaction between bromobenzene and phenylacetylene. Palladium diphosphane was used as a catalyst, copper(I) bromide as a co-catalyst and trimethylamine as a base. The reaction mechanism was studied both in the gas phase and in dichloromethane solution using PCM method. The complete catalytic cycle is thermodynamically strongly shifted toward products (diphenylacetylene and regenerated palladium catalyst) and is exothermic being in accordance with experimental data. The rate-determining step is the oxidative addition, since the highest point on the Gibbs energy graph of the complete reaction is the transition state of this step. This conclusion is also supported by recent experimental data. The computed energy profile suggests that the transmetalation step is initiated by the dissociation of neutral ligand, while the activation Gibbs energy of this step is 0.1 kcal mol(-1) in the gas phase. PMID:22160651

  19. Au, Bi, Co and Nb cross-section measured by quasimonoenergetic neutrons from p + 7Li reaction in the energy range of 18-36 MeV

    NASA Astrophysics Data System (ADS)

    Majerle, M.; Bém, P.; Novák, J.; Šimečková, E.; Štefánik, M.

    2016-09-01

    Au, Bi, Co and Nb samples were irradiated several times with quasi-monoenergetic neutrons from p + 7Li reaction in the energy range of 18-36 MeV. The activities of the samples were measured with the HPGe detector and the reaction rates were calculated. The cross-sections were extracted using the SAND-II method with the reference cross-sections from the EAF-2010 database. The uncertainties of the final results are discussed.

  20. Antibody response to Helicobacter pylori excretory antigen and the cross reaction study.

    PubMed

    Sasidharan, S; Uyub, A M

    2009-01-01

    Helicobacter pylori is recognized as a major case of gastritis and peptic ulcer and a key factor in the development of gastric cancer, gastric lymphoma, and non-ulcerative dyspepsia in man. The detection of antibodies specific for strains of H. pylori has demonstrated the value of serology for providing evidence of infection. The present study was conducted to detect the antigenic proteins of excretory antigen of H. pylori with Western blotting and examine whether anti-H. pylori IgG and IgA antibodies from H. pylori positive patients cross-react with antigens from other common bacterial pathogens. By using SDS-PAGE, 20 different proteins were found in the excretory antigen. By Western blotting and absorption studies, there were indications that anti-H. pylori IgA antibodies directed against 54 kDa, 50 kDa and 27 kDa cross-reacted with antigens from other bacteria, and that H. pylori proteins of 99 kDa, 88 kDa and 81 kDa possibly shared similar epitope with antigens of other pathogens not tested in the absorption studies. The cross-reactivity occurred in this study was not significantly affect the performance of the in-house ELISA.

  1. "Homeopathic" palladium nanoparticle catalysis of cross carbon-carbon coupling reactions.

    PubMed

    Deraedt, Christophe; Astruc, Didier

    2014-02-18

    Catalysis by palladium derivatives is now one of the most important tools in organic synthesis. Whether researchers design palladium nanoparticles (NPs) or nanoparticles occur as palladium complexes decompose, these structures can serve as central precatalysts in common carbon-carbon bond formation. Palladium NPs are also valuable alternatives to molecular catalysts because they do not require costly and toxic ligands. In this Account, we review the role of "homeopathic" palladium catalysts in carbon-carbon coupling reactions. Seminal studies from the groups of Beletskaya, Reetz, and de Vries showed that palladium NPs can catalyze Heck and Suzuki-Miyaura reactions with aryl iodides and, in some cases, aryl bromides at part per million levels. As a result, researchers coined the term "homeopathic" palladium catalysis. Industry has developed large-scale applications of these transformations. In addition, chemists have used Crooks' concept of dendrimer encapsulation to set up efficient nanofilters for Suzuki-Miyaura and selective Heck catalysis, although these transformations required high PdNP loading. With arene-centered, ferrocenyl-terminated dendrimers containing triazolyl ligands in the tethers, we designed several generations of dendrimers to compare their catalytic efficiencies, varied the numbers of Pd atoms in the PdNPs, and examined encapsulation vs stabilization. The catalytic efficiencies achieved "homeopathic" (TON = 540 000) behavior no matter the PdNP size and stabilization type. The TON increased with decreasing the Pd/substrate ratio, which suggested a leaching mechanism. Recently, we showed that water-soluble arene-centered dendrimers with tri(ethylene glycol) (TEG) tethers stabilized PdNPs involving supramolecular dendritic assemblies because of the interpenetration of the TEG branches. Such PdNPs are stable and retain their "homeopathic" catalytic activities for Suzuki-Miyaura reactions for months. (TONs can reach 2.7 × 10(6) at 80 °C for aryl

  2. Determination of the {sup 233}Pa(n,f) reaction cross section from 11.5 to 16.5 MeV neutron energy by the hybrid surrogate ratio approach

    SciTech Connect

    Nayak, B. K.; Saxena, A.; Biswas, D. C.; Mirgule, E. T.; John, B. V.; Santra, S.; Vind, R. P.; Choudhury, R. K.; Ganesan, S.

    2008-12-15

    A new hybrid surrogate ratio approach has been employed to determine neutron-induced fission cross sections of {sup 233}Pa in the energy range of 11.5 to 16.5 MeV for the first time. The fission probability of {sup 234}Pa and {sup 236}U compound nuclei produced in {sup 232}Th({sup 6}Li, {alpha}){sup 234}Pa and {sup 232}Th({sup 6}Li, d){sup 236}U transfer reaction channels has been measured at E{sub lab}=38.0 MeV in the excitation energy range of 17.0 to 22.0 MeV within the framework of the absolute surrogate method. The {sup 233}Pa(n,f) cross sections are then deduced from the measured fission decay probability ratios of {sup 234}Pa and {sup 236}U compound nuclei using the surrogate ratio method. The {sup 233}Pa(n,f) cross section data from the present experiment along with the data from the literature, covering the neutron energy range of 1.0 to 16.5 MeV have been compared with the predictions of statistical model code EMPIRE-2.19. While the present data are consistent with the model predictions, there is a discrepancy between the earlier experimental data and EMPIRE-2.19 predictions in the neutron energy range of 7.0 to 10.0 MeV.

  3. State-resolved differential and integral cross sections for the Ne + H2 (+) (v = 0-2, j = 0) → NeH(+) + H reaction.

    PubMed

    Wu, Hui; Yao, Cui-Xia; He, Xiao-Hu; Zhang, Pei-Yu

    2016-05-14

    State-to-state quantum dynamic calculations for the proton transfer reaction Ne + H2 (+) (v = 0-2, j = 0) are performed on the most accurate LZHH potential energy surface, with the product Jacobi coordinate based time-dependent wave packet method including the Coriolis coupling. The J = 0 reaction probabilities for the title reaction agree well with previous results in a wide range of collision energy of 0.2-1.2 eV. Total integral cross sections are in reasonable agreement with the available experiment data. Vibrational excitation of the reactant is much more efficient in enhancing the reaction cross sections than translational and rotational excitation. Total differential cross sections are found to be forward-backward peaked with strong oscillations, which is the indication of the complex-forming mechanism. As the collision energy increases, state-resolved differential cross section changes from forward-backward symmetric peaked to forward scattering biased. This forward bias can be attributed to the larger J partial waves, which makes the reaction like an abstraction process. Differential cross sections summed over two different sets of J partial waves for the v = 0 reaction at the collision energy of 1.2 eV are plotted to illustrate the importance of large J partial waves in the forward bias of the differential cross sections.

  4. State-resolved differential and integral cross sections for the Ne + H2+ (v = 0-2, j = 0) → NeH+ + H reaction

    NASA Astrophysics Data System (ADS)

    Wu, Hui; Yao, Cui-Xia; He, Xiao-Hu; Zhang, Pei-Yu

    2016-05-01

    State-to-state quantum dynamic calculations for the proton transfer reaction Ne + H2+ (v = 0-2, j = 0) are performed on the most accurate LZHH potential energy surface, with the product Jacobi coordinate based time-dependent wave packet method including the Coriolis coupling. The J = 0 reaction probabilities for the title reaction agree well with previous results in a wide range of collision energy of 0.2-1.2 eV. Total integral cross sections are in reasonable agreement with the available experiment data. Vibrational excitation of the reactant is much more efficient in enhancing the reaction cross sections than translational and rotational excitation. Total differential cross sections are found to be forward-backward peaked with strong oscillations, which is the indication of the complex-forming mechanism. As the collision energy increases, state-resolved differential cross section changes from forward-backward symmetric peaked to forward scattering biased. This forward bias can be attributed to the larger J partial waves, which makes the reaction like an abstraction process. Differential cross sections summed over two different sets of J partial waves for the v = 0 reaction at the collision energy of 1.2 eV are plotted to illustrate the importance of large J partial waves in the forward bias of the differential cross sections.

  5. Reaction Dynamics of O((3)P) + Propyne: I. Primary Products, Branching Ratios, and Role of Intersystem Crossing from Crossed Molecular Beam Experiments.

    PubMed

    Vanuzzo, Gianmarco; Balucani, Nadia; Leonori, Francesca; Stranges, Domenico; Nevrly, Vaclav; Falcinelli, Stefano; Bergeat, Astrid; Casavecchia, Piergiorgio; Cavallotti, Carlo

    2016-07-14

    We performed synergic experimental/theoretical studies on the mechanism of the O((3)P) + propyne reaction by combining crossed molecular beams experiments with mass-spectrometric detection and time-of-flight analysis at 9.2 kcal/mol collision energy (Ec) with ab initio electronic structure calculations at a high level of theory of the relevant triplet and singlet potential energy surfaces (PESs) and statistical calculations of branching ratios (BRs) taking into account intersystem crossing (ISC). In this paper (I) we report the results of the experimental investigation, while the accompanying paper (II) shows results of the theoretical investigation with comparison to experimental results. By exploiting soft electron ionization detection to suppress/mitigate the effects of the dissociative ionization of reactants, products, and background gases, product angular and velocity distributions at different charge-to-mass ratios were measured. From the laboratory data angular and translational energy distributions in the center-of-mass system were obtained for the five competing most important product channels, and product BRs were derived. The reactive interaction of O((3)P) with propyne under single collision conditions is mainly leading to the rupture of the three-carbon atom chain, with production of the radical products methylketenyl + atomic hydrogen (BR = 0.04), methyl + ketenyl (BR = 0.10), and vinyl + formyl (BR = 0.11) and the molecular products ethylidene/ethylene + carbon monoxide (BR = 0.74) and propandienal + molecular hydrogen (BR = 0.01). Because some of the products can only be formed via ISC from the entrance triplet to the low-lying singlet PES, we infer from their BRs an amount of ISC larger than 80%. This value is dramatically large when compared to the negligible ISC reported for the O((3)P) reaction with the simplest alkyne, acetylene. At the same time, it is much larger than that (∼20%) recently observed in the related reaction of the three

  6. 1,4-Diketones from Cross-Conjugated Dienones: Potassium Permanganate-Interrupted Nazarov Reaction.

    PubMed

    Kwon, Yonghoon; Schatz, Devon J; West, Frederick G

    2015-08-17

    A domino potassium permanganate-interrupted Nazarov reaction to yield syn-2,3-disubstituted 1,4-diketones via a decarbonylative cleavage of the Nazarov oxyallyl intermediate, believed to be without precedent, is presented. This process allows syn substituents to be established stereospecifically on the 2-carbon bridge connecting the ketone carbonyl carbons, and the formation of one carbon-carbon and two carbon-oxygen bonds. Two carbon-carbon bonds are cleaved in this process. PMID:26138361

  7. Role of oxygen radical reactions in the browning and cross-linking of lysozyme by glucose

    SciTech Connect

    Hull, C.J.; Thorpe, S.R.; Baynes, J.W.

    1986-05-01

    Lysozyme (LZM) was used as a model protein for studies on the effects of oxygen on the Maillard reaction. During a 4 wk incubation in 0.25 M glucose (0.2 M phosphate buffer, pH 7.4, 37/sup 0/C) the kinetics of glycation of LZM were similar under air and N/sub 2/, yielding approx.2 mol Lys modified per mol LZM. Fructoselysine (FL) was the major Lys derivative formed under air and N/sub 2/, while N/sup epsilon/-carboxymethyllysine (CML) accounted for approx.30% of FL formed at 4 wk under air. A loss of 1 mol Arg per mol LZM was also observed under both air and N/sub 2/, with greater loss from LZM dimer vs. monomer, suggesting a role for Arg in the crosslinking reaction. Dimer and monomer did not differ in content of Lys, FL or CML (under air), but dimer was 4 times as fluorescent as monomer, suggesting that crosslink structures are fluorescent. Despite significant differences in kinetics of crosslinking, browning and development of fluorescence of LZM under air vs. N/sub 2/, products formed had similar absorbance and fluorescence spectra. Based on inhibition by chelators and radical scavengers, the more rapid crosslinking and development of fluorescence under air was shown to result from oxygen radical reactions. These results indicate that both radical and non-radical processes may contribute to the Maillard reaction, but that the browning, fluorescence and crosslinking of protein may proceed in the absence of oxygen and oxygen radicals.

  8. Development of a General, Sequential, Ring Closing Metathesis/Intramolecular Cross-Coupling Reaction for the Synthesis of Polyunsaturated Macrolactones

    PubMed Central

    Denmark, Scott E.; Muhuhi, Joseck M.

    2010-01-01

    A general strategy for the construction of macrocyclic lactones containing conjugated Z,Z-1,3-diene subunits has been is described. The centerpiece of the strategy is a sequential ring-closing metathesis that forms an unsaturated siloxane ring followed by an intramolecular cross-coupling reaction with a pendant alkenyl iodide. A highly modular assembly of the various precursors allowed the preparation of unsaturated macrolactones containing 11-, 12-, 13- and 14-membered rings. Although the ring closing metathesis process proceeded uneventfully, the intramolecular cross-coupling required extensive optimization of palladium source, solvent, fluoride source and particularly fluoride hydration level. Under the optimal conditions (including syringe pump high dilution), the macrolactones were produced in 53-78% yield as single stereoisomers. A benzo fused 12-membered ring macrolactone containing an E,Z-1,3-diene unit was also prepared by the same general strategy. The E-2-styryl iodide was prepared by a novel Heck reaction of an aryl nonaflate with vinyltrimethylsilane followed by iododesilylation with ICl. PMID:20666473

  9. Cross sections for {alpha}-particle induced reactions on {sup 115,116}Sn around the Coulomb barrier

    SciTech Connect

    Filipescu, D.; Avrigeanu, V.; Glodariu, T.; Mihai, C.; Bucurescu, D.; Ivascu, M.; Cata-Danil, I.; Stroe, L.; Deleanu, D.; Ghita, D. G.; Marginean, N.; Marginean, R.; Negret, A.; Pascu, S.; Sava, T.; Suliman, G.; Zamfir, N. V.; Sima, O.; Cata-Danil, G.

    2011-06-15

    The cross sections of the {sup 115}Sn({alpha},{gamma}){sup 119}Te, {sup 115}Sn({alpha},n){sup 118}Te, and {sup 116}Sn({alpha},n){sup 119}Te reactions (both on ground and isomeric states) have been measured at effective center-of-mass energies from 9.3 to 14.8 MeV. During a first experiment, enriched self-supporting {sup 115}Sn (51.2%) + {sup 116}Sn (24.4%) foils were bombarded with an {alpha} beam delivered by the Bucharest IFIN-HH Tandem Accelerator. In a second experiment, a highly enriched {sup 116}Sn target was irradiated in order to disentangle the experimental cross section contributions due to {sup 115}Sn({alpha},{gamma}){sup 119}Te and {sup 115}Sn({alpha},n){sup 118}Te reactions obtained in the first measurement. The beam-induced activity was measured with two large volume HPGe detectors in close geometry. The experimental results were compared with theoretical predictions obtained in the framework of the statistical model.

  10. Experimental differential cross sections, level densities, and spin cutoffs as a testing ground for nuclear reaction codes

    SciTech Connect

    Voinov, Alexander V.; Grimes, Steven M.; Brune, Carl R.; Burger, Alexander; Gorgen, Andreas; Guttormsen, Magne; Larsen, Ann -Cecilie; Massey, Thomas N.; Siem, Sunniva

    2013-11-08

    Proton double-differential cross sections from 59Co(α,p)62Ni, 57Fe(α,p)60Co, 56Fe(7Li,p)62Ni, and 55Mn(6Li,p)60Co reactions have been measured with 21-MeV α and 15-MeV lithium beams. Cross sections have been compared against calculations with the empire reaction code. Different input level density models have been tested. It was found that the Gilbert and Cameron [A. Gilbert and A. G. W. Cameron, Can. J. Phys. 43, 1446 (1965)] level density model is best to reproduce experimental data. Level densities and spin cutoff parameters for 62Ni and 60Co above the excitation energy range of discrete levels (in continuum) have been obtained with a Monte Carlo technique. Furthermore, excitation energy dependencies were found to be inconsistent with the Fermi-gas model.

  11. Optimisation of the reaction conditions for the production of cross-linked starch with high resistant starch content.

    PubMed

    Kahraman, Kevser; Koksel, Hamit; Ng, Perry K W

    2015-05-01

    The optimum reaction conditions (temperature and pH) for the preparation of cross-linked (CL) corn and wheat starches with maximum resistant starch (RS) content were investigated by using response surface methodology (RSM). According to the preliminary results, five levels were selected for reaction temperature (38-70 °C) and pH (10-12) in the main study. RS contents of the CL corn and wheat starch samples increased with increasing temperature and pH, and pH had a greater influence on RS content than had temperature. The maximum RS content (with a maximum p value of 0.4%) was obtained in wheat starch cross-linked at 38 °C and pH 12. In the case of CL corn starch, the optimum condition was 70 °C and pH 12. CL corn and wheat starch samples were also produced separately under the optimum conditions and their RS contents were 80.4% and 83.9%, respectively. These results were also in agreement with the values predicted by RSM.

  12. Visible Light Photocatalytic Radical-Radical Cross-Coupling Reactions of Amines and Carbonyls: A Route to 1,2-Amino Alcohols.

    PubMed

    Ding, Wei; Lu, Liang-Qiu; Liu, Jing; Liu, Dan; Song, Hai-Tao; Xiao, Wen-Jing

    2016-08-19

    An intermolecular radical-radical cross-coupling reaction of secondary and tertiary amines with aryl ketones and aldehydes has been developed using visible light photoredox catalysis. This reaction provides an efficient and straightforward approach to some useful 1,2-amino alcohols in moderate to good yields under mild conditions.

  13. Lewis Acid Catalyzed Regiospecific Cross-Dehydrative Coupling Reaction of 2-Furylcarbinols with β-Keto Amides or 4-Hydroxycoumarins: A Route to Furyl Enols.

    PubMed

    Miao, Maozhong; Luo, Yi; Li, Hongli; Xu, Xin; Chen, Zhengkai; Xu, Jianfeng; Ren, Hongjun

    2016-06-17

    Lewis acid catalyzed directly dehydrative carbon-carbon bond formation reaction of 2-furylcarbinols with β-keto amides provides a straightforward method for regioselective synthesis of (Z)-furyl enols. Moreover, this Lewis acid catalyzed cross-coupling reaction can be extended to an interesting heterocyclic version featuring a functionalized 3-furyl-4-hydroxycoumarin synthesis. PMID:27224045

  14. Stereodivergent hydrogermylations of α-trifluoromethylated alkynes and their applications in cross-coupling reactions.

    PubMed

    Schweizer, Stéphane; Tresse, Cédric; Bisseret, Philippe; Lalevée, Jacques; Evano, Gwilherm; Blanchard, Nicolas

    2015-04-01

    The hydrometalation of alkynes with group 14 elements such as tin- or silyl hydrides is a classical transformation in organic synthesis. Strangely, among the group 14 elements, the use of germanium hydrides is rarely seen. Two efficient, stereodivergent, and broadly applicable routes to (Z)- and (E)-α-CF3-vinylgermanes by regio- and stereoselective hydrogermylation of α-trifluoromethylated alkynes under radical or transition-metal-catalyzed conditions are reported. Furthermore, we demonstrate that the resulting stereodefined fluorinated building blocks are remarkable cross-coupling partners, provided that the vinylgermane is appropriately tuned electronically, as demonstrated by the synthesis of trisubstituted (Z)- and (E)-α-trifluoromethylated alkenes.

  15. Importance of level structure in nuclear reaction cross-section calculations. Revision 1

    SciTech Connect

    Gardner, M.A.; Gardner, D.G.

    1985-11-07

    It is shown that level-density expressions cannot adequately represent or substitute for level structure information when making calculations of the Hauser-Feshbach type for cross sections or isomer-ratios for nuclei in the first few MeV above their ground state. It is stated that such discrete level information should include both experimentally confirmed and theoretically predicted levels. The utility of discrete level information to optimize level density calculations, to compute isomer ratios, in deriving dipole strength functions, and in the analysis of primary gamma ray spectra is emphasized, especially for nuclei far from the line of stability. 29 refs., 12 figs., 6 tabs. (DWL)

  16. Cobalt-mediated diastereoselective cross-coupling reactions between cyclic halohydrins and arylmagnesium reagents.

    PubMed

    Hammann, Jeffrey M; Steib, Andreas K; Knochel, Paul

    2014-12-19

    Cyclic TBS-protected iodohydrins (and bromohydrins) undergo a highly diastereoselective cross-coupling with various aryl- and heteroarylmagnesium reagents in the presence of THF-soluble CoCl2·2LiCl and TMEDA as a ligand leading to trans-2-arylcyclohexanol derivatives in good yields and dr up to >99:1. A range of functional groups are tolerated in the Grignard reagent (e.g., COOR, CN, CF3, SF5). The use of heterocyclic iodohydrins leads to trans-3,4-disubstituted pyrrolidines and tetrahydrofurans. PMID:25470419

  17. On the radical nature of iron-catalyzed cross-coupling reactions.

    PubMed

    Hedström, Anna; Izakian, Zakieh; Vreto, Irma; Wallentin, Carl-Johan; Norrby, Per-Ola

    2015-04-01

    The radical nature of iron-catalyzed cross-coupling between Grignard reagents and alkyl halides has been studied by using a combination of competitive kinetic experiments and DFT calculations. In contrast to the corresponding coupling with aryl halides, which commences through a classical two-electron oxidative addition/reductive elimination sequence, the presented data suggest that alkyl halides react through an atom-transfer-initiated radical pathway. Furthermore, a general iodine-based quenching methodology was developed to enable the determination of highly accurate concentrations of Grignard reagents, a capability that facilitates and increases the information output of kinetic investigations based on these substrates. PMID:25703202

  18. Probing dynamics of fusion reactions through cross-section and spin distribution measurement

    NASA Astrophysics Data System (ADS)

    Kaur, Maninder; Behera, B. R.; Singh, Gulzar; Singh, Varinderjit; Madhavan, N.; Muralithar, S.; Nath, S.; Gehlot, J.; Mohanto, G.; Mukul, Ish; Siwal, D.; Thakur, M.; Kapoor, K.; Sharma, P.; Banerjee, T.; Jhingan, A.; Varughese, T.; Bala, Indu; Nayak, B. K.; Saxena, A.; Chatterjee, M. B.; Stevenson, P. D.

    2016-05-01

    Present work aims to explicate the effect of entrance channel mass asymmetry on fusion dynamics for the Compound Nucleus 80Sr populated through two different channels, 16O+64Zn and 32S+48Ti, using cross-section and spin distribution measurements as probes. The evaporation spectra studies for these systems, reported earlier indicate the presence of dynamical effects for mass symmetric 32S+48Ti system.The CCDEF and TDHF calculations have been performed for both the systems and an attempt has been made to explain the reported deviations in the α-particle spectrum for the mass symmetric system.

  19. Measurement of evaporation residue cross-sections of the reaction 30Si + 238U at subbarrier energies

    SciTech Connect

    Nishio, K.; Ikezoe, H.; Mitsuoka, S.; Nagame, Y.; Tsukada, K.; Tsuruta, K.; Hofmann, S.; Hessberger, F. P.; Ackermann, D.; Heinz, S.; Khuyagbaatar, J.; Kindler, B.; Kojouharov, I.; Lommel, B.; Mazzocco, M.; Schoett, H. J.; Antalic, S.; Saro, S.; Comas, V. F.; Heredia, J. A.

    2007-02-26

    The reaction 30Si + 238U {yields} 268Sg* was studied at beam energies close to the Coulomb barrier. At the above barrier energy of Ec.m. = 144.0 MeV (center-of-mass energy at half thickness of the target), we measured three decay chains of 263Sg produced by evaporation of five neutrons. The cross-section was (67{sub -37}{sup +67}) pb. At subbarrier energy of Ec.m. = 133.0 MeV we measured three spontaneously fissioning nuclei which we assigned to the isotope 264Sg. The half-life of (120{sub -44}{sup +126}) ms was determined. The production cross-section was (10{sub -6}{sup +10}) pb, which is about four orders magnitude larger than the calculation based on the one-dimensional barrier penetration model in the fusion process, showing fusion enhancement caused by the prolate deformation of 238U. At Ec.m. = 128.0 MeV an upper cross-section limit of 15 pb was measured. Compared to excitation functions measured for the lighter system 16O + 238U {yields} 254Fm*, a reduction of the fusion probability was observed at low beam energies indicating increasing competition from quasifission processes.

  20. Characterization and Dynamics of Substituted Ruthenacyclobutanes Relevant to the Olefin Cross-Metathesis Reaction

    PubMed Central

    Blake, Garrett; VanderVelde, David G.; Grubbs, Robert H.

    2011-01-01

    The reaction of the phosphonium alkylidene [(H2IMes)RuCl2=CHP(Cy)3)]+ BF4– with propene, 1-butene, and 1-hexene at –45 °C affords various substituted, metathesis-active ruthenacycles. These metallacycles were found to equilibrate over extended reaction times in response to decreases in ethylene concentrations, which favored increased populations of α-monosubstituted and α,α’-disubstituted (both cis and trans) ruthenacycles. On an NMR timescale, rapid chemical exchange was found to preferentially occur between the β-hydrogens of the cis and trans stereoisomers prior to olefin exchange. Exchange on an NMR timescale was also observed between the α- and β-methylene groups of the monosubstituted ruthenacycle (H2IMes)Cl2Ru(CHRCH2CH2) (R = CH3, CH2CH3, (CH2)3CH3). EXSY NMR experiments at –87 °C were used to determine the activation energies for both of these exchange processes. In addition, new methods have been developed for the direct preparation of metathesis-active ruthenacyclobutanes via the protonolysis of dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(benzylidene) bis(pyridine)ruthenium(II) and its 3-bromopyridine analog. Using either trifluoroacetic acid or silica-bound toluenesulfonic acid as the proton source, the ethylene-derived ruthenacyclobutane (H2IMes)Cl2Ru(CH2CH2CH2) was observed in up to 98% yield via NMR at –40 °C. On the basis of these studies, mechanisms accounting for the positional and stereochemical exchange within ruthenacyclobutanes are proposed, as well as the implications of these dynamics towards olefin metathesis catalyst and reaction design are described. PMID:21452876

  1. Combined Use of Absolute and Differential Seismic Arrival Time Data to Improve Absolute Event Location

    NASA Astrophysics Data System (ADS)

    Myers, S.; Johannesson, G.

    2012-12-01

    Arrival time measurements based on waveform cross correlation are becoming more common as advanced signal processing methods are applied to seismic data archives and real-time data streams. Waveform correlation can precisely measure the time difference between the arrival of two phases, and differential time data can be used to constrain relative location of events. Absolute locations are needed for many applications, which generally requires the use of absolute time data. Current methods for measuring absolute time data are approximately two orders of magnitude less precise than differential time measurements. To exploit the strengths of both absolute and differential time data, we extend our multiple-event location method Bayesloc, which previously used absolute time data only, to include the use of differential time measurements that are based on waveform cross correlation. Fundamentally, Bayesloc is a formulation of the joint probability over all parameters comprising the multiple event location system. The Markov-Chain Monte Carlo method is used to sample from the joint probability distribution given arrival data sets. The differential time component of Bayesloc includes scaling a stochastic estimate of differential time measurement precision based the waveform correlation coefficient for each datum. For a regional-distance synthetic data set with absolute and differential time measurement error of 0.25 seconds and 0.01 second, respectively, epicenter location accuracy is improved from and average of 1.05 km when solely absolute time data are used to 0.28 km when absolute and differential time data are used jointly (73% improvement). The improvement in absolute location accuracy is the result of conditionally limiting absolute location probability regions based on the precise relative position with respect to neighboring events. Bayesloc estimates of data precision are found to be accurate for the synthetic test, with absolute and differential time measurement

  2. Metal- and reagent-free highly selective anodic cross-coupling reaction of phenols.

    PubMed

    Elsler, Bernd; Schollmeyer, Dieter; Dyballa, Katrin Marie; Franke, Robert; Waldvogel, Siegfried R

    2014-05-12

    The direct oxidative cross-coupling of phenols is a very challenging transformation, as homo-coupling is usually strongly preferred. Electrochemical methods circumvent the use of oxidizing reagents or metal catalysts and are therefore highly attractive. Employing electrolytes with a high capacity for hydrogen bonding, such as methanol with formic acid or 1,1,1,3,3,3-hexafluoro-2-propanol, a direct electrolysis in an undivided cell provides mixed 2,2'-biphenols with high selectivity. This mild method tolerates a variety of moieties, for example, tert-butyl groups, which are not compatible with other strong electrophilic media but vital for later catalytic applications of the formed products. PMID:24644088

  3. Reaction-diffusion degradation model for delayed erosion of cross-linked polyanhydride biomaterials.

    PubMed

    Domanskyi, Sergii; Poetz, Katie L; Shipp, Devon A; Privman, Vladimir

    2015-05-28

    We develop a theoretical model to explain the long induction interval of water intake that precedes the onset of erosion due to degradation caused by hydrolysis in the recently synthesized and studied cross-linked polyanhydrides. Various kinetic mechanisms are incorporated in the model in an attempt to explain the experimental data for the mass loss profile. Our key finding is that the observed long induction interval is attributable to the nonlinear dependence of the degradation rate constants on the local water concentration, which essentially amounts to the breakdown of the standard rate-equation approach, potential causes for which are then discussed. Our theoretical results offer physical insights into which microscopic studies will be required to supplement the presently available macroscopic mass-loss data in order to fully understand the origin of the observed behavior.

  4. ABSOLUTE POLARIMETRY AT RHIC.

    SciTech Connect

    OKADA; BRAVAR, A.; BUNCE, G.; GILL, R.; HUANG, H.; MAKDISI, Y.; NASS, A.; WOOD, J.; ZELENSKI, Z.; ET AL.

    2007-09-10

    Precise and absolute beam polarization measurements are critical for the RHIC spin physics program. Because all experimental spin-dependent results are normalized by beam polarization, the normalization uncertainty contributes directly to final physics uncertainties. We aimed to perform the beam polarization measurement to an accuracy Of {Delta}P{sub beam}/P{sub beam} < 5%. The absolute polarimeter consists of Polarized Atomic Hydrogen Gas Jet Target and left-right pairs of silicon strip detectors and was installed in the RHIC-ring in 2004. This system features proton-proton elastic scattering in the Coulomb nuclear interference (CNI) region. Precise measurements of the analyzing power A{sub N} of this process has allowed us to achieve {Delta}P{sub beam}/P{sub beam} = 4.2% in 2005 for the first long spin-physics run. In this report, we describe the entire set up and performance of the system. The procedure of beam polarization measurement and analysis results from 2004-2005 are described. Physics topics of AN in the CNI region (four-momentum transfer squared 0.001 < -t < 0.032 (GeV/c){sup 2}) are also discussed. We point out the current issues and expected optimum accuracy in 2006 and the future.

  5. Differential cross sections and recoil polarizations for the reaction γp→K+Σ0

    DOE PAGES

    Dey, B.; Meyer, C. A.; Bellis, M.; McCracken, M. E.; Williams, M.; Adhikari, K. P.; Aghasyan, M.; Anghinolfi, M.; Ball, J.; Battaglieri, M.; et al

    2010-08-06

    Here, high-statistics measurements of differential cross sections and recoil polarizations for the reactionmore » $$\\gamma p \\rightarrow K^+ \\Sigma^0$$ have been obtained using the CLAS detector at Jefferson Lab. We cover center-of-mass energies ($$\\sqrt{s}$$) from 1.69 to 2.84 GeV, with an extensive coverage in the $K^+$ production angle. Independent measurements were made using the $$K^{+}p\\pi^{-}$$($$\\gamma$$) and $$K^{+}p$$($$\\pi^-,\\gamma$$) final-state topologies, and were found to exhibit good agreement. Our differential cross sections show good agreement with earlier CLAS, SAPHIR and LEPS results, while offering better statistical precision and a 300-MeV increase in $$\\sqrt{s}$$ coverage. Above $$\\sqrt{s} \\approx 2.5$$ GeV, $t$- and $u$-channel Regge scaling behavior can be seen at forward- and backward-angles, respectively. Our recoil polarization ($$P_\\Sigma$$) measurements represent a substantial increase in kinematic coverage and enhanced precision over previous world data. At forward angles we find that $$P_\\Sigma$$ is of the same magnitude but opposite sign as $$P_\\Lambda$$, in agreement with the static SU(6) quark model prediction of $$P_\\Sigma \\approx -P_\\Lambda$$. This expectation is violated in some mid- and backward-angle kinematic regimes, where $$P_\\Sigma$$ and $$P_\\Lambda$$ are of similar magnitudes but also have the same signs. In conjunction with several other meson photoproduction results recently published by CLAS, the present data will help constrain the partial wave analyses being performed to search for missing baryon resonances.« less

  6. How low does iron go? Chasing the active species in fe-catalyzed cross-coupling reactions.

    PubMed

    Bedford, Robin B

    2015-05-19

    The catalytic cross-coupling reactions of organic halides or related substrates with organometallic nucleophiles form the cornerstone of many carbon-carbon bond-forming processes. While palladium-based catalysts typically mediate such reactions, there are increasing concerns about the long-term sustainability of palladium in synthesis. This is due to the high cost of palladium, coupled with its low natural abundance, environmentally deleterious extraction (∼6 g of metal are produced per ton of ore), toxicity, and competition for its use from the automotive and consumer electronics sectors. Therefore, there is a growing interest in replacing palladium-based catalysts with those incorporating more earth-abundant elements. With its low cost, high natural abundance, and low toxicity, iron makes a particularly appealing alternative, and accordingly, the development of iron-catalyzed cross-coupling is undergoing explosive growth. However, our understanding of the mechanisms that underpin the iron-based catalytic cycles is still very much in its infancy. Mechanistic insight into catalytic reactions is not only academically important but also allows us to maximize the efficiency of processes or even to develop entirely new transformations. Key to the development of robust mechanistic models for cross-coupling is knowing the lowest oxidation state in the cycle. Once this is established, we can explore subsequent redox processes and build the catalytic manifold. Until we know with confidence what the lowest oxidation state is, any cycles proposed are largely just guesswork. To date, Fe(-II), Fe(-I), Fe(0), Fe(I), and Fe(II) have been proposed as contenders for the lowest-oxidation-state species in the cycle in iron-catalyzed cross-coupling; the aim of this Account is to pull together the various pieces of evidence in support, or otherwise, of each of these suggestions in turn. There currently exists no direct evidence that oxidation states below Fe(0) are active in the

  7. How low does iron go? Chasing the active species in fe-catalyzed cross-coupling reactions.

    PubMed

    Bedford, Robin B

    2015-05-19

    The catalytic cross-coupling reactions of organic halides or related substrates with organometallic nucleophiles form the cornerstone of many carbon-carbon bond-forming processes. While palladium-based catalysts typically mediate such reactions, there are increasing concerns about the long-term sustainability of palladium in synthesis. This is due to the high cost of palladium, coupled with its low natural abundance, environmentally deleterious extraction (∼6 g of metal are produced per ton of ore), toxicity, and competition for its use from the automotive and consumer electronics sectors. Therefore, there is a growing interest in replacing palladium-based catalysts with those incorporating more earth-abundant elements. With its low cost, high natural abundance, and low toxicity, iron makes a particularly appealing alternative, and accordingly, the development of iron-catalyzed cross-coupling is undergoing explosive growth. However, our understanding of the mechanisms that underpin the iron-based catalytic cycles is still very much in its infancy. Mechanistic insight into catalytic reactions is not only academically important but also allows us to maximize the efficiency of processes or even to develop entirely new transformations. Key to the development of robust mechanistic models for cross-coupling is knowing the lowest oxidation state in the cycle. Once this is established, we can explore subsequent redox processes and build the catalytic manifold. Until we know with confidence what the lowest oxidation state is, any cycles proposed are largely just guesswork. To date, Fe(-II), Fe(-I), Fe(0), Fe(I), and Fe(II) have been proposed as contenders for the lowest-oxidation-state species in the cycle in iron-catalyzed cross-coupling; the aim of this Account is to pull together the various pieces of evidence in support, or otherwise, of each of these suggestions in turn. There currently exists no direct evidence that oxidation states below Fe(0) are active in the

  8. Direct measurement of the 4He (12C, 16O) γ reaction cross section near stellar energies

    NASA Astrophysics Data System (ADS)

    Sagara, Kenshi

    2014-09-01

    The 12C+4He-->16O + γ reaction is one of the key reactions in stellar He-burning, but its total cross section at stellar energy (Ecm = 0.3 MeV) has not been measured yet, in spite of many experiments made in the world for about a half century. At Kyushu University Tandem accelerator Laboratory (KUTL), we have been making direct measurement of the 4He (12C, 16O) γ total cross section below Ecm = 2.4 MeV for about 20 years. We have measured the total cross section at Ecm = 2.4, 1.5 and 1.2 MeV. Now we are preparing to measure the cross section at 1.0 MeV. The direct measurement was made from Ecm = 5 MeV down to 1.9 MeV at Ruhr University, Bochum. We use a pulsed 12C beam and a windowless 4He target, and detect all the 16O recoils in a charge state. A usually continuum 12C beam from our tandem accelerator is pulsed by a pre-buncher, a main buncher, and a beam chopper. Our tandem accelerator was designed to be used at the acceleration voltage of 6-10 MV. For the 4He (12C, 16O) γ experiment we need to use it at 1.3-1.8 MV where beam transmission is very low, then we have invented an acceleration-deceleration method for the tandem accelerator. We have developed a blow-in windowless He target based on an original idea. To separate 16O recoils from the 12C beam, we developed a recoil-mass separator. To reject 12C backgrounds, we developed a long-time chopper, and an ionization chamber. Now, we are preparing to measure time-of-flight of 16O recoils and 12C backgrounds. Many original instruments and the experimental results will be presented. Finally we discuss what are necessary for future direct measurement of the 4He (12C, 16O) γ total cross section below 1.0 MeV, down to 0.7 MeV. A dynamitron accelerator and hard-working researchers may be inevitable. The 12C+4He-->16O + γ reaction is one of the key reactions in stellar He-burning, but its total cross section at stellar energy (Ecm = 0.3 MeV) has not been measured yet, in spite of many experiments made in the world

  9. Mechanistic Significance of the Si–O–Pd Bond in the Palladium-Catalyzed Cross-Coupling Reactions of Arylsilanolates

    PubMed Central

    2016-01-01

    Through the combination of reaction kinetics (both stoichiometric and catalytic), solution- and solid-state characterization of arylpalladium(II) arylsilanolates, and computational analysis, the intermediacy of covalent adducts containing Si–O–Pd linkages in the cross-coupling reactions of arylsilanolates has been unambiguously established. Two mechanistically distinct pathways have been demonstrated: (1) transmetalation via a neutral 8-Si-4 intermediate that dominates in the absence of free silanolate (i.e., stoichiometric reactions of arylpalladium(II) arylsilanolate complexes), and (2) transmetalation via an anionic 10-Si-5 intermediate that dominates in the cross-coupling under catalytic conditions (i.e., in the presence of free silanolate). Arylpalladium(II) arylsilanolate complexes bearing various phosphine ligands have been isolated, fully characterized, and evaluated for their kinetic competence under thermal (stoichiometric) and anionic (catalytic) conditions. Comparison of the rates for thermal and anionic activation suggested, but did not prove, that intermediates containing the Si–O–Pd linkage were involved in the cross-coupling process. The isolation of a coordinatively unsaturated, T-shaped arylpalladium(II) arylsilanolate complex ligated with t-Bu3P allowed the unambiguous demonstration of the operation of both pathways involving 8-Si-4 and 10-Si-5 intermediates. Three kinetic regimes were identified: (1) with 0.5–1.0 equiv of added silanolate (with respect to arylpalladium bromide), thermal transmetalation via a neutral 8-Si-4 intermediate; (2) with 1.0–5.0 equiv of added silanolate, activated transmetalation via an anionic 10-Si-5 intermediate; and (3) with >5.0 equiv of added silanolate, concentration-independent (saturation) activated transmetalation via an anionic 10-Si-5 intermediate. Transition states for the intramolecular transmetalation of neutral (8-Si-4) and anionic (10-Si-5) intermediates have been located computationally

  10. Total Reaction Cross Section Excitation Function Studies for 6He Interaction with 181Ta, 59Co, natSi, 9Be Nuclei

    NASA Astrophysics Data System (ADS)

    Sobolev, Yu. G.; Penionzhkevich, Yu. E.; Borcea, C.; Demekhina, N. A.; Eshanov, A. G.; Ivanov, M. P.; Kabdrakhimova, G. D.; Kabyshev, A. M.; Kugler, A.; Kuterbekov, K. A.; Lukyanov, K. V.; Maj, A.; Maslov, V. A.; Negret, A.; Skobelev, N. K.; Testov, D.; Trzaska, W. H.; Voskobojnik, E. I.; Zemlyanaya, E. V.

    2015-06-01

    Total reaction cross section excitation functions σR(E) were measured for 6He secondary beam particles on 181Ta, 59Co, natSi and 9Be targets in a wide energy range by direct and model-independent method. This experimental method was based on prompt n-γ 4π-technique applied in event-by event mode. A high efficiency CsI(Tl) γ-spectrometer was used for the detection of reaction products (prompt γ-quanta and neutrons) accompanying each reaction event. Using the ACCULINNA fragment-separator 6He fragments (produced by 11B primary beam with 9Be target) are separated and transported to n-γ shielded experimental cave at FLNR JINR. The measured total reaction cross section data σR(E) for the above mentioned reactions are compared with a theoretical calculation based on the optical potential with the real part having the double-folding form.

  11. Absolute Equilibrium Entropy

    NASA Technical Reports Server (NTRS)

    Shebalin, John V.

    1997-01-01

    The entropy associated with absolute equilibrium ensemble theories of ideal, homogeneous, fluid and magneto-fluid turbulence is discussed and the three-dimensional fluid case is examined in detail. A sigma-function is defined, whose minimum value with respect to global parameters is the entropy. A comparison is made between the use of global functions sigma and phase functions H (associated with the development of various H-theorems of ideal turbulence). It is shown that the two approaches are complimentary though conceptually different: H-theorems show that an isolated system tends to equilibrium while sigma-functions allow the demonstration that entropy never decreases when two previously isolated systems are combined. This provides a more complete picture of entropy in the statistical mechanics of ideal fluids.

  12. Evaporation residue cross sections for the {sup 64}Ni + {sup 144,154}Sm reaction -- Energy dissipation in hot nuclei

    SciTech Connect

    Back, B.B.; Blumenthal, D.J.; Davids, C.N.

    1995-08-01

    The fission hindrance of hot nuclei was deduced recently from an enhanced emission of GDR {gamma} rays, neutrons and charged particles prior to scission of heavy nuclei. In the most recent experiments addressing this topic, namely new measurements of the pre-scission {gamma} rays and evaporation residues from the {sup 32}S + {sup 184}W reaction, a rather sharp transition from negligible to full one-body dissipation occurs over the excitation energy region E{sub exc} = 60-100 MeV. However, the cross section does not appear to level out or start to decline again at the upper end of the energy range as expected in this interpretation. It is therefore clearly desirable to extend the excitation energy range to look for such an effect in order to either corroborate or refute this interpretation.

  13. Functionalization of Hydrogenated Graphene: Transition-Metal-Catalyzed Cross-Coupling Reactions of Allylic C-H Bonds.

    PubMed

    Chua, Chun Kiang; Sofer, Zdeněk; Pumera, Martin

    2016-08-26

    The chemical functionalization of hydrogenated graphene can modify its physical properties and lead to better processability. Herein, we describe the chemical functionalization of hydrogenated graphene through a dehydrogenative cross-coupling reaction between an allylic C-H bond and the α-C-H bond of tetrahydrothiophen-3-one using Cu(OTf)2 as the catalyst and DDQ as the oxidant. The chemical functionalization was confirmed by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy and visualized by scanning electron microscopy. The functionalized hydrogenated graphene material demonstrated improved dispersion stability in water, bringing new quality to the elusive hydrogenated graphene (graphane) materials. Hydrogenated graphene provides broad possibilities for chemical modifications owing to its reactivity.

  14. Activation cross-sections of proton induced reactions on vanadium in the 37-65 MeV energy range

    NASA Astrophysics Data System (ADS)

    Ditrói, F.; Tárkányi, F.; Takács, S.; Hermanne, A.

    2016-08-01

    Experimental excitation functions for proton induced reactions on natural vanadium in the 37-65 MeV energy range were measured with the activation method using a stacked foil irradiation technique. By using high resolution gamma spectrometry cross-section data for the production of 51,48Cr, 48V, 48,47,46,44m,44g,43Sc and 43,42K were determined. Comparisons with the earlier published data are presented and results predicted by different theoretical codes (EMPIRE and TALYS) are included. Thick target yields were calculated from a fit to our experimental excitation curves and compared with the earlier experimental yield data. Depth distribution curves to be used for thin layer activation (TLA) are also presented.

  15. Differential cross sections for the reactions {gamma}p{yields}p{eta} and {gamma}p{yields}p{eta}{sup '}

    SciTech Connect

    Williams, M.; Krahn, Z.; Applegate, D.; Bellis, M.; Meyer, C. A.; Dey, B.; Dickson, R.; McCracken, M. E.; Moriya, K.; Schumacher, R. A.; Adhikari, K. P.; Careccia, S. L.; Dodge, G. E.; Guler, N.; Klein, A.; Mayer, M.; Nepali, C. S.; Niroula, M. R.; Seraydaryan, H.; Tkachenko, S.

    2009-10-15

    High-statistics differential cross sections for the reactions {gamma}p{yields}p{eta} and {gamma}p{yields}p{eta}{sup '} have been measured using the CEBAF large acceptance spectrometer (CLAS) at Jefferson Lab for center-of-mass energies from near threshold up to 2.84 GeV. The {eta}{sup '} results are the most precise to date and provide the largest energy and angular coverage. The {eta} measurements extend the energy range of the world's large-angle results by approximately 300 MeV. These new data, in particular the {eta}{sup '} measurements, are likely to help constrain the analyses being performed to search for new baryon resonance states.

  16. Differential cross sections and spin density matrix elements for the reaction {gamma}p{yields}p{omega}

    SciTech Connect

    Williams, M.; Applegate, D.; Bellis, M.; Meyer, C. A.; Dey, B.; Dickson, R.; Krahn, Z.; McCracken, M. E.; Moriya, K.; Schumacher, R. A.; Adhikari, K. P.; Careccia, S. L.; Dodge, G. E.; Klein, A.; Mayer, M.; Nepali, C. S.; Niroula, M. R.; Seraydaryan, H.; Tkachenko, S.; Weinstein, L. B.

    2009-12-15

    High-statistics differential cross sections and spin-density matrix elements for the reaction {gamma}p{yields}p{omega} have been measured using the CEBAF large acceptance spectrometer (CLAS) at Jefferson Lab for center-of-mass (c.m.) energies from threshold up to 2.84 GeV. Results are reported in 112 10-MeV wide c.m. energy bins, each subdivided into cos{theta}{sub c.m.}{sup {omega}} bins of width 0.1. These are the most precise and extensive {omega} photoproduction measurements to date. A number of prominent structures are clearly present in the data. Many of these have not previously been observed due to limited statistics in earlier measurements.

  17. Low-energy cross sections in the {sup 12}C({alpha},{gamma}){sup 16}O reaction

    SciTech Connect

    Katsuma, M.

    2008-09-15

    The low-energy {sup 12}C({alpha},{gamma}){sup 16}O reaction is analyzed with the potential model. The potentials are chosen from the deep potential describing the {alpha}-particle nuclear rainbow phenomena at high energies. Below E{sub c.m.}=1 MeV, the cross section is found to be dominated by the E2 transition to the ground state of {sup 16}O. No enhancement of the E1 component at low energies is predicted. The extrapolated astrophysical S-factors at E{sub c.m.}=0.3 MeV are S{sub E2}=150 keV b and S{sub E1}=3 keV b.

  18. [Aspirin-induced angioedema of the nape of the neck with naproxen cross-reaction: a case report].

    PubMed

    Ghislain, P D; Ghislain, E

    2000-05-01

    We report a case of angioedema limited to the nape of the neck. The symptoms occurred every morning for fifteen days, two or three hours after taking aspirin. The patient took salicylic acid, 100mg per day, orally for two years. The angioedema occurred alone, without urticaria. When aspirin was stopped, the symptoms disappeared. A few weeks later, the patient took napoxen, with occurrence of more pronounced symptoms. The causality score was I3 for both drugs. The most common side-effects of aspirin intake are asthma and urticaria/angioedema. The mechanism of this hypersensitivity is unknown. There are numerous cross-reactions between aspirin and other NSAIDs. This case points out the importance of accurate history taking concerning self-medication for the diagnosis of angioedema.

  19. Total and partial capture cross sections in reactions with deformed nuclei at energies near and below the Coulomb barrier

    SciTech Connect

    Kuzyakin, R. A. Sargsyan, V. V.; Adamian, G. G.; Antonenko, N. V.

    2013-06-15

    Within the quantum diffusion approach, the capture of a projectile nucleus by a target nucleus is studied at bombarding energies above and below the Coulomb barrier. The effects of deformation of interacting nuclei and neutron transfer between them on the total and partial capture cross sections and the mean angular momentum of the captured system are studied. The results obtained for the {sup 16}O + {sup 112}Cd, {sup 152}Sm, and {sup 184}W; {sup 19}F +{sup 175}Lu; {sup 28}Si +{sup 94,100}Mo and {sup 154}Sm; {sup 40}Ca +{sup 96}Zr; {sup 48}Ca+ {sup 90}Zr; and {sup 64}Ni +{sup 58,64}Ni, {sup 92,96}Zr, and {sup 100}Mo reactions are in good agreement with available experimental data.

  20. Functionalization of Hydrogenated Graphene: Transition-Metal-Catalyzed Cross-Coupling Reactions of Allylic C-H Bonds.

    PubMed

    Chua, Chun Kiang; Sofer, Zdeněk; Pumera, Martin

    2016-08-26

    The chemical functionalization of hydrogenated graphene can modify its physical properties and lead to better processability. Herein, we describe the chemical functionalization of hydrogenated graphene through a dehydrogenative cross-coupling reaction between an allylic C-H bond and the α-C-H bond of tetrahydrothiophen-3-one using Cu(OTf)2 as the catalyst and DDQ as the oxidant. The chemical functionalization was confirmed by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy and visualized by scanning electron microscopy. The functionalized hydrogenated graphene material demonstrated improved dispersion stability in water, bringing new quality to the elusive hydrogenated graphene (graphane) materials. Hydrogenated graphene provides broad possibilities for chemical modifications owing to its reactivity. PMID:27496619