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Sample records for intermediates reaction

  1. Reactions of stabilized Criegee Intermediates

    Science.gov (United States)

    Vereecken, Luc; Harder, Hartwig; Novelli, Anna

    2014-05-01

    Carbonyl oxides (Criegee intermediates) were proposed as key intermediates in the gas phase ozonolysis of alkenes in 1975 by Rudolf Criegee. Despite the importance of ozonolysis in atmospheric chemistry, direct observation of these intermediates remained elusive, with only indirect experimental evidence for their role in the oxidation of hydrocarbons, e.g. through scavenging experiments. Direct experimental observation of stabilized CI has only been achieved since 2008. Since then, a concerted effort using experimental and theoretical means is in motion to characterize the chemistry and kinetics of these reactive intermediates. We present the results of theoretical investigations of the chemistry of Criegee intermediates with a series of coreactants which may be of importance in the atmosphere, in experimental setups, or both. This includes the CI+CI cross-reaction, which proceeds with a rate coefficient near the collision limit and can be important in experimental conditions. The CI + alkene reactions show strong dependence of the rate coefficient depending on the coreactants, but is generally found to be rather slow. The CI + ozone reaction is sufficiently fast to occur both in experiment and the free troposphere, and acts as a sink for CI. The reaction of CI with hydroperoxides, ROOH, is complex, and leads both to the formation of oligomers, as to the formation of reactive etheroxides, with a moderately fast rate coefficient. The importance of these reactions is placed in the context of the reaction conditions in different atmospheric environments ranging from unpolluted to highly polluted.

  2. Photonuclear reactions at intermediate energy

    International Nuclear Information System (INIS)

    Koch, J.H.

    1982-01-01

    The dominant feature of photonuclear reactions at intermediate energies is the excitation of the δ resonance and one can therefore use such reactions to study the dynamics of δ propagation in a nucleus. Following an introductory section the author comments on photoabsorption on a single nucleon in Section II. A review of the δ-n Greens function and of the photonuclear amplitude is given in Section III. Results for photoabsorption on 4 He are shown in Section IV and compared with the data. Coherent π 0 photoproduction is discussed in Section V and calculations for 12 C are compared to recent measurements. (Auth.)

  3. On intermediate structures in heavy ion reactions

    International Nuclear Information System (INIS)

    Rotter, I.

    1977-01-01

    The conceptions of the nuclear reaction theory are reinvestigated on the basis of the continuum shell model. The correlation of the resonance states via the continuum can lead to intermediate structures in the cross section. (Auth.)

  4. Transfer and breakup reactions at intermediate energies

    International Nuclear Information System (INIS)

    Stokstad, R.G.

    1986-04-01

    The origin of the quasi-elastic peak in peripheral heavy-ion reactions is discussed in terms of inelastic scattering and transfer reactions to unbound states of the primary projectile-like fragment. The situation is analogous to the use of reverse kinematics in fusion reactions, a technique in which the object of study is moving with nearly the beam velocity. It appears that several important features of the quasi-elastic peak may be explained by this approach. Projectile-breakup reactions have attractive features for the study of nuclear structure. They may also be used to determine the partition of excitation energy in peripheral reactions. At intermediate energies, neutron-pickup reactions leading to four-body final states become important. Examples of experiments are presented that illustrate these points. 15 refs., 14 figs

  5. Fission in intermediate energy heavy ion reactions

    International Nuclear Information System (INIS)

    Wilhelmy, J.B.; Begemann-Blaich, M.; Blaich, T.; Boissevain, J.; Fowler, M.M.; Gavron, A.; Jacak, B.V.; Lysaght, P.S.; Britt, H.C.; Fields, D.J.; Hansen, L.F.; Lanier, R.G.; Massoletti, D.J.; Namboodiri, M.M.; Remington, B.A.; Sangster, T.C.; Struble, G.L.; Webb, M.L.; Chan, Y.D.; Dacai, A.; Harmon, A.; Leyba, J.; Pouliot, J.; Stokstad, R.G.; Hansen, O.; Levine, M.J.; Thorn, C.E.; Trautmann, W.; Dichter, B.; Kaufman, S.; Videbaek, F.; Fraenkel, Z.; Mamane, G.; Cebra, D.; Westfall, G.D.

    1989-01-01

    A systematic study of reaction mechanisms at intermediate energies (50-100 MeV/A) has been performed at the Lawrence Berkeley Laboratory's BeValac using medium weight projectiles on medium and heavy element targets. A gas and plastic phoswich detector system was employed which gave large geometric coverage and a wide dynamic response. The particles identified with the gas detectors could be characterized into three components - intermediate mass fragments (IMF), fission fragments (FF) and heavy residues (HR). Major observed features are: The reaction yields are similar in the 50 to 100 MeV/A range, central collisions have high multiplicty of IMF's with broad angular correlations consistent with a large participant region, effects of final state Coulomb interactions are observed and give information on the size and temporal behavior of the source, true fission yields are dependent on target fissility and correlated with relatively peripheral collisions. Analysis of fission and evaporation yields implies limiting conditions for which fission decay remains a viable deexcitation channel. (orig.)

  6. Fission in intermediate energy heavy ion reactions

    International Nuclear Information System (INIS)

    Wilhelmy, J.B.; Begemann-Blaich, M.; Blaich, T.

    1989-01-01

    A systematic study of reaction mechanisms at intermediate energies (50--100 MeV/A) has been performed at the Lawrence Berkeley Laboratory's BeValac using medium weight projectiles on medium and heavy element targets. A gas and plastic phoswich detector system was employed which gave large geometric coverage and a wide dynamic response. The particles identified with the gas detectors could be characterized into three components - intermediate mass fragments (IMF), fission fragments (FF) and heavy residues (HR). Major observed features are: the reaction yields are similar in the 50 to 100 MeV/A range, central collisions have high multiplicity of IMF's with broad angular correlations consistent with a large participant region, effects of final state Coulomb interactions are observed and give information on the size and temporal behavior of the source, true fission yields are dependent on target fissility and correlated with relatively peripheral collisions. Analysis of fission and evaporation yields implies limiting conditions for which fission decay remains a viable deexcitation channel. 7 figs

  7. Nucleon charge-exchange reactions at intermediate energy

    Energy Technology Data Exchange (ETDEWEB)

    Alford, W.P. [Western Ontario Univ., London, ON (Canada). Dept. of Physics]|[TRIUMF, Vancouver, BC (Canada); Spicer, B.M. [Melbourne Univ., Parkville, VIC (Australia). School of Physics

    1997-12-31

    An historical review of the development of ideas pertaining to Gamow-Teller giant resonances is given, and a description of the emergence of techniques for the study of charge exchange reactions - particularly the technical advances which yielded the recent volume of new date. The present status of charge exchange reactions is reviewed and assessed. Evidence is presented from the {sup 14}C(p,n) reaction for the dominance of the spin-isospin component of the nucleon-nucleon interaction in intermediate energy reactions. In (p,n) reactions the Gamow-Teller giant resonance dominates the spectra, with higher multipoles contributing. By contrast, in (n,p) reactions in the heavier nuclei, the Gamow-Teller transitions are substantially Pauli-blocked and the spin dipole resonance dominates, with contributions from higher multipoles. Discussions of the multipole decomposition process, used to obtain from the data the contributions of the different multipoles, and the contributions of the multipoles, are given. 226 refs., 19 figs.

  8. Nucleon charge-exchange reactions at intermediate energy

    International Nuclear Information System (INIS)

    Alford, W.P.; Spicer, B.M.

    1997-01-01

    An historical review of the development of ideas pertaining to Gamow-Teller giant resonances is given, and a description of the emergence of techniques for the study of charge exchange reactions - particularly the technical advances which yielded the recent volume of new date. The present status of charge exchange reactions is reviewed and assessed. Evidence is presented from the 14 C(p,n) reaction for the dominance of the spin-isospin component of the nucleon-nucleon interaction in intermediate energy reactions. In (p,n) reactions the Gamow-Teller giant resonance dominates the spectra, with higher multipoles contributing. By contrast, in (n,p) reactions in the heavier nuclei, the Gamow-Teller transitions are substantially Pauli-blocked and the spin dipole resonance dominates, with contributions from higher multipoles. Discussions of the multipole decomposition process, used to obtain from the data the contributions of the different multipoles, and the contributions of the multipoles, are given

  9. Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides

    Science.gov (United States)

    Taatjes, Craig A.

    2017-05-01

    The carbonyl oxide intermediates in the ozonolysis of alkenes, often known as Criegee intermediates, are potentially important reactants in Earth's atmosphere. For decades, careful analysis of ozonolysis systems was employed to derive an understanding of the formation and reactions of these species. Recently it has proved possible to synthesize at least some of these intermediates separately from ozonolysis, and hence to measure their reaction kinetics directly. Direct measurements have allowed new or more detailed understanding of each type of gas-phase reaction that carbonyl oxides undergo, often acting as a complement to highly detailed ozonolysis experiments. Moreover, the use of direct characterization methods to validate increasingly accurate theoretical investigations can enhance their impact well beyond the set of specific reactions that have been measured. Reactions that initiate particles or fuel their growth could be a new frontier for direct measurements of Criegee intermediate chemistry.

  10. INTERMEDIATE STAGES OF REACTIONS FORMING CARBIDES OF TITANIUM, ZIRCONIUM, VANADIUM, NIOBIUM, AND TANTALIUM

    Science.gov (United States)

    intermediate and final products, and also during the calculation of approximate heat values of their formation, the passage of the reaction is confirmed...for obtaining TiC, and ZrC through the stage of intermediate oxides Ti2O3, Ti3O5, TiO and Zr2O3, ZrO, respectively and also for the reaction of...forming carbides of V (from V2O3 + 5C), of Nb and Ta (from Nb2O5 + 7C and Ta205 + 7C) through the stage of intermediate oxides VO, V4O and TaO2, Ta4O. The

  11. Role of compound nuclei in intermediate-energy heavy-ion reactions

    International Nuclear Information System (INIS)

    Moretto, L.G.; Wozniak, G.J.

    1988-05-01

    Hot compound nuclei are frequently produced in intermediate-energy reactions through a variety of processes. Their decay is shown to be an important and at times dominant source of complex fragments, high energy-gamma rays, and even pions

  12. 27Al MAS NMR spectroscopic identification of reaction intermediates in the carbothermal reduction and nitridation of alumina

    International Nuclear Information System (INIS)

    Jung, Woo-Sik; Chae, Seen-Ae

    2010-01-01

    The reaction intermediates in the carbothermal reduction and nitridation (CRN) reaction of γ-Al 2 O 3 were identified by 27 Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. This identification ruled out the possibility of a reaction mechanism involving the gaseous reaction intermediates. In the CRN reaction of γ-Al 2 O 3 , AlO 4 units were converted to AlN stepwise via AlN x O 4-x (x = 1, 2, 3) intermediates, while AlO 6 units were more slowly converted to AlN than AlO 4 units and the NMR peaks of partially nitridated AlO 6 units were not detected. The NMR peak intensities of partially nitridated AlO 4 units became weaker with increasing reaction temperature.

  13. On light cluster production in nucleon induced reactions at intermediate energy

    Energy Technology Data Exchange (ETDEWEB)

    Lacroix, D.; Blideanu, V.; Durand, D

    2004-09-01

    A dynamical model dedicated to nucleon induced reaction between 30-150 MeV is presented. It considers different stages of the reaction: the approaching phase, the in-medium nucleon-nucleon collisions, the cluster formation and the secondary de-excitation process. The notions of influence area and phase-space exploration during the reaction are introduced. The importance of the geometry of the reaction and of the conservation laws are underlined. The model is able to globally reproduce the absolute cross sections for the emission of neutron and light charged particles for proton and neutron induced reactions on heavy and intermediate mass targets ({sup 56}Fe and {sup 208}Pb). (authors)

  14. On light cluster production in nucleon induced reactions at intermediate energy

    International Nuclear Information System (INIS)

    Lacroix, D.; Blideanu, V.; Durand, D.

    2004-09-01

    A dynamical model dedicated to nucleon induced reaction between 30-150 MeV is presented. It considers different stages of the reaction: the approaching phase, the in-medium nucleon-nucleon collisions, the cluster formation and the secondary de-excitation process. The notions of influence area and phase-space exploration during the reaction are introduced. The importance of the geometry of the reaction and of the conservation laws are underlined. The model is able to globally reproduce the absolute cross sections for the emission of neutron and light charged particles for proton and neutron induced reactions on heavy and intermediate mass targets ( 56 Fe and 208 Pb). (authors)

  15. Macroscopic/microscopic simulation of nuclear reactions at intermediate energies

    International Nuclear Information System (INIS)

    Lacroix, D.; Van Lauwe, A.; Durand, D.

    2003-01-01

    An event generator, HIPSE (Heavy-Ion Phase-Space Exploration), dedicated to the description of nuclear collisions in the intermediate energy range is presented. The model simulates events for reactions close to the fusion barrier (5-10 MeV/A) up to higher energy (100 MeV/A) and it gives access to the phase-space explored during the collision. The development of HIPSE has been largely influenced by experimental observations. We have separated the reaction into 4 steps: contact, fragment formation, chemical freeze-out, and in-flight deexcitation. HIPSE will be useful for a study of various mechanisms such as neck fragmentation or multi-fragmentation

  16. Organotrichlorogermane synthesis by the reaction of elemental germanium, tetrachlorogermane and organic chloride via dichlorogermylene intermediate.

    Science.gov (United States)

    Okamoto, Masaki; Asano, Takuya; Suzuki, Eiichi

    2004-08-07

    Organotrichlorogermanes were synthesized by the reaction of elemental germanium, tetrachlorogermane and organic chlorides, methyl, propyl, isopropyl and allyl chlorides. Dichlorogermylene formed by the reaction of elemental germanium with tetrachlorogermane was the reaction intermediate, which was inserted into the carbon-chlorine bond of the organic chloride to give organotrichlorogermane. When isopropyl or allyl chloride was used as an organic chloride, organotrichlorogermane was formed also in the absence of tetrachlorogermane. These chlorides were converted to hydrogen chloride, which subsequently reacted with elemental germanium to give the dichlorogermylene intermediate. The reaction of elemental germanium, tetrachlorogermane and organic chlorides provides a simple and easy method for synthesizing organotrichlorogermanes, and all the raw materials are easily available.

  17. The role of phosphate in a multistep enzymatic reaction: reactions of the substrate and intermediate in pieces.

    Science.gov (United States)

    Kholodar, Svetlana A; Allen, C Leigh; Gulick, Andrew M; Murkin, Andrew S

    2015-02-25

    Several mechanistically unrelated enzymes utilize the binding energy of their substrate's nonreacting phosphoryl group to accelerate catalysis. Evidence for the involvement of the phosphodianion in transition state formation has come from reactions of the substrate in pieces, in which reaction of a truncated substrate lacking its phosphorylmethyl group is activated by inorganic phosphite. What has remained unknown until now is how the phosphodianion group influences the reaction energetics at different points along the reaction coordinate. 1-Deoxy-D-xylulose-5-phosphate (DXP) reductoisomerase (DXR), which catalyzes the isomerization of DXP to 2-C-methyl-D-erythrose 4-phosphate (MEsP) and subsequent NADPH-dependent reduction, presents a unique opportunity to address this concern. Previously, we have reported the effect of covalently linked phosphate on the energetics of DXP turnover. Through the use of chemically synthesized MEsP and its phosphate-truncated analogue, 2-C-methyl-D-glyceraldehyde, the current study revealed a loss of 6.1 kcal/mol of kinetic barrier stabilization upon truncation, of which 4.4 kcal/mol was regained in the presence of phosphite dianion. The activating effect of phosphite was accompanied by apparent tightening of its interactions within the active site at the intermediate stage of the reaction, suggesting a role of the phosphodianion in disfavoring intermediate release and in modulation of the on-enzyme isomerization equilibrium. The results of kinetic isotope effect and structural studies indicate rate limitation by physical steps when the covalent linkage is severed. These striking differences in the energetics of the natural reaction and the reactions in pieces provide a deeper insight into the contribution of enzyme-phosphodianion interactions to the reaction coordinate.

  18. Compound nuclei, binary decay, and multifragmentation in intermediate-energy heavy-ion reactions

    International Nuclear Information System (INIS)

    Moretto, L.G.; Wozniak, G.J.

    1988-07-01

    Hot compound nuclei, frequently produced in intermediate-energy reactions through a variety of processes, are shown to be an important and at times dominant source of complex fragments. 13 refs., 12 figs

  19. Intermediate energy heavy ion reactions. A program for CELSIUS

    International Nuclear Information System (INIS)

    Jakobsson, B.

    1986-02-01

    The accelerator system under construction in Uppsala with the ECR-source + the K equals 200 synchrocyclotron + the CELSIUS synchrotron ring for storage, cooling and acceleration opens up possibilities for a very fruitful heavy ion physics program. Some recently obtained results and some recent ideas on intermediate energy reactions are discussed and speculations are made about some experiments where the unconventional qualities of CELSIUS beams could be utilized. (author)

  20. Fragment mass distribution of proton-induced spallation reaction with intermediate energy

    International Nuclear Information System (INIS)

    Fan Sheng; Ye Yanlin; Xu Chuncheng; Chen Tao; Sobolevsky, N.M.

    2000-01-01

    The test of part benchmark of SHIELD code is finished. The fragment cross section and mass distribution and excitation function of the residual nuclei from proton-induced spallation reaction on thin Pb target with intermediate energy have been calculated by SHIELD code. And the results are in good agreement with measured data. The fragment mass distribution of the residual nuclei from proton-induced spallation reaction on thick Pb target with incident energy 1.6 GeV have been simulated

  1. A few aspects of intermediate energy heavy ion reactions

    International Nuclear Information System (INIS)

    Guet, C.

    1982-10-01

    Some aspects of reactions induced by intermediate energy heavy ions, with a special emphasis of 85 MeV/nucleon 12 C data, are discussed and compared to low energy and relativistic energy features. Transition from mean field to independant nucleon picture is advocated by an increase of nuclear transparency illuminated by reaction cross section estimations. Projectile-like fragment distributions, while demonstrating a typical high energy fragmentation behaviour, exhibit low energy regime distortions. Light fragments, associated to large parallel momentum transfer may result from total explosion. Proton emission is investigated and discussed in terms of opposite models such as thermal equilibrium and nucleon-nucleon scattering. First pion production data are well explained by single nucleon-nucleon inelastic scattering

  2. Isovector couplings for nucleon charge-exchange reactions at intermediate energies

    International Nuclear Information System (INIS)

    Love, W.G.; Nakayama, K.; Franey, M.A.

    1987-01-01

    The isovector parts of the effective nucleon-nucleon interaction are studied by examination of the reaction /sup 14/C(p,n) at intermediate energies near zero momentum transfer with use of recently developed G-matrix and free--t-matrix interactions. The spin-independent coupling (V/sub tau/) exhibits a strong energy and density dependence which, in the case of the G matrix based on the Bonn potential, significantly improves the agreement between calculated values of chemical bondV/sub σ//sub tau//V/sub tau/chemical bond 2 at q = 0 and those recently extracted from the reaction /sup 14/C

  3. Hydrozirconation of lithium alkynylselenolate anions. Generation and reactions of alpha-zirconated vinyl selenide intermediates

    Science.gov (United States)

    Dabdoub; Begnini; Guerrero; Baroni

    2000-01-14

    Lithium alkynylselenolate anions react completely with 1.0 equiv of Cp(2)Zr(H)Cl in THF at room temperature to give exclusively the alpha-zirconated vinylselenolate intermediates 23-27, which by treatment with an alkyl halide afforded the alpha-zirconated vinyl alkylselenide intermediates 29-33. Reaction of 29-33 with butyltellurenyl bromide results in the formation of ketene telluro(seleno) acetals 35-39 with total control of the regio- and stereochemistry. The synthetic utility of the ketene telluro(seleno) acetals obtained here was demonstrated by reaction of 36 with butyllithium. This promotes the exclusive and stereospecific removal of the tellurium moiety and enables formation of the corresponding selenium-containing allylic alcohol of type 44, alpha-(alkylseleno)-alpha,beta-unsaturated aldehyde 45, ester 46, or carboxylic acid 47, after reaction with different types of electrophiles.

  4. A paradigm shift for radical SAM reactions: The organometallic intermediate Ω is central to catalysis.

    Science.gov (United States)

    Byer, Amanda S; Yang, Hao; McDaniel, Elizabeth C; Kathiresan, Venkatesan; Impano, Stella; Pagnier, Adrien; Watts, Hope; Denler, Carly; Vagstad, Anna; Piel, Jörn; Duschene, Kaitlin S; Shepard, Eric M; Shields, Thomas P; Scott, Lincoln G; Lilla, Edward A; Yokoyama, Kenichi; Broderick, William E; Hoffman, Brian M; Broderick, Joan B

    2018-06-28

    Radical S-adenosyl-L-methionine (SAM) en-zymes comprise a vast superfamily catalyzing diverse reactions essential to all life through ho-molytic SAM cleavage to liberate the highly-reactive 5-deoxyadenosyl radical (5-dAdo•). Our recent observation of a catalytically compe-tent organometallic intermediate Ω that forms dur-ing reaction of the radical SAM (RS) enzyme py-ruvate formate-lyase activating-enzyme (PFL-AE) was therefore quite surprising, and led to the question of its broad relevance in the superfamily. We now show that Ω in PFL-AE forms as an in-termediate under a variety of mixing order condi-tions, suggesting it is central to catalysis in this enzyme. We further demonstrate that Ω forms in a suite of RS enzymes chosen to span the totality of superfamily reaction types, implicating Ω as essential in catalysis across the RS superfamily. Finally, EPR and electron nuclear double reso-nance spectroscopy establish that Ω involves an Fe-C5 bond between 5-dAdo• and the [4Fe-4S] cluster. An analogous organometallic bond is found in the well-known adenosylcobalamin (co-enzyme B12) cofactor used to initiate radical reac-tions via a 5'-dAdo• intermediate. Generation of a 5'-dAdo• intermediate via homolytic metal-carbon bond cleavage thus appears to be similar for Ω and coenzyme B12. However coenzyme B12 is involved in enzymes catalyzing of only a small number (~12) of distinct reactions, while the RS superfamily has more than 100,000 distinct se-quences and over 80 reaction types character-ized to date. The appearance of Ω across the RS superfamily therefore dramatically enlarges the sphere of bio-organometallic chemistry in Nature.

  5. Photocatalytic degradation of paracetamol: intermediates and total reaction mechanism.

    Science.gov (United States)

    Moctezuma, Edgar; Leyva, Elisa; Aguilar, Claudia A; Luna, Raúl A; Montalvo, Carlos

    2012-12-01

    The advanced oxidation of paracetamol (PAM) promoted by TiO(2)/UV system in aqueous medium was investigated. Monitoring this reaction by HPLC and TOC, it was demonstrated that while oxidation of paracetamol is quite efficient under these conditions, its mineralization is not complete. HPLC indicated the formation of hydroquinone, benzoquinone, p-aminophenol and p-nitrophenol in the reaction mixtures. Further evidence of p-nitrophenol formation was obtained following the reaction by UV-vis spectroscopy. Continuous monitoring by IR spectroscopy demonstrated the breaking of the aromatic amide present in PAM and subsequent formation of several aromatic intermediate compounds such as p-aminophenol and p-nitrophenol. These aromatic compounds were eventually converted into trans-unsaturated carboxylic acids. Based on these experimental results, an alternative deacylation mechanism for the photocatalytic oxidation of paracetamol is proposed. Our studies also demonstrated IR spectroscopy to be a useful technique to investigate oxidative mechanisms of pharmaceutical compounds. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Reaction intermediates in the catalytic Gif-type oxidation from nuclear inelastic scattering

    Energy Technology Data Exchange (ETDEWEB)

    Rajagopalan, S., E-mail: rajagopalan78@hotmail.com [Indira Gandhi Centre for Atomic Research, Materials Science Group (India); Asthalter, T., E-mail: t.asthalter@web.de [Universität Stuttgart, Institute of Physical Chemistry (Germany); Rabe, V.; Laschat, S. [Universität Stuttgart, Institute of Organic Chemistry (Germany)

    2016-12-15

    Nuclear inelastic scattering (NIS) of synchrotron radiation, also known as nuclear resonant vibrational spectroscopy (NRVS), has been shown to provide valuable insights into metal-centered vibrations at Mössbauer-active nuclei. We present a study of the iron-centered vibrational density of states (VDOS) during the first step of the Gif-type oxidation of cyclohexene with a novel trinuclear Fe{sub 3}(μ{sub 3}-O) complex as catalyst precursor. The experiments were carried out on shock-frozen solutions for different combinations of reactants: Fe{sub 3}(μ{sub 3}-O) in pyridine solution, Fe{sub 3}(μ{sub 3}-O) plus Zn/acetic acid in pyridine without and with addition of either oxygen or cyclohexene, and Fe{sub 3}(μ{sub 3}-O)/Zn/acetic acid/pyridine/cyclohexene (reaction mixture) for reaction times of 1 min, 5 min, and 30 min. The projected VDOS of the Fe atoms was calculated on the basis of pseudopotential density functional calculations. Two possible reaction intermediates were identified as [Fe{sup (III)}(C{sub 5}H{sub 5}N){sub 2}(O{sub 2}CCH{sub 3}){sub 2}]{sup +} and Fe{sup (II)}(C{sub 5}H{sub 5}N){sub 4}(O{sub 2}CCH{sub 3}){sub 2}, yielding evidence that NIS (NRVS) allows to identify the presence of iron-centered intermediates also in complex reaction mixtures.

  7. Chemical Exchange Saturation Transfer in Chemical Reactions: A Mechanistic Tool for NMR Detection and Characterization of Transient Intermediates.

    Science.gov (United States)

    Lokesh, N; Seegerer, Andreas; Hioe, Johnny; Gschwind, Ruth M

    2018-02-07

    The low sensitivity of NMR and transient key intermediates below detection limit are the central problems studying reaction mechanisms by NMR. Sensitivity can be enhanced by hyperpolarization techniques such as dynamic nuclear polarization or the incorporation/interaction of special hyperpolarized molecules. However, all of these techniques require special equipment, are restricted to selective reactions, or undesirably influence the reaction pathways. Here, we apply the chemical exchange saturation transfer (CEST) technique for the first time to NMR detect and characterize previously unobserved transient reaction intermediates in organocatalysis. The higher sensitivity of CEST and chemical equilibria present in the reaction pathway are exploited to access population and kinetics information on low populated intermediates. The potential of the method is demonstrated on the proline-catalyzed enamine formation for unprecedented in situ detection of a DPU stabilized zwitterionic iminium species, the elusive key intermediate between enamine and oxazolidinones. The quantitative analysis of CEST data at 250 K revealed the population ratio of [Z-iminium]/[exo-oxazolidinone] 0.02, relative free energy +8.1 kJ/mol (calculated +7.3 kJ/mol), and free energy barrier of +45.9 kJ/mol (ΔG ⧧ calc. (268 K) = +42.2 kJ/mol) for Z-iminium → exo-oxazolidinone. The findings underpin the iminium ion participation in enamine formation pathway corroborating our earlier theoretical prediction and help in better understanding. The reliability of CEST is validated using 1D EXSY-build-up techniques at low temperature (213 K). The CEST method thus serves as a new tool for mechanistic investigations in organocatalysis to access key information, such as chemical shifts, populations, and reaction kinetics of intermediates below the standard NMR detection limit.

  8. Intermediates detected by visible spectroscopy during the reaction of nitrite with deoxyhemoglobin: the effect of nitrite concentration and diphosphoglycerate.

    Science.gov (United States)

    Nagababu, Enika; Ramasamy, Somasundaram; Rifkind, Joseph M

    2007-10-16

    The reaction of nitrite with deoxyhemoglobin (deoxyHb) results in the reduction of nitrite to NO, which binds unreacted deoxyHb forming Fe(II)-nitrosylhemoglobin (Hb(II)NO). The tight binding of NO to deoxyHb is, however, inconsistent with reports implicating this reaction with hypoxic vasodilation. This dilemma is resolved by the demonstration that metastable intermediates are formed in the course of the reaction of nitrite with deoxyHb. The level of intermediates is quantitated by the excess deoxyHb consumed over the concentrations of the final products formed. The dominant intermediate has a spectrum that does not correspond to that of Hb(III)NO formed when NO reacts with methemoglobin (MetHb), but is similar to metHb resulting in the spectroscopic determinations of elevated levels of metHb. It is a delocalized species involving the heme iron, the NO, and perhaps the beta-93 thiol. The putative role for red cell reacted nitrite on vasodilation is associated with reactions involving the intermediate. (1) The intermediate is less stable with a 10-fold excess of nitrite and is not detected with a 100-fold excess of nitrite. This observation is attributed to the reaction of nitrite with the intermediate producing N2O3. (2) The release of NO quantitated by the formation of Hb(II)NO is regulated by changes in the distal heme pocket as shown by the 4.5-fold decrease in the rate constant in the presence of 2,3-diphosphoglycerate. The regulated release of NO or N2O3 as well as the formation of the S-nitroso derivative of hemoglobin, which has also been reported to be formed from the intermediates generated during nitrite reduction, should be associated with any hypoxic vasodilation attributed to the RBC.

  9. Aspartate aminotransferase: the kinetic barriers facing the covalent intermediates on the reaction pathway

    International Nuclear Information System (INIS)

    Kirsch, J.F.; Julin, D.A.; McLeish, M.; Wiesinger, H.

    1986-01-01

    The intermediates, aldimine (A), quinonoid (Q) and ketimine (K), along the transaminase reaction coordinate were probed by isotope transfer and solvent exchange kinetics. Less than 0.003% of 3 H is transferred from C/sub α/[ 3 H]-aspartate to pyridoxamine phosphate in the cytoplasmic aspartate aminotransferase (cAATase) reaction implying either that Q does not exist as a kinetically competent intermediate or that there is a rapid exchange of isotope with solvent. The ratio of the rate constants for C/sub α/ hydrogen exchange vs keto acid product formation (k/sub exge//k/sub prod/) are 2.5 and 0.5 for the reactions of cAATase with C/sub α/ [ 2 H]-aspartate and mitochondrial (m) AATase with C/sub α/[ 2 H]-glutamate respectively. The latter reaction was also probed from the α-keto-glutarate side with carbonyl 0-18 enriched keto acid. This experiment gave k/sub exge//k/sub prod/ = 1.0 for oxygen-18 exchange in α-ketoglutarate versus amino acid formation. The two exchange experiments with mAATase are interpreted in terms of a model in which the rate constant for diffusion of water from the active site is comparable with those for product forming steps

  10. Multifragmentation in intermediate energy 129Xe-induced heavy-ion reactions

    International Nuclear Information System (INIS)

    Tso, Kin.

    1996-05-01

    The 129 Xe-induced reactions on nat Cu, 89 Y, 165 Ho, and 197 Au at bombarding energies of E/A = 40 ampersand 60 MeV have been studied theoretically and experimentally in order to establish the underlying mechanism of multifragmentation at intermediate energy heavy-Ion collisions. Nuclear disks formed in central heavy-ion collisions, as simulated by means of Boltzmann-like kinetic equations, break up into several fragments due to a new kind of Rayleigh-like surface instability. A sheet of liquid, stable in the limit of non-interacting surfaces, is shown to become unstable due to surface-surface interactions. The onset of this instability is determined analytically. A thin bubble behaves like a sheet and is susceptible to the surface instability through the crispation mode. The Coulomb effects associated with the depletion of charges in the central cavity of nuclear bubbles are investigated. The onset of Coulomb instability is demonstrated for perturbations of the radial mode. Experimental intermediate-mass-fragment multiplicity distributions for the 129 Xe-induced reactions are shown to be binomial at each transverse energy. From these distributions, independent of the specific target, an elementary binary decay probability p can be extracted that has a thermal dependence. Thus it is inferred that multifragmentation is reducible to a combination of nearly independent emission processes. If sequential decay is assumed, the increase of p with transverse energy implies a contraction of the emission time scale. The sensitivity of p to the lower Z threshold in the definition of intermediate-mass-fragments points to a physical Poisson simulations of the particle multiplicities show that the weak auto-correlation between the fragment multiplicity and the transverse energy does not distort a Poisson distribution into a binomial distribution. The effect of device efficiency on the experimental results has also been studied

  11. Reactions and reaction intermediates on iron surfaces--1. Methanol, ethanol, and isopropanol on Fe(100). 2. Hydrocarbons and carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Benziger, J.B.; Madix, R.J.

    1980-09-01

    Temperature-programed desorption and ESCA showed that the alcohols formed alkoxy intermediates on Fe(100) surfaces at room temperature, but that the methoxy and ethoxy species were much more stable than the isopropoxy intermediate. The alkoxy species reacted above 400/sup 0/K by decomposing into carbon monoxide and hydrogen, hydrogenation to alcohol, and scission of C-C and C-O bonds with hydrogenation of the hydrocarbon fragments. Ethylene, acetylene, and cis-2-butene formed stable, unidentified surface species. Methyl chloride formed stable surface methyl groups which decomposed into hydrogen and surface carbide at 475/sup 0/K. Formic and acetic acids yielded stable carboxylate intermediates which decomposed above 490/sup 0/K to hydrogen, carbon monoxide, and carbon dioxide. The studies suggested that the alkoxy surface species may be important intermediates in the Fischer-Tropsch reaction on iron.

  12. Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH+allene reaction

    International Nuclear Information System (INIS)

    Raman, Arjun S.; Justine Bell, M.; Lau, K.-C.; Butler, Laurie J.

    2007-01-01

    These velocity map imaging experiments characterize the photolytic generation of one of the two radical intermediates formed when OH reacts via an addition mechanism with allene. The CH 2 CCH 2 OH radical intermediate is generated photolytically from the photodissociation of 2-chloro-2-propen-1-ol at 193 nm. Detecting the Cl atoms using [2+1] resonance-enhanced multiphoton ionization evidences an isotropic angular distribution for the Cl+CH 2 CCH 2 OH photofragments, a spin-orbit branching ratio for Cl( 2 P 1/2 ):Cl( 2 P 3/2 ) of 0.28, and a bimodal recoil kinetic energy distribution. Conservation of momentum and energy allows us to determine from this data the internal energy distribution of the nascent CH 2 CCH 2 OH radical cofragment. To assess the possible subsequent decomposition pathways of this highly vibrationally excited radical intermediate, we include electronic structure calculations at the G3//B3LYP level of theory. They predict the isomerization and dissociation transition states en route from the initial CH 2 CCH 2 OH radical intermediate to the three most important product channels for the OH+allene reaction expected from this radical intermediate: formaldehyde+C 2 H 3 , H+acrolein, and ethene+CHO. We also calculate the intermediates and transition states en route from the other radical adduct, formed by addition of the OH to the center carbon of allene, to the ketene+CH 3 product channel. We compare our results to a previous theoretical study of the O+allyl reaction conducted at the CBS-QB3 level of theory, as the two reactions include several common intermediates

  13. Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH +allene reaction

    Science.gov (United States)

    Raman, Arjun S.; Justine Bell, M.; Lau, Kai-Chung; Butler, Laurie J.

    2007-10-01

    These velocity map imaging experiments characterize the photolytic generation of one of the two radical intermediates formed when OH reacts via an addition mechanism with allene. The CH2CCH2OH radical intermediate is generated photolytically from the photodissociation of 2-chloro-2-propen-1-ol at 193nm. Detecting the Cl atoms using [2+1] resonance-enhanced multiphoton ionization evidences an isotropic angular distribution for the Cl +CH2CCH2OH photofragments, a spin-orbit branching ratio for Cl(P1/22):Cl(P3/22) of 0.28, and a bimodal recoil kinetic energy distribution. Conservation of momentum and energy allows us to determine from this data the internal energy distribution of the nascent CH2CCH2OH radical cofragment. To assess the possible subsequent decomposition pathways of this highly vibrationally excited radical intermediate, we include electronic structure calculations at the G3//B3LYP level of theory. They predict the isomerization and dissociation transition states en route from the initial CH2CCH2OH radical intermediate to the three most important product channels for the OH +allene reaction expected from this radical intermediate: formaldehyde+C2H3, H +acrolein, and ethene+CHO. We also calculate the intermediates and transition states en route from the other radical adduct, formed by addition of the OH to the center carbon of allene, to the ketene+CH3 product channel. We compare our results to a previous theoretical study of the O +allyl reaction conducted at the CBS-QB3 level of theory, as the two reactions include several common intermediates.

  14. Trapping and Characterization of a Reaction Intermediate in Carbapenem Hydrolysis by B. cereus Metallo-β-lactamase

    Science.gov (United States)

    Tioni, Mariana F.; Llarrull, Leticia I.; Poeylaut-Palena, Andrés A.; Martí, Marcelo A.; Saggu, Miguel; Periyannan, Gopal R.; Mata, Ernesto G.; Bennett, Brian; Murgida, Daniel H.; Vila, Alejandro J.

    2009-01-01

    Metallo-β-lactamases hydrolyze most β-lactam antibiotics. The lack of a successful inhibitor for them is related to the previous failure to characterize a reaction intermediate with a clinically useful substrate. Stopped-flow experiments together with rapid freeze-quench EPR and Raman spectroscopies were used to characterize the reaction of Co(II)-BcII with imipenem. These studies show that Co(II)-BcII is able to hydrolyze imipenem both in the mono- and dinuclear forms. In contrast to the situation met for penicillin, the species that accumulates during turnover is an enzyme-intermediate adduct in which the β-lactam bond has already been cleaved. This intermediate is a metal-bound anionic species, with a novel resonant structure, that is stabilized by the metal ion at the DCH or Zn2 site. This species has been characterized based on its spectroscopic features. This represents a novel, previously unforeseen intermediate, that is related to the chemical nature of carbapenems, as confirmed by the finding of a similar intermediate for meropenem. Since carbapenems are the only substrates cleaved by B1, B2 and B3 lactamases, the identification of this intermediate could be exploited as a first step towards the design of transition state based inhibitors for all three classes of metallo-β-lactamases. PMID:18980308

  15. Central collisions in intermediate energy heavy-ion reactions

    International Nuclear Information System (INIS)

    Wong, C.Y.

    1979-01-01

    The critical collisions in intermediate energy heavy-ion reactions are examined from both a microscopic and macroscopic viewpoint. In the microscopic description the proper tool is the extended TDHF approximation involving both the mean field and the particle collisions. To understand the underlying physics, the effect of the mean field and the effect of particle collisions are studied separately. It is found that th sudden increase in the density of the overlapping region can cause the volcano effect, leading to the complete disintegration of one of the nuclei. The self-consistent mean field also gives rise to the bunching instability when the two Fermi spheres of the colliding nucleons separate. The collision between nucleons, on the other hand, leads to irreversible dissipation, thermalization, and the possibility of a hydrodynamical description of the dynamics. Next is studied the dynamics of central collisions using the hydrodynamical description for many combinations of targets and projectiles at different energies. The formation of shock waves, sidesplash, and the complete disintegration of the whole nucleus are examined. Nuclear viscosity is found to affect the angular distribution of the reaction products and also the maximum compression ratio achieved during the collision. 28 references

  16. Insights into the carboxyltransferase reaction of pyruvate carboxylase from the structures of bound product and intermediate analogues

    Science.gov (United States)

    Lietzan, Adam D.; St. Maurice, Martin

    2014-01-01

    Pyruvate carboxylase (PC) is a biotin-dependent enzyme that catalyzes the MgATP- and bicarbonate-dependent carboxylation of pyruvate to oxaloacetate, an important anaplerotic reaction in central metabolism. The carboxyltransferase (CT) domain of PC catalyzes the transfer of a carboxyl group from carboxybiotin to the accepting substrate, pyruvate. It has been hypothesized that the reactive enolpyruvate intermediate is stabilized through a bidentate interaction with the metal ion in the CT domain active site. Whereas bidentate ligands are commonly observed in enzymes catalyzing reactions proceeding through an enolpyruvate intermediate, no bidentate interaction has yet been observed in the CT domain of PC. Here, we report three X-ray crystal structures of the Rhizobium etli PC CT domain with the bound inhibitors oxalate, 3-hydroxypyruvate, and 3-bromopyruvate. Oxalate, a stereoelectronic mimic of the enolpyruvate intermediate, does not interact directly with the metal ion. Instead, oxalate is buried in a pocket formed by several positively charged amino acid residues and the metal ion. Furthermore, both 3-hydroxypyruvate and 3-bromopyruvate, analogs of the reaction product oxaloacetate, bind in an identical manner to oxalate suggesting that the substrate maintains its orientation in the active site throughout catalysis. Together, these structures indicate that the substrates, products and intermediates in the PC-catalyzed reaction are not oriented in the active site as previously assumed. The absence of a bidentate interaction with the active site metal appears to be a unique mechanistic feature among the small group of biotin-dependent enzymes that act on α-keto acid substrates. PMID:24157795

  17. L-myo-inosose-1 as a probable intermediate in the reaction catalyzed by myo-inositol oxygenase

    International Nuclear Information System (INIS)

    Naber, N.I.; Swan, J.S.; Hamilton, G.A.

    1986-01-01

    In previous investigations, it was necessary to have Fe(II) and cysteine present in order to assay the catalytic activity of purified hog kidney myo-inositol oxygenase. In the present study it was found that, if this purified nonheme iron enzyme is slowly frozen in solution with glutathione and stored at -20 degrees C, it is fully active in the absence of activators if catalase is present to remove adventitious H 2 O 2 . With this simpler assay system it was possible to clarify the effects of several variables on the enzymic reaction. Thus, the maximum velocity is pH-dependent with a maximum around pH 9.5, but the apparent Km for myo-inositol (air atmosphere) remains constant at 5.0 mM throughout a broad pH range. The enzyme is quite specific for its substrate myo-inositol, is very sensitive to oxidants and reductants, but is not affected by a variety of complexing agents, nucleotides, sulfhydryl reagents, etc. In other experiments it was found that L-myo-inosose-1, a potential intermediate in the enzymic reaction, is a potent competitive inhibitor (Ki = 62 microM), while other inososes and a solution thought to contain D-glucodialdehyde, another potential intermediate, are weak inhibitors. Also, both a kinetic deuterium isotope effect (kH/kD = 2.1) and a tritium isotope effect (kH/kT = 7.5) are observed for the enzymic reaction when [1-2H]- and [1-3H]-myo-inositol are used as reactants. These latter results are considered strong evidence that the oxygenase reaction proceeds by a pathway involving L-myo-inosose-1 as an intermediate rather than by an alternative pathway that would have D-glucodialdehyde as the intermediate

  18. Structural Analysis of Substrate, Reaction Intermediate, and Product Binding in Haemophilus influenzae Biotin Carboxylase

    Science.gov (United States)

    Broussard, Tyler C.; Pakhomova, Svetlana; Neau, David B.; Bonnot, Ross; Waldrop, Grover L.

    2015-01-01

    Acetyl-CoA carboxylase catalyzes the first and regulated step in fatty acid synthesis. In most Gram-negative and Gram-positive bacteria, the enzyme is composed of three proteins: biotin carboxylase, a biotin carboxyl carrier protein (BCCP), and carboxyltransferase. The reaction mechanism involves two half-reactions with biotin carboxylase catalyzing the ATP-dependent carboxylation of biotin-BCCP in the first reaction. In the second reaction, carboxyltransferase catalyzes the transfer of the carboxyl group from biotin-BCCP to acetyl-CoA to form malonyl-CoA. In this report, high-resolution crystal structures of biotin carboxylase from Haemophilus influenzae were determined with bicarbonate, the ATP analogue AMPPCP; the carboxyphosphate intermediate analogues, phosphonoacetamide and phosphonoformate; the products ADP and phosphate; and the carboxybiotin analogue N1′-methoxycarbonyl biotin methyl ester. The structures have a common theme in that bicarbonate, phosphate, and the methyl ester of the carboxyl group of N1′-methoxycarbonyl biotin methyl ester all bound in the same pocket in the active site of biotin carboxylase and as such utilize the same set of amino acids for binding. This finding suggests a catalytic mechanism for biotin carboxylase in which the binding pocket that binds tetrahedral phosphate also accommodates and stabilizes a tetrahedral dianionic transition state resulting from direct transfer of CO2 from the carboxyphosphate intermediate to biotin. PMID:26020841

  19. Coincidence measurements of intermediate mass fragments produced in /sup 32/S-induced reactions on Ag at E/A = 22.5 MeV

    International Nuclear Information System (INIS)

    Fields, D.J.; Lynch, W.G.; Nayak, T.K.

    1986-01-01

    Single- and two-particle inclusive cross sections for the production of light nuclei and intermediate mass fragments, 3< or =Z< or =24, were measured at angles well beyond the grazing angle for /sup 32/S-induced reactions on Ag at 720 MeV. Information about fragment multiplicities and reaction dynamics was extracted from measurements of light particles, intermediate mass fragments, and targetlike residues in coincidence with intermediate mass fragments. Incomplete linear momentum transfer and non-compound-particle emission are important features of collisions producing intermediate mass fragments. About half of the incident kinetic energy in these collisions is converted into internal excitation. The mean multiplicity of intermediate mass fragments is of the order of 1. Particle correlations are strongly enhanced in the plane which contains the intermediate mass fragment and the beam axis

  20. Inclusive quasielastic neutrino reactions in 12C and 16O at intermediate energies

    International Nuclear Information System (INIS)

    Singh, S.K.; Oset, E.

    1993-01-01

    Inclusive quasielastic neutrino (antineutrino) reactions on 12 C and 16 O at intermediate energies (50< E<400 MeV) are studied to investigate the effects of the nuclear medium on the total cross section and the energy spectrum of the outgoing leptons. The calculations are done in the local density approximation and various nuclear effects like Pauli blocking, Fermi motion, and strong-interaction renormalizations due to the presence of nucleons are taken into account. The corrections due to Coulomb effects are included which have been hitherto neglected in inclusive reactions. The results presented here are applicable to the inclusive reactions with neutrino beams planned to look for neutrino oscillations in the Los Alamos experiments or the experiments with underground detectors looking for atmospheric or solar flare neutrinos

  1. (γ,2n) reactions in complexe nuclei at intermediate energies

    International Nuclear Information System (INIS)

    Pinheiro Filho, J. de D.

    1976-01-01

    The Monte Carlo Method has been used in the intranuclear cascade model for the calculation of the cross sections of the (γ,2n) reactions in complex nuclei 9 Be, 12 C, 16 O, 59 Co, 103 Rh, 127 I, 197 Au and 209 Bi at intermediate energies (200MeV-1000MeV). The initial photon-interaction via the photomesonic and quasi-deuteron mechanisms have been taken into account. The nuclear model used was a degenerate Fermi gas of nucleons, and the Pauli exclusion principle was considered in all secondary interactions. To improve accuracy in the results of the calculations, 30000 cascades have been followed for each target nucleus at a given incident photon energy. The probabilities of the various (γ,2n) reactions, as well as the correspondent cross section obtained, are summarized in tables and graphs. New data on the cross sections of the 59 Co (γ,2n) and 209 Bi (γ,2n) reactions at photon energies between 300 MeV and 1000MeV are also reported. These measurements were obtained with the Bremsstrahlung beams of the Frascati 1 GeV Electron Synchrotron. A comparison between all existing data in the literature on the (γ,2n) reaction cross sections and the estimates by the Monte Carlo Method, is presented. (Author) [pt

  2. Calculation for fission decay from heavy ion reactions at intermediate energies

    International Nuclear Information System (INIS)

    Blaich, T.; Begemann-Blaich, M.; Fowler, M.M.; Wilhelmy, J.B.; Britt, H.C.; Fields, D.J.; Hansen, L.F.; Namboodiri, M.N.; Sangster, T.C.; Fraenkel, Z.

    1992-01-01

    A detailed deexcitation calculation is presented for target residues resulting from intermediate-energy heavy ion reactions. The model involves an intranuclear cascade, subsequent fast nucleon emission, and final decay by statistical evaporation including fission. Results are compared to data from bombardments with Fe and Nb projectiles on targets of Ta, Au, and Th at 100 MeV/nucleon. The majority of observable features are reproduced with this simple approach, making obvious the need for involving new physical phenomena associated with multifragmentation or other collective dissipation mechanisms

  3. [Intermediate energy studies of polarization transfer, polarized deuteron scattering, and (p,π+-) reactions: Rapporteur's report

    International Nuclear Information System (INIS)

    Moss, J.M.

    1985-01-01

    An overview of intermediate energy (80 to 1000 MeV) study contributions to the International Polarization Symposium in Osaka, Japan, August 1985 is presented in this report. Contributions fall into three categories: polarization transfer, polarized deuteron scattering and polarized (p,π +- ) reactions

  4. Multifragmentation in intermediate energy 129Xe-induced heavy-ion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Tso, Kin [Univ. of California, Berkeley, CA (United States)

    1996-05-01

    The 129Xe-induced reactions on natCu, 89Y, 165Ho, and 197Au at bombarding energies of E/A = 40 & 60 MeV have been studied theoretically and experimentally in order to establish the underlying mechanism of multifragmentation at intermediate energy heavy-Ion collisions. Nuclear disks formed in central heavy-ion collisions, as simulated by means of Boltzmann-like kinetic equations, break up into several fragments due to a new kind of Rayleigh-like surface instability. A sheet of liquid, stable in the limit of non-interacting surfaces, is shown to become unstable due to surface-surface interactions. The onset of this instability is determined analytically. A thin bubble behaves like a sheet and is susceptible to the surface instability through the crispation mode. The Coulomb effects associated with the depletion of charges in the central cavity of nuclear bubbles are investigated. The onset of Coulomb instability is demonstrated for perturbations of the radial mode. Experimental intermediate-mass-fragment multiplicity distributions for the 129Xe-induced reactions are shown to be binomial at each transverse energy. From these distributions, independent of the specific target, an elementary binary decay probability p can be extracted that has a thermal dependence. Thus it is inferred that multifragmentation is reducible to a combination of nearly independent emission processes. If sequential decay is assumed, the increase of p with transverse energy implies a contraction of the emission time scale. The sensitivity of p to the lower Z threshold in the definition of intermediate-mass-fragments points to a physical Poisson simulations of the particle multiplicities show that the weak auto-correlation between the fragment multiplicity and the transverse energy does not distort a Poisson distribution into a binomial distribution. The effect of device efficiency on the experimental results has also been studied.

  5. Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy

    KAUST Repository

    Michalak, William D.

    2013-01-31

    The product selectivity during 1,3-butadiene hydrogenation on monodisperse, colloidally synthesized, Pt nanoparticles was studied under reaction conditions with kinetic measurements and in situ sum frequency generation (SFG) vibrational spectroscopy. SFG was performed with the capping ligands intact in order to maintain nanoparticle size by reduced sintering. Four products are formed at 75 C: 1-butene, cis-2-butene, trans-2-butene, and n-butane. Ensembles of Pt nanoparticles with average diameters of 0.9 and 1.8 nm exhibit a ∼30% and ∼20% increase in the full hydrogenation products, respectively, as compared to Pt nanoparticles with average diameters of 4.6 and 6.7 nm. Methyl and methylene vibrational stretches of reaction intermediates observed under working conditions using SFG were used to correlate the stable reaction intermediates with the product distribution. Kinetic and SFG results correlate with previous DFT predictions for two parallel reaction pathways of 1,3-butadiene hydrogenation. Hydrogenation of 1,3-butadiene can initiate with H-addition at internal or terminal carbons leading to the formation of 1-buten-4-yl radical (metallocycle) and 2-buten-1-yl radical intermediates, respectively. Small (0.9 and 1.8 nm) nanoparticles exhibited vibrational resonances originating from both intermediates, while the large (4.6 and 6.7 nm) particles exhibited vibrational resonances originating predominately from the 2-buten-1-yl radical. This suggests each reaction pathway competes for partial and full hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites. © 2012 American Chemical Society.

  6. The Intermediate Velocity Source in the 40Ca + 197Au Reaction at 35 AMeV

    International Nuclear Information System (INIS)

    Planeta, R.; Sosin, Z.; Hachaj, P.

    2001-01-01

    The creation of hot Ca-like fragments and the emission of intermediate velocity particles was studied in the 40 Ca+ 197 Au reaction at 35 AMeV. For peripheral collisions the primary projectile-like fragment was reconstructed using the AMPHORA 4π detector system. The particle distributions are compared with the predictions of a Monte Carlo code which calculates the nucleon transfer and clustering probabilities according to the system density of states. The velocity distributions of charged particles projected on the beam direction can be explained if emissions from the hot projectile-like fragment and the target-like fragment are supplemented by an emission from an intermediate velocity source located between them. The properties of the intermediate velocity source are properly described, including the 2 D/ 3 T/ 3 He effect. (author)

  7. Specialized reactions: reactions at intermediate energies: Baryon--nucleus collisions, 150 MeV--1 GeV

    International Nuclear Information System (INIS)

    Igo, G.

    1974-01-01

    The high energy collision approximation proposed by Glauber to describe experimental data at the upper end of the intermediate range is reviewed. Some aspects of the model which limit its validity are outlined. Elastic scattering of protons from light nuclei is discussed in the framework of the Glauber model. For data in the energy region near 200 MeV, the plane wave impulse approximation (PWIA) and the distorted wave impulse approximation (DWIA) are applied. Quasielastic scattering is treated by considering (p,p') and (p,2p) reactions with light nuclei. A short discussion of the high resolution spectrometer facility at LAMPF and the SPES 1 facility at Saturne is given. (46 figures, 3 tables, 102 references) (U.S.)

  8. Progress in applyiong the FKK multistep reaction theory to intermediate-energy data evaluation

    International Nuclear Information System (INIS)

    Chadwick, M.B.; Young, P.G.

    1994-01-01

    Recent developments to the physics modeling in the FKK-GNASH code system are reviewed. We describe modifications to include a linking of multistep direct and multistep compound processes, which are important when the incident energy is less than about 30 MeV. A model for multiple preequilibrium emission is given, and compared with experimental measurements of proton reactions on 90 Zr at 160 MeV. We also give some preliminary observations concerning FKK calculations which use both normal and non-normal DWBA matrix elements. We describe the application of the FKK-GNASH code to a range of nuclear data applications, including intermediate energy reactions of importance in the accelerator transmutation of waste, and fast neutron and proton cancer radiation treatment. We outline areas where further work is needed for the accurate modeling of nuclear reactions using the FKK theory

  9. Roles of different initial Maillard intermediates and pathways in meat flavor formation for cysteine-xylose-glycine model reaction systems.

    Science.gov (United States)

    Hou, Li; Xie, Jianchun; Zhao, Jian; Zhao, Mengyao; Fan, Mengdie; Xiao, Qunfei; Liang, Jingjing; Chen, Feng

    2017-10-01

    To explore initial Maillard reaction pathways and mechanisms for maximal formation of meaty flavors in heated cysteine-xylose-glycine systems, model reactions with synthesized initial Maillard intermediates, Gly-Amadori, TTCA (2-threityl-thiazolidine-4-carboxylic acids) and Cys-Amadori, were investigated. Relative relativities were characterized by spectrophotometrically monitoring the development of colorless degradation intermediates and browning reaction products. Aroma compounds formed were determined by solid-phase microextraction combined with GC-MS and GC-olfactometry. Gly-Amadori showed the fastest reaction followed by Cys-Amadori then TTCA. Free glycine accelerated reaction of TTCA, whereas cysteine inhibited that of Gly-Amadori due to association forming relatively stable thiazolidines. Cys-Amadori/Gly had the highest reactivity in development of both meaty flavors and brown products. TTCA/Gly favored yielding meaty flavors, whereas Gly-Amadori/Cys favored generation of brown products. Conclusively, initial formation of TTCA and pathway involving TTCA with glycine were more applicable to efficiently produce processed-meat flavorings in a cysteine-xylose-glycine system. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Ketene as a Reaction Intermediate in the Carbonylation of Dimethyl Ether to Methyl Acetate over Mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, Burcin

    2015-01-01

    Unprecedented insight into the carbonylation of dimethyl ether over Mordenite is provided through the identification of ketene (CH2CO) as a reaction intermediate. The formation of ketene is predicted by detailed DFT calculations and verified experimentally by the observation of doubly deuterated ...

  11. Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Carraher, Jack McCaslin [Iowa State Univ., Ames, IA (United States)

    2014-01-01

    Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding ‘greener’ sources of commodity chemicals and fuels.

  12. Angular dependences of the tensor analyzing powers in the dd→3Hen reaction at intermediate energies

    International Nuclear Information System (INIS)

    Ladygin, V.P.; Ladygina, N.B.

    2002-01-01

    The tensor analyzing powers A yy , A xx , and A xz in the dd→ 3 Hen reaction at intermediate energies are considered in the framework of the one-nucleon-exchange approximation. Their strong sensitivity to the 3 He and deuteron spin structure at short distances is shown

  13. Intermediate and high energy nuclear reactions at the hadronic structural level

    Energy Technology Data Exchange (ETDEWEB)

    Slowinski, B [Institute of Physics, Warsaw, University of Technology, Poland, Institute of Atomic Energy, Swierk, (Poland)

    1997-12-31

    Form tens of MeV to several hundred of GeV is stretched out quite a large interval of energy when the interaction between hadrons (for instance, pion/nucleon-nucleus and nucleus-nucleus reactions) can be described by the considerably simplified way with still acceptable accuracy. This happens because in this energy region hadrons (i.e. pions, nucleons etc.) remain quasiparticles of nuclear matter mostly without revealing any internal structure, their de Broglie`s wavelength is much shorter as compared to the average intranuclear nucleon`s distance, and the energy transfers in the reaction are, on the average, significantly greater than the binding energy of nucleons inside nuclei. Consequently an approach to the analysis of these phenomena based on simple geometric and probabilistic considerations is justifiable, especially for many practical purposes, in particular, for shielding and dosimetric estimations, material behaviour prediction, as well as for the approximate evaluation of electronuclear breeding effects in different composites of target materials, for nuclear passivation problems and so on. In this work basic physical reasons of such a simplified picture of intermediate and high energy nuclear reactions are presented. The most usual phenomenological models of hadronic multiple emission/production and recent results of the cascade evaporation type models, are also discussed. 2 figs.

  14. Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III Reaction Intermediate Models of Peroxidase Enzymes

    Directory of Open Access Journals (Sweden)

    Samuel Hernández Anzaldo

    2016-06-01

    Full Text Available The spectroscopic and kinetic characterization of two intermediates from the H2O2 oxidation of three dimethyl ester [(proto, (meso, (deuteroporphyrinato (picdien]Fe(III complexes ([FePPPic], [FeMPPic] and [FeDPPic], respectively pinch-porphyrin peroxidase enzyme models, with s = 5/2 and 3/2 Fe(III quantum mixed spin (qms ground states is described herein. The kinetic study by UV/Vis at λmax = 465 nm showed two different types of kinetics during the oxidation process in the guaiacol test for peroxidases (1–3 + guaiacol + H2O2 → oxidation guaiacol products. The first intermediate was observed during the first 24 s of the reaction. When the reaction conditions were changed to higher concentration of pinch-porphyrins and hydrogen peroxide only one type of kinetics was observed. Next, the reaction was performed only between pinch-porphyrins-Fe(III and H2O2, resulting in only two types of kinetics that were developed during the first 0–4 s. After this time a self-oxidation process was observed. Our hypotheses state that the formation of the π-cation radicals, reaction intermediates of the pinch-porphyrin-Fe(III family with the ligand picdien [N,N’-bis-pyridin-2-ylmethyl-propane-1,3-diamine], occurred with unique kinetics that are different from the overall process and was involved in the oxidation pathway. UV-Vis, 1H-NMR and ESR spectra confirmed the formation of such intermediates. The results in this paper highlight the link between different spectroscopic techniques that positively depict the kinetic traits of artificial compounds with enzyme-like activity.

  15. A computational study of a recreated G protein-GEF reaction intermediate competent for nucleotide exchange: fate of the Mg ion.

    Directory of Open Access Journals (Sweden)

    Mériam Ben Hamida-Rebaï

    Full Text Available Small G-proteins of the superfamily Ras function as molecular switches, interacting with different cellular partners according to their activation state. G-protein activation involves the dissociation of bound GDP and its replacement by GTP, in an exchange reaction that is accelerated and regulated in the cell by guanine-nucleotide exchange factors (GEFs. Large conformational changes accompany the exchange reaction, and our understanding of the mechanism is correspondingly incomplete. However, much knowledge has been derived from structural studies of blocked or inactive mutant GEFs, which presumably closely represent intermediates in the exchange reaction and yet which are by design incompetent for carrying out the nucleotide exchange reaction. In this study we have used comparative modelling to recreate an exchange-competent form of a late, pre-GDP-ejection intermediate species in Arf1, a well-characterized small G-protein. We extensively characterized three distinct models of this intermediate using molecular dynamics simulations, allowing us to address ambiguities related to the mutant structural studies. We observed in particular the unfavorable nature of Mg2+ associated forms of the complex and the establishment of closer Arf1-GEF contacts in its absence. The results of this study shed light on GEF-mediated activation of this small G protein and on predicting the fate of the Mg ion at a critical point in the exchange reaction. The structural models themselves furnish additional targets for interfacial inhibitor design, a promising direction for exploring potentially druggable targets with high biological specificity.

  16. Reaction of iminopropadienones with amines--formation of zwitterionic intermediates, ketenes, and ketenimines.

    Science.gov (United States)

    Veedu, Rakesh Naduvile; Kokas, Okanya J; Couturier-Tamburelli, Isabelle; Koch, Rainer; Aycard, Jean-Pierre; Borget, Fabien; Wentrup, Curt

    2008-10-09

    Five aryliminopropadienones 4a- d have been synthesized by flash vacuum thermolysis (FVT) by using two different precursors in each case. These compounds were deposited at 50 K at a pressure of ca. 10(-6) mbar together with three different nucleophiles, namely, trimethylamine (TMA), dimethylamine (DMA), and diethylamine (DEA), in order to study their reactions as neat solids during warm-up by FTIR spectroscopy. The reaction with TMA showed that a zwitterionic species (5 and/or 6) was formed in all the cases. With DMA and DEA, an alpha-oxoketenimine and/or an imidoylketene (7 and 8 or 9 and 10) was formed as the final product. In addition, several bands were observed, which can be assigned to zwitterionic intermediates (11 or 12). Optimized structures and vibrational spectra for all products were calculated at the B3LYP/6-31G(d) level of theory by using the polarizable continuum model (epsilon = 5).

  17. Nitric oxide formation from the reaction of nitrite with carp and rabbit hemoglobin at intermediate oxygen saturations

    DEFF Research Database (Denmark)

    Jensen, Frank Bo

    2008-01-01

    The nitrite reductase activity of deoxyhemoglobin has received much recent interest because the nitric oxide produced in this reaction may participate in blood flow regulation during hypoxia. The present study used spectral deconvolution to characterize the reaction of nitrite with carp and rabbit...... hemoglobin at different constant oxygen tensions that generate the full range of physiological relevant oxygen saturations. Carp is a hypoxia-tolerant species with very high hemoglobin oxygen affinity, and the high R-state character and low redox potential of the hemoglobin is hypothesized to promote...... NO generation from nitrite. The reaction of nitrite with deoxyhemoglobin leads to a 1 : 1 formation of nitrosylhemoglobin and methemoglobin in both species. At intermediate oxygen saturations, the reaction with deoxyhemoglobin is clearly favored over that with oxyhemoglobin, and the oxyhemoglobin reaction...

  18. Kinetics and mechanisms of reactions involving small aromatic reactive intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Lin, M.C. [Emory Univ., Atlanta, GA (United States)

    1993-12-01

    Small aromatic radicals such as C{sub 6}H{sub 5}, C{sub 6}H{sub 5}O and C{sub 6}H{sub 4} are key prototype species of their homologs. C{sub 6}H{sub 5} and its oxidation product, C{sub 6}H{sub 5}O are believed to be important intermediates which play a pivotal role in hydrocarbon combustion, particularly with regard to soot formation. Despite their fundamental importance, experimental data on the reaction mechanisms and reactivities of these species are very limited. For C{sub 6}H{sub 5}, most kinetic data except its reactions with NO and NO{sub 2}, were obtained by relative rate measurements. For C{sub 6}H{sub 5}O, the authors have earlier measured its fragmentation reaction producing C{sub 5}H{sub 5} + CO in shock waves. For C{sub 6}H{sub 4}, the only rate constant measured in the gas phase is its recombination rate at room temperature. The authors have proposed to investigate systematically the kinetics and mechanisms of this important class of molecules using two parallel laser diagnostic techniques--laser resonance absorption (LRA) and resonance enhanced multiphoton ionization mass spectrometry (REMPI/MS). In the past two years, study has been focused on the development of a new multipass adsorption technique--the {open_quotes}cavity-ring-down{close_quotes} technique for kinetic applications. The preliminary results of this study appear to be quite good and the sensitivity of the technique is at least comparable to that of the laser-induced fluorescence method.

  19. Angular dependences of the tensor analyzing powers in the dd → 3Hen reaction at intermediate energies

    International Nuclear Information System (INIS)

    Ladygin, V.P.; Ladygina, N.B.; )

    2002-01-01

    The tensor analyzing powers A yy , A xx , and A xz in the dd → 3 Hen reaction at intermediate energies are considered in the framework of the one-nucleon-exchange approximation. Their strong sensitivity to the 3 He and deuteron spin structure at short distances is shown [ru

  20. Broadband Microwave Study of Reaction Intermediates and Products Through the Pyrolysis of Oxygenated Biofuels

    Science.gov (United States)

    Abeysekera, Chamara; Hernandez-Castillo, Alicia O.; Fritz, Sean; Zwier, Timothy S.

    2017-06-01

    The rapidly growing list of potential plant-derived biofuels creates a challenge for the scientific community to provide a molecular-scale understanding of their combustion. Development of accurate combustion models rests on a foundation of experimental data on the kinetics and product branching ratios of their individual reaction steps. Therefore, new spectroscopic tools are necessary to selectively detect and characterize fuel components and reactive intermediates generated by pyrolysis and combustion. Substituted furans, including furanic ethers, are considered second-generation biofuel candidates. Following the work of the Ellison group, an 8-18 GHz microwave study was carried out on the unimolecular and bimolecular decomposition of the smallest furanic ether, 2-methoxy furan, and it`s pyrolysis intermediate, the 2-furanyloxy radical, formed in a high-temperature pyrolysis source coupled to a supersonic expansion. Details of the experimental setup and analysis of the spectrum of the radical will be discussed.

  1. Perspective: Spectroscopy and kinetics of small gaseous Criegee intermediates

    International Nuclear Information System (INIS)

    Lee, Yuan-Pern

    2015-01-01

    The Criegee intermediates, carbonyl oxides proposed by Criegee in 1949 as key intermediates in the ozonolysis of alkenes, play important roles in many aspects of atmospheric chemistry. Because direct detection of these gaseous intermediates was unavailable until recently, previous understanding of their reactions, derived from indirect experimental evidence, had great uncertainties. Recent laboratory detection of the simplest Criegee intermediate CH 2 OO and some larger members, produced from ultraviolet irradiation of corresponding diiodoalkanes in O 2 , with various methods such as photoionization, ultraviolet absorption, infrared absorption, and microwave spectroscopy opens a new door to improved understanding of the roles of these Criegee intermediates. Their structures and spectral parameters have been characterized; their significant zwitterionic nature is hence confirmed. CH 2 OO, along with other products, has also been detected directly with microwave spectroscopy in gaseous ozonolysis reactions of ethene. The detailed kinetics of the source reaction, CH 2 I + O 2 , which is critical to laboratory studies of CH 2 OO, are now understood satisfactorily. The kinetic investigations using direct detection identified some important atmospheric reactions, including reactions with NO 2 , SO 2 , water dimer, carboxylic acids, and carbonyl compounds. Efforts toward the characterization of larger Criegee intermediates and the investigation of related reactions are in progress. Some reactions of CH 3 CHOO are found to depend on conformation. This perspective examines progress toward the direct spectral characterization of Criegee intermediates and investigations of the associated reaction kinetics, and indicates some unresolved problems and prospective challenges for this exciting field of research

  2. Workshop on hadron structure from photo-reactions at intermediate energies: Proceedings

    International Nuclear Information System (INIS)

    Nathan, A.M.; Sandorfi, A.M.

    1992-01-01

    This report contains papers on the following topics: The proton compton effect: Recent measurements of the electric and magnetic polorizabilities of the proton; experiments on the electric polarizability of the neutron; chiral symmetry and nucleon polarizabilities; chiral model predictions for electromagnetic polarizabilities of the nucleon, a consumer report; the polarizabilities of bound nucleons; nucleon polarizability in free space and in nuclear matter; mechanisms of photon scattering on nucleons at intermediate energies; pion polarizabilities in chiral perturbation theory; pion polarizabilities and the shielding of σ(700)-meson exchange in γγ→ππ processes; pion and kaon polarizabilities in the quark confinement model; radiative pion photoproduction and pion polarizabilities; pion and sigma polarizabilities and radiative transitions; the quadrupole amplitude in the γΝ-Δ transition; pion photoproduction and the γΝ-Δ amplitudes; effective- lagrangians, Watson's theorem, and the E2/M1 mixing ratio in the excitation of the delta resonance; new measurements of the p(rvec γ, π o ) reaction; multipole analyses and photo-decay couplings at intermediate energies; compton scattering off the proton; connections between compton scattering and pion photoproduction in the delta region; single-pion electroproduction and the transverse one-half and scalar helicity transition form factors; relativistic effects, QCD mixing angles, and Ν → Νγ and Δ → γΝ transition form factors; electroproduction studies of the Ν → Δ transition at bates and CEBAF

  3. Chemically activated formation of organic acids in reactions of the Criegee intermediate with aldehydes and ketones.

    Science.gov (United States)

    Jalan, Amrit; Allen, Joshua W; Green, William H

    2013-10-21

    Reactions of the Criegee intermediate (CI, ˙CH2OO˙) are important in atmospheric ozonolysis models. In this work, we compute the rates for reactions between ˙CH2OO˙ and HCHO, CH3CHO and CH3COCH3 leading to the formation of secondary ozonides (SOZ) and organic acids. Relative to infinitely separated reactants, the SOZ in all three cases is found to be 48-51 kcal mol(-1) lower in energy, formed via 1,3-cycloaddition of ˙CH2OO˙ across the C=O bond. The lowest energy pathway found for SOZ decomposition is intramolecular disproportionation of the singlet biradical intermediate formed from cleavage of the O-O bond to form hydroxyalkyl esters. These hydroxyalkyl esters undergo concerted decomposition providing a low energy pathway from SOZ to acids. Geometries and frequencies of all stationary points were obtained using the B3LYP/MG3S DFT model chemistry, and energies were refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. RRKM calculations were used to obtain microcanonical rate coefficients (k(E)) and the reservoir state method was used to obtain temperature and pressure dependent rate coefficients (k(T, P)) and product branching ratios. At atmospheric pressure, the yield of collisionally stabilized SOZ was found to increase in the order HCHO reactions were found to be the most sensitive parameters determining SOZ and organic acid yield.

  4. Angular distributions of intermediate mass fragments emitted in 30 MeV/u 40Ar induced reactions

    International Nuclear Information System (INIS)

    Gou Quanbu; Zhu Yongtai; Xu Hushan; Wei Zhiyong; Lu Jun; Zhang Yuhu; Wang Qi; Li Songlin; Wu Zhongli

    1999-01-01

    The angular distributions of intermediate mass fragments with charge numbers from 3 to 24 emitted in 30 MeV/u 40 Ar + 58,64 Ni and 115 In reactions over an angular range of 5 degree-140 degree have been measured. In different angular region an exponential distribution function dσ/dΩ = N exp(-θ/α) was used to fit the measured angular distributions. The decay factor α which can be connected with the interaction time τ and the factor N which is related to the intensity of the emission sources have been extracted. The relationship of α(Z) and N(Z) with Z for different reaction systems and different angular regions has been discussed. The different behavior of dσ/dΩ, α(Z), and N(Z) for the three studied reaction systems exists mainly in the middle and backward angular regions. The dependencies of angular distributions on isospin and the size of reaction systems have also been discussed

  5. Angular dependences of the tensor analyzing powers in the dd -> sup 3 Hen reaction at intermediate energies

    CERN Document Server

    Ladygin, V P

    2002-01-01

    The tensor analyzing powers A sub y sub y , A sub x sub x , and A sub x sub z in the dd -> sup 3 Hen reaction at intermediate energies are considered in the framework of the one-nucleon-exchange approximation. Their strong sensitivity to the sup 3 He and deuteron spin structure at short distances is shown

  6. Experimental determination of the effective nucleon-nucleon interaction for p-nucleus reactions at intermediate energies

    International Nuclear Information System (INIS)

    McClelland, J.B.; Aas, B.; Azizi, A.

    1982-01-01

    A complete measurement of the polarization transfer observables has been made for the first time in the (p,p') reaction at intermediate energies. Measurements are reported for the 12 C(p,p') 12 C reaction to the 1 + , T = 0(12.71 MeV) and 1 + , T = 1(15.11 MeV) states at 500 MeV at laboratory scattering angles of 3.5 0 , 5.5 0 , 7.5 0 , and 12.0 0 . Linear combinations of these observables are shown to exhibit a very selective dependence on the isoscalar and isovector spin-dependent components of the nucleon-nucleon interaction. To the extent of the validity of the single collision approximation, these amplitudes are compared directly to the free nucleon-nucleon amplitudes at small momentum transfers

  7. Detection of Reaction Intermediates in Mg2+-Dependent DNA Synthesis and RNA Degradation by Time-Resolved X-Ray Crystallography.

    Science.gov (United States)

    Samara, Nadine L; Gao, Yang; Wu, Jinjun; Yang, Wei

    2017-01-01

    Structures of enzyme-substrate/product complexes have been studied for over four decades but have been limited to either before or after a chemical reaction. Recently using in crystallo catalysis combined with X-ray diffraction, we have discovered that many enzymatic reactions in nucleic acid metabolism require additional metal ion cofactors that are not present in the substrate or product state. By controlling metal ions essential for catalysis, the in crystallo approach has revealed unprecedented details of reaction intermediates. Here we present protocols used for successful studies of Mg 2+ -dependent DNA polymerases and ribonucleases that are applicable to analyses of a variety of metal ion-dependent reactions. © 2017 Elsevier Inc. All rights reserved.

  8. Workshop on hadron structure from photo-reactions at intermediate energies: Proceedings

    Energy Technology Data Exchange (ETDEWEB)

    Nathan, A.M.; Sandorfi, A.M. [eds.

    1992-10-01

    This report contains papers on the following topics: The proton compton effect: Recent measurements of the electric and magnetic polorizabilities of the proton; experiments on the electric polarizability of the neutron; chiral symmetry and nucleon polarizabilities; chiral model predictions for electromagnetic polarizabilities of the nucleon, a consumer report; the polarizabilities of bound nucleons; nucleon polarizability in free space and in nuclear matter; mechanisms of photon scattering on nucleons at intermediate energies; pion polarizabilities in chiral perturbation theory; pion polarizabilities and the shielding of {sigma}(700)-meson exchange in {gamma}{gamma}{yields}{pi}{pi} processes; pion and kaon polarizabilities in the quark confinement model; radiative pion photoproduction and pion polarizabilities; pion and sigma polarizabilities and radiative transitions; the quadrupole amplitude in the {gamma}{Nu}-{Delta} transition; pion photoproduction and the {gamma}{Nu}-{Delta} amplitudes; effective- lagrangians, Watson`s theorem, and the E2/M1 mixing ratio in the excitation of the delta resonance; new measurements of the p({rvec {gamma}}, {pi}{sup o}) reaction; multipole analyses and photo-decay couplings at intermediate energies; compton scattering off the proton; connections between compton scattering and pion photoproduction in the delta region; single-pion electroproduction and the transverse one-half and scalar helicity transition form factors; relativistic effects, QCD mixing angles, and {Nu} {yields} {Nu}{gamma} and {Delta} {yields} {gamma}{Nu} transition form factors; electroproduction studies of the {Nu} {yields} {Delta} transition at bates and CEBAF.

  9. II. The intermediate velocity source in the 40Ca+40Ca reaction at Elab=35 AMeV

    International Nuclear Information System (INIS)

    Sosin, Z.; Planeta, R.; Ciszek, T.

    2001-01-01

    The shape of the velocity distributions of charged particles projected on the beam direction can be explained if emissions from the hot projectile-like fragment and the target-like fragment are supplemented by an emission from an intermediate velocity source located between them. The creation of this source is predicted by a two-stage reaction model where, in the second stage, some of the nucleons identified in the first stage as participants form a group of clusters located in the region between the colliding nuclei. The cluster coalescence process is governed on the average by the maximum value of entropy, although its fluctuations are also significant. The properties of the intermediate velocity source are precisely described, including the isotopic composition of the emitted particles. (orig.)

  10. Intermediate structure and threshold phenomena

    International Nuclear Information System (INIS)

    Hategan, Cornel

    2004-01-01

    The Intermediate Structure, evidenced through microstructures of the neutron strength function, is reflected in open reaction channels as fluctuations in excitation function of nuclear threshold effects. The intermediate state supporting both neutron strength function and nuclear threshold effect is a micro-giant neutron threshold state. (author)

  11. Heme-bound nitroxyl, hydroxylamine, and ammonia ligands as intermediates in the reaction cycle of cytochrome c nitrite reductase: a theoretical study.

    Science.gov (United States)

    Bykov, Dmytro; Plog, Matthias; Neese, Frank

    2014-01-01

    In this article, we consider, in detail, the second half-cycle of the six-electron nitrite reduction mechanism catalyzed by cytochrome c nitrite reductase. In total, three electrons and four protons must be provided to reach the final product, ammonia, starting from the HNO intermediate. According to our results, the first event in this half-cycle is the reduction of the HNO intermediate, which is accomplished by two PCET reactions. Two isomeric radical intermediates, HNOH(•) and H2NO(•), are formed. Both intermediates are readily transformed into hydroxylamine, most likely through intramolecular proton transfer from either Arg114 or His277. An extra proton must enter the active site of the enzyme to initiate heterolytic cleavage of the N-O bond. As a result of N-O bond cleavage, the H2N(+) intermediate is formed. The latter readily picks up an electron, forming H2N(+•), which in turn reacts with Tyr218. Interestingly, evidence for Tyr218 activity was provided by the mutational studies of Lukat (Biochemistry 47:2080, 2008), but this has never been observed in the initial stages of the overall reduction process. According to our results, an intramolecular reaction with Tyr218 in the final step of the nitrite reduction process leads directly to the final product, ammonia. Dissociation of the final product proceeds concomitantly with a change in spin state, which was also observed in the resonance Raman investigations of Martins et al. (J Phys Chem B 114:5563, 2010).

  12. Intermediate resonance excitation in the {gamma}p->p{pi}{sup 0}{pi}{sup 0} reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ahrens, J. [Institut fuer Kernphysik, Universitaet Mainz, D-55099 Mainz (Germany); Altieri, S. [INFN, Sezione di Pavia, I-27100 Pavia (Italy); Dipartimento di Fisica Nucleare e Teorica, Universita di Pavia, I-27100 Pavia (Italy); Annand, J.R.M. [Department of Physics and Astronomy, University of Glasgow (United Kingdom)] (and others)

    2005-09-29

    The helicity dependence of the total cross section for the {gamma}->p->->p{pi}{sup 0}{pi}{sup 0} reaction has been measured for the first time at incident photon energies from 400 to 800 MeV. The measurement, performed at the tagged photon beam facility of the MAMI accelerator in Mainz, used the large acceptance detector DAPHNE and a longitudinally polarized frozen-spin target. This channel is found to be excited predominantly when the photon and proton have a parallel spin orientation, most likely due to the intermediate production of the D{sub 13}(1520) resonance. However, the contribution of the antiparallel spin configuration, arising from other reaction mechanisms, is also not negligible. This result gives important new information to resolve the existing model discrepancies in the identification of the nucleon resonances contributing to this channel.

  13. Intermediate-energy nuclear chemistry workshop

    International Nuclear Information System (INIS)

    Butler, G.W.; Giesler, G.C.; Liu, L.C.; Dropesky, B.J.; Knight, J.D.; Lucero, F.; Orth, C.J.

    1981-05-01

    This report contains the proceedings of the LAMPF Intermediate-Energy Nuclear Chemistry Workshop held in Los Alamos, New Mexico, June 23-27, 1980. The first two days of the Workshop were devoted to invited review talks highlighting current experimental and theoretical research activities in intermediate-energy nuclear chemistry and physics. Working panels representing major topic areas carried out indepth appraisals of present research and formulated recommendations for future research directions. The major topic areas were Pion-Nucleus Reactions, Nucleon-Nucleus Reactions and Nuclei Far from Stability, Mesonic Atoms, Exotic Interactions, New Theoretical Approaches, and New Experimental Techniques and New Nuclear Chemistry Facilities

  14. Intermediate-energy nuclear chemistry workshop

    Energy Technology Data Exchange (ETDEWEB)

    Butler, G.W.; Giesler, G.C.; Liu, L.C.; Dropesky, B.J.; Knight, J.D.; Lucero, F.; Orth, C.J.

    1981-05-01

    This report contains the proceedings of the LAMPF Intermediate-Energy Nuclear Chemistry Workshop held in Los Alamos, New Mexico, June 23-27, 1980. The first two days of the Workshop were devoted to invited review talks highlighting current experimental and theoretical research activities in intermediate-energy nuclear chemistry and physics. Working panels representing major topic areas carried out indepth appraisals of present research and formulated recommendations for future research directions. The major topic areas were Pion-Nucleus Reactions, Nucleon-Nucleus Reactions and Nuclei Far from Stability, Mesonic Atoms, Exotic Interactions, New Theoretical Approaches, and New Experimental Techniques and New Nuclear Chemistry Facilities.

  15. Neutron-proton bremsstrahlung from intermediate energy heavy-ion reactions as a probe of the nuclear symmetry energy?

    International Nuclear Information System (INIS)

    Yong, G.-C.; Li Baoan; Chen Liewen

    2008-01-01

    Hard photons from neutron-proton bremsstrahlung in intermediate energy heavy-ion reactions are examined as a potential probe of the nuclear symmetry energy within a transport model. Effects of the symmetry energy on the yields and spectra of hard photons are found to be generally smaller than those due to the currently existing uncertainties of both the in-medium nucleon-nucleon cross sections and the photon production probability in the elementary process pn→pnγ. Very interestingly, nevertheless, the ratio of hard photon spectra R 1/2 (γ) from two reactions using isotopes of the same element is not only approximately independent of these uncertainties but also quite sensitive to the symmetry energy. For the head-on reactions of 132 Sn + 124 Sn and 112 Sn + 112 Sn at E beam /A=50 MeV, for example, the R 1/2 (γ) displays a rise up to 15% when the symmetry energy is reduced by about 20% at ρ=1.3ρ 0 which is the maximum density reached in these reactions

  16. On the chemistry of ethanol on basic oxides: revising mechanisms and intermediates in the Lebedev and Guerbet reactions.

    Science.gov (United States)

    Chieregato, Alessandro; Velasquez Ochoa, Juliana; Bandinelli, Claudia; Fornasari, Giuseppe; Cavani, Fabrizio; Mella, Massimo

    2015-01-01

    A common way to convert ethanol into chemicals is by upgrading it over oxide catalysts with basic features; this method makes it possible to obtain important chemicals such as 1-butanol (Guerbet reaction) and 1,3-butadiene (Lebedev reaction). Despite their long history in chemistry, the details of the close inter-relationship of these reactions have yet to be discussed properly. Our present study focuses on reactivity tests, in situ diffuse reflectance infrared Fourier transform spectroscopy, MS analysis, and theoretical modeling. We used MgO as a reference catalyst with pure basic features to explore ethanol conversion from its very early stages. Based on the obtained results, we formulate a new mechanistic theory able to explain not only our results but also most of the scientific literature on Lebedev and Guerbet chemistry. This provides a rational description of the intermediates shared by the two reaction pathways as well as an innovative perspective on the catalyst requirements to direct the reaction pathway toward 1-butanol or butadiene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Homoaromatics as intermediates in the substitution reactions of 1,2,4,5-tetrazines with ammonia and hydrazine

    International Nuclear Information System (INIS)

    Counotte-Potman, A.D.

    1981-01-01

    This thesis describes some nucleophilic substitution reactions between the red 1,2,4,5-tetrazines and hydrazine-hydrate or ammonia. Special attention was paid to the occurrence of the Ssub(N) (ANRORC) mechanism in these substitution reactions. This mechanism comprises a sequence of reactions, involving the Addition of a Nucleopile to a heteroaromatic species, followed by a Ring-Opening and Ring Closure reaction to the substitution product. 3-Alkyl(aryl)-1,2,4,5-tetrazines were found to undergo a Chichibabin hydrazination into 6-hydrazino-3-alkyl(aryl)-1,2,4,5-tetrazines on treatment with hydrazine-hydrate. The first step in this reaction sequence was the formation of a homoaromatic sigma-adduct. Subsequently an open-chain intermediate was observed by NMR, on raising the temperature. Finally the hydrazino compound is formed by ring closure. This reaction sequence can be considered as an Ssub(N)(ANRORC) process. With 15 N-labelled hydrazine, only part of the label was found to be built in the 1,2,4,5-tetrazine ring of the 6-hydrazino compounds. This is the first example of a reaction in which both the hydrazino compound with the 15 N-label in the ring and with the 15 N-label in the exocyclic hydrazino group are formed according to the Ssub(N)(ANRORC) mechanism. (Auth.)

  18. Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy

    KAUST Repository

    Michalak, William D.; Krier, James M.; Komvopoulos, Kyriakos; Somorjai, Gabor A.

    2013-01-01

    hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites. © 2012 American Chemical

  19. Does shoe heel design influence ground reaction forces and knee moments during maximum lunges in elite and intermediate badminton players?

    Directory of Open Access Journals (Sweden)

    Wing-Kai Lam

    Full Text Available Lunge is one frequently executed movement in badminton and involves a unique sagittal footstrike angle of more than 40 degrees at initial ground contact compared with other manoeuvres. This study examined if the shoe heel curvature design of a badminton shoe would influence shoe-ground kinematics, ground reaction forces, and knee moments during lunge.Eleven elite and fifteen intermediate players performed five left-forward maximum lunge trials with Rounded Heel Shoe (RHS, Flattened Heel Shoe (FHS, and Standard Heel Shoes (SHS. Shoe-ground kinematics, ground reaction forces, and knee moments were measured by using synchronized force platform and motion analysis system. A 2 (Group x 3 (Shoe ANOVA with repeated measures was performed to determine the effects of different shoes and different playing levels, as well as the interaction of two factors on all variables.Shoe effect indicated that players demonstrated lower maximum vertical loading rate in RHS than the other two shoes (P < 0.05. Group effect revealed that elite players exhibited larger footstrike angle, faster approaching speed, lower peak horizontal force and horizontal loading rates but higher vertical loading rates and larger peak knee flexion and extension moments (P < 0.05. Analysis of Interactions of Group x Shoe for maximum and mean vertical loading rates (P < 0.05 indicated that elite players exhibited lower left maximum and mean vertical loading rates in RHS compared to FHS (P < 0.01, while the intermediate group did not show any Shoe effect on vertical loading rates.These findings indicate that shoe heel curvature would play some role in altering ground reaction force impact during badminton lunge. The differences in impact loads and knee moments between elite and intermediate players may be useful in optimizing footwear design and training strategy to minimize the potential risks for impact related injuries in badminton.

  20. Extending the Kawai-Kerman-McVoy Statistical Theory of Nuclear Reactions to Intermediate Structure via Doorways

    International Nuclear Information System (INIS)

    Arbanas, Goran; Bertulani, C.A.; Dean, D.J.; Kerman, A.K.; Roche, K.J.

    2011-01-01

    Kawai, Kerman, and McVoy have shown that a statistical treatment of many open channels that are coupled by direct reactions leads to modifications of the Hauser- Feshbach expression for energy-averaged cross section (Ann. of Phys. 75 (1973) 156). The energy averaging interval for this cross section is on the order of the width of single particle resonances, 1MeV, revealing only a gross structure in the cross section. When the energy-averaging interval is decreased down to a width of a doorway state 0.1 MeV, a so-called intermediate structure may be observed in cross sections. We extend the Kawai-Kerman-McVoy theory into the intermediate structure by leveraging a theory of doorway states developed by Feshbach, Kerman, and Lemmer (Ann. of Phys. 42 (1967) 230). As a byproduct of the extension, an alternative derivation of the central result of the Kawai-Kerman-McVoy theory is suggested. We quantify the effect of the approximations used in derivation by performing numerical computations for a large set of compound nuclear states.

  1. Bacillus anthracis o-succinylbenzoyl-CoA synthetase: reaction kinetics and a novel inhibitor mimicking its reaction intermediate.

    Science.gov (United States)

    Tian, Yang; Suk, Dae-Hwan; Cai, Feng; Crich, David; Mesecar, Andrew D

    2008-11-25

    o-Succinylbenzoyl-CoA (OSB-CoA) synthetase (EC 6.2.1.26) catalyzes the ATP-dependent condensation of o-succinylbenzoate (OSB) and CoA to form OSB-CoA, the fourth step of the menaquinone biosynthetic pathway in Bacillus anthracis. Gene knockout studies have highlighted this enzyme as a potential target for the discovery of new antibiotics. Here we report the first studies on the kinetic mechanism of B. anthracis OSB-CoA synthetase, classifying it as an ordered bi uni uni bi ping-pong mechanism. Through a series of pre-steady-state and steady-state kinetic studies in conjunction with direct binding studies, it is demonstrated that CoA, the last substrate to bind, strongly activates the first half-reaction after the first round of turnover. The activation of the first half-reaction is most likely achieved by CoA stabilizing conformations of the enzyme in the "F" form, which slowly isomerize back to the E form. Thus, the kinetic mechanism of OSB-CoA synthetase may be more accurately described as an ordered bi uni uni bi iso ping-pong mechanism. The substrate specificity of OSB-CoA synthetase was probed using a series of OSB analogues with alterations in the carboxylate groups. OSB-CoA shows a strong preference for OSB over all of the analogues tested as none were active except 4-[2-(trifluoromethyl)phenyl]-4-oxobutyric acid which exhibited a 100-fold decrease in k(cat)/K(m). On the basis of an understanding of OSB-CoA synthetase's kinetic mechanism and substrate specificity, a reaction intermediate analogue of OSB-AMP, 5'-O-{N-[2-(trifluoromethyl)phenyl]-4-oxobutyl}adenosine sulfonamide (TFMP-butyl-AMS), was designed and synthesized. This inhibitor was found to be an uncompetitive inhibitor to CoA and a mixed-type inhibitor to ATP and OSB with low micromolar inhibition constants. Collectively, these results should serve as an important forerunner to more detailed and extensive inhibitor design studies aimed at developing lead compounds against the OSB-CoA synthetase

  2. Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

    Science.gov (United States)

    Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

    2017-11-21

    Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

  3. Cross-Aldol Reaction of Activated Carbonyls with Nitrosocarbonyl Intermediates: Stereoselective Synthesis toward α-Hydroxy-β-amino Esters and Amides.

    Science.gov (United States)

    Mallik, Sumitava; Bhajammanavar, Vinod; Ramakrishna, Isai; Baidya, Mahiuddin

    2017-07-21

    A practical and flexible strategy toward α-hydroxy-β-amino esters and amides, which are important biological motifs, based on an organocatalytic cross-aldol reaction of in situ-generated nitrosocarbonyl intermediates followed by hydrogenation is presented. The protocol features operational simplicity, high yields, a wide substrate scope, and high regio- and diastereoselectivity profiles. The utility of this method was showcased through the synthesis of bestatin analogues and indole formation.

  4. Computational Chemical Kinetics for the Reaction of Criegee Intermediate CH2OO with HNO3 and Its Catalytic Conversion to OH and HCO.

    Science.gov (United States)

    Raghunath, P; Lee, Yuan-Pern; Lin, M C

    2017-05-25

    The kinetics and mechanisms for the reaction of the Criegee intermediate CH 2 OO with HNO 3 and the unimolecular decomposition of its reaction product CH 2 (O)NO 3 are important in atmospheric chemistry. The potential-energy profile of the reactions predicted with the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ method shows that the initial association yields a prereaction complex that isomerizes by H migration to yield excited intermediate nitrooxymethyl hydroperoxide NO 3 CH 2 OOH* with internal energy ∼44 kcal mol -1 . A fragmentation of this excited intermediate produces CH 2 (O)NO 3 + OH with its transition state located 5.0 kcal mol -1 below that of the reactants. Further decomposition of CH 2 (O)NO 3 produces HCO + HNO 3 , forming a catalytic cycle for destruction of CH 2 OO by HNO 3 . The rate coefficients and product-branching ratios were calculated in the temperature range 250-700 K at pressure 20-760 Torr (N 2 ) using the variational-transition-state and Rice-Ramsperger-Kassel-Marcus (RRKM) theories. The predicted total rate coefficient for reaction CH 2 OO + HNO 3 at 295 K, 5.1 × 10 -10 cm 3 molecule -1 s -1 , agrees satisfactorily with the experimental value, (5.4 ± 1.0) × 10 -10 cm 3 molecule -1 s -1 . The predicted branching ratios at 295 K are 0.21 for the formation of NO 3 CH 2 OOH and 0.79 for CH 2 (O)NO 3 + OH at a pressure of 40 Torr (N 2 ), and 0.79 for the formation of NO 3 CH 2 OOH and 0.21 for CH 2 (O)NO 3 + OH at 760 Torr (N 2 ). This new catalytic conversion of CH 2 OO to HCO + OH by HNO 3 might have significant impact on atmospheric chemistry.

  5. Investigation of the O+allyl addition/elimination reaction pathways from the OCH2CHCH2 radical intermediate

    International Nuclear Information System (INIS)

    FitzPatrick, Benjamin L.; Lau, K.-C.; Butler, Laurie J.; Lee, S.-H.; Lin, Jim Jr-Min

    2008-01-01

    These experiments study the preparation of and product channels resulting from OCH 2 CHCH 2 , a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH 2 CHCH 2 radicals; these undergo a facile ring opening to the OCH 2 CHCH 2 radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcal/mol. To elucidate the product channels resulting from the OCH 2 CHCH 2 radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C 3 H 4 O (acrolein)+H, C 2 H 4 +HCO (formyl radical), and H 2 CO (formaldehyde)+C 2 H 3 . A small signal from C 2 H 2 O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at m/e=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C 2 H 5 +CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to

  6. Investigation of the O+allyl addition/elimination reaction pathways from the OCH2CHCH2 radical intermediate

    Science.gov (United States)

    Fitzpatrick, Benjamin L.; Lau, Kai-Chung; Butler, Laurie J.; Lee, Shih-Huang; Lin, Jim-Min, Jr.

    2008-08-01

    These experiments study the preparation of and product channels resulting from OCH2CHCH2, a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH2CHCH2 radicals; these undergo a facile ring opening to the OCH2CHCH2 radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcal/mol. To elucidate the product channels resulting from the OCH2CHCH2 radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C3H4O (acrolein)+H, C2H4+HCO (formyl radical), and H2CO (formaldehyde)+C2H3. A small signal from C2H2O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at m/e=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C2H5+CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to each of these product channels

  7. Does shoe heel design influence ground reaction forces and knee moments during maximum lunges in elite and intermediate badminton players?

    Science.gov (United States)

    Lam, Wing-Kai; Ryue, Jaejin; Lee, Ki-Kwang; Park, Sang-Kyoon; Cheung, Jason Tak-Man; Ryu, Jiseon

    2017-01-01

    Lunge is one frequently executed movement in badminton and involves a unique sagittal footstrike angle of more than 40 degrees at initial ground contact compared with other manoeuvres. This study examined if the shoe heel curvature design of a badminton shoe would influence shoe-ground kinematics, ground reaction forces, and knee moments during lunge. Eleven elite and fifteen intermediate players performed five left-forward maximum lunge trials with Rounded Heel Shoe (RHS), Flattened Heel Shoe (FHS), and Standard Heel Shoes (SHS). Shoe-ground kinematics, ground reaction forces, and knee moments were measured by using synchronized force platform and motion analysis system. A 2 (Group) x 3 (Shoe) ANOVA with repeated measures was performed to determine the effects of different shoes and different playing levels, as well as the interaction of two factors on all variables. Shoe effect indicated that players demonstrated lower maximum vertical loading rate in RHS than the other two shoes (P badminton lunge. The differences in impact loads and knee moments between elite and intermediate players may be useful in optimizing footwear design and training strategy to minimize the potential risks for impact related injuries in badminton.

  8. Bioorthogonal Cycloadditions with Sub-Millisecond Intermediates.

    Science.gov (United States)

    Qing, Yujia; Pulcu, Gökçe Su; Bell, Nicholas A W; Bayley, Hagan

    2018-01-26

    Tetrazine- and sydnone-based click reactions have emerged as important bioconjugation strategies with fast kinetics and N 2 or CO 2 as the only byproduct. Mechanistic studies of these reactions have focused on the initial rate-determining cycloaddition steps. The subsequent N 2 or CO 2 release from the bicyclic intermediates has been approached mainly through computational studies, which have predicted lifetimes of femtoseconds. In the present study, bioorthogonal cycloadditions involving N 2 or CO 2 extrusion have been examined experimentally at the single-molecule level by using a protein nanoreactor. At the resolution of this approach, the reactions appeared to occur in a single step, which places an upper limit on the lifetimes of the intermediates of about 80 μs, which is consistent with the computational work. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Quantum Chemical Investigation of the Transition States and Intermediates for the Reaction of the Nitrosonium Ion with the Pentaammineazidocobalt(III) Ion.

    Science.gov (United States)

    Rotzinger, François P

    2016-12-19

    The water exchange reaction on Co(NH 3 ) 5 OH 2 3+ was investigated with various density functionals and basis sets. A Gibbs activation energy (ΔG ⧧ ) agreeing with experiment was obtained with the long-range-corrected functionals ωB97X-D3 and LC-BOP-LRD, SMD hydration, and modified Karlsruhe def2-TZVP basis sets. This computational technique was then applied to the reaction of NO + with Co(NH 3 ) 5 N 3 2+ . All of the possible pathways were investigated, NO + attack at the terminal N of Co(NH 3 ) 5 N 3 2+ via the E and the Z isomers of the transition states, and NO + attack at the bound N of azide, also via both isomers. The most favorable pathway proceeds via the attack at the bound N via the Z isomer. This leads to the intermediate with an oxatetrazole ligand bound to Co(III) at the N in the 3-position, Co(NH 3 ) 5 (cycl-N 4 O) 3+ , which undergoes N 2 elimination to yield the Co(NH 3 ) 5 N 2 O 3+ intermediate. The subsequent substitution of N 2 O by water follows the I d mechanism with retention of the configuration. No evidence for the existence of the square-pyramidal pentacoordinated intermediate Co(NH 3 ) 5 3+ was found. All of the investigated intermediates, Co(NH 3 ) 5 N 2 3+ , Co(NH 3 ) 5 [E-N(N 2 )(NO)] 3+ , Co(NH 3 ) 5 (E-ON 4 ) 3+ , Co(NH 3 ) 5 ON 2 3+ , Co(NH 3 ) 5 (cycl-N 4 O) 3+ , and Co(NH 3 ) 5 N 2 O 3+ , exhibit short lifetimes of less than ∼60 μs and react via the I d mechanism.

  10. The major/minor concept: dependence of the selectivity of homogeneously catalyzed reactions on reactivity ratio and concentration ratio of the intermediates.

    Science.gov (United States)

    Schmidt, Thomas; Dai, Zhenya; Drexler, Hans-Joachim; Hapke, Marko; Preetz, Angelika; Heller, Detlef

    2008-07-07

    The homogeneously catalyzed asymmetric hydrogenation of prochiral olefins with cationic Rh(I) complexes is one of the best-understood selection processes. For some of the catalyst/substrate complexes, experimental proof points out the validation of the major/minor principle; the concentration-deficient minor substrate complex, which has very high reactivity, yields the excess enantiomer. As exemplified by the reaction system of [Rh(dipamp)(MeOH)2]+/methyl (Z)-alpha-acetamidocinnamate (dipamp=1,2-bis((o-methoxyphenyl)phenylphosphino)ethane), all six of the characteristic reaction rate constants have been previously identified. Recently, it was found that the major substrate complex can also yield the major enantiomer (lock-and-key principle). The differential equation system that results from the reaction sequence can be solved numerically for different hydrogen partial pressures by including the known equilibrium constants. The result displays the concentration-time dependence of all species that exist in the catalytic cycle. On the basis of the known constants as well as further experimental evidence, this work focuses on the examination of all principal possibilities resulting from the reaction sequence and leading to different results for the stereochemical outcome. From the simulation, the following conclusions can be drawn: 1) When an intermediate has extreme reactivity, its stationary concentration can become so small that it can no longer be the source of product selectivity; 2) in principle, the major/minor and lock-and-key principles can coexist depending on the applied pressure; 3) thermodynamically determined intermediate ratios can be completely converted under reaction conditions for a selection process; and 4) the increase in enantioselectivity with increasing hydrogen partial pressure, a phenomenon that is experimentally proven but theoretically far from being well-understood, can be explained by applying both the lock-and-key as well as the major

  11. Catecholase activity of dicopper(II)-bispidine complexes: stabilities and structures of intermediates, kinetics and reaction mechanism.

    Science.gov (United States)

    Born, Karin; Comba, Peter; Daubinet, André; Fuchs, Alexander; Wadepohl, Hubert

    2007-01-01

    A mechanism for the oxidation of 3,5-di-tert-butylcatechol (dtbc) with dioxygen to the corresponding quinone (dtbq), catalyzed by bispidine-dicopper complexes (bispidines are various mono- and dinucleating derivatives of 3,7-diazabicyclo[3.3.1]nonane with bis-tertiary-amine-bispyridyl or bis-tertiary-amine-trispyridyl donor sets), is proposed on the basis of (1) the stoichiometry of the reaction as well as the stabilities and structures [X-ray, density functional theory (B3LYP, TZV)] of the bispidine-dicopper(II)-3,4,5,6-tetrachlorcatechol intermediates, (2) formation kinetics and structures (molecular mechanics, MOMEC) of the end-on peroxo-dicopper(II) complexes and (3) kinetics of the stoichiometric (anaerobic) and catalytic (aerobic) copper-complex-assisted oxidation of dtbc. This involves (1) the oxidation of the dicopper(I) complexes with dioxygen to the corresponding end-on peroxo-dicopper(II) complexes, (2) coordination of dtbc as a bridging ligand upon liberation of H(2)O(2) and (3) intramolecular electron transfer to produce dtbq, which is liberated, and the dicopper(I) catalyst. Although the bispidine complexes have reactivities comparable to those of recently published catalysts with macrocyclic ligands, which seem to reproduce the enzyme-catalyzed process in various reaction sequences, a strikingly different oxidation mechanism is derived from the bispidine-dicopper-catalyzed reaction.

  12. Isoporphyrin Intermediate in Heme Oxygenase Catalysis

    Science.gov (United States)

    Evans, John P.; Niemevz, Fernando; Buldain, Graciela; de Montellano, Paul Ortiz

    2008-01-01

    Human heme oxygenase-1 (hHO-1) catalyzes the O2- and NADPH-dependent oxidation of heme to biliverdin, CO, and free iron. The first step involves regiospecific insertion of an oxygen atom at the α-meso carbon by a ferric hydroperoxide and is predicted to proceed via an isoporphyrin π-cation intermediate. Here we report spectroscopic detection of a transient intermediate during oxidation by hHO-1 of α-meso-phenylheme-IX, α-meso-(p-methylphenyl)-mesoheme-III, and α-meso-(p-trifluoromethylphenyl)-mesoheme-III. In agreement with previous experiments (Wang, J., Niemevz, F., Lad, L., Huang, L., Alvarez, D. E., Buldain, G., Poulos, T. L., and Ortiz de Montellano, P. R. (2004) J. Biol. Chem. 279, 42593–42604), only the α-biliverdin isomer is produced with concomitant formation of the corresponding benzoic acid. The transient intermediate observed in the NADPH-P450 reductase-catalyzed reaction accumulated when the reaction was supported by H2O2 and exhibited the absorption maxima at 435 and 930 nm characteristic of an isoporphyrin. Product analysis by reversed phase high performance liquid chromatography and liquid chromatography electrospray ionization mass spectrometry of the product generated with H2O2 identified it as an isoporphyrin that, on quenching, decayed to benzoylbiliverdin. In the presence of H218O2, one labeled oxygen atom was incorporated into these products. The hHO-1-isoporphyrin complexes were found to have half-lives of 1.7 and 2.4 h for the p-trifluoromethyl- and p-methyl-substituted phenylhemes, respectively. The addition of NADPH-P450 reductase to the H2O2-generated hHO-1-isoporphyrin complex produced α-biliverdin, confirming its role as a reaction intermediate. Identification of an isoporphyrin intermediate in the catalytic sequence of hHO-1, the first such intermediate observed in hemoprotein catalysis, completes our understanding of the critical first step of heme oxidation. PMID:18487208

  13. Bacillus anthracis o-succinylbenzoyl-CoA synthetase: reaction kinetics and a novel inhibitor mimicking its reaction intermediate

    Science.gov (United States)

    Tian, Yang; Suk, Dae-Hwan; Cai, Feng; Crich, David; Mesecar, Andrew D.

    2009-01-01

    O-succinylbenzoyl-CoA (OSB-CoA) synthetase (EC 6.2.1.26) catalyzes the ATP-dependent condensation of o-succinylbenzoate (OSB) and CoA to form OSB-CoA, the fourth step of the menaquinone biosynthetic pathway in Bacillus anthracis. Gene knockout studies have highlighted this enzyme as a potential target for the discovery of new antibiotics. Here we report the first studies on the kinetic mechanism of B. anthracis OSB-CoA synthetase, classifying it as an ordered Bi Uni Uni Bi ping-pong mechanism. Through a series of pre-steady-state and steady-state kinetic studies in conjunction with direct-binding studies, it is demonstrated that CoA, the last substrate to bind, strongly activates the first half-reaction after the first round of turnover. The activation of the first-half reaction is most likely achieved by CoA stabilizing conformations of the enzyme in the ‘F’ form, which slowly isomerize back to the E form. Thus, the kinetic mechanism of OSB-CoA synthetase may be more accurately described as an ordered Bi Uni Uni Bi Iso ping-pong mechanism. The substrate specificity of OSB-CoA synthetase was probed using a series of OSB analogs with alterations in the carboxylate groups. OSB-CoA shows a strong preference for OSB over all of the analogs tested as none were active except 4-(2-trifluoromethylphenyl)-4-oxobutyric acid which exhibited a 100-fold decrease in kcat/Km. Based on an understanding of OSB-CoA synthetase’s kinetic mechanism and substrate specificity, a reaction intermediate analog of OSB-AMP, 5’-O-(N-(2-trifluoromethylphenyl)-4-oxobutyl) adenosine sulfonamide (TFMP-butyl-AMS), was designed and synthesized. This inhibitor was found to be an uncompetitive inhibitor to CoA and a mixed-type inhibitor to ATP and OSB with low micromolar inhibition constants. Collectively, these results should serve as an important forerunner to more detailed and extensive inhibitor design studies aimed at developing lead compounds against the OSB-CoA synthetase class of

  14. Intermediate behaviour of reaction mechanisms in 27Al + 63Cu collisions at 13.4 MeV/nucleon

    International Nuclear Information System (INIS)

    Bougault, R.

    1983-09-01

    This experiment aimed to investigate the nuclear reaction mechanisms in the energy transition region between 10 and 20 MeV/Nucleon. So, collisions between 27 Al (projectile) and 63 Cu (target) were studied for a bombarding energy of 13.4 MeV/nucleon. For that purpose, projectile-like fragments were detected at the grazing angle (thetasub(g)) for that system by a spectrometer and an E-ΔE telescope. A second telescope was set at various angles for light particle detection; both inclusive and coincident measurements were performed. Isotope production at angle thetasub(g) cannot be clearly explained neither by inelastic transfers nor by ''cold'' projectile fragmentation. This production seems rather to occur through an intermediate process where the Al nucleus is slowed down, and excited, and then dissociates. Moreover, kinematical correlations between fragments show evidence for a mechanism where the projectile is splitted after picking up some nucleons to the target. Finally, light particles are shown to araise essentially from a fusion-like system thermalized at T=3,5 MeV; such a temperature may be considered as an intermediate value [fr

  15. Formation of Reactive Intermediates, Color, and Antioxidant Activity in the Maillard Reaction of Maltose in Comparison to d-Glucose.

    Science.gov (United States)

    Kanzler, Clemens; Schestkowa, Helena; Haase, Paul T; Kroh, Lothar W

    2017-10-11

    In this study, the Maillard reaction of maltose and d-glucose in the presence of l-alanine was investigated in aqueous solution at 130 °C and pH 5. The reactivity of both carbohydrates was compared in regards of their degradation, browning, and antioxidant activity. In order to identify relevant differences in the reaction pathways, the concentrations of selected intermediates such as 1,2-dicarbonyl compounds, furans, furanones, and pyranones were determined. It was found, that the degradation of maltose predominantly yields 1,2-dicarbonyls that still carry a glucosyl moiety and thus subsequent reactions to HMF, furfural, and 2-acetylfuran are favored due to the elimination of d-glucose, which is an excellent leaving group in aqueous solution. Consequently, higher amounts of these heterocycles are formed from maltose. 3-deoxyglucosone and 3-deoxygalactosone represent the only relevant C 6 -1,2-dicarbonyls in maltose incubations and are produced in nearly equimolar amounts during the first 60 min of heating as byproducts of the HMF formation.

  16. Surface intermediates on metal electrodes at high temperatures

    DEFF Research Database (Denmark)

    Zachau-Christiansen, Birgit; Jacobsen, Torben; Bay, Lasse

    1998-01-01

    The mechanisms widely conceived for the O(2)-reduction or H(2)-oxidation reactions in SOFC's involve intermediate O/H species adsorbed on the electrode surface. The presence of these intermediates is investigated by linear sweep voltammetry. In air at moderate temperatures (500 degrees C) Pt...

  17. Intermediate nuclear structure for 2ν2β decay of 48Ca studied by (p, n) and (n, p) reactions at 300 MeV

    International Nuclear Information System (INIS)

    Sakai, H.; Yako, K.

    2009-01-01

    The two neutrino double beta (2ν2β) decay proceeds through a sequence of Gamow-Teller (GT) transitions, namely from the parent nucleus to the intermediate nucleus and then from the intermediate nucleus to the final daughter nucleus. The nuclear matrix element M 2ν for the 2ν2β - decay thus consists of the 2β - decay matrix elements for the parent nucleus decay and the 2β - decay matrix elements for the intermediate nucleus decay. These 2β - decay matrix elements can be studied experimentally through the (p, n) reaction for the parent nucleus decay and the (n, p) reaction for the intermediate nucleus decay. The 2ν2β-decay nucleus, 4 8C a is studied. The charge exchange (p, n) and (n, p) measurements at 300 MeV were performed using the neutron time-of-flight facility and the (n,p) facility, respectively, at RCNP. The (p, n) measurement on 4 8C a and the (n,p) measurement on 4 8T i provided us, for the first time, reliable B(GT - ) and B(GT + ) strength distributions up to high excitation energy of 30 MeV of the intermediate nucleus 4 8S c. The multipole decomposition analysis was applied to the angular distributions of the cross section spectra to extract the ΔL = 0 components, which are used to deduce B(GT ± ). Figure shows the double differential cross Nb sections for 4 8C a(p, n)4 8S c (left panel) and 4 8T i(n,p)4 8S c (right panel) reactions. The histograms show the results of the multi-pole decomposition analyses. It is very surprising to find sizable amount of ΔL = 0 yield, i.e. B(GT + ) strength in the highly excited energy region (> 10 MeV). The obtained B(GT ± ) distribution in 4 8S c as well as corresponding nuclear matrix elements M 2ν are compared with theoretical shell model calculation. In this talk, new results will be presented and their implication to the nuclear matrix elements for the 2ν2β-decay will be discussed (author)

  18. A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states

    International Nuclear Information System (INIS)

    Nguyen, Trong-Nghia; Putikam, Raghunath; Lin, M. C.

    2015-01-01

    We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH 2 OO and anti/syn-CH 3 C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH 2 OO and anti-CH 3 C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH 3 C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring C–H bonds. For syn-CH 3 C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH 3 group by the terminal O atom producing CH 2 C(H)O–OH. At 298 K, the intramolecular insertion process in CH 2 OO was found to be 600 times faster than the commonly assumed ring-closing reaction

  19. Reactivity of Criegee Intermediates toward Carbon Dioxide.

    Science.gov (United States)

    Lin, Yen-Hsiu; Takahashi, Kaito; Lin, Jim Jr-Min

    2018-01-04

    Recent theoretical work by Kumar and Francisco suggested that the high reactivity of Criegee intermediates (CIs) could be utilized for designing efficient carbon capture technologies. Because the anti-CH 3 CHOO + CO 2 reaction has the lowest barrier in their study, we chose to investigate it experimentally. We probed anti-CH 3 CHOO with its strong UV absorption at 365 nm and measured the rate coefficient to be ≤2 × 10 -17 cm 3 molecule -1 s -1 at 298 K, which is consistent with our theoretical value of 2.1 × 10 -17 cm 3  molecule -1 s -1 at the QCISD(T)/CBS//B3LYP/6-311+G(2d,2p) level but inconsistent with their results obtained at the M06-2X/aug-cc-pVTZ level, which tends to underestimate the barrier heights. The experimental result indicates that the reaction of a Criegee intermediate with atmospheric CO 2 (400 ppmv) would be inefficient (k eff < 0.2 s -1 ) and cannot compete with other decay processes of Criegee intermediates like reactions with water vapor (∼10 3 s -1 ) or thermal decomposition (∼10 2 s -1 ).

  20. Surface Intermediates on Metal Electrodes at High Temperature

    DEFF Research Database (Denmark)

    Zachau-Christiansen, Birgit; Jacobsen, Torben; Bay, Lasse

    1997-01-01

    The mechanisms widely suggested for the O2-reduc-tion or H2-oxidation SOFC reactions involve inter-mediate O/H species adsorbed on the electrode surface. The presence of these intermediates is investigated by linear sweep voltammetry. In airat moderate temperatures (500øC) Pt in contact with YSZ...

  1. Role of interference of states of intermediate nuclei in exchange processes

    International Nuclear Information System (INIS)

    Belyaeva, T.L.; Zelenskaya, N.S.; Teplov, I.B.

    1982-01-01

    Role of interference of intermediate nucleus states for exchange processes in reactions with alpha particles on 11 B, 7 Li and 6 Li light nuclei was investigated when considering exactly the process dynamics in the method of distorted waves with a finite interaction radius. The process dynamics, in particular, the overlapping degree of wave functions of bound states and interaction potentials, affects considerably the reaction cross section in the rections with alpha particles on nuclei of 1p shell. If in the reaction selection rules permit the excitation of components of intermediate system states with maximum values of #betta# 1 and #betta# 2 orbital moments at the given N 1 and N 2 , the contribution of such components to the cross section will be determining. When components of intermediate system states with maximum #betta# 1 (or #betta# 2 ) are forbidden with selection rules, several intermediate states can have approximately similar overlapping integrals

  2. Flavin-N5 Covalent Intermediate in a Nonredox Dehalogenation Reaction Catalyzed by an Atypical Flavoenzyme.

    Science.gov (United States)

    Dai, Yumin; Kizjakina, Karina; Campbell, Ashley C; Korasick, David A; Tanner, John J; Sobrado, Pablo

    2018-01-04

    The flavin-dependent enzyme 2-haloacrylate hydratase (2-HAH) catalyzes the conversion of 2-chloroacrylate, a major component in the manufacture of acrylic polymers, to pyruvate. The enzyme was expressed in Escherichia coli, purified, and characterized. 2-HAH was shown to be monomeric in solution and contained a non-covalent, yet tightly bound, flavin adenine dinucleotide (FAD). Although the catalyzed reaction was redox-neutral, 2-HAH was active only in the reduced state. A covalent flavin-substrate intermediate, consistent with the flavin-acrylate iminium ion, was trapped with cyanoborohydride and characterized by mass spectrometry. Small-angle X-ray scattering was consistent with 2-HAH belonging to the succinate dehydrogenase/fumarate reductase family of flavoproteins. These studies establish 2-HAH as a novel noncanonical flavoenzyme. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Secondary Interactions Arrest the Hemiaminal Intermediate To Invert the Modus Operandi of Schiff Base Reaction: A Route to Benzoxazinones.

    Science.gov (United States)

    Patel, Ketan; Deshmukh, Satej S; Bodkhe, Dnyaneshwar; Mane, Manoj; Vanka, Kumar; Shinde, Dinesh; Rajamohanan, Pattuparambil R; Nandi, Shyamapada; Vaidhyanathan, Ramanathan; Chikkali, Samir H

    2017-04-21

    Discovered by Hugo Schiff, condensation between amine and aldehyde represents one of the most ubiquitous reactions in chemistry. This classical reaction is widely used to manufacture pharmaceuticals and fine chemicals. However, the rapid and reversible formation of Schiff base prohibits formation of alternative products, of which benzoxazinones are an important class. Therefore, manipulating the reactivity of two partners to invert the course of this reaction is an elusive target. Presented here is a synthetic strategy that regulates the sequence of Schiff base reaction via weak secondary interactions. Guided by the computational models, reaction between 2,3,4,5,6-pentafluoro-benzaldehyde with 2-amino-6-methylbenzoic acid revealed quantitative (99%) formation of 5-methyl-2-(perfluorophenyl)-1,2-dihydro-4H-benzo[d][1,3]oxazin-4-one (15). Electron donating and electron withdrawing ortho-substituents on 2-aminobenzoic acid resulted in the production of benzoxazinones 9-36. The mode of action was tracked using low temperature NMR, UV-vis spectroscopy, and isotopic ( 18 O) labeling experiments. These spectroscopic mechanistic investigations revealed that the hemiaminal intermediate is arrested by the hydrogen-bonding motif to yield benzoxazinone. Thus, the mechanistic investigations and DFT calculations categorically rule out the possibility of in situ imine formation followed by ring-closing, but support instead hydrogen-bond assisted ring-closing to prodrugs. This unprecedented reaction represents an interesting and competitive alternative to metal catalyzed and classical methods of preparing benzoxazinone.

  4. Singlet channel coupling in deuteron elastic scattering at intermediate energies

    International Nuclear Information System (INIS)

    Al-Khalili, J.S.; Tostevin, J.A.; Johnson, R.C.

    1990-01-01

    Intermediate energy deuteron elastic scattering is investigated in a three-body model incorporating relativistic kinematics. The effects of deuteron breakup to singlet spin intermediate states, on the elastic scattering observables for the 58 Ni(d vector, d) 58 Ni reaction at 400 and 700 MeV, are studied quantitatively. The singlet-breakup contributions to the elastic amplitude are estimated within an approximate two-step calculation. The calculation makes an adiabatic approximation in the intermediate states propagator which allows the use of closure over the np intermediate states continuum. The singlet channel coupling is found to produce large effects on the calculated reaction tensor analysing power A yy , characteristic of a dynamically induced second-rank tensor interaction. By inspection of the calculated breakup amplitudes we show this induced interaction to be of the T L tensor type. (orig.)

  5. Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study

    Directory of Open Access Journals (Sweden)

    Shinichi Yamabe

    2014-01-01

    Full Text Available Wolff–Kishner reduction reactions were investigated by DFT calculations for the first time. B3LYP/6-311+G(d,p SCRF=(PCM, solvent = 1,2-ethanediol optimizations were carried out. To investigate the role of the base catalyst, the base-free reaction was examined by the use of acetone, hydrazine (H2N–NH2 and (H2O8. A ready reaction channel of acetone → acetone hydrazine (Me2C=N–NH2 was obtained. The channel involves two likely proton-transfer routes. However, it was found that the base-free reaction was unlikely at the N2 extrusion step from the isopropyl diimine intermediate (Me2C(H–N=N–H. Two base-catalyzed reactions were investigated by models of the ketone, H2N–NH2 and OH−(H2O7. Here, ketones are acetone and acetophenone. While routes of the ketone → hydrazone → diimine are similar, those from the diimines are different. From the isopropyl diimine, the N2 extrusion and the C–H bond formation takes place concomitantly. The concomitance leads to the propane product concertedly. From the (1-phenylethyl substituted diimine, a carbanion intermediate is formed. The para carbon of the phenyl ring of the anion is subject to the protonation, which leads to a 3-ethylidene-1,4-cyclohexadiene intermediate. Its [1,5]-hydrogen migration gives the ethylbenzene product. For both ketone substrates, the diimines undergoing E2 reactions were found to be key intermediates.

  6. Mechanism of ({sup 14}N, {sup 12}B) reactions at intermediate energy leading to large spin-polarization of {sup 12}B

    Energy Technology Data Exchange (ETDEWEB)

    Mitsuoka, Shin-ichi [Osaka Univ., Ibaraki (Japan). Research Center for Nuclear Physics; Shimoda, Tadashi; Miyatake, Hiroari [and others

    1996-05-01

    To study mechanisms of the ({sup 14}N, {sup 12}B) reactions at intermediate energies, double differential cross section and nuclear spin-polarization of the {sup 12}B projectile-like fragments have been measured as a function of longitudinal momentum in the angular range of 0deg - 9deg. Large spin-polarization of the reaction products {sup 12}B has been observed in the {sup 9}Be({sup 14}N, {sup 12}B) reaction at 39.3 MeV/u. The momentum distributions at forward angles exhibit characteristic features which can not be understood by the current projectile fragmentation picture. It is shown that by assuming the existence of direct two-proton transfer process in addition to the fragmentation process, both the cross section and polarization of {sup 12}B fragments are successfully explained. The target and incident energy dependence of the momentum distribution are also explained reasonably. (author)

  7. Approach to photocatalysis at the molecular level. Design of photocatalysts, detection of intermediate species, and reaction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Anpo, Masakazu [Department of Applied Chemistry, University of Osaka Prefecture, Gakuen-cho, Sakai, Osaka (Japan)

    1995-08-01

    The characterization of the Cu{sup +}/ZSM-5 catalysts prepared via reduction of ion-exchanged Cu{sup 2+}/ZSM-5 samples and highly dispersed Ti-oxide catalysts anchored on Vycor glass has been undertaken by in-situ photoluminescence, EPR, XAFS (XANES and FT-EXAFS), and FT-IR spectroscopy. UV-irradiation of the Cu{sup +}/ZSM-5 catalyst in the presence of NO leads to the direct photocatalytic decomposition of NO into N{sub 2} and O{sub 2} at normal temperatures. UV-irradiation of the highly dispersed anchored Ti-oxide catalyst in the presence of CO{sub 2} and H{sub 2}O also leads to the evolution of CH{sub 4}, CO, and CH{sub 3}OH at normal temperatures. The clarification of the coordination structure of the active surface sites and the direct detection of the reaction precursors and intermediate species in these photocatalytic systems contributed significantly in characterizing the molecular scale reaction mechanisms. Based on these results, the design of highly concentrated and efficient photocatalysts has successfully been achieved by application of the sol-gel method

  8. A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Trong-Nghia [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Department of Physical Chemistry, Hanoi University of Science and Technology, Hanoi (Viet Nam); Putikam, Raghunath; Lin, M. C., E-mail: chemmcl@emory.edu [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China)

    2015-03-28

    We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH{sub 2}OO and anti/syn-CH{sub 3}C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH{sub 2}OO and anti-CH{sub 3}C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH{sub 3}C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring C–H bonds. For syn-CH{sub 3}C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH{sub 3} group by the terminal O atom producing CH{sub 2}C(H)O–OH. At 298 K, the intramolecular insertion process in CH{sub 2}OO was found to be 600 times faster than the commonly assumed ring-closing reaction.

  9. The deterioration of intermediate moisture foods

    Science.gov (United States)

    Labruza, T. P.

    1971-01-01

    Deteriorative reactions are low and food quality high if intermediate moisture content of a food is held at a water activity of 0.6 to 0.75. Information is of interest to food processing and packaging industry.

  10. Novel Reagents for Multi-Component Reactions

    Science.gov (United States)

    Wang, Yanguang; Basso, Andrea; Nenajdenko, Valentine G.; Gulevich, Anton V.; Krasavin, Mikhail; Bushkova, Ekaterina; Parchinsky, Vladislav; Banfi, Luca; Basso, Andrea; Cerulli, Valentina; Guanti, Giuseppe; Riva, Renata; Rozentsveig, Igor B.; Rozentsveig, Gulnur N.; Popov, Aleksandr V.; Serykh, Valeriy J.; Levkovskaya, Galina G.; Cao, Song; Shen, Li; Liu, Nianjin; Wu, Jingjing; Li, Lina; Qian, Xuhong; Chen, Xiaopeng; Wang, Hongbo; Feng, Jinwu; Wang, Yanguang; Lu, Ping; Heravi, Majid M.; Sadjadi, Samaheh; Kazemizadeh, Ali Reza; Ramazani, Ali; Kudyakova, Yulia S.; Goryaeva, Marina V.; Burgart, Yanina V.; Saloutin, Victor I.; Mossetti, Riccardo; Pirali, Tracey; Tron, Gian Cesare; Rozhkova, Yulia S.; Mayorova, Olga A.; Shklyaev, Yuriy V.; Zhdanko, Alexander G.; Nenajdenko, Valentine G.; Stryapunina, Olga G.; Plekhanova, Irina V.; Glushkov, Vladimir A.; Shklyaev, Yurii V.

    Ketenimines are a class of versatile and highly reactive intermediates that can participate in a variety of organic reactions, such as nucleophilic additions, radical additions, [2 + 2] and [2 + 4] cycloadditions, and sigmatropic rearrangements. In this presentation, we report on a series of multi-component reactions that involve a ketenimine intermediate. These reactions could furnish diverse heterocyclic compounds, including functionalized iminocoumarin, iminodihydroqunolines, iminothiochromens, pyrrolines, isoquinolines, pyridines, β-lactams, imino-1,2-dihydrocoumarins, and benzimidazoles.

  11. Role of the reaction intermediates in determining PHIP (parahydrogen induced polarization) effect in the hydrogenation of acetylene dicarboxylic acid with the complex [Rh (dppb)]+ (dppb: 1,4-bis(diphenylphosphino)butane)

    International Nuclear Information System (INIS)

    Reineri, F.; Aime, S.; Gobetto, R.; Nervi, C.

    2014-01-01

    This study deals with the parahydrogenation of the symmetric substrate acetylene dicarboxylic acid catalyzed by a Rh(I) complex bearing the chelating diphosphine dppb (1,4-bis(diphenylphosphino)butane). The two magnetically equivalent protons of the product yield a hyperpolarized emission signal in the 1 H-NMR spectrum. Their polarization intensity varies upon changing the reaction solvent from methanol to acetone. A detailed analysis of the hydrogenation pathway is carried out by means of density functional theory calculations to assess the structure of hydrogenation intermediates and their stability in the two solvents. The observed polarization effects have been accounted on the basis of the obtained structures. Insights into the lifetime of a short-lived reaction intermediate are also obtained

  12. Low energy ion-molecule reactions

    International Nuclear Information System (INIS)

    Farrar, J.M.

    1986-01-01

    The authors work during the past year has focused on several problems in the condensation reactions of C + and CH 3 + with small molecules, particularly hydrocarbons. Their emphasis has been on understanding the dynamics of collision complex formation and isomerization of transient intermediates along the reaction coordinate. In many ionic reactions, intermediates having non-classical valence structures may be nearly as stable as their classical analogs, in contrast with neutral systems where the non-classical structures are much less stable. The C + + NH 3 system shows this behavior, indicating that the non-classical HCNH 2 + structure formed by insertion of C + into the N-H bond serves as a precursor to the products. N-H bond cleavage in this intermediate to form HCNH + occurs over a large barrier and occurs more readily than the 1,2 hydrogen atom shift to form the classical H 2 C = NH + intermediate. Their experimental kinetic energy distribution for this channel is consistent with the presence of a large exit channel barrier. Their recently published work on C + + H 2 O also demonstrates this phenomenon. The CHOH + hydroxycarbene cation serves as the initial intermediate and isomerization to the classical H 2 CO + cation is competitive with O-H or C-H cleavage to yield the formyl, HCO + , or isoformyl, COH + , cations. They have also completed studies on the reactions of C + with O 2 , CH 3 OH, HCN, and the two-carbon containing hydrocarbons ethane, ethylene, and acetylene

  13. Carbon monosulfide: a useful synthetic intermediate

    International Nuclear Information System (INIS)

    Kramer, M.P.

    1986-01-01

    The physical properties of carbon monosulfide, CS, are well documented. The molecule has been observed in interstellar space and is found to be a common intermediate in the thermal decomposition of carbon disulfide and other sulfur compounds. Interestingly enough, the chemistry of carbon monosulfide, a molecule that is isovalent with carbon monoxide, has received little attention. The explosive nature of the carbon monosulfide monomer, which hindered previous workers, was overcome by the development of special handling techniques. The ability to produce carbon monosulfide in gram quantities had lead to synthesis of novel compounds and to a more direct synthetic route for certain known compounds. Specifically, the following general reaction demonstrates the capabilities of carbon monosulfide on the synthetic scale. CS + RXY → RXC(S)Y;(X = N,S), (Y = H, Cl). Note: The initial product formed in the reaction can be an unstable intermediate

  14. Temperature-scan cryocrystallography reveals reaction intermediates in bacteriophytochrome

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Xiaojing; Ren, Zhong; Kuk, Jane; Moffat, Keith (UC)

    2012-03-27

    Light is a fundamental signal that regulates important physiological processes such as development and circadian rhythm in living organisms. Phytochromes form a major family of photoreceptors responsible for red light perception in plants, fungi and bacteria. They undergo reversible photoconversion between red-absorbing (Pr) and far-red-absorbing (Pfr) states, thereby ultimately converting a light signal into a distinct biological signal that mediates subsequent cellular responses. Several structures of microbial phytochromes have been determined in their dark-adapted Pr or Pfr states. However, the structural nature of initial photochemical events has not been characterized by crystallography. Here we report the crystal structures of three intermediates in the photoreaction of Pseudomonas aeruginosa bacteriophytochrome (PaBphP). We used cryotrapping crystallography to capture intermediates, and followed structural changes by scanning the temperature at which the photoreaction proceeded. Light-induced conformational changes in PaBphP originate in ring D of the biliverdin (BV) chromophore, and E-to-Z isomerization about the C{sub 15} = C{sub 16} double bond between rings C and D is the initial photochemical event. As the chromophore relaxes, the twist of the C{sub 15} methine bridge about its two dihedral angles is reversed. Structural changes extend further to rings B and A, and to the surrounding protein regions. These data indicate that absorption of a photon by the Pfr state of PaBphP converts a light signal into a structural signal via twisting and untwisting of the methine bridges in the linear tetrapyrrole within the confined protein cavity.

  15. Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO2.

    Science.gov (United States)

    Huang, Hao-Li; Chao, Wen; Lin, Jim Jr-Min

    2015-09-01

    Criegee intermediates are thought to play a role in atmospheric chemistry, in particular, the oxidation of SO2, which produces SO3 and subsequently H2SO4, an important constituent of aerosols and acid rain. However, the impact of such oxidation reactions is affected by the reactions of Criegee intermediates with water vapor, because of high water concentrations in the troposphere. In this work, the kinetics of the reactions of dimethyl substituted Criegee intermediate (CH3)2COO with water vapor and with SO2 were directly measured via UV absorption of (CH3)2COO under near-atmospheric conditions. The results indicate that (i) the water reaction with (CH3)2COO is not fast enough (kH2O SO2 at a near-gas-kinetic-limit rate (kSO2 = 1.3 × 10(-10) cm(3) s(-1)). These observations imply a significant fraction of atmospheric (CH3)2COO may survive under humid conditions and react with SO2, very different from the case of the simplest Criegee intermediate CH2OO, in which the reaction with water dimer predominates in the CH2OO decay under typical tropospheric conditions. In addition, a significant pressure dependence was observed for the reaction of (CH3)2COO with SO2, suggesting the use of low pressure rate may underestimate the impact of this reaction. This work demonstrates that the reactivity of a Criegee intermediate toward water vapor strongly depends on its structure, which will influence the main decay pathways and steady-state concentrations for various Criegee intermediates in the atmosphere.

  16. Intermediates and Generic Convergence to Equilibria

    DEFF Research Database (Denmark)

    Marcondes de Freitas, Michael; Wiuf, Carsten; Feliu, Elisenda

    2017-01-01

    Known graphical conditions for the generic and global convergence to equilibria of the dynamical system arising from a reaction network are shown to be invariant under the so-called successive removal of intermediates, a systematic procedure to simplify the network, making the graphical conditions...

  17. Freeze-quench (57)Fe-Mössbauer spectroscopy: trapping reactive intermediates.

    Science.gov (United States)

    Krebs, Carsten; Bollinger, J Martin

    2009-01-01

    (57)Fe-Mössbauer spectroscopy is a method that probes transitions between the nuclear ground state (I=1/2) and the first nuclear excited state (I=3/2). This technique provides detailed information about the chemical environment and electronic structure of iron. Therefore, it has played an important role in studies of the numerous iron-containing proteins and enzymes. In conjunction with the freeze-quench method, (57)Fe-Mössbauer spectroscopy allows for monitoring changes of the iron site(s) during a biochemical reaction. This approach is particularly powerful for detection and characterization of reactive intermediates. Comparison of experimentally determined Mössbauer parameters to those predicted by density functional theory for hypothetical model structures can then provide detailed insight into the structures of reactive intermediates. We have recently used this methodology to study the reactions of various mononuclear non-heme-iron enzymes by trapping and characterizing several Fe(IV)-oxo reaction intermediates. In this article, we summarize these findings and demonstrate the potential of the method. © Springer Science+Business Media B.V. 2009

  18. Medium effects in direct reactions

    International Nuclear Information System (INIS)

    Karakoc, M; Bertulani, C

    2013-01-01

    We discuss medium corrections of the nucleon-nucleon (NN) cross sections and their influence on direct reactions at intermediate energies ≳50 MeV/nucleon. The results obtained with free NN cross sections are compared with those obtained with a geometrical treatment of Pauli-blocking and Dirac-Bruecker methods. We show that medium corrections may lead to sizable modifications for collisions at intermediate energies and that they are more pronounced in reactions involving weakly bound nuclei.

  19. Search for ternary fragmentation in the reaction 856 MeV 98Mo + 51V: Kinematic probing of intermediate-mass-fragment emissions

    International Nuclear Information System (INIS)

    Vardaci, Emanuele; Kaplan, Morton; Parker, Winifred E.; Moses, David J.; Boger, J.T.; Gilfoyle, G.T.; McMahan, M.A.; Montoya, M.

    2000-05-01

    A new technique has been applied to coincidence measurements between fission fragments (FF) and intermediate mass fragments (IMF) emitted from the composite system 149 65 Tb at an excitation energy of 224 MeV. The method permits simultaneous observation of IMF emissions along and normal to the FF separation axes. For the integrated total of 0.10 +-0.02 IMF emitted per fission, we find no significant correlation with FF direction, suggesting that IMFs associated with fission reactions are predominantly emitted from the system prior to fission

  20. The effects of reactants ratios, reaction temperatures and times on Maillard reaction products of the L-ascorbic acid/L-glutamic acid system

    Directory of Open Access Journals (Sweden)

    Yong-Yan ZHOU

    2016-01-01

    Full Text Available Abstract The transformation law of the Maillard reaction products with three different reactants ratios - equimolar reactants, excess L-glutamic acid and excess L-ascorbic acid reaction respectively, five different temperatures, and different time conditions for the L-ascorbic acid / L-glutamic acid system were investigated. Results showed that, the increase of the reaction time and temperature led to the increase of the browning products, uncoloured intermediate products, as well as aroma compounds. Compared with the equimolar reaction system, the excess L-ascorbic acid reaction system produced more browning products and uncoloured intermediate products, while the aroma compounds production remained the same. In the excess L-glutamic acid system, the uncoloured intermediate products increased slightly, the browning products remained the same, while the aroma compounds increased.

  1. Phenomena and significance of intermediate spillover in electrocatalysis of oxygen and hydrogen electrode reactions

    Directory of Open Access Journals (Sweden)

    Jakšić Jelena M.

    2012-01-01

    conductivity and non-exchanged initial pure mono-bronze spillover and catalytic properties. The underpotential spillover double layer (DL charging and discharging properties of the primary oxide (M-OH, interrelated with the interactive self-catalytic effect of dipole-oriented water molecules, has also been proved and pointed out as the phenomenological appearance and aspect of the interactive spillover featuring intermediates. In fact, phenomenological aspects of spillover for the main reacting intermediate species in oxygen and hydrogen electrode reactions along with earned and withdrawn theoretical knowledge represent the basic concepts and aims of the present study.

  2. Reaction Intermediate Analogues as Bisubstrate Inhibitors of Pantothenate Synthetase

    OpenAIRE

    Xu, Zhixiang; Yin, Wei; Martinelli, Leonardo K.; Evans, Joanna; Chen, Jinglei; Yu, Yang; Wilson, Daniel J.; Mizrahi, Valerie; Qiao, Chunhua; Aldrich, Courtney C.

    2014-01-01

    The biosynthesis of pantothenate, the core of coenzyme A (CoA), has been considered an attractive target for the development of antimicrobial agents since this pathway is essential in prokaryotes, but absent in mammals. Pantothenate synthetase, encoded by the gene panC, catalyzes the final condensation of pantoic acid with β–alanine to afford pantothenate via an intermediate pantoyl adenylate. We describe the synthesis and biochemical characterization of five PanC inhibitors that mimic the in...

  3. Intermediate energy nuclear physics (Task C) and charge exchange reactions (Task W). Technical progress report, October 1, 1985-October 1, 1986

    International Nuclear Information System (INIS)

    Kraushaar, J.J.

    1986-10-01

    This report describes the experimental work in intermediate energy research carried out over the past year at the University of Colorado. The experimental program is very broad in nature, ranging from investigations in pion-nucleus interactions, nucleon charge exchange, inelastic electron scattering, and nucleon transfer reactions. The experiments were largely carried out at the Los Alamos Meson Physics Facility, but important programs were conducted at the Tri-University Meson Facility at the University of British Columbia, the Indiana University Cyclotron Facility and Netherlands Institute for Nuclear Physics Research (NIKHEF-K)

  4. Future possibilities with intermediate-energy neutron beams

    International Nuclear Information System (INIS)

    Brady, F.P.

    1987-01-01

    Future possibilities for using neutrons of intermediate energies (50 - 200 MeV) as a probe of the nucleus are discussed. Some of the recent thinking concerning a systematic approach for studying elastic and inelastic scattering of electrons and hadrons and the important role of medium- and intermediate-energy neutrons in such a programme is reviewed. The advantages of neutrons in this energy range over neutrons with lower energies and over intermediate-energy pions for determining nuclear-transition and ground state densities, and for distinguishing proton from neutron density (isovector sensitivity), are noted. The important role of (n,p) charge exchange reactions in nuclear excitation studies is also reviewed. Experimental methods for utilizing neutrons as probes in elastic, inelastic, and charge exchange studies at these energies are discussed

  5. Rate Constant Change of Photo Reaction of Bacteriorhodopsin Observed in Trimeric Molecular System.

    Science.gov (United States)

    Tsujiuchi, Yutaka; Masumoto, Hiroshi; Goto, Takashi

    2016-04-01

    To elucidate the time evolution of photo reaction of bacteriorhodopsin in glycerol mixed purple membrane at around 196 K under irradiation by red light, a kinetic model was constructed. The change of absorption with irradiation at times of 560 nm and 412 nm was analyzed for the purpose of determining reaction rates of photo reaction of bacteriorhodopsin and its product M intermediate. In this study it is shown that reaction rates of conversion from bacteriorhodopsin to the M intermediate can be explained by a set of linear differential equations. This model analysis concludes that bacteriorhodopsin in which constitutes a trimer unit with other two bacteriorhodopsin molecules changes into M intermediates in the 1.73 of reaction rate, in the initial step, and according to the number of M intermediate in a trimer unit, from three to one, the reaction rate of bacteriorhodopsin into M intermediates smaller as 1.73, 0.80, 0.19 which caused by influence of inter-molecular interaction between bacteriorhodopsin.

  6. Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

    KAUST Repository

    Wang, Zhandong

    2017-11-28

    Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

  7. Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

    KAUST Repository

    Wang, Zhandong; Popolan-Vaida, Denisia M.; Chen, Bingjie; Moshammer, Kai; Mohamed, Samah; Wang, Heng; Sioud, Salim; Raji, Misjudeen; Kohse-Hö inghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Leone, Stephen R.; Sarathy, Mani

    2017-01-01

    Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

  8. Intermediate phase evolution in YBCO thin films grown by the TFA process

    International Nuclear Information System (INIS)

    Zalamova, K; Pomar, A; Palau, A; Puig, T; Obradors, X

    2010-01-01

    The YBCO thin film growth process from TFA precursors involves a complex reaction path which includes several oxide, fluoride and oxyfluoride intermediate phases, and the final microstructure and properties of the films are strongly influenced by the morphological and chemical evolution of these intermediate phases. In this work we present a study of the evolution of the intermediate phases involved in the TFA YBCO growth process under normal pressure conditions and we show that the oxygen partial pressure during pyrolysis of the TFA precursors is an important parameter. The Cu phase after the TFA pyrolysis can be either CuO, Cu 2 O or a mixture of both as the oxygen partial pressure is modified. The kinetics evolution of the intermediate phases has been determined for films pyrolysed in oxygen and nitrogen atmospheres and it is concluded that non-equilibrium phase transformations influence the reaction path towards epitaxial YBCO films and its microstructure. The intermediate phase evolution in these two series of films is summarized in kinetic phase diagrams.

  9. The pentadehydro-Diels-Alder reaction.

    Science.gov (United States)

    Wang, Teng; Naredla, Rajasekhar Reddy; Thompson, Severin K; Hoye, Thomas R

    2016-04-28

    In the classic Diels-Alder [4 + 2] cycloaddition reaction, the overall degree of unsaturation (or oxidation state) of the 4π (diene) and 2π (dienophile) pairs of reactants dictates the oxidation state of the newly formed six-membered carbocycle. For example, in the classic Diels-Alder reaction, butadiene and ethylene combine to produce cyclohexene. More recent developments include variants in which the number of hydrogen atoms in the reactant pair and in the resulting product is reduced by, for example, four in the tetradehydro-Diels-Alder (TDDA) and by six in the hexadehydro-Diels-Alder (HDDA) reactions. Any oxidation state higher than tetradehydro (that is, lacking more than four hydrogens) leads to the production of a reactive intermediate that is more highly oxidized than benzene. This increases the power of the overall process substantially, because trapping of the reactive intermediate can be used to increase the structural complexity of the final product in a controllable and versatile manner. Here we report an unprecedented overall 4π + 2π cycloaddition reaction that generates a different, highly reactive intermediate known as an α,3-dehydrotoluene. This species is in the same oxidation state as a benzyne. Like benzynes, α,3-dehydrotoluenes can be captured by various trapping agents to produce structurally diverse products that are complementary to those arising from the HDDA process. We call this new cycloisomerization process a pentadehydro-Diels-Alder (PDDA) reaction-a nomenclature chosen for chemical taxonomic reasons rather than mechanistic ones. In addition to alkynes, nitriles (RC≡N), although non-participants in aza-HDDA reactions, readily function as the 2π component in PDDA cyclizations to produce, via trapping of the α,3-(5-aza)dehydrotoluene intermediates, pyridine-containing products.

  10. Mechanisms of deterioration of intermediate moisture food systems

    Science.gov (United States)

    Labuza, T. P.

    1972-01-01

    A study of shelf stability in intermediate moisture foods was made. Major efforts were made to control lipid oxidation and nonenzymatic browning. In order to determine means of preventing these reactions, model systems were developed having the same water activity content relationship of intermediate moisture foods. Models were based on a cellulose-lipid and protein-lipid system with glycerol added as the humectant. Experiments with both systems indicate that lipid oxidation is promoted significantly in the intermediate moisture range. The effect appeared to be related to increased mobility of either reactants or catalysts, since when the amount of water in the system reached a level where capillary condensation occurred and thus free water was present, the rates of oxidation increased. With added glycerol, which is water soluble and thus increases the amount of mobile phase, the increase in oxidation rate occurs at a lower relative humidity. The rates of oxidation were maximized at 61% RH and decreased again at 75% RH probably due to dilution. No significant non-enzymatic browning occurred in the protein-lipid systems. Prevention of oxidation by the use of metal chelating agents was enhanced in the cellulose system, whereas, with protein present, the lipid soluble chain terminating antioxidants (such as BHA) worked equally as well. Preliminary studies of foods adjusted to the intermediate moisture range bear out the results of oxidation in model systems. It can be concluded that for most fat containing intermediate moisture foods, rancidity will be the reaction most limiting stability.

  11. Breakup reactions at intermediate and high energy

    International Nuclear Information System (INIS)

    Shotter, A.C.; Bice, A.N.

    1981-01-01

    Having considered some general aspects of peripheral break-up reactions involving heavy ions for the incident energy range 10-2000 MeV/A, specific experiments carried out at Berkeley in 1980 in the energy range 10-20 MeV/A are discussed. These indicate that sequential break-up processes from non-sequential inelastic processes both play significant roles in the mechanism. (UK)

  12. Needs for experiment and theory in intermediate energy reactions

    International Nuclear Information System (INIS)

    Blann, M.

    1991-01-01

    We summarize several reasons intermediate energy data are needed in both basic and applied science. The status of the data base at energies up to 2 GeV is cursorily reviewed. Experimental excitation functions, single and double differential cross sections are compared with predictions of the nuclear model code ALICE. The strengths and weaknesses of the code to reproduce data are summarized. Opinions are given as to areas where data are too few or totally lacking, yet are needed for the verification of models and theories. (author). 25 refs, 22 figs

  13. Covalent functionalization of graphene with reactive intermediates.

    Science.gov (United States)

    Park, Jaehyeung; Yan, Mingdi

    2013-01-15

    Graphene, a material made exclusively of sp(2) carbon atoms with its π electrons delocalized over the entire 2D network, is somewhat chemically inert. Covalent functionalization can enhance graphene's properties including opening its band gap, tuning conductivity, and improving solubility and stability. Covalent functionalization of pristine graphene typically requires reactive species that can form covalent adducts with the sp(2) carbon structures in graphene. In this Account, we describe graphene functionalization reactions using reactive intermediates of radicals, nitrenes, carbenes, and arynes. These reactive species covalently modify graphene through free radical addition, CH insertion, or cycloaddition reactions. Free radical additions are among the most common reaction, and these radicals can be generated from diazonium salts and benzoyl peroxide. Electron transfer from graphene to aryl diazonium ion or photoactivation of benzoyl peroxide yields aryl radicals that subsequently add to graphene to form covalent adducts. Nitrenes, electron-deficient species generated by thermal or photochemical activation of organic azides, can functionalize graphene very efficiently. Because perfluorophenyl nitrenes show enhanced bimolecular reactions compared with alkyl or phenyl nitrenes, perfluorophenyl azides are especially effective. Carbenes are used less frequently than nitrenes, but they undergo CH insertion and C═C cycloaddition reactions with graphene. In addition, arynes can serve as a dienophile in a Diels-Alder type reaction with graphene. Further study is needed to understand and exploit the chemistry of graphene. The generation of highly reactive intermediates in these reactions leads to side products that complicate the product composition and analysis. Fundamental questions remain about the reactivity and regioselectivity of graphene. The differences in the basal plane and the undercoordinated edges of graphene and the zigzag versus arm-chair configurations

  14. (p,n) reaction at intermediate energy

    International Nuclear Information System (INIS)

    Goodman, C.D.

    1979-01-01

    The use of the (p,n) reaction in exploring effective interactions is reviewed. Some recent data on self-conjugate nuclei taken at the Indiana University Cyclotron Facility (IUCF) are presented, and the differences between low- and high-energy data are emphasized. Experimental problems and techniques used are briefly described. It is concluded that forward-angle (p,n) spectra at energies greater than 100 MeV are dominated by Gamow-Teller (GT) transitions, while Fermi transitions (IAS transitions) dominate near 45 MeV. Prominent GT transitions are expected from a pion-exchange interaction, and it is expected that OPEP is the dominant component of the interaction in the energy range of 100 to 200 MeV. 27 figures, 2 tables

  15. Studies of complex fragment emission in heavy ion reactions

    International Nuclear Information System (INIS)

    Charity, R.J.; Sobotka, L.G.

    1993-01-01

    The study of intermediate-energy heavy-ion nuclear reactions is reported. This work has two foci: the properties of nuclear matter under abnormal conditions, in this energy domain, predominately low densities and the study of the relevant reaction mechanisms. Nuclear matter properties, such as phase transitions, are reflected in the dynamics of the reactions. The process leads to an understanding of the reaction mechanism themselves and therefore to the response characteristics of finite, perhaps non-equilibrium, strongly interacting systems. The program has the following objectives: to study energy, mass, and angular momentum deposition by studying incomplete fusion reactions; to gain confidence in the understanding of how highly excited systems decompose by studying all emissions from the highly excited systems; to push these kinds of studies into the intermediate energy domain (where intermediate mass fragment emission is not improbable) with excitation function studies; and to learn about the dynamics of the decays using particle-particle correlations. The last effort focuses on simple systems, where definitive statements are possible. These avenues of research share a common theme, large complex fragment production. It is this feature, more than any other, which distinguishes the intermediate energy domain

  16. Intermediate energy charge-exchange reactions induced by polarized 3He

    International Nuclear Information System (INIS)

    Kim, B.T.

    1998-01-01

    Spin polarization transfer is proven to be very useful in obtaining detailed information of the continuum nuclear responses. The data, taken for the (vector p,vector n) reactions, have enabled us to separate the response into the spin longitudinal and transverse components. These partial nuclear responses have been successfully used to make critical tests of nuclear structure models. In the present paper, we first summarize the results of the data and the theoretical analyses made so far. We then discuss information obtainable from the ( 3 vector He,vector t) reaction, emphasizing on the differences and similarities in comparison with the (vector p,vector n) reaction. The results of numerical calculations made for ( 3 vector He,vector t) reactions based on the microscopic distorted wave impulse approximation will also be reported. (orig.)

  17. Nitrenes, carbenes, diradicals, and ylides. Interconversions of reactive intermediates.

    Science.gov (United States)

    Wentrup, Curt

    2011-06-21

    Rearrangements of aromatic and heteroaromatic nitrenes and carbenes can be initiated with either heat or light. The thermal reaction is typically induced by flash vacuum thermolysis, with isolation of the products at low temperatures. Photochemical experiments are conducted either under matrix isolation conditions or in solution at ambient temperature. These rearrangements are usually initiated by ring expansion of the nitrene or carbene to a seven-membered ring ketenimine, carbodiimide, or allene (that is, a cycloheptatetraene or an azacycloheptatetraene when a nitrogen is involved). Over the last few years, we have found that two types of ring opening take place as well. Type I is an ylidic ring opening that yields nitrile ylides or diazo compounds as transient intermediates. Type II ring opening produces either dienylnitrenes (for example, from 2-pyridylnitrenes) or 1,7-(1,5)-diradicals (such as those formed from 2-quinoxalinylnitrenes), depending on which of these species is better stabilized by resonance. In this Account, we describe our achievements in elucidating the nature of the ring-opened species and unraveling the connections between the various reactive intermediates. Both of these ring-opening reactions are found, at least in some cases, to dominate the subsequent chemistry. Examples include the formation of ring-opened ketenimines and carbodiimides, as well as the ring contraction reactions that form five-membered ring nitriles (such as 2- and 3-cyanopyrroles from pyridylnitrenes, N-cyanoimidazoles from 2-pyrazinyl and 4-pyrimidinylnitrenes, N-cyanopyrazoles from 2-pyrimidinylnitrenes and 3-pyridazinylnitrenes, and so forth). The mechanisms of formation of the open-chain and ring-contraction products were unknown at the onset of this study. In the course of our investigation, several reactions with three or more consecutive reactive intermediates have been unraveled, such as nitrene, seven-membered cyclic carbodiimide, and open-chain nitrile ylide

  18. MCNP6 fragmentation of light nuclei at intermediate energies

    Energy Technology Data Exchange (ETDEWEB)

    Mashnik, Stepan G., E-mail: mashnik@lanl.gov [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Kerby, Leslie M. [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); University of Idaho, Moscow, ID 83844 (United States)

    2014-11-11

    Fragmentation reactions induced on light target nuclei by protons and light nuclei of energies around 1 GeV/nucleon and below are studied with the latest Los Alamos Monte Carlo transport code MCNP6 and with its cascade-exciton model (CEM) and Los Alamos version of the quark-gluon string model (LAQGSM) event generators, version 03.03, used as stand-alone codes. Such reactions are involved in different applications, like cosmic-ray-induced single event upsets (SEU's), radiation protection, and cancer therapy with proton and ion beams, among others; therefore, it is important that MCNP6 simulates them as well as possible. CEM and LAQGSM assume that intermediate-energy fragmentation reactions on light nuclei occur generally in two stages. The first stage is the intranuclear cascade (INC), followed by the second, Fermi breakup disintegration of light excited residual nuclei produced after the INC. Both CEM and LAQGSM account also for coalescence of light fragments (complex particles) up to {sup 4}He from energetic nucleons emitted during INC. We investigate the validity and performance of MCNP6, CEM, and LAQGSM in simulating fragmentation reactions at intermediate energies and discuss possible ways of further improving these codes.

  19. Statistical properties of multistep enzyme-mediated reactions

    OpenAIRE

    de Ronde, Wiet H.; Daniels, Bryan C.; Mugler, Andrew; Sinitsyn, Nikolai A.; Nemenman, Ilya

    2008-01-01

    Enzyme-mediated reactions may proceed through multiple intermediate conformational states before creating a final product molecule, and one often wishes to identify such intermediate structures from observations of the product creation. In this paper, we address this problem by solving the chemical master equations for various enzymatic reactions. We devise a perturbation theory analogous to that used in quantum mechanics that allows us to determine the first () and the second (variance) cumu...

  20. Gamow Teller strength from charge exchange reactions at intermediate energies

    International Nuclear Information System (INIS)

    Haeusser, O.

    1989-07-01

    Detailed studies of the spin-isospin structure of nuclear excitations are possible at TRIUMF's medium resolution spectrometer using the (n,p), ( p → , p →/ ) and (p,n) reactions. We discuss here results on isospin symmetry of inelastic nucleon scattering reactions populating isospin triads in A=6 and A=12 nuclei. The β + Gamow Teller strength function from (n,p) reactions on (sd) and (fp) shell targets is found to be substantially quenched compared to current nuclear structure models using the free-nucleon axial-vector coupling constant. (Author) 22 refs., 3 figs

  1. ESL intermediate/advanced writing

    CERN Document Server

    Munoz Page, Mary Ellen; Jaskiewicz, Mary

    2011-01-01

    Master ESL (English as a Second Language) Writing with the study guide designed for non-native speakers of English. Skill-building lessons relevant to today's topics help ESL students write complete sentences, paragraphs, and even multi-paragraph essays. It's perfect for classroom use or self-guided writing preparation.DETAILS- Intermediate drills for improving skills with parallel structure, mood, correct shifting errors & dangling participles- Advanced essay drills focusing on narrative, descriptive, process, reaction, comparison and contrast- Superb preparation for students taking the TOEFL

  2. The hexadehydro-Diels-Alder reaction.

    Science.gov (United States)

    Hoye, Thomas R; Baire, Beeraiah; Niu, Dawen; Willoughby, Patrick H; Woods, Brian P

    2012-10-11

    Arynes (aromatic systems containing, formally, a carbon-carbon triple bond) are among the most versatile of all reactive intermediates in organic chemistry. They can be 'trapped' to give products that are used as pharmaceuticals, agrochemicals, dyes, polymers and other fine chemicals. Here we explore a strategy that unites the de novo generation of benzynes-through a hexadehydro-Diels-Alder reaction-with their in situ elaboration into structurally complex benzenoid products. In the hexadehydro-Diels-Alder reaction, a 1,3-diyne is engaged in a [4+2] cycloisomerization with a 'diynophile' to produce the highly reactive benzyne intermediate. The reaction conditions for this simple, thermal transformation are notable for being free of metals and reagents. The subsequent and highly efficient trapping reactions increase the power of the overall process. Finally, we provide examples of how this de novo benzyne generation approach allows new modes of intrinsic reactivity to be revealed.

  3. The nuclear reaction matrix

    International Nuclear Information System (INIS)

    Krenciglowa, E.M.; Kung, C.L.; Kuo, T.T.S.; Osnes, E.; and Department of Physics, State University of New York at Stony Brook, Stony Brook, New York 11794)

    1976-01-01

    Different definitions of the reaction matrix G appropriate to the calculation of nuclear structure are reviewed and discussed. Qualitative physical arguments are presented in support of a two-step calculation of the G-matrix for finite nuclei. In the first step the high-energy excitations are included using orthogonalized plane-wave intermediate states, and in the second step the low-energy excitations are added in, using harmonic oscillator intermediate states. Accurate calculations of G-matrix elements for nuclear structure calculations in the Aapprox. =18 region are performed following this procedure and treating the Pauli exclusion operator Q 2 /sub p/ by the method of Tsai and Kuo. The treatment of Q 2 /sub p/, the effect of the intermediate-state spectrum and the energy dependence of the reaction matrix are investigated in detail. The present matrix elements are compared with various matrix elements given in the literature. In particular, close agreement is obtained with the matrix elements calculated by Kuo and Brown using approximate methods

  4. Anodic Cyclization Reactions and the Mechanistic Strategies That Enable Optimization.

    Science.gov (United States)

    Feng, Ruozhu; Smith, Jake A; Moeller, Kevin D

    2017-09-19

    Oxidation reactions are powerful tools for synthesis because they allow us to reverse the polarity of electron-rich functional groups, generate highly reactive intermediates, and increase the functionality of molecules. For this reason, oxidation reactions have been and continue to be the subject of intense study. Central to these efforts is the development of mechanism-based strategies that allow us to think about the reactive intermediates that are frequently central to the success of the reactions and the mechanistic pathways that those intermediates trigger. For example, consider oxidative cyclization reactions that are triggered by the removal of an electron from an electron-rich olefin and lead to cyclic products that are functionalized for further elaboration. For these reactions to be successful, the radical cation intermediate must first be generated using conditions that limit its polymerization and then channeled down a productive desired pathway. Following the cyclization, a second oxidation step is necessary for product formation, after which the resulting cation must be quenched in a controlled fashion to avoid undesired elimination reactions. Problems can arise at any one or all of these steps, a fact that frequently complicates reaction optimization and can discourage the development of new transformations. Fortunately, anodic electrochemistry offers an outstanding opportunity to systematically probe the mechanism of oxidative cyclization reactions. The use of electrochemical methods allows for the generation of radical cations under neutral conditions in an environment that helps prevent polymerization of the intermediate. Once the intermediates have been generated, a series of "telltale indicators" can be used to diagnose which step in an oxidative cyclization is problematic for less successful transformation. A set of potential solutions to address each type of problem encountered has been developed. For example, problems with the initial

  5. Supercritical carbon dioxide versus toluene as reaction media in silica functionalisation: Synthesis and characterisation of bonded aminopropyl silica intermediate.

    Science.gov (United States)

    Ashu-Arrah, Benjamin A; Glennon, Jeremy D

    2017-06-09

    This research reports supercritical carbon dioxide versus toluene as reaction media in silica functionalisation for use in liquid chromatography. Bonded aminopropyl silica (APS) intermediates were prepared when porous silica particles (Exsil-pure, 3μm) were reacted with 3-aminopropyltriethoxysilane (3-APTES) or N,N-dimethylaminopropyltrimethoxysilane (DMAPTMS) using supercritical carbon dioxide (sc-CO 2 ) and toluene as reaction media. Covalent bonding to silica was confirmed using elemental microanalysis (CHN), thermogravimetric analysis (TGA), zeta potential (ξ), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, scanning electron microscopy (SEM) and solid-state nuclear magnetic resonance (CP/MAS NMR) spectroscopy. The results demonstrate that under sc-CO 2 conditions of 100°C/414bar in a substantial reduced time of 3h, the surface coverage of APS (evaluated from%C obtained from elemental analysis) prepared with APTES (%C: 8.03, 5.26μmol/m -2 ) or DMAPTES (%C: 5.12, 4.58μmol/m 2 ) is somewhat higher when compared to organic based reactions under reflux in toluene at a temperature of 110°C in 24h with APTES (%C: 7.33, 4.71μmol/m 2 ) and DMAPTMS (%C: 4.93, 4.38μmol/m 2 ). Zeta potential measurements revealed a change in electrostatic surface charge from negative values for bare Exsil-pure silica to positive for functionalised APS materials indicating successful immobilization of the aminosilane onto the surface of silica. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Synthetic routes to some isotopically labelled intermediates for diterpenoid biosynthesis

    International Nuclear Information System (INIS)

    Dawson, R.M.; Godfrey, I.M.; Hogg, R.W.; Knox, J.R.

    1989-01-01

    The exo-15-hydrogen of ent-kaurene can be exchanged through a reversible ene reaction in a convenient and efficient procedure which has the potential for giving high specific activity 3 H-labelling. Copalol, the (Z)-double bond stereoisomer, and the allylic alcohol isomers ent-manool and ent-epimanool have been obtained through divergent synthetic pathways involving a 15,16-bisnor ketone intermediate. These pathways have also allowed the four compounds to be obtained with 14 C-labelling. A method, involving a Wittig reaction to form a vinyl bromide intermediate, has been developed for obtaining copalol, as the trityl ether derivative, with stereospecific isotopic labelling of one or the other of the hydrogens of the exocyclic methylene group. 27 refs., figs

  7. Novel pathway of SO2 oxidation in the atmosphere: reactions with monoterpene ozonolysis intermediates and secondary organic aerosol

    Science.gov (United States)

    Ye, Jianhuai; Abbatt, Jonathan P. D.; Chan, Arthur W. H.

    2018-04-01

    Ozonolysis of monoterpenes is an important source of atmospheric biogenic secondary organic aerosol (BSOA). While enhanced BSOA formation has been associated with sulfate-rich conditions, the underlying mechanisms remain poorly understood. In this work, the interactions between SO2 and reactive intermediates from monoterpene ozonolysis were investigated under different humidity conditions (10 % vs. 50 %). Chamber experiments were conducted with ozonolysis of α-pinene or limonene in the presence of SO2. Limonene SOA formation was enhanced in the presence of SO2, while no significant changes in SOA yields were observed during α-pinene ozonolysis. Under dry conditions, SO2 primarily reacted with stabilized Criegee intermediates (sCIs) produced from ozonolysis, but at 50 % RH heterogeneous uptake of SO2 onto organic aerosol was found to be the dominant sink of SO2, likely owing to reactions between SO2 and organic peroxides. This SO2 loss mechanism to organic peroxides in SOA has not previously been identified in experimental chamber studies. Organosulfates were detected and identified using an electrospray ionization-ion mobility spectrometry-high-resolution time-of-flight mass spectrometer (ESI-IMS-TOF) when SO2 was present in the experiments. Our results demonstrate the synergistic effects between BSOA formation and SO2 oxidation through sCI chemistry and SO2 uptake onto organic aerosol and illustrate the importance of considering the chemistry of organic and sulfur-containing compounds holistically to properly account for their reactive sinks.

  8. Isoporphyrin intermediate in heme oxygenase catalysis. Oxidation of alpha-meso-phenylheme.

    Science.gov (United States)

    Evans, John P; Niemevz, Fernando; Buldain, Graciela; de Montellano, Paul Ortiz

    2008-07-11

    Human heme oxygenase-1 (hHO-1) catalyzes the O2- and NADPH-dependent oxidation of heme to biliverdin, CO, and free iron. The first step involves regiospecific insertion of an oxygen atom at the alpha-meso carbon by a ferric hydroperoxide and is predicted to proceed via an isoporphyrin pi-cation intermediate. Here we report spectroscopic detection of a transient intermediate during oxidation by hHO-1 of alpha-meso-phenylheme-IX, alpha-meso-(p-methylphenyl)-mesoheme-III, and alpha-meso-(p-trifluoromethylphenyl)-mesoheme-III. In agreement with previous experiments (Wang, J., Niemevz, F., Lad, L., Huang, L., Alvarez, D. E., Buldain, G., Poulos, T. L., and Ortiz de Montellano, P. R. (2004) J. Biol. Chem. 279, 42593-42604), only the alpha-biliverdin isomer is produced with concomitant formation of the corresponding benzoic acid. The transient intermediate observed in the NADPH-P450 reductase-catalyzed reaction accumulated when the reaction was supported by H2O2 and exhibited the absorption maxima at 435 and 930 nm characteristic of an isoporphyrin. Product analysis by reversed phase high performance liquid chromatography and liquid chromatography electrospray ionization mass spectrometry of the product generated with H2O2 identified it as an isoporphyrin that, on quenching, decayed to benzoylbiliverdin. In the presence of H218O2, one labeled oxygen atom was incorporated into these products. The hHO-1-isoporphyrin complexes were found to have half-lives of 1.7 and 2.4 h for the p-trifluoromethyl- and p-methyl-substituted phenylhemes, respectively. The addition of NADPH-P450 reductase to the H2O2-generated hHO-1-isoporphyrin complex produced alpha-biliverdin, confirming its role as a reaction intermediate. Identification of an isoporphyrin intermediate in the catalytic sequence of hHO-1, the first such intermediate observed in hemoprotein catalysis, completes our understanding of the critical first step of heme oxidation.

  9. Electron transfer reactions

    CERN Document Server

    Cannon, R D

    2013-01-01

    Electron Transfer Reactions deals with the mechanisms of electron transfer reactions between metal ions in solution, as well as the electron exchange between atoms or molecules in either the gaseous or solid state. The book is divided into three parts. Part 1 covers the electron transfer between atoms and molecules in the gas state. Part 2 tackles the reaction paths of oxidation states and binuclear intermediates, as well as the mechanisms of electron transfer. Part 3 discusses the theories and models of the electron transfer process; theories and experiments involving bridged electron transfe

  10. [Intermediate energy nuclear physics

    International Nuclear Information System (INIS)

    1989-01-01

    This report summarizes work in experimental Intermediate Energy Nuclear Physics carried out between October 1, 1988 and October 1, 1989 at the Nuclear Physics Laboratory of the University of Colorado, Boulder, under grant DE-FG02-86ER-40269 with the United States Department of Energy. The experimental program is very broadly based, including pion-nucleon studies at TRIUMF, inelastic pion scattering and charge exchange reactions at LAMPF, and nucleon charge exchange at LAMPF/WNR. In addition, a number of other topics related to accelerator physics are described in this report

  11. Nucleon induced reactions

    International Nuclear Information System (INIS)

    Gmuca, S.; Antalik, R.; Kristiak, J.

    1988-01-01

    The collection contains full texts of 37 contributions; all fall within the INIS Subject Scope. The topics treated include some unsolved problems of nuclear reactions and relevant problems of nuclear structure at low and intermediate energies. (Z.S.)

  12. Kinetics of formation of acrylamide and Schiff base intermediates from asparagine and glucose

    DEFF Research Database (Denmark)

    Hedegaard, Rikke Susanne Vingborg; Frandsen, Henrik; Skibsted, Leif H.

    2008-01-01

    From the concentration of glucose and asparagine as reactants and of acrylamide as product each determined by LC-MS during reaction in an acetonitrile/water (68:32) model system at pH 7.6 (0.04 M phosphate buffer) and from the relative concentration of the Schiff base intermediate, the decarboxyl......From the concentration of glucose and asparagine as reactants and of acrylamide as product each determined by LC-MS during reaction in an acetonitrile/water (68:32) model system at pH 7.6 (0.04 M phosphate buffer) and from the relative concentration of the Schiff base intermediate...

  13. MCNP6 Simulation of Light and Medium Nuclei Fragmentation at Intermediate Energies

    Energy Technology Data Exchange (ETDEWEB)

    Mashnik, Stepan Georgievich [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Kerby, Leslie Marie [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Idaho, Moscow, ID (United States)

    2015-08-24

    Fragmentation reactions induced on light and medium nuclei by protons and light nuclei of energies around 1 GeV/nucleon and below are studied with the Los Alamos transport code MCNP6 and with its CEM03.03 and LAQGSM03.03 event generators. CEM and LAQGSM assume that intermediate-energy fragmentation reactions on light nuclei occur generally in two stages. The first stage is the intranuclear cascade (INC), followed by the second, Fermi breakup disintegration of light excited residual nuclei produced after the INC. CEM and LAQGSM account also for coalescence of light fragments (complex particles) up to sup>4He from energetic nucleons emitted during INC. We investigate the validity and performance of MCNP6, CEM, and LAQGSM in simulating fragmentation reactions at intermediate energies and discuss possible ways of further improving these codes.

  14. Probing the Catalytic Mechanism of S-Ribosylhomocysteinase (LuxS) with Catalytic Intermediates and Substrate Analogues

    Energy Technology Data Exchange (ETDEWEB)

    Gopishetty, Bhaskar; Zhu, Jinge; Rajan, Rakhi; Sobczak, Adam J.; Wnuk, Stanislaw F.; Bell, Charles E.; Pei, Dehua; (OSU); (FIU)

    2009-05-12

    S-Ribosylhomocysteinase (LuxS) cleaves the thioether bond in S-ribosylhomocysteine (SRH) to produce homocysteine (Hcys) and 4,5-dihydroxy-2,3-pentanedione (DPD), the precursor of the type II bacterial quorum sensing molecule (AI-2). The catalytic mechanism of LuxS comprises three distinct reaction steps. The first step involves carbonyl migration from the C1 carbon of ribose to C2 and the formation of a 2-ketone intermediate. The second step shifts the C=O group from the C2 to C3 position to produce a 3-ketone intermediate. In the final step, the 3-ketone intermediate undergoes a {beta}-elimination reaction resulting in the cleavage of the thioether bond. In this work, the 3-ketone intermediate was chemically synthesized and shown to be chemically and kinetically competent in the LuxS catalytic pathway. Substrate analogues halogenated at the C3 position of ribose were synthesized and reacted as time-dependent inhibitors of LuxS. The time dependence was caused by enzyme-catalyzed elimination of halide ions. Examination of the kinetics of halide release and decay of the 3-ketone intermediate catalyzed by wild-type and mutant LuxS enzymes revealed that Cys-84 is the general base responsible for proton abstraction in the three reaction steps, whereas Glu-57 likely facilitates substrate binding and proton transfer during catalysis.

  15. Nucleon charge exchange reaction and antiproton elastic scattering at intermediate energies

    International Nuclear Information System (INIS)

    Kronenfeld, J.

    1985-02-01

    This work treats the medium energy nuclear (p,n) charge exchange reaction to analog states and the low energy elastic scattering of antiprotons and investigates the central aspects of a microscopic theory based on multiple-scattering series which are pertinent to these reactions. A two-step term of the Distorted Wave Impulse Approximation (DWIA) in treating the (p,n) reaction, was included. For the very absorptive p-bar interaction with nuclei we conjecture that a partial infinite summation, constituing a renormalization of the single scattering term of the optical potential series provides the dominant feature of this interaction. In this work the excitation of analog states is calculated and it was found that the (p,n) reaction is described fairly well by the DWIA. In the first part of the work the (p,n) reaction in the energy range 100-200 MeV was treated. The DWIA calculations were based on eikonalization. In the second part of the work the p-barA interaction with the selfconsistent scheme mentioned above, for scattering energies 30-120 MeV, was examined. (author)

  16. Photonucleon reactions in 40Ca at intermediate energies

    International Nuclear Information System (INIS)

    Adler, J.-O.; Bulow, B.; Jonsson, G.G.; Lindgren, K.

    1976-01-01

    The yields of the reactions 40 Ca(γ,n) 39 Ca* and 40 Ca(γ,p) 39 K* to the first three excited states have been measured for bremsstrahlung with end-point energies in the region 100-750 MeV. The C 2 S values for the first excited state were deduced from the pion photoproduction contribution to the measured yields. (Auth.)

  17. Angular evolution of peripheral heavy ion reactions at intermediate energies

    International Nuclear Information System (INIS)

    Blumenfeld, Y.; Chomaz, P.; Frascaria, N.; Garron, J.P.; Jacmart, J.C; Roynette, J.C

    1985-01-01

    Energy spectra and angular distributions of projectile-like fragments have been measured in the vicinity of the grazing angle for the 40 Ar+ 40 Ca and 40 Ar+ 208 Pb reactions at 44MeV/nucleon. Measurements of the 40 Ar+ 40 Ca system at 27MeV/nucleon and 20 Ne+ 208 Pb reaction at 44MeV/nucleon at one angle have also been performed. For fragments with charge and mass close to the projectile numerous deviations from the standard fragmentation model have been observed including rapidly changing shapes of the angular distributions with the fragment mass. Moreover the isotopic distributions and mean fragment velocities are strongly dependent on detection angle. A surface transfer reaction component dominant at the grazing angle can be separated from a second component which cannot be entirely accounted for by a simple fragmentation mechanism

  18. Experimental determination of primary and intermediate ions in a flame front

    Energy Technology Data Exchange (ETDEWEB)

    Fialkov, A.B.; Fialkov, B.S.

    1988-10-01

    A procedure is described for determining the primary and intermediate ions in the front of a flame rarefied using mass spectrometry. By using the method proposed here, primary CHO(+) and CHO2(+) ions as well as a series of short-lived intermediate ions have been identified. The possibility of using this method for obtaining quantitative data on the characteristic lifetimes of ions and rate constants of ion-molecular reactions in flames is demonstrated. 16 references.

  19. Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

    Science.gov (United States)

    Carraher, Jack McCaslin

    Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding 'greener' sources of commodity chemicals and fuels. High-valent Chromium from Hydroperoxido-Chromium(III). The decomposition of pentaaquahydroperoxido chromium(III) ion (hereafter Cr aqOOH2+) in acidic aqueous solutions is kinetically complex and generates mixtures of products (Craq3+, HCrO 4-, H2O2, and O2). The yield of high-valent chromium products (known carcinogens) increased from a few percent at pH 1 to 70 % at pH 5.5 (near biological pH). Yields of H 2O2 increased with acid concentration. The reproducibility of the kinetic data was poor, but became simplified in the presence of H2O2 or 2,2‧-azinobis(3-ethylbenzothiazoline-6-sulfonate) dianion (ABTS2-). Both are capable of scavenging strongly oxidizing intermediates). The observed rate constants (pH 1, [O2] ≤ 0.03 mM) in the presence of these scavengers are independent of [scavenger] and within the error are the same (k,ABTS2- = (4.9 +/- 0.2) x 10-4 s-1 and kH2O2 = (5.3 +/- 0.7) x 10-4 s-1); indicating involvement of the scavengers in post-rate determining steps. In the presence of either scavenger, decomposition of CrOOH2+ obeyed a two-term rate law, k obs / s-1 = (6.7 +/- 0.7) x 10-4 + (7.6 +/- 1.1) x 10-4 [H+]. Effect of [H+] on the kinetics and the product distribution, cleaner kinetics in the presence of scavengers, and independence of kobs on [scavenger] suggest a dual-pathway mechanism for the decay of Craq OOH2+. The H+-catalyzed path

  20. Absorption-Fluctuation Theorem for Nuclear Reactions: Brink-Axel, Incomplete Fusion and All That

    International Nuclear Information System (INIS)

    Hussein, M. S.

    2008-01-01

    We discuss the connection between absorption, averages and fluctuations in nuclear reactions. The fluctuations in the entrance channel result in the compound-nucleus Hauser-Feshbach cross section, and the fluctuations in the intermediate channels result in modifications of multistep reaction cross sections, while the fluctuations in the final channel result in hybrid cross sections that can be used to describe incomplete fusion reactions. We discuss the latter in detail and comment on the validity of the assumptions used in the development of the Surrogate method. We also discuss the theory of multistep reactions with regards to intermediate state fluctuations and the energy dependence and non-locality of the intermediate-channel optical potentials

  1. Dynamics of light, intermediate, heavy and superheavy nuclear ...

    Indian Academy of Sciences (India)

    2014-05-01

    May 1, 2014 ... Various features related to the dynamics of competing decay modes of nuclear systems are explored by addressing the experimental data of a number of reactions in light, intermediate, heavy and superheavy mass regions. The DCM, being a non-statistical description for the decay of a com- pound nucleus ...

  2. Deeply inelastic collisions as a source of intermediate mass fragments at E/A = 27 MeV

    International Nuclear Information System (INIS)

    Borderie, B.; Montoya, M.; Rivet, M.F.; Jouan, D.; Cabot, C.; Fuchs, H.; Gardes, D.; Gauvin, H.; Jacquet, D.; Monnet, F.

    1988-01-01

    Intermediate-mass fragments detected in coincidence with heavy residues were measured in 40 Ar induced reactions on Ag at E/A = 27 MeV. From the observed characteristics, it is inferred that intermediate-mass fragments associated with the so-called intermediate-velocity source come mainly from deeply inelastic collisions occurring after or at the same time as preequilibrium particle emission. (orig.)

  3. Crystalline state photoreactions direct observation of reaction processes and metastable intermediates

    CERN Document Server

    Ohashi, Yuji

    2014-01-01

    Offering some 300 references, this book focuses on chemical reactions in the crystalline state. The reactions span many fields in inorganic and organic chemistry, making this a useful resource for inorganic, organic and physical chemists and graduate students.

  4. Synchrotron photoionization mass spectrometry study of intermediates in fuel-rich 1,2-dimethoxyethane flame

    International Nuclear Information System (INIS)

    Lin, Z. K.; Han, D. L.; Li, S. F.; Li, Y. Y.; Yuan, T.

    2009-01-01

    Intermediates in a fuel-rich premixed laminar 1,2-dimethoxyethane (DME) flame are studied by molecular beam mass spectrometry combined with tunable synchrotron vacuum ultraviolet photoionization. About 30 intermediate species are identified in the present work, and their mole fraction profiles are evaluated. The experimental results show that the formations of intermediates, both hydrocarbons and oxygenated hydrocarbons, are closely linked to the structure of fuel, which is consistent with the previous reports. Species produced from H atom abstraction and beta scission of DME usually have much higher concentrations than others. The oxygen atoms in DME are considered to act as partitions of the primary intermediates; therefore farther reactions among these primary intermediates are difficult to occur, resulting in absence of most large intermediate species.

  5. The MHD intermediate shock interaction with an intermediate wave: Are intermediate shocks physical?

    International Nuclear Information System (INIS)

    Wu, C.C.

    1988-01-01

    Contrary to the usual belief that MHD intermediate shocks are extraneous, the authors have recently shown by numerical solutions of dissipative MHD equations that intermediate shocks are admissible and can be formed through nonlinear steepening from a continuous wave. In this paper, he clarifies the differences between the conventional view and the results by studying the interaction of an MHD intermediate shock with an intermediate wave. The study reaffirms his results. In addition, the study shows that there exists a larger class of shocklike solutions in the time-dependent dissiaptive MHD equations than are given by the MHD Rankine-Hugoniot relations. it also suggests a mechanism for forming rotational discontinuities through the interaction of an intermediate shock with an intermediate wave. The results are of importance not only to the MHD shock theory but also to studies such as magnetic field reconnection models

  6. Studies of heavy-ion reactions and transuranic nuclei

    International Nuclear Information System (INIS)

    Schroeder, W.U.

    1993-08-01

    This report contain papers on the following topics: The Cold-Fusion Saga; Decay Patterns of Dysprosium Nuclei Produced in 32 S + 118,124 Sn Fusion Reactions; Unexpected Features of Reactions Between Very Heavy Ions at Intermediate Bombarding Energies; Correlations Between Neutrons and Charged Products from the Dissipative Reaction 197 Au+ 208 Pb at E/A = 29 MeV; Dissipative Dynamics of Projectile-Like Fragment Production in the Reaction 209 Bi+ 136 Xe at E/A = 28.2 MeV; Dynamical Production of Intermediate-Mass Fragments in Peripheral 209 Bi+ 136 Xe Collisions at E lab /A = 28.2 MeV; The Rochester 960-Liter Neutron Multiplicity Meter; A Simple Pulse Processing Concept for a Low-Cost Pulse-Shape-Based Particle Identification; A One-Transistor Preamplifier for PMT Anode Signals; A Five-Channel Multistop TDC/Event Handler for the SuperBall Neutron Multiplicity Meter; Construction of the SuperBall -- a 16,000-Liter Neutron Detector for Calorimetric Studies of Intermediate-Energy Heavy-Ion Reactions; A Computer Code for Light Detection Efficiency Calculations for Photo-multipliers of a Neutron Detector; Evaluation of Gd-Loaded Liquid Scintillators for the SuperBall Neutron Calorimeter; and Measurement of the Interaction of Cosmic-Ray μ - with a Muon Telescope

  7. Intermediate species measurement during iso-butanol auto-ignition

    KAUST Repository

    Ji, Weiqi

    2015-10-01

    © 2015 The Combustion Institute.Published by Elsevier Inc. All rights reserved. This work presents the time histories of intermediate species during the auto-ignition of iso-butanol at high pressure and intermediate temperature conditions obtained using a rapid compression machine and recently developed fast sampling system. Iso-butanol ignition delays were acquired for iso-butanol/O2 mixture with an inert/O2 ratio of 7.26, equivalence ratio of 0.4, in the temperature range of 840-950 K and at pressure of 25 bar. Fast sampling and gas chromatography were used to acquire and quantify the intermediate species during the ignition delay of the same mixture at P = 25.3 bar and T = 905 K. The ignition delay times and quantitative measurements of the mole fraction time histories of methane, ethene, propene, iso-butene, iso-butyraldehyde, iso-butanol, and carbon monoxide were compared with predictions from the detailed mechanisms developed by Sarathy et al., Merchant et al., and Cai et al. It is shown that while the Sarathy mechanism well predicts the overall ignition delay time, it overpredicts ethene by a factor of 6-10, underpredicts iso-butene by a factor of 2, and overpredicts iso-butyraldehyde by a factor of 2. Reaction path and sensitivity analyses were carried out to identify the reactions responsible for the observed inadequacy. The rates of iso-butanol hydrogen atom abstraction by OH radical and the beta-scission reactions of hydroxybutyl radicals were updated based on recently published quantum calculation results. Significant improvements were achieved in predicting ignition delay at high pressures (25 and 30 bar) and the species concentrations of ethene and iso-butene. However, the updated mechanism still overpredicts iso-butyraldehyde concentrations. Also, the updated mechanism degrades the prediction in ignition delay at lower pressure (15 bar) compared to the original mechanism developed by Sarathy et al.

  8. Intermediate species measurement during iso-butanol auto-ignition

    KAUST Repository

    Ji, Weiqi; Zhang, Peng; He, Tanjin; Wang, Zhi; Tao, Ling; He, Xin; Law, Chung K.

    2015-01-01

    © 2015 The Combustion Institute.Published by Elsevier Inc. All rights reserved. This work presents the time histories of intermediate species during the auto-ignition of iso-butanol at high pressure and intermediate temperature conditions obtained using a rapid compression machine and recently developed fast sampling system. Iso-butanol ignition delays were acquired for iso-butanol/O2 mixture with an inert/O2 ratio of 7.26, equivalence ratio of 0.4, in the temperature range of 840-950 K and at pressure of 25 bar. Fast sampling and gas chromatography were used to acquire and quantify the intermediate species during the ignition delay of the same mixture at P = 25.3 bar and T = 905 K. The ignition delay times and quantitative measurements of the mole fraction time histories of methane, ethene, propene, iso-butene, iso-butyraldehyde, iso-butanol, and carbon monoxide were compared with predictions from the detailed mechanisms developed by Sarathy et al., Merchant et al., and Cai et al. It is shown that while the Sarathy mechanism well predicts the overall ignition delay time, it overpredicts ethene by a factor of 6-10, underpredicts iso-butene by a factor of 2, and overpredicts iso-butyraldehyde by a factor of 2. Reaction path and sensitivity analyses were carried out to identify the reactions responsible for the observed inadequacy. The rates of iso-butanol hydrogen atom abstraction by OH radical and the beta-scission reactions of hydroxybutyl radicals were updated based on recently published quantum calculation results. Significant improvements were achieved in predicting ignition delay at high pressures (25 and 30 bar) and the species concentrations of ethene and iso-butene. However, the updated mechanism still overpredicts iso-butyraldehyde concentrations. Also, the updated mechanism degrades the prediction in ignition delay at lower pressure (15 bar) compared to the original mechanism developed by Sarathy et al.

  9. Kinetic intermediates en route to the final serpin-protease complex: studies of complexes of α1-protease inhibitor with trypsin.

    Science.gov (United States)

    Maddur, Ashoka A; Swanson, Richard; Izaguirre, Gonzalo; Gettins, Peter G W; Olson, Steven T

    2013-11-01

    Serpin protein protease inhibitors inactivate their target proteases through a unique mechanism in which a major serpin conformational change, resulting in a 70-Å translocation of the protease from its initial reactive center loop docking site to the opposite pole of the serpin, kinetically traps the acyl-intermediate complex. Although the initial Michaelis and final trapped acyl-intermediate complexes have been well characterized structurally, the intermediate stages involved in this remarkable transformation are not well understood. To better characterize such intermediate steps, we undertook rapid kinetic studies of the FRET and fluorescence perturbation changes of site-specific fluorophore-labeled derivatives of the serpin, α1-protease inhibitor (α1PI), which report the serpin and protease conformational changes involved in transforming the Michaelis complex to the trapped acyl-intermediate complex in reactions with trypsin. Two kinetically resolvable conformational changes were observed in the reactions, ascribable to (i) serpin reactive center loop insertion into sheet A with full protease translocation but incomplete protease distortion followed by, (ii) full conformational distortion and movement of the protease and coupled serpin conformational changes involving the F helix-sheet A interface. Kinetic studies of calcium effects on the labeled α1PI-trypsin reactions demonstrated both inactive and low activity states of the distorted protease in the final complex that were distinct from the intermediate distorted state. These studies provide new insights into the nature of the serpin and protease conformational changes involved in trapping the acyl-intermediate complex in serpin-protease reactions and support a previously proposed role for helix F in the trapping mechanism.

  10. Mechanism of action of clostridial glycine reductase: Isolation and characterization of a covalent acetyl enzyme intermediate

    International Nuclear Information System (INIS)

    Arkowitz, R.A.; Abeles, R.H.

    1991-01-01

    Clostridial glycine reductase consists of proteins A, B, and C and catalyzes the reaction glycine + P i + 2e - → acetyl phosphate + NH 4 + . Evidence was previously obtained that is consistent with the involvement of an acyl enzyme intermediate in this reaction. The authors now demonstrate that protein C catalyzes exchange of [ 32 P]P i into acetyl phosphate, providing additional support for an acetyl enzyme intermediate on protein C. Furthermore, they have isolated acetyl protein C and shown that it is qualitatively, catalytically competent. Acetyl protein C can be obtained through the forward reaction from protein C and Se-(carboxymethyl)selenocysteine-protein A, which is generated by the reaction of glycine with proteins A and B. Acetyl protein C can also be generated through the reverse reaction by the addition of acetyl phosphate to protein C. Both procedures lead to the same acetyl enzyme. The acetyl enzyme reacts with P i to give acetyl phosphate. When [ 14 C]acetyl protein C is denaturated with TCA and redissolved with urea, radioactivity remained associated with the protein. Treatment with KBH 4 removes all the radioactivity associated with protein C, resulting in the formation of [ 14 C]ethanol. They conclude that a thiol group on protein C is acetylated. Proteins A and C together catalyze the exchange of tritium atoms from [ 3 H]H 2 O into acetyl phosphate. This exchange reaction supports the proposal that an enol of the acetyl enzyme is an intermediate in the reaction sequence

  11. Carbonylation as a key reaction in anaerobic acetone activation by Desulfococcus biacutus.

    Science.gov (United States)

    Gutiérrez Acosta, Olga B; Hardt, Norman; Schink, Bernhard

    2013-10-01

    Acetone is activated by aerobic and nitrate-reducing bacteria via an ATP-dependent carboxylation reaction to form acetoacetate as the first reaction product. In the activation of acetone by sulfate-reducing bacteria, acetoacetate has not been found to be an intermediate. Here, we present evidence of a carbonylation reaction as the initial step in the activation of acetone by the strictly anaerobic sulfate reducer Desulfococcus biacutus. In cell suspension experiments, CO was found to be a far better cosubstrate for acetone activation than CO2. The hypothetical reaction product, acetoacetaldehyde, is extremely reactive and could not be identified as a free intermediate. However, acetoacetaldehyde dinitrophenylhydrazone was detected by mass spectrometry in cell extract experiments as a reaction product of acetone, CO, and dinitrophenylhydrazine. In a similar assay, 2-amino-4-methylpyrimidine was formed as the product of a reaction between acetoacetaldehyde and guanidine. The reaction depended on ATP as a cosubstrate. Moreover, the specific activity of aldehyde dehydrogenase (coenzyme A [CoA] acylating) tested with the putative physiological substrate was found to be 153 ± 36 mU mg(-1) protein, and its activity was specifically induced in extracts of acetone-grown cells. Moreover, acetoacetyl-CoA was detected (by mass spectrometry) after the carbonylation reaction as the subsequent intermediate after acetoacetaldehyde was formed. These results together provide evidence that acetoacetaldehyde is an intermediate in the activation of acetone by sulfate-reducing bacteria.

  12. Force, reaction time, and precision of Kung Fu strikes.

    Science.gov (United States)

    Neto, Osmar Pinto; Bolander, Richard; Pacheco, Marcos Tadeu Tavares; Bir, Cynthia

    2009-08-01

    The goal was to compare values of force, precision, and reaction time of several martial arts punches and palm strikes performed by advanced and intermediate Kung Fu practitioners, both men and women. 13 Kung Fu practitioners, 10 men and three women, participated. Only the men, three advanced and seven intermediate, were considered for comparisons between levels. Reaction time values were obtained using two high speed cameras that recorded each strike at 2500 Hz. Force of impact was measured by a load cell. For comparisons of groups, force data were normalized by participant's body mass and height. Precision of the strikes was determined by a high speed pressure sensor. The results show that palm strikes were stronger than punches. Women in the study presented, on average, lower values of reaction time and force but higher values of precision than men. Advanced participants presented higher forces than intermediate participants. Significant negative correlations between the values of force and precision and the values of force and reaction time were also found.

  13. A study of the nucleus-nucleus total reaction cross section of stable systems at intermediate energies: An application to 12C

    Science.gov (United States)

    Hu, Liyuan; Song, Yushou; Hou, Yingwei; Liu, Huilan; Li, Hui

    2018-07-01

    A semi-microscopic analytical expression of the nucleus-nucleus total reaction cross section (σR) was proposed based on the strong absorption model. It is suitable for stable nuclei at intermediate energies. The matter density distributions of nuclei and the nucleon-nucleon total cross section were both considered. Particularly, the Fermi motion effect of the nucleons in a nucleus was also taken into account. The parametrization of σR was applied to the colliding systems including 12C. The experimental data at energies from 30 to 1000 MeV/nucleon were well reproduced, according to which an approach of deriving σR without adjustable parameters was developed. The necessity of considering the Fermi motion effect in the parametrization was discussed.

  14. Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

    Science.gov (United States)

    Lu, Xiu Hui; Yu, Hai Bin; Wu, Wei Rong; Xu, Yue Hua

    Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second-order Møller-Plesset (MP2)/6-31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero-point energy (ZPE) and CCSD(T)/6-31G* single-point calculations. From the PES obtained with the CCSD(T)//MP2/6-31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four-membered ring intermediate, INT2, which is a barrier-free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four-membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier-free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier-free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol.

  15. Oxidative demethylation of lanosterol in cholesterol biosynthesis: accumulation of sterol intermediates

    International Nuclear Information System (INIS)

    Shafiee, A.; Trzaskos, J.M.; Paik, Y.K.; Gaylor, J.L.

    1986-01-01

    With [ 3 H-24,25]-dihydrolanosterol as substrate, large-scale metabolic formation of intermediates of lanosterol demethylation was carried out to identify all compounds in the metabolic process. Utilizing knowledge of electron transport of lanosterol demethylation, we interrupted the demethylation reaction allowing accumulation and confirmation of the structure of the oxygenated intermediates lanost-8-en-3 beta,32-diol and 3 beta-hydroxylanost-8-en-32-al, as well as the demethylation product 4,4-dimethyl-cholesta-8,14-dien-3 beta-ol. Further metabolism of the delta 8.14-diene intermediate to a single product 4,4-dimethyl-cholest-8-en-3 beta-ol occurs under interruption conditions in the presence of 0.5 mM CN-1. With authentic compounds, each intermediate has been rigorously characterized by high performance liquid chromatography and gas-liquid chromatography plus mass spectral analysis of isolated and derivatized sterols. Intermediates that accumulated in greater abundance were further characterized by ultraviolet, 1 H-NMR, and infrared spectroscopy of the isolated sterols

  16. Organometallic copper I, II or III species in an intramolecular dechlorination reaction

    KAUST Repository

    Poater, Albert

    2013-03-15

    The present paper gives insight into an intramolecular dechlorination reaction involving Copper (I) and an ArCH2Cl moiety. The discussion of the presence of a CuIII organometallic intermediate becomes a challenge, and because of the lack of clear experimental detection of this proposed intermediate, and due to the computational evidence that it is less stable than other isomeric species, it can be ruled out for the complex studied here. Our calculations are completely consistent with the key hypothesis of Karlin et al. that TMPA-CuI is the substrate of intramolecular dechlorination reactions as well as the source to generate organometallic species. However the organometallic character of some intermediates has been refused because computationally these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction pathway explains the experimental difficulties to trap other intermediates. © Springer-Verlag Berlin Heidelberg 2013.

  17. Tensor polarized deuteron targets for intermediate energy physics experiments

    International Nuclear Information System (INIS)

    Meyer, W.; Schilling, E.

    1985-03-01

    At intermediate energies measurements from a tensor polarized deuteron target are being prepared for the following reactions: the photodisintegration of the deuteron, the elastic pion-deuteron scattering and the elastic electron-deuteron scattering. The experimental situation of the polarization experiments for these reactions is briefly discussed in section 2. In section 3 the definitions of the deuteron polarization and the possibilities to determine the vector and tensor polarization are given. Present tensor polarization values and further improvements in this field are reported in section 4. (orig.)

  18. dd →3 Hen Reaction at Intermediate Energies

    International Nuclear Information System (INIS)

    Ladygina, N. B.

    2012-01-01

    The dd → 3 Hen reaction is considered at the energies between 200 and 520 MeV. The Alt-Grassberger-Sandhas equations are iterated up to the lowest order terms over the nucleon-nucleon t-matrix. The parameterized 3He wave function including five components is used. The angular dependence of the differential cross section and energy dependence of tensor analyzing power T 20 at the zero scattering angle are presented in comparison with the experimental data. (author)

  19. Characterizing millisecond intermediates in hemoproteins using rapid-freeze-quench resonance Raman spectroscopy.

    Science.gov (United States)

    Matsumura, Hirotoshi; Moënne-Loccoz, Pierre

    2014-01-01

    The combination of rapid freeze quenching (RFQ) with resonance Raman (RR) spectroscopy represents a unique tool with which to investigate the nature of short-lived intermediates formed during the enzymatic reactions of metalloproteins. Commercially available equipment allows trapping of intermediates within a millisecond to second time scale for low-temperature RR analysis resulting in the direct detection of metal-ligand vibrations and porphyrin skeletal vibrations in hemoproteins. This chapter briefly discusses RFQ-RR studies carried out previously in our laboratory and presents, as a practical example, protocols for the preparation of RFQ samples of the reaction of metmyoglobin with nitric oxide (NO) under anaerobic conditions. Also described are important controls and practical procedures for the analysis of these samples by low-temperature RR spectroscopy.

  20. Neutrino-nucleus collision at intermediate energy

    International Nuclear Information System (INIS)

    Kosmas, T.S.; Oset, E.

    1999-01-01

    Neutrino-nucleus reactions at low and intermediate energy up to E ν = 500 MeV are studied for the most interesting nuclei from an experimental point of view. We focus on neutrino-nucleus cross-sections of semi-inclusive processes, for which recent measurements from radiochemical experiments at LAMPF and KARMEN laboratories are available. The method employed uses the modified Lindhard function for the description of the particle-hole excitations of the final nucleus via a local density approximation. (authors)

  1. A thiamin-bound, pre-decarboxylation reaction intermediate analogue in the pyruvate dehydrogenase E1 subunit induces large scale disorder-to-order transformations in the enzyme and reveals novel structural features in the covalently bound adduct.

    Science.gov (United States)

    Arjunan, Palaniappa; Sax, Martin; Brunskill, Andrew; Chandrasekhar, Krishnamoorthy; Nemeria, Natalia; Zhang, Sheng; Jordan, Frank; Furey, William

    2006-06-02

    The crystal structure of the E1 component from the Escherichia coli pyruvate dehydrogenase multienzyme complex (PDHc) has been determined with phosphonolactylthiamin diphosphate (PLThDP) in its active site. PLThDP serves as a structural and electrostatic analogue of the natural intermediate alpha-lactylthiamin diphosphate (LThDP), in which the carboxylate from the natural substrate pyruvate is replaced by a phosphonate group. This represents the first example of an experimentally determined, three-dimensional structure of a thiamin diphosphate (ThDP)-dependent enzyme containing a covalently bound, pre-decarboxylation reaction intermediate analogue and should serve as a model for the corresponding intermediates in other ThDP-dependent decarboxylases. Regarding the PDHc-specific reaction, the presence of PLThDP induces large scale conformational changes in the enzyme. In conjunction with the E1-PLThDP and E1-ThDP structures, analysis of a H407A E1-PLThDP variant structure shows that an interaction between His-407 and PLThDP is essential for stabilization of two loop regions in the active site that are otherwise disordered in the absence of intermediate analogue. This ordering completes formation of the active site and creates a new ordered surface likely involved in interactions with the lipoyl domains of E2s within the PDHc complex. The tetrahedral intermediate analogue is tightly held in the active site through direct hydrogen bonds to residues His-407, Tyr-599, and His-640 and reveals a new, enzyme-induced, strain-related feature that appears to aid in the decarboxylation process. This feature is almost certainly present in all ThDP-dependent decarboxylases; thus its inclusion in our understanding of general thiamin catalysis is important.

  2. Theoretical analysis of consecutive reactions in adiabatic stirred tank reactors

    International Nuclear Information System (INIS)

    Jo, Byung Wook; Kim, Sun Il; Hong, Won Hae; Cha, Wol Suk; Kim, Soong Pyung; Kim, Jung Gyu

    1990-01-01

    By mathematical model for the case of the consecutive first-order exothermic reaction in an adiabatic CSTR, the effects of the system parameter i. e. relative residence time, heat of reaction and thermal sensitivity of reaction rate constant, on the concentration profile of the intermediate product of a consecutive reaction were obtained as follows. For fixed values of the ratio of the reaction rate constants t 1 / t 2 , the ratio of the correponding system parameter α where α>1 and the sensitivities of the reaction rate constants S1 and S2, the maximum value of the intermediate production dimensionless concentration increases with increase in the values of the relative energy parameter E1 and E2 and it decreases with a decrease in E1 and E2. For fixed values of the ratio of the reaction rate constants t 1 / t 2 , the ratio of the corresponding system parameter α where α 1 and t 2 and it increases with a decrease in S1 and S2. For fixed values of the ratio of the reaction rate constants t 1 / t 2 , the ratio of the corresponding system parameters α where α=1 and the relative energy parameters E1 and E2, the maximum value of the intermediate product dimensionless is constant with either increase or decrease in the sensitivities of the reaction rate constants S1 and S2. (Author)

  3. Cluster Analysis of Time-Dependent Crystallographic Data: Direct Identification of Time-Independent Structural Intermediates

    Science.gov (United States)

    Kostov, Konstantin S.; Moffat, Keith

    2011-01-01

    The initial output of a time-resolved macromolecular crystallography experiment is a time-dependent series of difference electron density maps that displays the time-dependent changes in underlying structure as a reaction progresses. The goal is to interpret such data in terms of a small number of crystallographically refinable, time-independent structures, each associated with a reaction intermediate; to establish the pathways and rate coefficients by which these intermediates interconvert; and thereby to elucidate a chemical kinetic mechanism. One strategy toward achieving this goal is to use cluster analysis, a statistical method that groups objects based on their similarity. If the difference electron density at a particular voxel in the time-dependent difference electron density (TDED) maps is sensitive to the presence of one and only one intermediate, then its temporal evolution will exactly parallel the concentration profile of that intermediate with time. The rationale is therefore to cluster voxels with respect to the shapes of their TDEDs, so that each group or cluster of voxels corresponds to one structural intermediate. Clusters of voxels whose TDEDs reflect the presence of two or more specific intermediates can also be identified. From such groupings one can then infer the number of intermediates, obtain their time-independent difference density characteristics, and refine the structure of each intermediate. We review the principles of cluster analysis and clustering algorithms in a crystallographic context, and describe the application of the method to simulated and experimental time-resolved crystallographic data for the photocycle of photoactive yellow protein. PMID:21244840

  4. Detecting Elusive Intermediates in Carbohydrate Conversion: A Dynamic Ensemble of Acyclic Glucose-Catalyst Complexes

    DEFF Research Database (Denmark)

    Meier, Sebastian; Karlsson, Magnus; Jensen, Pernille Rose

    2017-01-01

    within few seconds prior to reaching a steady state. Exchange between the acyclic intermediates increases at conditions that favor epimerization. Species accounting for less than 0.05% of total glucose can be monitored with sub-second time resolution to allow kinetic analysis of intermediate formation...... and catalytic conversion. Epimerization occurs 2-3 orders of magnitude-fold faster than the binding of acyclic glucose to the catalyst at near-optimum reaction conditions. The current study brings insight in to the nature of acyclic intermediate-catalyst complexes of very low population and into experimental...... strategies for characterizing very minor intermediates in carbohydrate conversion to value-added compounds....

  5. Elimination of intermediate species in multiscale stochastic reaction networks

    DEFF Research Database (Denmark)

    Cappelletti, Daniele; Wiuf, Carsten

    2016-01-01

    such as the substrate-enzyme complex in the Michaelis-Menten mechanism. Such species are virtually in all real-world networks, they are typically short-lived, degraded at a fast rate and hard to observe experimentally. We provide conditions under which the Markov process of a multiscale reaction network...

  6. The Cascade-Exciton Approach to Nuclear Reactions. (Foundation and Achievements)

    International Nuclear Information System (INIS)

    Mashnik, S.G.

    1994-01-01

    The relativistic kinetic equations describing nuclear reactions at intermediate energies are obtained on the dynamical basis. These equations are analyzed and realized in several versions of the Cascade Exciton Model (CEM). The CEM assumes that reactions occur in three stages: the intranuclear cascade, pre-equilibrium and the evaporative ones. A large variety of experimental data on hadron- and photonuclear reactions in the bombarding energy range up to several GeV are analyzed in this approach. The contributions of different pion and photon absorption mechanisms and the relative role of different particle and photon production mechanisms in these reactions are estimated. The CEM describes adequately nuclear reactions at intermediate energies and has one of the best predictive powers as compared to other available modern models. 55 refs., 10 figs., 1 tab

  7. Ammonia oxidation at high pressure and intermediate temperatures

    DEFF Research Database (Denmark)

    Song, Yu; Hashemi, Hamid; Christensen, Jakob Munkholt

    2016-01-01

    were interpreted in terms of a detailed chemical kinetic model. The rate constant for the reaction of the important intermediate H2NO with O2 was determined from ab initio calculations to be 2.3 × 102 T2.994 exp (−9510 K/T) cm3 mol−1 s−1. The agreement between experimental results and model work...

  8. High-energy intermediates in protein unfolding characterized by thiol labeling under nativelike conditions.

    Science.gov (United States)

    Malhotra, Pooja; Udgaonkar, Jayant B

    2014-06-10

    A protein unfolding reaction usually appears to be so dominated by a large free energy barrier that identifying and characterizing high-energy intermediates and, hence, dissecting the unfolding reaction into multiple structural transitions have proven to be a challenge. In particular, it has been difficult to identify any detected high-energy intermediate with the dry (DMG) and wet (WMG) molten globules that have been implicated in the unfolding reactions of at least some proteins. In this study, a native-state thiol labeling methodology was used to identify high-energy intermediates, as well as to delineate the barriers to the disruption of side chain packing interactions and to site-specific solvent exposure in different regions of the small protein, single-chain monellin (MNEI). Labeling studies of four single-cysteine-containing variants of MNEI have identified three high-energy intermediates, populated to very low extents under nativelike conditions. A significant dispersion in the opening rates of the cysteine side chains has allowed multiple steps, leading to the loss of side chain packing, to be resolved temporally. A detailed structural analysis of the positions of the four cysteine residue positions, which are buried to different depths within the protein, has suggested a direct correlation with the structure of a DMG, detected in previous studies. It is observed that side chain packing within the core of the protein is maintained, while that at the surface is disrupted, in the DMG. The core of the protein becomes solvent-exposed only in a WMG populated after the rate-limiting step of unfolding at high denaturant concentrations.

  9. Electro-oxidation of methanol on gold in alkaline media: Adsorption characteristics of reaction intermediates studied using time resolved electro-chemical impedance and surface plasmon resonance techniques

    Science.gov (United States)

    Assiongbon, K. A.; Roy, D.

    2005-12-01

    Electro-catalytic oxidation of methanol is the anode reaction in direct methanol fuel cells. We have studied the adsorption characteristics of the intermediate reactants of this multistep reaction on a gold film electrode in alkaline solutions by combining surface plasmon resonance (SPR) measurements with Fourier transform electro-chemical impedance spectroscopy (FT-EIS). Methanol oxidation in this system shows no significant effects of "site poisoning" by chemisorbed CO. Our results suggest that OH - chemisorbed onto Au acts as a stabilizing agent for the surface species of electro-active methanol. Double layer charging/discharging and adsorption/desorption of OH - show more pronounced effects than adsorption/oxidation of methanol in controlling the surface charge density of the Au substrate. These effects are manifested in both the EIS and the SPR data, and serve as key indicators of the surface reaction kinetics. The data presented here describe the important role of adsorbed OH - in electro-catalysis of methanol on Au, and demonstrate how SPR and FT-EIS can be combined for quantitative probing of catalytically active metal-solution interfaces.

  10. Hydrogen-bonded intermediates and transition states during spontaneous and acid-catalyzed hydrolysis of the carcinogen (+)-anti-BPDE.

    Science.gov (United States)

    Palenik, Mark C; Rodriguez, Jorge H

    2014-07-07

    Understanding mechanisms of (+)-anti-BPDE detoxification is crucial for combating its mutagenic and potent carcinogenic action. However, energetic-structural correlations of reaction intermediates and transition states during detoxification via hydrolysis are poorly understood. To gain mechanistic insight we have computationally characterized intermediate and transition species associated with spontaneous and general-acid catalyzed hydrolysis of (+)-anti-BPDE. We studied the role of cacodylic acid as a proton donor in the rate limiting step. The computed activation energy (ΔG‡) is in agreement with the experimental value for hydrolysis in a sodium cacodylate buffer. Both types of, spontaneous and acid catalyzed, BPDE hydrolysis can proceed through low-entropy hydrogen bonded intermediates prior to formation of transition states whose energies determine reaction activation barriers and rates.

  11. The (3He,t) and (d,2He)reactions at intermediate energies

    International Nuclear Information System (INIS)

    Brockstedt, A.

    1987-09-01

    The ( 3 He,t) reaction has been studied at 0.6-2.3 GeV at small scattering angles, 0-7 degrees, on various nuclei ( 12 C, 13 C, 26 Mg, 40 Ca, 48 Ca, 54 Fe, 90 Zr, 159 Tb, 208 Pb) including a proton target. The reaction is a single-step reaction and selects the spin-isospin channel. Angular distributions for low-lying states in 12 N are well described by DWIA calculations. From 13 C to 13 N transitions the ratio J στ /J τ , at momentum transfer, q, close to zero, is derived. The ratio remains roughly constant in the region 300 - 700 MeV/nucleon. The position of the quasi-free peak is shifted compared with free nucleon-nucleon scattering. The shift is towards higher excitation energies at q approx 1.4 fm -1 , and towards lower excitation energies at q approx 2.5 fm -1 . The p( 3 He,t)Δ ++ reaction is analysed as one-pion exchange and the ( 3 He,t) form factor is extracted. The shape and position of the Δ resonance seem to be independent of target mass for the targets studied. Compared with the p to Δ ++ transition the position is shifted towards lower excitation energy in nuclei. The (d,2p[ 1 S 0 ]) reaction, with the two protons in an 1 S 0 state labelled 2 He, is studied at 0.65 and 2.0 GeV at small angles, 0-4 degrees, on some of the targets used in the ( 3 He,t) experiment (p, 12 C, 40 Ca, 54 Fe). This reaction is also a one-step reaction that can be used for studies of spin-isospin excitations. Cross sections and tensor analysing powers are determined for the p(d, 2 He)n reaction. These results are compared with PWIA calculations. The Δ resonance in carbon is also here shifted down in excitation energy compared with the proton target. (author)

  12. Palladium-Catalysed Coupling Reactions

    NARCIS (Netherlands)

    de Vries, Johannes G.; Beller, M; Blaser, HU

    2012-01-01

    Palladium-catalysed coupling reactions have gained importance as a tool for the production of pharmaceutical intermediates and to a lesser extent also for the production of agrochemicals, flavours and fragrances, and monomers for polymers. In this review only these cases are discussed where it seems

  13. Noncanonical Reactions of Flavoenzymes

    Directory of Open Access Journals (Sweden)

    Pablo Sobrado

    2012-11-01

    Full Text Available Enzymes containing flavin cofactors are predominantly involved in redox reactions in numerous cellular processes where the protein environment modulates the chemical reactivity of the flavin to either transfer one or two electrons. Some flavoenzymes catalyze reactions with no net redox change. In these reactions, the protein environment modulates the reactivity of the flavin to perform novel chemistries. Recent mechanistic and structural data supporting novel flavin functionalities in reactions catalyzed by chorismate synthase, type II isopentenyl diphosphate isomerase, UDP-galactopyranose mutase, and alkyl-dihydroxyacetonephosphate synthase are presented in this review. In these enzymes, the flavin plays either a direct role in acid/base reactions or as a nucleophile or electrophile. In addition, the flavin cofactor is proposed to function as a “molecular scaffold” in the formation of UDP-galactofuranose and alkyl-dihydroxyacetonephosphate by forming a covalent adduct with reaction intermediates.

  14. The three transglycosylation reactions catalyzed by cyclodextrin glycosyltransferase from Bacillus circulans (strain 251) proceed via different kinetic mechanisms

    NARCIS (Netherlands)

    Veen, Bart A. van der; Alebeek, Gert-Jan W.M. van; Uitdehaag, Joost C.M.; Dijkstra, Bauke W.; Dijkhuizen, Lubbert

    Cyclodextrin glycosyltransferase (CGTase) catalyzes three transglycosylation reactions via a double displacement mechanism involving a covalent enzyme-intermediate complex (substituted-enzyme intermediate). Characterization of the three transglycosylation reactions, however, revealed that they

  15. Low energy ion-molecule reactions

    Energy Technology Data Exchange (ETDEWEB)

    Farrar, J.M. [Univ. of Rochester, NY (United States)

    1993-12-01

    This project is concerned with elucidating the dynamics of elementary ion-molecule reactions at collision energies near and below 1 eV. From measurements of the angular and energy distributions of the reaction products, one can infer intimathe details about the nature of collisions leading to chemical reaction, the geometries and lifetimes of intermediate complexes that govern the reaction dynamics, and the collision energy dependence of these dynamical features. The author employs crossed-beam low energy mass spectrometry technology developed over the last several years, with the focus of current research on proton transfer and hydrogen atom transfer reactions of te O{sup {minus}} ion with species such as HF, H{sub 2}O, and NH{sub 3}.

  16. Basic reactions induced by radiation

    International Nuclear Information System (INIS)

    Charlesby, A.

    1980-01-01

    This paper summarises some of the basic reactions resulting from exposure to high energy radiation. In the initial stages energy is absorbed, but not necessarily at random, giving radical and ion species which may then react to promote the final chemical change. However, it is possible to intervene at intermediate stages to modify or reduce the radiation effect. Under certain conditions enhanced reactions are also possible. Several expressions are given to calculate radiation yield in terms of energy absorbed. Some analogies between radiation-induced reactions in polymers, and those studied in radiobiology are outlined. (author)

  17. Use of Isotopes for Studying Reaction Mechanisms

    Indian Academy of Sciences (India)

    In the first part of this series, we discussed how isotopes can be used as markers to determine the nature of intermediates in chemical reactions. The second part covered the effect of isotopes on equilibria and reactions, in processes where the bond to the isotopic a tom is broken. We showed with specific examples how.

  18. Explore the reaction mechanism of the Maillard reaction: a density functional theory study.

    Science.gov (United States)

    Ren, Ge-Rui; Zhao, Li-Jiang; Sun, Qiang; Xie, Hu-Jun; Lei, Qun-Fang; Fang, Wen-Jun

    2015-05-01

    The mechanism of Maillard reaction has been investigated by means of density functional theory calculations in the gaseous phase and aqueous solution. The Maillard reaction is a cascade of consecutive and parallel reaction. In the present model system study, glucose and glycine were taken as the initial reactants. On the basis of previous experimental results, the mechanisms of Maillard reaction have been proposed, and the possibility for the formation of different compounds have been evaluated through calculating the relative energy changes for different steps of reaction under different pH conditions. Our calculations reveal that the TS3 in Amadori rearrangement reaction is the rate-determining step of Maillard reaction with the activation barriers of about 66.7 and 68.8 kcal mol(-1) in the gaseous phase and aqueous solution, respectively. The calculation results are in good agreement with previous studies and could provide insights into the reaction mechanism of Maillard reaction, since experimental evaluation of the role of intermediates in the Maillard reaction is quite complicated.

  19. CuInSe2 nano-crystallite reaction kinetics using solid state reaction from Cu2Se and In2Se3 powders

    International Nuclear Information System (INIS)

    Hsiang, Hsing-I; Lu, Li-Hsin; Chang, Yu-Lun; Ray, Dahtong; Yen, Fu-Su

    2011-01-01

    Highlights: → CuInSe 2 phase increased gradually accompanied with a decrease in γ-In 2 Se 3 and no intermediate phase during calcination. → CuInSe 2 formation from Cu 2 Se and In 2 Se 3 powders follows a one-dimensional diffusion-controlled reaction with apparent activation energy of about 122.5 kJ/mol. → The solid reaction kinetics may be dominated by the diffusion of In 3+ ions. - Abstract: The reaction mechanism and CuInSe 2 formation kinetics using a solid state reaction from Cu 2 Se and In 2 Se 3 powders synthesized using a heating up process were investigated using X-ray diffractomy (XRD) and transmission electron microscopy (TEM). It was observed that the CuInSe 2 phase increased gradually, accompanied with a decrease in γ-In 2 Se 3 with no intermediate phase as the calcination temperature and soaking time were increased. The reaction kinetics was analyzed using the Avrami and polynomial kinetic model, suggesting that CuInSe 2 formation from Cu 2 Se and In 2 Se 3 powders follows a diffusion-controlled reaction with an apparent activation energy of about 122.5-182.3 kJ/mol. Cu 2 Se and In 2 Se 3 phases react and directly transform into CIS without the occurrence of any intermediate phase and the size of the newly formed CuInSe 2 crystallites was close to that of the Cu 2 Se reactant particle based on the TEM results, which indicated that the solid reaction kinetics may be dominated by the diffusion of In 3+ ions.

  20. Fast screening of analytes for chemical reactions by reactive low-temperature plasma ionization mass spectrometry.

    Science.gov (United States)

    Zhang, Wei; Huang, Guangming

    2015-11-15

    Approaches for analyte screening have been used to aid in the fine-tuning of chemical reactions. Herein, we present a simple and straightforward analyte screening method for chemical reactions via reactive low-temperature plasma ionization mass spectrometry (reactive LTP-MS). Solution-phase reagents deposited on sample substrates were desorbed into the vapor phase by action of the LTP and by thermal desorption. Treated with LTP, both reagents reacted through a vapor phase ion/molecule reaction to generate the product. Finally, protonated reagents and products were identified by LTP-MS. Reaction products from imine formation reaction, Eschweiler-Clarke methylation and the Eberlin reaction were detected via reactive LTP-MS. Products from the imine formation reaction with reagents substituted with different functional groups (26 out of 28 trials) were successfully screened in a time of 30 s each. Besides, two short-lived reactive intermediates of Eschweiler-Clarke methylation were also detected. LTP in this study serves both as an ambient ionization source for analyte identification (including reagents, intermediates and products) and as a means to produce reagent ions to assist gas-phase ion/molecule reactions. The present reactive LTP-MS method enables fast screening for several analytes from several chemical reactions, which possesses good reagent compatibility and the potential to perform high-throughput analyte screening. In addition, with the detection of various reactive intermediates (intermediates I and II of Eschweiler-Clarke methylation), the present method would also contribute to revealing and elucidating reaction mechanisms. Copyright © 2015 John Wiley & Sons, Ltd.

  1. Intermediate Energy Activation File (IEAF-99)

    International Nuclear Information System (INIS)

    Korovin, Yu.; Konobeev, A.; Pereslavtsev, P.; Stankovskij, A.; Fischer, U.; Moellendorff, U. von

    1999-01-01

    Nuclear data library IEAF-99, elaborated to study processes of interactions of intermediate energy neutrons with materials in accelerator driven systems, is described. The library is intended for activation and transmutation studies for materials irradiated by neutrons. IEAF-99 contains evaluated neutron induced reaction cross sections at the energies 0-150 MeV for 665 stable and unstable nuclei from C to Po. Approximately 50,000 excitation functions are included in the library. The IEAF-99 data are written in the ENDF-6 format combining MF = 3,6 MT = 5 data recording. (author)

  2. Crystal structure of the covalent intermediate of amylosucrase from Neisseria polysaccharea

    DEFF Research Database (Denmark)

    Jensen, Malene H; Mirza, Osman Asghar; Albenne, Cecile

    2004-01-01

    The alpha-retaining amylosucrase from the glycoside hydrolase family 13 performs a transfer reaction of a glucosyl moiety from sucrose to an acceptor molecule. Amylosucrase has previously been shown to be able to use alpha-D-glucopyranosyl fluoride as a substrate, which suggested that it could also...... the first covalent intermediate of an alpha-retaining glycoside hydrolase where the glucosyl moiety is identical to the expected biologically relevant entity. Comparison to other enzymes with anticipated glucosylic covalent intermediates suggests that this structure is a representative model...... for such intermediates. Analysis of the active site shows how oligosaccharide binding disrupts the putative nucleophilic water binding site found in the hydrolases of the GH family 13. This reveals important parts of the structural background for the shift in function from hydrolase to transglycosidase seen...

  3. On the reaction of the nitroso group with olefins. Mechanisms of ene reactions

    International Nuclear Information System (INIS)

    Seymour, C.A.; Greene, F.D.

    1982-01-01

    Intra- and intermolecular isotope effects point to a two-step process for the reaction of pentafluoronitrosobenzene with tetramethylethylene to afford the ene product, rate-determining formation of an intermediate (for which the arizidine N-oxide is suggested) followed by C-H (or C-D) cleavage to the ene product

  4. Exploring the chemical kinetics of partially oxidized intermediates by combining experiments, theory, and kinetic modeling.

    Science.gov (United States)

    Hoyermann, Karlheinz; Mauß, Fabian; Olzmann, Matthias; Welz, Oliver; Zeuch, Thomas

    2017-07-19

    Partially oxidized intermediates play a central role in combustion and atmospheric chemistry. In this perspective, we focus on the chemical kinetics of alkoxy radicals, peroxy radicals, and Criegee intermediates, which are key species in both combustion and atmospheric environments. These reactive intermediates feature a broad spectrum of chemical diversity. Their reactivity is central to our understanding of how volatile organic compounds are degraded in the atmosphere and converted into secondary organic aerosol. Moreover, they sensitively determine ignition timing in internal combustion engines. The intention of this perspective article is to provide the reader with information about the general mechanisms of reactions initiated by addition of atomic and molecular oxygen to alkyl radicals and ozone to alkenes. We will focus on critical branching points in the subsequent reaction mechanisms and discuss them from a consistent point of view. As a first example of our integrated approach, we will show how experiment, theory, and kinetic modeling have been successfully combined in the first infrared detection of Criegee intermediates during the gas phase ozonolysis. As a second example, we will examine the ignition timing of n-heptane/air mixtures at low and intermediate temperatures. Here, we present a reduced, fuel size independent kinetic model of the complex chemistry initiated by peroxy radicals that has been successfully applied to simulate standard n-heptane combustion experiments.

  5. Electrophilic aromatic substitution over zeolites generates Wheland-type reaction intermediates

    NARCIS (Netherlands)

    Chowdhury, Abhishek Dutta; Houben, Klaartje; Whiting, Gareth T.; Chung, Sangho; Baldus, Marc; Weckhuysen, Bert M.

    2018-01-01

    The synthesis of many industrial bulk and fine chemicals frequently involves electrophilic aromatic substitution (SEAr) reactions. The most widely practiced example of the SEAr mechanism is the zeolite-catalysed ethylation of benzene, using ethylene as an alkylating agent. However, the current

  6. Multipulse spectroscopy on the wild-type and YM210W Bacterial Reaction Centre uncovers a new intermediate state in the special pair excited state

    Science.gov (United States)

    Cohen Stuart, T. A.; van Grondelle, R.

    2009-06-01

    The Bacterial Reaction Centre (BRC) has a complex electronic excited state, P ∗, that evolves into subsequent charge separated product states P +H - and P +B -. Pump-dump-probe spectroscopy on the wild-type BRC and on YM210W, a mutant with a stabilized, long-lived P ∗ excited state, has uncovered a new charge-separated state in both BRC's. When P ∗ is dumped, a fraction of its population is transferred to this state that has a strong Stark shift in the accessory bacteriochlorophyll (B M) region which serves as a signature for P + and a lifetime highly comparable to the slow phase of P ∗ decay. This lead us propose this intermediate to be P +/P -.

  7. A low stringency polymerase chain reaction approach to the identification of Biomphalaria glabrata and B. tenagophila, intermediate snail hosts of Schistosoma mansoni in Brazil

    Directory of Open Access Journals (Sweden)

    Teofânia HDA Vidigal

    1996-12-01

    Full Text Available The low stringency-polymerase chain reaction (LS-PCR with a pair of specific primers for the amplification of the 18S rRNA gene was evaluated as a means of differentiating between the two Schistosoma mansoni intermediate host species in Brazil: Biomphalaria glabrata and B. tenagophila. Individual snails obtained from different states of Brazil were used and the amplification patterns obtained showed a high degree of genetic variability in these species. Nevertheless, 4 and 3 clearly defined specific diagnostic bands was observed in individuals from B. glabrata and B. tenagophila respectively. The detection of snail specific diagnostic bands suggests the possibility of reliable species differentiation at the DNA level using LS-PCR.

  8. Investigating radical cation chain processes in the electrocatalytic Diels-Alder reaction.

    Science.gov (United States)

    Imada, Yasushi; Okada, Yohei; Chiba, Kazuhiro

    2018-01-01

    Single electron transfer (SET)-triggered radical ion-based reactions have proven to be powerful options in synthetic organic chemistry. Although unique chain processes have been proposed in various photo- and electrochemical radical ion-based transformations, the turnover number, also referred to as catalytic efficiency, remains unclear in most cases. Herein, we disclose our investigations of radical cation chain processes in the electrocatalytic Diels-Alder reaction, leading to a scalable synthesis. A gram-scale synthesis was achieved with high current efficiency of up to 8000%. The reaction monitoring profiles showed sigmoidal curves with induction periods, suggesting the involvement of intermediate(s) in the rate determining step.

  9. Spectroscopic approaches to resolving ambiguities of hyper-polarized NMR signals from different reaction cascades

    DEFF Research Database (Denmark)

    Jensen, Pernille Rose; Meier, Sebastian

    2016-01-01

    The influx of exogenous substrates into cellular reaction cascades on the seconds time scale is directly observable by NMR spectroscopy when using nuclear spin polarization enhancement. Conventional NMR assignment spectra for the identification of reaction intermediates are not applicable...... in these experiments due to the non-equilibrium nature of the nuclear spin polarization enhancement. We show that ambiguities in the intracellular identification of transient reaction intermediates can be resolved by experimental schemes using site-specific isotope labelling, optimised referencing and response...

  10. Theory of nuclear structure and reactions. Annual technical progress report, April 1, 1984-March 31, 1985

    International Nuclear Information System (INIS)

    Macfarlane, M.H.; Serot, B.D.

    1985-01-01

    In the period covered by this report, work focused on five main areas: (1) relativistic effects in intermediate-energy nuclear reactions; (2) the role of quarks and gluons in nuclear physics; (3) quantum hadrodynamics and relativistic nuclear mean-field theory; (4) structure and reaction effects in intermediate-energy nuclear reactions; and (5) weak and electromagnetic interactions in nuclei. Results and publications in these areas are summarized. Publications are listed

  11. Kinetic aspects of the Maillard reaction: a critical review

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    2001-01-01

    The literature concerning the kinetics of the Maillard reaction was critically discussed according to the initial, intermediate and advanced stages, as this is the way the Maillard reaction is traditionally analysed. For each stage, a division is made between simple kinetics and complex kinetics.

  12. Ion-molecule reactions: their role in radiation chemistry

    International Nuclear Information System (INIS)

    Lias, S.G.; Ausloos, P.

    1975-01-01

    A comprehensive review of ion--molecule reactions is presented, including information from mass spectrometric, organic chemistry, and NMR studies, from theoretical calculations, and from gas and liquid phase radiation chemistry. Special emphasis is placed on interpreting the role of ion--molecule reactions in systems under high energy irradiation. The discussion is presented under the following chapter headings: ion--molecule reactions and their role in radiation chemistry; unimolecular processes: the nature and structure of ionic intermediates in radiolysis; ion lifetimes and the fate of unreactive ions; kinetics and mechanisms of ion--molecule reactions; proton transfer reactions; negative atom and two-atom transfer reactions; condensation reactions; and, association or clustering reactions

  13. Studies of complex fragment emission in heavy ion reactions

    International Nuclear Information System (INIS)

    Sobotka, L.G.

    1989-01-01

    The production of large fragments, fragments with mass between light particles and fission fragments, in intermediate and high energy nuclear reactions has fostered the proposal of a number of novel reaction mechanisms. These include liquid-vapor equilibrium and nuclear shattering. Temporarily left in the wake of these exciting proposed mechanisms was the old standard, statistical decay of compound nuclei. To be sure, the standard treatment of compound nucleus decay did not deal with large fragment production. However, this omission was not due to any fundamental deficiency of statistical models, but rather an uncertainty concerning exactly how to splice large fragment emission into statistical models. A large portion of our program deals with this problem. Specifically, by studying the yields of large fragments produced in sufficiently low energy reactions we are attempting to deduce the asymmetry and l-wave dependence of large fragment emission from compound nuclear intermediates. This, however, is only half of the problem. Since the novel mechanisms proposed for large fragment emission were spawned by intermediate and high energy reaction data, we must also realize the relevance of the compound nucleus mechanisms at high energies. It is not unreasonable to suspect that compound nucleus-like objects are formed with less than complete momentum transfer and perhaps less than complete mass transfer. Therefore the study of energy, mass, and angular momentum transfer in incomplete fusion and non-compound reactions. This thread joins the apparently divergent subjects covered in this report

  14. Pulse radiolysis study of the intermediates formed in ionic liquids. Intermediate spectra in the p-terphenyl solution in the ionic liquid methyltributylammonium bis[(trifluoromethyl)sulfonyl]imide

    International Nuclear Information System (INIS)

    Grodkowski, J.; Kocia, R.; Mirkowski, J.

    2006-01-01

    Room temperature ionic liquids (Il) are non-volatile,and non-flammable and serve as good solvents for various reactions, mainly for g reen processing . To understand the effect of these solvents on the chemical reactions, the rate constants of several elementary reactions in ionic liquids have been studied by the pulse radiolysis technique. In this study, the formation of intermediates derived from p-terphenyl (Tp) in the ionic liquid methyl tributylammonium bis[(trifluoromethyl)sulfonyl] imide (R 4 NNTf 2 ) solutions have been studied by pulse radiolysis as a part of broader studies concerning CO 2 reduction. The registered spectra can be explained by CO 2 reaction with solvated and dry electrons thus eliminating one path of TP ·- formation. Some TP ·- are formed by reaction of excited TP *- states with Tea. Direct reactions involving Tp, TP ·- , CO 2 and CO 2 ·- are too slow to be observed in pulse radiolysis time scale

  15. Limits for Stochastic Reaction Networks

    DEFF Research Database (Denmark)

    Cappelletti, Daniele

    Reaction systems have been introduced in the 70s to model biochemical systems. Nowadays their range of applications has increased and they are fruitfully used in dierent elds. The concept is simple: some chemical species react, the set of chemical reactions form a graph and a rate function...... is associated with each reaction. Such functions describe the speed of the dierent reactions, or their propensities. Two modelling regimes are then available: the evolution of the dierent species concentrations can be deterministically modelled through a system of ODE, while the counts of the dierent species...... at a certain time are stochastically modelled by means of a continuous-time Markov chain. Our work concerns primarily stochastic reaction systems, and their asymptotic properties. In Paper I, we consider a reaction system with intermediate species, i.e. species that are produced and fast degraded along a path...

  16. Multiple scattering theory and applications for intermediate energy reactions of nuclei

    International Nuclear Information System (INIS)

    Ludeking, L.D.

    1979-01-01

    Interactions of two composite clusters are treated in a multiple scattering framework whereby many-particle operators are decomposed into a systematic and finite series such that there is an ordered sequestering according to particle rank. Thus, an N-body operator is written as the superposition of all distinct groupings of interactions that occur between particle pairs, triplets, quartets, etc., such that all groupings contain at least one particle from each of the composite systems. It is demonstrated how the transition operator, a reaction operator, and an optical potential may be described in this context. The general structure of such decompositions is shown, and the connection to the standard multiple-scattering prescriptions, delineated. The direct reaction amplitude for stripping and pickup is described, and the two potential formula of Gell-Mann and Goldberger is derived. The multiple scattering formalism for direct reactions is constructed in the eikonal approximation. The sensitivity of the transition cross section to the target density and nucleon-nucleon density correlations are examined in this framework. The limitations of the zero-range approximation to the deuteron vertex function are examined by comparison with the finite-range vertex function at a range of energies. 25 figures, 5 tables

  17. Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes.

    Science.gov (United States)

    Liwosz, Timothy W; Chemler, Sherry R

    2013-06-21

    We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.

  18. Catalytic Ozonation of Phenolic Wastewater: Identification and Toxicity of Intermediates

    Directory of Open Access Journals (Sweden)

    Mahdi Farzadkia

    2014-01-01

    Full Text Available A new strategy in catalytic ozonation removal method for degradation and detoxification of phenol from industrial wastewater was investigated. Magnetic carbon nanocomposite, as a novel catalyst, was synthesized and then used in the catalytic ozonation process (COP and the effects of operational conditions such as initial pH, reaction time, and initial concentration of phenol on the degradation efficiency and the toxicity assay have been investigated. The results showed that the highest catalytic potential was achieved at optimal neutral pH and the removal efficiency of phenol and COD is 98.5% and 69.8%, respectively. First-order modeling demonstrated that the reactions were dependent on the initial concentration of phenol, with kinetic constants varying from 0.038 min−1  ([phenol]o = 1500 mg/L to 1.273 min−1 ([phenol]o = 50 mg/L. Bioassay analysis showed that phenol was highly toxic to Daphnia magna (LC50 96 h=5.6 mg/L. Comparison of toxicity units (TU of row wastewater (36.01 and the treated effluent showed that TU value, after slightly increasing in the first steps of ozonation for construction of more toxic intermediates, severely reduced at the end of reaction (2.23. Thus, COP was able to effectively remove the toxicity of intermediates which were formed during the chemical oxidation of phenolic wastewaters.

  19. Direct single-molecule dynamic detection of chemical reactions.

    Science.gov (United States)

    Guan, Jianxin; Jia, Chuancheng; Li, Yanwei; Liu, Zitong; Wang, Jinying; Yang, Zhongyue; Gu, Chunhui; Su, Dingkai; Houk, Kendall N; Zhang, Deqing; Guo, Xuefeng

    2018-02-01

    Single-molecule detection can reveal time trajectories and reaction pathways of individual intermediates/transition states in chemical reactions and biological processes, which is of fundamental importance to elucidate their intrinsic mechanisms. We present a reliable, label-free single-molecule approach that allows us to directly explore the dynamic process of basic chemical reactions at the single-event level by using stable graphene-molecule single-molecule junctions. These junctions are constructed by covalently connecting a single molecule with a 9-fluorenone center to nanogapped graphene electrodes. For the first time, real-time single-molecule electrical measurements unambiguously show reproducible large-amplitude two-level fluctuations that are highly dependent on solvent environments in a nucleophilic addition reaction of hydroxylamine to a carbonyl group. Both theoretical simulations and ensemble experiments prove that this observation originates from the reversible transition between the reactant and a new intermediate state within a time scale of a few microseconds. These investigations open up a new route that is able to be immediately applied to probe fast single-molecule physics or biophysics with high time resolution, making an important contribution to broad fields beyond reaction chemistry.

  20. NO-oxygen scavenger or reaction intermediate in the decomposition of N2O?

    Czech Academy of Sciences Publication Activity Database

    Nováková, Jana; Sobalík, Zdeněk

    2006-01-01

    Roč. 111, 3-4 (2006), s. 195-202 ISSN 1011-372X R&D Projects: GA AV ČR 1ET400400413 Institutional research plan: CEZ:AV0Z40400503 Keywords : 15N2 18O and 15N2 18 O + 14N 16O decomposition * role of NOx intermediates * Fe-zeolites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.772, year: 2006

  1. Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air.

    Science.gov (United States)

    Zhao, Yue; Wingen, Lisa M; Perraud, Véronique; Greaves, John; Finlayson-Pitts, Barbara J

    2015-05-21

    Ozonolysis of alkenes is an important source of secondary organic aerosol (SOA) in the atmosphere. However, the mechanisms by which stabilized Criegee intermediates (SCI) react to form and grow the particles, and in particular the contributions from oligomers, are not well understood. In this study, ozonolysis of trans-3-hexene (C6H12), as a proxy for small alkenes, was investigated with an emphasis on the mechanisms of particle formation and growth. Ozonolysis experiments were carried out both in static Teflon chambers (18-20 min reaction times) and in a glass flow reactor (24 s reaction time) in the absence and presence of OH or SCI scavengers, and under different relative humidity (RH) conditions. The chemical composition of polydisperse and size-selected SOA particles was probed using different mass spectrometric techniques and infrared spectroscopy. Oligomers having SCI as the chain unit are found to be the dominant components of such SOA particles. The formation mechanism for these oligomers suggested by our results follows the sequential addition of SCI to organic peroxy (RO2) radicals, in agreement with previous studies by Moortgat and coworkers. Smaller particles are shown to have a relatively greater contribution from longer oligomers. Higher O/C ratios are observed in smaller particles and are similar to those of oligomers resulting from RO2 + nSCI, supporting a significant role for longer oligomers in particle nucleation and early growth. Under atmospherically relevant RH of 30-80%, water vapor suppresses oligomer formation through scavenging SCI, but also enhances particle nucleation. Under humid conditions, or in the presence of formic or hydrochloric acid as SCI scavengers, peroxyhemiacetals are formed by the acid-catalyzed particle phase reaction between oligomers from RO2 + nSCI and a trans-3-hexene derived carbonyl product. In contrast to the ozonolysis of trans-3-hexene, oligomerization involving RO2 + nSCI does not appear to be prevalent in the

  2. Contribution to the study of πN→π1π2N reactions with creation of an intermediate N*sub(3/2) (1236) isobare from 0.4 to 1.5 GeV

    International Nuclear Information System (INIS)

    Merlo, J.P.

    1976-10-01

    The one pion production reaction π + p→π + pπ 0 has been studied up to 1.5 GeV. The π 0 angular distribution measured by counter techniques has been compared to bubble chamber data. Angular distributions are interpreted in the hypothesis of formation of the intermediate N*sub(3/2) (1236) isobar. Angular distributions for isobar production and decay in one pion production reactions πN→π 1 N* (N*→π 2 N) are calculated. π + p→π + pπ 0 experimental results are reported and analyzed. An estimation of the pion-isobar partial wave amplitudes in reaction π + p→π 0 N*sub(3/2)sup(++) (1236) has been tempted. Comparison with π + p phase shift analyses is made. Bubble chamber data for π - p→π - π + n channel are presented [fr

  3. Sodium-sodium intermediate heat exchangers design problems

    International Nuclear Information System (INIS)

    Chandramohan, R.

    1975-01-01

    This paper deals briefly with the calculation methods adapted, in working-out the stresses due to fluid pressures (normal as well as transient), weights, piping-reactions, vibration in the tube-bundle and also the thermal stresses during normal and transient conditions, for the mechanical design of intermediate heat-exchanger. The thermal stress evaluation of the tube-sheet is given particular emphasis. A brief outline of the design problems connected with the Na-Na exchangers of large size sodium cooled fast reactor plants is also given. (author)

  4. Effect of surface structure on catalytic reactions: A sum frequency generation surface vibrational spectroscopy study

    International Nuclear Information System (INIS)

    McCrea, Keith R.

    2001-01-01

    In the results discussed above, it is clear that Sum Frequency Generation (SFG) is a unique tool that allows the detection of vibrational spectra of adsorbed molecules present on single crystal surfaces under catalytic reaction conditions. Not only is it possible to detect active surface intermediates, it is also possible to detect spectator species which are not responsible for the measured turnover rates. By correlating high-pressure SFG spectra under reaction conditions and gas chromatography (GC) kinetic data, it is possible to determine which species are important under reaction intermediates. Because of the flexibility of this technique for studying surface intermediates, it is possible to determine how the structures of single crystal surfaces affect the observed rates of catalytic reactions. As an example of a structure insensitive reaction, ethylene hydrogenation was explored on both Pt(111) and Pt(100). The rates were determined to be essentially the same. It was observed that both ethylidyne and di-(sigma) bonded ethylene were present on the surface under reaction conditions on both crystals, although in different concentrations. This result shows that these two species are not responsible for the measured turnover rate, as it would be expected that one of the two crystals would be more active than the other, since the concentration of the surface intermediate would be different on the two crystals. The most likely active intermediates are weakly adsorbed molecules such as(pi)-bonded ethylene and ethyl. These species are not easily detected because their concentration lies at the detection limit of SFG. The SFG spectra and GC data essentially show that ethylene hydrogenation is structure insensitive for Pt(111) and Pt(100). SFG has proven to be a unique and excellent technique for studying adsorbed species on single crystal surfaces under high-pressure catalytic reactions. Coupled with kinetic data obtained from gas chromatography measurements, it can

  5. Moessbauer- and EPR-Snapshots of an Enzymatic Reaction: The Cytochrome P450 Reaction Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Schuenemann, V. [University of Luebeck, Institute of Physics (Germany); Jung, C. [Max-Delbrueck-Center for Molecular Medicine (Germany); Lendzian, F. [Technical University, PC 14, Max-Volmer Laboratory for Biophysical Chemistry (Germany); Barra, A.-L. [Grenoble High Magnetic Field Laboratory (France); Teschner, T.; Trautwein, A. X. [University of Luebeck, Institute of Physics (Germany)

    2004-12-15

    In this communication we present a complimentary Moessbauer- and EPR-study of the time dependance of the reaction of substrate free P450cam with peracetic acid within a time region ranging from 8 ms up to 5 min. An Fe(IV) species as well as a tyrosyl radical residing on the amino acid residue Tyr96 have been identified as reaction intermediates. These species possibly are formed by the reduction of compound I by means of transferring an electron from Tyr 96 to the heme moiety.

  6. Moessbauer- and EPR-Snapshots of an Enzymatic Reaction: The Cytochrome P450 Reaction Cycle

    International Nuclear Information System (INIS)

    Schuenemann, V.; Jung, C.; Lendzian, F.; Barra, A.-L.; Teschner, T.; Trautwein, A. X.

    2004-01-01

    In this communication we present a complimentary Moessbauer- and EPR-study of the time dependance of the reaction of substrate free P450cam with peracetic acid within a time region ranging from 8 ms up to 5 min. An Fe(IV) species as well as a tyrosyl radical residing on the amino acid residue Tyr96 have been identified as reaction intermediates. These species possibly are formed by the reduction of compound I by means of transferring an electron from Tyr 96 to the heme moiety.

  7. Correlations between reaction product yields as a tool for probing heavy-ion reaction scenarios

    International Nuclear Information System (INIS)

    Gawlikowicz, W.; Agnihotri, D. K.; Baldwin, S. A.; Schroeder, W. U.; Toke, J.; Charity, R. J.; Sarantites, D. G.; Sobotka, L. G.; Souza, R. T. de; Barczyk, T.; Grotowski, K.; Micek, S.; Planeta, R.; Sosin, Z.

    2010-01-01

    Experimental multidimensional joint distributions of neutrons and charged reaction products were analyzed for 136 Xe + 209 Bi reactions at E/A=28, 40, and 62 MeV and were found to exhibit several different types of prominent correlation patterns. Some of these correlations have a simple explanation in terms of the system excitation energy and pose little challenge to most statistical decay theories. However, several other types of correlation patterns are difficult to reconcile with some, but not other, possible reaction scenarios. In this respect, correlations between the average atomic numbers of intermediate-mass fragments, on the one hand, and light particle multiplicities, on the other, are notable. This kind of multiparticle correlation provides a useful tool for probing reaction scenarios, which is different from the traditional approach of interpreting inclusive yields of individual reaction products.

  8. Intermediates and the folding of proteins L and G

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Scott; Head-Gordon, Teresa

    2003-07-01

    We use a minimalist protein model, in combination with a sequence design strategy, to determine differences in primary structure for proteins L and G that are responsible for the two proteins folding through distinctly different folding mechanisms. We find that the folding of proteins L and G are consistent with a nucleation-condensation mechanism, each of which is described as helix-assisted {beta}-1 and {beta}-2 hairpin formation, respectively. We determine that the model for protein G exhibits an early intermediate that precedes the rate-limiting barrier of folding and which draws together misaligned secondary structure elements that are stabilized by hydrophobic core contacts involving the third {beta}-strand, and presages the later transition state in which the correct strand alignment of these same secondary structure elements is restored. Finally the validity of the targeted intermediate ensemble for protein G was analyzed by fitting the kinetic data to a two-step first order reversible reaction, proving that protein G folding involves an on-pathway early intermediate, and should be populated and therefore observable by experiment.

  9. CUE USAGE IN VOLLEYBALL: A TIME COURSE COMPARISON OF ELITE, INTERMEDIATE AND NOVICE FEMALE PLAYERS

    Directory of Open Access Journals (Sweden)

    P Vansteenkiste

    2015-01-01

    Full Text Available This study compared visual search strategies in adult female volleyball players of three levels. Video clips of the attack of the opponent team were presented on a large screen and participants reacted to the final pass before the spike. Reaction time, response accuracy and eye movement patterns were measured. Elite players had the highest response accuracy (97.50 ± 3.5% compared to the intermediate (91.50 ± 4.7% and novice players (83.50 ± 17.6%; p<0.05. Novices had a remarkably high range of reaction time but no significant differences were found in comparison to the reaction time of elite and intermediate players. In general, the three groups showed similar gaze behaviour with the apparent use of visual pivots at moments of reception and final pass. This confirms the holistic model of image perception for volleyball and suggests that expert players extract more information from parafoveal regions.

  10. Chemical reactions induced by fast neutron irradiation

    International Nuclear Information System (INIS)

    Katsumura, Y.

    1989-01-01

    Here, several studies on fast neutron irradiation effects carried out at the reactor 'YAYOI' are presented. Some indicate a significant difference in the effect from those by γ-ray irradiation but others do not, and the difference changes from subject to subject which we observed. In general, chemical reactions induced by fast neutron irradiation expand in space and time, and there are many aspects. In the time region just after the deposition of neutron energy in the system, intermediates are formed densely and locally reflecting high LET of fast neutrons and, with time, successive reactions proceed parallel to dissipation of localized energy and to diffusion of the intermediates. Finally the reactions are completed in longer time region. If we pick up the effects which reserve the locality of the initial processes, a significant different effect between in fast neutron radiolysis and in γ-ray radiolysis would be derived. If we observe the products generated after dissipation and diffusion in longer time region, a clear difference would not be observed. Therefore, in order to understand the fast neutron irradiation effects, it is necessary to know the fundamental processes of the reactions induced by radiations. (author)

  11. Intercomparison of codes for intermediate energy nuclear data: The first step

    International Nuclear Information System (INIS)

    Blann, M.; Gruppelaar, H.; Nagel, P.; Rodens, J.

    1994-01-01

    Several weak points of the intermediate energy nuclear data calculated in this exercise are described as introduction to some of the areas needing discussion at this meeting. These include nuclear structure effects on precompound spectra, large variations between codes in predicted total reaction cross sections, and in total neutron and proton multiplicities. INC codes don't reflect correct experimental Q values, and may have difficulties at very low angles due to overestimation of the quasi-elastic peak. We raise questions as to additional reaction properties (beyond n and p spectra) which may need benchmarking

  12. The decay of hot nuclei formed in La-induced reactions at intermediate energies

    International Nuclear Information System (INIS)

    Libby, B.; Mignerey, A.C.; Madani, H.; Marchetti, A.A.; Colonna, M.; DiToro, M.

    1992-01-01

    The decay of hot nuclei formed in lanthanum-induced reactions utilizing inverse kinematics has been studied from E/A = 35 to 55 MeV. At each bombarding energy studied, the probability for the multiple emission of complex fragments has been found to be independent of target. Global features (total charge, source velocity) of the reaction La + Al at E/A = 45 MeV have been reproduced by coupling a dynamical model to study the collision stage of the reaction to a statistical model of nuclear decay

  13. Exploration of the Singlet O2 Oxidation of 8-Oxoguanine by Guided-Ion Beam Scattering and Density Functional Theory: Changes of Reaction Intermediates, Energetics, and Kinetics upon Protonation/Deprotonation and Hydration.

    Science.gov (United States)

    Sun, Yan; Lu, Wenchao; Liu, Jianbo

    2017-02-09

    8-Oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) is one of the most common DNA lesions resulting from reactive oxygen species and ionizing radiation, and is involved in mutagenesis, carcinogenesis, and cell death. Notably, 8-oxodGuo is more reactive toward singlet (a 1 Δ g ) O 2 than the undamaged guanosine, and the lesions arising from the secondary oxidation of 8-oxodGuo are more mutagenic. Herein the 1 O 2 oxidation of free base 8-oxoguanine (8-oxoG) was investigated at different initial conditions including protonated [8-oxoG + H] + , deprotonated [8-oxoG - H] - , and their monohydrates. Experiment was carried out on a guided-ion beam scattering tandem mass spectrometer. Measurements include the effects of collision energy (E col ) on reaction cross sections over a center-of-mass E col range from 0.1 to 0.5 eV. The aim of this study is to quantitatively probe the sensitivity of the early stage of 8-oxoG oxidation to ionization and hydration. Density functional theory and Rice-Ramsperger-Kassel-Marcus calculations were performed to identify the intermediates and the products along reaction pathways and locate accessible reaction potential energy surfaces, and to rationalize reaction outcomes from energetic and kinetic points of view. No product was observed for the reaction of [8-oxoG + H] + ·W 0,1 (W = H 2 O) because insurmountable barriers block the addition of 1 O 2 to reactant ions. Neither was [8-oxoG - H] - reactive with 1 O 2 , in this case due to the rapid decay of transient intermediates to starting reactants. However, the nonreactivity of [8-oxoG - H] - was inverted by hydration; as a result, 4,5-dioxetane of [8-oxoG - H] - was captured as the main oxidation product. Reaction cross section for [8-oxoG - H] - ·W + 1 O 2 decreases with increasing E col and becomes negligible above 0.3 eV, indicating that the reaction is exothermic and has no barriers above reactants. The contrasting oxidation behaviors of [8-oxoG + H] + ·W 0,1 and [8-oxoG - H] - ·W 0

  14. Abiotic reaction of iodate with sphagnum peat and other natural organic matter

    International Nuclear Information System (INIS)

    Steinberg, S.M.; Kimble, G.; Schmett, G.T.; Emerson, D.W.; Turner, M.F.; Rudin, M.

    2008-01-01

    Previous studies have shown that iodine (including 129 I) can be strongly retained in organic-rich surface soils and sediment and that a large fraction of soluble iodine may be associated with dissolved humic material. Iodate (IO 3 - ) reacts with natural organic matter (NOM) producing either hypoiodous acid (HIO) or I 2 as an intermediate. This intermediate is subsequently incorporated into the organic matter. Based on reactions of model compounds, we infer that iodine reacts with peat by aromatic substitution of hydrogen on phenolic constituents of the peat. Alternatively, the intermediate, HIO or I 2 , may be reduced to iodide (I - ). The pH (and temperature) dependence of the IO 3 - reaction (reduction) has been explored with sphagnum peat, alkali lignin, and several model compounds. The incorporation of iodine into NOM has been verified by pyrolysis gas chromatography/mass spectrometry (GC/MS). Model compound studies indicate that reduction of IO 3 - to HIO may result from reaction with hydroquinone (or semiquinone) moieties of the peat. (author)

  15. Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key Intermediate in Catalytic Hydroaminoalkylation Reactions

    KAUST Repository

    Hamzaoui, Bilel

    2015-09-25

    Intermolecular catalytic hydroaminoalkylation of unactivated alkene occurs with silica-supported azazirconacyclopropane [[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)(η2-NMeCH2)(NMe2)]. Mechanistic studies were conducted using surface organometallic chemistry (SOMC) concepts to identify the key surface intermediates. The azametallacyclopentene intermediate {[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)[η2-NMeCH2CH(Me)CH2](NMe2)} was isolated after treating with 1-propylene and characterized by FT-IR spectroscopy, elemental analysis, 1H 13C HETCOR, DARR SS-NMR and DQ TQ SS-NMR. The regeneration of the catalyst was conducted by dimethylamine protonolysis to yield the pure amine.

  16. Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key Intermediate in Catalytic Hydroaminoalkylation Reactions

    KAUST Repository

    Hamzaoui, Bilel; Pelletier, Jé ré mie D. A.; El Eter, Mohamad; Chen, Yin; Abou-Hamad, Edy; Basset, Jean-Marie

    2015-01-01

    Intermolecular catalytic hydroaminoalkylation of unactivated alkene occurs with silica-supported azazirconacyclopropane [[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)(η2-NMeCH2)(NMe2)]. Mechanistic studies were conducted using surface organometallic chemistry (SOMC) concepts to identify the key surface intermediates. The azametallacyclopentene intermediate {[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)[η2-NMeCH2CH(Me)CH2](NMe2)} was isolated after treating with 1-propylene and characterized by FT-IR spectroscopy, elemental analysis, 1H 13C HETCOR, DARR SS-NMR and DQ TQ SS-NMR. The regeneration of the catalyst was conducted by dimethylamine protonolysis to yield the pure amine.

  17. A BGO detector array and its application in intermediate energy heavy ion experiments

    International Nuclear Information System (INIS)

    Li Zuyu; Jin Genming; He Zhiyong; Duan Limin; Wu Heyu; Qi Yujin; Luo Qingzheng; Zhang Baoguo; Wen Wanxin; Dai Guangxi

    1996-01-01

    A BGO crystal (Bi 4 Ge 3 O 12 ) as the E detector of ΔE-E for identification of reaction products has been used for detecting the charged particles emitting from the 25 MeV 40 Ar induced reaction. The responses of the BGO crystal to various light charged particles were measured. A close-packed hexagonal array consisting of thirteen ΔE-E telescopes (Si-BGO) has been developed to detect the light charged particles interfering with each other in intermediate-energy heavy-ion induced reactions. Some applications of this telescope array are also described. (orig.)

  18. Intermediates of radiolytic transformations of 6-aminophenalenone in ethanol

    International Nuclear Information System (INIS)

    Semenova, G.V.; Ponomarev, A.V.; Kartasheva, L.I.; Pikaev, A.K.

    1992-01-01

    Pulsed radiolysis method is used to study transformations intermediates of 6-aminophenalenone in ethanol. In alkaline medium the main product is radical-anion of 6-aminophenalenone, which optical absorption spectrum contains two bands with maxima at 355 and 400 nm. The particle precursors are e s , CH 3 CHOH and CH 3 CHO - radicals. In neutral and acid medium radical-anions are protonated in reactions with alcohol and hydrogen ions. The resulting H-adduct of 6-aminophenalenone has optical absorption maxima at 350 and 390 nm. Availability of two maxima is related to two various product structures. Molar extinction coefficients of radical-anions and H-adducts of 6-aminophenalenone and rate constants of reactions with their participation are estimated

  19. Transesterification of Jatropha curcas oil glycerides: Theoretical and experimental studies of biodiesel reaction

    Energy Technology Data Exchange (ETDEWEB)

    Neyda C. Om Tapanes; Donato A. Gomes Aranda; Jose W. de Mesquita Carneiro; Octavio A. Ceva Antunes [Universidade Federal do Rio de Janeiro, Rio de Janeiro (Brazil). Laboratorio GREENTEC

    2008-08-15

    Vegetal oil, also known as triglycerides, is a mixture of fatty acid triesters of glycerol. In the triglycerides alkyl chains of Jatropha curcas oil, predominate the palmitic, oleic and linoleic fatty acids. The process usually used to convert these triglycerides to biodiesel is called transesterification. The overall process is a sequence of three equivalent, consecutive and reversible reactions, in which di- and monoglycerides are formed as intermediates. Semi-empirical AM1 molecular orbital calculations were used to investigate the reaction pathways of base-catalyzed transesterification of glycerides of palmitic, oleic and linoleic acid. The most probable pathway and the rate determining-step of the reactions were estimated from the molecular orbital calculations. Our results suggest the formation of only one tetrahedral intermediate, which in a subsequent step rearranges to form the products. The rate determining-step is the break of this tetrahedral intermediate. 27 refs., 6 figs., 4 tabs.

  20. Chemical reaction networks as a model to describe UVC- and radiolytically-induced reactions of simple compounds.

    Science.gov (United States)

    Dondi, Daniele; Merli, Daniele; Albini, Angelo; Zeffiro, Alberto; Serpone, Nick

    2012-05-01

    When a chemical system is submitted to high energy sources (UV, ionizing radiation, plasma sparks, etc.), as is expected to be the case of prebiotic chemistry studies, a plethora of reactive intermediates could form. If oxygen is present in excess, carbon dioxide and water are the major products. More interesting is the case of reducing conditions where synthetic pathways are also possible. This article examines the theoretical modeling of such systems with random-generated chemical networks. Four types of random-generated chemical networks were considered that originated from a combination of two connection topologies (viz., Poisson and scale-free) with reversible and irreversible chemical reactions. The results were analyzed taking into account the number of the most abundant products required for reaching 50% of the total number of moles of compounds at equilibrium, as this may be related to an actual problem of complex mixture analysis. The model accounts for multi-component reaction systems with no a priori knowledge of reacting species and the intermediates involved if system components are sufficiently interconnected. The approach taken is relevant to an earlier study on reactions that may have occurred in prebiotic systems where only a few compounds were detected. A validation of the model was attained on the basis of results of UVC and radiolytic reactions of prebiotic mixtures of low molecular weight compounds likely present on the primeval Earth.

  1. Medium Effects in Reactions with Rare Isotopes

    International Nuclear Information System (INIS)

    Bertulani, C A; Karakoç, M

    2012-01-01

    We discuss medium effects in knockout reactions with rare isotopes of weakly-bound nuclei at intermediate energies. We show that the poorly known corrections may lead to sizable modifications of knockout cross sections and momentum dsitributions.

  2. Contribution to the study of πN → π1π2N reactions with creation of an intermediate N*3/2(1236) isobar from 0.4 to 1.5 GeV

    International Nuclear Information System (INIS)

    Merlo, J.P.

    1976-01-01

    The one pion production reaction π + p → π + pπ 0 has been studied up to 1.5 GeV. The π 0 angular distribution measured by counter techniques has been compared to bubble chamber data. Angular distributions are interpreted in the hypothesis of formation of the intermediate N * 3/2 (1236) isobar. Angular distributions for isobar production and decay in one pion production reactions πN → π 1 N * (N * → π 2 N], are calculated in chapter II. π + p → π + pπ 0 experimental results are reported and analyzed in chapter III. An estimation of the pion-isobar partial wave amplitudes in reaction π + p → π 0 N *++ 3/2 (1236) has been tempted. Comparison with π + p phase shift analyses is made. Bubble chamber data for π - p → π - π + n channel are presented at the end of chapter III. (author) [fr

  3. Intermediate obtained from photoionization, serving as precursor for the synthesis of Schiff’s base

    Directory of Open Access Journals (Sweden)

    R. Sanjeev

    2014-05-01

    Full Text Available In this article, we have introduced an intermediate benzyl carbocation (formed as a result of photoionization which serves as precursor for the synthesis of Schiff’s base. Lifetimes of many carbocations were determined from our laboratory. During the determination of the lifetimes, our endeavor was to obtain a carbocation with high selectivity, s = knu/kH2O. The selectivity is the ratio of the rate constant of the reaction of carbocation with an externally added nucleophile, (nu, aniline to that of the rate constant of the water. Our intention was to obtain a carbocation with high selectivity, so that one can pave a path for the synthesis of Schiff’s base by the reaction of the carbocation intermediate with aniline. DOI: http://dx.doi.org/10.4314/bcse.v28i2.13

  4. Giant resonances in heavy-ion reactions

    International Nuclear Information System (INIS)

    Hussein, M.S.

    1982-11-01

    The several roles of multipole giant resonances in heavy-ion reactions are discussed. In particular, the modifications in the effective ion-ion potencial due to the virtual excitation of giant resonances at low energies, are considered and estimated for several systems. Real excitation of giant resonances in heavy-ion reactions at intermediate energies are then discussed and their importance in the approach phase of deeply inelastic processes in emphasized. Several demonstrative examples are given. (Author) [pt

  5. Emsission of intermediate mass fragments in the p(1.9 GeV)+natNI reaction

    International Nuclear Information System (INIS)

    Bubak, A.

    2004-06-01

    The emission of the intermediate mass fragments (IMFs; 2 ≤ Z ≤ 14) produced in the interaction of 1.9 GeV protons with nickel ( nat Ni) has been a subject of interest of the present study. Energy spectra of isotopically and elementally identified ejectiles have been measured at angles 15 and 120 with the respect to the beam direction. The identification of the emitted IMFs has been performed by means of the Bragg curve spectroscopy and the time-of-flight technique (TOF). The Bragg curve detectors (BCDs) were employed for the charge identification, whereas the TOF method combined with the BCD, for the mass identification. The main task of the present PhD thesis was to built appropriate data acquisition system, to perform the experiment on the internal beam of the COSY accelerator, to propose the methodology of the off-line analysis of the data, to apply it to the event-by-event stored data, and to perform the phenomenological analysis of the obtained data. The results, experimental procedures, and different techniques of the element and isotope identification by means of the BCD + TOF are presented. The determination of the power law parameter τ characterizing the mass and charge distributions of the reaction products is discussed. Various methods of the nuclear matter temperature determination, the comparison between nuclear matter thermometers, and the discussion of the obtained results, shown in the energy-temperature diagram (the so called caloric curve), are presented as well. The results suggest two different mechanisms of the IMFs production: from the equilibrated (IMFs measured at 120 ), and non-equilibrated (IMFs measured at 15 ) state of the nucleus. (orig.)

  6. Intermediate-scale sodium-concrete reaction tests with basalt and limestone concrete

    International Nuclear Information System (INIS)

    Hassberger, J.A.; Muhlestein, L.D.

    1981-01-01

    Ten tests were performed to investigate the chemical reactions and rate and extent of attack between sodium and basalt and limestone concretes. Test temperatures ranged from 510 to 870 0 C (950 to 1600 0 F) and test times from 2 to 24 hours. Sodium hydroxide was added to some of the tests to assess the impact of a sodium hydroxide-aided reaction on the overall penetration characteristics. Data suggest that the sodium penetration of concrete surfaces is limited. Penetration of basalt concrete in the presence of sodium hydroxide is shown to be less severe than attack by the metallic sodium alone. Presence of sodium hydroxide changes the characteristics of sodium penetration of limestone concrete, but no major differences in bulk penetration were observed as compared to penetration by metallic sodium

  7. Systematics of intermediate-energy single-nucleon removal cross sections

    Science.gov (United States)

    Tostevin, J. A.; Gade, A.

    2014-11-01

    There is now a large and increasing body of experimental data and theoretical analyses for reactions that remove a single nucleon from an intermediate-energy beam of neutron- or proton-rich nuclei. In each such measurement, one obtains the inclusive cross section for the population of all bound final states of the mass A -1 reaction residue. These data, from different regions of the nuclear chart, and that involve weakly and strongly bound nucleons, are compared with theoretical expectations. These calculations include an approximate treatment of the reaction dynamics and shell-model descriptions of the projectile initial state, the bound final states of the residues, and the single-particle strengths computed from their overlap functions. The results are discussed in the light of recent data, more exclusive tests of the eikonal dynamical description, and calculations that take input from more microscopic nuclear structure models.

  8. A Networks Approach to Modeling Enzymatic Reactions.

    Science.gov (United States)

    Imhof, P

    2016-01-01

    Modeling enzymatic reactions is a demanding task due to the complexity of the system, the many degrees of freedom involved and the complex, chemical, and conformational transitions associated with the reaction. Consequently, enzymatic reactions are not determined by precisely one reaction pathway. Hence, it is beneficial to obtain a comprehensive picture of possible reaction paths and competing mechanisms. By combining individually generated intermediate states and chemical transition steps a network of such pathways can be constructed. Transition networks are a discretized representation of a potential energy landscape consisting of a multitude of reaction pathways connecting the end states of the reaction. The graph structure of the network allows an easy identification of the energetically most favorable pathways as well as a number of alternative routes. © 2016 Elsevier Inc. All rights reserved.

  9. Intermediate treatments

    Science.gov (United States)

    John R. Jones; Wayne D. Shepperd

    1985-01-01

    Intermediate treatments are those applied after a new stand is successfully established and before the final harvest. These include not only intermediate cuttings - primarily thinning - but also fertilization, irrigation, and protection of the stand from damaging agents.

  10. Structure of a low-population intermediate state in the release of an enzyme product.

    Science.gov (United States)

    De Simone, Alfonso; Aprile, Francesco A; Dhulesia, Anne; Dobson, Christopher M; Vendruscolo, Michele

    2015-01-09

    Enzymes can increase the rate of biomolecular reactions by several orders of magnitude. Although the steps of substrate capture and product release are essential in the enzymatic process, complete atomic-level descriptions of these steps are difficult to obtain because of the transient nature of the intermediate conformations, which makes them largely inaccessible to standard structure determination methods. We describe here the determination of the structure of a low-population intermediate in the product release process by human lysozyme through a combination of NMR spectroscopy and molecular dynamics simulations. We validate this structure by rationally designing two mutations, the first engineered to destabilise the intermediate and the second to stabilise it, thus slowing down or speeding up, respectively, product release. These results illustrate how product release by an enzyme can be facilitated by the presence of a metastable intermediate with transient weak interactions between the enzyme and product.

  11. Recoil properties of radionuclides formed in photospallation reactions on complex nuclei at intermediate energies

    International Nuclear Information System (INIS)

    Haba, Hiromitsu; Oura, Yasuji; Shibata, Seiichi; Furukawa, Michiaki; Fujiwara, Ichiro

    2001-01-01

    A short review is given on our studies of recoil properties of radionuclides formed in photospallation reactions induced by bremsstrahlung of end-point energies (E 0 ) from 600 to 1100 MeV, in which the thick-target thick-catcher method was employed. The measurements have been successful on 14, 24, 26, 31, 21 and 20 nuclides from nat V, nat Cu, 93 Nb, nat Ag, nat Ta, and 197 Au, respectively. Reflecting the resonance character in a photonuclear reaction, the mean ranges FW and BW in the forward and backward directions, respectively, are E 0 -independent at the studied energies and classified into two groups accounting for the (γ, xn) (x ≥ 1) and (γ, xnyp) (x, y ≥ 1) processes. The forward-to-backward ratios (F/B) are independent of the mass difference (ΔA) between a product (A p ) and a target (A t ) and also of A t . The kinematic properties of the product nuclei were analyzed by the two-step vector velocity model. The forward velocity ν after the first step of photon-reaction is quite different from that of proton-reaction at proton energies of E p ≤ 3 GeV, though the difference disappears at higher energies. On the other hand, the mean kinetic energy T of the residual nucleus in the second step is almost equal to that of proton-reaction irrespective of E p . A comparison with T values calculated by the PICA (Photon-Induced Intranuclear Cascade Analysis) code at E 0 =400 MeV was also performed. It was found that although the code well reproduces the experimental results of nat V and nat Cu, the same calculation for heavier targets gives T values lower than the experimental results, indicating some nuclear-structure effect, such as a medium effect notably at A t ≥ 100. An average kinetic energy carried off by the emitted particles ε s =T/(ΔA/A t ) of both photon- and proton-reactions seem to increase with an increase of A t up to around A t =100, and become almost constant at larger A t , implying some change in the nuclear structure effect in this

  12. Preparation of dispersible graphene through organic functionalization of graphene using a zwitterion intermediate cycloaddition approach

    NARCIS (Netherlands)

    Zhang, Xiaoyan; Browne, Wesley R.; Feringa, Ben L.

    2012-01-01

    Highly functionalized graphene were obtained through a zwitterion intermediate cycloaddition onto exfoliated graphene flakes under new reaction conditions. The functionalized graphene obtained formed stable dispersions in common solvents, including dimethylformamide (DMF), CHCl3 and water. Its

  13. Final Technical Report: Vibrational Spectroscopy of Transient Combustion Intermediates Trapped in Helium Nanodroplets

    Energy Technology Data Exchange (ETDEWEB)

    Douberly, Gary Elliott [Univ. of Georgia, Athens, GA (United States)

    2017-11-16

    The objective of our experimental research program is to isolate and stabilize transient intermediates and products of prototype combustion reactions. This will be accomplished by Helium Nanodroplet Isolation, a novel technique where liquid helium droplets freeze out high energy metastable configurations of a reacting system, permitting infrared spectroscopic characterizations of products and intermediates that result from hydrocarbon radical reactions with molecular oxygen and other small molecules relevant to combustion environments. The low temperature (0.4 K) and rapid cooling associated with He droplets provides a perfectly suited medium to isolate and probe a broad range of molecular radical and carbene systems important to combustion chemistry. The sequential addition of molecular species to He droplets often leads to the stabilization of high-energy, metastable cluster configurations that represent regions of the potential energy surface far from the global minimum. Single and double resonance IR laser spectroscopy techniques, along with Stark and Zeeman capabilities, are being used to probe the structural and dynamical properties of these systems.

  14. Intermediate structures in alpha scattering on 28Si nuclei

    International Nuclear Information System (INIS)

    Kamys, B.; Bobrovska, A.; Budzanovski, A. et al.

    1975-01-01

    Excitation functions and angular distributions of α-particles scattering on 28 Si nuclei, measured by various authors, are analyzed. Theoretical processing of results is divided into two stages: statistical analysis and analysis in terms of the Regge pole model (RPM). The aim of the statistical analysis is to demonstrate that the structure of excitation curves contains resonance effects. RMP with non-resonance background, described by the optical model (OM), is used to obtain data on properties of intermediate resonances. Autocorrelation functions for one elastic and two inelastic scattering channels are calculated. The mean width of compound states is about 100keV, which is in a good agreement with results of other authores. An analysis of correlation coefficients calculated for all pairs of excitation curves for elastic and two inelastic channels points to the existence of intermediate resonances in each of investigated reaction channels. In the case of large-angle scattering the contribution of potential interaction into the total cross-section is 20-30%, and that of resonance scattering is 50-60%. Energy dependence of Regge pole parameters has also been studied to obtain data on the existence and properties of intermediate resonances

  15. Reaction between uranium hexafluoride and trimethylsilylhalides

    Energy Technology Data Exchange (ETDEWEB)

    Brown, D; Berry, J A [UKAEA Atomic Energy Research Establishment, Harwell. Chemistry Div.; Holloway, J H; Staunton, G M [Leicester Univ. (UK). Dept. of Chemistry

    1938-07-01

    Reactions involving 1.1:1 molar ratios of uranium hexafluoride to either trimethylsilylchloride or trimethylsilylbromide in halocarbon solutions yield ..beta..-UF/sub 5/ at room temperature. With 2 mol equivalents of trimethylsilylchloride the product is UF/sub 4/. The reactions appear to proceed via the intermediate formation of unstable brown uranium(VI) chloride and bromide fluorides. Calculations show that UClF/sub 5/ and UCl/sub 2/F/sub 4/ are thermodynamically unstable with respect to the loss of chlorine at room temperature.

  16. Quantum Mechanics/Molecular Mechanics Study of the Sialyltransferase Reaction Mechanism.

    Science.gov (United States)

    Hamada, Yojiro; Kanematsu, Yusuke; Tachikawa, Masanori

    2016-10-11

    The sialyltransferase is an enzyme that transfers the sialic acid moiety from cytidine 5'-monophospho-N-acetyl-neuraminic acid (CMP-NeuAc) to the terminal position of glycans. To elucidate the catalytic mechanism of sialyltransferase, we explored the potential energy surface along the sialic acid transfer reaction coordinates by the hybrid quantum mechanics/molecular mechanics method on the basis of the crystal structure of sialyltransferase CstII. Our calculation demonstrated that CstII employed an S N 1-like reaction mechanism via the formation of a short-lived oxocarbenium ion intermediate. The computational barrier height was 19.5 kcal/mol, which reasonably corresponded with the experimental reaction rate. We also found that two tyrosine residues (Tyr156 and Tyr162) played a vital role in stabilizing the intermediate and the transition states by quantum mechanical interaction with CMP.

  17. Communications: Elementary oxygen electrode reactions in the aprotic Li-air battery

    DEFF Research Database (Denmark)

    Hummelshøj, Jens Strabo; Blomquist, Jakob; Datta, Soumendu

    2010-01-01

    We discuss the electrochemical reactions at the oxygen electrode of an aprotic Li-air battery. Using density functional theory to estimate the free energy of intermediates during the discharge and charge of the battery, we introduce a reaction free energy diagram and identify possible origins...

  18. A novel microfluidic rapid freeze-quench device for trapping reactions intermediates for high field EPR analysis.

    Science.gov (United States)

    Kaufmann, Royi; Yadid, Itamar; Goldfarb, Daniella

    2013-05-01

    Rapid freeze quench electron paramagnetic resonance (RFQ)-EPR is a method for trapping short lived intermediates in chemical reactions and subjecting them to EPR spectroscopy investigation for their characterization. Two (or more) reacting components are mixed at room temperature and after some delay the mixture is sprayed into a cold trap and transferred into the EPR tube. A major caveat in using commercial RFQ-EPR for high field EPR applications is the relatively large amount of sample needed for each time point, a major part of which is wasted as the dead volume of the instrument. The small sample volume (∼2μl) needed for high field EPR spectrometers, such as W-band (∼3.5T, 95GHz), that use cavities calls for the development of a microfluidic based RFQ-EPR apparatus. This is particularly important for biological applications because of the difficulties often encountered in producing large amounts of intrinsically paramagnetic proteins and spin labeled nucleic acid and proteins. Here we describe a dedicated microfluidic based RFQ-EPR apparatus suitable for small volume samples in the range of a few μl. The device is based on a previously published microfluidic mixer and features a new ejection mechanism and a novel cold trap that allows collection of a series of different time points in one continuous experiment. The reduction of a nitroxide radical with dithionite, employing the signal of Mn(2+) as an internal standard was used to demonstrate the performance of the microfluidic RFQ apparatus. Copyright © 2013 Elsevier Inc. All rights reserved.

  19. Projectile and target fragmentation at intermediate energies (20 MeV <= E/A <= 100 MeV)

    International Nuclear Information System (INIS)

    Dayras, R.A.

    1985-04-01

    In order to follow the evolution of the reaction mechanisms in the transition region of the intermediate energy range, detailed studies of projectile-like fragments from a 44 MeV/u 40 Ar projectile bombarding 27 Al and sup(NAT)T: targets have been made. Experimental results are given. Discussion of the data is presented: transfer reactions, isotopic distributions, the fragmentation model, and abrasion model are used in the discussion

  20. Catalyzed oxidation reactions. IV. Picolinic acid catalysis of chromic acid oxidations

    International Nuclear Information System (INIS)

    Rocek, J.; Peng, T.Y.

    1977-01-01

    Picolinic acid and several closely related acids are effective catalysts in the chromic acid oxidation of primary and secondary alcohols; the oxidation of other substrates is accelerated only moderately. The reaction is first order in chromium-(VI), alcohol, and picolinic acid; it is second order in hydrogen ions at low acidity and approaches acidity independence at high perchloric acid concentrations. A primary deuterium kinetic isotope effect is observed at high but not at low acidities. At low acidity the reaction has a considerably lower activation energy and more negative activation entropy than at higher acidities. The reactive intermediate in the proposed mechanism is a negatively charged termolecular complex formed from chromic acid, picolinic acid, and alcohol. The rate-limiting step of the reaction changes with the acidity of the solution. At higher acidities the intermediate termolecular complex is formed reversibly and the overall reaction rate is determined by the rate of its decomposition into reaction products; at low acidities the formation of the complex is irreversible and hence rate limiting. Picolinic acids with a substituent in the 6 position show a greatly reduced catalytic activity. This observation is interpreted as suggesting a square pyramidal or octahedral structure for the reactive chromium (VI) intermediate. The temperature dependence of the deuterium isotope effect has been determined and the significance of the observed large values for E/sub a//sup D/ - E/sub a//sup H/ and A/sup D//A/sup H/ is discussed

  1. A novel tool for studying auxin-metabolism: the inhibition of grapevine indole-3-acetic acid-amido synthetases by a reaction intermediate analogue.

    Directory of Open Access Journals (Sweden)

    Christine Böttcher

    Full Text Available An important process for the regulation of auxin levels in plants is the inactivation of indole-3-acetic acid (IAA by conjugation to amino acids. The conjugation reaction is catalysed by IAA-amido synthetases belonging to the family of GH3 proteins. Genetic approaches to study the biological significance of these enzymes have been hampered by large gene numbers and a high degree of functional redundancy. To overcome these difficulties a chemical approach based on the reaction mechanism of GH3 proteins was employed to design a small molecule inhibitor of IAA-amido synthetase activity. Adenosine-5'-[2-(1H-indol-3-ylethyl]phosphate (AIEP mimics the adenylated intermediate of the IAA-conjugation reaction and was therefore proposed to compete with the binding of MgATP and IAA in the initial stages of catalysis. Two grapevine IAA-amido synthetases with different catalytic properties were chosen to test the inhibitory effects of AIEP in vitro. GH3-1 has previously been implicated in the grape berry ripening process and is restricted to two amino acid substrates, whereas GH3-6 conjugated IAA to 13 amino acids. AIEP is the most potent inhibitor of GH3 enzymes so far described and was shown to be competitive against MgATP and IAA binding to both enzymes with K(i-values 17-68-fold lower than the respective K(m-values. AIEP also exhibited in vivo activity in an ex planta test system using young grape berries. Exposure to 5-20 µM of the inhibitor led to decreased levels of the common conjugate IAA-Asp and reduced the accumulation of the corresponding Asp-conjugate upon treatment with a synthetic auxin. AIEP therefore represents a novel chemical probe with which to study IAA-amido synthetase function.

  2. Slow and fast pyrolysis of Douglas-fir lignin: Importance of liquid-intermediate formation on the distribution of products

    International Nuclear Information System (INIS)

    Zhou, Shuai; Pecha, Brennan; Kuppevelt, Michiel van; McDonald, Armando G.; Garcia-Perez, Manuel

    2014-01-01

    The formation of liquid intermediates and the distribution of products were studied under slow and fast pyrolysis conditions. Results indicate that monomers are formed from lignin oligomeric products during secondary reactions, rather than directly from the native lignin. Lignin from Douglas-fir (Pseudotsuga menziesii) wood was extracted using the milled wood enzyme lignin isolation method. Slow pyrolysis using a microscope with hot-stage captured the liquid formation (>150 °C), shrinking, swelling (foaming), and evaporation behavior of lignin intermediates. The activation energy (E a ) for 5–80% conversions was 213 kJ mol −1 , and the pre-exponential factor (log A) was 24.34. Fast pyrolysis tests in a wire mesh reactor were conducted (300–650 °C). The formation of the liquid intermediate was visualized with a fast speed camera (250 Hz), showing the existence of three well defined steps: formation of lignin liquid intermediates, foaming and liquid intermediate swelling, and evaporation and droplet shrinking. GC/MS and UV-Fluorescence of the mesh reactor condensate revealed lignin oligomer formation but no mono-phenols were seen. An increase in pyrolytic lignin yield was observed as temperature increased. The molar mass determined by ESI-MS was not affected by pyrolysis temperature. SEM of the char showed a smooth surface with holes, evidence of a liquid intermediate with foaming; bursting from these foams could be responsible for the removal of lignin oligomers. Py-GC/MS studies showed the highest yield of guaiacol compounds at 450–550 °C. - Highlights: • The formation of a liquid intermediate phase is a critical step during lignin pyrolysis. • The lignin oligomers are thermally ejected from the liquid intermediate phase. • The mono-phenols are formed mainly from the secondary reactions of lignin oligomers

  3. Intermediate- and high-energy reactions of uranium with neon and carbon

    International Nuclear Information System (INIS)

    McGaughey, P.L.

    1982-11-01

    Target fragment production from the interactions of 1.0, 3.0, 4.8, and 12 GeV 12 C and 5.0, 8.0, 20, and 42 GeV 20 Ne with uranium has been measured using off-line gamma-ray spectroscopic techniques. The experimental charge and mass yield distributions are generally consistent with the concepts of limiting fragmentation and factorization at energies of 3.0 GeV and above. The total projectile kinetic energy was found to be the relevant scaling parameter for the comparison of reactions induced by projectiles of different sizes. Light fragments with mass number less than 60 were found to violate limiting fragmentation, and had excitation functions that were strongly increasing with projectile energy until 8.0 to 12.0 GeV. With the 1.0 GeV 12 C beam the pattern of mass yields was quite different from that of all the other reactions, with the normal peak in the fission mass region (80 < A < 145), but with much lower yields below mass number 60 and between mass numbers 145 and 210, indicating that these fragments are formed primarily in very energetic reactions in which large excitation energies are transferred to and significant amounts of mass are removed from the target nucleus. Theoretical predictions of the intra-nuclear cascade, nuclear fireball, and nuclear firestreak models are compared with the experimental results. The intra-nuclear cascade and nuclear firestreak models are both able to predict the general shapes of the experimental distributions, with the exception of the yields for the lightest fragments

  4. (Studies of target fragmentation in intermediate energy, relativistic and ultra-relativistic nuclear collisions)

    Energy Technology Data Exchange (ETDEWEB)

    Loveland, W.D.

    1991-08-01

    The work described herein is part of a project involving the study of low energy (< 10 MeV/A), intermediate energy (10--100 MeV/A) and relativistic (> 250 MeV/A) heavy ion reactions. In the low energy regime, we published a monograph on the properties of the heaviest elements and used that publication as a basis for making a set of best'' semi-empirical predictions of heavy element decay properties. The intermediate energy research effort focussed upon the completion of studies already begun and the initiation of a number of new experiments. In our study of a interaction of 21 MeV/nucleon {sup 129}Xe with {sup 197}Au, we compared the characteristics of the observed deep inelastic phenomena with various models of dissipative reactions and found significant discrepancies between observations and predictions. These discrepancies seemed to be caused by an improper treatment of pre-equilibrium in the early stages of the collision. In our study of the relativistic interaction of 400 MeV/nucleon {sup 12}C with {sup 197}Au, we reported the first direct physical measurement of the properties of the spallation residues from a nucleus-nucleus collision. We found the residue energies to be much lower than those predicted by the intranuclear cascade model, indicating some substantial modifications of that model are needed. But, we also found, indications of significant, non-zero values of the residue transverse momentum, a finding that calls into question the interpretation of a number of radiochemical recoil studies of the kinematics of high energy reactions. A program of performing numerical simulations of intermediate and high energy nuclear collisions using the QMD model was initiated.

  5. Mechanistic Insight into the Dehydro-Diels-Alder Reaction of Styrene-Ynes.

    Science.gov (United States)

    Kocsis, Laura S; Kagalwala, Husain N; Mutto, Sharlene; Godugu, Bhaskar; Bernhard, Stefan; Tantillo, Dean J; Brummond, Kay M

    2015-12-04

    The Diels-Alder reaction represents one of the most thoroughly studied and well-understood synthetic transformations for the assembly of six-membered rings. Although intramolecular dehydro-Diels-Alder (IMDDA) reactions have previously been employed for the preparation of naphthalene and dihydronaphthalene substrates, low yields and product mixtures have reduced the impact and scope of this reaction. Through the mechanistic studies described within, we have confirmed that the thermal IMDDA reaction of styrene-ynes produces a naphthalene product via loss of hydrogen gas from the initially formed cycloadduct, a tetraenyl intermediate. Alternatively, the dihydronaphthalene product is afforded from the same tetraenyl intermediate via a radical isomerization process. Moreover, we have identified conditions that can be used to achieve efficient, high-yielding, and selective IMDDA reactions of styrene-ynes to form either naphthalene or dihydronaphthalene products. The operational simplicity and retrosynthetic orthogonality of this method for the preparation of naphthalenes and dihydronaphthalenes makes this transformation appealing for the synthesis of medicinal and material targets. The mechanistic studies within may impact the development of other thermal transformations.

  6. Emission of high-energy, light particles from intermediate-energy heavy-ion reactions

    International Nuclear Information System (INIS)

    Ball, J.B.; Auble, R.L.

    1982-01-01

    One of the early surprises in examining reaction products from heavy ion reactions at 10 MeV/nucleon and above was the large yield of light particles emitted and the high energies to which the spectra of these particles extended. The interpretation of the origin of the high energy light ions has evolved from a picture of projectile excitation and subsequent evaporation to one of pre-equilibrium (or nonequilibrium) emission. The time scale for particle emission has thus moved from one that occurs following the initial collision to one that occurs at the very early stages of the collision. Research at ORNL on this phenomenon is reviewed

  7. Surface Interrogation Scanning Electrochemical Microscopy for a Photoelectrochemical Reaction: Water Oxidation on a Hematite Surface.

    Science.gov (United States)

    Kim, Jae Young; Ahn, Hyun S; Bard, Allen J

    2018-03-06

    To understand the pathway of a photoelectrochemical (PEC) reaction, quantitative knowledge of reaction intermediates is important. We describe here surface interrogation scanning electrochemical microscopy for this purpose (PEC SI-SECM), where a light pulse to a photoactive semiconductor film at a given potential generates intermediates that are then analyzed by a tip generated titrant at known times after the light pulse. The improvements were demonstrated for photoelectrochemical water oxidation (oxygen evolution) reaction on a hematite surface. The density of photoactive sites, proposed to be Fe 4+ species, on a hematite surface was successfully quantified, and the photoelectrochemical water oxidation reaction dynamics were elucidated by time-dependent redox titration experiments. The new configuration of PEC SI-SECM should find expanded usage to understand and investigate more complicated PEC reactions with other materials.

  8. An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

    Energy Technology Data Exchange (ETDEWEB)

    Svelle, Stian

    2004-07-01

    The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

  9. Study of nuclear reactions involving heavy nuclei and intermediate- and high-energy protons and an application in nuclear reactor physics (ADS)

    International Nuclear Information System (INIS)

    Matuoka, Paula Fernanda Toledo

    2016-01-01

    In the present work, intermediate- and high-energy nuclear reactions involving heavy nuclei and protons were studied with the Monte Carlo CRISP (Rio - Ilheus - Sao Paulo Collaboration) model. The most relevant nuclear processes studied were intranuclear cascade and fission-evaporation competition. Preliminary studies showed fair agreement between CRISP model calculation and experimental data of multiplicity of evaporated neutrons (E 20 MeV) were emitted mostly in the intranuclear cascade stage, while evaporation presented larger neutron multiplicity. Fission cross section of 209 mb and spallation cross section of 1788 mb were calculated { both in agreement with experimental data. The fission process resulted in a symmetric mass distribution. Another Monte Carlo code, MCNP, was used for radiation transport in order to understand the role of a spallation neutron source in a ADS (Accelerator Driven System) nuclear reactor. Initially, a PWR reactor was simulated to study the isotopic compositions in spent nuclear fuel. As a rst attempt, a spallation neutron source was adapted to an industrial size nuclear reactor. The results showed no evidence of incineration of transuranic elements and modifications were suggested. (author)

  10. Fragmentation processes in nuclear reactions

    International Nuclear Information System (INIS)

    Legrain, R.

    1984-08-01

    Projectile and nuclear fragmentation are defined and processes referred to are recalled. The two different aspects of fragmentation are considered but the emphasis is also put on heavy ion induced reactions. The preliminary results of an experiment performed at GANIL to study peripheral heavy ions induced reactions at intermediate energy are presented. The results of this experiment will illustrate the characteristics of projectile fragmentation and this will also give the opportunity to study projectile fragmentation in the transition region. Then nuclear fragmentation is considered which is associated with more central collisions in the case of heavy ion induced reactions. This aspect of fragmentation is also ilustrated with two heavy ion experiments in which fragments emitted at large angle have been observed

  11. Quantum chemical study of the elementary reactions in zirconium oxide atomic layer deposition

    International Nuclear Information System (INIS)

    Widjaja, Yuniarto; Musgrave, Charles B.

    2002-01-01

    Elementary reactions in atomic layer deposition of zirconia using zirconium tetrachloride and water are investigated using the density functional theory. The atomistic mechanisms of the two deposition half cycles on the Zr-OH and Zr-Cl surface sites are investigated. Both half reactions proceed through the formation of stable intermediates, resulting in high barriers for HCl formation. We find that the intermediate stability is lowered as the surface temperature is raised. However, increasing temperature also increases the dissociation free-energy barrier, which in turn results in increased desorption of adsorbed precursors

  12. Status of experimental data of proton-induced reactions for intermediate-energy nuclear data evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Yukinobu; Kawano, Toshihiko [Kyushu Univ., Fukuoka (Japan); Yamano, Naoki; Fukahori, Tokio

    1998-11-01

    The present status of experimental data of proton-induced reactions is reviewed, with particular attention to total reaction cross section, elastic and inelastic scattering cross section, double-differential particle production cross section, isotope production cross section, and activation cross section. (author)

  13. Coat Protein Mutations That Alter the Flux of Morphogenetic Intermediates through the ϕX174 Early Assembly Pathway.

    Science.gov (United States)

    Blackburn, Brody J; Li, Shuaizhi; Roznowski, Aaron P; Perez, Alexis R; Villarreal, Rodrigo H; Johnson, Curtis J; Hardy, Margaret; Tuckerman, Edward C; Burch, April D; Fane, Bentley A

    2017-12-15

    Two scaffolding proteins orchestrate ϕX174 morphogenesis. The internal scaffolding protein B mediates the formation of pentameric assembly intermediates, whereas the external scaffolding protein D organizes 12 of these intermediates into procapsids. Aromatic amino acid side chains mediate most coat-internal scaffolding protein interactions. One residue in the internal scaffolding protein and three in the coat protein constitute the core of the B protein binding cleft. The three coat gene codons were randomized separately to ascertain the chemical requirements of the encoded amino acids and the morphogenetic consequences of mutation. The resulting mutants exhibited a wide range of recessive phenotypes, which could generally be explained within a structural context. Mutants with phenylalanine, tyrosine, and methionine substitutions were phenotypically indistinguishable from the wild type. However, tryptophan substitutions were detrimental at two sites. Charged residues were poorly tolerated, conferring extreme temperature-sensitive and lethal phenotypes. Eighteen lethal and conditional lethal mutants were genetically and biochemically characterized. The primary defect associated with the missense substitutions ranged from inefficient internal scaffolding protein B binding to faulty procapsid elongation reactions mediated by external scaffolding protein D. Elevating B protein concentrations above wild-type levels via exogenous, cloned-gene expression compensated for inefficient B protein binding, as did suppressing mutations within gene B. Similarly, elevating D protein concentrations above wild-type levels or compensatory mutations within gene D suppressed faulty elongation. Some of the parental mutations were pleiotropic, affecting multiple morphogenetic reactions. This progressively reduced the flux of intermediates through the pathway. Accordingly, multiple mechanisms, which may be unrelated, could restore viability. IMPORTANCE Genetic analyses have been

  14. Photoinitiated reactions in weakly bonded complexes

    International Nuclear Information System (INIS)

    Wittig, C.

    1993-01-01

    This paper discusses photoinitiated reactions in weakly bonded binary complexes in which the constituents are only mildly perturbed by the intermolecular bond. Such complexes, with their large zero point excursions, set the stage for events that occur following electronic excitation of one of the constituents. This can take several forms, but in all cases, entrance channel specificity is imposed by the character of the complex as well as the nature of the photoinitiation process. This has enabled us to examine aspects of bimolecular processes: steric effects, chemical branching ratios, and inelastic scattering. Furthermore, monitoring reactions directly in the time domain can reveal mechanisms that cannot be inferred from measurements of nascent product excitations. Consequently, we examined several systems that had been studied previously by our group with product state resolution. With CO 2 /HI, in which reaction occurs via a HOCO intermediate, the rates agree with RRKM predictions. With N 2 O/HI, the gas phase single collision reaction yielding OH + N 2 has been shown to proceed mainly via an HNNO intermediate that undergoes a 1,3-hydrogen shift to the OH + N 2 channel. With complexes, ab initio calculations and high resolution spectroscopic studies of analogous systems suggest that the hydrogen, while highly delocalized, prefers the oxygen to the nitrogen. We observe that OH is produced with a fast risetime (< 250 fs) which can be attributed to either direct oxygen-side attack or rapid HNNO decomposition and/or a termolecular contribution involving the nearby iodine

  15. Catalytic effect of KF-846 on the reforming of the primary intermediates from the co-pyrolysis of pubescens and LDPE

    International Nuclear Information System (INIS)

    Liu, Wen-wu; Hu, Chang-wei; Tong, Dong-mei; Yang, Yu; Li, Gui-ying; Zhu, Liang-fang; Tang, Jin-Qiang

    2014-01-01

    Highlights: • Reforming reactions were inhibited by H 2 , decrease of acidity and low temperature. • There was a synergistic effect on producing hydrogen between Ni and Mo. • The lattice oxygen over catalyst employed might transfer into the intermediates. • Co-pyrolysis, low temperature and N 2 could restrain oxygen transfer to some extent. - Abstract: Co-pyrolysis is regarded as an effective approach to upgrade the quality of pyrolysis products. In this work the activity of KF-846 was evaluated by co-pyrolysis of pubescens and low density polyethylene under different experimental conditions including catalytic mode, pyrolytic atmosphere and temperature, etc. The results showed that the fresh KF-846 exerted strong effects of cyclization, aromatization, hydrogen transfer and vapor-catalytic reforming reactions on the primary intermediates from the co-pyrolysis. The hydrogen-rich gases indicated a synergistic effect between Ni and Mo over KF-846 on producing hydrogen. More importantly, the reforming reactions might be inhibited to some extent by H 2 atmosphere, the low temperature and the decrease of acidity over catalyst. Furthermore, it was deduced that the oxygen over the lattice of catalyst or some intermediates might transfer into other intermediates, possibly resulting in more products with high oxygen content, but it was presumed that the low temperature, co-pyrolysis process and N 2 atmosphere could repress the trend to a certain degree. The mass and energy balance of co-pyrolysis were analyzed, and the main reaction pathways were also proposed. The interference in pyrolysis by regulating the catalytic mode, pyrolytic atmosphere and temperature, acidity over catalyst might posses a certain guiding significance for the pyrolytic technology and the design/selection of catalysts employed

  16. Design of the US-CRBRP sodium/water reaction pressure relief system

    International Nuclear Information System (INIS)

    Kruger, G.B.; Murdock, T.B.; Rodwell, E.; Sane, J.O.

    1976-01-01

    Protection against intermediate sodium system overpressure from the sodium/water reaction associated with large leaks within the CRBRP Steam Generators is provided by the sodium/water reaction pressure relief system (SWRPRS). This system consists of rupture disks connected to the intermediate sodium piping adjacent to the inlet to the superheater and outlet from the evaporator modules. The rupture discs relieve into piping that leads to reaction produce separator tanks, which in turn are vented to a centrifugal separator and flare stack arranged to burn hydrogen gas exhausting into the atmosphere. Analyses have been conducted using the TRANSWRAP Computer Code to predict the system pressures and flow rates during the large leak event. Experimental tests to be conducted in the large leak test rig (LLTR) will be used to confirm the analysis techniques used in the design

  17. Workshop on hadron structure from photo-reactions at intermediate energies: Proceedings

    Energy Technology Data Exchange (ETDEWEB)

    Nathan, A.M.; Sandorfi, A.M. (eds.)

    1992-01-01

    This report contains papers on the following topics: The proton compton effect: Recent measurements of the electric and magnetic polorizabilities of the proton; experiments on the electric polarizability of the neutron; chiral symmetry and nucleon polarizabilities; chiral model predictions for electromagnetic polarizabilities of the nucleon, a consumer report; the polarizabilities of bound nucleons; nucleon polarizability in free space and in nuclear matter; mechanisms of photon scattering on nucleons at intermediate energies; pion polarizabilities in chiral perturbation theory; pion polarizabilities and the shielding of [sigma](700)-meson exchange in [gamma][gamma][yields][pi][pi] processes; pion and kaon polarizabilities in the quark confinement model; radiative pion photoproduction and pion polarizabilities; pion and sigma polarizabilities and radiative transitions; the quadrupole amplitude in the [gamma][Nu]-[Delta] transition; pion photoproduction and the [gamma][Nu]-[Delta] amplitudes; effective- lagrangians, Watson's theorem, and the E2/M1 mixing ratio in the excitation of the delta resonance; new measurements of the p([rvec [gamma

  18. Analysis for mass distribution of proton-induced reactions in intermediate energy range

    CERN Document Server

    Xiao Yu Heng

    2002-01-01

    The mass and charge distribution of residual products produced in the spallation reactions needs to be studied, because it can provide useful information for the disposal of nuclear waste and residual radioactivity generated by the spallation neutron target system. In present work, the Many State Dynamical Model (MSDM) is based on the Cascade-Exciton Model (CEM). The authors use it to investigate the mass distribution of Nb, Au and Pb proton-induced reactions in energy range from 100 MeV to 3 GeV. The agreement between the MSDM simulations and the measured data is good in this energy range, and deviations mainly show up in the mass range of 90 - 150 for the high energy proton incident upon Au and Pb

  19. Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide.

    Science.gov (United States)

    Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min

    2017-02-09

    The reaction of the simplest Criegee intermediate CH 2 OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10 -13 cm 3 s -1 . The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

  20. Theoretical study of the Cs isotope exchange reaction of CsI + Cs' → Cs + ICs' (Contract research)

    International Nuclear Information System (INIS)

    Kobayashi, Takanori; Hashimoto, Masashi; Yokoyama, Keiichi

    2015-12-01

    To discuss the exchange reaction of Cs isotope by CsI + Cs' → Cs + ICs', the structure and chemical properties of Cs 2 I intermediate and potential energy surface of the entrance reaction are calculated using M06/def2-TZVPPD density functional calculation. The calculation shows that the reaction to the intermediate has no barrier and the two Cs-I bonds of Cs 2 I are chemically equivalent. These results suggest that the rate of the Cs exchange reaction of CsI + Cs' → Cs + ICs' is as high as the collision rate. (author)

  1. One-Pot Conversion of Carbohydrates into Furan Derivatives via Furfural and 5-Hydroxylmethylfurfural as Intermediates.

    Science.gov (United States)

    Liu, Bing; Zhang, Zehui

    2016-08-23

    Recently, there has been growing interest in the transformation of renewable biomass into value-added fuels and chemicals. The catalytic conversion of naturally abundant carbohydrates can generate two-important furan chemicals: 5-hydroxymethylfurfural (HMF) from C6 carbohydrates and furfural from C5 carbohydrates. Both HMF and furfural have received great interest as precursors in the synthesis of commodity chemicals and liquid fuels. In recent years, a trend has emerged to integrate sequential catalytic processes involving multistep reactions for the direct one-pot transformation of carbohydrates into the aimed fuels and chemicals. One-pot reactions have remarkably unique and environmentally friendly benefits, including the fact that isolation and purification of intermediate compounds can be avoided. Herein, the present article aims to review recent advances in the one-pot conversion of carbohydrates into furan derivatives via furfural and HMF as intermediates. Special attention will be paid to the catalytic systems, mechanistic insight, reaction pathways, and catalyst stability. It is expected that this review will guide researchers to develop effective catalytic systems for the one-pot transformation of carbohydrates into furan derivatives. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Enhancing Activity for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Busch, Michael; Halck, Niels Bendtsen

    2014-01-01

    Electrochemical production of hydrogen, facilitated in electrolyzers, holds great promise for energy storage and solar fuel production. A bottleneck in the process is the catalysis of the oxygen evolution reaction, involving the transfer of four electrons. The challenge is that the binding energies...... of all reaction intermediates cannot be optimized individually. However, experimental investigations have shown that drastic improvements can be realized for manganese and cobalt-based oxides if gold is added to the surface or used as substrate. We propose an explanation for these enhancements based...... that the oxygen evolution reaction overpotential decreases by 100–300 mV for manganese oxides and 100 mV for cobalt oxides....

  3. Transition Metal Donor-Peptide-Acceptor Complexes: From Intramolecular Electron Transfer Reactions to the Study of Reactive Intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Isied, Stephan S.

    2003-03-11

    The trans-polyproline (PII) oligomers (Figure 1) are unusually rigid peptide structures which have been extensively studied by our group for peptide mediated intramolecular electron transfer (ET) at long distances. We have previously studied ET across a series of metal ion donor (D) acceptor (A) oligoproline peptides with different distances, driving forces and reorganizational energies. The majority of these experiments involve generating the ET intermediate using pulse radiolysis methods, although more recently photochemical methods are also used. Results of these studies showed that ET across peptides can vary by more than twelve orders of magnitude. Using ruthenium bipyridine donors, ET reaction rate constants across several proline residues (n = 4 - 9) occurred in the millisecond (ms) to {micro}s timescale, thus limiting the proline peptide conformational motions to only minor changes (far smaller than the large changes that occur on the ms to sec timescale, such as trans to cis proline isomerization). The present report describes our large data base of experimental results for D-peptide-A complexes in terms of a model where the involvement of both superexchange and hopping (hole and electron) mechanisms account for the long range ET rate constants observed. Our data shows that the change from superexchange to hopping mechanisms occurs at different distances depending on the type of D and A and their interactions with the peptides. Our model is also consistent with generalized models for superexchange and hopping which have been put forward by a number of theoretical groups to account for long range ET phenomena.

  4. Reactions of alkylnitrosoureas in aqueous solution

    International Nuclear Information System (INIS)

    Snyder, J.K.; Stock, L.M.

    1980-01-01

    The acid- and base-catalyzed decompositions of N-methyl-,N,N'-dimethyl-, and N,N',N'-trimethyl-N-nitrosourea in aqueous solution have been studied. Below pH 2, the N-methyl compound undergoes both denitrosation and hydrolysis to yield methylurea, nitrous acid, methylamine, nitrogen, and carbon dioxide. The acid-catalyzed denitrosation and hydrolysis of the trimethylnitrosourea are somewhat more rapid than the corresponding reactions of N-methyl-N-nitrosourea. The solvent isotope effect, k/sub H 2 O//k/sub D 2 O/ = 1.3, and the absence of chloride ion catalysis suggest that the denitrosation reaction proceeds by a rate-determining proton transfer which is followed by the rapid loss of the nitroso group. The results for the hydrolysis reaction are compatible with a formulation in which a hydrate of the nitrosourea is protonated in a rate-determining step to form a tetrahedral intermediate which subsequently decomposes to yield methyldiazonium hydroxide and a carbamic acid derivative. The base-catalyzed reactions of the mono, di-, and trimethylnitrosoureas are first order in hydroxide ion over a broad pH range. The hydrolysis of N-methyl-N-nitrosourea yields methanol and derivatives of carbamic acid. Salt effects on the reaction rate are negligible except for the influence of lithium ion. The rate constants for the hydrolysis of the mono- and dimethyl compounds depend upon the buffer concentrationat pH 9.5. The rate constants for the hydrolysis of the trimethyl compound also depend upon the buffer concentration, but a limiting value is not achieved. The solvent isotope effect for the base-catalyzed reaction, the exchange reaction of water- 18 O with the carbonyl group of the urea, and the fact that N-methyl-N-nitrosourea is hydrolyzed about 2.2 x 10 4 times more rapidly than N,N',N'-trimethyl-N-nitrosourea suggest that the hydrolysis occurs by a mechanism in which a tetrahedral intermediate is formed

  5. Isospin non-conservation in 14N(d,d')14N reaction

    International Nuclear Information System (INIS)

    Aoki, Y.; Sanada, J.; Yagi, K.; Kunori, S.; Higashi, Y.

    1978-01-01

    The deuteron inelastic scattering experiments on 14 N are made at E sub(d) = 10.03, 11.65, 14.82 and 17.88 MeV, laying an emphasis on the isospin-forbidden excitation of the 2.31 MeV (0 + , T = 1) state. In order to clarify the reaction mechanism, we have performed analyses assuming both the direct reaction mechanism and the compound nucleus formation. For the above isospin-forbidden transition, the calculation in the second-order DWBA which assumes the isospin mixing in the intermediate channels, reproduces fairly well the strong energy dependence of the angular distribution and the cross section. For the isospin-allowed transition the simple DWBA calculation gives reasonable agreement with the experiment. The present calculation shows that the observed isospin violation is well accounted for by the direct multi-step reaction mechanism assuming the isospin mixing in the intermediate channels. (author)

  6. Intermediate neutron spectrum problems and the intermediate neutron spectrum experiment

    International Nuclear Information System (INIS)

    Jaegers, P.J.; Sanchez, R.G.

    1996-01-01

    Criticality benchmark data for intermediate energy spectrum systems does not exist. These systems are dominated by scattering and fission events induced by neutrons with energies between 1 eV and 1 MeV. Nuclear data uncertainties have been reported for such systems which can not be resolved without benchmark critical experiments. Intermediate energy spectrum systems have been proposed for the geological disposition of surplus fissile materials. Without the proper benchmarking of the nuclear data in the intermediate energy spectrum, adequate criticality safety margins can not be guaranteed. The Zeus critical experiment now under construction will provide this necessary benchmark data

  7. Constraining statistical-model parameters using fusion and spallation reactions

    Directory of Open Access Journals (Sweden)

    Charity Robert J.

    2011-10-01

    Full Text Available The de-excitation of compound nuclei has been successfully described for several decades by means of statistical models. However, such models involve a large number of free parameters and ingredients that are often underconstrained by experimental data. We show how the degeneracy of the model ingredients can be partially lifted by studying different entrance channels for de-excitation, which populate different regions of the parameter space of the compound nucleus. Fusion reactions, in particular, play an important role in this strategy because they fix three out of four of the compound-nucleus parameters (mass, charge and total excitation energy. The present work focuses on fission and intermediate-mass-fragment emission cross sections. We prove how equivalent parameter sets for fusion-fission reactions can be resolved using another entrance channel, namely spallation reactions. Intermediate-mass-fragment emission can be constrained in a similar way. An interpretation of the best-fit IMF barriers in terms of the Wigner energies of the nascent fragments is discussed.

  8. Correlations and currents in 3He studied with the (e, e'pp) reaction

    NARCIS (Netherlands)

    Groep, David Leo

    2000-01-01

    Nucleon-nucleon correlations, especially those of short-range character, can be well studied with electron-induced two-nucleon knockout reactions at intermediate electron energies. However, these reactions are not only driven by one-body currents, i.e., coupling of the virtual photon to one of

  9. Oxidation reactions of bilirubin in aqueous solutions

    International Nuclear Information System (INIS)

    Mohan, Hari; Gopinathan, C.

    1990-01-01

    The radical cation of bilirubin (BR) has been tentatively identified as a transient intermediate in the reactions of BR with different oxidizing species such as Br 2 - , I 2 - and CH 3 I . OH. The rate constants for these reactions have been determined as 2.4 x 10 9 , l.0 x 10 9 and 2.7 x 10 9 dm 3 mol -1 s -1 , respectively. Biliverdin is likely to be among the stable products formed on oxidation of BR by these oxidizing species. (author)

  10. Role of the metal oxidation state in the SNS-Cr catalyst for ethylene trimerization: Isolation of Di- and trivalent cationic intermediates

    NARCIS (Netherlands)

    Jabri, A.; Temple, C.N.; Crewdson, P.; Gambarotta, S.; Korobkov, I.V.; Duchateau, R.

    2006-01-01

    The reaction of the highly selective [CySCH2CH2N(H)CH2CH2SCy]CrCl3 catalyst precursor with alkyl aluminum activators was examined with the aim of isolating reactive intermediates. Reaction with Me3Al afforded a cationic trivalent chromium alkyl species

  11. Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

    Science.gov (United States)

    Rappoport, Dmitrij; Galvin, Cooper J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán

    2014-03-11

    While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.

  12. Measurement of Fragment Mass Distributions in Neutron-induced Fission of 238U and 232Th at Intermediate Energies

    International Nuclear Information System (INIS)

    Simutkin, V.D.

    2008-01-01

    Conceptual analysis of accelerator-driven systems assumes extensive use of nuclear data on neutron-induced reactions at intermediate energies. In particular, information about the fission fragment yields from the 238 U(n,f) and 232 Th(n,f) reactions is of particular interest at neutron energies from 10 to 200 MeV. However, there is a lack of such data for both 238 U and 232 Th. Up to now, the intermediate energy measurements have been performed for 238 U only, and there are no data for the 232 Th(n,f) reaction. The aim of the work is to provide such data. Fission fragment mass distributions for the 232 Th(n,f) and 238 U(n,f) reactions have been measured for the incident neutron energies 32.8 MeV, 45.3 MeV and 59.9 MeV. The experiments have been performed at the neutron beam facility of the Universite Catholique de Louvain, Belgium. A multi-section Frisch-gridded ionization chamber has been used as a fission fragment detector. The data obtained have been interpreted in terms of the multimodal random neck-rupture model (MMRNRM). (authors)

  13. An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

    Energy Technology Data Exchange (ETDEWEB)

    Svelle, Stian

    2004-07-01

    The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

  14. The origin of nuclear spin and its effect durning intermediate energy heavy ion collisions

    International Nuclear Information System (INIS)

    Zhang Guoqiang; Cao Xiguang; Fu Yao; Ma Yugang; Cai Xiangzhou; Wang Hongwei; Fang Deqing; Tian Wendong; Chen Jingen; Guo Wei; Liu Guihua

    2010-01-01

    We use the heavy-ion phase-space exploration (HIPSE) model to discuss the origin of the nuclear spin and its effect in Intermediate energy nuclear reaction. It is found that the spin of projectile depends on the impact parameter of the reaction system heavily, while on the violence lightly by contrast. Some interesting multifragmentation phenomena related to the spin are shown, especially those of phase transition. At the same time, the role of excited energy for multifragmentation is also invested. We find the later plays a more robust role durning the nuclear disintegration. (authors)

  15. Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates**

    Science.gov (United States)

    Draksharapu, Apparao; Angelone, Davide; Quesne, Matthew G; Padamati, Sandeep K; Gómez, Laura; Hage, Ronald; Costas, Miquel; Browne, Wesley R; de Visser, Sam P

    2015-01-01

    FeIII–hypohalite complexes have been implicated in a wide range of important enzyme-catalyzed halogenation reactions including the biosynthesis of natural products and antibiotics and post-translational modification of proteins. The absence of spectroscopic data on such species precludes their identification. Herein, we report the generation and spectroscopic characterization of nonheme FeIII–hypohalite intermediates of possible relevance to iron halogenases. We show that FeIII-OCl polypyridylamine complexes can be sufficiently stable at room temperature to be characterized by UV/Vis absorption, resonance Raman and EPR spectroscopies, and cryo-ESIMS. DFT methods rationalize the pathways to the formation of the FeIII-OCl, and ultimately FeIV=O, species and provide indirect evidence for a short-lived FeII-OCl intermediate. The species observed and the pathways involved offer insight into and, importantly, a spectroscopic database for the investigation of iron halogenases. PMID:25663379

  16. Intermediate-scale tests of sodium interactions with calcite and dolomite aggregate concretes

    International Nuclear Information System (INIS)

    Randich, E.; Acton, R.U.

    1983-09-01

    Two intermediate-scale tests were performed to compare the behavior of calcite and dolomite aggregate concretes when attacked by molten sodium. The tests were performed as part of an interlaboratory comparison between Sandia National Laboratories and Hanford Engineering Development Laboratories. Results of the tests at Sandia National Laboratories are reported here. The results show that both concretes exhibit similar exothermic reactions with molten sodium. The large difference in reaction vigor suggested by thermodynamic considerations of CO 2 release from calcite and dolomite was not realized. Penetration rates of 1.4 to 1.7 mm/min were observed for short periods of time with reaction zone temperatures in excess of 800 0 C during the energetic attack. The penetration was not uniform over the entire sodium-concrete contact area. Rapid attack may be localized due to inhomogeneities in the concrete. The chemical reaction zone is less then one cm thick for the calcite concrete but is about seven cm thick for the dolomite concrete

  17. Kinetics and reaction mechanism for aminolysis of benzyl 4-pyridyl carbonate in H2O: Effect of modification of nucleofuge from 2-pyridyl oxide to 4-pyridyl oxide on reactivity and reaction mechanism

    International Nuclear Information System (INIS)

    Kang, Ji Sun; Um, Ikhwan

    2012-01-01

    Pseudo-first-order rate constants k amine have been measured spectrophotometrically for the reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in H 2 O at 25.0.deg.C. The plots of k amine vs. [amine] curve upward, indicating that the reactions proceed through a stepwise mechanism with two intermediates, a zwitterionic tetrahedral intermediate T ± and its deprotonated form T - . This contrasts to the report that the corresponding reactions of benzyl 2-pyridyl carbonate 5 proceed through a forced concerted pathway. The k amine values for the reactions of 6 have been dissected into the second-order rate constant Kk 2 and the third order rate constant Kk 3 . The Brφnsted-type plots are linear with β nuc = 0.94 and 1.18 for Kk 2 and Kk 3 , respectively. The Kk 2 for the reaction of 6 is smaller than the second-order rate constant k N for the corresponding reaction of 5, although 4-pyridyl oxide in 6 is less basic and a better nucleofuge than 2-pyridyl oxide in 5

  18. Explaining the atypical reaction profiles of heme enzymes with a novel mechanistic hypothesis and kinetic treatment.

    Directory of Open Access Journals (Sweden)

    Kelath Murali Manoj

    Full Text Available Many heme enzymes show remarkable versatility and atypical kinetics. The fungal extracellular enzyme chloroperoxidase (CPO characterizes a variety of one and two electron redox reactions in the presence of hydroperoxides. A structural counterpart, found in mammalian microsomal cytochrome P450 (CYP, uses molecular oxygen plus NADPH for the oxidative metabolism (predominantly hydroxylation of substrate in conjunction with a redox partner enzyme, cytochrome P450 reductase. In this study, we employ the two above-mentioned heme-thiolate proteins to probe the reaction kinetics and mechanism of heme enzymes. Hitherto, a substrate inhibition model based upon non-productive binding of substrate (two-site model was used to account for the inhibition of reaction at higher substrate concentrations for the CYP reaction systems. Herein, the observation of substrate inhibition is shown for both peroxide and final substrate in CPO catalyzed peroxidations. Further, analogy is drawn in the "steady state kinetics" of CPO and CYP reaction systems. New experimental observations and analyses indicate that a scheme of competing reactions (involving primary product with enzyme or other reaction components/intermediates is relevant in such complex reaction mixtures. The presence of non-selective reactive intermediate(s affords alternate reaction routes at various substrate/product concentrations, thereby leading to a lowered detectable concentration of "the product of interest" in the reaction milieu. Occam's razor favors the new hypothesis. With the new hypothesis as foundation, a new biphasic treatment to analyze the kinetics is put forth. We also introduce a key concept of "substrate concentration at maximum observed rate". The new treatment affords a more acceptable fit for observable experimental kinetic data of heme redox enzymes.

  19. Evaluation of potential reaction mechanisms leading to the formation of coniferyl alcohol α-linkages in lignin: a density functional theory study.

    Science.gov (United States)

    Watts, Heath D; Mohamed, Mohamed Naseer Ali; Kubicki, James D

    2011-12-21

    Five potential reaction mechanisms, each leading to the formation of an α-O-4-linked coniferyl alcohol dimer, and one scheme leading to the formation of a recently proposed free-radical coniferyl alcohol trimer were assessed using density functional theory (DFT) calculations. These potential reaction mechanisms were evaluated using both the calculated Gibbs free energies, to predict the spontaneity of the constituent reactions, and the electron-density mapped Fukui function, to determine the most reactive sites of each intermediate species. The results indicate that each reaction in one of the six mechanisms is thermodynamically favorable to those in the other mechanisms; what is more, the Fukui function for each free radical intermediate corroborates with the thermochemical results for this mechanism. This mechanism proceeds via the formation of two distinct free-radical intermediates, which then react to produce the four α-O-4 stereoisomers.

  20. Combined cross-linked enzyme aggregates of horseradish peroxidase and glucose oxidase for catalyzing cascade chemical reactions.

    Science.gov (United States)

    Nguyen, Le Truc; Yang, Kun-Lin

    2017-05-01

    Cascade reactions involved unstable intermediates are often encountered in biological systems. In this study, we developed combined cross-linked enzyme aggregates (combi-CLEA) to catalyze a cascade reaction which involves unstable hydrogen peroxide as an intermediate. The combi-CLEA contains two enzymes̶ glucose oxidase (GOx) and horseradish peroxidase (HRP) which are cross-linked together as solid aggregates. The first enzyme GOx catalyzes the oxidation of glucose and produces hydrogen peroxide, which is used by the second enzyme HRP to oxidize 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS). The apparent reaction rate of the cascade reaction reaches 10.5±0.5μM/min when the enzyme ratio is 150:1 (GOx:HRP). Interestingly, even in the presence of catalase, an enzyme that quickly decomposes hydrogen peroxide, the reaction rate only decreases by 18.7% to 8.3±0.3μM/min. This result suggests that the intermediate hydrogen peroxide is not decomposed by catalase due to a short diffusion distance between GOx and HRP in the combi-CLEA. Scanning electron microscopy images suggest that combi-CLEA particles are hollow spheres and have an average diameter around 250nm. Because of their size, combi-CLEA particles can be entrapped inside a nylon membrane for detecting glucose by using the cascade reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Oxidase catalysis via aerobically generated hypervalent iodine intermediates

    Science.gov (United States)

    Maity, Asim; Hyun, Sung-Min; Powers, David C.

    2018-02-01

    The development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Oxidase catalysis, in which O2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O2 reduction. Direct O2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O2 and the disparate electron inventories of four-electron O2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents—a broadly useful class of selective two-electron oxidants—from O2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.

  2. Analysis of the nucleon-nucleus reactions by the quantum molecular dynamics

    International Nuclear Information System (INIS)

    Chiba, Satoshi; Niita, Koji; Maruyama, Toshiki; Fukahori, Tokio; Takada, Hiroshi; Iwamoto, Akira

    1995-01-01

    The quantum molecular dynamics + statistical decay model has been applied to analyze the nucleon-induced nuclear reactions in the energy range from 50 to 3 GeV in order to verify its applicability to light-ion induced nuclear reactions. It was found that the present approach could give a quantitative description of various cross sections such as (p,p'), (p,n), (n,p) reactions from a wide range of targets and also target-like isotope production cross sections from p+Fe reaction, showing its basic ability as a tool for the study of intermediate energy nuclear reactions and nuclear data evaluation. (author)

  3. Studies of heavy-ion reactions and transuranic nuclei. Progress report, September 1, 1992--August 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, W.U.

    1993-08-01

    This report contain papers on the following topics: The Cold-Fusion Saga; Decay Patterns of Dysprosium Nuclei Produced in {sup 32}S + {sup 118,124}Sn Fusion Reactions; Unexpected Features of Reactions Between Very Heavy Ions at Intermediate Bombarding Energies; Correlations Between Neutrons and Charged Products from the Dissipative Reaction {sup 197}Au+{sup 208}Pb at E/A = 29 MeV; Dissipative Dynamics of Projectile-Like Fragment Production in the Reaction {sup 209}Bi+{sup 136}Xe at E/A = 28.2 MeV; Dynamical Production of Intermediate-Mass Fragments in Peripheral {sup 209}Bi+{sup 136}Xe Collisions at E{sub lab}/A = 28.2 MeV; The Rochester 960-Liter Neutron Multiplicity Meter; A Simple Pulse Processing Concept for a Low-Cost Pulse-Shape-Based Particle Identification; A One-Transistor Preamplifier for PMT Anode Signals; A Five-Channel Multistop TDC/Event Handler for the SuperBall Neutron Multiplicity Meter; Construction of the SuperBall -- a 16,000-Liter Neutron Detector for Calorimetric Studies of Intermediate-Energy Heavy-Ion Reactions; A Computer Code for Light Detection Efficiency Calculations for Photo-multipliers of a Neutron Detector; Evaluation of Gd-Loaded Liquid Scintillators for the SuperBall Neutron Calorimeter; and Measurement of the Interaction of Cosmic-Ray {mu}{sup {minus}} with a Muon Telescope.

  4. Surface-Activated Coupling Reactions Confined on a Surface.

    Science.gov (United States)

    Dong, Lei; Liu, Pei Nian; Lin, Nian

    2015-10-20

    Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density

  5. Insights into reaction mechanisms in heterogeneous catalysis revealed by in situ NMR spectroscopy.

    Science.gov (United States)

    Blasco, Teresa

    2010-12-01

    This tutorial review intends to show the possibilities of in situ solid state NMR spectroscopy in the elucidation of reaction mechanisms and the nature of the active sites in heterogeneous catalysis. After a brief overview of the more usual experimental devices used for in situ solid state NMR spectroscopy measurements, some examples of applications taken from the recent literature will be presented. It will be shown that in situ NMR spectroscopy allows: (i) the identification of stable intermediates and transient species using indirect methods, (ii) to prove shape selectivity in zeolites, (iii) the study of reaction kinetics, and (iv) the determination of the nature and the role played by the active sites in a catalytic reaction. The approaches and methodology used to get this information will be illustrated here summarizing the most relevant contributions on the investigation of the mechanisms of a series of reactions of industrial interest: aromatization of alkanes on bifunctional catalysts, carbonylation reaction of methanol with carbon monoxide, ethylbenzene disproportionation, and the Beckmann rearrangement reaction. Special attention is paid to the research carried out on the role played by carbenium ions and alkoxy as intermediate species in the transformation of hydrocarbon molecules on solid acid catalysts.

  6. Photochemical and radiation chemistry investigations of reaction kinetics of dissolved electrons in water and ammonium-water mixtures

    International Nuclear Information System (INIS)

    Telser, T.

    1986-01-01

    In the reaction of hydrated electrons in aqueous alkaline solutions, an intermediate product is observed. In this work, this intermediate product was determined to be a long life photoactive product in double flash experiments, which reacts at a speed constant K = 1x10 9 M -1 s -1 in a reaction of the 2nd order. It is formed in a reaction of the 1st order with reference to the electron concentration (e aq - → X, 2X → H 2 ). The alkaline metal cations of the solution appear as reaction partners of the hydrated electrons. The hydrated metal atoms formed were observed in the UV spectrum as absorpton bands at 270 nm. Pulse radiolytic measurements confirm the conclusions of the photochemical experiments. (RB) [de

  7. A brief overview of models of nucleon-induced reactions

    International Nuclear Information System (INIS)

    Carlson, B.V.

    2003-01-01

    The basic features of low to intermediate energy nucleon-induced reactions are discussed within the contexts of the optical model, the statistical model, preequilibrium and intranuclear cascade models. The calculation of cross sections and other scattering quantities are described. (author)

  8. Theoretical study of intermediate-mass fragments in proton-nucleus reactions at 200 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Sabra, Mohammad S. [NASA Marshall Space Flight Center, USRA Space Science Department, Huntsville, AL (United States)

    2017-03-15

    We have analyzed energy spectra, angular distributions, and mass and charge distributions of intermediate-mass fragments (IMFs) from the interaction of {sup 27}Al, {sup 59}Co, and {sup 197}Au with 200 MeV protons. Calculations within the modified statistical model with final-state interaction were performed using SAPTON code. Within the experimental uncertainty and constraint, SAPTON shows good agreement with the data, and suggests that the IMFs are produced after the intra-nuclear cascade stage, and during the surface coalescence, as well as the evaporation/fission stages. (orig.)

  9. tRNAGlu increases the affinity of glutamyl-tRNA synthetase for its inhibitor glutamyl-sulfamoyl-adenosine, an analogue of the aminoacylation reaction intermediate glutamyl-AMP: mechanistic and evolutionary implications.

    Science.gov (United States)

    Blais, Sébastien P; Kornblatt, Jack A; Barbeau, Xavier; Bonnaure, Guillaume; Lagüe, Patrick; Chênevert, Robert; Lapointe, Jacques

    2015-01-01

    For tRNA-dependent protein biosynthesis, amino acids are first activated by aminoacyl-tRNA synthetases (aaRSs) yielding the reaction intermediates aminoacyl-AMP (aa-AMP). Stable analogues of aa-AMP, such as aminoacyl-sulfamoyl-adenosines, inhibit their cognate aaRSs. Glutamyl-sulfamoyl-adenosine (Glu-AMS) is the best known inhibitor of Escherichia coli glutamyl-tRNA synthetase (GluRS). Thermodynamic parameters of the interactions between Glu-AMS and E. coli GluRS were measured in the presence and in the absence of tRNA by isothermal titration microcalorimetry. A significant entropic contribution for the interactions between Glu-AMS and GluRS in the absence of tRNA or in the presence of the cognate tRNAGlu or of the non-cognate tRNAPhe is indicated by the negative values of -TΔSb, and by the negative value of ΔCp. On the other hand, the large negative enthalpy is the dominant contribution to ΔGb in the absence of tRNA. The affinity of GluRS for Glu-AMS is not altered in the presence of the non-cognate tRNAPhe, but the dissociation constant Kd is decreased 50-fold in the presence of tRNAGlu; this result is consistent with molecular dynamics results indicating the presence of an H-bond between Glu-AMS and the 3'-OH oxygen of the 3'-terminal ribose of tRNAGlu in the Glu-AMS•GluRS•tRNAGlu complex. Glu-AMS being a very close structural analogue of Glu-AMP, its weak binding to free GluRS suggests that the unstable Glu-AMP reaction intermediate binds weakly to GluRS; these results could explain why all the known GluRSs evolved to activate glutamate only in the presence of tRNAGlu, the coupling of glutamate activation to its transfer to tRNA preventing unproductive cleavage of ATP.

  10. Reaction Kinetics of Acetone Peroxide Formation and Structure Investigations Using Raman Spectroscopy and X-ray Diffraction

    DEFF Research Database (Denmark)

    Jensen, Lars; Mortensen, Peter Mølgaard; Trane, Rasmus

    2009-01-01

    functional theory (DFT)/Hartree-Fock approach. It was not possible from this to assess with certainty which intermediate products formed most extensively in an acetone/hydrogen peroxide mixture. However, it was concluded that the most likely reaction mixture is a mixture of the different intermediate...

  11. Semi-classical approaches for the proton emission in intermediate energy heavy ion reactions

    International Nuclear Information System (INIS)

    Gregoire, C.; Scheuter, F.; Remaud, B.; Sebille, F.

    1984-05-01

    Semi-classical approaches are proposed to study the transition between the one- and two-body processes in intermediate energy heavy ion collisions. The Landau-Vlasov equation is used as a transport equation for nucleons in the nuclear matter. We apply our formalism to the fast proton ejection. On the one hand, the effects of the nucleon-nucleon collisions are studied for the particles which travel through the nucleus cores. On the other hand, the inertial emission turns out to be an important proton emission mechanism. Our results conflict the interpretation of the proton spectra in terms of moving sources. Reasonable agreements with the experimental data are found without reference to any thermal equilibrium

  12. Review of heavy ion reaction mechanisms

    International Nuclear Information System (INIS)

    Ngo, C.

    1986-04-01

    We review some of the many aspects of heavy-ion reaction mechanisms observed at bombarding energies smaller than approximately 50 MeV/u that is to say in what is called the low bombarding energy domain and the intermediate bombarding energy domain. We emphasize the results concerning the use of very heavy projectiles which has led to the observation of new mechanisms

  13. Reactions of acid bisphosphonodithioates with nitriles

    International Nuclear Information System (INIS)

    Kutyrev, G.A.; Korolev, O.S.; Yarkova, E.G.; Cherkasov, R.A.; Pudovik, A.N.

    1986-01-01

    The reactions of acid bisphosphonodithioates with aceto- and benzo-nitriles go with the intermediate formation of a 1:1 adduct, which breaks down into a thioamide and a cyclic trithiopyrophosphonate. The stability of the latter falls with the lengthening of the carbon chain in the original thiophosphorus reactant. A detailed analysis of IR and NMR spectra is given to confirm these results

  14. The nuclear reaction n + 3He -> 1H + 3H as proximity reaction

    International Nuclear Information System (INIS)

    Hilber, H.C.

    1982-01-01

    The present thesis tries to give by means of the nuclear reaction n + 3 He -> 1 H + 3 H as proximity reaction on the three-particle system 3 He + 9 Be -> 1 H + 3 H + 8 Be an experimental verification to the second term of a multiple scattering series. The study of these rescattering effects is of great interest for the present theory of the final-state interaction. At three incident energies (7.08 MeV, 8.98 MeV, and 6.37 MeV) to detector telescopes identify the exit channel of the three-particle system in list-mode coincidence experiments according to protons and tritons. Peaks on the kinematical curves occur. The detailed study of their kinematic behaviour allows to exclude the inconcurrence to the proximity reaction lying cascade decays via intermediate states in 4 He, 9 B, and 11 B. Regarding the Coulomb interaction the experimental results can be also explained in the sense of the classical kinematics by the proximity model. (orig.) [de

  15. Multiple particles production for hadron-hadron reactions with finite hadronization time

    International Nuclear Information System (INIS)

    Arbex, N.

    1991-01-01

    Experimental data on multiple particle production for proton-proton reaction are analysed in the context of a very simple analytical model. The model exhibits the essential features of hydrodynamical calculations as, e.g., the formation of an intermediate object, which undergoes expansion. The simultaneous analysis of different types of data allows for the conclusion that such data reflect the dynamics of this intermediate object and have a very deem connection to the elementary processes. (author)

  16. Quantum chemical study of penicillin: Reactions after acylation

    Science.gov (United States)

    Li, Rui; Feng, Dacheng; Zhu, Feng

    The density functional theory methods were used on the model molecules of penicillin to determine the possible reactions after their acylation on ?-lactamase, and the results were compared with sulbactam we have studied. The results show that, the acylated-enzyme tetrahedral intermediate can evolves with opening of ?-lactam ring as well as the thiazole ring; the thiazole ring-open products may be formed via ?-lactam ring-open product or from tetrahedral intermediate directly. Those products, in imine or enamine form, can tautomerize via hydrogen migration. In virtue of the water-assisted, their energy barriers are obviously reduced.

  17. Reaction studies of hot silicon, germanium and carbon atoms

    International Nuclear Information System (INIS)

    Gaspar, P.P.

    1990-01-01

    The goal of this project was to increase the authors understanding of the interplay between the kinetic and electronic energy of free atoms and their chemical reactivity by answering the following questions: (1) what is the chemistry of high-energy carbon silicon and germanium atoms recoiling from nuclear transformations; (2) how do the reactions of recoiling carbon, silicon and germanium atoms take place - what are the operative reaction mechanisms; (3) how does the reactivity of free carbon, silicon and germanium atoms vary with energy and electronic state, and what are the differences in the chemistry of these three isoelectronic atoms? This research program consisted of a coordinated set of experiments capable of achieving these goals by defining the structures, the kinetic and internal energy, and the charge states of the intermediates formed in the gas-phase reactions of recoiling silicon and germanium atoms with silane, germane, and unsaturated organic molecules, and of recoiling carbon atoms with aromatic molecules. The reactions of high energy silicon, germanium, and carbon atoms created by nuclear recoil were studied with substrates chosen so that their products illuminated the mechanism of the recoil reactions. Information about the energy and electronic state of the recoiling atoms at reaction was obtained from the variation in end product yields and the extent of decomposition and rearrangement of primary products (usually reactive intermediates) as a function of total pressure and the concentration of inert moderator molecules that remove kinetic energy from the recoiling atoms and can induce transitions between electronic spin states. 29 refs

  18. Report of seminar on relativistic approach to nuclear reaction and nuclear structure

    International Nuclear Information System (INIS)

    1986-05-01

    A seminar on 'Relativistic Approach to Nuclear Reaction and Nuclear Structure' was held in 1985 at Osaka University. This booklet includes twenty-four reports given at the seminar, which deal with: Conventional Nonrelativistic Description of Nuclear Matter and Nuclear Spin-Orbit Interactions; Relativistic Approach to Nuclear Structure; Atomic and Molecular Structure Calculations; Electromagnetic Interaction in Nucleus and Relativistic Effect; Nuclear Magnetic Moment in the Relativistic Mean Field Theory, Effective Mass and Particle-Vibration Coupling in the Relativistic σ-ω Model; Gauge Invariance in Relativistic Many-Body Theory; Relativistic Description of Nucleon-Nucleon Interaction in Review; σ-Particle in NN Interaction; Nuclear Optical Potentials Based on the Brueckner-Hartree-Fock Approach; Elastic Backscattering and Optical Potential; Description of Intermediate-Energy Nuclear Reactions; Dirac Phenomenology at E(p) = 65 MeV; Relativistic Impulse Approximation; Reaction Studies with Intermediate Energy Deuterons at SATURNE; Folding Model for Intermediate-Energy Deutron Scattering; Folding Model for Polarized Deutron Scattering at 700 MeV; Dirac Approach Problems and a Different Viewpoint; Relativistic Approach and EMC Effect; Quasielastic Electron Scattering; Response Function of Quasielastic Electron Scattering; Relativistic Hartree Response Function for Quasielastic Electron Scattering on 12 C and 40 Ca; Backflow-, Retardation- and Relativistic Effects on the Longitudinal Response Function of Nuclear Matter; Pion-Photoproduction in the σ-ω Model. (Nogami, K.)

  19. Online monitoring of chemical reactions by polarization-induced electrospray ionization.

    Science.gov (United States)

    Meher, Anil Kumar; Chen, Yu-Chie

    2016-09-21

    Polarization-induced electrospray ionization (PI-ESI) is a simple technique for instant generation of gas-phase ions directly from a microliter-sized droplet for mass spectrometric analysis. A sample droplet was placed over a dielectric substrate and in proximity (2-3 mm) to the inlet of a mass spectrometer. Owing to the polarization effect induced by the high electric field provided by the mass spectrometer, the droplet was polarized and the electrospray was generated from the apex of the droplet. The polarization-induced electrospray could last for tens of seconds, which was sufficiently long to monitor fast reactions occurring within few seconds. Thus, we demonstrated the feasibility of using the droplet-based PI-ESI MS for the online monitoring of fast reactions by simply mixing two droplets (5-10 μL) containing reactants on a dielectric substrate placed in front of a mass spectrometer applied with a high voltage (-4500 V). Schiff base reactions and oxidation reactions that can generate intermediates/products within a few seconds were selected as the model reactions. The ionic reaction species generated from intermediates and products can be simultaneously monitored by PI-ESI MS in real time. We also used this approach to selectively detect acetone from a urine sample, in which acetone was derivatized in situ. In addition, the possibility of using this approach for quantitative analysis of acetone from urine samples was examined. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Beyond the volcano limitations in electrocatalysis - oxygen evolution reaction

    DEFF Research Database (Denmark)

    Halck, Niels Bendtsen; Petrykin, Valery; Krtil, Petr

    2014-01-01

    Oxygen evolution catalysis is restricted by the interdependence of adsorption energies of the reaction intermediates and the surface reactivity. The interdependence reduces the number of degrees of freedom available for catalyst optimization. Here it is demonstrated that this limitation can be re...

  1. Storage Stability and Improvement of Intermediate Moisture Foods, Phase 3

    Science.gov (United States)

    Labuza, T. P.

    1975-01-01

    Methods were determined for the improvement of shelf-life stability of intermediate moisture foods (IMF). Microbial challenge studies showed that protection against molds and Staphylococcus aureus could be achieved by a combination of antimicrobial agents, humectants and food acids. Potassium sorbate and propylene glycol gave the best results. It was also confirmed that the maximum in heat resistance shown by vegetative pathogens at intermediate water activities also occurred in a solid food. Glycols and sorbitol both achieve browning inhibition because of their action as a medium for reaction and effect on viscosity of the adsorbed phase. Chemical availability results showed rapid lysine loss before visual discoloration occurred. This is being confirmed with a biological test using Tetrahymena pyriformis W. Accelerated temperature tests show that effectiveness of food antioxidants against rancidity development can be predicted; however, the protection factor changes with temperature. BHA was found to be the best antioxidant for iron catalyzed oxidation.

  2. Energy damping and intermediate velocity fragment emission in peripheral Kr+Au collisions at 43 MeV/u

    International Nuclear Information System (INIS)

    Stuttge, L.; Adloff, J.C.; Bilwes, B.; Bilwes, R.; Cosmo, F.; Glaser, M.; Rudolf, G.; Scheibling, F.

    1991-01-01

    Triple and four-fold coincidences among fragments have been measured in the reaction 197 Au( 84 Kr,X) at 43 MeV/u. All events showing the projectile-like nucleus and fission fragments of the target-like nucleus, and all events with one additional intermediate velocity fragment, were analysed in the frame of a dissipative collision and a participant-spectator model. The mechanism is basically that of a dissipative collision but the emission of the intermediate velocity fragment by the target differs from an equilibrated evaporation. (author) 16 refs., 10 figs

  3. Photo- and radiation chemical studies of intermediates involved in excited-state electron-transfer reactions

    International Nuclear Information System (INIS)

    Hoffman, M.Z.

    1985-01-01

    Excited-state inter- and intramolecular electron-transfer reactions lie at the heart of the most photochemical solar energy conversion schemes. The authors research, which has utilized the techniques of continuous and pulsed photolysis and radiolysis, has focused on three general aspects of these reactions involving transition metal coordination complexes and electron donor-acceptor complexes: i) the effect of solution medium on the properties and quenching of the excited states; ii) the control of the quantum yields of formation of redox products; iii) the mechanism by which reduced species interact with water to yield H 2 homogeneously and heterogeneously. EDTA is among the most popular sacrificial electron donors used in model systems. Its role is to scavenge the oxidized form of the photosensitizer in order to prevent its rapid reaction with the reduced form of the electron relay species that results from the electron-transfer quenching of the excited photosensitizer. In systems involving MV 2+ , the radicals resulting from the oxidation of EDTA can eventually lead to the generation of a second equivalent of MV + ; the reducing agent is believed to be a radical localized on the carbon atom alpha to the carboxylate group. The reaction of radiolytically-generated OH/H with EDTA produces this radical directly via H-abstraction or indirectly via deprotonation of the carbon atom adjacent to the nitrogen radical site in the oxidized amine moiety; it reduces MV 2+ with rate constants of 2.8 x 10 9 , 7.6 x 10 9 , and 8.5 x 10 6 M -1 s -1 at pH 12.5, 8.3, and 4.7, respectively. Degradative decarboxylation of EDTA-radicals and their back electron-transfer reactions are enhanced in acidic solution causing the yield of MV + to be severely diminished

  4. Glycosylation intermediates studied using low temperature 1H- and 19F-DOSY NMR

    DEFF Research Database (Denmark)

    Qiao, Yan; Ge, Wenzhi; Jia, Lingyu

    2016-01-01

    Low temperature 1H- and 19F-DOSY have been used for analyzing reactive intermediates in glycosylation reactions, where a glycosyl trichloroacetimidate donor has been activated using different catalysts. The DOSY protocols have been optimized for low temperature experiments and provided new insight...

  5. Reactions of melatonin with radicals in deoxygenated aqueous solution

    International Nuclear Information System (INIS)

    Stasica, P.; Ulanski, P.; Rosiak, J.M.

    1998-01-01

    Reactions of melatonin (N-acetyl-5-methoxytryptamine) with radiolytically generated radicals were studied. Reaction of melatonin with OH radicals is diffusion-controlled (k=1.2 x 10 10 dm 3 mol -1 x s -1 ), the main (but not the only one) intermediate being the indolyl-type radical, while the rate constant for the reaction with hydrated electrons is k=4.3 x 10 8 dm 3 x mol -1 x s -1 . Melatonin is capable of scavenging tert-butanol radicals, while its reactivity towards polymer radicals of poly(acrylic acid) and poly(vinyl pyrrolidone) is very low. (author)

  6. Effect of an intermediate tungsten layer on thermal properties of TiC coatings ion plated onto molybdenum

    International Nuclear Information System (INIS)

    Fukutomi, M.; Fujitsuka, M.; Shikama, T.; Okada, M.

    1985-01-01

    Among the various low-Z coating-substrate systems proposed for fusion reactor first-wall applications, molybdenum coated with titanium carbide is considered very promising since it has a good capability of receiving heat from the plasma. The thermal stabilities of TiC layers ion plated onto the molybdenum substrate are discussed with particular reference to the interfacial reaction between the TiC coating and molybdenum. The deposition of an intermediate tungsten layer was found to be very effective in suppressing the formation of reaction layers, resulting in a marked improvement in thermal stabilities of TiC--Mo systems. Thermal shock test using a pulsed electron beam showed that the TiC coatings remained adherent to the molybdenum substrates during energy depositions high enough to melt the substrates within the area of beam deposition. The melt area of the TiC coatings apparently decreased when a tungsten intermediate layer was applied

  7. Statistical distribution of partial widths in the microscopic theory of nuclear reactions

    International Nuclear Information System (INIS)

    Bunakov, V.E.; Ogloblin, S.G.

    1978-01-01

    Using the microscopic theory of nuclear reaction the distribution function of neutron reduced partial widths is obtained. It is shown that the distribution of reduced partial widths of a radiative transition is of the same form. The distribution obtained differs from the Porter-Thomas law for neutron widths only in the presence of intermediate structures. It is noteworthy that the presence of an intermediate structure leads to a greater dispersion

  8. High heat flux testing of TiC coated molybdenum with a tungsten intermediate layer

    International Nuclear Information System (INIS)

    Fujitsuka, Masakazu; Fukutomi, Masao; Okada, Masatoshi

    1988-01-01

    The use of low atomic number (Z) material coatings for fusion reactor first-wall components has proved to be a valuable technique to reduce the plasma radiation losses. Molybdenum coated with titanium carbide is considered very promising since it has a good capability of receiving heat from the plasma. An interfacial reaction between the TiC film and the molybdenum substrate, however, causes a severe deterioration of the film at elevated temperatures. In order to solve this problem a TiC coated molybdenum with an intermediate tungsten layer was developed. High temperature properties of this material was evaluated by a newly devised electron beam heating apparatus. TiC coatings prepared on a vacuum-heat-treated molybdenum with a tungsten intermediate layer showed good high temperature stability and survived 2.0 s pulses of heating at a power density as high as 53 MW/m 2 . The melt area of the TiC coatings in high heat flux testings also markedly decreased when a tungsten intermediate layer was applied. The melting mechanism of the TiC coatings with and without a tungsten intermediate layer was discussed by EPMA measurements. (author)

  9. Intermediality and media change

    OpenAIRE

    2012-01-01

    This book is about intermediality as an approach to analysing and understanding media change. Intermediality and Media Change is critical of technological determinism that characterises 'new media discourse' about the ongoing digitalization, framed as a revolution and creating sharp contrasts between old and new media. Intermediality instead emphasises paying attention to continuities between media of all types and privileges a comparative perspective on technological changes in media over ti...

  10. Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis

    Science.gov (United States)

    Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

    2017-06-01

    Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes.

  11. Multistage reaction pathways in detonating high explosives

    International Nuclear Information System (INIS)

    Li, Ying; Kalia, Rajiv K.; Nakano, Aiichiro; Nomura, Ken-ichi; Vashishta, Priya

    2014-01-01

    Atomistic mechanisms underlying the reaction time and intermediate reaction products of detonating high explosives far from equilibrium have been elusive. This is because detonation is one of the hardest multiscale physics problems, in which diverse length and time scales play important roles. Here, large spatiotemporal-scale reactive molecular dynamics simulations validated by quantum molecular dynamics simulations reveal a two-stage reaction mechanism during the detonation of cyclotrimethylenetrinitramine crystal. Rapid production of N 2 and H 2 O within ∼10 ps is followed by delayed production of CO molecules beyond ns. We found that further decomposition towards the final products is inhibited by the formation of large metastable carbon- and oxygen-rich clusters with fractal geometry. In addition, we found distinct unimolecular and intermolecular reaction pathways, respectively, for the rapid N 2 and H 2 O productions

  12. Multistage reaction pathways in detonating high explosives

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ying [Collaboratory for Advanced Computing and Simulations, Department of Physics and Astronomy, Department of Computer Science, and Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, California 90089-0242 (United States); Argonne Leadership Computing Facility, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Kalia, Rajiv K.; Nakano, Aiichiro; Nomura, Ken-ichi; Vashishta, Priya [Collaboratory for Advanced Computing and Simulations, Department of Physics and Astronomy, Department of Computer Science, and Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, California 90089-0242 (United States)

    2014-11-17

    Atomistic mechanisms underlying the reaction time and intermediate reaction products of detonating high explosives far from equilibrium have been elusive. This is because detonation is one of the hardest multiscale physics problems, in which diverse length and time scales play important roles. Here, large spatiotemporal-scale reactive molecular dynamics simulations validated by quantum molecular dynamics simulations reveal a two-stage reaction mechanism during the detonation of cyclotrimethylenetrinitramine crystal. Rapid production of N{sub 2} and H{sub 2}O within ∼10 ps is followed by delayed production of CO molecules beyond ns. We found that further decomposition towards the final products is inhibited by the formation of large metastable carbon- and oxygen-rich clusters with fractal geometry. In addition, we found distinct unimolecular and intermolecular reaction pathways, respectively, for the rapid N{sub 2} and H{sub 2}O productions.

  13. Multifragment emission times in Xe induced reactions

    Energy Technology Data Exchange (ETDEWEB)

    Moroni, A. [INFN and Dipartimento di Fisica, Via Celoria 16, 20133 Milano (Italy); Bowman, D.R. [AECL Research, Chalk River Laboratories, Chalk River, Ont. (Canada); Bruno, M. [Dipartimento di Fisica and INFN, Via Irnerio 46, 40126 Bologna (Italy); Buttazzo, P. [Dipartimento di Fisica and INFN, Via A. Valerio 2, 34127 Trieste (Italy); Celano, L. [INFN, Via Amendola 173, 70126 Bari (Italy); Colonna, N. [INFN, Via Amendola 173, 70126 Bari (Italy); D`Agostino, M. [Dipartimento di Fisica and INFN, Via Irnerio 46, 40126 Bologna (Italy); Dinius, J.D. [NSCL, Michigan State University, E. Lansing, 48824 MI (United States); Ferrero, A. [INFN and Dipartimento di Fisica, Via Celoria 16, 20133 Milano (Italy); Fiandri, M.L. [Dipartimento di Fisica and INFN, Via Irnerio 46, 40126 Bologna (Italy); Gelbke, K. [NSCL, Michigan State University, E. Lansing, 48824 MI (United States); Glasmacher, T. [NSCL, Michigan State University, E. Lansing, 48824 MI (United States); Gramegna, F. [INFN Laboratori Nazionali di Legnaro, Via Romea 4, 35020 Legnaro (Italy); Handzy, D.O. [NSCL, Michigan State University, E. Lansing, 48824 MI (United States); Horn, D. [AECL Research, Chalk River Laboratories, Chalk River, Ont. (Canada); Hsi Wenchien [NSCL, Michigan State University, E. Lansing, 48824 MI (United States); Huang, M. [NSCL, Michigan State University, E. Lansing, 48824 MI (United States); Iori, I. [INFN and Dipartimento di Fisica, Via Celoria 16, 20133 Milano (Italy); Lisa, M. [NSCL, Michigan State University, E. Lansing, 48824 MI (United States); Lynch, W.G. [NSCL, Michigan State University, E. Lansing, 48824 MI (United States); Margagliotti, G.V. [Dipartimento di Fisica and INFN, Via A. Valerio 2, 34127 Trieste (Italy); Mastinu, P.F. [Dipartimento di Fisica and INFN, Via Irnerio 46, 40126 Bologna (Italy); Milazzo, P.M. [Dipartimento di Fisica and INFN, Via Irnerio 46, 40126 Bologna (Italy); Montoya, C.

    1995-02-06

    Multifragment emission is studied in {sup 129}Xe+{sup nat}Cu reactions. The emission process for central collisions occurs on a time scale of similar 200fm/c at 30MeV/n. Intermediate-mass-fragment yields, velocity correlation functions and emission velocities of Z=6 fragments are compared with predictions of statistical decay models. ((orig.)).

  14. Evolution of reaction mechanisms for the reaction 36Ar + 58Ni studied from 32 to 95 A*MeV with the INDRA multidetector

    International Nuclear Information System (INIS)

    De Filippo, E.

    1995-03-01

    In the context of the multifragmentation study program with the 4π INDRA detector at GANIL, the reaction 36 Ar + 58 Ni has been studied at seven different energies ranging from 32 to 95 A*MeV. After a brief description of the detector characteristics and of the data treatment, results on the evolution of intermediate mass fragments (IMF) distributions with incident energy and a first outlook about reaction mechanisms are presented. (author). 15 refs., 10 figs

  15. Intermediate Fragment

    DEFF Research Database (Denmark)

    Kruse Aagaard, Anders

    2015-01-01

    This text and its connected exhibition are aiming to reflect both on the thoughts, the processes and the outcome of the design and production of the artefact ‘Intermediate Fragment’ and making as a contemporary architectural tool in general. Intermediate Fragment was made for the exhibition ‘Enga...... of realising an exhibition object was conceived, but expanded, refined and concretised through this process. The context of the work shown here is an interest in a tighter, deeper connection between experimentally obtained material knowledge and architectural design....

  16. Intermediate products of radiolytic conversions of 6-aminophenalenone in ethanol

    International Nuclear Information System (INIS)

    Semenova, G.V.; Ponomarev, A.V.; Kartasheva, L.I.; Pikaev, A.K.

    1992-01-01

    Intermediate products of the conversions of 6-aminophenalenone in ethanol were investigated by pulse radiolysis. In alkaline medium the main product is the 6-aminophenalenone radical cation, the optical absorption spectrum of which contains two bands with maxima at 355 and 400 nm. The precursors of this particle are e s , CH 3 CHOH and CH 3 CHO - radicals. In neutral and acid medium, radical cations are protonated in reactions with alcohol and hydrogen ions. The H-adduct of 6-aminophenalenone that arises has optical absorption maxima at 350 and 390 nm. The presence of two maxima is due to two different structures of the product. The molar extinction coefficients of the radical anions and H-adducts of 6-aminophenalenone and the rate constants of the reactions involving them were estimated. 6 refs., 4 figs., 2 tabs

  17. Glucose and Fructose to Platform Chemicals: Understanding the Thermodynamic Landscapes of Acid-Catalysed Reactions Using High-Level ab Initio Methods

    Energy Technology Data Exchange (ETDEWEB)

    Assary, Rajeev S.; Kim, Taijin; Low, John; Greeley, Jeffrey P.; Curtiss, Larry A.

    2012-12-28

    Molecular level understanding of acid-catalysed conversion of sugar molecules to platform chemicals such as hydroxy-methyl furfural (HMF), furfuryl alcohol (FAL), and levulinic acid (LA) is essential for efficient biomass conversion. In this paper, the high-level G4MP2 method along with the SMD solvation model is employed to understand detailed reaction energetics of the acid-catalysed decomposition of glucose and fructose to HMF. Based on protonation free energies of various hydroxyl groups of the sugar molecule, the relative reactivity of gluco-pyranose, fructo-pyranose and fructo-furanose are predicted. Calculations suggest that, in addition to the protonated intermediates, a solvent assisted dehydration of one of the fructo-furanosyl intermediates is a competing mechanism, indicating the possibility of multiple reaction pathways for fructose to HMF conversion in aqueous acidic medium. Two reaction pathways were explored to understand the thermodynamics of glucose to HMF; the first one is initiated by the protonation of a C2–OH group and the second one through an enolate intermediate involving acyclic intermediates. Additionally, a pathway is proposed for the formation of furfuryl alcohol from glucose initiated by the protonation of a C2–OH position, which includes a C–C bond cleavage, and the formation of formic acid. The detailed free energy landscapes predicted in this study can be used as benchmarks for further exploring the sugar decomposition reactions, prediction of possible intermediates, and finally designing improved catalysts for biomass conversion chemistry in the future.

  18. Recent research on nuclear reaction using high-energy proton and neutron

    Energy Technology Data Exchange (ETDEWEB)

    Shibata, Tokushi [Tokyo Univ., Tanashi (Japan). Inst. for Nuclear Study

    1997-11-01

    The presently available high-energy neutron beam facilities are introduced. Then some interesting research on nuclear reaction using high-energy protons are reported such as the intermediate mass fragments emission and neutron spectrum measurements on various targets. As the important research using high-energy neutron, the (p,n) reactions on Mn, Fe, and Ni, the elastic scattering of neutrons, and the shielding experiments are discussed. (author)

  19. Governance-Default Risk Relationship and the Demand for Intermediated and Non-Intermediated Debt

    Directory of Open Access Journals (Sweden)

    Husam Aldamen

    2012-09-01

    Full Text Available This paper explores the impact of corporate governance on the demand for intermediated debt (asset finance, bank debt, non-bank private debt and non-intermediated debt (public debt in the Australian debt market. Relative to other countries the Australian debt market is characterised by higher proportions of intermediated or private debt with a lower inherent level of information asymmetry in that private lenders have greater access to financial information (Gray, Koh & Tong 2009. Our firm level, cross-sectional evidence suggests that higher corporate governance impacts demand for debt via the mitigation of default risk. However, this relationship is not uniform across all debt types. Intermediated debt such as bank and asset finance debt are more responsive to changes in governance-default risk relationship than non-bank and non-intermediated debt. The implication is that a firm’s demand for different debt types will reflect its governance-default risk profile.

  20. Substrate-Coated Illumination Droplet Spray Ionization: Real-Time Monitoring of Photocatalytic Reactions

    Science.gov (United States)

    Zhang, Hong; Li, Na; Zhao, Dandan; Jiang, Jie; You, Hong

    2017-09-01

    Real-time monitoring of photocatalytic reactions facilitates the elucidation of the mechanisms of the reactions. However, suitable tools for real-time monitoring are lacking. Herein, a novel method based on droplet spray ionization named substrate-coated illumination droplet spray ionization (SCI-DSI) for direct analysis of photocatalytic reaction solution is reported. SCI-DSI addresses many of the analytical limitations of electrospray ionization (ESI) for analysis of photocatalytic-reaction intermediates, and has potential for both in situ analysis and real-time monitoring of photocatalytic reactions. In SCI-DSI-mass spectrometry (MS), a photocatalytic reaction occurs by loading sample solutions onto the substrate-coated cover slip and by applying UV light above the modified slip; one corner of this slip adjacent to the inlet of a mass spectrometer is the high-electric-field location for launching a charged-droplet spray. After both testing and optimizing the performance of SCI-DSI, the value of this method for in situ analysis and real-time monitoring of photocatalytic reactions was demonstrated by the removal of cyclophosphamide (CP) in TiO2/UV. Reaction times ranged from seconds to minutes, and the proposed reaction intermediates were captured and identified by tandem mass spectrometry. Moreover, the free hydroxyl radical (·OH) was identified as the main radicals for CP removal. These results show that SCI-DSI is suitable for in situ analysis and real-time monitoring of CP removal under TiO2-based photocatalytic reactions. SCI-DSI is also a potential tool for in situ analysis and real-time assessment of the roles of radicals during CP removal under TiO2-based photocatalytic reactions. Graphical Abstract[Figure not available: see fulltext.

  1. Sequential reduction–oxidation for photocatalytic degradation of tetrabromobisphenol A: Kinetics and intermediates

    International Nuclear Information System (INIS)

    Guo, Yaoguang; Lou, Xiaoyi; Xiao, Dongxue; Xu, Lei; Wang, Zhaohui; Liu, Jianshe

    2012-01-01

    Highlights: ► Sequential photocatalytic reduction–oxidation degradation of TBBPA was firstly examined. ► Different atmospheres were found to have significant effect on debromination reaction. ► A possible sequential photocatalytic reduction–oxidation pathway was proposed. - Abstract: C-Br bond cleavage is considered as a key step to reduce their toxicities and increase degradation rates for most brominated organic pollutants. Here a sequential reduction/oxidation strategy (i.e. debromination followed by photocatalytic oxidation) for photocatalytic degradation of tetrabromobisphenol A (TBBPA), one of the most frequently used brominated flame retardants, was proposed on the basis of kinetic analysis and intermediates identification. The results demonstrated that the rates of debromination and even photodegradation of TBBPA strongly depended on the atmospheres, initial TBBPA concentrations, pH of the reaction solution, hydrogen donors, and electron acceptors. These kinetic data and byproducts identification obtained by GC–MS measurement indicated that reductive debromination reaction by photo-induced electrons dominated under N 2 -saturated condition, while oxidation reaction by photoexcited holes or hydroxyl radicals played a leading role when air was saturated. It also suggested that the reaction might be further optimized for pretreatment of TBBPA-contaminated wastewater by a two-stage reductive debromination/subsequent oxidative decomposition process in the UV-TiO 2 system by changing the reaction atmospheres.

  2. Measurement of Fragment Mass Distributions in Neutron-induced Fission of {sup 238}U and {sup 232}Th at Intermediate Energies

    Energy Technology Data Exchange (ETDEWEB)

    Simutkin, V.D. [Uppsala University, P.O Box 525, SE-751 20 Uppsala (Sweden)

    2008-07-01

    Conceptual analysis of accelerator-driven systems assumes extensive use of nuclear data on neutron-induced reactions at intermediate energies. In particular, information about the fission fragment yields from the {sup 238}U(n,f) and {sup 232}Th(n,f) reactions is of particular interest at neutron energies from 10 to 200 MeV. However, there is a lack of such data for both {sup 238}U and {sup 232}Th. Up to now, the intermediate energy measurements have been performed for {sup 238}U only, and there are no data for the {sup 232}Th(n,f) reaction. The aim of the work is to provide such data. Fission fragment mass distributions for the {sup 232}Th(n,f) and {sup 238}U(n,f) reactions have been measured for the incident neutron energies 32.8 MeV, 45.3 MeV and 59.9 MeV. The experiments have been performed at the neutron beam facility of the Universite Catholique de Louvain, Belgium. A multi-section Frisch-gridded ionization chamber has been used as a fission fragment detector. The data obtained have been interpreted in terms of the multimodal random neck-rupture model (MMRNRM). (authors)

  3. Microwave-assisted synthesis of α-aryl malonates: Key intermediates for the

    Directory of Open Access Journals (Sweden)

    Mohamed A. Ibrahim

    2016-11-01

    Full Text Available We disclose a new microwave-assisted protocol for the effective α-arylation of diethyl malonate. The coupling of aryl halides with diethyl malonate proceeds smoothly in short reaction time in the presence of a catalytic amount of Cu(OTf2, 2-picolinic acid and Cs2CO3 in toluene using microwave irradiation. The resulting α-aryl malonates are then used as key intermediates for synthesis of variety of heterocyclic compounds, including benzodiazepines, isoquinolines and pyrrolopyridine scaffolds.

  4. Kaon production in intermediate-energy nuclear collisions

    International Nuclear Information System (INIS)

    Russkikh, V.N.; Ivanov, Yu.B.

    1992-01-01

    Production of positive kaons in nuclear collisions at intermediate energies (∝ 1-2 GeV/nucleon) is studied within the 3-dimensional fluid dynamics combined with the hadrochemical kinetics for strangeness production. Sensitivity of the kaon probe to a form of the nuclear equation of state is analyzed. The model reproduces total and differential cross sections of Ne+NaF→K + +X and Ne+Pb→K + +X reactions at E lab =2.1 GeV/nucleon, provided a soft equation of state is used. The pion-production data are also well described employing the same equation of state. Predictions are made for the current experiment on kaon production at the SIS accelerator. The obtained results are compared with the predictions of other models. (orig.)

  5. Kinetic investigation of heterogeneous catalytic reactions by means of the kinetic isotope method

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, F; Dermietzel, J [Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung

    1978-09-01

    The application of the kinetic isotope method to heterogeneous catalytic processes is possible for surface compounds by using the steady-state relation. However, the characterization of intermediate products becomes ambiguous if sorption rates are of the same order of magnitude as surface reactions rates. The isotopic exchange reaction renders possible the estimation of sorption rates.

  6. Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

    Energy Technology Data Exchange (ETDEWEB)

    Wink, D A [National Cancer Inst., Frederick, MD (United States); Desrosiers, M F [National Inst. of Standards and Technology, Gaithersburg, MD (United States)

    1991-01-01

    The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3.5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant (BR{sub 2}{sup -}). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive inter-mediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented. (author).

  7. Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

    International Nuclear Information System (INIS)

    Wink, D.A.; Desrosiers, M.F.

    1991-01-01

    The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3.5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant (BR 2 - ). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive inter-mediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented. (author)

  8. Control of Maillard Reactions in Foods: Strategies and Chemical Mechanisms.

    Science.gov (United States)

    Lund, Marianne N; Ray, Colin A

    2017-06-14

    Maillard reactions lead to changes in food color, organoleptic properties, protein functionality, and protein digestibility. Numerous different strategies for controlling Maillard reactions in foods have been attempted during the past decades. In this paper, recent advances in strategies for controlling the Maillard reaction and subsequent downstream reaction products in food systems are critically reviewed. The underlying mechanisms at play are presented, strengths and weaknesses of each strategy are discussed, and reasonable reaction mechanisms are proposed to reinforce the evaluations. The review includes strategies involving addition of functional ingredients, such as plant polyphenols and vitamins, as well as enzymes. The resulting trapping or modification of Maillard targets, reactive intermediates, and advanced glycation endproducts (AGEs) are presented with their potential unwanted side effects. Finally, recent advances in processing for control of Maillard reactions are discussed.

  9. Stellar evolution and the triple-α reactions

    International Nuclear Information System (INIS)

    Suda, Takuma

    2014-01-01

    Nuclear reaction rates play a crucial role in the evolution of stars. For low-mass stars, the triple-α reaction controls the helium burning stars in the red giant and asymptotic giant branch (AGB) phase. More importantly, the cross section of the triple-α reaction has a great impact on the helium ignition at the center of the electron degenerate helium core of red giants and on the helium shell flashes of AGB stars. It is to be noted that stellar evolution models are influenced not only by the value of the cross section, but also by the temperature dependence of the reaction rate. In this paper, I present the impact of the triple-α reaction rates on the evolution of low-mass metal-free stars and intermediate-mass AGB stars. According to the previous study, the constraint on the triple-α reaction rate is derived based on stellar evolution theory. It is found that the recent revisions of the rate proposed by nuclear physics calculations satisfy the condition for the ignition of the helium core flash in low-mass stars

  10. Atmospheric fates of Criegee intermediates in the ozonolysis of isoprene.

    Science.gov (United States)

    Nguyen, Tran B; Tyndall, Geoffrey S; Crounse, John D; Teng, Alexander P; Bates, Kelvin H; Schwantes, Rebecca H; Coggon, Matthew M; Zhang, Li; Feiner, Philip; Milller, David O; Skog, Kate M; Rivera-Rios, Jean C; Dorris, Matthew; Olson, Kevin F; Koss, Abigail; Wild, Robert J; Brown, Steven S; Goldstein, Allen H; de Gouw, Joost A; Brune, William H; Keutsch, Frank N; Seinfeld, John H; Wennberg, Paul O

    2016-04-21

    We use a large laboratory, modeling, and field dataset to investigate the isoprene + O3 reaction, with the goal of better understanding the fates of the C1 and C4 Criegee intermediates in the atmosphere. Although ozonolysis can produce several distinct Criegee intermediates, the C1 stabilized Criegee (CH2OO, 61 ± 9%) is the only one observed to react bimolecularly. We suggest that the C4 Criegees have a low stabilization fraction and propose pathways for their decomposition. Both prompt and non-prompt reactions are important in the production of OH (28% ± 5%) and formaldehyde (81% ± 16%). The yields of unimolecular products (OH, formaldehyde, methacrolein (42 ± 6%) and methyl vinyl ketone (18 ± 6%)) are fairly insensitive to water, i.e., changes in yields in response to water vapor (≤4% absolute) are within the error of the analysis. We propose a comprehensive reaction mechanism that can be incorporated into atmospheric models, which reproduces laboratory data over a wide range of relative humidities. The mechanism proposes that CH2OO + H2O (k(H2O)∼ 1 × 10(-15) cm(3) molec(-1) s(-1)) yields 73% hydroxymethyl hydroperoxide (HMHP), 6% formaldehyde + H2O2, and 21% formic acid + H2O; and CH2OO + (H2O)2 (k(H2O)2∼ 1 × 10(-12) cm(3) molec(-1) s(-1)) yields 40% HMHP, 6% formaldehyde + H2O2, and 54% formic acid + H2O. Competitive rate determinations (kSO2/k(H2O)n=1,2∼ 2.2 (±0.3) × 10(4)) and field observations suggest that water vapor is a sink for greater than 98% of CH2OO in a Southeastern US forest, even during pollution episodes ([SO2] ∼ 10 ppb). The importance of the CH2OO + (H2O)n reaction is demonstrated by high HMHP mixing ratios observed over the forest canopy. We find that CH2OO does not substantially affect the lifetime of SO2 or HCOOH in the Southeast US, e.g., CH2OO + SO2 reaction is a minor contribution (production by stabilized Criegees is likely unimportant in regions dominated by the reactivity of ozone with isoprene. In contrast

  11. Studies of complex fragment emission in heavy ion reactions

    International Nuclear Information System (INIS)

    Charity, R.J.; Sobotka, L.G.

    1992-01-01

    Our work involves the study of intermediate energy heavy-ion nuclear reactions. This work has two foci. On the one hand, we desire to learn about the properties of nuclear matter under abnormal conditions, in this energy domain, predominately low densities. This purpose runs abreast of the second, which is the study of the relevant reaction mechanisms. The two objectives are inexorably linked because our experimental laboratory for studying nuclear matter properties is a dynamic one. We are forced to ask how nuclear matter properties, such as phase transitions, are reflected in the dynamics of the reactions. It may be that irrefutable information about nuclear matter will not be extracted from the reaction work. Nevertheless, we are compelled to undertake this effort not only because it is the only game in town and as yet we do not know that information cannot be extracted, but also because of our second objective. The process leads to an understanding of the reaction mechanism themselves and therefore to the response characteristics of finite, perhaps non-equilibrium, strongly interacting systems. Our program has been: To study energy, mass, and angular momentum deposition by studying incomplete fusion reactions. To gain confidence that we understand how highly excited systems decompose by studying all emissions from the highly excited systems. To push these kinds of studies into the intermediate energy domain, with excitation function studies. And attempt to learn about the dynamics of the decays using particle-particle correlations. In the last effort, we have decided to focus on simple systems, where we believe, definitive statements are possible. These avenues of research share a common theme, large complex fragment production

  12. From QCA (Quantum Cellular Automata) to Organocatalytic Reactions with Stabilized Carbenium Ions.

    Science.gov (United States)

    Gualandi, Andrea; Mengozzi, Luca; Manoni, Elisabetta; Giorgio Cozzi, Pier

    2016-06-01

    What do quantum cellular automata (QCA), "on water" reactions, and SN 1-type organocatalytic transformations have in common? The link between these distant arguments is the practical access to useful intermediates and key products through the use of stabilized carbenium ions. Over 10 years, starting with a carbenium ion bearing a ferrocenyl group, to the 1,3-benzodithiolylium carbenium ion, our group has exploited the use of these intermediates in useful and practical synthetic transformations. In particular, we have applied the use of carbenium ions to stereoselective organocatalytic alkylation reactions, showing a possible solution for the "holy grail of organocatalysis". Examples of the use of these quite stabilized intermediates are now also considered in organometallic chemistry. On the other hand, the stable carbenium ions are also applied to tailored molecules adapted to quantum cellular automata, a new possible paradigm for computation. Carbenium ions are not a problem, they can be a/the solution! © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Slow and fast pyrolysis of Douglas-fir lignin: Importance of liquid-intermediate formation on the distribution of products

    NARCIS (Netherlands)

    Zhou, Shuai; Pecha, Brennan; van Kuppevelt, Michiel; McDonald, Armando G.; Garcia-Perez, Manuel

    2014-01-01

    The formation of liquid intermediates and the distribution of products were studied under slow and fast pyrolysis conditions. Results indicate that monomers are formed from lignin oligomeric products during secondary reactions, rather than directly from the native lignin. Lignin from Douglas-fir

  14. The quantum theory of statistical multistep nucleus reactions

    CERN Document Server

    Zhivopistsev, F A

    2002-01-01

    The phenomenological models and quantum approaches to the description of the statistical multistep nuclear reactions are discussed. The basic advantages and deficiencies of various modifications of the quantum theory of the statistical multistep direct reactions: Feshbach-Kerman-Koonin formalism, the generalized model of the statistical multistep reactions (GMSMR) are considered in detail. The possibility of obtaining the consistent description of the experimental spectra for the reactions with nucleons is shown by the particular examples. Further improvement and development of the quantum formalism for the more complete and consecutive description of various mechanisms of the component particle formalism in the output channel, the correct of the unbound state densities of the intermediate and finite nuclei are needed for the analysis of the inclusive reactions with participation of the component particles, (and with an account of the contributions to the cross sections of the nucleus cluster and shell areas)...

  15. The extended sum-rule model view of light and intermediate mass fragment emission in nuclear reactions at intermediate energies

    International Nuclear Information System (INIS)

    Brancus, I.M.; Rebel, H.; Wentz, J.; Corcalciuc, V.

    1989-11-01

    The original sum-rule model worked out by Wilczynski et al. and successfully used for a global description of complete and incomplete fusion reactions has been extended by a term accounting for dissipative processes of the dinuclear system on its way to fusion. When applying to light and heavy ion collisions with various targets at energies in the transitional region, the new term proves to be rather essential for reproducing the element distributions of the fragments emitted from rather asymmetric systems. (orig.) [de

  16. Spectator tagging in quasi-free pn-reactions on deuterium at PROMICE/WASA, CELSIUS

    International Nuclear Information System (INIS)

    Bilger, R.; Brodowski, W.; Calen, H.; Clement, H.; Dunin, V.; Dyring, J.; Ekstroem, C.; Fransson, K.; Greiff, J.; Gustafsson, L.; Haeggstroem, S.; Hoeistad, B.; Johanson, J.; Johansson, A.; Johansson, T.; Khoukaz, A.; Kilian, K.; Koch, I.; Kullander, S.; Kupsc, A.; Marciniewski, P.; Morosov, B.; Neubauer, T.; Oelert, W; Ruber, R.; Shwartz, B.; Stepaniak, J.; Sukhanov, A.; Sukhanov, A.; Sundberg, P.; Turowiecki, A.; Wagner, G.; Wilhelmi, Z.; Wilkin, C.; Zabierowski, J.; Zernov, A.; Zlomanczuk, J.

    2000-01-01

    A set of silicon detectors has been added to the PROMICE/WASA (P/W) experiment at CELSIUS. These detectors have been used for spectator-proton tagging in proton deuteron collisions to investigate proton-neutron reactions at intermediate energies. The performance of the setup has been tested by measuring the pd → dπ o p spectator reaction

  17. Energy and Molecules from Photochemical/Photocatalytic Reactions. An Overview

    Directory of Open Access Journals (Sweden)

    Davide Ravelli

    2015-01-01

    Full Text Available Photocatalytic reactions have been defined as those processes that require both a (not consumed catalyst and light. A previous definition was whether such reactions brought a system towards or away from the (thermal equilibrium. This consideration brings in the question whether a part of the photon energy is incorporated into the photochemical reaction products. Data are provided for representative organic reactions involving or not molecular catalysts and show that energy storage occurs only when a heavily strained structure is generated, and in that case only a minor part of photon energy is actually stored (ΔG up to 25 kcal·mol−1. The green role of photochemistry/photocatalysis is rather that of forming highly reactive intermediates under mild conditions.

  18. Isolation and Spectroscopic Characterization of Reactive Species in Atmospheric and Interstellar Reactions

    Science.gov (United States)

    Relph, Rachael A.

    2011-12-01

    A critical element to the study of chemical reactions is the characterization of reaction intermediates. Methods have been developed to isolate these transient species in the gas phase and when combined with infrared spectroscopy have proven to be excellent tools for determining the structure and reactivity of key intermediates. The studies presented here exploit these technologies to better understand the chemistry of species involved in atmospheric and interstellar reactions. An excellent example of their utility is in the study of the formation of proton hydrates and HONO in the upper atmosphere by sequential addition of water molecules onto the nitrosonium ion. This reaction only proceeds to products after addition of the fourth water molecule, and isolation and characterization of the intermediate trihydrate, NO+(H 2O)3, shows that this species is formed in three isomeric forms, each with a different water network that controls the degree of bond formation between the nitrosonium ion and an activated water molecule. Many isomeric structures are also seen in the clustering reactions of acetylene which may be a mechanism for the formation of benzene cation in interstellar space. The spectroscopy of the trimer, (C2H2)3 + indicates that this species exists in two major isomer classes; covalent forms, one of which may be benzene, and an ion-molecule complex, comprised of a loosely bound acetylene on a dimer core. Interestingly, this dimer core is different from the cyclobutadiene-like structure observed in dimerized acetylene, and proves to be a robust species on the potential energy surface as it survives further clustering events. Two structural isomers of CO3 -and NO3 - are also investigated, and found to have drastically different infrared spectra which are analyzed in the context of their electronic structure. Isomers in these systems are prepared under different expansion conditions which accounts for their unique spectral signatures.

  19. Microwave-Assisted Organic Synthesis Using Benign Reaction Medium and Reagents

    Science.gov (United States)

    Account of chemical reactions expedited by microwave (MW) exposure of neat reactants for the rapid one-pot assembly of heterocyclic compounds from in situ generated reactive intermediates via enamines or using hypervalent iodine reagents will be described that can be adapted for ...

  20. MHD intermediate shock discontinuities: Pt. 1

    International Nuclear Information System (INIS)

    Kennel, C.F.; Blandford, R.D.; Coppi, P.

    1989-01-01

    Recent numerical investigations have focused attention once more on the role of intermediate shocks in MHD. Four types of intermediate shock are identified using a graphical representation of the MHD Rankine-Hugoniot conditions. This same representation can be used to exhibit the close relationship of intermediate shocks to switch-on shocks and rotational discontinuities. The conditions under which intermediate discontinuities can be found are elucidated. The variations in velocity, pressure, entropy and magnetic-field jumps with upstream parameters in intermediate shocks are exhibited graphically. The evolutionary arguments traditionally advanced against intermediate shocks may fail because the equations of classical MHD are not strictly hyperbolic. (author)

  1. Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study.

    Science.gov (United States)

    Du, Bingnan; Wang, Wenmin; Wang, Yang; Qi, Zhenghang; Tian, Jiaqi; Zhou, Jie; Wang, Xiaochen; Han, Jianlin; Ma, Jing; Pan, Yi

    2018-02-16

    A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C-S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu II intermediate, O-O bond homolysis induced C-S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C-S bond cleavage and transformations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. [Studies of target fragmentation in intermediate energy, relativistic and ultra-relativistic nuclear collisions

    International Nuclear Information System (INIS)

    Loveland, W.D.

    1991-08-01

    The work described herein is part of a project involving the study of low energy ( 250 MeV/A) heavy ion reactions. In the low energy regime, we published a monograph on the properties of the heaviest elements and used that publication as a basis for making a set of ''best'' semi-empirical predictions of heavy element decay properties. The intermediate energy research effort focussed upon the completion of studies already begun and the initiation of a number of new experiments. In our study of a interaction of 21 MeV/nucleon 129 Xe with 197 Au, we compared the characteristics of the observed deep inelastic phenomena with various models of dissipative reactions and found significant discrepancies between observations and predictions. These discrepancies seemed to be caused by an improper treatment of pre-equilibrium in the early stages of the collision. In our study of the relativistic interaction of 400 MeV/nucleon 12 C with 197 Au, we reported the first direct physical measurement of the properties of the spallation residues from a nucleus-nucleus collision. We found the residue energies to be much lower than those predicted by the intranuclear cascade model, indicating some substantial modifications of that model are needed. But, we also found, indications of significant, non-zero values of the residue transverse momentum, a finding that calls into question the interpretation of a number of radiochemical recoil studies of the kinematics of high energy reactions. A program of performing numerical simulations of intermediate and high energy nuclear collisions using the QMD model was initiated

  3. Gold-Catalyzed Formal C-C Bond Insertion Reaction of 2-Aryl-2-diazoesters with 1,3-Diketones.

    Science.gov (United States)

    Ren, Yuan-Yuan; Chen, Mo; Li, Ke; Zhu, Shou-Fei

    2018-06-29

    The transition-metal-catalyzed formal C-C bond insertion reaction of diazo compounds with monocarbonyl compounds is well established, but the related reaction of 1,3-diketones instead gives C-H bond insertion products. Herein, we report a protocol for a gold-catalyzed formal C-C bond insertion reaction of 2-aryl-2-diazoesters with 1,3-diketones, which provides efficient access to polycarbonyl compounds with an all-carbon quaternary center. The aryl ester moiety plays a crucial role in the unusual chemoselectivity, and the addition of a Brønsted acid to the reaction mixture improves the yield of the C-C bond insertion product. A reaction mechanism involving cyclopropanation of a gold carbenoid with an enolate and ring-opening of the resulting donor-acceptor-type cyclopropane intermediate is proposed. This mechanism differs from that of the traditional Lewis-acid-catalyzed C-C bond insertion reaction of diazo compounds with monocarbonyl compounds, which involves a rearrangement of a zwitterion intermediate as a key step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Pion- and proton-nucleus interactions at intermediate energy

    International Nuclear Information System (INIS)

    Dehnhard, D.

    1992-12-01

    We report on scattering and reaction experiments on light nuclei using the π-meson and proton beams from the Los Alamos Meson Physics Facility (LAMPF) and the Indiana University Cyclotron Facility (IUCF). Differential cross sections, cross section asymmetries, and angular correlation functions have been measured in order to test models of the reaction mechanism and of nuclear structure. At LAMPF we have measured asymmetries for pion scattering from polarized 13 C which are uniquely sensitive to the isoscalar spin density. In order to determine details of the reaction mechanism, we have obtained approval for a scattering experiment on polarized 3 He for which the nuclear structure is very well known. We have completed data taking for two studies of elastic scattering of π + from 6 Li and l3 C. The detailed differential cross sections from these experiments will be used to constrain theoretical analyses of previous polarization experiments done at the Pierre-Scherrer-Institute (PSI) and at LAMPF. We have analyzed π-triton coincidence events from the 4 He(π,π' t)p reaction and have found evidence for direct triton knockout from 4 He. We have extended these angular correlation measurements to higher energies and to 2 H and 3 He targets. At IUCF we have performed the first 4 He(p,n) experiment at intermediate energies, T p = 100, 147, and 200 MeV, in a search for previously reported narrow states in 4 Li of widths of ∼ 1 MeV. Within the statistics of the data we have found no evidence for such narrow structures

  5. Reaction-transport simulations of non-oxidative methane conversion with continuous hydrogen removal: Homogeneous-heterogeneous methane reaction pathways

    International Nuclear Information System (INIS)

    Li, Lin; Borry, Richard W.; Iglesia, Enrique

    2000-01-01

    Detailed kinetic-transport models were used to explore thermodynamic and kinetic barriers in the non-oxidative conversion of CH4 via homogeneous and homogeneous-heterogeneous pathways and the effects of continuous hydrogen removal and of catalytic sites on attainable yields of useful C2-C10 products. The homogeneous kinetic model combines separately developed models for low-conversion pyrolysis and for chain growth to form large aromatics and carbon. The H2 formed in the reaction decreases CH4 pyrolysis rates and equilibrium conversions and it favors the formation of lighter products. The removal of H2 along tubular reactors with permeable walls increases reaction rates and equilibrium CH4 conversions. C2-C10 yields reach values greater than 90 percent at intermediate values of dimensionless transport rates (delta=1-10), defined as the ratio hydrogen transport and methane conversion rates. Homogeneous reactions require impractical residence times, even with H2 removal, because of slow initiation and chain transfer rates. The introduction of heterogeneous chain initiation pathways using surface sites that form methyl radicals eliminates the induction period without influencing the homogeneous product distribution. Methane conversion, however, occurs predominately in the chain transfer regime, within which individual transfer steps and the formation of C2 intermediates become limited by thermodynamic constraints. Catalytic sites alone cannot overcome these constraints. Catalytic membrane reactors with continuous H2 removal remove these thermodynamic obstacles and decrease the required residence time. Reaction rates become limited by homogeneous reactions of C2 products to form C6+ aromatics. Higher delta values lead to subsequent conversion of the desired C2-C10 products to larger polynuclear aromatics. We conclude that catalytic methane pyrolysis at the low temperatures required for restricted chain growth and the elimination of thermodynamics constraints via

  6. Surface-Bound Intermediates in Low-Temperature Methanol Synthesis on Copper. Participants and Spectators

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yong; Mei, Donghai; Peden, Charles HF; Campbell, Charles T.; Mims, Charles A.

    2015-11-03

    The reactivity of surface adsorbed species present on copper catalysts during methanol synthesis at low temperatures was studied by simultaneous infrared spectroscopy (IR) and mass spectroscopy (MS) measurements during “titration” (transient surface reaction) experiments with isotopic tracing. The results show that adsorbed formate is a major bystander species present on the surface under steady-state methanol synthesis reaction conditions, but it cannot be converted to methanol by reaction with pure H2, nor with H2 plus added water. Formate-containing surface adlayers for these experiments were produced during steady state catalysis in (a) H2:CO2 (with substantial formate coverage) and (b) moist H2:CO (with no IR visible formate species). Both these reaction conditions produce methanol at steady state with relatively high rates. Adlayers containing formate were also produced by (c) formic acid adsorption. Various "titration" gases were used to probe these adlayers at modest temperatures (T = 410-450K) and 6 bar total pressure. Methanol gas (up to ~1% monolayer equivalent) was produced in "titration" from the H2:CO2 catalytic adlayers by H2 plus water, but not by dry hydrogen. The decay in the formate IR features accelerated in the presence of added water vapor. The H2:CO:H2O catalytic adlayer produced similar methanol titration yields in H2 plus water but showed no surface formate features in IR (less than 0.2% monolayer coverage). Finally, formate from formic acid chemisorption produced no methanol under any titration conditions. Even under (H2:CO2) catalytic reaction conditions, isotope tracing showed that pre-adsorbed formate from formic acid did not contribute to the methanol produced. Although non-formate intermediates exist during low temperature methanol synthesis on copper which can be converted to methanol gas

  7. A kinetic model for the glucose/glycine Maillard reaction pathways

    NARCIS (Netherlands)

    Martins, S.I.F.S.; Boekel, van M.A.J.S.

    2005-01-01

    A comprehensive kinetic model for the glucose/glycine Maillard reaction is proposed based on an approach called multiresponse kinetic modelling. Special attention was paid to reactants, intermediates and end products: -fructose, N-(1-deoxy--fructos-1-yl)-glycine (DFG), 1-deoxy-2,3-hexodiulose and

  8. Communication: The Al + CO2 → AlO + CO reaction: Experiment vs. theory

    Science.gov (United States)

    Sun, Zhi; Moore, Kevin B.; Schaefer, Henry F.

    2017-11-01

    Based on their highly sophisticated crossed-beam experimental studies of the Al + CO2 → AlO + CO reaction, Honma and Hirata have directly challenged the results of earlier theoretical studies of this system. We report high level theoretical studies of this system. It is shown that, consistent with Honma-Hirata experimental conclusions, the previous theoretical prediction of a substantial barrier height for this reaction was incorrect. However, for the structures of the possible intermediates, in agreement with the 1992 theoretical study of Sakai, we find striking disagreement with the experimental conclusion that the O-C-O moiety is nearly linear. The energies of the three entrance channel intermediates lie 14.4, 15.2, and 16.4 kcal mol-1 below separated Al + CO2.

  9. A condition variation study for radioiodination via triazene intermediates

    International Nuclear Information System (INIS)

    Foster, N.I.; Heindel, N.D.; Dannals, R.; Burns, H.D.

    1981-01-01

    Pyrrolidyl triazenes prepared by interception of the diazonium transient in the Sandmeyer reaction of amines can serve as useful intermediates in the iodination and radioiodination of aryl rings. Decomposition of such triazenes in the presence of iodide is acid-catalyzed and is sensitive to choice of solvent, acid, and triazene structure. A condition variation study by HPLC of four different solvent systems and two non-nucleophilic acids was carried out on the 123 I iodination of the triazenes of p-nitroaniline, p-anisidine and p-toluidine. This method has proven .useful in radiolabelling of two pharmaceutical analogs which were not amenable to labelling through the classic Sandmeyer method. (author)

  10. Review of recent experiments in intermediate energy nuclear physics

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, P D [Carnegie-Mellon Univ., Pittsburgh, PA (USA)

    1978-01-01

    The data generated at intermediate-energy accelerator facilities has expanded rapidly over the past few years. A number of recent experiments chosen for their impact on nuclear structure questions are reviewed. Proton scattering together with pionic and muonic atom X-ray measurements are shown to be giving very precise determinations of gross nuclear properties. Pion scattering and reaction data although less precise, are starting to generate a new understanding of wave functions of specific nuclear states. Specific examples where new unpublished data are now available are emphasized. In addition, other medium-energy experiments that are starting to contribute to nuclear structure physics are summarized.

  11. Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

    Science.gov (United States)

    Wink, David A.; Desrosiers, Marc F.

    The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3,5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant ( .Br -2). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive intermediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide radical. Unexpectedly, addition of DBNBS to a solution containing dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented.

  12. Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction

    Energy Technology Data Exchange (ETDEWEB)

    Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Trevitt, Adam J.; Wilson, Kevin R.; Leone, Stephen R.

    2010-03-16

    The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and the result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.

  13. An efficient synthesis of symmetric and unsymmetric bis-(β-aminoamides) via Ugi multicomponent reaction.

    Science.gov (United States)

    La Spisa, Fabio; Feo, Alberto; Mossetti, Riccardo; Tron, Gian Cesare

    2012-12-07

    A library of symmetrical and unsymmetrical bis-(β-aminoamides) has been prepared starting from symmetrical secondary diamines by using a double Ugi four-component reaction. A sacrifical Mumm rearrangement, thanks to the use of 2-hydroxymethyl benzoic acid, is necessary to suppress the competing split-Ugi reaction, increasing the yield and simplifying the purification step. The scope, the reaction conditions, and the role of water in trapping the nitrilium intermediate are also discussed.

  14. Reaction studies of hot silicon and germanium radicals. Period covered: September 1, 1977--August 31, 1978

    International Nuclear Information System (INIS)

    Gaspar, P.P.

    1978-01-01

    The experimental approach to attaining the goals of this research program is briefly outlined and the progress made in the last year is reviewed in sections entitled: primary steps in the reaction of recoiling silicon and germanium atoms and the identification of reactive intermediates; thermally induced silylene and germylene reactions; the role of ionic reactions in the chemistry of recoiling silicon atoms and other ion-molecule reactions studies; and silicon free radical chemistry

  15. Explorations into Chemical Reactions and Biochemical Pathways.

    Science.gov (United States)

    Gasteiger, Johann

    2016-12-01

    A brief overview of the work in the research group of the present author on extracting knowledge from chemical reaction data is presented. Methods have been developed to calculate physicochemical effects at the reaction site. It is shown that these physicochemical effects can quite favourably be used to derive equations for the calculation of data on gas phase reactions and on reactions in solution such as aqueous acidity of alcohols or carboxylic acids or the hydrolysis of amides. Furthermore, it is shown that these physicochemical effects are quite effective for assigning reactions into reaction classes that correspond to chemical knowledge. Biochemical reactions constitute a particularly interesting and challenging task for increasing our understanding of living species. The BioPath.Database is a rich source of information on biochemical reactions and has been used for a variety of applications of chemical, biological, or medicinal interests. Thus, it was shown that biochemical reactions can be assigned by the physicochemical effects into classes that correspond to the classification of enzymes by the EC numbers. Furthermore, 3D models of reaction intermediates can be used for searching for novel enzyme inhibitors. It was shown in a combined application of chemoinformatics and bioinformatics that essential pathways of diseases can be uncovered. Furthermore, a study showed that bacterial flavor-forming pathways can be discovered. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode.

    Science.gov (United States)

    Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

    2016-04-18

    Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na(1/3)Ru(2/3)]O2 slabs delivers a capacity of 180 mAh g(-1) (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g(-1) (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes.

  17. Angular correlations and fragmentation in intermediate energy heavy ion collisions

    International Nuclear Information System (INIS)

    Kristiansson, Anders.

    1990-05-01

    Intermediate energy heavy-ion collisions have been studied from 35 A MeV up to 94 A MeV at various accelerators. Angular correlations between light particles and detection of projectile- and target-fragments have been used to investigate the reaction mechanisms in this transition region between low- and high energy. An excess of correlations is observed in the particle-particle elastic scattering plane. This excess increases with particle mass and can be understood in terms of momentum conservation. The fragmentation measurements gives an indication that both energy and momentum transfer to the spectator volumes does occur. (author)

  18. Photo-fenton degradation of diclofenac: identification of main intermediates and degradation pathway.

    Science.gov (United States)

    Pérez-Estrada, Leónidas A; Malato, Sixto; Gernjak, Wolfgang; Agüera, Ana; Thurman, E Michael; Ferrer, Imma; Fernández-Alba, Amadeo R

    2005-11-01

    In recent years, the presence of pharmaceuticals in the aquatic environment has been of growing interest. These new contaminants are important because many of them are not degraded under the typical biological treatments applied in the wastewater treatment plants and represent a continuous input into the environment. Thus, compounds such as diclofenac are present in surface waters in all Europe and a crucial need for more enhanced technologies that can reduce its presence in the environment has become evident. In this sense, advanced oxidation processes (AOPs) represent a good choice for the treatment of hazardous nonbiodegradable pollutants. This work deals with the solar photodegradation of diclofenac, an antiinflammatory drug, in aqueous solutions by photo-Fenton reaction. A pilot-scale facility using a compound parabolic collector (CPC) reactor was used for this study. Results obtained show rapid and complete oxidation of diclofenac after 60 min, and total mineralization (disappearance of dissolved organic carbon, DOC) after 100 min of exposure to sunlight. Although diclofenac precipitates during the process at low pH, its degradation takes place in the homogeneous phase governed by a precipitation-redissolution-degradation process. Establishment of the reaction pathway was made possible by a thorough analysis of the reaction mixture identifying the main intermediate products generated. Gas chromatography-mass spectrometry (GC/ MS) and liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOF-MS) were used to identify 18 intermediates, in two tentative degradation routes. The main one was based on the initial hydroxylation of the phenylacetic acid moiety in the C-4 position and subsequent formation of a quinone imine derivative that was the starting point for further multistep degradation involving hydroxylation, decarboxylation, and oxidation reactions. An alternative route was based on the transient preservation of the biphenyl amino moiety

  19. Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads

    NARCIS (Netherlands)

    Niemi, Marja; Tkachenko, Nikolai V.; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

    2008-01-01

    Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C-60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results

  20. Thermodynamics of random reaction networks.

    Science.gov (United States)

    Fischer, Jakob; Kleidon, Axel; Dittrich, Peter

    2015-01-01

    Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha) and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa -1.5 for linear and -1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks.

  1. Studies of complex fragment emission in heavy ion reactions: Progress report, September 1, 1987--August 31, 1988

    International Nuclear Information System (INIS)

    Sobotka, L.G.

    1988-01-01

    The production of large fragments, fragments with mass between light particles and fission fragments, in intermediate and high energy nuclear reactions has fostered the proposal of a number of novel reaction mechanisms. These include liquid-vapor equilibrium and nuclear shattering. Temporarily left in the wake of these exciting proposed mechanisms was the old standard, statistical decay of compound nuclei. To be sure, the standard treatment of compound nucleus decay did not deal with large fragment production. However, this emission was not due to any fundamental deficiency of statistical models, but rather an uncertainty concerning exactly how to splice large fragment emission into statistical models. A large portion of our program deals with this problem. Specifically, by studying the yields of large fragments produced in sufficiently low energy reactions we are attempting to deduce the asymmetry and l-wave dependence of large fragment emission from compound nuclear intermediates. This, however, is only half of the problem. Since the novel mechanisms proposed for large fragment emission were spawned by intermediate and high energy reaction data, we must also realize the relevance of the compound nucleus mechanisms at high energies. It is not unreasonable to suspect that compound nucleus-like objects are formed with less than complete momentum transfer and perhaps less than complete mass transfer. Therefore the study of large fragment production in low energy reactions should go hand in hand with the study of energy, mass, and angular momentum transfer in incomplete fusion and non-compound reactions. This thread joins the apparently divergent subjects covered in this report

  2. Probing properties of neutron stars with terrestrial nuclear reactions

    International Nuclear Information System (INIS)

    Li Baoan; Chen Liewen; Ko, C.M.; Steiner, Andrew W.; Yong Gaochan

    2006-01-01

    Heavy-ion reactions induced by neutron-rich nuclei provide the unique opportunity in terrestrial laboratories to constrain the nuclear symmetry energy Esym in a broad density range. A conservative constraint, 32(ρ/ρ0)0.7 < Esym(ρ) < 32(ρ/ρ0)1.1, around the nuclear matter saturation density ρ0 has recently been obtained from analyzing the isospin diffusion data within a transport model for intermediate energy heavy-ion reactions. This subsequently puts a stringent constraint on properties of neutron stars, especially their radii and cooling mechanisms

  3. Ab Initio Nuclear Structure and Reaction Calculations for Rare Isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Draayer, Jerry P. [Louisiana State Univ., Baton Rouge, LA (United States)

    2014-09-28

    We have developed a novel ab initio symmetry-adapted no-core shell model (SA-NCSM), which has opened the intermediate-mass region for ab initio investigations, thereby providing an opportunity for first-principle symmetry-guided applications to nuclear structure and reactions for nuclear isotopes from the lightest p-shell systems to intermediate-mass nuclei. This includes short-lived proton-rich nuclei on the path of X-ray burst nucleosynthesis and rare neutron-rich isotopes to be produced by the Facility for Rare Isotope Beams (FRIB). We have provided ab initio descriptions of high accuracy for low-lying (including collectivity-driven) states of isotopes of Li, He, Be, C, O, Ne, Mg, Al, and Si, and studied related strong- and weak-interaction driven reactions that are important, in astrophysics, for further understanding stellar evolution, X-ray bursts and triggering of s, p, and rp processes, and in applied physics, for electron and neutrino-nucleus scattering experiments as well as for fusion ignition at the National Ignition Facility (NIF).

  4. Ab Initio Nuclear Structure and Reaction Calculations for Rare Isotopes

    International Nuclear Information System (INIS)

    Draayer, Jerry P.

    2014-01-01

    We have developed a novel ab initio symmetry-adapted no-core shell model (SA-NCSM), which has opened the intermediate-mass region for ab initio investigations, thereby providing an opportunity for first-principle symmetry-guided applications to nuclear structure and reactions for nuclear isotopes from the lightest p-shell systems to intermediate-mass nuclei. This includes short-lived proton-rich nuclei on the path of X-ray burst nucleosynthesis and rare neutron-rich isotopes to be produced by the Facility for Rare Isotope Beams (FRIB). We have provided ab initio descriptions of high accuracy for low-lying (including collectivity-driven) states of isotopes of Li, He, Be, C, O, Ne, Mg, Al, and Si, and studied related strong- and weak-interaction driven reactions that are important, in astrophysics, for further understanding stellar evolution, X-ray bursts and triggering of s, p, and rp processes, and in applied physics, for electron and neutrino-nucleus scattering experiments as well as for fusion ignition at the National Ignition Facility (NIF).

  5. Intramolecular charge transfer of 4-(dimethylamino)benzonitrile probed by time-resolved fluorescence and transient absorption: No evidence for two ICT states and a πσ* reaction intermediate

    International Nuclear Information System (INIS)

    Zachariasse, Klaas A.; Druzhinin, Sergey I.; Senyushkina, Tamara; Kovalenko, Sergey A.

    2009-01-01

    For the double exponential fluorescence decays of the locally excited (LE) and intramolecular charge transfer (ICT) states of 4-(dimethylamino)benzonitrile (DMABN) in acetonitrile (MeCN) the same times τ 1 and τ 2 are observed. This means that the reversible LE ICT reaction, starting from the initially excited LE state, can be adequately described by a two state mechanism. The most important factor responsible for the sometimes experimentally observed differences in the nanosecond decay time, with τ 1 (LE) 1 (ICT), is photoproduct formation. By employing a global analysis of the LE and ICT fluorescence response functions with a time resolution of 0.5 ps/channel in 1200 channels reliable kinetic and thermodynamic data can be obtained. The arguments presented in the literature in favor of a πσ* state with a bent CN group as an intermediate in the ICT reaction of DMABN are discussed. From the appearance of an excited state absorption (ESA) band in the spectral region between 700 and 800 nm in MeCN for N,N-dimethylanilines with CN, Br, F, CF 3 , and C(=O)OC 2 H 2 p-substituents, it is concluded that this ESA band cannot be attributed to a πσ * state, as only the C-C≡N group can undergo the required 120 deg. bending.

  6. Information acquisition and financial intermediation

    OpenAIRE

    Boyarchenko, Nina

    2012-01-01

    This paper considers the problem of information acquisition in an intermediated market, where the specialists have access to superior technology for acquiring information. These informational advantages of specialists relative to households lead to disagreement between the two groups, changing the shape of the intermediation-constrained region of the economy and increasing the frequency of periods when the intermediation constraint binds. Acquiring the additional information is, however, cost...

  7. Tandem ring-closing metathesis/isomerization reactions for the total synthesis of violacein

    DEFF Research Database (Denmark)

    Petersen, Mette Terp; Nielsen, Thomas Eiland

    2013-01-01

    A series of 5-substituted 2-pyrrolidinones was synthesized through a one-pot ruthenium alkylidene-catalyzed tandem RCM/isomerization/nucleophilic addition sequence. The intermediates resulting from RCM/isomerization showed reactivity toward electrophiles in aldol condensation reactions which...

  8. Intermediate-energy nuclear theory. Progress report, July 1, 1977--June 30, 1978

    International Nuclear Information System (INIS)

    Bryan, R.A.

    1978-03-01

    The research reported has centered on the nucleon-nucleon interaction at medium energies, with especial emphasis on the reaction NN → NNπ up to 800 MeV. Elastic NN scattering near the pion production threshold was also investigated, both through phase-shift analysis of data and theoretical interpretation of the intermediate-range force. The quasi-elastic amplitude N anti N → ππ for 4m/sub pi/ 2 less than or equal to t less than or equal to 50m/sub pi/ 2 was studied because of its bearing on the NN problem; a simple but useful model was developed. Finally, work on the pion-photoproduction reaction γN → πΔ was completed, and the close correspondence with the amplitude NN → NNπ exploited. A list of publications is included

  9. Formation of large target residues in intermediate energy nuclear collisions

    International Nuclear Information System (INIS)

    Loveland, W.; Aleklett, K.; Sihver, L.; Xu, Z.; Seaborg, G.T.

    1987-04-01

    We have used radiochemical techniques to measure the yields, angular distributions and velocity spectra of the large (A/sub frag/ ≥ 2/3 A/sub tgt/) target residues from the fragmentation of 197 Au by intermediate energy 12 C, 20 Ne, 32 S, 40 Ar, 84 Kr, and 139 La projectiles. The fragment moving frame angular distributions are asymmetric for the lighter projectiles (C-Ar). The fragment velocity spectra are Maxwellian for the Kr induced reactions and non-Maxwellian for the reactions induced by the lighter ions. We interpret these results in terms of a change in the dominant fragment production mechanism(s) from one(s) involving a fast non-equilibrium process for the lighter ions to a slow, equilibrium process for Kr. Comparison of the measured yields and angular distributions with calculations made using a Boltzmann transport equation with appropriate modifications for Pauli blocking, etc., show excellent agreement between data and theory. 12 refs., 12 figs

  10. Reaction of acid esters of methylenebis(phosphonous acid) with carbonyl compounds

    International Nuclear Information System (INIS)

    Novikova, Z.S.; Odinets, I.L.; Lutsenko, I.F.

    1987-01-01

    The reaction of methylenebis(phosphonites) containing two hydrophosphoryl groupings with aliphatic and aromatic aldehydes and ketones in the presence of alkali metal fluorides leads to methylenebis(α-hydroxyalkylphosphinates). The reaction of methylenebis(phosphonites) containing one hydrophosphoryl groupings with carbonyl compounds in the presence of alkali metal fluorides proceeds with the formation of a new type of heterocyclic phosphorus compound, viz., 1,2λ 3 ,4λ 5 -oxadiphospholanes. The reaction of acid esters of methylenebis(phosphonous) acid with carbonyl compounds in the presence of alkali metal alkoxides or a tertiary amine is accompanied by phosphinate-phosphonate rearrangement of the intermediately formed α-hydroxylalkylphosphinates

  11. Parameterization of α-nucleus total reaction cross section at intermediate energies

    International Nuclear Information System (INIS)

    Alvi, M A; Abdulmomen, M A

    2008-01-01

    Applying a Coulomb correction factor to the Glauber model we have derived a closed expression for α-nucleus total reaction cross section, σ R . Under the approximation of rigid projectile model, the elastic S-matrix element S el (b) is evaluated from the phenomenological N-α amplitude and a Gaussian fit to the Helm's model form factor. Excellent agreements with the experimental data have been achieved by performing two-parameter fits to the α-nucleus σ R data in the energy range about 75 to 193 MeV. One of the parameters was found to be energy independent while the other, as expected, shows the energy dependence similar to that of N-α total cross section.

  12. Doorway states in nuclear reactions as a manifestation of the 'super-radiant' mechanism

    International Nuclear Information System (INIS)

    Auerbach, N.; Zelevinsky, V.

    2007-01-01

    A mechanism is considered for generating doorway states and intermediate structure in low-energy nuclear reactions as a result of collectivization of widths of unstable intrinsic states coupled to common decay channels. At the limit of strong continuum coupling, the segregation of broad ('super-radiating') and narrow ('trapped') states occurs revealing the separation of direct and compound processes. We discuss the conditions for the appearance of intermediate structure in this process and doorways related to certain decay channels

  13. Hydrogen electrode reaction: A complete kinetic description

    International Nuclear Information System (INIS)

    Quaino, P.M.; Gennero de Chialvo, M.R.; Chialvo, A.C.

    2007-01-01

    The kinetic description of the hydrogen electrode reaction (HER) in the whole range of overpotentials (-0.2 < η (V) < 0.40) is presented. The Volmer-Heyrovsky-Tafel mechanism was solved considering simultaneously the following items: (i) the diffusional contribution of the molecular hydrogen from and towards the electrode surface, (ii) the forward and backward reaction rates of each elementary step and (iii) a Frumkin type adsorption for the reaction intermediate. In order to verify the descriptive capability of the kinetic expressions derived, an experimental study of the HER was carried out on a rotating platinum disc electrode in acid solution. From the correlation of these results the elementary kinetic parameters were evaluated and several aspects related to the kinetic mechanism were discussed. Finally, the use of these kinetic expressions to interpret results obtained on microelectrodes is also analysed

  14. RuO4-mediated oxidation of secondary amines: Part 1. Are hydroxylamines main intermediates?

    Directory of Open Access Journals (Sweden)

    Florea Cristina A.

    2016-01-01

    Full Text Available The RuO4-catalyzed oxidation of secondary amines Bn-NH-CH2R (1a-b; R=H, Me gave mainly amides, but minute amounts of nitrones PhCH=N(O-CH2R (9a-b and traces of Bn-N(OH-CH2R (R=H, 4a were also detected. In the presence of cyanide, up to 22 reaction products were identified, but mainly α-aminonitriles. Comparison of the oxidation products of 1a-b with those of 4a-b, 9a-b, and Bn-N(O=CHR (10a-b showed that 4a-b cannot be main reaction intermediates formed from 1a-b.

  15. Silver nanoparticle catalysed redox reaction: An electron relay effect

    International Nuclear Information System (INIS)

    Mallick, Kaushik; Witcomb, Mike; Scurrell, Mike

    2006-01-01

    A silver cluster shows efficient catalytic activity in a redox reaction because the cluster acts as the electron relay centre behaving alternatively as an acceptor and as a donor of electrons. An effective transfer of electrons is possible when the redox potential of the cluster is intermediate between the electron donor and electron acceptor system

  16. Glutamate availability is important in intramuscular amino acid metabolism and TCA cycle intermediates but does not affect peak oxidative metabolism.

    Science.gov (United States)

    Mourtzakis, M; Graham, T E; González-Alonso, J; Saltin, B

    2008-08-01

    Muscle glutamate is central to reactions producing 2-oxoglutarate, a tricarboxylic acid (TCA) cycle intermediate that essentially expands the TCA cycle intermediate pool during exercise. Paradoxically, muscle glutamate drops approximately 40-80% with the onset of exercise and 2-oxoglutarate declines in early exercise. To investigate the physiological relationship between glutamate, oxidative metabolism, and TCA cycle intermediates (i.e., fumarate, malate, 2-oxoglutarate), healthy subjects trained (T) the quadriceps of one thigh on the single-legged knee extensor ergometer (1 h/day at 70% maximum workload for 5 days/wk), while their contralateral quadriceps remained untrained (UT). After 5 wk of training, peak oxygen consumption (VO2peak) in the T thigh was greater than that in the UT thigh (PTCA cycle intermediates. In the UT thigh, peak exercise (vs. rest) induced an increase in fumarate (0.33+/-0.07 vs. 0.02+/-0.01 mmol/kg dry wt (dw), PTCA cycle, glutamate and TCA cycle intermediates do not directly affect VO2peak in either trained or untrained muscle.

  17. Real time monitoring of accelerated chemical reactions by ultrasonication-assisted spray ionization mass spectrometry.

    Science.gov (United States)

    Lin, Shu-Hsuan; Lo, Ta-Ju; Kuo, Fang-Yin; Chen, Yu-Chie

    2014-01-01

    Ultrasonication has been used to accelerate chemical reactions. It would be ideal if ultrasonication-assisted chemical reactions could be monitored by suitable detection tools such as mass spectrometry in real time. It would be helpful to clarify reaction intermediates/products and to have a better understanding of reaction mechanism. In this work, we developed a system for ultrasonication-assisted spray ionization mass spectrometry (UASI-MS) with an ~1.7 MHz ultrasonic transducer to monitor chemical reactions in real time. We demonstrated that simply depositing a sample solution on the MHz-based ultrasonic transducer, which was placed in front of the orifice of a mass spectrometer, the analyte signals can be readily detected by the mass spectrometer. Singly and multiply charged ions from small and large molecules, respectively, can be observed in the UASI mass spectra. Furthermore, the ultrasonic transducer used in the UASI setup accelerates the chemical reactions while being monitored via UASI-MS. The feasibility of using this approach for real-time acceleration/monitoring of chemical reactions was demonstrated. The reactions of Girard T reagent and hydroxylamine with steroids were used as the model reactions. Upon the deposition of reactant solutions on the ultrasonic transducer, the intermediate/product ions are readily generated and instantaneously monitored using MS within 1 s. Additionally, we also showed the possibility of using this reactive UASI-MS approach to assist the confirmation of trace steroids from complex urine samples by monitoring the generation of the product ions. Copyright © 2014 John Wiley & Sons, Ltd.

  18. Glutamate availability is important in intramuscular amino acid metabolism and TCA cycle intermediates but does not affect peak oxidative metabolism

    DEFF Research Database (Denmark)

    Mourtzakis, M.; Graham, T.E.; Gonzalez-Alonso, J.

    2008-01-01

    Muscle glutamate is central to reactions producing 2-oxoglutarate, a tricarboxylic acid (TCA) cycle intermediate that essentially expands the TCA cycle intermediate pool during exercise. Paradoxically, muscle glutamate drops approximately 40-80% with the onset of exercise and 2-oxoglutarate...... declines in early exercise. To investigate the physiological relationship between glutamate, oxidative metabolism, and TCA cycle intermediates (i.e., fumarate, malate, 2-oxoglutarate), healthy subjects trained (T) the quadriceps of one thigh on the single-legged knee extensor ergometer (1 h/day at 70......% maximum workload for 5 days/wk), while their contralateral quadriceps remained untrained (UT). After 5 wk of training, peak oxygen consumption (VO2peak) in the T thigh was greater than that in the UT thigh (Pglutamate infusion. Peak...

  19. Some clues about the interphase reaction between ZnO and MnO2 oxides

    International Nuclear Information System (INIS)

    Rubio-Marcos, F.; Quesada, A.; Garcia, M.A.; Banares, M.A.; Fierro, J.L.G.; Martin-Gonzalez, M.S.; Costa-Kraemer, J.L.; Fernandez, J.F.

    2009-01-01

    Raman spectroscopy is used to evidence both the nature of the interphase reaction between ZnO and MnO 2 particles and its kinetic evolution. Zn cations migrate from the ZnO grains during oxygen vacancies formation process and diffuse into the MnO 2 particles leading to an interphase region with an intermediate valence Mn +3 -O-Mn +4 . Large amounts of desorbed Zn cations promote the formation of ZnMn 2 O 4 structure, in addition to the intermediate valence state. The system evolves towards complete formation of the spinel phase at higher thermal treatment times. The reactivity of the ZnO plays an important role in the formation of this interphase. Low-reactivity ZnO powder, in which the oxygen vacancies are previously produced, shows a stabilization of the intermediate valence state with very limited formation of the spinel phase. A clear correlation between the amount of the intermediate state interphase and the magnetic properties has been established. - Graphical abstract: Recently new room temperature interphase magnetism has been reported to appear in ZnO-MnO 2 system. Raman spectroscopy is used to evidence both the nature of the interphase reaction and the kinetic. The interphase evolved towards complete formation of the spinel phase. The reactivity of the ZnO plays an important role in the formation of this interphase. Finally, a clear correlation between the amount of the intermediate valence state and the interphase magnetic properties has been established.

  20. Oxoferryl-Porphyrin Radical Catalytic Intermediate in Cytochrome bd Oxidases Protects Cells from Formation of Reactive Oxygen Species*

    Science.gov (United States)

    Paulus, Angela; Rossius, Sebastiaan Gijsbertus Hendrik; Dijk, Madelon; de Vries, Simon

    2012-01-01

    The quinol-linked cytochrome bd oxidases are terminal oxidases in respiration. These oxidases harbor a low spin heme b558 that donates electrons to a binuclear heme b595/heme d center. The reaction with O2 and subsequent catalytic steps of the Escherichia coli cytochrome bd-I oxidase were investigated by means of ultra-fast freeze-quench trapping followed by EPR and UV-visible spectroscopy. After the initial binding of O2, the O–O bond is heterolytically cleaved to yield a kinetically competent heme d oxoferryl porphyrin π-cation radical intermediate (compound I) magnetically interacting with heme b595. Compound I accumulates to 0.75–0.85 per enzyme in agreement with its much higher rate of formation (∼20,000 s−1) compared with its rate of decay (∼1,900 s−1). Compound I is next converted to a short lived heme d oxoferryl intermediate (compound II) in a phase kinetically matched to the oxidation of heme b558 before completion of the reaction. The results indicate that cytochrome bd oxidases like the heme-copper oxidases break the O–O bond in a single four-electron transfer without a peroxide intermediate. However, in cytochrome bd oxidases, the fourth electron is donated by the porphyrin moiety rather than by a nearby amino acid. The production of reactive oxygen species by the cytochrome bd oxidase was below the detection level of 1 per 1000 turnovers. We propose that the two classes of terminal oxidases have mechanistically converged to enzymes in which the O–O bond is broken in a single four-electron transfer reaction to safeguard the cell from the formation of reactive oxygen species. PMID:22287551

  1. Report of the workshop on 'light particle-induced reactions'

    International Nuclear Information System (INIS)

    1992-01-01

    The study meeting on light particle (mass number = 3 - 11)-induced reation was held for three days from December 5 to 7, 1991 at the Research Center for Nuclear Physics, Osaka University. This book records the report based on the lectures presented at the meeting. In the new facility of the RCNP, the experiment on the nuclear reaction using 400 MeV polarized protons and 200 MeV polarized deuterons is about to begin. When the acceleration of polarized He-3 beam which is being developed at present becomes feasible, by combining it with the high resolution spectrometer GRAND RAIDEN, it is expected that the unique, high accuracy research using the polarized He-3 having intermediate energy (540 MeV) becomes possible. At this time, by focusing attention to what new physics is developed by the nuclear reaction induced by the composite particles having the intermediate energy of mass number 3 - 11, this study meeting was planned and held. As the results, 29 lectures collected in this book were to cover wide fields, and active discussion was carried out. (K.I.)

  2. Synthesis of cyclopentadiene-fused chromanones via one-pot multicomponent reactions.

    Science.gov (United States)

    Ghandi, Mehdi; Ghomi, Ali-Tabatabaei; Kubicki, Maciej

    2013-03-15

    We have developed one-pot method for the synthesis of functionalized novel cyclopentadiene-fused chromanone scaffolds. A variety of 4-oxo-2,4-dihydrocyclopenta[c]chromene-1,2-dicarboxylates were obtained in moderate to good yields via condensation of 2-hydroxybenzaldehydes and ethyl acetoacetate with 1:1 acetylenecarboxylate-isocyanides in toluene. These reactions presumably proceed via reaction of the in situ generated 3-acetyl-2H-chromen-2-ones with acetylenecarboxylate-isocyanide zwitterionic intermediates through Michael addition/intramolecular cyclization and double [1,5] acyl shift rearrangement cascade.

  3. Discourses and Models of Intermediality

    OpenAIRE

    Schröter, Jens

    2011-01-01

    In his article "Discourses and Models of Intermediality" Jens Schröter discusses the question as to what relations do different discourses pose between different "media." Schröter identifies four models of discourse: 1) synthetic intermediality: a "fusion" of different media to super-media, a model with roots in the Wagnerian concept of Gesamtkunstwerk with political connotations, 2) formal (or transmedial) intermediality: a concept based on formal structures not "specific" to one medium but ...

  4. A General Strategy for Nanohybrids Synthesis via Coupled Competitive Reactions Controlled in a Hybrid Process

    OpenAIRE

    Wang, Rongming; Yang, Wantai; Song, Yuanjun; Shen, Xiaomiao; Wang, Junmei; Zhong, Xiaodi; Li, Shuai; Song, Yujun

    2015-01-01

    A new methodology based on core alloying and shell gradient-doping are developed for the synthesis of nanohybrids, realized by coupled competitive reactions, or sequenced reducing-nucleation and co-precipitation reaction of mixed metal salts in a microfluidic and batch-cooling process. The latent time of nucleation and the growth of nanohybrids can be well controlled due to the formation of controllable intermediates in the coupled competitive reactions. Thus, spatiotemporal-resolved synthesi...

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

    Energy Technology Data Exchange (ETDEWEB)

    T Chen; D Mullins

    2011-12-31

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

  6. Sequential series for nuclear reactions

    International Nuclear Information System (INIS)

    Izumo, Ko

    1975-01-01

    A new time-dependent treatment of nuclear reactions is given, in which the wave function of compound nucleus is expanded by a sequential series of the reaction processes. The wave functions of the sequential series form another complete set of compound nucleus at the limit Δt→0. It is pointed out that the wave function is characterized by the quantities: the number of degrees of freedom of motion n, the period of the motion (Poincare cycle) tsub(n), the delay time t sub(nμ) and the relaxation time tausub(n) to the equilibrium of compound nucleus, instead of the usual quantum number lambda, the energy eigenvalue Esub(lambda) and the total width GAMMAsub(lambda) of resonance levels, respectively. The transition matrix elements and the yields of nuclear reactions also become the functions of time given by the Fourier transform of the usual ones. The Poincare cycles of compound nuclei are compared with the observed correlations among resonance levels, which are about 10 -17 --10 -16 sec for medium and heavy nuclei and about 10 -20 sec for the intermediate resonances. (auth.)

  7. Studies of complex fragment emission in heavy ion reactions: Progress report, September 1, 1986 through August 31, 1987

    International Nuclear Information System (INIS)

    Sobotka, L.G.

    1987-01-01

    The production of large fragments, fragments with mass between light particles and fission fragments, in intermediate and high energy nuclear reactions has fostered the proposal of a number of novel reaction mechanisms. These include liquid-vapor equilibrium and nuclear shattering. Temporarily left in the wake of these exciting proposed mechanisms was the old standard, statistical decay of compound nuclei. To be sure, the standard treatment of compound nucleus decay did not deal with large fragment production. However, this omission was not due to any fundamental deficiency of statistical models, but rather an uncertainty concerning exactly how to splice large fragment emission into statistical models. A large portion of our program deals with this problem. Specifically, by studying the yields of large fragments produced in sufficiently low energy reactions we are attempting to deduce the asymmetry and l-wave dependence of large fragment emission from compound nuclear intermediates. This, however, is only half of the problem. Since the novel mechanisms proposed for large fragment emission were spawned by intermediate and high energy reaction data, we must also realize the relevance of the compound nucleus mechanisms at high energies. It is not unreasonable to suspect that compound nucleus-like objects are formed with less than complete momentum transfer and perhaps less than complete mass transfer. Therefore the study of large fragment production in low energy reactions should go hand in hand with the study of energy, mass, and angular momentum transfer in non-compound reactions. This thread joins the apparently divergent subjects covered in this report. 39 refs., 24 figs., 2 tabs

  8. Time-resolved resonance Raman spectroscopy of intermediates of bacteriorhodopsin: The bK(590) intermediate.

    Science.gov (United States)

    Terner, J; Hsieh, C L; Burns, A R; El-Sayed, M A

    1979-07-01

    We have combined microbeam and flow techniques with computer subtraction methods to obtain the resonance Raman spectrum of the short lived batho-intermediate (bK(590)) of bacteriorhodopsin. Comparison of the spectra obtained in (1)H(2)O and (2)H(2)O, as well as the fact that the bK(590) intermediate shows large optical red shifts, suggests that the Schiff base linkage of this intermediate is protonated. The fingerprint region of the spectrum of bK(590), sensitive to the isomeric configuration of the retinal chromophore, does not resemble the corresponding region of the parent bR(570) form. The resonance Raman spectrum of bK(590) as well as the spectra of all of the other main intermediates in the photoreaction cycle of bacteriorhodopsin are discussed and compared with resonance Raman spectra of published model compounds.

  9. Synthesis and reactions of deuterated 2-(alkylimino)-3-nitrosooxazolidines, 3-alkly-1-(2-hydroxyethyl)-1-nitrosoureas, and related compounds as possible intermediates in the aqueous decomposition of 3-alkyl-1-(2-chloroethyl)-1-nitrosoureas

    International Nuclear Information System (INIS)

    Lown, J.W.; Chauhan, S.M.S.

    1981-01-01

    Decomposition of 1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea-α-d 2 (CCNU-α-d 2 ) (7) in pH 7.2 phosphate buffer or of CINO-α-d 2 (9) or CHNU-α-d 2 (8) with the addition of chloride ion gives rise to the same spectrum of products, including deuterium-free acetaldehyde (29), a mixture of the two deuterio-2-chloroethanols, 2-hydroxy-2,2-dideuterioethyl cyclohexyl carbamates, and vinyl chloride containing one deuterium (i.e., opposite the results obtained in the corresponding reaction of BCNU-α-d 4 ). The products were identified and the number and position of the deuterium labels determined by GC/MS. The results are interpreted in terms of two decomposition pathways for CCNU. The first decomposition pathway operating for CCNU is via an intermediate-2-chloroethanediazohydroxide or the equivalent 2-chloroethyl cation in agreement with the results of other workers. The second pathway may involve reversible conversion of CCNU-α-d 2 (7) to CINO-α-d 2 (9) and then ring opening of the latter to CHNU-α-d 2 (8). Independent decomposition of 8 provides evidence for its conversion to a 1.1-dideuterio-2-hydroxyethanediazohydroxide (41) leading to the isolated carbamates 36 and 44. The intermediacy of species 41 may account for the formation of 2-hydroxyethylated nucleosides observed when (2-chloroethyl)nitrosoureas react with DNA. An alternative ring-opening reaction of 9 leads to a 2-hydroxydiazoethyl cyclohexylcarbamate species (37), elimination of which and attack by halide ion may account for the vinyl halide species formed. Further evidence in support of these competing pathways employing additional specifically deuterated intermediates is described and discussed

  10. Role of Intermediate Filaments in Vesicular Traffic

    Directory of Open Access Journals (Sweden)

    Azzurra Margiotta

    2016-04-01

    Full Text Available Intermediate filaments are an important component of the cellular cytoskeleton. The first established role attributed to intermediate filaments was the mechanical support to cells. However, it is now clear that intermediate filaments have many different roles affecting a variety of other biological functions, such as the organization of microtubules and microfilaments, the regulation of nuclear structure and activity, the control of cell cycle and the regulation of signal transduction pathways. Furthermore, a number of intermediate filament proteins have been involved in the acquisition of tumorigenic properties. Over the last years, a strong involvement of intermediate filament proteins in the regulation of several aspects of intracellular trafficking has strongly emerged. Here, we review the functions of intermediate filaments proteins focusing mainly on the recent knowledge gained from the discovery that intermediate filaments associate with key proteins of the vesicular membrane transport machinery. In particular, we analyze the current understanding of the contribution of intermediate filaments to the endocytic pathway.

  11. Reaction studies of hot silicon and germanium radicals. Progress report, September 1, 1978-August 31, 1979

    International Nuclear Information System (INIS)

    Gaspar, P.P.

    1979-01-01

    The experimental approach to attaining the goals of this research program is briefly outlined and the progress made in the last year is reviewed in sections entitled: (a) Primary steps in the reaction of recoiling silicon and germanium atoms and the identification of reactive intermediates; (b) Thermally induced silylene and germylene reactions; (c) Silicon free radical chemistry; (d) The role of ionic reactions in the chemistry of recoiling silicon atoms

  12. Intermediality: Bridge to Critical Media Literacy.

    Science.gov (United States)

    Pailliotet, Ann Watts; Semali, Ladislaus; Rodenberg, Rita K.; Giles, Jackie K.; Macaul, Sherry L.

    2000-01-01

    Defines "intermediality" as the ability to critically read and write with and across varied symbol systems. Relates it to critical media literacy. Offers rationales for teaching critical media literacy in general, and intermedial instruction in particular. Identifies seven guiding intermedial elements: theory, texts, processes, contexts,…

  13. Using Physical Organic Chemistry To Shape the Course of Electrochemical Reactions.

    Science.gov (United States)

    Moeller, Kevin D

    2018-05-09

    While organic electrochemistry can look quite different to a chemist not familiar with the technique, the reactions are at their core organic reactions. As such, they are developed and optimized using the same physical organic chemistry principles employed during the development of any other organic reaction. Certainly, the electron transfer that triggers the reactions can require a consideration of new "wrinkles" to those principles, but those considerations are typically minimal relative to the more traditional approaches needed to manipulate the pathways available to the reactive intermediates formed downstream of that electron transfer. In this review, three very different synthetic challenges-the generation and trapping of radical cations, the development of site-selective reactions on microelectrode arrays, and the optimization of current in a paired electrolysis-are used to illustrate this point.

  14. Fragment production in 12-GeV proton-induced reactions

    International Nuclear Information System (INIS)

    Hirata, Yuichi; Ohnishi, Akira; Ohtsuka, Naohiko; Nara, Yasushi; Niida, Koji; Chiba, Satoshi; Takada, Hiroshi

    2000-01-01

    We study mass and angular distribution of Intermediate Mass Fragment (IMF) produced from p(12 GeV)+ 197 Au reaction by using JAM cascade model combined with percolation model. Although the mass distribution of IMF is well reproduced, the experimentally observed sideward peak of IMF angular distribution is not explained within present JAM + percolation model. (author)

  15. An Inverse Electron Demand Azo-Diels-Alder Reaction of o-Quinone Methides and Imino Ethers: Synthesis of Benzocondensed 1,3-Oxazines.

    Science.gov (United States)

    Osipov, Dmitry V; Osyanin, Vitaly A; Khaysanova, Guzel' D; Masterova, Elvira R; Krasnikov, Pavel E; Klimochkin, Yuri N

    2018-04-20

    We have studied the reactions of o-quinone methide precursors with imino ethers. The reaction provides a versatile route to substituted 1,3-benzoxazines. The proposed reaction mechanism involves the generation of the o-quinone methide intermediates, imino-Diels-Alder reaction, and elimination. This cascade process is a rare example of the participation of imino ethers as dienophiles.

  16. The samarium Grignard reaction. In situ formation and reactions of primary and secondary alkylsamarium(III) reagents

    Energy Technology Data Exchange (ETDEWEB)

    Curran, D.P.; Totleben, M.J. [Univ. of Pittsburgh, PA (United States)

    1992-07-15

    This work shows that primary and secondary radicals are rapidly reduced in THF/HMPA to form primary- and secondary-alkylsamarium reagents. The primary- and secondary-radicals can be formed either by direct SmI{sup 2} reductions of primary- and secondary-halides or by a previous rapid radical cyclization. The samarium reagents have moderate stability in solution, and they react with a variety of typical electrophiles, including aldehydes and ketones. The work further shows that organosamarium intermediates can be involved in the traditional samarium Barbier reaction of aldehydes and ketones conducted in THF/HMPA. A new procedure called the {open_quotes}samarium Grignard{close_quotes} method is introduced, and it is suggested that this new procedure will have considerably more scope and generality than the samarium Barbier reaction. 37 refs., 4 tabs.

  17. Metallo-Phosphorylation of Alkynes: Reaction of Alkynes with Cp2Zr(1-butene) ( PR3 ) and Chlorophosphate

    Institute of Scientific and Technical Information of China (English)

    XI Chan-Juan; LAI Chun-Bo; CHEN Chao; HONG Xiao-Yin

    2003-01-01

    @@ Phosphorylation of alkynes is an attractive reaction for the synthesis of stereodefined alkenylphosphonates that are useful intermediates in organic synthesis. Particularly interesting and challenging reactions are those involving the region- and stereo-selective simultaneous introductions of phosphate and other functional groups to multiple carbon-carbon bonds.[1,2

  18. Thermodynamics of random reaction networks.

    Directory of Open Access Journals (Sweden)

    Jakob Fischer

    Full Text Available Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa -1.5 for linear and -1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks.

  19. A Springloaded Metal-Ligand Mesocate Allows Access to Trapped Intermediates of Self-Assembly.

    Science.gov (United States)

    Bogie, Paul M; Holloway, Lauren R; Lyon, Yana; Onishi, Nicole C; Beran, Gregory J O; Julian, Ryan R; Hooley, Richard J

    2018-04-02

    A strained, "springloaded" Fe 2 L 3 iminopyridine mesocate shows highly variable reactivity upon postassembly reaction with competitive diamines. The strained assembly is reactive toward transimination in minutes at ambient temperature and allows observation of kinetically trapped intermediates in the self-assembly pathway. When diamines are used that can only form less favored cage products upon full equilibration, trapped ML 3 fragments with pendant, "hanging" NH 2 groups are selectively formed instead. Slight variations in diamine structure have large effects on the product outcome: less rigid diamines convert the mesocate to more favored self-assembled cage complexes under mild conditions and allow observation of heterocomplex intermediates in the displacement pathway. The mesocate allows control of equilibrium processes and direction of product outcomes via small, iterative changes in added subcomponent structure and provides a method of accessing metal-ligand cage structures not normally observed in multicomponent Fe-iminopyridine self-assembly.

  20. AAPH-mediated antioxidant reactions of secoisolariciresinol and SDG.

    Science.gov (United States)

    Hosseinian, Farah S; Muir, Alister D; Westcott, Neil D; Krol, Ed S

    2007-02-21

    Secoisolariciresinol (SECO ) is the major lignan found in flaxseed (Linum usitatissimum L.) and is present in a polymer that contains secoisolariciresinol diglucoside (SDG ). SECO, SDG and the polymer are known to have a number of health benefits, including reduction of serum cholesterol levels, delay in the onset of type II diabetes and decreased formation of breast, prostate and colon cancers. The health benefits of SECO and SDG may be partially attributed to their antioxidant properties. To better understand their antioxidant properties, SECO and SDG were oxidized using 2,2'-azobis(2-amidinopropane), an in vitro model of radical scavenging. The major lignan radical-scavenging oxidation products and their formation over time were determined. SDG was converted to four major products, which were the result of a phenoxyl radical intermediate. One of these products, a dimer of SDG, decomposed under the reaction conditions to form two of the other major products, and . SECO was converted to five major products, two of which were also the result of a phenoxyl radical intermediate. The remaining products were the result of an unexpected alkoxyl radical intermediate. The phenol oxidation products were stable under the reaction conditions, whereas two of the alcohol oxidation products decomposed. In general, only one phenol group on the lignans was oxidized, suggesting that the number of phenols per molecule may not predict radical scavenging antioxidant ability of lignans. Finally, SECO is a superior antioxidant to SDG, and it may be that the additional alcohol oxidation pathway contributes to its greater antioxidant ability.

  1. Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

    Science.gov (United States)

    Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

    2014-05-22

    Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

  2. Ab initio chemical kinetics for the HCCO + OH reaction

    Science.gov (United States)

    Mai, Tam V.-T.; Raghunath, P.; Le, Xuan T.; Huynh, Lam K.; Nam, Pham-Cam; Lin, M. C.

    2014-01-01

    The mechanism for the reaction of HCCO and OH has been investigated at different high-levels of theory. The reaction was found to occur on singlet and triplet potential energy surfaces with multiple accessible paths. Rate constants predicted by variational RRKM/ME calculations show that the reaction on both surfaces occurs primarily by barrierless OH attack at both C atoms producing excited intermediates which fragment to produce predominantly CO and 1,3HCOH with kS = 3.12 × 10-8T-0.59exp[-73.0/T] and kT = 6.29 × 10-11T0.13exp[108/T] cm3 molecule-1 s-1 at T = 300-2000 K, independent of pressure at P < 76 000 Torr.

  3. Energy, Electron Transfer and Photocatalytic Reactions of Visible Light Absorbing Transition Metal Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Schmehl, Russell H. [Tulane Univ., New Orleans, LA (United States)

    2016-03-02

    This is the final technical report for a project carried out at Tulane University of New Orleans that describes the development of light induced (solar) reactions geared toward decomposing water into its component elements : hydrogen and oxygen. Much of the work involved optimizing systems for absorbing visible light and undergoing light promoted reactions to generate very strong reducing agents that are capable of reacting with water to produce hydrogen. Additional portions of the research were collaborative efforts to put the strong reducing agents to work in reaction with hydrogen generation catalysts prepared elsewhere. Time resolved laser spectroscopic methods were used to evaluate the light induced reactions and characterize very reactive intermediate substances formed during the reactions.

  4. Non-equilibrium statistical mechanical approach for describing heavy ion reactions

    International Nuclear Information System (INIS)

    Sventek, J.S.

    1979-01-01

    With the availability of heavy-ion projectiles (A > 4) at low to intermediate energies (4 < E/A < 10), products showing various stages of relaxation for certain macroscopic variables (center-of-mass energy, orbital angular momentum, etc.) were produced in various reactions. The distributions for these macroscopic variables showed a correlation between the stage of relaxation reached and the net amount of mass transfer which had occurred in the reaction. There was also evidence that there was an asymmetry in the number of net transfers necessary for complete relaxation between stripping ad pickup reactions. A model for describing the time-evolution of these reactions has been formulated, the keystone of which is a master-equation approach for describing the time-dependence of the mass-asymmetry. This, coupled with deterministic equations of motion for the other macroscopic coordinates in the reaction lead to calculated distributions which provide an excellent qualitative description of these reactions, and, in some cases, quantitatively reproduce the experimental data quite well

  5. Study of energy deposition in heavy-ion reactions

    International Nuclear Information System (INIS)

    Mota, V. De La; Abgrall, P.; Sebille, F.; Haddad, F.

    1993-01-01

    An investigation of energy deposition mechanisms in heavy-ion reactions at intermediate energies is presented. Theoretical simulations are performed in the framework of the semi-classical Landau-Vlasov model. They emphasize the influence of the initial non-equilibrium conditions, and the connection with the incident energy is discussed. Characteristic times involved in the energy thermalization process and finite size effects are analyzed. (authors) 20 refs., 4 figs

  6. Quinine-Promoted, Enantioselective Boron-Tethered Diels-Alder Reaction by Anomeric Control of Transition State Conformation.

    Science.gov (United States)

    Scholl, Katie; Dillashaw, John; Timpy, Evan; Lam, Yu-Hong; DeRatt, Lindsey; Benton, Tyler R; Powell, Jacqueline P; Houk, Kendall N; Morgan, Jeremy B

    2018-05-01

    Diels-Alder reactions of tethered vinyl-metal species offer the opportunity to fashion highly functionalized diol intermediates for synthesis. We have developed the first enantioselective boron-tethered Diels-Alder reaction using quinine as a chiral promoter. Quinine recovery, enantioselectivity enhancement, and manipulation of the cyclohexene core are also investigated. DFT modeling calculations confirm the role of quinine as a bidentate ligand enhancing reaction rates. The enantioselectivity of the cycloaddition is proposed to originate from a boron-centered anomeric effect.

  7. Intermediate phases in the formation of the Cu-Ba-Y high-Tc superconductor from xerogel

    International Nuclear Information System (INIS)

    Arcon, I.; Bele, M.; Hribar, M.; Kodre, A.; Stuhec, M.; Pejovnik, S.; Frahm, R.

    1995-01-01

    In the synthesis of YBa 2 Cu 3 O 7-x superconductor ceramics by the sol-gel method, yttrium K EXAFS spectra of the intermediate products give evidence of the dynamics of the Y ion in the reaction. Together with previous data on Cu K and Ba L 3 EXAFS, the results give information on the processes in the amorphous phase, complementing the diffraction data on crystallite growth. ((orig.))

  8. Salient features of heavy ion reactions in the intermediate energy region

    International Nuclear Information System (INIS)

    Jakobsson, B.

    1987-01-01

    In this lecture the attention is focused on the most central and therefore generally also the most violent collisions. It is necessary to remember that the non-participating volumes could be very different for symmetric and asymmetric reactions. The onset of the multifragmentation channel or rather the cease of the fusion process is the first topic to be discussed. This question is directly related to the limitation in energy and momentum transfer and thus to the question about nuclear transparency. Exclusive data on multifragmentation on an event-by-event basis, which may help the model constructors, is presented as the second topic. In lecture the onset of fragmentation, fragment sizes in multifragmentation processes, the origin of light particle correlations and emission of pions and kaons close to the threshold are discussed

  9. Heavy residues from very mass asymmetric heavy ion reactions

    International Nuclear Information System (INIS)

    Hanold, K.A.

    1994-08-01

    The isotopic production cross sections and momenta of all residues with nuclear charge (Z) greater than 39 from the reaction of 26, 40, and 50 MeV/nucleon 129 Xe + Be, C, and Al were measured. The isotopic cross sections, the momentum distribution for each isotope, and the cross section as a function of nuclear charge and momentum are presented here. The new cross sections are consistent with previous measurements of the cross sections from similar reaction systems. The shape of the cross section distribution, when considered as a function of Z and velocity, was found to be qualitatively consistent with that expected from an incomplete fusion reaction mechanism. An incomplete fusion model coupled to a statistical decay model is able to reproduce many features of these reactions: the shapes of the elemental cross section distributions, the emission velocity distributions for the intermediate mass fragments, and the Z versus velocity distributions. This model gives a less satisfactory prediction of the momentum distribution for each isotope. A very different model based on the Boltzman-Nordheim-Vlasov equation and which was also coupled to a statistical decay model reproduces many features of these reactions: the shapes of the elemental cross section distributions, the intermediate mass fragment emission velocity distributions, and the Z versus momentum distributions. Both model calculations over-estimate the average mass for each element by two mass units and underestimate the isotopic and isobaric widths of the experimental distributions. It is shown that the predicted average mass for each element can be brought into agreement with the data by small, but systematic, variation of the particle emission barriers used in the statistical model. The predicted isotopic and isobaric widths of the cross section distributions can not be brought into agreement with the experimental data using reasonable parameters for the statistical model

  10. Electron-atom scattering at intermediate energies

    International Nuclear Information System (INIS)

    Kingston, A.E.; Walters, H.R.J.

    1982-01-01

    The problems of intermediate energy scattering are approached from the low and high energy ends. At low intermediate energies difficulties associated with the use of pseudostates and correlation terms are discussed, special consideration being given to nonphysical pseudoresonances. Perturbation methods appropriate to high intermediate energies are described and attempts to extend these high energy approximations down to low intermediate energies are studied. It is shown how the importance of electron exchange effects develops with decreasing energy. The problem of assessing the 'effective completeness' of pseudostate sets at intermediate energies is mentioned and an instructive analysis of a 2p pseudostate approximation to elastic e - -H scattering is given. It is suggested that at low energies the Pauli Exclusion Principle can act to hide short range defects in pseudostate approximations. (author)

  11. Full Kinetics from First Principles of the Chlorine Evolution Reaction over a RuO2 (110) Model Electrode.

    Science.gov (United States)

    Exner, Kai S; Anton, Josef; Jacob, Timo; Over, Herbert

    2016-06-20

    Current progress in modern electrocatalysis research is spurred by theory, frequently based on ab initio thermodynamics, where the stable reaction intermediates at the electrode surface are identified, while the actual energy barriers are ignored. This approach is popular in that a simple tool is available for searching for promising electrode materials. However, thermodynamics alone may be misleading to assess the catalytic activity of an electrochemical reaction as we exemplify with the chlorine evolution reaction (CER) over a RuO2 (110) model electrode. The full procedure is introduced, starting from the stable reaction intermediates, computing the energy barriers, and finally performing microkinetic simulations, all performed under the influence of the solvent and the electrode potential. Full kinetics from first-principles allows the rate-determining step in the CER to be identified and the experimentally observed change in the Tafel slope to be explained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Spin effects in intermediate-energy heavy-ion collisions

    International Nuclear Information System (INIS)

    Xu Jun; Li Baoan; Xia Yin; Shen Wenqing

    2014-01-01

    In this paper, we report and extend our recent work where the nucleon spin-orbit interaction and its spin degree of freedom were introduced explicitly for the first time in the isospin-dependent Boltzmann-Uehling-Uhlenbeck transport model for heavy-ion reactions. Despite of the significant cancellation of the time-even and time-odd spin-related mean-field potentials from the spin-orbit interaction,an appreciable local spin polarization is observed in heavy-ion collisions at intermediate energies because of the dominating role of the time-odd terms. It is also found that the spin up-down differential transverse flow in heavy-ion collisions is a useful probe of the strength, density dependence, and isospin dependence of the in-medium spin-orbit interaction, and its magnitude is still considerable even at smaller systems. (authors)

  13. Time-resolved resonance fluorescence spectroscopy for study of chemical reactions in laser-induced plasmas.

    Science.gov (United States)

    Liu, Lei; Deng, Leimin; Fan, Lisha; Huang, Xi; Lu, Yao; Shen, Xiaokang; Jiang, Lan; Silvain, Jean-François; Lu, Yongfeng

    2017-10-30

    Identification of chemical intermediates and study of chemical reaction pathways and mechanisms in laser-induced plasmas are important for laser-ablated applications. Laser-induced breakdown spectroscopy (LIBS), as a promising spectroscopic technique, is efficient for elemental analyses but can only provide limited information about chemical products in laser-induced plasmas. In this work, time-resolved resonance fluorescence spectroscopy was studied as a promising tool for the study of chemical reactions in laser-induced plasmas. Resonance fluorescence excitation of diatomic aluminum monoxide (AlO) and triatomic dialuminum monoxide (Al 2 O) was used to identify these chemical intermediates. Time-resolved fluorescence spectra of AlO and Al 2 O were used to observe the temporal evolution in laser-induced Al plasmas and to study their formation in the Al-O 2 chemistry in air.

  14. The intermediate state in Patd

    African Journals Online (AJOL)

    ) Jesus had assumed. (concerning the 'intermediate state') as existing, anything which does not exist. Three basic things about the intermediate state emerge from the parable: (a) Jesus recognizes that at the moment of death, in ipso articulo.

  15. Higher order antibunching in intermediate states

    International Nuclear Information System (INIS)

    Verma, Amit; Sharma, Navneet K.; Pathak, Anirban

    2008-01-01

    Since the introduction of binomial state as an intermediate state, different intermediate states have been proposed. Different nonclassical effects have also been reported in these intermediate states. But till now higher order antibunching is predicted in only one type of intermediate state, which is known as shadowed negative binomial state. Recently we have shown that the higher order antibunching is not a rare phenomenon [P. Gupta, P. Pandey, A. Pathak, J. Phys. B 39 (2006) 1137]. To establish our earlier claim further, here we have shown that the higher order antibunching can be seen in different intermediate states, such as binomial state, reciprocal binomial state, hypergeometric state, generalized binomial state, negative binomial state and photon added coherent state. We have studied the possibility of observing the higher order subpoissonian photon statistics in different limits of intermediate states. The effects of different control parameters on the depth of non classicality have also been studied in this connection and it has been shown that the depth of nonclassicality can be tuned by controlling various physical parameters

  16. Total Synthesis of (+)-Cytosporolide A via a Biomimetic Hetero-Diels-Alder Reaction.

    Science.gov (United States)

    Takao, Ken-Ichi; Noguchi, Shuji; Sakamoto, Shu; Kimura, Mizuki; Yoshida, Keisuke; Tadano, Kin-Ichi

    2015-12-23

    The first total synthesis of (+)-cytosporolide A was achieved by a biomimetic hetero-Diels-Alder reaction of (-)-fuscoatrol A with o-quinone methide generated from (+)-CJ-12,373. The dienophile, highly oxygenated caryophyllene sesquiterpenoid (-)-fuscoatrol A, was synthesized from the synthetic intermediate in our previous total synthesis of (+)-pestalotiopsin A. The o-quinone methide precursor, isochroman carboxylic acid (+)-CJ-12,373, was synthesized through a Kolbe-Schmitt reaction and an oxa-Pictet-Spengler reaction. The hetero-Diels-Alder reaction of these two compounds proceeded with complete chemo-, regio-, and stereoselectivity to produce the complicated pentacyclic ring system of the cytosporolide skeleton. This total synthesis unambiguously demonstrates that natural cytosporolide A has the structure previously suggested.

  17. Impact of physical exercise on reaction time in patients with Parkinson's disease-data from the Berlin BIG Study.

    Science.gov (United States)

    Ebersbach, Georg; Ebersbach, Almut; Gandor, Florin; Wegner, Brigitte; Wissel, Jörg; Kupsch, Andreas

    2014-05-01

    To determine whether physical activity may affect cognitive performance in patients with Parkinson's disease by measuring reaction times in patients participating in the Berlin BIG study. Randomized controlled trial, rater-blinded. Ambulatory care. Patients with mild to moderate Parkinson's disease (N=60) were randomly allocated to 3 treatment arms. Outcome was measured at the termination of training and at follow-up 16 weeks after baseline in 58 patients (completers). Patients received 16 hours of individual Lee Silverman Voice Treatment-BIG training (BIG; duration of treatment, 4wk), 16 hours of group training with Nordic Walking (WALK; duration of treatment, 8wk), or nonsupervised domestic exercise (HOME; duration of instruction, 1hr). Cued reaction time (cRT) and noncued reaction time (nRT). Differences between treatment groups in improvement in reaction times from baseline to intermediate and baseline to follow-up assessments were observed for cRT but not for nRT. Pairwise t test comparisons revealed differences in change in cRT at both measurements between BIG and HOME groups (intermediate: -52ms; 95% confidence interval [CI], -84/-20; P=.002; follow-up: 55ms; CI, -105/-6; P=.030) and between WALK and HOME groups (intermediate: -61ms; CI, -120/-2; P=.042; follow-up: -78ms; CI, -136/-20; P=.010). There was no difference between BIG and WALK groups (intermediate: 9ms; CI, -49/67; P=.742; follow-up: 23ms; CI, -27/72; P=.361). Supervised physical exercise with Lee Silverman Voice Treatment-BIG or Nordic Walking is associated with improvement in cognitive aspects of movement preparation. Copyright © 2014 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

  18. Advances in heterocycle synthesis via [3+m]-cycloaddition reactions involving an azaoxyallyl cation as the key intermediate.

    Science.gov (United States)

    Xuan, Jun; Cao, Xia; Cheng, Xiao

    2018-05-17

    Heterocyclic compounds are widely found in many natural isolates and medicinally relevant compounds, as well as some fine chemicals. The development of general and efficient methods for the construction of heterocyclic compounds is one of the most important tasks in synthetic organic chemistry. Along these lines, [3+m]-cycloaddition reactions involving in situ generated azaoxyallyl cations as the 3-atom units have emerged as a powerful method for the synthesis of nitrogen-containing heterocycles. In this feature article, we highlight recent advances in this rapidly growing area, mainly focusing on the reaction design as well as the reaction mechanism.

  19. Dry molten globule intermediates and the mechanism of protein unfolding.

    Science.gov (United States)

    Baldwin, Robert L; Frieden, Carl; Rose, George D

    2010-10-01

    New experimental results show that either gain or loss of close packing can be observed as a discrete step in protein folding or unfolding reactions. This finding poses a significant challenge to the conventional two-state model of protein folding. Results of interest involve dry molten globule (DMG) intermediates, an expanded form of the protein that lacks appreciable solvent. When an unfolding protein expands to the DMG state, side chains unlock and gain conformational entropy, while liquid-like van der Waals interactions persist. Four unrelated proteins are now known to form DMGs as the first step of unfolding, suggesting that such an intermediate may well be commonplace in both folding and unfolding. Data from the literature show that peptide amide protons are protected in the DMG, indicating that backbone structure is intact despite loss of side-chain close packing. Other complementary evidence shows that secondary structure formation provides a major source of compaction during folding. In our model, the major free-energy barrier separating unfolded from native states usually occurs during the transition between the unfolded state and the DMG. The absence of close packing at this barrier provides an explanation for why phi-values, derived from a Brønsted-Leffler plot, depend primarily on structure at the mutational site and not on specific side-chain interactions. The conventional two-state folding model breaks down when there are DMG intermediates, a realization that has major implications for future experimental work on the mechanism of protein folding. 2010 Wiley-Liss, Inc.

  20. A straightforward approach towards combined α-amino and α-hydroxy acids based on Passerini reactions

    Directory of Open Access Journals (Sweden)

    Ameer F. Zahoor

    2011-09-01

    Full Text Available Complex amino acids with an α-acyloxycarbonyl functionality in the side chain are easily available through epoxide opening by chelated enolates and subsequent oxidation/Passerini reaction. This protocol works with both, aldehyde and ketone intermediates, as long as the ketones are activated by electron-withdrawing groups. In principle Ugi reactions are also possible, allowing the generation of diamino acid derivatives.

  1. Photochemical transformation of phenylurea herbicides in surface waters: a model assessment of persistence, and implications for the possible generation of hazardous intermediates.

    Science.gov (United States)

    Fabbri, Debora; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

    2015-01-01

    This work models the phototransformation kinetics in surface waters of five phenylurea herbicides (diuron, fenuron, isoproturon, metoxuron and chlortoluron), for which important photochemical parameters are available in the literature (direct photolysis quantum yields and reaction rate constants with ·OH, CO3(-·) and the triplet states of chromophoric dissolved organic matter, (3)CDOM*). Model calculations suggest that isoproturon and metoxuron would be the least photochemically persistent and diuron the most persistent compound. Reactions with ·OH and (3)CDOM* would be the main phototransformation pathways for all compounds in the majority of environmental conditions. Reaction with CO3(-) could be important in waters with low dissolved organic carbon (DOC), while direct photolysis would be negligible for fenuron, quite important for chlortoluron, and somewhat significant for the other compounds. The direct photolysis of metoxuron and diuron is known to increase toxicity, and such a photoreaction pathway would be enhanced at intermediate DOC values (1-4 mg C L(1)). The reaction between phenylureas and ·OH is known to produce toxic intermediates, differently from (3)CDOM*. Therefore, the shift of reactivity from ·OH to (3)CDOM* with increasing DOC could reduce the environmental impact of photochemical transformation. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. The effect of layer thickness and composition on the kinetics of solid state reactions in the niobium-selenium system studied using superlattice reactants

    International Nuclear Information System (INIS)

    Fukuto, M.; Kevan, S.D.

    1997-01-01

    The ability to form an amorphous reaction intermediate by the low temperature interdiffusion of a modulated elemental reactant is shown to be a function of the overall composition as well as elemental layer thicknesses in the niobium-selenium system. For niobium-rich reactants, an amorphous reaction intermediate was observed to form upon low temperature annealing of reactants with modulation thicknesses less than 60 A. Further annealing of the amorphous intermediates led to the crystallization of Nb 2 Se, Nb 5 Se 4 or Nb 3 Se 4 depending upon the overall composition of the amorphous intermediate. Modulated elemental reactants with overall compositions containing more than two-thirds selenium were found to heterogeneously nucleate NbSe 2 at the reacting interfaces. The formation of the thermodynamically expected compounds Nb 2 Se 3 , NbSe 3 , and Nb 2 Se 9 at their respective compositions required extended high temperature annealing to react the dichalcogenide with the remaining elemental reactants. A striking difference between the evolution of the low angle diffraction patterns in these two composition regimes suggests the differences in the reaction kinetics result from a composition dependence of the diffusion coefficients. (orig.)

  3. Reaction between (Z)-arylchlorooximes and α-isocyanoacetamides: a procedure for the synthesis of aryl-α-ketoamide amides.

    Science.gov (United States)

    Giustiniano, Mariateresa; Mercalli, Valentina; Cassese, Hilde; Di Maro, Salvatore; Galli, Ubaldina; Novellino, Ettore; Tron, Gian Cesare

    2014-07-03

    (Z)-Arylchlorooximes and α-isocyanoacetamides undergo a smooth reaction to produce 1,3-oxazol-2-oxime derivatives in good yields. Opening of the oxazole ring and deoximation reaction give a facile access to aryl-α-ketoamide amides, a class of privileged scaffolds in medicinal chemistry and important synthetic intermediates in organic chemistry.

  4. Bridge mediated two-electron transfer reactions: Analysis of stepwise and concerted pathways

    International Nuclear Information System (INIS)

    Petrov, E.G.; May, V.

    2004-01-01

    A theory of nonadiabatic donor (D)-acceptor (A) two-electron transfer (TET) mediated by a single regular bridge (B) is developed. The presence of different intermediate two-electron states connecting the reactant state D -- BA with the product state DBA -- results in complex multiexponential kinetics. The conditions are discussed at which a reduction to two-exponential as well as single-exponential kinetics becomes possible. For the latter case the rate K TET is calculated, which describes the bridge-mediated reaction as an effective two-electron D-A transfer. In the limit of small populations of the intermediate TET states D - B - A, DB -- A, D - BA - , and DB - A - , K TET is obtained as a sum of the rates K TET (step) and K TET (sup) . The first rate describes stepwise TET originated by transitions of a single electron. It starts at D -- BA and reaches DBA -- via the intermediate state D - BA - . These transitions cover contributions from sequential as well as superexchange reactions all including reduced bridge states. In contrast, a specific two-electron superexchange mechanism from D -- BA to DBA -- defines K TET (sup) . An analytic dependence of K TET (step) and K TET (sup) on the number of bridging units is presented and different regimes of D-A TET are studied

  5. Photocatalytic degradation of metoprolol tartrate in suspensions of two TiO2-based photocatalysts with different surface area. Identification of intermediates and proposal of degradation pathways

    International Nuclear Information System (INIS)

    Abramović, Biljana; Kler, Sanja; Šojić, Daniela; Laušević, Mila; Radović, Tanja; Vione, Davide

    2011-01-01

    Highlights: ► Kinetics and efficiency of photocatalytic degradation of the β 1 -blocker metoprolol tartrate (MET). ► Two TiO 2 specimens employed. ► Faster degradation of MET, but slower mineralization, obtained with the TiO 2 specimen having lower surface area. ► Photocatalytic transformation pathways of MET including mineralization. - Abstract: This study investigates the efficiency of the photocatalytic degradation of metoprolol tartrate (MET), a widely used β 1 -blocker, in TiO 2 suspensions of Wackherr's “Oxyde de titane standard” and Degussa P25. The study encompasses transformation kinetics and efficiency, identification of intermediates and reaction pathways. In the investigated range of initial concentrations (0.01–0.1 mM), the photocatalytic degradation of MET in the first stage of the reaction followed approximately a pseudo-first order kinetics. The TiO 2 Wackherr induced a significantly faster MET degradation compared to TiO 2 Degussa P25 when relatively high substrate concentrations were used. By examining the effect of ethanol as a scavenger of hydroxyl radicals (·OH), it was shown that the reaction with ·OH played the main role in the photocatalytic degradation of MET. After 240 min of irradiation the reaction intermediates were almost completely mineralized to CO 2 and H 2 O, while the nitrogen was predominantly present as NH 4 + . Reaction intermediates were studied in detail and a number of them were identified using LC–MS/MS (ESI+), which allowed the proposal of a tentative pathway for the photocatalytic transformation of MET as a function of the TiO 2 specimen.

  6. Spectator tagging in quasi-free pn-reactions on deuterium at PROMICE/WASA, CELSIUS

    CERN Document Server

    Bilger, R; Calén, H; Clement, H; Dunin, V; Dyring, J; Ekström, C; Fransson, K; Greiff, J; Gustafsson, L; Häggström, S; Hoeistad, B; Johanson, J; Johansson, A; Johansson, T; Khoukaz, A; Kilian, K; Koch, I; Kullander, Sven; Kupsc, A; Marciniewski, P; Morosov, B; Neubauer, T; Oelert, W; Ruber, Roger J M Y; Shwartz, B A; Stepaniak, J; Sukhanov, A; Sukhanov, A; Sundberg, P; Turowiecki, A; Wagner, G; Wilhelmi, Z; Wilkin, C; Zabierowski, J; Zernov, A; Zlomanczuk, Yu

    2000-01-01

    A set of silicon detectors has been added to the PROMICE/WASA (P/W) experiment at CELSIUS. These detectors have been used for spectator-proton tagging in proton deuteron collisions to investigate proton-neutron reactions at intermediate energies. The performance of the setup has been tested by measuring the pd -> d pi sup o p sub s sub p sub e sub c sub t sub a sub t sub o sub r reaction

  7. [Therapy of intermediate uveitis].

    Science.gov (United States)

    Doycheva, D; Deuter, C; Zierhut, M

    2014-12-01

    Intermediate uveitis is a form of intraocular inflammation in which the vitreous body is the major site of inflammation. Intermediate uveitis is primarily treated medicinally and systemic corticosteroids are the mainstay of therapy. When recurrence of uveitis or side effects occur during corticosteroid therapy an immunosuppressive treatment is required. Cyclosporine A is the only immunosuppressive agent that is approved for therapy of uveitis in Germany; however, other immunosuppressive drugs have also been shown to be effective and well-tolerated in patients with intermediate uveitis. In severe therapy-refractory cases when conventional immunosuppressive therapy has failed, biologics can be used. In patients with unilateral uveitis or when the systemic therapy is contraindicated because of side effects, an intravitreal steroid treatment can be carried out. In certain cases a vitrectomy may be used.

  8. Analysis of the intermediate stage in the heavy ion interactions of 208Pb+197Au and 197Au+197Au

    International Nuclear Information System (INIS)

    Nasir, Tabassum; Khan, E.U.; Baluch, J.J.; Qureshi, I.E.; Sajid, M.; Shahzad, M.I.

    2008-01-01

    Two different projectiles 208 Pb and 197 Au at the same energy (11.67MeV/u) have been bombarded on 197 Au target to study heavy ion interactions using mica as a passive detector. In this paper we present results on the study of energy damping and time scale of the existence of di-nuclear composite system in the intermediate reaction step. The plots of Q-values as well as reaction cross sections in various angular bins of scattering angles suggest that K.E. damping was complete and dynamic equilibrium was established between the first and second reaction steps. The time scale of this duration was also determined

  9. Density functional theory study on water-gas-shift reaction over molybdenum disulfide

    DEFF Research Database (Denmark)

    Shi, X. R.; Wang, Shengguang; Hu, J.

    2009-01-01

    . The pathway for water-gas-shift reaction on both terminations has been carefully studied where the most favorable reaction path precedes the redox mechanism, namely the reaction takes place as follows: CO + H2O --> CO + OH + H --> CO + O + 2H --> CO2 + H-2. The most likely reaction candidates for the formate......Density functional theory calculations have been carried out to investigate the adsorption of reaction intermediates appearing during water-gas-shift reaction at the sulfur covered MoS2 (1 0 0)surfaces, Mo-termination with 37.5% S coverage and S-termination with 50% S coverage using periodic slabs...... species HCOO formation is the surface CO2 reaction with H as a side reaction of CO2 desorption on S-termination with 50% S coverage. The formed HCOO species will react further with adsorbed hydrogen yielding H2COO followed by breaking its C-O bond to form the surface CH2O and O species....

  10. Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

    Directory of Open Access Journals (Sweden)

    Masato Ohashi

    2014-09-01

    Full Text Available In this review, we summarize our recent development of palladium(0-catalyzed cross-coupling reactions of perfluoro organic compounds with organometallic reagents. The oxidative addition of a C–F bond of tetrafluoroethylene (TFE to palladium(0 was promoted by the addition of lithium iodide, affording a trifluorovinyl palladium(II iodide. Based on this finding, the first palladium-catalyzed cross-coupling reaction of TFE with diarylzinc was developed in the presence of lithium iodide, affording α,β,β-trifluorostyrene derivatives in excellent yield. This coupling reaction was expanded to the novel Pd(0/PR3-catalyzed cross-coupling reaction of TFE with arylboronates. In this reaction, the trifluorovinyl palladium(II fluoride was a key reaction intermediate that required neither an extraneous base to enhance the reactivity of organoboronates nor a Lewis acid additive to promote the oxidative addition of a C–F bond. In addition, our strategy utilizing the synergetic effect of Pd(0 and lithium iodide could be applied to the C–F bond cleavage of unreactive hexafluorobenzene (C6F6, leading to the first Pd(0-catalyzed cross-coupling reaction of C6F6 with diarylzinc compounds.

  11. Bioinspired intramolecular Diels-Alder reaction: a rapid access to the highly-strained cyclopropane-fused polycyclic skeleton.

    Science.gov (United States)

    Zhu, Shifa; Guo, Zhengjiang; Huang, Zhipeng; Jiang, Huanfeng

    2014-02-24

    A bioinsipred gold-catalyzed tandem Diels-Alder/Diels-Alder reaction of an enynal and a 1,3-diene, forming the highly-strained benzotricyclo[3.2.1.0(2,7) ]octane skeleton, was reported. In contrast, a Diels-Alder/Friedel-Crafts tandem reaction occurred instead when silver salts were used as the catalyst. Although both reactions experienced the similar Diels-Alder reaction of a pyrylium intermediate with a 1,3-diene, they have different reaction mechanisms. The former proceeded with a stepwise Diels-Alder reaction, while the latter one with a concerted one. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Traumatic Brain Injury Pathophysiology and Treatments: Early, Intermediate, and Late Phases Post-Injury

    Science.gov (United States)

    Algattas, Hanna; Huang, Jason H.

    2014-01-01

    Traumatic Brain Injury (TBI) affects a large proportion and extensive array of individuals in the population. While precise pathological mechanisms are lacking, the growing base of knowledge concerning TBI has put increased emphasis on its understanding and treatment. Most treatments of TBI are aimed at ameliorating secondary insults arising from the injury; these insults can be characterized with respect to time post-injury, including early, intermediate, and late pathological changes. Early pathological responses are due to energy depletion and cell death secondary to excitotoxicity, the intermediate phase is characterized by neuroinflammation and the late stage by increased susceptibility to seizures and epilepsy. Current treatments of TBI have been tailored to these distinct pathological stages with some overlap. Many prophylactic, pharmacologic, and surgical treatments are used post-TBI to halt the progression of these pathologic reactions. In the present review, we discuss the mechanisms of the pathological hallmarks of TBI and both current and novel treatments which target the respective pathways. PMID:24381049

  13. Application of enantioselective radical reactions: synthesis of (+)-ricciocarpins A and B.

    Science.gov (United States)

    Sibi, Mukund P; He, Liwen

    2004-05-27

    Enantioselective synthesis of (+)-ricciocarpins A and B has been achieved in 41 and 45% overall yields, respectively, starting from a beta-substituted oxazolidinone. The key steps in the strategy are an enantioselective conjugate radical addition and the addition of a furyl organometallic to a key aldehyde intermediate. [reaction--see text

  14. Structure and reactions of quantum halos

    International Nuclear Information System (INIS)

    Jensen, A.S.; Riisager, K.; Fedorov, D.V.; Garrido, E.

    2004-01-01

    This article provides an overview of the basic principles of the physics of quantum halo systems, defined as bound states of clusters of particles with a radius extending well into classically forbidden regions. Exploiting the consequences of this definition, the authors derive the conditions for occurrence in terms of the number of clusters, binding energy, angular momentum, cluster charges, and excitation energy. All these quantities must be small. The article discusses the transitions between different cluster divisions and the importance of thresholds for cluster or particle decay, with particular attention to the Efimov effect and the related exotic states. The pertinent properties can be described by the use of dimensionless variables. Then universal and specific properties can be distinguished, as shown in a series of examples selected from nuclear, atomic, and molecular systems. The neutron dripline is especially interesting for nuclei and negative ions for atoms. For molecules, in which the cluster division comes naturally, a wider range of possibilities exists. Halos in two dimensions have very different properties, and their states are easily spatially extended, whereas Borromean systems are unlikely and spatially confined. The Efimov effect and the Thomas collapse occur only for dimensions between 2.3 and 3.8 and thus not for 2. High-energy reactions directly probe the halo structure. The authors discuss the reaction mechanisms for high-energy nuclear few-body halo breakup on light, intermediate, and heavy nuclear targets. For light targets, the strong interaction dominates, while for heavy targets, the Coulomb interaction dominates. For intermediate targets these processes are of comparable magnitude. As in atomic and molecular physics, a geometric impact-parameter picture is very appropriate. Finally, the authors briefly consider the complementary processes involving electroweak probes available through beta decay, electromagnetic transitions, and

  15. Crystal structure of a trapped phosphate intermediate in vanadium apochloroperoxidase catalyzing a dephosphorylation reaction

    NARCIS (Netherlands)

    de Macedo-Ribeiro, S.; Renirie, R.; Wever, R.; Messerschmidt, A.

    2008-01-01

    The crystal structure of the apo form of vanadium chloroperoxidase from Curvularia inaequalis reacted with para-nitrophenylphosphate was determined at a resolution of 1.5 Å. The aim of this study was to solve structural details of the dephosphorylation reaction catalyzed by this enzyme. Since the

  16. Dynamical structure analysis of crystalline-state reaction and elucidation of chemical reactivity in crystalline environment

    International Nuclear Information System (INIS)

    Ohashi, Yuji

    2010-01-01

    It was found that a chiral alkyl group bonded to the cobalt atom in a cobalt complex crystal was racemized with retention of the single crystal form on exposure to visible light. Such reactions, which are called crystalline-state reactions, have been found in a variety of cobalt complex crystals. The concept of reaction cavity was introduced to explain the reaction rate quantitatively and the chirality of the photo-product. The new diffractometers and detectors were made for rapid data collection. The reaction mechanism was also elucidated using neutron diffraction analysis. The unstable reaction intermediates were analyzed using cryo-trapping method. The excited-state structures were obtained at the equilibrium state between ground and excited states. (author)

  17. Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC Techniques

    Directory of Open Access Journals (Sweden)

    Ahmed M. El-Sayed

    2014-01-01

    Full Text Available Phase transfer catalysts (PTCs have been widely used for the synthesis of organic compounds particularly in both liquid-liquid and solid-liquid heterogeneous reaction mixtures. They are known to accelerate reaction rates by facilitating formation of interphase transfer of species and making reactions between reagents in two immiscible phases possible. Application of PTC instead of traditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment. On the basis of numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many active intermediates. In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compounds and their multifused rings.

  18. Synthesis of 1,1-Diphenylethylene (DPE): The Marriage of a Grignard Reaction and a Column Chromatography Experiment

    Science.gov (United States)

    Alty, Lisa T.; France, Marcia B.; Alty, Isaac G.; Saber, Christine A.; Smith, Donna M.

    2016-01-01

    The synthesis of 1,1-diphenylethylene (DPE) via a Grignard reaction, followed by an acid-catalyzed dehydration reaction, yields a mixture of compounds. DPE is a high boiling liquid that cannot be purified using simple distillation. However, it is easily separated from the more polar starting material and intermediate alcohol using both thin layer…

  19. Greigite: a true intermediate on the polysulfide pathway to pyrite

    Directory of Open Access Journals (Sweden)

    Benning Liane G

    2007-03-01

    Full Text Available Abstract The formation of pyrite (FeS2 from iron monosulfide precursors in anoxic sediments has been suggested to proceed via mackinawite (FeS and greigite (Fe3S4. Despite decades of research, the mechanisms of pyrite formation are not sufficiently understood because solid and dissolved intermediates are oxygen-sensitive and poorly crystalline and therefore notoriously difficult to characterize and quantify. In this study, hydrothermal synchrotron-based energy dispersive X-ray diffraction (ED-XRD methods were used to investigate in situ and in real-time the transformation of mackinawite to greigite and pyrite via the polysulfide pathway. The rate of formation and disappearance of specific Bragg peaks during the reaction and the changes in morphology of the solid phases as observed with high resolution microscopy were used to derive kinetic parameters and to determine the mechanisms of the reaction from mackinawite to greigite and pyrite. The results clearly show that greigite is formed as an intermediate on the pathway from mackinawite to pyrite. The kinetics of the transformation of mackinawite to greigite and pyrite follow a zero-order rate law indicating a solid-state mechanism. The morphology of greigite and pyrite crystals formed under hydrothermal conditions supports this conclusion and furthermore implies growth of greigite and pyrite by oriented aggregation of nanoparticulate mackinawite and greigite, respectively. The activation enthalpies and entropies of the transformation of mackinawite to greigite, and of greigite to pyrite were determined from the temperature dependence of the rate constants according to the Eyring equation. Although the activation enthalpies are uncharacteristic of a solid-state mechanism, the activation entropies indicate a large increase of order in the transition state, commensurate with a solid-state mechanism.

  20. The heavy-ion total reaction cross-section and nuclear transparancy

    International Nuclear Information System (INIS)

    Rego, R.A.; Hussein, M.S.

    1982-10-01

    The total reaction cross section of heavy ions at intermediate energies is discussed. The special role played by the individual nucleon-nucleon collisions in determining the nuclear transparancy is analysed. Several competing effects arising from the nuclear and Coulomb interactions between the two ions are found to be important in determing σ sub(R) at lower energies. (Author) [pt

  1. The heavy-ion total reaction cross-section and nuclear transparency

    International Nuclear Information System (INIS)

    Rego, R.A.; Hussein, M.S.

    1982-01-01

    The total reaction cross section of heavy ions at intermediate energies is discussed. The special role played by the individual nucleon-nucleon collisions in determining the nuclear transparency is analysed. Several competing effects arising from the nuclear and Coulomb interactions between the two ions are found to be important in determining σ(sub R) at lower energies. (Author) [pt

  2. The role of collision terms for nucleon emission in intermediate energy heavy ion reactions

    International Nuclear Information System (INIS)

    Gregoire, C.; Scheuter, F.; Remaud, B.; Sebille, F.

    1984-01-01

    A semi-classical description of heavy ion collisions is developed with a particular attention to the nucleon flux from one partner through the other one. The phase-space extension of the nucleons is explicitly treated by means of the Wigner transform of the density matrix. Its dynamical evolution is obtained by solving the Landau-Vlasov equation, where collision terms are explicitely introduced. As a matter of fact, the experimental nucleon spectra usually described by a thermal source with an intermediate velocity (around vsub(beam)/2) are interpreted in our framework by the coexistence of one-and two-body dissipation. Multi-differential cross-sections d 2 σ/dEdΩ are computed for the 12 C(86MeV/u) + 12 C system and are compared with the experimental data. Comparisons are also given for the 16 O (20 MeV/u) + 197 Au system

  3. A Detailed Chemical Kinetic Reaction Mechanism for Oxidation of Four Small Alkyl Esters in Laminar Premixed Flames

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Westmoreland, P R; Dryer, F L; Chaos, M; Osswald, P; Kohse-Hoinghaus, K; Cool, T A; Wang, J; Yang, B; Hansen, N; Kasper, T

    2008-02-08

    A detailed chemical kinetic reaction mechanism has been developed for a group of four small alkyl ester fuels, consisting of methyl formate, methyl acetate, ethyl formate and ethyl acetate. This mechanism is validated by comparisons between computed results and recently measured intermediate species mole fractions in fuel-rich, low pressure, premixed laminar flames. The model development employs a principle of similarity of functional groups in constraining the H atom abstraction and unimolecular decomposition reactions in each of these fuels. As a result, the reaction mechanism and formalism for mechanism development are suitable for extension to larger oxygenated hydrocarbon fuels, together with an improved kinetic understanding of the structure and chemical kinetics of alkyl ester fuels that can be extended to biodiesel fuels. Variations in concentrations of intermediate species levels in these flames are traced to differences in the molecular structure of the fuel molecules.

  4. The adsorption and reaction of halogenated volatile organic compounds (VOC's) on metal oxides. 1998 annual progress report

    International Nuclear Information System (INIS)

    Goodman, D.W.; Haw, J.F.; Lunsford, J.

    1998-01-01

    'The goal of the research is to elucidate the properties of the materials responsible for the activation of halocarbons and the nature of the intermediates formed in the dissociative adsorption of this class of compounds. This information is essential for interpreting and predicting stoichiometric and catalytic pathways for the safe destruction of halocarbon pollutants. The specific objectives are: (1) to study the adsorption and reactivity of chloromethanes and chloroethanes on metal oxides; (2) to identify the reaction intermediates using spectroscopic methods; and (3) to develop kinetic models for the reaction of these halocarbons with oxide surfaces. This report summarizes work after 20 months of a 36-month project. Emphasis has been placed understanding the surfaces phases, as well as the bulk phases that are present during the reactions of chlorinated hydrocarbons with strongly basic metal oxides. Most of the research has been carried out with carbon tetrachloride.'

  5. Peroxidase-type reactions suggest a heterolytic/nucleophilic O–O joining mechanism in the heme-dependent chlorite dismutase†

    Science.gov (United States)

    Mayfield, Jeffrey A.; Blanc, Béatrice; Rodgers, Kenton R.; Lukat-Rodgers, Gudrun S.; DuBois, Jennifer L.

    2015-01-01

    Heme-containing chlorite dismutases (Clds) catalyze a highly unusual O–O bond forming reaction. The O–O cleaving reactions of hydrogen peroxide and peracetic acid (PAA) with the Cld from Dechloromonas aromatica (DaCld) were studied to better understand the Cl–O cleavage of the natural substrate and subsequent O–O bond formation. While reactions with H2O2 resulted in slow destruction of the heme, at acidic pH, heterolytic cleavage of the O–O bond of PAA cleanly yielded the ferryl porphyrin cation radical (Compound I). At alkaline pH, the reaction proceeds more rapidly and the first observed intermediate is a ferryl heme. Freezequench EPR confirmed that the latter has an uncoupled protein-based radical, indicating that Compound I is the first intermediate formed at all pH values and that radical migration is faster at alkaline pH. These results suggest by analogy that two-electron Cl–O bond cleavage to yield a ferryl-porphyrin cation radical is the most likely initial step in O–O bond formation from chlorite. PMID:24001266

  6. Effect of Intermediate Hosts on Emerging Zoonoses.

    Science.gov (United States)

    Cui, Jing-An; Chen, Fangyuan; Fan, Shengjie

    2017-08-01

    Most emerging zoonotic pathogens originate from animals. They can directly infect humans through natural reservoirs or indirectly through intermediate hosts. As a bridge, an intermediate host plays different roles in the transmission of zoonotic pathogens. In this study, we present three types of pathogen transmission to evaluate the effect of intermediate hosts on emerging zoonotic diseases in human epidemics. These types are identified as follows: TYPE 1, pathogen transmission without an intermediate host for comparison; TYPE 2, pathogen transmission with an intermediate host as an amplifier; and TYPE 3, pathogen transmission with an intermediate host as a vessel for genetic variation. In addition, we established three mathematical models to elucidate the mechanisms underlying zoonotic disease transmission according to these three types. Stability analysis indicated that the existence of intermediate hosts increased the difficulty of controlling zoonotic diseases because of more difficult conditions to satisfy for the disease to die out. The human epidemic would die out under the following conditions: TYPE 1: [Formula: see text] and [Formula: see text]; TYPE 2: [Formula: see text], [Formula: see text], and [Formula: see text]; and TYPE 3: [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text] Simulation with similar parameters demonstrated that intermediate hosts could change the peak time and number of infected humans during a human epidemic; intermediate hosts also exerted different effects on controlling the prevalence of a human epidemic with natural reservoirs in different periods, which is important in addressing problems in public health. Monitoring and controlling the number of natural reservoirs and intermediate hosts at the right time would successfully manage and prevent the prevalence of emerging zoonoses in humans.

  7. Revisiting the Kinetics and Mechanism of Bromate-Bromide Reaction

    Directory of Open Access Journals (Sweden)

    Côrtes Carlos Eduardo S.

    2001-01-01

    Full Text Available The bromate-bromide reaction was investigated in an acidity range not studied yet. The reaction was followed at the Br2/Br3- isosbestic point (lambda = 446 nm. It was observed a first-order behavior for bromate and bromide ions and a second-order behavior for H+ ion that results in the rate law nu = k[BrO3-][Br- ][H+]². This rate law suggests a mechanism involving two successive protonation of bromate followed by the interaction of the intermediate species H2BrO3+ with bromide. These results disagree with the obtained by other authors who observed a second-order behavior for the bromide and first-order for H+, and have proposed intermediate species like H2Br2O3 and HBr2O3-. The second-order for [H+] observed in the range 0.005 <= [H+] <= 2.77 mol L-1 sets down that the pKa of bromic acid, HBrO3, must be lower than -0.5 (T = 25 °C, different from all other values for this pKa proposed in the literature.

  8. Vinyl ethers, containing isothiocyanate group. 12. Reaction of 2-vinyloxyethylisothiocyanate with metallated ethoxyethene, methoxyalline and 2-alkynes: 2,3-disubstituted N-(2-vinyloxyethyl) pyrroles and 6-(vinyloxymethyl)-5,6-dihydropyridines

    International Nuclear Information System (INIS)

    Nedolya, N.A.; Brandsma, L.; Zinov'eva, V.P.; Trofimov, B.A.

    1997-01-01

    New route of synthesis of 1,2,3-trisubstituted pyrroles and 2,3,6-trisubstituted 5,6-dyhydropyridines by the reaction of lithiated alkoxyallenes and 2-alkynes with 2-vinyloxyethylisothiocyanate is found. It is shown that key intermediates are 1,3,4-azatrienes. Reaction of metallized ethoxyethene with 2-vinyloxyethyisothiocyanate (after intermediate alkylation) results in 1-(2-vinyloxyethyl)-1,3-azadiene

  9. The concern of emergence of multi-station reaction pathways that might make stepwise the mechanism of the 1,3-dipolar cycloadditions of azides and alkynes

    Science.gov (United States)

    Mohtat, Bita; Siadati, Seyyed Amir; Khalilzadeh, Mohammad Ali; Zareyee, Daryoush

    2018-03-01

    After hot debates on the concerted or stepwise nature of the mechanism of the catalyst-free 1,3-dipolar cycloadditions (DC)s, nowadays, it is being believed that for the reaction of each dipole and dipolarophile, there is a possibility that the reaction mechanism becomes stepwise, intermediates emerge, and the reaction becomes non-stereospecific. Yield of even minimal amounts of unwanted side products or stereoisomers as impurities could bring many troubles like difficult purification steps. In this project, we have made attempts to study all probable reaction channels of the azide cycloadditions with two functionalized alkynes, in order to answer this question: "is there any possibility that intermediates evolve in the catalyst-free click 1,3-DC reaction of azide-alkynes?". During the calculations, several multi-station reaction pathways supporting the stepwise and concerted mechanisms were detected. Also, the born-oppenheimer molecular dynamic (BOMD) simulation was used to find trustable geometries which could be emerged during the reaction coordinate.

  10. Chemical reactions on platinum-group metal surfaces studied by synchrotron-radiation-based spectroscopy

    International Nuclear Information System (INIS)

    Kondoh, Hiroshi; Nakai, Ikuyo; Nagasaka, Masanari; Amemiya, Kenta; Ohta, Toshiaki

    2009-01-01

    A new version of synchrotron-radiation-based x-ray spectroscopy, wave-length-dispersive near-edge x-ray absorption fine structure (dispersive-NEXAFS), and fast x-ray photoelectron spectroscopy have been applied to mechanistic studies on several surface catalytic reactions on platinum-group-metal surfaces. In this review, our approach using above techniques to understand the reaction mechanism and actual application studies on three well-known catalytic surface reactions, CO oxidation on Pt(111) and Pd(111), NO reduction on Rh(111), and H 2 O formation on Pt(111), are introduced. Spectroscopic monitoring of the progress of the surface reactions enabled us to detect reaction intermediates and analyze the reaction kinetics quantitatively which provides information on reaction order, rate constant, pre-exponential factor, activation energy and etc. Such quantitative analyses combined with scanning tunneling microscopy and kinetic Monte Carlo simulations revealed significant contribution of the adsorbate configurations and their dynamic changes to the reaction mechanisms of the above fundamental catalytic surface reactions. (author)

  11. Intermediate algebra & analytic geometry

    CERN Document Server

    Gondin, William R

    1967-01-01

    Intermediate Algebra & Analytic Geometry Made Simple focuses on the principles, processes, calculations, and methodologies involved in intermediate algebra and analytic geometry. The publication first offers information on linear equations in two unknowns and variables, functions, and graphs. Discussions focus on graphic interpretations, explicit and implicit functions, first quadrant graphs, variables and functions, determinate and indeterminate systems, independent and dependent equations, and defective and redundant systems. The text then examines quadratic equations in one variable, system

  12. Modeling of catalytically active metal complex species and intermediates in reactions of organic halides electroreduction.

    Science.gov (United States)

    Lytvynenko, Anton S; Kolotilov, Sergey V; Kiskin, Mikhail A; Eremenko, Igor L; Novotortsev, Vladimir M

    2015-02-28

    The results of quantum chemical modeling of organic and metal-containing intermediates that occur in electrocatalytic dehalogenation reactions of organic chlorides are presented. Modeling of processes that take place in successive steps of the electrochemical reduction of representative C1 and C2 chlorides - CHCl3 and Freon R113 (1,1,2-trifluoro-1,2,2-trichloroethane) - was carried out by density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2). It was found that taking solvation into account using an implicit solvent model (conductor-like screening model, COSMO) or considering explicit solvent molecules gave similar results. In addition to modeling of simple non-catalytic dehalogenation, processes with a number of complexes and their reduced forms, some of which were catalytically active, were investigated by DFT. Complexes M(L1)2 (M = Fe, Co, Ni, Cu, Zn, L1H = Schiff base from 2-pyridinecarbaldehyde and the hydrazide of 4-pyridinecarboxylic acid), Ni(L2) (H2L2 is the Schiff base from salicylaldehyde and 1,2-ethylenediamine, known as salen) and Co(L3)2Cl2, representing a fragment of a redox-active coordination polymer [Co(L3)Cl2]n (L3 is the dithioamide of 1,3-benzenedicarboxylic acid), were considered. Gradual changes in electronic structure in a series of compounds M(L1)2 were observed, and correlations between [M(L1)2](0) spin-up and spin-down LUMO energies and the relative energies of the corresponding high-spin and low-spin reduced forms, as well as the shape of the orbitals, were proposed. These results can be helpful for determination of the nature of redox-processes in similar systems by DFT. No specific covalent interactions between [M(L1)2](-) and the R113 molecule (M = Fe, Co, Ni, Zn) were found, which indicates that M(L1)2 electrocatalysts act rather like electron transfer mediators via outer-shell electron transfer. A relaxed surface scan of the adducts {M(L1)2·R113}(-) (M = Ni or Co) versus the distance between the

  13. An Aurivillius Oxide Based Cathode with Excellent CO2 Tolerance for Intermediate-Temperature Solid Oxide Fuel Cells.

    Science.gov (United States)

    Zhu, Yinlong; Zhou, Wei; Chen, Yubo; Shao, Zongping

    2016-07-25

    The Aurivillius oxide Bi2 Sr2 Nb2 MnO12-δ (BSNM) was used as a cobalt-free cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). To the best of our knowledge, the BSNM oxide is the only alkaline-earth-containing cathode material with complete CO2 tolerance that has been reported thus far. BSNM not only shows favorable activity in the oxygen reduction reaction (ORR) at intermediate temperatures but also exhibits a low thermal expansion coefficient, excellent structural stability, and good chemical compatibility with the electrolyte. These features highlight the potential of the new BSNM material as a highly promising cathode material for IT-SOFCs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Isotope yield ratios as a probe of the reaction dynamics

    International Nuclear Information System (INIS)

    Trautmann, W.; Hildenbrand, K.D.; Lynen, U.; Mueller, W.F.J.; Rabe, H.J.; Sann, H.; Stelzer, H.; Trockel, R.; Wada, R.; Brummund, N.; Glasow, R.; Kampert, K.H.; Santo, R.; Eckert, E.M.; Pochodzalla, J.; Bock, I.; Pelte, D.

    1987-04-01

    Isotopically resolved yields of particles and complex fragments from 12 C and 18 O induced reactions on 53 Ni, 54 Ni, Ag, and 197 Au in the intermediate range of bombarding energies 30 MeV ≤ E/A ≤ 84 MeV were measured. The systematic variation of the deduced isotope yield ratios with projectile and target is used to determine the degree of N/Z equilibration achieved and to establish time scales for the reaction process. A quantum statistical model is employed in order to derive entropies of the emitting systems from the measured isotope yield ratios. (orig.)

  15. Study of reactions for the production of uranium titrafluoride and uranium hexafluoride

    International Nuclear Information System (INIS)

    Guzella, M.F.R.

    1985-01-01

    The main production processes of uranium hexafluoride in pilot plants and industrial facilities are described. The known reactions confirmed in laboratory experiments that lead to Uf 6 or other intermediate fluorides are discussed. For the purpose of determining a thermodinamically feasible reaction involving the sulfur hexafluoride as fluorinating agent, a mock-up facility was designed and constructed as a part of the R and D work planned at the CDTN (Nuclebras Center for Nuclear Technology Development). IN the uranium tatrafluoride synthesis employing U 3 O 8 and SF 6 several experimental parameters are studied. The reaction time, gasflow, temperature and stoechiometic relations among reagents are described in detail. (Author) [pt

  16. Design of an intermediate-scale experiment to validate unsaturated- zone transport models

    International Nuclear Information System (INIS)

    Siegel, M.D.; Hopkins, P.L.; Glass, R.J.; Ward, D.B.

    1991-01-01

    An intermediate-scale experiment is being carried out to evaluate instrumentation and models that might be used for transport-model validation for the Yucca Mountain Site Characterization Project. The experimental test bed is a 6-m high x 3-m diameter caisson filled with quartz sand with a sorbing layer at an intermediate depth. The experiment involves the detection and prediction of the migration of fluid and tracers through an unsaturated porous medium. Pre-test design requires estimation of physical properties of the porous medium such as the relative permeability, saturation/pressure relations, porosity, and saturated hydraulic conductivity as well as geochemical properties such as surface complexation constants and empircial K d 'S. The pre-test characterization data will be used as input to several computer codes to predict the fluid flow and tracer migration. These include a coupled chemical-reaction/transport model, a stochastic model, and a deterministic model using retardation factors. The calculations will be completed prior to elution of the tracers, providing a basis for validation by comparing the predictions to observed moisture and tracer behavior

  17. A study on the hierarchy model of nuclear reactions

    International Nuclear Information System (INIS)

    Kitazoe, Yasuhiro; Sekiya, Tamotsu

    1975-01-01

    The application of the hierarchy model of nuclear reaction is discussed, and the hierarchy model means that the compound nucleus state is formed after several steps, at least, one step of reaction. This model was applied to the analysis of the observed cross sections of 235 U and some other elements. Neglecting exchange scattering effect, the equations for the total neutron cross section of 235 U were obtained. One of these equations describes explicitly the hierarchy of the transition from intermediate reaction state Xm into the compound nucleus state Xs, and another one describes the cross section averaged over an energy interval larger than the average level spacing of compound nucleus eigenvalues. The hierarchy of reaction mechanism was investigated in more detail, and the hierarchy model was applied to the case of unresolved energy region. It was not tried to evaluate the strength function in the mass region (A>140), since the effect of nuclear deformation was neglected in the task. (Iwase, T.)

  18. Unexpected Formation of Naphtyl 1,3-Diaminopropane-2-ol Derivative through Azetidinium Ion Intermediate

    International Nuclear Information System (INIS)

    Han, Minsoo; Hahn, Hohgyu

    2012-01-01

    The cause of depression is commonly associated with a deficiency of monoamine neurotransmitters such as serotonin, norepinephrine and dopamine in the brain. Inhibition of monoamine reuptake has been an effective pharmacological treatment of various CNS disorders.1 As a part of our continuing efforts to develop novel antidepressants for multiple therapeutic utilities, we designed diaminopropan-2-ol 1 through structure analysis and molecular modification and of currently marketed reuptake transporter based antidepressants. 3-amino-1,2-diol derivatives 7 were converted to the corresponding diaminopropan-2-ol derivatives 9 by the reaction with MsCl in the presence of triethylamine followed by the treatment of either amine or thiol. We proposed azetdinium ion 11 or azetidinium ylide 12 as an intermediate in the reaction, and prepared 7 analogues by similar manner

  19. Unexpected Formation of Naphtyl 1,3-Diaminopropane-2-ol Derivative through Azetidinium Ion Intermediate

    Energy Technology Data Exchange (ETDEWEB)

    Han, Minsoo; Hahn, Hohgyu [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2012-11-15

    The cause of depression is commonly associated with a deficiency of monoamine neurotransmitters such as serotonin, norepinephrine and dopamine in the brain. Inhibition of monoamine reuptake has been an effective pharmacological treatment of various CNS disorders.1 As a part of our continuing efforts to develop novel antidepressants for multiple therapeutic utilities, we designed diaminopropan-2-ol 1 through structure analysis and molecular modification and of currently marketed reuptake transporter based antidepressants. 3-amino-1,2-diol derivatives 7 were converted to the corresponding diaminopropan-2-ol derivatives 9 by the reaction with MsCl in the presence of triethylamine followed by the treatment of either amine or thiol. We proposed azetdinium ion 11 or azetidinium ylide 12 as an intermediate in the reaction, and prepared 7 analogues by similar manner.

  20. Removal behaviors of sulfamonomethoxine and its degradation intermediates in fresh aquaculture wastewater using zeolite/TiO2 composites.

    Science.gov (United States)

    Nomura, Youhei; Fukahori, Shuji; Fukada, Haruhisa; Fujiwara, Taku

    2017-10-15

    Removal efficiencies of sulfamonomethoxine (SMM) and its degradation intermediates formed by treatment with zeolite/TiO 2 composites through adsorption and photocatalysis were investigated in fresh aquaculture wastewater (FAWW). Coexistent substances in the FAWW showed no inhibitory effects against SMM adsorption. Although coexistent substances in the FAWW inhibited the photocatalytic decomposition of SMM, the composites mitigated the inhibition, possibly because of concentration of SMM on their surface by adsorption. LC/MS/MS analyses revealed that hydroxylation of amino phenyl and pyrimidinyl portions, transformation of the amino group in the amino phenyl portion into a nitroso group, and substitution of the methoxy group with a hydroxyl group occurring in the initial reaction resulted in the formation of various intermediates during the photocatalysis of SMM. All detected intermediates had a ring structure, and almost all intermediates disappeared at the same time SMM was completely decomposed. Ph-OH formed by hydroxylation of the phenyl portion was detected upon decomposition of SMM during photocatalysis. The removal of Ph-OH by the composites proceeded more rapidly than that by TiO 2 alone under ultraviolet irradiation. The SMM and Ph-OH were completely degraded by the composites within 30min, showing that the zeolite/TiO 2 composites were effective in removing SMM and its intermediates from FAWW. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Regularities of intermediate adsorption complex relaxation

    International Nuclear Information System (INIS)

    Manukova, L.A.

    1982-01-01

    The experimental data, characterizing the regularities of intermediate adsorption complex relaxation in the polycrystalline Mo-N 2 system at 77 K are given. The method of molecular beam has been used in the investigation. The analytical expressions of change regularity in the relaxation process of full and specific rates - of transition from intermediate state into ''non-reversible'', of desorption into the gas phase and accumUlation of the particles in the intermediate state are obtained

  2. FINANCIAL INTERMEDIATION, ENTREPRENEURSHIP AND ECONOMIC GROWTH

    OpenAIRE

    Wenli Cheng

    2007-01-01

    This paper presents a simple general equilibrium model of financial intermediation, entrepreneurship and economic growth. In this model, the role of financial intermediation is to pool savings and to lend the pooled funds to an entrepreneur, who in turn invests the funds in a new production technology. The adoption of the new production technology improves individual real income. Thus financial intermediation promotes economic growth through affecting individuals’ saving behaviour and enabl...

  3. Theoretical Kinetic Study of the Formic Acid Catalyzed Criegee Intermediate Isomerization: Multistructural Anharmonicity and Atmospheric Implications

    KAUST Repository

    Monge Palacios, Manuel

    2018-01-29

    We performed a theoretical study on the double hydrogen shift isomerization reaction of a six carbon atom Criegee intermediate (C6-CI), catalyzed by formic acid (HCOOH), to produce vinylhydroperoxide (VHP), C6-CI+HCOOH→VHP+HCOOH. This Criegee intermediate can serve as a surrogate for larger CIs derived from important volatile organic compounds like monoterpenes, whose reactivity is not well understood and are difficult to handle computationally. The reactant HCOOH exerts a pronounced catalytic effect on the studied reaction by lowering the barrier height, but the kinetic enhancement is hindered by the multistructural anharmonicity. First, the rigid ring-structure adopted by the saddle point to facilitate simultaneous transfer of two atoms does not allow formation of as many conformers as those formed by the reactant C6-CI. And second, the flexible carbon chain of C6-CI facilitates the formation of stabilizing intramolecular C–H···O hydrogen bonds; this stabilizing effect is less pronounced in the saddle point structure due to its tightness and steric effects. Thus, the contribution of the reactant C6-CI conformers to the multistructural partition function is larger than that of the saddle point conformers. The resulting low multistructural anharmonicity factor partially cancels out the catalytic effect of the carboxylic acid, yielding in a moderately large rate coefficient, k(298 K) = 4.9·10-13 cm3 molecule-1 s-1. We show that carboxylic acids may promote the conversion of stabilized Criegee intermediates into vinylhydroperoxides in the atmosphere, which generates OH radicals and leads to secondary organic aerosol, thereby affecting the oxidative capacity of the atmosphere and ultimately the climate.

  4. Some Intermediate-Level Violin Concertos.

    Science.gov (United States)

    Abramson, Michael

    1997-01-01

    Contends that many violin students attempt difficult concertos before they are technically or musically prepared. Identifies a variety of concertos at the intermediate and advanced intermediate-level for students to study and master before attempting the advanced works by Bach and Mozart. Includes concertos by Vivaldi, Leclair, Viotti, Haydn,…

  5. Desaturation reactions catalyzed by soluble methane monooxygenase.

    Science.gov (United States)

    Jin, Y; Lipscomb, J D

    2001-09-01

    Soluble methane monooxygenase (MMO) is shown to be capable of catalyzing desaturation reactions in addition to the usual hydroxylation and epoxidation reactions. Dehydrogenated products are generated from MMO-catalyzed oxidation of certain substrates including ethylbenzene and cyclohexadienes. In the reaction of ethylbenzene, desaturation of ethyl C-H occurred along with the conventional hydroxvlations of ethyl and phenyl C-Hs. As a result, styrene is formed together with ethylphenols and phenylethanols. Similarly, when 1,3- and 1,4-cyclohexadienes were used as substrates, benzene was detected as a product in addition to the corresponding alcohols and epoxides. In all cases, reaction conditions were found to significantly affect the distribution among the different products. This new activity of MMO is postulated to be associated with the chemical properties of the substrates rather than fundamental changes in the nature of the oxygen and C-H activation chemistries. The formation of the desaturated products is rationalized by formation of a substrate cationic intermediate, possibly via a radical precursor. The cationic species is then proposed to partition between recombination (alcohol formation) and elimination (alkene production) pathways. This novel function of MMO indicates close mechanistic kinship between the hydroxylation and desaturation reactions catalyzed by the nonheme diiron clusters.

  6. Thermal ion-molecule reactions in oxygen-containing molecules

    International Nuclear Information System (INIS)

    Kumakura, Minoru

    1981-02-01

    The energetics of ions and the thermal ion-molecule reactions in oxygen-containing molecules have been studied with a modified time-of-flight mass spectrometer. It was found that the translational energy of ion can be easily obtained from analysis of the decay curve using the time-of-flight mass spectrometer. The condensation-elimination reactions proceeded via cross- and homo-elimination mechanism in which the nature of intermediate-complex could be correlated with the nature of reactant ion. It was elucidated that behavior of poly-atomic oxygen-containing ions on the condensation-elimination reactions is considerably influenced by their oxonium ion structures having functional groups. In addition, the rate constants of the condensation-elimination reactions have affected with the energy state of reactant ion and the dipole moment and/or the polarizability of neutral molecule. It was clarified that the rate constants of the ion-molecule clustering reactions in poly-atomic oxygen-containing molecules such as cyclic ether of six member rings are very large and the cluster ions are stable owing to the large number of vibrational degree of freedom in the cluster ions. (author)

  7. Theoretical insights into the sites and mechanisms for base catalyzed esterification and aldol condensation reactions over Cu.

    Science.gov (United States)

    Neurock, Matthew; Tao, Zhiyuan; Chemburkar, Ashwin; Hibbitts, David D; Iglesia, Enrique

    2017-04-28

    Condensation and esterification are important catalytic routes in the conversion of polyols and oxygenates derived from biomass to fuels and chemical intermediates. Previous experimental studies show that alkanal, alkanol and hydrogen mixtures equilibrate over Cu/SiO 2 and form surface alkoxides and alkanals that subsequently promote condensation and esterification reactions. First-principle density functional theory (DFT) calculations were carried out herein to elucidate the elementary paths and the corresponding energetics for the interconversion of propanal + H 2 to propanol and the subsequent C-C and C-O bond formation paths involved in aldol condensation and esterification of these mixtures over model Cu surfaces. Propanal and hydrogen readily equilibrate with propanol via C-H and O-H addition steps to form surface propoxide intermediates and equilibrated propanal/propanol mixtures. Surface propoxides readily form via low energy paths involving a hydrogen addition to the electrophilic carbon center of the carbonyl of propanal or via a proton transfer from an adsorbed propanol to a vicinal propanal. The resulting propoxide withdraws electron density from the surface and behaves as a base catalyzing the activation of propanal and subsequent esterification and condensation reactions. These basic propoxides can readily abstract the acidic C α -H of propanal to produce the CH 3 CH (-) CH 2 O* enolate, thus initiating aldol condensation. The enolate can subsequently react with a second adsorbed propanal to form a C-C bond and a β-alkoxide alkanal intermediate. The β-alkoxide alkanal can subsequently undergo facile hydride transfer to form the 2-formyl-3-pentanone intermediate that decarbonylates to give the 3-pentanone product. Cu is unique in that it rapidly catalyzes the decarbonylation of the C 2n intermediates to form C 2n-1 3-pentanone as the major product with very small yields of C 2n products. This is likely due to the absence of Brønsted acid sites

  8. Fluctuation-Induced Pattern Formation in a Surface Reaction

    DEFF Research Database (Denmark)

    Starke, Jens; Reichert, Christian; Eiswirth, Markus

    2006-01-01

    Spontaneous nucleation, pulse formation, and propagation failure have been observed experimentally in CO oxidation on Pt(110) at intermediate pressures ($\\approx 10^{-2}$mbar). This phenomenon can be reproduced with a stochastic model which includes temperature effects. Nucleation occurs randomly...... due to fluctuations in the reaction processes, whereas the subsequent damping out essentially follows the deterministic path. Conditions for the occurence of stochastic effects in the pattern formation during CO oxidation on Pt are discussed....

  9. Synthesis of sp3-rich scaffolds for molecular libraries through complexity-generating cascade reactions

    DEFF Research Database (Denmark)

    Flagstad, Thomas; Min, Geanna; Bonnet, K.

    2016-01-01

    An efficient strategy for the synthesis of complex small molecules from simple building blocks is presented. Key steps of the strategy include tandem Petasis and Diels–Alder reactions, and divergent complexity-generating cyclization cascades from a key dialdehyde intermediate. The methodology...

  10. Oxidation of Refractory Benzothiazoles with PMS/CuFe2O4: Kinetics and Transformation Intermediates

    KAUST Repository

    Zhang, Tao; Chen, Yin; Leiknes, TorOve

    2016-01-01

    Benzothiazole (BTH) and its derivatives, 2-(methylthio)bezothiazole (MTBT), 2-benzothiazolsulfonate (BTSA) and 2-hydroxybenzothiazole (OHBT), are refractory pollutants ubiquitously existing in urban runoff at relatively high concentrations. Here, we report their oxidation by CuFe2O4-activated peroxomonosulfate (PMS/CuFe2O4), focusing on kinetics and transformation intermediates. These benzothiazoles can be efficiently degraded by this oxidation process which is confirmed to generate mainly sulfate radicals (with negligible hydroxyl-radical formation) under slightly acidic to neutral pH conditions. The molar exposure ratio of sulfate radical to residual PMS (i.e. Rct) of this process is a constant which is related to reaction condition and can be easily determined. Reaction rate constants of these benzothiazoles towards sulfate radical are (3.3 ± 0.3) × 109, (1.4 ± 0.3) × 109, (1.5 ± 0.1) × 109 and (4.7 ± 0.5) × 109 M-1s-1, respectively (pH 7 and 20 oC). Based on Rct and these rate constants, their degradation in the presence of organic matter can be well predicted. A number of transformation products were detected and tentatively identified using triple-quadruple/linear ion trap MS/MS and high-resolution MS. It appears that sulfate radicals attack BTH, MTBT and BTSA on their benzo ring via electron transfer, generating multiple hydroxylated intermediates which are reactive towards common oxidants. For OHBT oxidation, it prefers to break down the thiazole ring. Due to competitions of the transformation intermediates, a minimum PMS/pollutant molar ratio of 10-20 is required for effective degradation. The flexible PMS/CuFe2O4 could be a useful process to remove the benzothiazoles from low DOC waters like urban runoff or polluted groundwater.

  11. Oxidation of Refractory Benzothiazoles with PMS/CuFe2O4: Kinetics and Transformation Intermediates

    KAUST Repository

    Zhang, Tao

    2016-05-04

    Benzothiazole (BTH) and its derivatives, 2-(methylthio)bezothiazole (MTBT), 2-benzothiazolsulfonate (BTSA) and 2-hydroxybenzothiazole (OHBT), are refractory pollutants ubiquitously existing in urban runoff at relatively high concentrations. Here, we report their oxidation by CuFe2O4-activated peroxomonosulfate (PMS/CuFe2O4), focusing on kinetics and transformation intermediates. These benzothiazoles can be efficiently degraded by this oxidation process which is confirmed to generate mainly sulfate radicals (with negligible hydroxyl-radical formation) under slightly acidic to neutral pH conditions. The molar exposure ratio of sulfate radical to residual PMS (i.e. Rct) of this process is a constant which is related to reaction condition and can be easily determined. Reaction rate constants of these benzothiazoles towards sulfate radical are (3.3 ± 0.3) × 109, (1.4 ± 0.3) × 109, (1.5 ± 0.1) × 109 and (4.7 ± 0.5) × 109 M-1s-1, respectively (pH 7 and 20 oC). Based on Rct and these rate constants, their degradation in the presence of organic matter can be well predicted. A number of transformation products were detected and tentatively identified using triple-quadruple/linear ion trap MS/MS and high-resolution MS. It appears that sulfate radicals attack BTH, MTBT and BTSA on their benzo ring via electron transfer, generating multiple hydroxylated intermediates which are reactive towards common oxidants. For OHBT oxidation, it prefers to break down the thiazole ring. Due to competitions of the transformation intermediates, a minimum PMS/pollutant molar ratio of 10-20 is required for effective degradation. The flexible PMS/CuFe2O4 could be a useful process to remove the benzothiazoles from low DOC waters like urban runoff or polluted groundwater.

  12. Ion-molecular reactions initiated by β-decay of tritium in tritiated compounds

    International Nuclear Information System (INIS)

    Akulov, G.P.

    1976-01-01

    Ion-molecular reactions initiated by β-decay of tritium and tritiated hydrocarbons have been systematized. The review describes the theoretical and experimental foundation of the radiochemical method of this important type of chemical interactions investigation. The reactions of the molecular ions of HeT + with methane, ethane, propane, butane and also with cycloalkanes from C 3 to C 6 are discussed. The reactions under consideration have been united into two groups: reactions involving HeT + ions and those involving carbonic ions. From the experimental results available, the conclusions have been drawn about the reactivity of these intermediate formations, about the mechanism of their interaction with organic substances, and also about the perspectives of using the radiochemical method in studies of ion-molecular reactions. The experimental results published before May 1974 are examined. The bibliography includes 162 references

  13. A theoretical study of the reaction of O(3P) with an allyl radical C3H5

    Science.gov (United States)

    Park, Jong-Ho; Lee, Hohjai; Choi, Jong-Ho

    2003-11-01

    Ab initio calculations of the reaction of ground-state atomic oxygen [O(3P)] with an allyl radical (C3H5) have been carried out using the density functional method and the complete basis set model. On the calculated lowest doublet potential energy surface, the barrierless association of O(3P) to C3H5 forms three energy-rich addition intermediates, which are predicted to undergo subsequent isomerization and decomposition steps leading to various products: C3H4O+H, CH2O+C2H3, C2H4+CHO, C2H2O+CH3, C2H5+CO, C3H4+OH, and C2H4O+CH. The respective reaction mechanisms through the three addition intermediates are presented, and it has been found that the barrier height, reaction enthalpy, and the number of intermediates involved along the reaction coordinate are of extreme importance in understanding such reactive scattering processes. With the aid of Rice-Ramsperger-Kassel-Marcus calculations, the major reaction pathway is predicted to be the formation of acrolein (C3H4O)+H, which is consistent with the previous gas-phase bulk kinetic experiment performed by Gutman et al. [J. Phys. Chem. 94, 3652 (1990)]. For the minor C3H4+OH channel, which has been newly found in the recent crossed beam investigations, a second barrierless, direct H-atom abstraction from the central carbon of C3H5 is calculated to compete with the addition process due to the little C-H bond dissociation energy and the formation of a stable allene product. The dynamic and kinetic characteristics of the reaction mechanism are discussed on the basis of the comparison of prior statistical calculations to the nascent internal distributions of the observed OH product.

  14. Nitrogen atom transfer mediated by a new PN3P-pincer nickel core via a putative nitrido nickel intermediate

    KAUST Repository

    Yao, Changguang

    2018-02-13

    A 2nd generation PN3P-pincer azido nickel complex (PN3P)Ni(N3) reacts with isocyanides to afford monosubstituted carbodiimides under irradiation, presumably via a transient nitrido intermediate. The resulting species can further generate unsymmetrical carboddimides and the PN3P nickel halide complex, accomplishing a synthetic cycle for a complete nitrogen atom transfer reaction.

  15. Nitrogen atom transfer mediated by a new PN3P-pincer nickel core via a putative nitrido nickel intermediate

    KAUST Repository

    Yao, Changguang; Wang, Xiufang; Huang, Kuo-Wei

    2018-01-01

    A 2nd generation PN3P-pincer azido nickel complex (PN3P)Ni(N3) reacts with isocyanides to afford monosubstituted carbodiimides under irradiation, presumably via a transient nitrido intermediate. The resulting species can further generate unsymmetrical carboddimides and the PN3P nickel halide complex, accomplishing a synthetic cycle for a complete nitrogen atom transfer reaction.

  16. Stability and anti-glycation properties of intermediate moisture apple products fortified with green tea.

    Science.gov (United States)

    Lavelli, Vera; Corey, Mark; Kerr, William; Vantaggi, Claudia

    2011-07-15

    Intermediate moisture products made from blanched apple flesh and green tea extract (about 6mg of monomeric flavan 3-ols added per g of dry apple) or blanched apple flesh (control) were produced, and their quality attributes were investigated over storage for two months at water activity (a(w)) levels of 0.55 and 0.75, at 30°C. Products were evaluated for colour (L(∗), a(∗), and b(∗) Hunter's parameters), phytochemical contents (flavan 3-ols, chlorogenic acid, dihydrochalcones, ascorbic acid and total polyphenols), ferric reducing antioxidant potential, 2,2-diphenyl-1-(2,4,6-trinitrophenyl)hydrazyl radical-scavenging activity and ability to inhibit formation of fructose-induced advanced glycation end-products. During storage of the fortified and unfortified intermediate moisture apples, water availability was sufficient to support various chemical reactions involving phytochemicals, which degraded at different rates: ascorbic acid>flavan 3-ols>dihydrochalcones and chlorogenic acid. Colour variations occurred at slightly slower rates after green tea addition. In the intermediate moisture apple, antioxidant and anti-glycoxidative properties decreased at similar rates (half-life was about 80d at a(w) of 0.75, 30°C). In the green tea-fortified intermediate moisture apple, the antioxidant activity decreased at a slow rate (half-life was 165d at a(w) of 0.75, 30°C) and the anti-glycoxidative properties did not change, indicating that flavan 3-ol degradation involved the formation of derivatives that retained the properties of their parent compounds. Since these properties are linked to oxidative- and advanced glycation end-product-related diseases, these results suggest that green tea fortification of intermediate moisture apple products could be a valuable means of product innovation, to address consumers' nutritional needs. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. Welding. Performance Objectives. Intermediate Course.

    Science.gov (United States)

    Vincent, Kenneth

    Several intermediate performance objectives and corresponding criterion measures are listed for each of nine terminal objectives for an intermediate welding course. The materials were developed for a 36-week (3 hours daily) course designed to prepare the student for employment in the field of welding. Electric welding and specialized (TIG & MIG)…

  18. An analysis of the changes on intermediate products during the thermal processing of black garlic.

    Science.gov (United States)

    Yuan, Heng; Sun, Linjuan; Chen, Min; Wang, Jun

    2018-01-15

    The thermal processing of black garlic was simulated. Fresh garlic was incubated at 55°C with 80% humidity and sampled every 5 or 10days. The changes in relevant products were as follows: the fructan content was decreased by 84.79%, and the fructose content was increased by 508.11%. The contents of Maillard reaction intermediate products were first increased and then decreased. The colour of garlic gradually became dark and the pH decreased from 6.13 to 4.00. By analyzing these changes, the mechanism of black garlic formation and the changes on the Maillard reaction were revealed. The sweetness of black garlic resulted mainly from the fructose that was produced, and the black colour was largely due to the Maillard reaction between fructose/glucose and amino acids. An understanding of this process is useful to explain the formation mechanism of black garlic and could lead to better control of the quality of black garlic. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Spallation reactions - physics and applications

    International Nuclear Information System (INIS)

    Kelic, A.; Ricciardi, M.; Schmidt, K-H.

    2009-01-01

    -nucleon collisions with an intra-nuclear-cascade code. Most of the a lient features observed in the residual nuclide distributions are determined by the later de-excitation stage of the reaction due to the different possible de-excitation paths like evaporation of nucleons, light charged particles and intermediate mass fragments, fission and multi-fragmentation

  20. Program TOTELA calculating basic cross sections in intermediate energy region by using systematics

    International Nuclear Information System (INIS)

    Fukahori, Tokio; Niita, Koji

    2000-01-01

    Program TOTELA can calculate neutron- and proton-induced total, elastic scattering and reaction cross sections and angular distribution of elastic scattering in the intermediate energy region from 20 MeV to 3 GeV. The TOTELA adopts the systematics modified from that by Pearlstein to reproduce the experimental data and LA150 evaluation better. The calculated results compared with experimental data and LA150 evaluation are shown in figures. The TOTELA results can reproduce those data almost well. The TOTELA was developed to fill the lack of experimental data of above quantities in the intermediate energy region and to use for production of JENDL High Energy File. In the case that there is no experimental data of above quantities, the optical model parameters can be fitted by using TOTELA results. From this point of view, it is also useful to compare the optical model calculation by using RIPL with TOTELA results, in order to verify the parameter quality. Input data of TOTELA is only atomic and mass numbers of incident particle and target nuclide and input/output file names. The output of TOTELA calculation is in ENDF-6 format used in the intermediate energy nuclear data files. It is easy to modify the main routine by users. Details are written in each subroutine and main routine