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Sample records for reaction mechanism leading

  1. Reaction mechanisms

    International Nuclear Information System (INIS)

    Nguyen Trong Anh

    1988-01-01

    The 1988 progress report of the Reaction Mechanisms laboratory (Polytechnic School, France), is presented. The research topics are: the valence bond methods, the radical chemistry, the modelling of the transition states by applying geometric constraints, the long range interactions (ion - molecule) in gaseous phase, the reaction sites in gaseous phase and the mass spectroscopy applications. The points of convergence between the investigations of the mass spectroscopy and the theoretical chemistry teams, as well as the purposes guiding the research programs, are discussed. The published papers, the conferences, the congress communications and the thesis, are also reported [fr

  2. Investigation of reaction mechanisms during electroreduction of carbon dioxide on lead electrode for the production of organic compounds

    International Nuclear Information System (INIS)

    Innocent, B.

    2008-09-01

    The aim of this work was to promote the reduction of CO 2 through its electrochemical conversion (electro-synthesis) on a lead electrode into high added value products. Depending on the nature of electrolyte, the electro-reduction of carbon dioxide leads to different products. Various electrolytes (aqueous or organic, protic or aprotic) were used to study two mechanisms: hydrogenation (formation of formate) and electro-dimerization (synthesis of oxalate). Cyclic voltammetry studies have been carried out for electrochemically characterizing CO 2 reduction on Pb. The electrochemical investigation of the electrode electrolyte interface has shown that the process of CO 2 electro-reduction is a mass transfer control both in the organic and aqueous media. Electrochemical experiments (cyclic voltammetry, chrono-amperometry) coupled with in situ infrared reflectance spectroscopic techniques (SPAIRS, SNIFTIRS) have also shown that in aqueous medium (7 ≤pH≤9) hydrogeno-carbonate ions were reduced to formate. The modification of solvent (propylene carbonate) leads selectively to oxalate as the main reaction product. Long-term electrolyses were performed in a filter-press cell to deal large volumes. In aqueous medium, the reduction of HCO 3 - to HCOO - (R F = 89% at -2.5 mA cm -2 and 4 C) is always accompanied by the production of H 2 . (author)

  3. 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.

  4. Chemical kinetics and reaction mechanism

    International Nuclear Information System (INIS)

    Jung, Ou Sik; Park, Youn Yeol

    1996-12-01

    This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

  5. Lead extraction from Cathode Ray Tube (CRT) funnel glass: Reaction mechanisms in thermal reduction with addition of carbon (C).

    Science.gov (United States)

    Lu, Xingwen; Ning, Xun-An; Chen, Da; Chuang, Kui-Hao; Shih, Kaimin; Wang, Fei

    2018-06-01

    This study quantitatively determined the extraction of lead from CRT funnel glass and examined the mechanisms of thermally reducing lead in the products of sintering Pb-glass with carbon in the pre-heated furnace. The experimentally derived results indicate that a 90.3 wt% lead extraction efficiency can be achieved with 20 wt% of C addition at 950 °C for 3 min under air. The formation of viscous semi-liquid glass blocked the oxygen supply between the interaction of C and Pb-glass, and was highly effective for the extraction of metallic Pb. A maximum of 87.3% lead recover was obtained with a C to Na 2 CO 3 ratio of 1/3 at 1200 °C. The decrease of C/Na 2 CO 3 ratio enhanced the metallic lead recovery by increasing the glass viscosity for effective sedimentation of metallic lead in the bottom. However, with the further increase of temperature and treatment time, re-vitrification of lead back to silicate-glass matrix was detected in both Pb-glass/C and Pb-glass/C/Na 2 CO 3 systems. The findings indicated that with proper controls, using C as an inexpensive reagent can effectively reduce treatment time and energy, which is crucial to a waste-to-resource technology for economically recovering lead from the waste CRT glass. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Hadron reaction mechanisms

    International Nuclear Information System (INIS)

    Collins, P.D.B.; Martin, A.D.

    1982-01-01

    The mechanism of hadron scattering at high energies are reviewed in such a way as to combine the ideas of the parton model and quantum chromodynamics (QCD) with Regge theory and phenomenology. After a brief introduction to QCD and the basic features of hadron scattering data, scaling and the dimensional counting rules, the parton structure of hadrons, and the parton model for large momentum transfer processes, including scaling violations are discussed. Hadronic jets and the use of parton ideas in soft scattering processes are examined, attention being paid to Regge theory and its applications in exclusive and inclusive reactions, the relationship to parton exchange being stressed. The mechanisms of hadron production which build up cross sections, and hence the underlying Regge singularities, and the possible overlap of Regge and scaling regions are discussed. It is concluded that the key to understanding hadron reaction mechanisms seems to lie in the marriage of Regge theory with QCD. (author)

  7. Recyclization reactions leading to benzimidazoles

    International Nuclear Information System (INIS)

    Mamedov, Vakhid A; Murtazina, Anna M

    2011-01-01

    The published data on the recyclization reactions that afford benzimidazoles are generalized and systematized. Both classical and new methods of benzimidazole synthesis are considered. Attention is focused on the publications over the recent 10-15 years; of the earlier publications, only those unknown to the wide circle of chemists are analyzed.

  8. Recyclization reactions leading to benzimidazoles

    Science.gov (United States)

    Mamedov, Vakhid A.; Murtazina, Anna M.

    2011-05-01

    The published data on the recyclization reactions that afford benzimidazoles are generalized and systematized. Both classical and new methods of benzimidazole synthesis are considered. Attention is focused on the publications over the recent 10-15 years; of the earlier publications, only those unknown to the wide circle of chemists are analyzed.

  9. Reaction mechanisms of metal complexes

    CERN Document Server

    Hay, R W

    2000-01-01

    This text provides a general background as a course module in the area of inorganic reaction mechanisms, suitable for advanced undergraduate and postgraduate study and/or research. The topic has important research applications in the metallurgical industry and is of interest in the science of biochemistry, biology, organic, inorganic and bioinorganic chemistry. In addition to coverage of substitution reactions in four-, five- and six-coordinate complexes, the book contains further chapters devoted to isomerization and racemization reactions, to the general field of redox reactions, and to the reactions of coordinated ligands. It is relevant in other fields such as organic, bioinorganic and biological chemistry, providing a bridge to organic reaction mechanisms. The book also contains a chapter on the kinetic background to the subject with many illustrative examples which should prove useful to those beginning research. Provides a general background as a course module in the area of inorganic reaction mechanis...

  10. 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)

  11. Analysis of kinetic reaction mechanisms

    CERN Document Server

    Turányi, Tamás

    2014-01-01

    Chemical processes in many fields of science and technology, including combustion, atmospheric chemistry, environmental modelling, process engineering, and systems biology, can be described by detailed reaction mechanisms consisting of numerous reaction steps. This book describes methods for the analysis of reaction mechanisms that are applicable in all these fields. Topics addressed include: how sensitivity and uncertainty analyses allow the calculation of the overall uncertainty of simulation results and the identification of the most important input parameters, the ways in which mechanisms can be reduced without losing important kinetic and dynamic detail, and the application of reduced models for more accurate engineering optimizations. This monograph is invaluable for researchers and engineers dealing with detailed reaction mechanisms, but is also useful for graduate students of related courses in chemistry, mechanical engineering, energy and environmental science and biology.

  12. Mechanism of lead removal by waste materials

    International Nuclear Information System (INIS)

    Qaiser, S.; Saleemi, A.R.; Ahmed, M.M.

    2007-01-01

    Heavy metal ions are priority pollutants, due to their toxicity and mobility in natural water ecosystems. The discharge of heavy metals into aquatic ecosystems has become a matter of concern in Pakistan over the last few decades. These contaminants are introduced into the aquatic systems significantly as a result of various industrial operations. The metals of concern include lead, chromium, zinc, copper, nickel and uranium. Lead is one of the most hazardous and toxic metals. It is used as industrial raw material in the manufacture of storage batteries, pigments, leaded glass, fuels, photographic materials, matches and explosives. Conventional methods for treatment of dissolved lead include precipitation, adsorption, coagulation/notation, sedimentation, reverse osmosis and ion exchange. Each process has its merits and limitations in applications. Adsorption by activated carbon and ion exchange using commercial ion exchange resins are very expensive processes, especially for a developing country like Pakistan. The present research was conducted to identify some waste materials, which can be utilized to remove lead from industrial wastewater. Natural wastes in the form of leaves and ash have considerable amounts of CaO, MgO, Na/sub 2/O, SiO/sub 2/ and Al/sub 2/O/sub 3/ which can be utilized for precipitation and adsorption. Utilization of waste materials to remove lead from industrial wastewater is the basic theme of this research. The waste materials used in this research were maple leaves, pongamia pinata leaves, coal ash and maple ago leave ash. Parameters studied were reaction time, precipitant dose, pH and temperature. It was found that maple leaves ash has maximum lead removal capacity 19.24 mg g/sup -1/ followed by coal ash 13.2 mg g/sup -1/. The optimal pH was 5 for maple leaves and pongamia Pinata leaves; and 4 for coal ash and maple leaves ash. Removal capacity decreased with increase in temperature. The major removal mechanisms were adsorption and

  13. Reaction mechanisms in zeolite catalysis

    NARCIS (Netherlands)

    Rozanska, X.; Santen, van R.A.; Auerbach, S.C.; Carrado, K.A.; Dutta, P.D.

    2003-01-01

    A review; described are the most basic mechanistic reaction steps that are induced by zeolite catalysts. Details on the zeolitic properties that are relevant to mol. reactivity are also provided. The theor. methods and models at hand to allow the investigation of these reaction steps and that have

  14. Use of Isotopes for Studying Reaction Mechanisms

    Indian Academy of Sciences (India)

    of atoms during a chemical transformation. This strategy of determining reaction mechanisms is illustrated in the article with several examples. Introduction. When a reaction is carried out, the primary effort goes towards the identification of the product(s) of the reaction. A more time consuming endeavour, however, is the ...

  15. Lead free solder mechanics and reliability

    CERN Document Server

    Pang, John Hock Lye

    2012-01-01

    Lead-free solders are used extensively as interconnection materials in electronic assemblies and play a critical role in the global semiconductor packaging and electronics manufacturing industry. Electronic products such as smart phones, notebooks and high performance computers rely on lead-free solder joints to connect IC chip components to printed circuit boards. Lead Free Solder: Mechanics and Reliability provides in-depth design knowledge on lead-free solder elastic-plastic-creep and strain-rate dependent deformation behavior and its application in failure assessment of solder joint reliability. It includes coverage of advanced mechanics of materials theory and experiments, mechanical properties of solder and solder joint specimens, constitutive models for solder deformation behavior; numerical modeling and simulation of solder joint failure subject to thermal cycling, mechanical bending fatigue, vibration fatigue and board-level drop impact tests. This book also: Discusses the mechanical prope...

  16. Morphing of the Dissipative Reaction Mechanism

    International Nuclear Information System (INIS)

    Schroeder, W.U.; Toke, J.; Gawlikowicz, W.; Houck, M.A.; Lu, J.; Pienkowski, L.

    2003-01-01

    Important trends in the evolution of heavy-ion reaction mechanisms with bombarding energy and impact parameter are reviewed. Essential features of dissipative reactions appear preserved at E/A = 50-62 MeV, such as dissipative orbiting and multi-nucleon exchange. The relaxation of the A/Z asymmetry with impact parameter is slow. Non-equilibrium emission of light particles and clusters is an important process accompanying the evolution of the mechanism. Evidence is presented for a new mechanism of statistical cluster emission from hot, metastable primary reaction products, driven by surface entropy. These results suggest a plausible reinterpretation of multi-fragmentation. (authors)

  17. Morphing of the Dissipative Reaction Mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, W.U.; Toke, J.; Gawlikowicz, W.; Houck, M.A.; Lu, J.; Pienkowski, L. [Rochester Univ., Dept. of Chemistry, Rochester, NY (United States)

    2003-07-01

    Important trends in the evolution of heavy-ion reaction mechanisms with bombarding energy and impact parameter are reviewed. Essential features of dissipative reactions appear preserved at E/A = 50-62 MeV, such as dissipative orbiting and multi-nucleon exchange. The relaxation of the A/Z asymmetry with impact parameter is slow. Non-equilibrium emission of light particles and clusters is an important process accompanying the evolution of the mechanism. Evidence is presented for a new mechanism of statistical cluster emission from hot, metastable primary reaction products, driven by surface entropy. These results suggest a plausible reinterpretation of multi-fragmentation. (authors)

  18. 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.

  19. Enhancement Mechanisms of Low Energy Nuclear Reactions

    OpenAIRE

    Gareev, F. A.; Zhidkova, I. E.

    2005-01-01

    The review of possible stimulation mechanisms of LENR (low energy nuclear reaction) is represented. We have concluded that transmutation of nuclei at low energies and excess heat are possible in the framework of the modern physical theory - the universal resonance synchronization principle [1] and based on its different enhancement mechanisms of reaction rates are responsible for these processes [2]. The excitation and ionization of atoms may play role as a trigger for LENR. Superlow energy o...

  20. Nuclear excitations and reaction mechanisms

    International Nuclear Information System (INIS)

    Fallieros, S.; Levin, F.S.

    1990-01-01

    The main theme of this report is the study and interpretation of the sequence of events that occur during the collisions of nuclear particles. Some of the processes discussed in parts A and B involve short range interactions; others involve interactions of long range. In most of part A one of the particles in the initial or in the final state (or in both) is a photon, which serves as a probe of the second particle, which may be a nucleus, a proton, a pion or any other hadron. The complexity of the processes taking place during the collisions makes it necessary to simplify some aspects of the physical problem. This leads to the introduction of modals which are used to describe a limited number of features in as much detail as possible. The main interest is the understanding of the hadronic excitations which result from the absorption of a photon and the determination of the fundamental structure constants of the target particle. In part B, all the particles are hadrons. The purpose here is to develop and apply optimal quantal methods appropriate for describing the interacting systems. Of particular interest are three-particle collision systems in which the final state consists of three free particles. Part B also considers the process of nuclear fusion as catalyzed by bound muons

  1. Bimolecular reactions of carbenes: Proton transfer mechanism

    Science.gov (United States)

    Abu-Saleh, Abd Al-Aziz A.; Almatarneh, Mansour H.; Poirier, Raymond A.

    2018-04-01

    Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol-1 compared to the recently reported value of 128 kJ mol-1 for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies.

  2. 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

  3. Mechanisms of inorganic and organometallic reactions

    CERN Document Server

    The purpose of this series is to provide a continuing critical review of the literature concerned with mechanistic aspects of inorganic and organo­ metallic reactions in solution, with coverage being complete in each volume. The papers discussed are selected on the basis of relevance to the elucidation of reaction mechanisms and many include results of a nonkinetic nature when useful mechanistic information can be deduced. The period of literature covered by this volume is July 1982 through December 1983, and in some instances papers not available for inclusion in the previous volume are also included. Numerical results are usually reported in the units used by the original authors, except where data from different papers are com­ pared and conversion to common units is necessary. As in previous volumes material included covers the major areas of redox processes, reactions of the nonmetallic elements, reaction of inert and labile metal complexes and the reactions of organometallic compounds. While m...

  4. Biosorption of lead phosphates by lead-tolerant bacteria as a mechanism for lead immobilization.

    Science.gov (United States)

    Rodríguez-Sánchez, Viridiana; Guzmán-Moreno, Jesús; Rodríguez-González, Vicente; Flores-de la Torre, Juan Armando; Ramírez-Santoyo, Rosa María; Vidales-Rodríguez, Luz Elena

    2017-08-01

    The study of metal-tolerant bacteria is important for bioremediation of contaminated environments and development of green technologies for material synthesis due to their potential to transform toxic metal ions into less toxic compounds by mechanisms such as reduction, oxidation and/or sequestration. In this study, we report the isolation of seven lead-tolerant bacteria from a metal-contaminated site at Zacatecas, México. The bacteria were identified as members of the Staphylococcus and Bacillus genera by microscopic, biochemical and 16S rDNA analyses. Minimal inhibitory concentration of these isolates was established between 4.5 and 7.0 mM of Pb(NO 3 ) 2 in solid and 1.0-4.0 mM of Pb(NO 3 ) 2 in liquid media. A quantitative analysis of the lead associated to bacterial biomass in growing cultures, revealed that the percentage of lead associated to biomass was between 1 and 37% in the PbT isolates. A mechanism of complexation/biosorption of lead ions as inorganic phosphates (lead hydroxyapatite and pyromorphite) in bacterial biomass, was determined by Fourier transform infrared spectroscopy and X-ray diffraction analyses. Thus, the ability of the lead-tolerant isolates to transform lead ions into stable and highly insoluble lead minerals make them potentially useful for immobilization of lead in mining waste.

  5. Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

    Science.gov (United States)

    Gao, Connie W.; Allen, Joshua W.; Green, William H.; West, Richard H.

    2016-06-01

    Reaction Mechanism Generator (RMG) constructs kinetic models composed of elementary chemical reaction steps using a general understanding of how molecules react. Species thermochemistry is estimated through Benson group additivity and reaction rate coefficients are estimated using a database of known rate rules and reaction templates. At its core, RMG relies on two fundamental data structures: graphs and trees. Graphs are used to represent chemical structures, and trees are used to represent thermodynamic and kinetic data. Models are generated using a rate-based algorithm which excludes species from the model based on reaction fluxes. RMG can generate reaction mechanisms for species involving carbon, hydrogen, oxygen, sulfur, and nitrogen. It also has capabilities for estimating transport and solvation properties, and it automatically computes pressure-dependent rate coefficients and identifies chemically-activated reaction paths. RMG is an object-oriented program written in Python, which provides a stable, robust programming architecture for developing an extensible and modular code base with a large suite of unit tests. Computationally intensive functions are cythonized for speed improvements.

  6. Alcali-silica reactions: Mechanisms for crack formations

    DEFF Research Database (Denmark)

    Goltermann, Per

    2006-01-01

    Alkali-silica reactions (ASR) are found all over the world and cause a large number of damage, which have lead to different sets of requirements in the different countries for the aggregates, the cements and the admixtures. One of the reasons for the damage and the different requirements is that ......Alkali-silica reactions (ASR) are found all over the world and cause a large number of damage, which have lead to different sets of requirements in the different countries for the aggregates, the cements and the admixtures. One of the reasons for the damage and the different requirements...... is that the mechanical behavior of the ASR has not been fully investigated, although the chemical aspects of ASR have been dealt with in depth. This paper presents a unified, mechanical explanation of the ASR damage mechanism, covering the relevant aspects of the diffusion model; the stress-variations in the aggregate...

  7. Fracture mechanisms in lead zirconate titanate ceramics

    International Nuclear Information System (INIS)

    Freiman, S.W.; Chuck, L.; Mecholsky, J.J.; Shelleman, D.L.

    1986-01-01

    Lead Zirconate Titanate (PZT) ceramics can be formed over a wide range of PbTiO 3 /PbZrO 3 ratios and exist in a number of crystal structures. This study involved the use of various fracture mechanics techniques to determine critical fracture toughness, K /SUB IC/ , as a function of composition, microstructure, temperature, and electrical and thermal history. The results of these experiments indicate that variations in K /SUB IC/ are related to phase transformations in the material as well as to other toughening mechanisms such as twinning and microcracking. In addition, the strength and fracture toughness of selected PZT ceramics were determined using specimens in which a crack was introduced by a Vicker's hardness indentor. The variation of K /SUB IC/ with composition and microstructure was related to the extent of twin-crack interaction. Comparison of the plot of strength as a function of indentation load with that predicted from indentation fracture models indicates the presence of internal stresses which contribute to failure. The magnitude of these internal stresses has been correlated with electrical properties of the ceramic. Fractographic analysis was used to determine the magnitude of internal stresses in specimens failing from ''natural flaws.''

  8. Elucidating reaction mechanisms on quantum computers

    Science.gov (United States)

    Reiher, Markus; Wiebe, Nathan; Svore, Krysta M.; Wecker, Dave; Troyer, Matthias

    2017-07-01

    With rapid recent advances in quantum technology, we are close to the threshold of quantum devices whose computational powers can exceed those of classical supercomputers. Here, we show that a quantum computer can be used to elucidate reaction mechanisms in complex chemical systems, using the open problem of biological nitrogen fixation in nitrogenase as an example. We discuss how quantum computers can augment classical computer simulations used to probe these reaction mechanisms, to significantly increase their accuracy and enable hitherto intractable simulations. Our resource estimates show that, even when taking into account the substantial overhead of quantum error correction, and the need to compile into discrete gate sets, the necessary computations can be performed in reasonable time on small quantum computers. Our results demonstrate that quantum computers will be able to tackle important problems in chemistry without requiring exorbitant resources.

  9. Elucidating reaction mechanisms on quantum computers

    Science.gov (United States)

    Reiher, Markus; Wiebe, Nathan; Svore, Krysta M.; Wecker, Dave; Troyer, Matthias

    2017-01-01

    With rapid recent advances in quantum technology, we are close to the threshold of quantum devices whose computational powers can exceed those of classical supercomputers. Here, we show that a quantum computer can be used to elucidate reaction mechanisms in complex chemical systems, using the open problem of biological nitrogen fixation in nitrogenase as an example. We discuss how quantum computers can augment classical computer simulations used to probe these reaction mechanisms, to significantly increase their accuracy and enable hitherto intractable simulations. Our resource estimates show that, even when taking into account the substantial overhead of quantum error correction, and the need to compile into discrete gate sets, the necessary computations can be performed in reasonable time on small quantum computers. Our results demonstrate that quantum computers will be able to tackle important problems in chemistry without requiring exorbitant resources. PMID:28674011

  10. Elucidating reaction mechanisms on quantum computers.

    Science.gov (United States)

    Reiher, Markus; Wiebe, Nathan; Svore, Krysta M; Wecker, Dave; Troyer, Matthias

    2017-07-18

    With rapid recent advances in quantum technology, we are close to the threshold of quantum devices whose computational powers can exceed those of classical supercomputers. Here, we show that a quantum computer can be used to elucidate reaction mechanisms in complex chemical systems, using the open problem of biological nitrogen fixation in nitrogenase as an example. We discuss how quantum computers can augment classical computer simulations used to probe these reaction mechanisms, to significantly increase their accuracy and enable hitherto intractable simulations. Our resource estimates show that, even when taking into account the substantial overhead of quantum error correction, and the need to compile into discrete gate sets, the necessary computations can be performed in reasonable time on small quantum computers. Our results demonstrate that quantum computers will be able to tackle important problems in chemistry without requiring exorbitant resources.

  11. Reaction mechanisms in heavy ion fusion

    Directory of Open Access Journals (Sweden)

    Lubian J.

    2011-10-01

    Full Text Available We discuss the reaction mechanisms involved in heavy ion fusion. We begin with collisions of tightly bound systems, considering three energy regimes: energies above the Coulomb barrier, energies just below the barrier and deep sub-barrier energies. We show that channel coupling effects may influence the fusion process at above-barrier energies, increasing or reducing the cross section predicted by single barrier penetration model. Below the Coulomb barrier, it enhances the cross section, and this effect increases with the system’s size. It is argued that this behavior can be traced back to the increasing importance of Coulomb coupling with the charge of the collision partners. The sharp drop of the fusion cross section observed at deep sub-barrier energies is addressed and the theoretical approaches to this phenomenon are discussed. We then consider the reaction mechanisms involved in fusion reactions of weakly bound systems, paying particular attention to the calculations of complete and incomplete fusion available in the literature.

  12. Light ion reaction mechanisms and nuclear structure

    International Nuclear Information System (INIS)

    Robson, B.A.

    1986-01-01

    Of the many contributions to the subject 'Light ion reaction mechanism and nuclear structure', a few are selected and reviewed which highlight the present state of the field. Some contributions to the conference dealing with nuclear interactions are briefly outlined in the second section following an introductory section. Lane model calculations are compared with data for 9 Be and results are given showing angular distributions of the cross sections, the analyzing powers and the spin-rotation parameters for p - 40 Ca. Real central potential for d + 32 s resulting from the FB-analysis are compared with frozen density folding and delta-function folding. The third section deals with reaction mechanism. Data are cited which show near-side and far-side contributions to the calculated analyzing powers in the 116 Sn(d,p) 117 Sn (11.2 - ) transition. Calculations are compared with experimental A y and -(A yy + 2)/3. Also given are measurements of the cross sections and analyzing powers of the continuum energy spectra for the 58 Ni(p,p'x), along with relations between the analyzing powers and momentum transfer. The fourth section addresses nuclear structure. Cross sections and analyzing powers measured at 22 MeV for the reaction 208 Pb(p,t) 206 Pb(3 2 + ) are cited and considered. (Nogami, K.)

  13. Solid-state reactions to synthesize nanostructured lead selenide semiconductor powders by high-energy milling

    Energy Technology Data Exchange (ETDEWEB)

    Rojas-Chavez, H., E-mail: uu_gg_oo@yahoo.com.mx [Centro de Investigacion e Innovacion Tecnologica - IPN, Cerrada de CECATI s/n, Col. Santa Catarina, Del. Azcapotzalco (Mexico) and Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada - IPN, Legaria 694, Col. Irrigacion, Del. Miguel Hidalgo (Mexico); Reyes-Carmona, F. [Facultad de Quimica - UNAM, Circuito de la Investigacion Cientifica s/n, C.U. Del. Coyoacan (Mexico); Jaramillo-Vigueras, D. [Centro de Investigacion e Innovacion Tecnologica - IPN, Cerrada de CECATI s/n, Col. Santa Catarina, Del. Azcapotzalco (Mexico)

    2011-10-15

    Highlights: {yields} PbSe synthesized from PbO instead of Pb powder do not require an inert atmosphere. {yields} During high-energy milling oxygen has to be chemically reduced from the lead oxide. {yields} Solid-state and solid-gas chemical reactions promote both solid and gaseous products. -- Abstract: Both solid-solid and gas-solid reactions have been traced during high-energy milling of Se and PbO powders under vial (P, T) conditions in order to synthesize the PbSe phase. Chemical and thermodynamic arguments are postulated to discern the high-energy milling mechanism to transform PbO-Se micropowders onto PbSe-nanocrystals. A set of reactions were evaluated at around room temperature. Therefore an experimental campaign was designed to test the nature of reactions in the PbO-Se system during high-energy milling.

  14. Solid-state reactions to synthesize nanostructured lead selenide semiconductor powders by high-energy milling

    International Nuclear Information System (INIS)

    Rojas-Chavez, H.; Reyes-Carmona, F.; Jaramillo-Vigueras, D.

    2011-01-01

    Highlights: → PbSe synthesized from PbO instead of Pb powder do not require an inert atmosphere. → During high-energy milling oxygen has to be chemically reduced from the lead oxide. → Solid-state and solid-gas chemical reactions promote both solid and gaseous products. -- Abstract: Both solid-solid and gas-solid reactions have been traced during high-energy milling of Se and PbO powders under vial (P, T) conditions in order to synthesize the PbSe phase. Chemical and thermodynamic arguments are postulated to discern the high-energy milling mechanism to transform PbO-Se micropowders onto PbSe-nanocrystals. A set of reactions were evaluated at around room temperature. Therefore an experimental campaign was designed to test the nature of reactions in the PbO-Se system during high-energy milling.

  15. The mechanism of the modified Ullmann reaction

    NARCIS (Netherlands)

    Sperotto, Elena; Klink, Gerard P.M. van; Koten, Gerard van; Vries, Johannes G. de

    2010-01-01

    The copper-mediated aromatic nucleophilic substitution reactions developed by Fritz Ullmann and Irma Goldberg required stoichiometric amounts of copper and very high reaction temperatures. Recently, it was found that addition of relatively cheap ligands (diamines, aminoalcohols, diketones, diols)

  16. Microchannel boiling mechanisms leading to burnout

    International Nuclear Information System (INIS)

    Landram, C.S.; Riddle, R.A.

    1994-01-01

    The authors are analyzing the thermal performance of microchannel heat sinks to extend their applied heat loads beyond coolant single-phase limits. This is the first investigation of boiling in the narrow (50-μm) microchannels having typically high-aspect-ratio (of order 10/1) flow cross-sections. The prescription of local, wall-coolant, interfacial, two-phase correlations first required development of a validated, approximate, thermal-model accounting for conjugate heat transfer. The strongest mechanism for heat transfer in two-phase microchannel flow was found to be saturated boiling in a channel region near the heated base. When this region dried out, burnout occurred, both in the computations and in the experiment

  17. Insights into the mechanisms on chemical reactions: reaction paths for chemical reactions

    International Nuclear Information System (INIS)

    Dunning, T.H. Jr.; Rosen, E.; Eades, R.A.

    1987-01-01

    We report reaction paths for two prototypical chemical reactions: Li + HF, an electron transfer reaction, and OH + H 2 , an abstraction reaction. In the first reaction we consider the connection between the energetic terms in the reaction path Hamiltonian and the electronic changes which occur upon reaction. In the second reaction we consider the treatment of vibrational effects in chemical reactions in the reaction path formalism. 30 refs., 9 figs

  18. Reaction mechanism of dicofol removal by cellulase.

    Science.gov (United States)

    Wang, Ziyuan; Yang, Ting; Zhai, Zihan; Zhang, Boya; Zhang, Jianbo

    2015-10-01

    It remains unclear whether dicofol should be defined as a persistent organic pollutant. Its environmental persistence has gained attention. This study focused on its degradation by cellulase. Cellulase was separated using a gel chromatogram, and its degradation activity towards dicofol involved its endoglucanase activity. By analyzing the kinetic parameters of cellulase reacting with mixed substrates, it was shown that cellulase reacted on dicofol and carboxyl methyl cellulose through two different active centers. Thus, the degradation of dicofol was shown to be an oxidative process by cellulase. Next, by comparing the impacts of tert-butyl alcohol (a typical OH free-radical inhibitor) on the removal efficiencies of dicofol under both cellulase and Fenton reagent systems, it was shown that the removal of dicofol was initiated by OH free radicals produced by cellulase. Finally, 4,4'-dichloro-dibenzophenone and chloride were detected using gas chromatography mass spectrometry and ion chromatography analysis, which supported our hypothesis. The reaction mechanism was analyzed and involved an attack by OH free radicals at the orthocarbon of dicofol, resulting in the degradation product 4,4'-dichloro-dibenzophenone. Copyright © 2015. Published by Elsevier B.V.

  19. Report on research in progress in the reaction mechanism area

    International Nuclear Information System (INIS)

    Toledo, A.S. de; Canto, L.F.

    1982-01-01

    Research on reaction mechanisms which are being done by several groups in Brazil are reported. They are grouped in four types, namely, reactions induced by heavy and light ions, induced by electrons and finally by photons. (L.C.) [pt

  20. Report on research in progress in the reaction mechanism area

    Energy Technology Data Exchange (ETDEWEB)

    Toledo, A.S. de; Canto, L F [Sao Paulo Univ. (Brazil). Inst. de Fisica

    1982-09-01

    Research on reaction mechanisms which are being done by several groups in Brazil are reported. They are grouped in four types, namely, reactions induced by heavy and light ions, induced by electrons and finally by photons.

  1. 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.

  2. Reaction Mechanisms of Magnesium Potassium Phosphate Cement and its Application

    Science.gov (United States)

    Qiao, Fei

    magnesia. With the increase of magnesium ions in the solution, MgHPO4·7H2O is the first product precipitated, and its crystallization is accompanied with the increase of both pH and temperature. Beyond pH of 7, MgHPO4·7H 2O is transformed to Mg2KH(PO4)2·15H 2O, leading to a slight decrease of pH. The following dramatic increase of pH may be due to the formation of Mg2KH(PO4) 2·15H2O. Finally, Mg2KH(PO4) 2·15H2O gradually transforms to MgKPO4·6H 2O and leads to the second decrease of pH. Both increasing molar ratio of magnesium to phosphate (M/P) and decreasing the weight ratio of liquid to solid can speed up the reaction rate while addition of small amount of boron compounds can prolong the process even though the products are not changed. The retarding mechanism of boron compounds is related to their buffering effect on the pH of the solution, i.e. decreasing pH development rate, leads to delaying the formation of reaction products. The performance of MKPC based cementitious materials can be significantly influenced by M/P molar ratio, addition of setting retarder, water content, fly ash replacement of magnesia and aggregate usage. Therefore, the formulation of MKPC based materials is optimized in terms of workability, compressive strength, and cost consideration. With optimized formulation, MKPC mortars show high early compressive and flexural strength, superior bond strength to ordinary Portland cement mortar/concrete substrate, and low drying shrinkage. Undoubtedly, the mechanical properties of this cement is closely related to its inner composition and microstructure. The microstructure examination shows that the phase assemblage and the morphology characteristics of MKPC paste vary with the different formulae. In the formulation with lower M/P ratio of 2, KH2PO4 residues can be found in a flat, smooth, and bulky mass form. The reaction product MgKPO4·6H2O, can be observed as acicular crystal habit with large aspect ratio of 30. With the increase of M/P ratio

  3. Reaction mechanism of reductive decomposition of FGD gypsum with anthracite

    International Nuclear Information System (INIS)

    Zheng, Da; Lu, Hailin; Sun, Xiuyun; Liu, Xiaodong; Han, Weiqing; Wang, Lianjun

    2013-01-01

    Highlights: • The reaction mechanism was different if the molar ratio of C/CaSO 4 was different. • The yield of CaO rises with an increase in temperature. • The optimal ratio of C/CaSO 4 = 1.2:1. • The decomposition process is mainly apparent solid–solid reaction with liquid-phase involved. - Abstract: The process of decomposition reaction between flue gas desulfurization (FGD) gypsum and anthracite is complex, which depends on the reaction conditions and atmosphere. In this study, thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA-FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and the experiment in a tubular reactor were used to characterize the decomposition reaction in a nitrogen atmosphere under different conditions. The reaction mechanism analysis showed that the decomposition reaction process and mechanism were different when the molar proportion of C/CaSO 4 was changed. The experiment results showed that appropriate increase in the C/CaSO 4 proportion and higher temperatures were suitable for the formation of the main production of CaO, which can help us to understand the solid state reaction mechanism better. Via kinetic analysis of the reaction between anthracite and FGD gypsum under the optimal molar ratio of C/CaSO 4 , the mechanism model of the reaction was confirmed and the decomposition process was a two-step reaction which was in accordance with apparent solid–solid reaction

  4. 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.

  5. Investigations on organolead compounds V. Lead---lead bond cleavage reactions of hexaphenyldilead

    NARCIS (Netherlands)

    Willemsens, L.C.; Kerk, G.J.M. van der

    1968-01-01

    It has been shown that a number of nucleophilic and weakly electrophilic reagents (organolithium and organomagnesium compounds, metallic lithium, potassium permanganate, sodium ethoxide, diaryl disulphides, sulphur, ozone, hypochlorous acid and iodine/iodide) selectively cleave the lead---lead bond

  6. [Reaction mechanism studies of heavy ion induced nuclear reactions]: Annual progress report, October 1987

    International Nuclear Information System (INIS)

    Mignerey, A.C.

    1987-10-01

    The experiments which this group has been working on seek to define the reaction mechanisms responsible for complex fragment emission in heavy ion reactions. The reactions studied are La + La, La + Al, and La + Cu at 46.8 MeV/u; and Ne + Ag and Ne + Au reactions at 250 MeV/u. Another experimental program at the Oak Ridge Hollifield Heavy Ion Research Facility (HHIRF) is designed to measure the excitation energy division between reaction products in asymmetric deep inelastic reactions. A brief description is given of progress to date, the scientific goals of this experiment and the plastic phoswich detectors developed for this experiment

  7. Confining Domains Lead to Reaction Bursts: Reaction Kinetics in the Plasma Membrane

    Science.gov (United States)

    Kalay, Ziya; Fujiwara, Takahiro K.; Kusumi, Akihiro

    2012-01-01

    Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity. PMID:22479350

  8. Confining domains lead to reaction bursts: reaction kinetics in the plasma membrane.

    Directory of Open Access Journals (Sweden)

    Ziya Kalay

    Full Text Available Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity.

  9. KINETICS AND MECHANISM OF REACTION OF ACIDIC ...

    African Journals Online (AJOL)

    The kinetics and mechanism of the oxidation of two phenoxazine dyes namely Nile blue (7-amino-3-diethylamino-8,9-benzo phenoxazine chloride, NB+) and Meldola\\'s blue (3- dimethylamino-8,9-benzo phenoxazine chloride, MB+) with acidic chlorite and hypochlorous acid have been investigated using a UV-visible and a ...

  10. Nuclear excitations and reaction mechanisms. Progress report

    International Nuclear Information System (INIS)

    Fallieros, S.; Levin, F.S.

    1986-01-01

    Theoretical research is being conducted on the following topics: photon scattering, gauge invariance and the extension of Siefert's Theorem; retardation effects in photonuclear absorption and the Cabibbo Radicati Sum Rule; isovector transition densities, currents and response functions; the electric polarizability, the magnetic susceptibility and the distribution of oscillator strengths in some elementary systems; relativistic models and processes; properties of skyrmions; multiquark compound bags and the charge form factor of the A = 3 nuclei; nuclear reaction theory; three-particle scattering theory; deuteron-nucleus model calculations; asymptotia in three-particle scattering systems; and time-dependent approach to few-nucleon collisions. Progress in each of these areas is reviewed briefly. A list of invited talks and of publications for the fiscal year 1986 is included. 27 refs

  11. Centrality in Hadron-Carbon, Hadron-Lead, and Lead-Lead Reactions at 158 GeV/c

    International Nuclear Information System (INIS)

    Rybicki, A.

    2006-08-01

    A study of centrality in p + C, π + C, p + Pb, π + Pb, and Pb + Pb reactions is made. The analysis is performed by means of a simple geometrical model. The mean number of elementary collisions, , is estimated in minimum bias p + C reactions. For the specific case of the carbon nucleus, estimates on appear to depend strongly on assumed nuclear densities. Most realistic of the presented assumptions result in a value of 1.71 ± 0.05. Additional quantities, like predictions for the total inelastic cross-section in p + C reactions, or the number of participants in minimum bias C + C collisions, are given. The analysis is subsequently extended to minimum bias π + C, π + Pb, and p + Pb reactions. Estimates are given for the mean number of elementary collisions as well as for the contribution of single collisions P(1). A comparison with experimental data is made. Finally, the impact parameter dependence of p + Pb and Pb + Pb collisions is discussed. In view of future studies, various aspects of the analysis are discussed in detail; a bibliography of used references is included. (author)

  12. Kinetic mechanism for modeling of electrochemical reactions.

    Science.gov (United States)

    Cervenka, Petr; Hrdlička, Jiří; Přibyl, Michal; Snita, Dalimil

    2012-04-01

    We propose a kinetic mechanism of electrochemical interactions. We assume fast formation and recombination of electron donors D- and acceptors A+ on electrode surfaces. These mediators are continuously formed in the electrode matter by thermal fluctuations. The mediators D- and A+, chemically equivalent to the electrode metal, enter electrochemical interactions on the electrode surfaces. Electrochemical dynamics and current-voltage characteristics of a selected electrochemical system are studied. Our results are in good qualitative agreement with those given by the classical Butler-Volmer kinetics. The proposed model can be used to study fast electrochemical processes in microsystems and nanosystems that are often out of the thermal equilibrium. Moreover, the kinetic mechanism operates only with the surface concentrations of chemical reactants and local electric potentials, which facilitates the study of electrochemical systems with indefinable bulk.

  13. Lead telluride with increased mechanical stability for cylindrical thermoelectric generators

    International Nuclear Information System (INIS)

    Schmitz, Andreas

    2013-01-01

    The aim of this work is to improve the mechanical stability of lead telluride (PbTe), trying to vary its mechanical properties independently from its thermoelectric properties. Thus the influence of material preparation as well as different dopants on the mechanical and thermoelectric properties of lead telluride is being analysed. When using appropriately set process parameters, milling and sintering of lead telluride increases the material's hardness. With sintering temperatures exceeding 300 C stable material of high relative density can be achieved. Milling lead telluride generates lattice defects leading to a reduction of the material's charge carrier density. These defects can be reduced by increased sintering temperatures. Contamination of the powder due to the milling process leads to bloating during thermal cycling and thus reduced density of the sintered material. In addition to that, evaporation of tellurium at elevated temperatures causes instability of the material's thermoelectric properties. Based on the experimental results obtained in this work, the best thermoelectric and mechanical properties can be obtained by sintering coarse powders at around 400 C. Within this work a concept was developed to vary the mechanical properties of lead telluride via synthesis of PbTe with electrically nondoping elements, which thus may keep the thermoelectric properties unchanged. Therefore, the mechanical and thermoelectric properties of Pb 1-x Ca x Te were investigated. Doping pure PbTe with calcium causes a significant increase of the material's hardness while only slightly decreasing the charge carrier density and thus keeping the thermoelectric properties apart from a slight reduction of the electrical conductivity nearly unchanged. The abovementioned concept is proven using sodium doped lead telluride, as it is used for thermoelectric generators: The additional doping with calcium again increases the material's hardness while its thermoelectric properties

  14. Sugarcane bagasse gasification: Global reaction mechanism of syngas evolution

    International Nuclear Information System (INIS)

    Ahmed, I.I.; Gupta, A.K.

    2012-01-01

    Highlights: ► Gasification of sugarcane bagasse has been investigated using a semi batch reactor. ► Global reaction mechanism combining pyrolysis and gasification reactions is presented. ► High flow rates of syngas supported fragmentation and secondary reactions. ► CO flow rate increased at higher heating rates at the expense of CO 2 production. ► At high temperatures merger between pyrolysis and char gasification occurs. -- Abstract: Steam gasification of sugarcane bagasse has been investigated. A semi batch reactor with a fixed amount of sugarcane bagasse sample placed in steady flow of high temperature steam at atmospheric pressure has been used. The gasification of bagasse was examined at reactor and steam temperatures of 800, 900 and 1000 °C. The evolution of syngas flow rate and chemical composition has been monitored. The evolution of chemical composition and total flow rate of the syngas has been used to formulate a global reaction mechanism. The mechanism combines pyrolysis reaction mechanisms from the literature and steam gasification/reforming reactions. Steam gasification steps include steam–hydrocarbons reforming, char gasification and water gas shift reactions. Evidence of fragmentation, secondary ring opening reactions and tertiary reactions resulting in formation of gaseous hydrocarbons is supported by higher flow rates of syngas and hydrogen at high heating rates and high reactor temperatures. Increase in carbon monoxide flow rate at the expense of carbon dioxide flow rate with the increase in reactor temperature has been observed. This increase in the ratio of CO/CO 2 flow rate confirms the production of CO and CO 2 from the competing reaction routes. At 1000 °C gasification a total merging between the pyrolysis step and the char gasification step has been observed. This is attributed to acceleration of char gasification reactions and acceleration of steam–hydrocarbons reforming reactions. These hydrocarbons are the precursors to

  15. Electric reaction arising in bone subjected to mechanical loadings

    Science.gov (United States)

    Murasawa, Go; Cho, Hideo; Ogawa, Kazuma

    2006-03-01

    The aim of present study is the investigation of the electric reaction arising in bone subjected to mechanical loadings. Firstly, specimen was fabricated from femur of cow, and ultrasonic propagation in bone was measured by ultrasonic technique. Secondary, 4-point bending test was conducted up to fracture, and electric reaction arising in bone was measured during loading. Thirdly, cyclic 4-point bending test was conducted to investigate the effect of applied displacement speed on electric reaction.

  16. Reaction Mechanism of Mycobacterium Tuberculosis Glutamine Synthetase Using Quantum Mechanics/Molecular Mechanics Calculations.

    Science.gov (United States)

    Moreira, Cátia; Ramos, Maria J; Fernandes, Pedro Alexandrino

    2016-06-27

    This paper is devoted to the understanding of the reaction mechanism of mycobacterium tuberculosis glutamine synthetase (mtGS) with atomic detail, using computational quantum mechanics/molecular mechanics (QM/MM) methods at the ONIOM M06-D3/6-311++G(2d,2p):ff99SB//B3LYP/6-31G(d):ff99SB level of theory. The complete reaction undergoes a three-step mechanism: the spontaneous transfer of phosphate from ATP to glutamate upon ammonium binding (ammonium quickly loses a proton to Asp54), the attack of ammonia on phosphorylated glutamate (yielding protonated glutamine), and the deprotonation of glutamine by the leaving phosphate. This exothermic reaction has an activation free energy of 21.5 kcal mol(-1) , which is consistent with that described for Escherichia coli glutamine synthetase (15-17 kcal mol(-1) ). The participating active site residues have been identified and their role and energy contributions clarified. This study provides an insightful atomic description of the biosynthetic reaction that takes place in this enzyme, opening doors for more accurate studies for developing new anti-tuberculosis therapies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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.

  18. Reactions of a stable dialkylsilylene and their mechanisms

    Indian Academy of Sciences (India)

    Stable silylene; mechanisms; photoreaction; addition; insertion; DFT. 1. ... Some of these reactions provide useful ... Although much attention has been ... sis, structure, and spectroscopic properties of 1 that .... Because silylenes are usually in the singlet ground state ..... selective 1,2-/1,4-addition reactions of dialkylsilylenes.

  19. Tc1-mediated contact sensitivity reaction, its mechanism and regulation

    Directory of Open Access Journals (Sweden)

    Magdalena Zemelka-Wiącek

    2014-07-01

    Full Text Available The contact hypersensitivity reaction (CHS to haptens is a classic example of cell-mediated immune response. In the effector phase, two stages can be distinguished: an early component, that appears only 2 hours after subsequent contact with the hapten, and the late component that develops approximately 24 hours later which is mediated by TCRαβ+ cells. The effector lymphocytes may be CD4+ T helper 1 (Th1 cells or CD8+ T cytotoxic 1 (Tc1 cells, which depends on the employed hapten and/or mice strain. NKT lymphocytes play the crucial role in the CHS initiation, by supporting B1 cells in the antigen-specific IgM antibodies production. The development of an early component is essential for the recruitment of T effector (Teff cells to the side of hapten deposition and for the complete expansion of inflammatory reaction. The CHS reaction is under T regulatory (Treg cells control, both in the induction phase as well as in the effector phase. A new view of a negative regulation of the Tc1 mediated CHS response is based on the suppression induced by epicutaneous (EC application of protein antigen. The DNP-BSA skin application, on a gauze patch, leads to a state of immunosuppression. This maneuver results in rising the population of Treg cells with TCRαβ+CD4+CD25+Foxp3+ phenotype. The mechanism of suppression requires direct contact between Treg cells and Teff cells and the participation of CTLA-4 molecule is also necessary. The described method of evoking immune tolerance via EC immunization may contribute to elaborate a new method of allergic contact dermatitis therapy. This is because of its effectiveness, ease of induction and non-invasive protein antigen application.

  20. Effects of lead on the killing mechanisms of polymorphonuclear leukocytes

    International Nuclear Information System (INIS)

    Silberstein, C.F.

    1984-01-01

    The effects of lead on the killing mechanisms of rat polymorphonuclear leukocytes (PMN) were investigated, using male Long-Evans rats exposed to 1% lead acetate in the drinking water for varying periods of time to achieve blood lead levels ranging from 20-200 μg/dl. Studies of PMN bacterial and fungal killing activity, chemotaxis and phagocytosis demonstrated that: 1) bactericidal activity of PMN from rats exposed to lead was not altered; 2) chemotactic activity remained within normal limits; 3) the phagocytic ability of the PMN also remained unaltered. In addition to these normal findings, one major abnormality was demonstrated: a significant decrease in the ability of PMN from rats exposed to lead to kill Candida albicans. This defect was not related to age or to length of exposure. It could not be produced by addition of lead to the test system in vitro. Further investigation revealed significant decreases in PMN glucose-6-phosphate dehydrogenase, catalase, and myeloperoxidase activities. These data support two possible mechanisms for the abnormal fungicidal activity of PMN from lead-exposed rats: decrease in ability to reduce oxygen to active metabolites, or reduction in myeloperoxidase activity due to diminshed synthesis of the heme moiety required for its function

  1. Reaction mechanisms for barite dissolution and growth

    Energy Technology Data Exchange (ETDEWEB)

    Stack, Andrew G.

    2010-07-26

    In Stack and Rustad (2007), the reactive flux method (Rey and Hynes, 1996) and molecular dynamics (MD) were used to simulate the {001} barite-water interface structure and water exchange rate of aqueous barium ions and barium surface species. Atomic-level mineralwater interfacial structure and kinetics are being studied with increasing precision due to advances in spectroscopic methods at synchrotron x-ray sources as well as improved computational capacity. Better characterization of these interfaces in turn is leading to advances in the understanding of many macroscopic geochemical properties. Overall the barite-water interfacial structure was found to compare well to that estimated using X-ray reflectivity (XRR) measurements (Fenter et al., 2001), but there was an important difference: the MD predicted an intricate water structure present at the interface with one major peak and several minor peaks whereas the XRR found only a single layer of water. This discrepancy is thought to result from a limited resolution in the Fenter et al. (2001) study as well as over-coordination of surface sulfates by the MD model.

  2. Molecular extinction coefficients of lead sulfide and polymerized diaminobenzidine as final reaction products of histochemical phosphatase reactions

    NARCIS (Netherlands)

    van Noorden, C. J.; Jonges, G. N.

    1992-01-01

    Molar extinction coefficients of precipitated lead sulfide (PbS) and polymerized diaminobenzidine (polyDAB) have been determined at wavelengths of 450 nm and 480 nm, respectively, for quantitative histochemical analysis of phosphatase reactions. These values are essential for the conversion of

  3. Mechanism of the CO2-Ca(OH)2 reaction

    International Nuclear Information System (INIS)

    Chew, V.S.; Cheh, C.H.; Glass, R.W.

    1983-01-01

    Recent studies clearly showed the importance of moisture in achieving high Ca(OH) 2 absorbent utilization for removing CO 2 from gas streams at ambient temperatures. However, the role of moisture and the mechanism of the reaction was not well understood. This paper summarizes the results of a study of the mechanism of the CO 2 -Ca(OH) 2 reaction with emphasis on the role of moisture. The reaction between Ca(OH) 2 and CO 2 in moist N 2 was found to be first order with respect to the reactants with a rate constant of about 100 min -1 . At high humidities, the rate of reaction was chemically controlled, but at low humidities, the reaction rate was limited by the diffusion through the carbonate layer formed by the reaction. Calculations showed that capillary condensation could have occurred only in about 2% of the pore volume and was unlikely to have affected the reaction rate significantly by allowing the reaction to occur in the liquid phase. It was, therefore, concluded that the main role of moisture was to improve the Ca(OH) 2 utilization by lowering the resistance to diffusion through the carbonate layer

  4. A Light-Induced Reaction with Oxygen Leads to Chromophore Decomposition and Irreversible Photobleaching in GFP-Type Proteins.

    Science.gov (United States)

    Grigorenko, Bella L; Nemukhin, Alexander V; Polyakov, Igor V; Khrenova, Maria G; Krylov, Anna I

    2015-04-30

    Photobleaching and photostability of proteins of the green fluorescent protein (GFP) family are crucially important for practical applications of these widely used biomarkers. On the basis of simulations, we propose a mechanism for irreversible bleaching in GFP-type proteins under intense light illumination. The key feature of the mechanism is a photoinduced reaction of the chromophore with molecular oxygen (O2) inside the protein barrel leading to the chromophore's decomposition. Using quantum mechanics/molecular mechanics (QM/MM) modeling we show that a model system comprising the protein-bound Chro(-) and O2 can be excited to an electronic state of the intermolecular charge-transfer (CT) character (Chro(•)···O2(-•)). Once in the CT state, the system undergoes a series of chemical reactions with low activation barriers resulting in the cleavage of the bridging bond between the phenolic and imidazolinone rings and disintegration of the chromophore.

  5. Exploring chemical reaction mechanisms through harmonic Fourier beads path optimization.

    Science.gov (United States)

    Khavrutskii, Ilja V; Smith, Jason B; Wallqvist, Anders

    2013-10-28

    Here, we apply the harmonic Fourier beads (HFB) path optimization method to study chemical reactions involving covalent bond breaking and forming on quantum mechanical (QM) and hybrid QM∕molecular mechanical (QM∕MM) potential energy surfaces. To improve efficiency of the path optimization on such computationally demanding potentials, we combined HFB with conjugate gradient (CG) optimization. The combined CG-HFB method was used to study two biologically relevant reactions, namely, L- to D-alanine amino acid inversion and alcohol acylation by amides. The optimized paths revealed several unexpected reaction steps in the gas phase. For example, on the B3LYP∕6-31G(d,p) potential, we found that alanine inversion proceeded via previously unknown intermediates, 2-iminopropane-1,1-diol and 3-amino-3-methyloxiran-2-ol. The CG-HFB method accurately located transition states, aiding in the interpretation of complex reaction mechanisms. Thus, on the B3LYP∕6-31G(d,p) potential, the gas phase activation barriers for the inversion and acylation reactions were 50.5 and 39.9 kcal∕mol, respectively. These barriers determine the spontaneous loss of amino acid chirality and cleavage of peptide bonds in proteins. We conclude that the combined CG-HFB method further advances QM and QM∕MM studies of reaction mechanisms.

  6. The Electronic Flux in Chemical Reactions. Insights on the Mechanism of the Maillard Reaction

    Science.gov (United States)

    Flores, Patricio; Gutiérrez-Oliva, Soledad; Herrera, Bárbara; Silva, Eduardo; Toro-Labbé, Alejandro

    2007-11-01

    The electronic transfer that occurs during a chemical process is analysed in term of a new concept, the electronic flux, that allows characterizing the regions along the reaction coordinate where electron transfer is actually taking place. The electron flux is quantified through the variation of the electronic chemical potential with respect to the reaction coordinate and is used, together with the reaction force, to shed light on reaction mechanism of the Schiff base formation in the Maillard reaction. By partitioning the reaction coordinate in regions in which different process might be taking place, electronic reordering associated to polarization and transfer has been identified and found to be localized at specific transition state regions where most bond forming and breaking occur.

  7. Reaction mechanisms of ruthenium tetroxide mediated oxidations of organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Froehaug, Astrid Elisabeth

    1995-12-31

    This thesis reports a study of the mechanism of ruthenium tetroxide mediated oxidations of saturated hydrocarbons, ethers, alkenes and alcohols. Several methods were used. The RuO{sub 4}-mediated oxidations of adamantane and cis-decalin were studied in CCl{sub 4}-CH{sub 3}CN-H{sub 2}O and in acetone-water. The rate of reaction was found to be moderately influenced by the polarity of the solvent. Solvent properties other than the polarity were also found to influence the reaction rates. From the oxidations of adamantane and adamantane-1,3,5,7-d{sub 4} two primary kinetic deuterium isotope effects were found. These were comparable with the deuterium isotope effects found for the analogous oxidations of cis-decalin and cis-decalin-d{sub 18}. The results seem to exclude both a one step hydride abstraction reaction mechanism and a one step concerted mechanism, as well as a scheme where two such mechanisms compete. The observations may be explained by a two step reaction mechanism consisting of a pre-equilibrium with formation of a substrate-RuO{sub 4} complex followed by a concerted rate determining reaction. The RuO{sub 4}-mediated oxidation of ethers was of kinetic second order with a small enthalpy of activation and a large negative entropy of activation. Oxidation of cyclopropylmethyl methyl ether gave methyl cyclopropanecarboxylate, no rearranged products were observed. On RuO{sub 4} oxidations in CCl{sub 4} with NaIO{sub 4} as stoichiometric oxidant, no chlorinated products were observed. Several observations not in agreement with a hydride or a hydrogen abstraction mechanism may be explained by assuming that the reaction proceeds by either a concerted reaction or by a reversible oxidative addition of the ether to RuO{sub 4} followed by a slow concerted step. 228 refs., 9 figs., 27 tabs.

  8. Reaction mechanisms in cellulose pyrolysis: a literature review

    Energy Technology Data Exchange (ETDEWEB)

    Molton, P.M.; Demmitt, T.F.

    1977-08-01

    A bibliographic review of 195 references is presented outlining the history of the research into the mechanisms of cellulose pyrolysis. Topics discussed are: initial product identification, mechanism of initial formation of levoglucosan, from cellulose and from related compounds, decomposition of cellulose to other compounds, formation of aromatics, pyrolysis of levoglucosan, crosslinking of cellulose, pyrolytic reactions of cellulose derivatives, and the effects of inorganic salts on the pyrolysis mechanism. (JSR)

  9. Removing antimony from waste lead storage batteries alloy by vacuum displacement reaction technology.

    Science.gov (United States)

    Liu, Tiantian; Qiu, Keqiang

    2018-04-05

    With the wide application of lead acid battery, spent lead acid battery has become a serious problem to environmental protection and human health. Though spent battery can be a contaminant if not handled properly, it is also an important resource to obtain refined lead. Nowadays, the Sb-content in lead storage batteries is about 0.5-3 wt%, which is higher than the Sb-content in the crude lead. However, there are few reports about the process of removing antimony from high-antimony lead bullion. In this study, vacuum displacement reaction technology, a new process for removing antimony from high-antimony lead melts, was investigated. During this process, lead oxide was added to the system and antimony from lead melts was converted into antimony trioxide, which easily was evaporated under vacuum so that antimony was removed from lead melts. The experimental results demonstrated that Sb-content in lead melts decreased from 2.5% to 23 ppm under following conditions: mass ratio of PbO/lead bullion of 0.33, residual gas pressure of 30 Pa, melt temperature of 840 °C, reaction time of 60 min. The distillate gotten can be used as by-product to produce antimony white. Moreover, this study is of importance to recycling of waste lead storage batteries alloy. Copyright © 2018 Elsevier B.V. All rights reserved.

  10. Low Energy Electrons as Probing Tool for Astrochemical Reaction Mechanisms

    Science.gov (United States)

    Hendrik Bredehöft, Jan; Swiderek, Petra; Hamann, Thorben

    ionized and the reaction barrier is drastically lowered so that instant reaction between ethylene and ammonia occurs. This hydroamination reaction by means of low energy electrons or an analogous reaction mechanism could also help in clarifying the formation of the intermediate molecules observed in interstellar dust clouds. The formation for example of formamide from CO and NH3 could be facilitated by a very similar process. Formamide is a very interesting molecule in Astrochemistry as well as Astrobiology, since it is the smallest molecule with a peptide bond, the kind of bond that forms proteins from amino acids. Such ionisation-driven reactions leading to the formation of larger molecules appear to be more generally relevant than previously thought as will be discussed in this contribution. [1] Cazaux S., Caselli P., Tielens A.G.G.M., Le Bourlot J., Walmsley M: Molecular Hydrogen formation on grain surfaces. J of Phys. Conf. Series 6 (2005), 155-160 [2] Muñoz Caro G.M., Meierhenrich U.J., Schutte U.W., Barbier B., Arcones Segovia A., Rosen-n bauer H., Thiemann W.H.-P., Brack A. and Greenberg J.M.: Amino acids from ultraviolet irradiation of interstellar ice analogues. Nature 416 (2002), 403-406 [3] Bredehüft, J.H., Meierhenrich U.: Amino acid structures from UV irradiation of simulated interstellar ices. in Takenaka N. (ed): Recent Developments of Chemistry and Photochemistry in Ice. Transworld Research Network, Kerala, India (2008) [4] Cooper G., Kimmich N., Belisle W., Sarinana J., Brabham K. and Garrel L.: Carbonaceous meteorites as a source of sugar-related organic compounds for the early Earth. Nature 414 (2001), 879-883 [5] Meierhenrich U.J., Muñoz Caro G.M., Schutte W.A., Thiemann W.H.-P. Barbier B., Brack n A.: Precursors of biological cofactors from ultraviolet irradiation of circumstellar/interstellar ice analogs. Chemistry -A European Journal 11 (2005), 4895-4900 [6] Matthews C.N. and Minard R.D.: Hydrogen cyanide polymers, comets and the origin of life

  11. Mechano-chemical synthesis of strontium britholites: Reaction mechanism

    International Nuclear Information System (INIS)

    Gmati, N.; Boughzala, K.; Bouzouita, K.; Abdellaoui, M.

    2011-01-01

    The britholites have gained a great interest thanks to their potential applications as matrices for the confinement of the byproducts in the nuclear industry such as minor actinides and long-lived fission products. However, the preparation of britholites requires high temperatures, above 1200 C. In this work, we strive to prepare these kinds of compounds by a mechano-chemical synthesis at room temperature from the starting materials SrF 2 , SrCO 3 , Sr 2 P 2 O 7 , La 2 O 3 and SiO 2 using a planetary ball mill. The obtained results showed that the prepared products were carbonated apatites and the corresponding powders contained some unreacted silica and lanthana. To obtain pure britholites, a heat-treatment at 1100 C was required. The mechanism involved in the different steps of the reaction is discussed in this paper. The obtained results suggest that the use of raw materials containing no carbonate is expected to directly lead to pure britholites by appropriate milling at room temperature. (authors)

  12. Blaming for a better future: future orientation and associated intolerance of personal uncertainty lead to harsher reactions toward innocent victims.

    Science.gov (United States)

    Bal, Michèlle; van den Bos, Kees

    2012-07-01

    People are often encouraged to focus on the future and strive for long-term goals. This noted, the authors argue that this future orientation is associated with intolerance of personal uncertainty, as people usually cannot be certain that their efforts will pay off. To be able to tolerate personal uncertainty, people adhere strongly to the belief in a just world, paradoxically resulting in harsher reactions toward innocent victims. In three experiments, the authors show that a future orientation indeed leads to more negative evaluations of an innocent victim (Study 1), enhances intolerance of personal uncertainty (Study 2), and that experiencing personal uncertainty leads to more negative evaluations of a victim (Study 3). So, while a future orientation enables people to strive for long-term goals, it also leads them to be harsher toward innocent victims. One underlying mechanism causing these reactions is intolerance of personal uncertainty, associated with a future orientation.

  13. New mechanism of spiral wave initiation in a reaction-diffusion-mechanics system.

    Directory of Open Access Journals (Sweden)

    Louis D Weise

    Full Text Available Spiral wave initiation in the heart muscle is a mechanism for the onset of dangerous cardiac arrhythmias. A standard protocol for spiral wave initiation is the application of a stimulus in the refractory tail of a propagating excitation wave, a region that we call the "classical vulnerable zone." Previous studies of vulnerability to spiral wave initiation did not take the influence of deformation into account, which has been shown to have a substantial effect on the excitation process of cardiomyocytes via the mechano-electrical feedback phenomenon. In this work we study the effect of deformation on the vulnerability of excitable media in a discrete reaction-diffusion-mechanics (dRDM model. The dRDM model combines FitzHugh-Nagumo type equations for cardiac excitation with a discrete mechanical description of a finite-elastic isotropic material (Seth material to model cardiac excitation-contraction coupling and stretch activated depolarizing current. We show that deformation alters the "classical," and forms a new vulnerable zone at longer coupling intervals. This mechanically caused vulnerable zone results in a new mechanism of spiral wave initiation, where unidirectional conduction block and rotation directions of the consequently initiated spiral waves are opposite compared to the mechanism of spiral wave initiation due to the "classical vulnerable zone." We show that this new mechanism of spiral wave initiation can naturally occur in situations that involve wave fronts with curvature, and discuss its relation to supernormal excitability of cardiac tissue. The concept of mechanically induced vulnerability may lead to a better understanding about the onset of dangerous heart arrhythmias via mechano-electrical feedback.

  14. New mechanism of spiral wave initiation in a reaction-diffusion-mechanics system.

    Science.gov (United States)

    Weise, Louis D; Panfilov, Alexander V

    2011-01-01

    Spiral wave initiation in the heart muscle is a mechanism for the onset of dangerous cardiac arrhythmias. A standard protocol for spiral wave initiation is the application of a stimulus in the refractory tail of a propagating excitation wave, a region that we call the "classical vulnerable zone." Previous studies of vulnerability to spiral wave initiation did not take the influence of deformation into account, which has been shown to have a substantial effect on the excitation process of cardiomyocytes via the mechano-electrical feedback phenomenon. In this work we study the effect of deformation on the vulnerability of excitable media in a discrete reaction-diffusion-mechanics (dRDM) model. The dRDM model combines FitzHugh-Nagumo type equations for cardiac excitation with a discrete mechanical description of a finite-elastic isotropic material (Seth material) to model cardiac excitation-contraction coupling and stretch activated depolarizing current. We show that deformation alters the "classical," and forms a new vulnerable zone at longer coupling intervals. This mechanically caused vulnerable zone results in a new mechanism of spiral wave initiation, where unidirectional conduction block and rotation directions of the consequently initiated spiral waves are opposite compared to the mechanism of spiral wave initiation due to the "classical vulnerable zone." We show that this new mechanism of spiral wave initiation can naturally occur in situations that involve wave fronts with curvature, and discuss its relation to supernormal excitability of cardiac tissue. The concept of mechanically induced vulnerability may lead to a better understanding about the onset of dangerous heart arrhythmias via mechano-electrical feedback.

  15. Reaction mechanisms in the radiolysis of peptides, polypeptides and proteins

    Energy Technology Data Exchange (ETDEWEB)

    Garrison, W.M.

    1985-01-01

    The purpose of this review is to bring together and to correlate the wide variety of experimental studies that provide information on the reaction products and reaction mechanisms involved in the radiolysis of peptides, polypeptides and proteins (including chromosomal proteins) in both aqueous and solid-state systems. The comparative radiation chemistry of these systems is developed in terms of specific reactions of the peptide main-chain and the aliphatic, aromatic-unsaturated and sulfur-containing side-chains. Information obtained with the various experimental techniques of product analysis, competition kinetics, spin-trapping, pulse radiolysis and ESR spectroscopy is included. 147 refs.

  16. Reaction mechanisms in the radiolysis of peptides, polypeptides and proteins

    International Nuclear Information System (INIS)

    Garrison, W.M.

    1985-01-01

    The purpose of this review is to bring together and to correlate the wide variety of experimental studies that provide information on the reaction products and reaction mechanisms involved in the radiolysis of peptides, polypeptides and proteins (including chromosomal proteins) in both aqueous and solid-state systems. The comparative radiation chemistry of these systems is developed in terms of specific reactions of the peptide main-chain and the aliphatic, aromatic-unsaturated and sulfur-containing side-chains. Information obtained with the various experimental techniques of product analysis, competition kinetics, spin-trapping, pulse radiolysis and ESR spectroscopy is included. 147 refs

  17. Reaction mechanisms for on-surface synthesis of covalent nanostructures

    International Nuclear Information System (INIS)

    Björk, J

    2016-01-01

    In recent years, on-surface synthesis has become an increasingly popular strategy to form covalent nanostructures. The approach has great prospects for facilitating the manufacture of a range of fascinating materials with atomic precision. However, the on-surface reactions are enigmatic to control, currently restricting its bright perspectives and there is a great need to explore how the reactions are governed. The objective of this topical review is to summarize theoretical work that has focused on comprehending on-surface synthesis protocols through studies of reaction mechanisms. (topical review)

  18. Cyclodextrin-Catalyzed Organic Synthesis: Reactions, Mechanisms, and Applications

    Directory of Open Access Journals (Sweden)

    Chang Cai Bai

    2017-09-01

    Full Text Available Cyclodextrins are well-known macrocyclic oligosaccharides that consist of α-(1,4 linked glucose units and have been widely used as artificial enzymes, chiral separators, chemical sensors, and drug excipients, owing to their hydrophobic and chiral interiors. Due to their remarkable inclusion capabilities with small organic molecules, more recent interests focus on organic reactions catalyzed by cyclodextrins. This contribution outlines the current progress in cyclodextrin-catalyzed organic reactions. Particular emphases are given to the organic reaction mechanisms and their applications. In the end, the future directions of research in this field are proposed.

  19. The dynamics of the Hg + Br2 reaction: elucidation of the reaction mechanism for the Br exchange reaction.

    Science.gov (United States)

    Jambrina, P G; Menéndez, M; Aoiz, F J

    2017-06-28

    In spite of its importance in the Hg atmospheric chemistry, the dynamics of the Hg + Br 2 → HgBr + Br reaction is poorly understood. In this article, we have carried out a comprehensive study of the reaction mechanism of this reaction by means of quasiclassical trajectories (QCTs) on an existing ab initio potential energy surface (PES). The reaction has a non trivial dynamics, as a consequence of its large endothermicity, the presence of a deep potential well, and the competition between the Br exchange and the collision induced dissociation processes. Our calculations demonstrate that insertion is only relevant at energies just above the reaction threshold and that, at energies above 2.3 eV, HgBr formation typically takes place via a sort of frustrated dissociation. In order to compare directly with the results obtained in extensive cross molecular beam experiments for the homologous reaction with I 2 , angular distributions in the laboratory frame for Hg + Br 2 have been simulated under similar experimental conditions. The lack of agreement at the highest energies considered suggests that either the two reactions have substantially different mechanisms or that calculations on a single PES cannot account for the dynamics at those energies.

  20. Reaction mechanism and reaction coordinates from the viewpoint of energy flow

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wenjin; Ma, Ao, E-mail: aoma@uic.edu [Department of Bioengineering, The University of Illinois at Chicago, 851 South Morgan Street, Chicago, Illinois 60607 (United States)

    2016-03-21

    Reaction coordinates are of central importance for correct understanding of reaction dynamics in complex systems, but their counter-intuitive nature made it a daunting challenge to identify them. Starting from an energetic view of a reaction process as stochastic energy flows biased towards preferred channels, which we deemed the reaction coordinates, we developed a rigorous scheme for decomposing energy changes of a system, both potential and kinetic, into pairwise components. The pairwise energy flows between different coordinates provide a concrete statistical mechanical language for depicting reaction mechanisms. Application of this scheme to the C{sub 7eq} → C{sub 7ax} transition of the alanine dipeptide in vacuum revealed novel and intriguing mechanisms that eluded previous investigations of this well studied prototype system for biomolecular conformational dynamics. Using a cost function developed from the energy decomposition components by proper averaging over the transition path ensemble, we were able to identify signatures of the reaction coordinates of this system without requiring any input from human intuition.

  1. Reaction mechanism and reaction coordinates from the viewpoint of energy flow

    International Nuclear Information System (INIS)

    Li, Wenjin; Ma, Ao

    2016-01-01

    Reaction coordinates are of central importance for correct understanding of reaction dynamics in complex systems, but their counter-intuitive nature made it a daunting challenge to identify them. Starting from an energetic view of a reaction process as stochastic energy flows biased towards preferred channels, which we deemed the reaction coordinates, we developed a rigorous scheme for decomposing energy changes of a system, both potential and kinetic, into pairwise components. The pairwise energy flows between different coordinates provide a concrete statistical mechanical language for depicting reaction mechanisms. Application of this scheme to the C 7eq → C 7ax transition of the alanine dipeptide in vacuum revealed novel and intriguing mechanisms that eluded previous investigations of this well studied prototype system for biomolecular conformational dynamics. Using a cost function developed from the energy decomposition components by proper averaging over the transition path ensemble, we were able to identify signatures of the reaction coordinates of this system without requiring any input from human intuition.

  2. Rapid Synthesis of Lead Oxide Nanorods by One-step Solid-state Chemical Reaction at Room Temperature

    Institute of Scientific and Technical Information of China (English)

    CAO, Ya-Li(曹亚丽); JIA, Dian-Zeng(贾殿赠); LIU, Lang(刘浪); LUO, Jian-Min(骆建敏)

    2004-01-01

    A simple and facile method was reported to synthesize lead oxide nanorods. Nanorods of lead oxide were obtained directly from grinding solid metal salt and sodium hydroxide in agate mortar with the assistance of a suitable nonionic surfactant in only one step, which is different from the result of hydroxide in solution. The product has been characterized by XRD, TEM and SEM. The formation mechanism of rod-like morphology is discussed and the surfactant plays an important soft-template role in modifying the interface of solid-state reaction and according process of rod-formation.

  3. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, Brian P [Colorado School of Mines, Golden, CO (United States)

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer

  4. Computer-assisted study on the reaction between pyruvate and ylide in the pathway leading to lactyl-ThDP.

    Science.gov (United States)

    Alvarado, Omar; Jaña, Gonzalo; Delgado, Eduardo J

    2012-08-01

    In this study the formation of the lactyl-thiamin diphosphate intermediate (L-ThDP) is addressed using density functional theory calculations at X3LYP/6-31++G(d,p) level of theory. The study includes potential energy surface scans, transition state search, and intrinsic reaction coordinate calculations. Reactivity is analyzed in terms of Fukui functions. The results allow to conclude that the reaction leading to the formation of L-ThDP occurs via a concerted mechanism, and during the nucleophilic attack on the pyruvate molecule, the ylide is in its AP form. The calculated activation barrier for the reaction is 19.2 kcal/mol, in agreement with the experimental reported value.

  5. Structure and Reaction Mechanism of Pyrrolysine Synthase (PylD)

    KAUST Repository

    Quitterer, Felix; Beck, Philipp; Bacher, Adelbert; Groll, Michael

    2013-01-01

    The final step in the biosynthesis of the 22nd genetically encoded amino acid, pyrrolysine, is catalyzed by PylD, a structurally and mechanistically unique dehydrogenase. This catalyzed reaction includes an induced-fit mechanism achieved by major structural rearrangements of the N-terminal helix upon substrate binding. Different steps of the reaction trajectory are visualized by complex structures of PylD with substrate and product. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Structure and Reaction Mechanism of Pyrrolysine Synthase (PylD)

    KAUST Repository

    Quitterer, Felix

    2013-05-29

    The final step in the biosynthesis of the 22nd genetically encoded amino acid, pyrrolysine, is catalyzed by PylD, a structurally and mechanistically unique dehydrogenase. This catalyzed reaction includes an induced-fit mechanism achieved by major structural rearrangements of the N-terminal helix upon substrate binding. Different steps of the reaction trajectory are visualized by complex structures of PylD with substrate and product. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A facile and expedient one-pot three-component reaction leading to ...

    Indian Academy of Sciences (India)

    Sci. Vol. 124, No. 5, September 2012, pp. 1007–1012. c Indian Academy of Sciences. A facile and expedient one-pot three-component reaction leading to multifunctionalized stabilized phosphorus ylides. ZAHRA HASSANI. ∗ and ZEINAB ESFANDIARPOUR. Department of New Materials, International Center for Science, ...

  8. Method of determining paper-deposited materials, eg. lead, by their reaction with radioactive krypton

    International Nuclear Information System (INIS)

    Tolgyessy, J.; Pruzinec, J.

    1976-01-01

    The invention claims a method of determining substances on a paper carrier based on the substance reaction with 85 Kr gas and the measurement of radioactivity of the kryptonate formed. Lead is shown as an example. Different amounts of lead acetate were deposited on Whatman 2 chromatographic paper as was an unknown sample of Pb salt. The paper was exposed to a 2.5 mCi 85 Kr atmosphere for 48 hours. The activity of the individual spots was then measured, a calibration curve established and the amount of lead in the analyzed sample read-out. (Ha)

  9. Reaction mechanisms of CO2 activation and catalytic reduction

    International Nuclear Information System (INIS)

    Wolff, Niklas von

    2016-01-01

    The use of CO 2 as a C1 chemical feedstock for the fine chemical industry is interesting both economically and ecologically, as CO 2 is non-toxic, abundant and cheap. Nevertheless, transformations of CO 2 into value-added products is hampered by its high thermodynamic stability and its inertness toward reduction. In order to design new catalysts able to overcome this kinetic challenge, a profound understanding of the reaction mechanisms at play in CO 2 reduction is needed. Using novel N/Si+ frustrated Lewis pairs (FLPs), the influence of CO 2 adducts and different hydro-borane reducing agents on the reaction mechanism in the catalytic hydroboration of CO 2 were investigated, both by DFT calculations and experiments. In a second step, the reaction mechanism of a novel reaction for the creation of C-C bonds from CO 2 and pyridyl-silanes (C 5 H 4 N-SiMe 3 ) was analyzed by DFT calculations. It was shown that CO 2 plays a double role in this transformation, acting both as a catalyst and a C1-building block. The fine understanding of this transformation then led to the development of a novel approach for the synthesis of sulfones and sulfonamides. Starting from SO 2 and aromatic silanes/amine silanes, these products were obtained in a single step under metal-free conditions. Noteworthy, sulfones and sulfonamides are common motifs in organic chemistry and found in a variety of highly important drugs. Finally, this concept was extended to aromatic halides as coupling partners, and it was thus shown for the first time that a sulfonylative Hiyama reaction is a possible approach to the synthesis of sulfones. (author) [fr

  10. High resolution studies of pion-nucleus reaction mechanism

    International Nuclear Information System (INIS)

    Morris, C.L.

    1983-01-01

    Pion inelastic scattering is generally well described as a first order process using the DWIA. This is especially true for a large body of inelastic scattering data to low-lying collective states which is well-described by form factors obtained in (e,e') and the DWIA. Some data for which this model does not work are presented. Higher order reaction mechanisms have been invoked to explain some of these data. However, no model of these second order processes gives a satisfactory explanation of the entire data set. Experimentally, more data for pion-induced transitions to low-spin unnatural-parity states which have been studied by other probes would be useful in sorting out the reaction mechanisms responsible for the anomalous cross sections observed for the 1 + states in 12 C. Theoretically, a consistent evaluation of possible second-order diagrams in inelastic scattering, such as is being attempted for DCX 22 , would be useful

  11. Photonuclear reactions in the GNASH code: Benchmarking model calculations for reactions on lead up to 140 MeV

    International Nuclear Information System (INIS)

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

    1994-08-01

    The authors have developed the GNASH code to include photonuclear reactions for incident energies up to 140 MeV. Photoabsorption is modeled through the giant resonance at the lower energies, and the quasideuteron mechanism at the higher energies, and the angular momentum coupling of the incident photon to the target is properly accounted for. After the initial interaction, primary and multiple preequilibrium emission of fast particles can occur before compound nucleus decay from the equilibrated compound nucleus. The angular distributions from compound nucleus decay are taken as isotropic, and those from preequilibrium emission (which they obtain from a phase-space model which conserves momentum) are forward-peaked. To test the new modeling they apply the code to calculate photonuclear reactions on 208 Pb for incident energies up to 140 MeV

  12. Reaction mechanism in high energy heavy-ion collisions

    International Nuclear Information System (INIS)

    Tanihata, Isao.

    1982-04-01

    The reaction mechanism in high energy heavy-ion collision is discussed. The discussion is mainly based on the experimental data. Empirical equations have been given for the total cross-sections of nucleus-nucleus reactions and the reaction cross-sections. These cross-sections are well described by the geometrical size of the colliding nuclei. The cross-sections are also understood by microscopic calculation. The charged particle multiplicity gives additional information about the geometrical aspect of heavy ion collision. The data suggested that the total energy, independent of projectile size, is most important for determining the multiplicity. The inclusive proton spectrum in a heavy ion collision showed two distinct regions. The one is the fragment region, and the other the participant region. The spectral shapes of inclusive pion spectra are reasonably well explained by the Coulomb interaction of pions with nuclear fragments. The high energy heavy ion reaction occurs in the overlap region of the projectile and target. This has been tested by measuring the number of participants for various reactions. The space and the time structure of the collision are also discussed in this paper as well as the dynamical aspects of the collision. (Kato, T.)

  13. A Practical Quantum Mechanics Molecular Mechanics Method for the Dynamical Study of Reactions in Biomolecules.

    Science.gov (United States)

    Mendieta-Moreno, Jesús I; Marcos-Alcalde, Iñigo; Trabada, Daniel G; Gómez-Puertas, Paulino; Ortega, José; Mendieta, Jesús

    2015-01-01

    Quantum mechanics/molecular mechanics (QM/MM) methods are excellent tools for the modeling of biomolecular reactions. Recently, we have implemented a new QM/MM method (Fireball/Amber), which combines an efficient density functional theory method (Fireball) and a well-recognized molecular dynamics package (Amber), offering an excellent balance between accuracy and sampling capabilities. Here, we present a detailed explanation of the Fireball method and Fireball/Amber implementation. We also discuss how this tool can be used to analyze reactions in biomolecules using steered molecular dynamics simulations. The potential of this approach is shown by the analysis of a reaction catalyzed by the enzyme triose-phosphate isomerase (TIM). The conformational space and energetic landscape for this reaction are analyzed without a priori assumptions about the protonation states of the different residues during the reaction. The results offer a detailed description of the reaction and reveal some new features of the catalytic mechanism. In particular, we find a new reaction mechanism that is characterized by the intramolecular proton transfer from O1 to O2 and the simultaneous proton transfer from Glu 165 to C2. Copyright © 2015 Elsevier Inc. All rights reserved.

  14. Clustering mechanism of oxocarboxylic acids involving hydration reaction: Implications for the atmospheric models

    Science.gov (United States)

    Liu, Ling; Kupiainen-Määttä, Oona; Zhang, Haijie; Li, Hao; Zhong, Jie; Kurtén, Theo; Vehkamäki, Hanna; Zhang, Shaowen; Zhang, Yunhong; Ge, Maofa; Zhang, Xiuhui; Li, Zesheng

    2018-06-01

    The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with different reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acid, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reactions using density functional theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. Under atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, and the product can further participate in the clustering process. The differences in cluster structures and properties induced by the hydration reaction lead to significant differences in cluster formation rates and pathways at relatively low temperatures.

  15. Evidence for leading mesons in anti p4He reactions at 0.6 GeV/c incident momentum

    International Nuclear Information System (INIS)

    Breivik, F.O.; Haatuft, A.; Halsteinslid, A.

    1990-05-01

    In a previous report, evidence has been shown for leading mesons in anti p Ne - reactions at 0.6 Gev/c incident momentum. In this report evidence is shown for leading mesons in anti p 4 He reactions at the same incident momentum, based on data from the same detector. In anti p Ne - reactions, only kaons are observed as leading mesons in K o s-events, and only pions are observed as leading mesons in Λ o -events. In anti p He - reactions this is not longer true, since also pions behave as leading mesons in K o s-events. 5 refs., 9 figs

  16. Transglycosylation reactions, a main mechanism of phenolics incorporation in coffee melanoidins: Inhibition by Maillard reaction.

    Science.gov (United States)

    Moreira, Ana S P; Nunes, Fernando M; Simões, Cristiana; Maciel, Elisabete; Domingues, Pedro; Domingues, M Rosário M; Coimbra, Manuel A

    2017-07-15

    Under roasting conditions, polysaccharides depolymerize and also are able to polymerize, forming new polymers through non-enzymatic transglycosylation reactions (TGRs). TGRs can also occur between carbohydrates and aglycones, such as the phenolic compounds present in daily consumed foods like coffee. In this study, glycosidically-linked phenolic compounds were quantified in coffee melanoidins, the polymeric nitrogenous brown-colored compounds formed during roasting, defined as end-products of Maillard reaction. One third of the phenolics present were in glycosidically-linked form. In addition, the roasting of solid-state mixtures mimicking coffee beans composition allowed the conclusion that proteins play a regulatory role in TGRs extension and, consequently, modulate melanoidins composition. Overall, the results obtained showed that TGRs are a main mechanism of phenolics incorporation in melanoidins and are inhibited by amino groups through Maillard reaction. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Mechanisms of leading edge protrusion in interstitial migration

    Science.gov (United States)

    Wilson, Kerry; Lewalle, Alexandre; Fritzsche, Marco; Thorogate, Richard; Duke, Tom; Charras, Guillaume

    2013-01-01

    While the molecular and biophysical mechanisms underlying cell protrusion on two-dimensional substrates are well understood, our knowledge of the actin structures driving protrusion in three-dimensional environments is poor, despite relevance to inflammation, development and cancer. Here we report that, during chemotactic migration through microchannels with 5 μm × 5 μm cross-sections, HL60 neutrophil-like cells assemble an actin-rich slab filling the whole channel cross-section at their front. This leading edge comprises two distinct F-actin networks: an adherent network that polymerizes perpendicular to cell-wall interfaces and a ‘free’ network that grows from the free membrane at the cell front. Each network is polymerized by a distinct nucleator and, due to their geometrical arrangement, the networks interact mechanically. On the basis of our experimental data, we propose that, during interstitial migration, medial growth of the adherent network compresses the free network preventing its retrograde movement and enabling new polymerization to be converted into forward protrusion. PMID:24305616

  18. Nuclear and hadronic reaction mechanisms producing spin asymmetry

    Indian Academy of Sciences (India)

    naka

    are predominantly u and d quarks, act as the leading partons to form the hyperons. Extension of the quark recombination concept with this mechanism is successful in providing a good account of the anomalous spin observables. Another kind of anomaly, the non-zero analysing power and spin depolarization in the A ...

  19. 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.

  20. Products and stability of phosphate reactions with lead under freeze-thaw cycling in simple systems

    Energy Technology Data Exchange (ETDEWEB)

    Hafsteinsdottir, Erla G., E-mail: erla.hafsteinsdottir@gmail.com [Department of Environment and Geography, Macquarie University, NSW 2109 (Australia); White, Duanne A., E-mail: duanne.white@mq.edu.au [Department of Environment and Geography, Macquarie University, NSW 2109 (Australia); Gore, Damian B., E-mail: damian.gore@mq.edu.au [Department of Environment and Geography, Macquarie University, NSW 2109 (Australia); Stark, Scott C., E-mail: scott.stark@aad.gov.au [Environmental Protection and Change, Australian Antarctic Division, Department of Sustainability, Environment, Water, Population and Communities, Tasmania 7050 (Australia)

    2011-12-15

    Orthophosphate fixation of metal contaminated soils in environments that undergo freeze-thaw cycles is understudied. Freeze-thaw cycling potentially influences the reaction rate, mineral chemical stability and physical breakdown of particles during fixation. This study determines what products form when phosphate (triple superphosphate [Ca(H{sub 2}PO{sub 4}){sub 2}] or sodium phosphate [Na{sub 3}PO{sub 4}]) reacts with lead (PbSO{sub 4} or PbCl{sub 2}) in simple chemical systems in vitro, and assesses potential changes in formation during freeze-thaw cycles. Systems were subjected to multiple freeze-thaw cycles from +10 deg. C to -20 deg. C and then analysed by X-ray diffractometry. Pyromorphite formed in all systems and was stable over multiple freeze-thaw cycles. Low temperature lead orthophosphate reaction efficiency varied according to both phosphate and lead source; the most time-efficient pyromorphite formation was observed when PbSO{sub 4} and Na{sub 3}PO{sub 4} were present together. These findings have implications for the manner in which metal contaminated materials in freezing ground can be treated with phosphate. - Highlights: > Formation of lead phosphate products in cold environments is identified. > Potential change in formation during freeze-thaw cycling is assessed. > Lead phosphate reaction efficiency varies according to phosphate and lead source. > Pyromorphite formation is stable during 240 freeze-thaw cycles. - Pyromorphite, formed from Pb phosphate fixation, is stable during multiple freeze-thaw cycles but the efficiency of the fixation depends on the phosphate source and the type of Pb mineral.

  1. Products and stability of phosphate reactions with lead under freeze-thaw cycling in simple systems

    International Nuclear Information System (INIS)

    Hafsteinsdottir, Erla G.; White, Duanne A.; Gore, Damian B.; Stark, Scott C.

    2011-01-01

    Orthophosphate fixation of metal contaminated soils in environments that undergo freeze-thaw cycles is understudied. Freeze-thaw cycling potentially influences the reaction rate, mineral chemical stability and physical breakdown of particles during fixation. This study determines what products form when phosphate (triple superphosphate [Ca(H 2 PO 4 ) 2 ] or sodium phosphate [Na 3 PO 4 ]) reacts with lead (PbSO 4 or PbCl 2 ) in simple chemical systems in vitro, and assesses potential changes in formation during freeze-thaw cycles. Systems were subjected to multiple freeze-thaw cycles from +10 deg. C to -20 deg. C and then analysed by X-ray diffractometry. Pyromorphite formed in all systems and was stable over multiple freeze-thaw cycles. Low temperature lead orthophosphate reaction efficiency varied according to both phosphate and lead source; the most time-efficient pyromorphite formation was observed when PbSO 4 and Na 3 PO 4 were present together. These findings have implications for the manner in which metal contaminated materials in freezing ground can be treated with phosphate. - Highlights: → Formation of lead phosphate products in cold environments is identified. → Potential change in formation during freeze-thaw cycling is assessed. → Lead phosphate reaction efficiency varies according to phosphate and lead source. → Pyromorphite formation is stable during 240 freeze-thaw cycles. - Pyromorphite, formed from Pb phosphate fixation, is stable during multiple freeze-thaw cycles but the efficiency of the fixation depends on the phosphate source and the type of Pb mineral.

  2. High-energy nuclear reaction mechanisms - fission, fragmentation and spallation

    International Nuclear Information System (INIS)

    Kaufman, S.B.

    1987-01-01

    Measurements of the correlations in kinetic energy, mass, charge, and angle of coincident fragments formed in high-energy nuclear reactions have helped to characterize the processes of fission, fragmentation and spallation. For example, fission or fission-like two-body breakup mechanisms result in a strong angular correlation between two heavy fragments; in addition, the momentum transfer in the reaction can be deduced from the correlation. Another example is the multiplicity of light charged particles associated with a given heavy fragment, which is a measure of the violence of the collision, thus distinguishing between central and peripheral collisions. A summary of what has been learned about these processes from such studies will be given, along with some suggestions for further experiments

  3. Quantum Mechanics/Molecular Mechanics Free Energy Maps and Nonadiabatic Simulations for a Photochemical Reaction in DNA: Cyclobutane Thymine Dimer.

    Science.gov (United States)

    Mendieta-Moreno, Jesús I; Trabada, Daniel G; Mendieta, Jesús; Lewis, James P; Gómez-Puertas, Paulino; Ortega, José

    2016-11-03

    The absorption of ultraviolet radiation by DNA may result in harmful genetic lesions that affect DNA replication and transcription, ultimately causing mutations, cancer, and/or cell death. We analyze the most abundant photochemical reaction in DNA, the cyclobutane thymine dimer, using hybrid quantum mechanics/molecular mechanics (QM/MM) techniques and QM/MM nonadiabatic molecular dynamics. We find that, due to its double helix structure, DNA presents a free energy barrier between nonreactive and reactive conformations leading to the photolesion. Moreover, our nonadiabatic simulations show that most of the photoexcited reactive conformations return to standard B-DNA conformations after an ultrafast nonradiative decay to the ground state. This work highlights the importance of dynamical effects (free energy, excited-state dynamics) for the study of photochemical reactions in biological systems.

  4. Reaction mechanisms for enhancing carbon dioxide mineral sequestration

    Science.gov (United States)

    Jarvis, Karalee Ann

    Increasing global temperature resulting from the increased release of carbon dioxide into the atmosphere is one of the greatest problems facing society. Nevertheless, coal plants remain the largest source of electrical energy and carbon dioxide gas. For this reason, researchers are searching for methods to reduce carbon dioxide emissions into the atmosphere from the combustion of coal. Mineral sequestration of carbon dioxide reacted in electrolyte solutions at 185°C and 2200 psi with olivine (magnesium silicate) has been shown to produce environmentally benign carbonates. However, to make this method feasible for industrial applications, the reaction rate needs to be increased. Two methods were employed to increase the rate of mineral sequestration: reactant composition and concentration were altered independently in various runs. The products were analyzed with complete combustion for total carbon content. Crystalline phases in the product were analyzed with Debye-Scherrer X-ray powder diffraction. To understand the reaction mechanism, single crystals of San Carlos Olivine were reacted in two solutions: (0.64 M NaHCO3/1 M NaCl) and (5.5 M KHCO3) and analyzed with scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), and fluctuation electron microscopy (FEM) to study the surface morphology, atomic crystalline structure, composition and amorphous structure. From solution chemistry studies, it was found that increasing the activity of the bicarbonate ion increased the conversion rate of carbon dioxide to magnesite. The fastest conversion, 60% conversion in one hour, occurred in a solution of 5.5 M KHCO3. The reaction product particles, magnesium carbonate, significantly increased in both number density and size on the coupon when the bicarbonate ion activity was increased. During some experiments reaction vessel corrosion also altered the mineral sequestration mechanism. Nickel ions from vessel

  5. A discrete model to study reaction-diffusion-mechanics systems.

    Science.gov (United States)

    Weise, Louis D; Nash, Martyn P; Panfilov, Alexander V

    2011-01-01

    This article introduces a discrete reaction-diffusion-mechanics (dRDM) model to study the effects of deformation on reaction-diffusion (RD) processes. The dRDM framework employs a FitzHugh-Nagumo type RD model coupled to a mass-lattice model, that undergoes finite deformations. The dRDM model describes a material whose elastic properties are described by a generalized Hooke's law for finite deformations (Seth material). Numerically, the dRDM approach combines a finite difference approach for the RD equations with a Verlet integration scheme for the equations of the mass-lattice system. Using this framework results were reproduced on self-organized pacemaking activity that have been previously found with a continuous RD mechanics model. Mechanisms that determine the period of pacemakers and its dependency on the medium size are identified. Finally it is shown how the drift direction of pacemakers in RDM systems is related to the spatial distribution of deformation and curvature effects.

  6. New Mechanism of Low Energy Nuclear Reactions Using Superlow

    Science.gov (United States)

    Gareev, F. A.; Zhidkova, I. E.

    2006-03-01

    We proposed a new mechanism of LENR (low energy nuclear reactions) cooperative processes in the whole system - nuclei+atoms+condensed matter can occur at smaller threshold than the corresponding ones assoiciated with free constituents. The cooperative processes can be induced and enhanced by (``superlow energy'') external fields. The excess heat is the emission of internal energy, and transmutations from LENR are the result of redistribution of the internal energy of the whole system. A review of possible stimulation mechanisms of LENR is presented. We have concluded that transmutation of nuclei at low energies and excess heat are possible in the framework of the known fundamental physical laws: The universal resonance synchronization principle, and based on it, different enhancement mechanisms of reaction rates are responsible for these processes. The excitation and ionization of atoms may play the role of a trigger for LENR. F.A. Gareev, I.E. Zhidkova, E-print arXiv Nucl-th/0511092 v1 30 Nov 2005. F.A. Gareev, In: FPB-98, Novosibirsk, June 1998, p.92; F.A.Gareev, G.F. Gareeva, in: Novosibirsk, July 2000, p.161. F.A. Gareev, I.E. Zhidkova and Yu.L. Ratis, Preprint JINR P4-2004-68, Dubna, 2004. F.A. Gareev, I.E. Zhidkova, E-print arXiv Nucl-th/0505021 9 May 2005.

  7. A discrete model to study reaction-diffusion-mechanics systems.

    Directory of Open Access Journals (Sweden)

    Louis D Weise

    Full Text Available This article introduces a discrete reaction-diffusion-mechanics (dRDM model to study the effects of deformation on reaction-diffusion (RD processes. The dRDM framework employs a FitzHugh-Nagumo type RD model coupled to a mass-lattice model, that undergoes finite deformations. The dRDM model describes a material whose elastic properties are described by a generalized Hooke's law for finite deformations (Seth material. Numerically, the dRDM approach combines a finite difference approach for the RD equations with a Verlet integration scheme for the equations of the mass-lattice system. Using this framework results were reproduced on self-organized pacemaking activity that have been previously found with a continuous RD mechanics model. Mechanisms that determine the period of pacemakers and its dependency on the medium size are identified. Finally it is shown how the drift direction of pacemakers in RDM systems is related to the spatial distribution of deformation and curvature effects.

  8. Mechanisms by Which Dehydration May Lead to Chronic Kidney Disease.

    Science.gov (United States)

    Roncal-Jimenez, C; Lanaspa, M A; Jensen, T; Sanchez-Lozada, L G; Johnson, R J

    2015-01-01

    Dehydration, a condition that characterizes excessive loss of body water, is well known to be associated with acute renal dysfunction; however, it has largely been considered reversible and to be associated with no long-term effects on the kidney. Recently, an epidemic of chronic kidney disease has emerged in Central America in which the major risk factor seems to be recurrent heat-associated dehydration. This has led to studies investigating whether recurrent dehydration may lead to permanent kidney damage. Three major potential mechanisms have been identified, including the effects of vasopressin on the kidney, the activation of the aldose reductase-fructokinase pathway, and the effects of chronic hyperuricemia. The discovery of these pathways has also led to the recognition that mild dehydration may be a risk factor in progression of all types of chronic kidney diseases. Furthermore, there is some evidence that increasing hydration, particularly with water, may actually prevent CKD. Thus, a whole new area of investigation is developing that focuses on the role of water and osmolarity and their influence on kidney function and health. © 2015 S. Karger AG, Basel.

  9. Chlorination of tramadol: Reaction kinetics, mechanism and genotoxicity evaluation.

    Science.gov (United States)

    Cheng, Hanyang; Song, Dean; Chang, Yangyang; Liu, Huijuan; Qu, Jiuhui

    2015-12-01

    Tramadol (TRA) is one of the most detected analgesics in environmental matrices, and it is of high significance to study the reactivity of TRA during chlorination considering its potential toxicity to the environment. The chlorine/TRA reaction is first order with respect to the TRA concentration, and a combination of first-order and second-order with respect to chlorine concentration. The pH dependence of the observed rate constants (kobs) showed that the TRA oxidation reactivity increased with increasing pH. kobs can be quantitatively described by considering all active species including Cl2, Cl2O and HOCl, and the individual rate constants of HOCl/TRA(0), HOCl/TRAH(+), Cl2/TRA and Cl2O/TRA reactions were calculated to be (2.61±0.29)×10(3)M(-1)s(-1), 14.73±4.17M(-1)s(-1), (3.93±0.34)×10(5)M(-1)s(-1) and (5.66±1.83)×10(6)M(-1)s(-1), respectively. Eleven degradation products were detected with UPLC-Q-TOF-MS, and the corresponding structures of eight products found under various pH conditions were proposed. The amine group was proposed to be the initial attack site under alkaline pH conditions, where reaction of the deprotonated amine group with HOCl is favorable. Under acidic and neutral pH conditions, however, two possible reaction pathways were proposed. One is an electrophilic substitution on the aromatic ring, and another is an electrophilic substitution on the nitrogen, leading to an N-chlorinated intermediate, which can be further oxidized. Finally, the SOS/umu test showed that the genotoxicity of TRA chlorination products increased with increasing dosage of chlorine, which was mostly attributed to the formation of some chlorine substitution products. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Reaction mechanism and spectroscopy of transfer reactions induced by heavy ions

    International Nuclear Information System (INIS)

    Lemaire, M.-C.

    1977-01-01

    The specific features displayed by data on heavy ion elastic and inelastic angular distributions are discussed, and their physical origin is pointed out from semi-classical calculations in counterpart ambiguities in the phenomenological description of the optical potential appear. Two nucleon transfer reactions induced by heavy ions successfully point out important contributions of a two-step process where the transfer is proceeding via target and residual nucleus inelastic excitation. At incident energies not too high above the Coulomb barrier, such process produces clear shape changes between different final state angular distributions. At higher incident energy, the angular distributions are forward peaked and display oscillations for both mechanisms. As for four-nucleon transfer reactions, the existing data suggest that the nucleons are well transferred into a Os relative

  11. Radiation-protective drugs and their reaction mechanisms

    International Nuclear Information System (INIS)

    Livesey, J.C.; Reed, D.J.; Adamson, L.F.

    1985-01-01

    The objective of this book is to provide the reader with a concise review of radioprotective drugs and their reaction mechanisms. The first chapter reviews the effect of radiation on biological systems at the atomic, molecular, and subcellular levels. The second chapter discusses endogenous factors that influence radioresistance. Chapter 3 presents the main theme of the book, chemical radioprotection and its mechanisms, and examines the basis of natural radioprotection and how it may be affected by exogenous chemicals. Chapter 4, the Therapy of Radiation Damage, is a very brief general discussion that only touches on some of the experimental approaches to therapy. Chapter 5 contains recommendations for future research. The two appendices list research in progress in the United States and some radioprotective compounds of possible investigational interest. Also included is a brief discussion of structure-activity relationships

  12. Mechanisms of polyphosphate glucokinase and polyphosphate kinase reactions

    International Nuclear Information System (INIS)

    Pepin, C.A.; Robinson, N.A.; Wood, H.G.

    1986-01-01

    Polyphosphate glucokinase [poly(P)GK] catalyzes the following reaction: poly(P)/sub n/ + glucose → poly(P)/sub n-1/ + G-6-P. With long chain poly(P) [n=750 to 400] the mechanism appeared to be processive, in which there is phosphorylation of glucose without release of intermediate sizes of the poly(P) until the chain is about 100, thereafter there were intermediate sizes formed apparently by a non-processive process. Poly(P) kinase catalyzes the following reaction: ATP + poly(P)/sub n/ ↔ ADP + poly(P)/sub n + 1/. Using short chain 32 [P] poly(P) as a primer and non-radioactive ATP, long chain poly(P) is formed processively. The resulting chain has a short length labeled with 32 [P] contributed by the primer on one end and the remainder is made up of unlabeled (P) from the ATP. The authors have used this 32 [P] poly(P) as a substrate with poly(P)GK. If the mechanism of the poly(P)GK were initially processive, there would be a 50% chance the phosphate would be utilized from the unlabeled end and 50% of the 32 [P] would remain in the shortened chain. However, all the 32 [P] was lost when 20% of the poly(P) was converted to G-6-P. In contrast, with poly(P) kinase, the % of poly(P) utilized was equivalent to the % of 32 [P] converted to ATP, which is consistent with a strictly processive mechanism. Even though the mechanism of poly(P)GK appeared to be processive with long chains, the on and off rate of poly(P) from the enzyme is such that there is random removal of (P) from both ends of the poly(P) chain

  13. The chemistry of the carbothermal synthesis of β-SiC : reaction mechanism, reaction rate and grain growth

    NARCIS (Netherlands)

    van Dijen, F.K.; Metselaar, R.

    1991-01-01

    Evidence is given that in the present case the reaction mechanism of ß-SiC formation from silica and carbon is a direct solid-state reaction in which silica migrates over the silicon carbide surface to the carbon. A high value (440 kJ/mol) of activation energy is obtained for this reaction. This

  14. Mechanism of chimera formation during the Multiple Displacement Amplification reaction

    Directory of Open Access Journals (Sweden)

    Stockwell Timothy B

    2007-04-01

    Full Text Available Abstract Background Multiple Displacement Amplification (MDA is a method used for amplifying limiting DNA sources. The high molecular weight amplified DNA is ideal for DNA library construction. While this has enabled genomic sequencing from one or a few cells of unculturable microorganisms, the process is complicated by the tendency of MDA to generate chimeric DNA rearrangements in the amplified DNA. Determining the source of the DNA rearrangements would be an important step towards reducing or eliminating them. Results Here, we characterize the major types of chimeras formed by carrying out an MDA whole genome amplification from a single E. coli cell and sequencing by the 454 Life Sciences method. Analysis of 475 chimeras revealed the predominant reaction mechanisms that create the DNA rearrangements. The highly branched DNA synthesized in MDA can assume many alternative secondary structures. DNA strands extended on an initial template can be displaced becoming available to prime on a second template creating the chimeras. Evidence supports a model in which branch migration can displace 3'-ends freeing them to prime on the new templates. More than 85% of the resulting DNA rearrangements were inverted sequences with intervening deletions that the model predicts. Intramolecular rearrangements were favored, with displaced 3'-ends reannealing to single stranded 5'-strands contained within the same branched DNA molecule. In over 70% of the chimeric junctions, the 3' termini had initiated priming at complimentary sequences of 2–21 nucleotides (nts in the new templates. Conclusion Formation of chimeras is an important limitation to the MDA method, particularly for whole genome sequencing. Identification of the mechanism for chimera formation provides new insight into the MDA reaction and suggests methods to reduce chimeras. The 454 sequencing approach used here will provide a rapid method to assess the utility of reaction modifications.

  15. 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.

  16. On the knock-out mechanism for the 12C(P,α)9B reaction

    International Nuclear Information System (INIS)

    Hassan, M.Y.M.; Ismail, E.H.; Rabie, A.

    1978-01-01

    The mechanism of the reaction 12 C(P,α) 9 B is studied using zero range distorted wave Born approximation. The knock out mechanism is assumed to represent this reaction both in the forward and backward angles. (orig.) [de

  17. Pacing Lead-Induced Granuloma in the Atrium: A Foreign Body Reaction to Polyurethane

    Directory of Open Access Journals (Sweden)

    Shinagawa Yoko

    2013-01-01

    Full Text Available We described a case of an 82-year-old male who presented with a granuloma entrapping the polyurethane-coated pacing lead at the site of contact on the atrium. He had been paced for 8 years without symptoms or signs suggestive of an allergic reaction to the pacemaker system and died from thrombosis of the superior mesenteric artery and heart failure. A histological examination of the nodule showed an incidental granuloma with multinucleated giant cells. No granuloma was found in the heart or the lung.

  18. The void nucleation mechanism within lead phase during spallation of leaded brass

    Science.gov (United States)

    Yang, Yang; Wang, Can; Chen, Xingzhi; Chen, Kaiguo; Hu, Haibo; Fu, Yanan

    2018-07-01

    The incipient spall behaviours of Cu-34%Zn-3%Pb leaded brass samples with annealed and cryogenic-treated conditions were loaded using one-stage light gas gun experiments. The effect of Pb-phase on dynamic damage nucleation in leaded brass specimens was investigated by means of optical microscopy, scanning electron microscopy and x-ray computer tomography. It was found that the voids of incipient spall were mainly nucleated in the interior of the lead (no tensile stress would be produced within lead according to the impact theory) instead of nucleated at the phase interface as expected by quasi-static damage fracture theory. A nucleation model is proposed in the present work that is the asymmetry high compression zones in the centre of the lead-phase were formed by the rarefaction wave convergence effects of matrix/quasi-spherical lead interface, which caused adiabatic temperature rise that exceeded melting point of lead due to severe plastic deformation, finally led to local melting and void nucleation. In addition, the spall strength and damage rate increased with the increase in the Pb-phase number.

  19. Optimized reaction mechanism rate rules for ignition of normal alkanes

    KAUST Repository

    Cai, Liming

    2016-08-11

    The increasing demand for cleaner combustion and reduced greenhouse gas emissions motivates research on the combustion of hydrocarbon fuels and their surrogates. Accurate detailed chemical kinetic models are an important prerequisite for high fidelity reacting flow simulations capable of improving combustor design and operation. The development of such models for many new fuel components and/or surrogate molecules is greatly facilitated by the application of reaction classes and rate rules. Accurate and versatile rate rules are desirable to improve the predictive accuracy of kinetic models. A major contribution in the literature is the recent work by Bugler et al. (2015), which has significantly improved rate rules and thermochemical parameters used in kinetic modeling of alkanes. In the present study, it is demonstrated that rate rules can be used and consistently optimized for a set of normal alkanes including n-heptane, n-octane, n-nonane, n-decane, and n-undecane, thereby improving the predictive accuracy for all the considered fuels. A Bayesian framework is applied in the calibration of the rate rules. The optimized rate rules are subsequently applied to generate a mechanism for n-dodecane, which was not part of the training set for the optimized rate rules. The developed mechanism shows accurate predictions compared with published well-validated mechanisms for a wide range of conditions.

  20. 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.

  1. BlenX-based compositional modeling of complex reaction mechanisms

    Directory of Open Access Journals (Sweden)

    Judit Zámborszky

    2010-02-01

    Full Text Available Molecular interactions are wired in a fascinating way resulting in complex behavior of biological systems. Theoretical modeling provides a useful framework for understanding the dynamics and the function of such networks. The complexity of the biological networks calls for conceptual tools that manage the combinatorial explosion of the set of possible interactions. A suitable conceptual tool to attack complexity is compositionality, already successfully used in the process algebra field to model computer systems. We rely on the BlenX programming language, originated by the beta-binders process calculus, to specify and simulate high-level descriptions of biological circuits. The Gillespie's stochastic framework of BlenX requires the decomposition of phenomenological functions into basic elementary reactions. Systematic unpacking of complex reaction mechanisms into BlenX templates is shown in this study. The estimation/derivation of missing parameters and the challenges emerging from compositional model building in stochastic process algebras are discussed. A biological example on circadian clock is presented as a case study of BlenX compositionality.

  2. Reaction mechanisms and staggering in S+Ni collisions

    International Nuclear Information System (INIS)

    D'Agostino, M.; Bruno, M.; Gulminelli, F.; Morelli, L.; Baiocco, G.; Bardelli, L.; Barlini, S.; Cannata, F.; Casini, G.; Geraci, E.; Gramegna, F.; Kravchuk, V.L.; Marchi, T.; Moroni, A.; Ordine, A.; Raduta, Ad.R.

    2011-01-01

    The reactions 32 S+ 58 Ni and 32 S+ 64 Ni are studied at 14.5 A MeV. After a selection of the collision mechanism, we show that important even-odd effects are present in the isotopic fragment distributions when the excitation energy is small. Close to the multifragmentation threshold this staggering appears hidden by the rapid variation of the production yields with the fragment size. Once this effect is accounted for, the staggering appears to be a universal feature of fragment production, slightly enhanced when the emission source is neutron poor. A closer look at the behavior of the production yields as a function of the neutron excess N-Z, reveals that odd-even effects cannot be explained by pairing effects in the nuclear masses alone, but depend in a more complex way on the de-excitation chain.

  3. On the mechanism of effective chemical reactions with turbulent mixing of reactants and finite rate of molecular reactions

    Energy Technology Data Exchange (ETDEWEB)

    Vorotilin, V. P., E-mail: VPVorotilin@yandex.ru [Russian Academy of Sciences, Institute of Applied Mechanics (Russian Federation)

    2017-01-15

    A generalization of the theory of chemical transformation processes under turbulent mixing of reactants and arbitrary values of the rate of molecular reactions is presented that was previously developed for the variant of an instantaneous reaction [13]. The use of the features of instantaneous reactions when considering the general case, namely, the introduction of the concept of effective reaction for the reactant volumes and writing a closing conservation equation for these volumes, became possible due to the partition of the whole amount of reactants into “active” and “passive” classes; the reactants of the first class are not mixed and react by the mechanism of instantaneous reactions, while the reactants of the second class approach each other only through molecular diffusion, and therefore their contribution to the reaction process can be neglected. The physical mechanism of reaction for the limit regime of an ideal mixing reactor (IMR) is revealed and described. Although formally the reaction rate in this regime depends on the concentration of passive fractions of the reactants, according to the theory presented, the true (hidden) mechanism of the reaction is associated only with the reaction of the active fractions of the reactants with vanishingly small concentration in the volume of the reactor. It is shown that the rate constant of fast chemical reactions can be evaluated when the mixing intensity of reactants is much less than that needed to reach the mixing conditions in an IMR.

  4. Pannus-Related Mechanical Valve Dysfunction Leading to Hemodynamic Shock

    Directory of Open Access Journals (Sweden)

    Manabu Shiraishi

    2012-02-01

    Full Text Available Mechanical prosthetic valve dysfunction caused by pannus formation is rare. Pannus restricts movement of prosthetic valve leaflets, resulting in severe aortic regurgitation. We describe the case of a 77-year-old woman who presented to the emergency room with increasing dyspnea, ischemia, and shock secondary to mechanical aortic valve dysfunction. Transesophageal echocardiography showed a blockade of the leaflets of the mechanical aortic valve, with severe aortic regurgitation. She underwent emergent cardiac surgery for aortic valve replacement. Pannus formation should be considered as a potential cause of acute severe aortic regurgitation in a patient with a small-sized mechanical aortic prosthesis in the supra-annular position. On a pathological exam, extensive pannus was found on the ventricular side of the prosthetic valve, extending from the ring into the central orifice. [Arch Clin Exp Surg 2012; 1(1.000: 50-53

  5. Basic Mechanisms Leading to Fatigue Failure of Structural Materials

    Czech Academy of Sciences Publication Activity Database

    Polák, Jaroslav; Petráš, Roman; Mazánová, Veronika

    2016-01-01

    Roč. 69, č. 2 (2016), s. 289-294 ISSN 0972-2815. [International Conference on CREEP , FATIGUE and CREEP -FATIGUE INTERACTION /7./. Kalpakkam, 19.01.2016-22.01.2016] R&D Projects: GA ČR(CZ) GA13-23652S Institutional support: RVO:68081723 Keywords : Damage mechanism * Fatigue crack initiation * Austenitic steel * Oxide cracking Subject RIV: JL - Materials Fatigue, Friction Mechanics Impact factor: 0.533, year: 2016

  6. An efficient quantum mechanical method for radical pair recombination reactions.

    Science.gov (United States)

    Lewis, Alan M; Fay, Thomas P; Manolopoulos, David E

    2016-12-28

    The standard quantum mechanical expressions for the singlet and triplet survival probabilities and product yields of a radical pair recombination reaction involve a trace over the states in a combined electronic and nuclear spin Hilbert space. If this trace is evaluated deterministically, by performing a separate time-dependent wavepacket calculation for each initial state in the Hilbert space, the computational effort scales as O(Z 2 log⁡Z), where Z is the total number of nuclear spin states. Here we show that the trace can also be evaluated stochastically, by exploiting the properties of spin coherent states. This results in a computational effort of O(MZlog⁡Z), where M is the number of Monte Carlo samples needed for convergence. Example calculations on a strongly coupled radical pair with Z>10 6 show that the singlet yield can be converged to graphical accuracy using just M=200 samples, resulting in a speed up by a factor of >5000 over a standard deterministic calculation. We expect that this factor will greatly facilitate future quantum mechanical simulations of a wide variety of radical pairs of interest in chemistry and biology.

  7. Molecular and cellular mechanisms that lead to Candida biofilm formation

    NARCIS (Netherlands)

    ten Cate, J.M.; Klis, F.M.; Pereira-Cenci, T.; Crielaard, W.; de Groot, P.W.J.

    2009-01-01

    Fungal infections in the oral cavity are mainly caused by C. albicans, but other Candida species are also frequently identified. They are increasing in prevalence, especially in denture-wearers and aging people, and may lead to invasive infections, which have a high mortality rate. Attachment to

  8. An experimental and theoretical study of reaction mechanisms between nitriles and hydroxylamine.

    Science.gov (United States)

    Vörös, Attila; Mucsi, Zoltán; Baán, Zoltán; Timári, Géza; Hermecz, István; Mizsey, Péter; Finta, Zoltán

    2014-10-28

    The industrially relevant reaction between nitriles and hydroxylamine yielding amidoximes was studied in different molecular solvents and in ionic liquids. In industry, this procedure is carried out on the ton scale in alcohol solutions and the above transformation produces a significant amount of unexpected amide by-product, depending on the nature of the nitrile, which can cause further analytical and purification issues. Although there were earlier attempts to propose mechanisms for this transformation, the real reaction pathway is still under discussion. A new detailed reaction mechanistic explanation, based on theoretical and experimental proof, is given to augment the former mechanisms, which allowed us to find a more efficient, side-product free procedure. Interpreting the theoretical results obtained, it was shown that the application of specific imidazolium, phosphonium and quaternary ammonium based ionic liquids could decrease simultaneously the reaction time while eliminating the amide side-product, leading to the targeted product selectively. This robust and economic procedure now affords a fast, selective amide free synthesis of amidoximes.

  9. A reaction mechanism for gasoline surrogate fuels for large polycyclic aromatic hydrocarbons

    KAUST Repository

    Raj, Abhijeet

    2012-02-01

    This work aims to develop a reaction mechanism for gasoline surrogate fuels (n-heptane, iso-octane and toluene) with an emphasis on the formation of large polycyclic aromatic hydrocarbons (PAHs). Starting from an existing base mechanism for gasoline surrogate fuels with the largest chemical species being pyrene (C 16H 10), this new mechanism is generated by adding PAH sub-mechanisms to account for the formation and growth of PAHs up to coronene (C 24H 12). The density functional theory (DFT) and the transition state theory (TST) have been adopted to evaluate the rate constants for several PAH reactions. The mechanism is validated in the premixed laminar flames of n-heptane, iso-octane, benzene and ethylene. The characteristics of PAH formation in the counterflow diffusion flames of iso-octane/toluene and n-heptane/toluene mixtures have also been tested for both the soot formation and soot formation/oxidation flame conditions. The predictions of the concentrations of large PAHs in the premixed flames having available experimental data are significantly improved with the new mechanism as compared to the base mechanism. The major pathways for the formation of large PAHs are identified. The test of the counterflow diffusion flames successfully predicts the PAH behavior exhibiting a synergistic effect observed experimentally for the mixture fuels, irrespective of the type of flame (soot formation flame or soot formation/oxidation flame). The reactions that lead to this synergistic effect in PAH formation are identified through the rate-of-production analysis. © 2011 The Combustion Institute.

  10. Reaction mechanism of hydroxymaleimide induced by γ-irradiation in alcohol solvents

    International Nuclear Information System (INIS)

    Nakagawa, Seiko

    2010-01-01

    Methanol and 2-propanol solutions of hydroxymaleimide were irradiated with γ-ray and mechanism of its γ-irradiation-induced reactions was investigated through final-product analyses using high performance liquid chromatography (HPLC) coupled with mass spectroscopy. An addition reaction of a solvent radical toward hydroxymaleimide was dominant among its oxygen-free γ-irradiation-induced reactions in its alcohol solutions while it is known that electron attachment toward hydroxyphthalimide or hydroxysuccinimide is dominant among their γ-irradiation-induced reactions. The radical adduct abstracts hydrogen from solvent molecule to re-produce a solvent radical. Therefore, the degradation efficiency of hydroxymaleimide was more than ten times larger than that of hydroxyphthalimide and hydroxysuccinimide. Dimer was also produced through electron attachment process in the solutions of hydroxymaleimide. In addition, it was found that the degradation efficiency increased with decrease in dose rate. An additional reaction of a solvent radical toward hydroxymaleimide competes with a radical-radical recombination. The latter was reduced, with the former leading to efficient degradation of hydroxymaleimide increased by irradiation at lower dose rate. On the contrary, the production yield of the adduct radical as well as the degradation efficiency of hydroxymaleimide was inhibited in the presence of oxygen.

  11. Reaction mechanism of hydroxymaleimide induced by γ-irradiation in alcohol solvents

    International Nuclear Information System (INIS)

    Nakagawa, Seiko

    2010-01-01

    Methanol and 2-propanol solutions of hydroxymaleimide were irradiated with γ-ray and mechanism of its γ-irradiation-induced reactions was investigated through final-product analyses using high performance liquid chromatography (HPLC) coupled with mass spectroscopy. An addition reaction of a solvent radical toward hydroxymaleimide was dominant among its oxygen-free γ-irradiation-induced reactions in its alcohol solutions while it is known that electron attachment toward hydroxyphthalimide or hydroxysuccinimide is dominant among their γ-irradiation-induced reactions. The radical adduct abstracts hydrogen from solvent molecule to re-produce a solvent radical. Therefore, the degradation efficiency of hydroxymaleimide was more than 10 times larger than that of hydroxyphthalimide and hydroxysuccinimide. Dimer was also produced through electron attachment process in the solutions of hydroxymaleimide. In addition, it was found that the degradation efficiency increased with decreasing the dose rate. An addition reaction of a solvent radical toward hydroxymaleimide competes with a radical-radical recombination. The latter was reduced and the former leading to efficient degradation of hydroxymaleimide increased by irradiation at lower dose rate. On the contrary, the production yield of the adduct radical as well as the degradation efficiency of hydroxymaleimide was inhibited in the presence of oxygen.

  12. Interfacial Reaction of Sn-Ag-Cu Lead-Free Solder Alloy on Cu: A Review

    Directory of Open Access Journals (Sweden)

    Liu Mei Lee

    2013-01-01

    Full Text Available This paper reviews the function and importance of Sn-Ag-Cu solder alloys in electronics industry and the interfacial reaction of Sn-Ag-Cu/Cu solder joint at various solder forms and solder reflow conditions. The Sn-Ag-Cu solder alloys are examined in bulk and in thin film. It then examines the effect of soldering conditions to the formation of intermetallic compounds such as Cu substrate selection, structural phases, morphology evolution, the growth kinetics, temperature and time is also discussed. Sn-Ag-Cu lead-free solder alloys are the most promising candidate for the replacement of Sn-Pb solders in modern microelectronic technology. Sn-Ag-Cu solders could possibly be considered and adapted in miniaturization technologies. Therefore, this paper should be of great interest to a large selection of electronics interconnect materials, reliability, processes, and assembly community.

  13. 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.

  14. Study on interfacial reaction between lead-free solders and alternative surface finishes

    International Nuclear Information System (INIS)

    Siti Rabiatul Aisha; Ourdjini, A.; Saliza Osman

    2007-01-01

    This study investigates the interfacial reactions occurring during reflow soldering between Sn-Ag-Cu lead-free solder and two surface finishes: electroless nickel/ immersion gold (ENIG) and immersion silver (IAg). The study focuses on interfacial reactions evolution and growth kinetics of intermetallic compounds (IMC) formed during soldering and isothermal ageing at 150 degree Celsius for up to 2000 hours. Optical and scanning electron microscopy were used to measure IMC thickness and examine the morphology of IMC respectively, whereas the IMC phases were identified by energy dispersive X-ray analysis (EDX). The results showed that the IMC formed on ENIG finish is thinner compared to that formed on IAg finish. For IAg surface finish, Cu 6 Sn 5 IMCs with scallop morphology are formed at the solder/ surface finish interface after reflow while a second IMC, Cu 3 Sn was formed between the copper and Cu 6 Sn 5 IMC after the isothermal ageing treatment. For ENIG surface finish both (Cu,Ni) 6 Sn 5 and (Ni,Cu) 3 Sn 4 are formed after soldering. Isothermal aging of the solder joints formed on ENIG finish was found to have a significant effect on the morphology of the intermetallics by transforming to more spherical and denser morphology in addition to increase i their thickness with increased ageing time. (author)

  15. The reaction of Lupinus angustifolius L. root meristematic cell nucleoli to lead.

    Science.gov (United States)

    Balcerzak, Lucja; Glińska, Sława; Godlewski, Mirosław

    2011-04-01

    The effect of 2-48 h treatment of Lupinus angustifolius L. roots with lead nitrate at the concentration of 10(-4) M on the nucleoli in meristematic cells was investigated. In the lead presence the number of ring-shaped as well as segregated nucleoli increased especially after 12-48 h of treatment, while spindle-shaped nucleoli appeared after 24 h and 48 h. Lead presence also increased the frequency of cells with silver-stained particles in the nucleus and the number of these particles especially from the 12th hour of treatment. It was accompanied by significant decline of nucleolar area. Analysis of these cells in transmission electron microscope confirmed the presence of ring-shaped and segregated nucleoli. Moreover, electron microscopy revealed compact structure nucleoli without granular component. Additionally, one to three oval-shaped fibrillar structures attached to nucleolus or lying free in the nucleoplasm were visible. The possible mechanism of lead toxicity to the nucleolus is briefly discussed.

  16. Reaction of Aldehydes/Ketones with Electron-Deficient 1,3,5-Triazines Leading to Functionalized Pyrimidines as Diels-Alder/Retro-Diels-Alder Reaction Products: Reaction Development and Mechanistic Studies.

    Science.gov (United States)

    Yang, Kai; Dang, Qun; Cai, Pei-Jun; Gao, Yang; Yu, Zhi-Xiang; Bai, Xu

    2017-03-03

    Catalytic inverse electron demand Diels-Alder (IEDDA) reactions of heterocyclic aza-dienes are rarely reported since highly reactive and electron-rich dienophiles are often found not compatible with strong acids such as Lewis acids. Herein, we disclose that TFA-catalyzed reactions of electron-deficient 1,3,5-triazines and electron-deficient aldehydes/ketones can take place. These reactions led to highly functionalized pyrimidines as products in fair to good yields. The reaction mechanism was carefully studied by the combination of experimental and computational studies. The reactions involve a cascade of stepwise inverse electron demand hetero-Diels-Alder (ihDA) reactions, followed by retro-Diels-Alder (rDA) reactions and elimination of water. An acid was required for both ihDA and rDA reactions. This mechanism was further verified by comparing the relative reactivity of aldehydes/ketones and their corresponding vinyl ethers in the current reaction system.

  17. The reaction mechanism of the (3HE,T) reaction and applications to nuclear structure

    NARCIS (Netherlands)

    1986-01-01

    In this thesis we present a study on the reaction meachanism of the (3He,t) reaction at 70-80 MeV bombarding energy and on structures of the residual nuclei excited in this reaction: 24-Al, 26-Al, 28-P, 32-Cl, 40-Sc, 42-Sc and 58-Cu... Zie: Summary

  18. Mechanism of electric fatigue crack growth in lead zirconate titanate

    International Nuclear Information System (INIS)

    Westram, Ilona; Oates, William S.; Lupascu, Doru C.; Roedel, Juergen; Lynch, Christopher S.

    2007-01-01

    A series of experiments was performed with through-thickness cracks in ferroelectric double cantilever beam (DCB) specimens. Cyclic electric fields of different amplitudes were applied which resulted in cyclic crack propagation perpendicular to the electric field direction. Crack propagation was observed optically and three regimes were identified: a pop-in from a notch, steady-state crack growth and a decrease of the crack growth rate with increasing cycle number. Crack growth only occurred if the applied field exceeded the coercive field strength of the material. Furthermore, the crack extended during each field reversal and the crack growth rate increased with increasing field. Based on the experimental observations, a mechanistic understanding was developed and contrasted with a nonlinear finite element analysis which quantified the stress intensity in the DCB specimens. The driving forces for crack formation at the notch and subsequent fatigue crack growth were computed based on the distribution of residual stresses due to ferroelectric switching. The finite element results are in good agreement with the experimental observations and support the proposed mechanism

  19. Study of the mechanism of Pb + Au reaction at 29 A.MeV

    International Nuclear Information System (INIS)

    Aboufirassi, M.

    1994-07-01

    The aim of this thesis is to demonstrate the binary character of Pb + Au reaction at 29 A.MeV and to study the decay modes of very excited nuclei produced. The experiment set up was performed at the GANIL in the scattering chamber NAUTILUS. It was composed by multi detectors of fragments (Z ≥8) and multi detectors of light charged particles. (Z<8). The analysis of events which lead to detection of more then 80 % of both total charge and total parallel momentum proved that two body final state is still present at this incident energy. This mechanism is similar to the mechanism of heavy ion reaction at low bombarding energy. We have shown that complete damping occurred leading to excitation energy as high as 6 Me V/u. The decay modes of deep inelastic products are evaporation residue or binary fission or multifragmentation. Analysing the fission products, we have estimated the aligned spin of deep inelastic products (45 h). Finally, the study of light charged particles detected with fission fragments has demonstrated that these particles are emitted essentially before fission. The temperature value of hot nuclei emitted at foreword angle is deduced of light particle spectra. (author)

  20. Theoretical Study of Sodium-Water Surface Reaction Mechanism

    Science.gov (United States)

    Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR).

  1. Theoretical study of sodium-water surface reaction mechanism

    International Nuclear Information System (INIS)

    Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

    2012-01-01

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

  2. Lead titanate nanotubes synthesized via ion-exchange method: Characteristics and formation mechanism

    International Nuclear Information System (INIS)

    Song Liang; Cao Lixin; Li Jingyu; Liu Wei; Zhang Fen; Zhu Lin; Su Ge

    2011-01-01

    Highlights: → Lead titanate nanotubes PbTi 3 O 7 were firstly synthesized by ion-exchange method. → Sodium titanate nanotubes have ion exchangeability. → Lead titanate nanotubes show a distinct red shift on absorption edge. - Abstract: A two-step method is presented for the synthesis of one dimensional lead titanate (PbTi 3 O 7 ) nanotubes. Firstly, titanate nanotubes were prepared by an alkaline hydrothermal process with TiO 2 nanopowder as precursor, and then lead titanate nanotubes were formed through an ion-exchange reaction. We found that sodium titanate nanotubes have ion exchangeability with lead ions, while protonated titanate nanotubes have not. For the first time, we distinguished the difference between sodium titanate nanotubes and protonated titanate nanotubes in the ion-exchange process, which reveals a layer space effect of nanotubes in the ion-exchange reaction. In comparison with sodium titanate, the synthesized lead titanate nanotubes show a narrowed bandgap.

  3. Dissolution mechanism of austenitic stainless steels in lead-bismuth eutectic at 500 deg. C

    International Nuclear Information System (INIS)

    Roy, M.

    2012-01-01

    In the framework of the future nuclear power plants studies, lead-bismuth eutectic (LBE) is foreseen as a coolant in the primary or the secondary circuit in three nuclear systems. The use of this liquid alloy induces corrosion issues for structural steels. In liquid lead alloys, steels can undergo two corrosion phenomena: dissolution or oxidation depending on the temperature and the dissolved oxygen content in LBE. The goal of this study is to identify the dissolution mechanisms of austenitic steels in LBE at 500 deg. C. Four Fe-Cr-Ni model austenitic steels, the 316L steel and five other industrial steels were corroded in LBE up to, respectively, 3000, 6000 and 200 h. The dissolution mechanism is identical for all steels: it starts by a preferential dissolution of chromium and nickel. This dissolution leads to the formation of a ferritic corrosion layer penetrated by LBE and containing between 5 and 10 at% of chromium and almost no nickel. This study demonstrates that dissolutions of nickel and chromium are linked. Otherwise, the corrosion kinetics is linear whatever the tested austenitic steel. The controlling steps of the austenitic steels' corrosion rates have been identified. Natural convection in the LBE bath leads to the formation of a diffusion boundary layer at the steel surface. Chromium diffusion in this diffusion boundary layer seems to control the corrosion rates of the model and industrial austenitic steels except the 316L steel. Indeed, the corrosion rate of the 316L steel is controlled by an interfacial reaction which is either the simultaneous dissolution of nickel and chromium in Ni, Cr compounds or the nickel and chromium dissolution catalyzed by the dissolved oxygen in LBE. This study has permitted to highlight the major role of chromium on the corrosion mechanisms and the corrosion rates of austenitic steels: the corrosion rate increases when chromium activity increases. Finally, the impact of the dissolved oxygen and the minor alloying

  4. Fluorometric detection of nitroaromatics by fluorescent lead complexes: A spectroscopic assessment of detection mechanism

    Science.gov (United States)

    Chattopadhyay, Tanmay; Chatterjee, Sourav; Majumder, Ishani; Ghosh, Soumen; Yoon, Sangee; Sim, Eunji

    2018-04-01

    Three Schiff base ligands such as 2-[(2-Hydroxy-3-methoxy-benzylidene)-amino]-2-hydroxymethyl-propane-1,3-diol (HL1), 2-[(2-Hydroxy-benzylidene)-amino]-2-hydroxymethyl-propane-1,3-diol (HL2), 2-[(3,5-Dichloro-2-hydroxy-benzylidene)-amino]-2-hydroxymethyl-propane-1,3-diol (HL3) have been synthesized by condensation of aldehydes (such as 3,5-Dichloro-2-hydroxy benzaldehyde, 2-Hydroxy-benzaldehyde, and 2-Hydroxy-3-methoxy-benzaldehyde) with Tris-(hydroxymethyl)amino methane and characterized by IR, UV-vis and 1H NMR spectroscopy. Then all these three ligands have been used to prepare Pb(II) complexes by reaction with lead(II) acetate tri-hydrate in methanol. In view of analytical and spectral (IR, UV-vis and Mass) studies, it has been concluded that, except HL2, other two ligands form 1:1 metal complexes (1 and 3) with lead. Between two complexes, complex 3 is highly fluorescent and this property has been used to identify the pollutant nitroaromatics. Finally, the quenching mechanism has been established by means of spectroscopic investigation.

  5. Study on the properties of leading protons and antiprotons from exclusive anti pp reactions at 32 GeV/c

    International Nuclear Information System (INIS)

    Bogolyubskij, M.Yu.; Borovikov, A.A.; Boos, Eh.G.

    1986-01-01

    The leading properties of protons and antiprotons from the nondiffractive events are studied for p-barp-exclusive reactions at 32 GeV/c. It is found that the relative leading effect of protons and antiprotons does not depend on the final-state multiplicity and that the longitudinal moments of the leading hadrons are uncorrelated, but a significant part of the transverse momentum of a leading hadron is compensated by the transverse momentum of another leading hadron. It is shown that these experimental facts are described well by a statistical jet-independent model but contradict the Lund string-fragmentation model

  6. Pre-equilibrium nuclear reactions: An introduction to classical and quantum-mechanical models

    International Nuclear Information System (INIS)

    Koning, A.J.; Akkermans, J.M.

    1999-01-01

    In studies of light-ion induced nuclear reactions one distinguishes three different mechanisms: direct, compound and pre-equilibrium nuclear reactions. These reaction processes can be subdivided according to time scales or, equivalently, the number of intranuclear collisions taking place before emission. Furthermore, each mechanism preferably excites certain parts of the nuclear level spectrum and is characterized by different types of angular distributions. This presentation includes description of the classical, exciton model, semi-classical models, with some selected results, and quantum mechanical models. A survey of classical versus quantum-mechanical pre-equilibrium reaction theory is presented including practical applications

  7. Reaction mechanisms for the synthesis of the heaviest elements from heavy ion reactions

    International Nuclear Information System (INIS)

    Gaeggeler, H.W.

    1988-10-01

    This review paper concerns fusion reactions with light heavy-ions, cold fusion, transfer reactions using light heavy-ions or heavy ions. In two appendices, methods for the separation and detection of nuclides in the domain of heaviest elements are described and a comment on the discovery of the element 104 is given. 51 figs., 10 tabs., 335 refs

  8. Optimized reaction mechanism rate rules for ignition of normal alkanes

    KAUST Repository

    Cai, Liming; Pitsch, Heinz; Mohamed, Samah; Raman, Venkat; Bugler, John; Curran, Henry; Sarathy, Mani

    2016-01-01

    fidelity reacting flow simulations capable of improving combustor design and operation. The development of such models for many new fuel components and/or surrogate molecules is greatly facilitated by the application of reaction classes and rate rules

  9. New MCRs: The first 4-component reaction leading to 2,4-disubstituted thiazoles

    NARCIS (Netherlands)

    Kolb, Jürgen; Beck, Barbara; Almstetter, Michael; Heck, Stefan; Herdtweck, Eberhardt; Dömling, Alexander

    2003-01-01

    New organic reactions allow chemical transformations which were previously not possible. Therefore, new reactions are important contributions to the progress in the field of organic synthesis. In this series we describe the design, scope, and limitations of newly-discovered multi-component reactions

  10. Mechanisms in adverse reactions to food. The sinuses

    DEFF Research Database (Denmark)

    Høst, A

    1995-01-01

    Food allergy is an extremely rare cause of chronic sinusitis. Mucosal inflammation in chronic sinusitis is rarely caused by allergic reactions to foods but rather viral infections in the upper respiratory tract.......Food allergy is an extremely rare cause of chronic sinusitis. Mucosal inflammation in chronic sinusitis is rarely caused by allergic reactions to foods but rather viral infections in the upper respiratory tract....

  11. Mechanism of tellurium isomers excitation in (γ, n) reactions

    International Nuclear Information System (INIS)

    Mazur, V.M.; Symochko, D.M.; Bigan, Z.M.; Poltorzhytska, T.V.; Derechkey, P.S.

    2012-01-01

    Isomeric yield ratios for the 119 Te, 121 Te, 123 Te, 127 Te, 129 Te nuclei were obtained in (γ, n) reactions with bremsstrahlung end point energies ranging 10 - 22 MeV with δE = 0.5 MeV step. Experimental isomeric ratios were used to calculate the cross-sections of (γ, n) m reactions, that were further compared with TALYS-1.4 calculations

  12. The Suzuki-Miyaura Cross-Coupling Reaction of Halogenated Aminopyrazoles: Method Development, Scope, and Mechanism of Dehalogenation Side Reaction.

    Science.gov (United States)

    Jedinák, Lukáš; Zátopková, Renáta; Zemánková, Hana; Šustková, Alena; Cankař, Petr

    2017-01-06

    The efficient Suzuki-Miyaura cross-coupling reaction of halogenated aminopyrazoles and their amides or ureas with a range of aryl, heteroaryl, and styryl boronic acids or esters has been developed. The method allowed incorporation of problematic substrates: aminopyrazoles bearing protected or unprotected pyrazole NH, as well as the free amino or N-amide group. Direct comparison of the chloro, bromo, and iodopyrazoles in the Suzuki-Miyaura reaction revealed that Br and Cl derivatives were superior to iodopyrazoles, as a result of reduced propensity to dehalogenation. Moreover, the mechanism and factors affecting the undesired dehalogenation side reaction were revealed.

  13. Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism

    Science.gov (United States)

    Zhao, Zhiqiang; Zhang, Zhaojun; Liu, Shu; Zhang, Dong H.

    2017-02-01

    Reactions occurring at a carbon atom through the Walden inversion mechanism are one of the most important and useful classes of reactions in chemistry. Here we report an accurate theoretical study of the simplest reaction of that type: the H+CH4 substitution reaction and its isotope analogues. It is found that the reaction threshold versus collision energy is considerably higher than the barrier height. The reaction exhibits a strong normal secondary isotope effect on the cross-sections measured above the reaction threshold, and a small but reverse secondary kinetic isotope effect at room temperature. Detailed analysis reveals that the reaction proceeds along a path with a higher barrier height instead of the minimum-energy path because the umbrella angle of the non-reacting methyl group cannot change synchronously with the other reaction coordinates during the reaction due to insufficient energy transfer from the translational motion to the umbrella mode.

  14. A reaction mechanism for gasoline surrogate fuels for large polycyclic aromatic hydrocarbons

    KAUST Repository

    Raj, Abhijeet; Charry Prada, Iran David; Amer, Ahmad Amer; Chung, Suk-Ho

    2012-01-01

    This work aims to develop a reaction mechanism for gasoline surrogate fuels (n-heptane, iso-octane and toluene) with an emphasis on the formation of large polycyclic aromatic hydrocarbons (PAHs). Starting from an existing base mechanism for gasoline

  15. Attention: Reaction Time and Accuracy Reveal Different Mechanisms

    Science.gov (United States)

    Prinzmetal, William; McCool, Christin; Park, Samuel

    2005-01-01

    The authors propose that there are 2 different mechanisms whereby spatial cues capture attention. The voluntary mechanism is the strategic allocation of perceptual resources to the location most likely to contain the target. The involuntary mechanism is a reflexive orienting response that occurs even when the spatial cue does not indicate the…

  16. Recent developments in semiclassical mechanics: eigenvalues and reaction rate constants

    International Nuclear Information System (INIS)

    Miller, W.H.

    1976-04-01

    A semiclassical treatment of eigenvalues for a multidimensional non-separable potential function and of the rate constant for a chemical reaction with an activation barrier is presented. Both phenomena are seen to be described by essentially the same semiclassical formalism, which is based on a construction of the total Hamiltonian in terms of the complete set of ''good'' action variables (or adiabatic invariants) associated with the minimum in the potential energy surface for the eigenvalue case, or the saddle point in the potential energy surface for the case of chemical reaction

  17. On the mechanism of photocatalytic reactions with eosin Y

    Directory of Open Access Journals (Sweden)

    Michal Majek

    2014-04-01

    Full Text Available A combined spectroscopic, synthetic, and apparative study has allowed a more detailed mechanistic rationalization of several recently reported eosin Y-catalyzed aromatic substitutions at arenediazonium salts. The operation of rapid acid–base equilibria, direct photolysis pathways, and radical chain reactions has been discussed on the basis of pH, solvent polarity, lamp type, absorption properties, and quantum yields. Determination of the latter proved to be an especially valuable tool for the distinction between radical chain and photocatalytic reactions.

  18. Sleep restriction may lead to disruption in physiological attention and reaction time

    Directory of Open Access Journals (Sweden)

    Arbind Kumar Choudhary

    2016-07-01

    Full Text Available Sleepiness is the condition where for some reason fails to go into a sleep state and will have difficulty in remaining awake even while carrying out activities. Sleep restriction occurs when an individual fails to get enough sleep due to high work demands. The mechanism between sleep restriction and underlying brain physiology deficits is not well assumed. The objective of the present study was to investigate the mental attention (P300 and reaction time [visual (VRT and auditory (ART] among night watchmen, at subsequent; first (1st day, fourth (4th day and seventh (7th day of restricted sleep period. After exclusion and inclusion criteria, the study was performed among 50 watchmen (age=18–35 years (n=50 after providing written informed consent and divided into two group. Group I-(Normal sleep (n=28 working in day time and used to have normal sleep in night (≥8 h; Group II-(Restricted sleep (n=22 - working in night time and used to have less sleep in night (≤3 h. Statistical significance between the different groups was determined by the independent student ʻtʼ test and the significance level was fixed at p≤0.05. We observed that among all normal and restricted sleep watchmen there was not any significant variation in Karolinska Sleepiness Scale (KSS score, VRT and ART, along with latency and amplitude of P300 on 1st day of restricted sleep. However at subsequent on 4th day and 7th day of restricted sleep, there was significant increase in (KSSscore, and prolongation of VRT and ART as well as alteration in latency and amplitude of P300 wave in restricted sleep watchmen when compare to normal sleep watchmen. The present finding concludes that loss of sleep has major impact in dynamic change in mental attention and reaction time among watchmen employed in night shift. Professional regulations and work schedules should integrate sleep schedules before and during the work period as an essential dimension for their healthy life.

  19. Sleep restriction may lead to disruption in physiological attention and reaction time.

    Science.gov (United States)

    Choudhary, Arbind Kumar; Kishanrao, Sadawarte Sahebrao; Dadarao Dhanvijay, Anup Kumar; Alam, Tanwir

    2016-01-01

    Sleepiness is the condition where for some reason fails to go into a sleep state and will have difficulty in remaining awake even while carrying out activities. Sleep restriction occurs when an individual fails to get enough sleep due to high work demands. The mechanism between sleep restriction and underlying brain physiology deficits is not well assumed. The objective of the present study was to investigate the mental attention (P300) and reaction time [visual (VRT) and auditory (ART)] among night watchmen, at subsequent; first (1st) day, fourth (4th) day and seventh (7th) day of restricted sleep period. After exclusion and inclusion criteria, the study was performed among 50 watchmen (age=18-35 years) (n=50) after providing written informed consent and divided into two group. Group I-(Normal sleep) (n=28) working in day time and used to have normal sleep in night (≥8 h); Group II-(Restricted sleep) (n=22) - working in night time and used to have less sleep in night (≤3 h). Statistical significance between the different groups was determined by the independent student ' t ' test and the significance level was fixed at p≤0.05. We observed that among all normal and restricted sleep watchmen there was not any significant variation in Karolinska Sleepiness Scale (KSS) score, VRT and ART, along with latency and amplitude of P300 on 1st day of restricted sleep. However at subsequent on 4th day and 7th day of restricted sleep, there was significant increase in (KSS)score, and prolongation of VRT and ART as well as alteration in latency and amplitude of P300 wave in restricted sleep watchmen when compare to normal sleep watchmen. The present finding concludes that loss of sleep has major impact in dynamic change in mental attention and reaction time among watchmen employed in night shift. Professional regulations and work schedules should integrate sleep schedules before and during the work period as an essential dimension for their healthy life.

  20. Visualization of reaction mechanism by CG based on quantum ...

    African Journals Online (AJOL)

    In this work, the change in the molecular configuration in fundamental chemical reactions such as, F + HCl ¨ HF + Cl, I + H2¨ HI + H, OH- + CH3Cl ¨ CH3OH + Cl-, and esterification of acetic acid and ethyl alcohol were visualized by the quantum chemical calculation MOPAC with PM5 Hamiltonian. The CG teaching material ...

  1. Tris(Cyclopentadienyl)Uranium-t-Butyl: Synthesis, reactions, and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Weydert, M.

    1993-04-01

    Compounds (RC[sub 5]H[sub 4])[sub 3]U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC[sub 5]H[sub 4])[sub 3]UCl with t-BuLi (R = t-Bu, Me[sub 3]Si). Reactions of (MeC[sub 5]H[sub 4])[sub 3]U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC[sub 5]H[sub 4])[sub 3]ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC[sub 5]H[sub 4])[sub 4]U compounds is next considered. Reaction of the trivalent (RC[sub 5]H[sub 4])[sub 3]U with (RC[sub 5]H[sub 4])[sub 2]Hg results in formation of (RC[sub 5]H[sub 4])[sub 4]U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)

  2. Tris(Cyclopentadienyl)Uranium-t-Butyl: Synthesis, reactions, and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Weydert, Marc [Univ. of California, Berkeley, CA (United States)

    1993-04-01

    Compounds (RC5H4)3U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC5H4)3UCl with t-BuLi (R = t-Bu, Me3Si). Reactions of (MeC5H4)3U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC5H4)3ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC5H4)4U compounds is next considered. Reaction of the trivalent (RC5H4)3U with (RC5H4)2Hg results in formation of (RC5H4)4U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)

  3. Reaction mechanism of O-acylhydroxamate with cysteine proteases

    Indian Academy of Sciences (India)

    WINTEC

    more stable than the reactant and hence the reaction enthalpy is found to be exothermic. ... healing, fertilization, cell differentiation and growth, ... to lower the side effects of drug administration. Since ... tozoa and plants. ... give turnover products or could produce a stable ad- ...... be due to the hydrolysis with water molecule.

  4. Iron Contamination Mechanism and Reaction Performance Research on FCC Catalyst

    Directory of Open Access Journals (Sweden)

    Zhaoyong Liu

    2015-01-01

    Full Text Available FCC (Fluid Catalytic Cracking catalyst iron poisoning would not only influence units’ product slate; when the poisoning is serious, it could also jeopardize FCC catalysts’ fluidization in reaction-regeneration system and further cause bad influences on units’ stable operation. Under catalytic cracking reaction conditions, large amount of iron nanonodules is formed on the seriously iron contaminated catalyst due to exothermic reaction. These nodules intensify the attrition between catalyst particles and generate plenty of fines which severely influence units’ smooth running. A dense layer could be formed on the catalysts’ surface after iron contamination and the dense layer stops reactants to diffuse to inner structures of catalyst. This causes extremely negative effects on catalyst’s heavy oil conversion ability and could greatly cut down gasoline yield while increasing yields of dry gas, coke, and slurry largely. Research shows that catalyst’s reaction performance would be severely deteriorated when iron content in E-cat (equilibrium catalyst exceeds 8000 μg/g.

  5. Mechanisms in adverse reactions to food. The ear

    DEFF Research Database (Denmark)

    Høst, A

    1995-01-01

    Otitis media with effusion is rarely caused by allergy to food. Allergic inflammation in the nasal mucosa, mainly due to IgE-mediated reactions to foods, may cause eustachian tube dysfunction and subsequent otitis media with effusion. Inflammatory mediators from the nasal mucosa transported via...

  6. Coupling Effect between Mechanical Loading and Chemical Reactions

    Czech Academy of Sciences Publication Activity Database

    Klika, Václav; Maršík, František

    2009-01-01

    Roč. 113, č. 44 (2009), s. 14689-14697 ISSN 1520-6106 R&D Projects: GA ČR(CZ) GA106/08/0557 Institutional research plan: CEZ:AV0Z20760514 Keywords : coupling * dynamic loading * reaction kinetics Subject RIV: FI - Traumatology, Orthopedics Impact factor: 3.471, year: 2009

  7. Unified connected theory of few-body reaction mechanisms in N-body scattering theory

    Science.gov (United States)

    Polyzou, W. N.; Redish, E. F.

    1978-01-01

    A unified treatment of different reaction mechanisms in nonrelativistic N-body scattering is presented. The theory is based on connected kernel integral equations that are expected to become compact for reasonable constraints on the potentials. The operators T/sub +-//sup ab/(A) are approximate transition operators that describe the scattering proceeding through an arbitrary reaction mechanism A. These operators are uniquely determined by a connected kernel equation and satisfy an optical theorem consistent with the choice of reaction mechanism. Connected kernel equations relating T/sub +-//sup ab/(A) to the full T/sub +-//sup ab/ allow correction of the approximate solutions for any ignored process to any order. This theory gives a unified treatment of all few-body reaction mechanisms with the same dynamic simplicity of a model calculation, but can include complicated reaction mechanisms involving overlapping configurations where it is difficult to formulate models.

  8. Kinetics and mechanism of the gas-phase reaction of Cl atoms and OH radicals with fluorobenzene at 296 K

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, MD

    2002-01-01

    Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with fluorobenzene, C6H5F, in 700 Torr of N-2 or air diluent at 296 K. Reaction of Cl atoms with C6H5F proceeds via two pathways: H-atom abstraction to give HCl and the C6H4F...... with Cl atoms via a mechanism which, at least in part, leads neither to production of C6H5Cl nor to reformation of C6H5F. As the steady-state Cl atom concentration is increased, the fraction of the C6H5F-Cl adduct undergoing reaction with Cl atoms increases causing an increase in the effective rate...

  9. Multilevel Quantum Mechanics Theories and Molecular Mechanics Calculations of the Cl- + CH3I Reaction in Water.

    Science.gov (United States)

    Liu, Peng; Li, Chen; Wang, Dunyou

    2017-10-19

    The Cl - + CH 3 I → CH 3 Cl + I - reaction in water was studied using combined multilevel quantum mechanism theories and molecular mechanics with an explicit water solvent model. The study shows a significant influence of aqueous solution on the structures of the stationary points along the reaction pathway. A detailed, atomic-level evolution of the reaction mechanism shows a concerted one-bond-broken and one-bond-formed mechanism, as well as a synchronized charge-transfer process. The potentials of mean force calculated with the CCSD(T) and DFT treatments of the solute produce a free activation barrier at 24.5 and 19.0 kcal/mol, respectively, which agrees with the experimental one at 22.0 kcal/mol. The solvent effects have also been quantitatively analyzed: in total, the solvent effects raise the activation energy by 20.2 kcal/mol, which shows a significant impact on this reaction in water.

  10. Nuclear reaction mechanisms. Progress report, June 1976--July 1977

    Energy Technology Data Exchange (ETDEWEB)

    Blann, M.

    1977-01-01

    Research under the subject contract is on heavy ion induced reactions, both on experimental measurement and theoretical interpretation. Measurements have included determination of elastic scattering, evaporation residue, fission, quasi elastic and deep inelastic scattering cross sections. From these data we have extracted information on fusion barrier heights and radii, nucleus-nucleus potentials and fission parameterizations at high angular momenta. We have started investigating influence of excitation energies on inverse cross sections and of precompound decay in heavy ion reactions, and have investigated multidimensional potential energy surfaces for heavy ion collisions. Work which has been published is listed in the Publications Section; work not yet published and/or in progress is discussed herein.

  11. Nuclear reaction mechanisms. Progress report, June 1976--July 1977

    International Nuclear Information System (INIS)

    Blann, M.

    1977-01-01

    Research under the subject contract is on heavy ion induced reactions, both on experimental measurement and theoretical interpretation. Measurements have included determination of elastic scattering, evaporation residue, fission, quasi elastic and deep inelastic scattering cross sections. From these data we have extracted information on fusion barrier heights and radii, nucleus-nucleus potentials and fission parameterizations at high angular momenta. We have started investigating influence of excitation energies on inverse cross sections and of precompound decay in heavy ion reactions, and have investigated multidimensional potential energy surfaces for heavy ion collisions. Work which has been published is listed in the Publications Section; work not yet published and/or in progress is discussed herein

  12. Illustration of reaction mechanism in polyatomic systems via computer movies

    International Nuclear Information System (INIS)

    Raff, L.M.

    1974-01-01

    The CD 4 + T* systems is suited for classroom illustration of reaction dynamics. Questions about the system can be illustrated by reducing selected many-body trajectories to a 16 mm color movie that represents the six-body motion in projected coordinates. Such a movie has been produced for this system. The production procedure used is reported, and a detailed description of the contents of the movie is given. (U.S.)

  13. On the mechanism of photocatalytic reactions with eosin Y

    OpenAIRE

    Majek, Michal; Filace, Fabiana; von Wangelin, Axel Jacobi

    2014-01-01

    Summary A combined spectroscopic, synthetic, and apparative study has allowed a more detailed mechanistic rationalization of several recently reported eosin Y-catalyzed aromatic substitutions at arenediazonium salts. The operation of rapid acid–base equilibria, direct photolysis pathways, and radical chain reactions has been discussed on the basis of pH, solvent polarity, lamp type, absorption properties, and quantum yields. Determination of the latter proved to be an especially valuable tool...

  14. Performance and mechanism for cadmium and lead adsorption from water and soil by corn straw biochar

    Institute of Scientific and Technical Information of China (English)

    Tong Chi; Jiane Zuo; Fenglin Liu

    2017-01-01

    Cadmium (Cd) and lead (Pb) in water and soil could be adsorbed by biochar produced fiom corn straw.Biochar pyrolyzed under 400℃ for 2 h could reach the ideal removal efficiencies (99.24% and 98.62% for Cd and Pb,respectively) from water with the biochar dosage of 20 g· L-1 and imtial concentration of 20 mg·L-1.The pH value of 4-7 was the optimal range for adsorption reaction.The adsorption mechanism was discussed on the basis of a range of characterizations,including X-ray diffraction (XRD),X-my photoelectron spectroscopy (XPS),Fourier transform infrared spectroscopy (FTIR) and Raman analysis;it was concluded as surface complexation with active sorption sites (-OH-COO-) coordination with π electrons (C =C,C =O) and precipitation with morganic anions (OH-,CO32-,SO42-) for both Cd and Pb.The sorption isotherms fit Langmuir model better than Freundlich model,and the saturated sorption capacities for Cd and Pb were 38.91 mg.g-1 and 28.99 mg· g-1,respectively.When mixed with soil,biochar could effectively increase alkalinity and reduce bioavailability of heavy metals.Thus,biochar derived from corn straw would be a green material for both removal of heavy metals and amelioration of soil.

  15. Novel error propagation approach for reducing H2S/O2 reaction mechanism

    International Nuclear Information System (INIS)

    Selim, H.; Gupta, A.K.; Sassi, M.

    2012-01-01

    A reduction strategy of hydrogen sulfide/oxygen reaction mechanism is conducted to simplify the detailed mechanism. Direct relation graph and error propagation methodology (DRGEP) has been used. A novel approach of direct elementary reaction error (DERE) has been developed in this study. The developed approach allowed for further reduction of the reaction mechanism. The reduced mechanism has been compared with the detailed mechanism under different conditions to emphasize its validity. The results obtained from the resulting reduced mechanism showed good agreement with that from the detailed mechanism. However, some discrepancies have been found for some species. Hydrogen and oxygen mole fractions showed the largest discrepancy of all combustion products. The reduced mechanism was also found to be capable of tracking the changes that occur in chemical kinetics through the change in reaction conditions. A comparison on the ignition delay time obtained from the reduced mechanism and previous experimental data showed good agreement. The reduced mechanism was used to track changes in mechanistic pathways of Claus reactions with the reaction progress.

  16. Development of a robust and compact kerosene–diesel reaction mechanism for diesel engines

    International Nuclear Information System (INIS)

    Tay, Kun Lin; Yang, Wenming; Mohan, Balaji; An, Hui; Zhou, Dezhi; Yu, Wenbin

    2016-01-01

    Highlights: • An approach is used to develop a robust kerosene–diesel reaction mechanism. • Ignition delay of the kerosene sub-mechanism is well validated with experiments. • The kerosene sub-mechanism reproduces the flame lift-off lengths of Jet-A reasonably well. • The kerosene sub-mechanism performs reasonably well under engine conditions. - Abstract: The use of kerosene fuels in internal combustion engines is getting more widespread. The North Atlantic Treaty Organization military is pushing for the use of a single fuel on the battlefield in order to reduce logistical issues. Moreover, in some countries, fuel adulteration is a serious matter where kerosene is blended with diesel and used in diesel engines. So far, most investigations done regarding the use of kerosene fuels in diesel engines are experimental and there is negligible simulation work done in this area possibly because of the lack of a robust and compact kerosene reaction mechanism. This work focuses on the development of a small but reliable kerosene–diesel reaction mechanism, suitable to be used for diesel engine simulations. The new kerosene–diesel reaction mechanism consists only of 48 species and 152 reactions. Furthermore, the kerosene sub-mechanism in this new mechanism is well validated for its ignition delay times and has proven to replicate kerosene combustion well in a constant volume combustion chamber and an optical engine. Overall, this new kerosene–diesel reaction mechanism is proven to be robust and practical for diesel engine simulations.

  17. NATO Advanced Research Workshop on the Mechanisms of Reactions of Organometallic Compounds with Surfaces

    CERN Document Server

    Williams, J

    1989-01-01

    A NATO Advanced Research Workshop on the "Mechanisms of Reactions of Organometallic Compounds with Surfaces" was held in St. Andrews, Scotland in June 1988. Many of the leading international researchers in this area were present at the workshop and all made oral presentations of their results. In addition, significant amounts of time were set aside for Round Table discussions, in which smaller groups considered the current status of mechanistic knowledge, identified areas of dispute or disagreement, and proposed experiments that need to be carried out to resolve such disputes so as to advance our understanding of this important research area. All the papers presented at the workshop are collected in this volume, together with summaries of the conclusions reached at the Round Table discussions. The workshop could not have taken place without financial support from NATO, and donations were also received from Associated Octel, Ltd., STC Ltd., and Epichem Ltd., for which the organisers are very grateful. The orga...

  18. 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

  19. Complex Reaction Environments and Competing Reaction Mechanisms in Zeolite Catalysis: Insights from Advanced Molecular Dynamics

    NARCIS (Netherlands)

    De Wispelaere, K.; Ensing, B.; Ghysels, A.; Meijer, E.J.; van Van Speybroeck, V.

    2015-01-01

    The methanol-to-olefin process is a showcase example of complex zeolite-catalyzed chemistry. At real operating conditions, many factors affect the reactivity, such as framework flexibility, adsorption of various guest molecules, and competitive reaction pathways. In this study, the strength of first

  20. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab

    2015-09-24

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  1. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab; Raj, Abhijeet; Al Shoaibi, Ahmed S.; Chung, Suk-Ho

    2015-01-01

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  2. Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium chemical reactions

    International Nuclear Information System (INIS)

    Roh, Heui-Seol

    2015-01-01

    Chemical energy transfer mechanisms at finite temperature are explored by a chemical energy transfer theory which is capable of investigating various chemical mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium. Gibbs energy fluxes are obtained as a function of chemical potential, time, and displacement. Diffusion, convection, internal convection, and internal equilibrium chemical energy fluxes are demonstrated. The theory reveals that there are chemical energy flux gaps and broken discrete symmetries at the activation chemical potential, time, and displacement. The statistical, thermodynamic theory is the unification of diffusion and internal convection chemical reactions which reduces to the non-equilibrium generalization beyond the quasi-equilibrium theories of migration and diffusion processes. The relationship between kinetic theories of chemical and electrochemical reactions is also explored. The theory is applied to explore non-equilibrium chemical reactions as an illustration. Three variable separation constants indicate particle number constants and play key roles in describing the distinct chemical reaction mechanisms. The kinetics of chemical energy transfer accounts for the four control mechanisms of chemical reactions such as activation, concentration, transition, and film chemical reactions. - Highlights: • Chemical energy transfer theory is proposed for non-, quasi-, and equilibrium. • Gibbs energy fluxes are expressed by chemical potential, time, and displacement. • Relationship between chemical and electrochemical reactions is discussed. • Theory is applied to explore nonequilibrium energy transfer in chemical reactions. • Kinetics of non-equilibrium chemical reactions shows the four control mechanisms

  3. Palladium-catalyzed three-component reaction of N-tosyl hydrazones, isonitriles and amines leading to amidines.

    Science.gov (United States)

    Dai, Qiang; Jiang, Yan; Yu, Jin-Tao; Cheng, Jiang

    2015-12-04

    A palladium-catalyzed three-component reaction between N-tosyl hydrazones, aryl isonitriles and amines was developed, leading to amidines in moderate to good yields. This procedure features the rapid construction of amidine frameworks with high diversity and complexity. Ketenimines serve as intermediates, which encounter nucleophilic attack by amines to produce amidines.

  4. Eletromagnetic radiation and the mechanical reactions arising from it

    CERN Document Server

    Schott, G A

    1912-01-01

    Fundamental equations of the electron theory ; transformation of the potentials ; other types of solution ; physical interpretation of the solutions obtained ; illustrative examples ; remarks on the solutions obtained and on the methods of calculating the potentials in general ; periodic motions ; on the distant field due to a moving charge ; pseudo-periodic and aperiodic motions ; on the field near the orbit of a moving charge or group ; the mechanical forces acting on electric charges in motion ; the motion of groups of electric charges ; on the Doppler effect ; on the disturbed motion of a ring of electrons ; on the field close to a point charge in motion ; the mechanical force exterted by an electron on itself ; the mechanical explanation of the electron ; the mechanics of the Lorentz electron ; problems illustrative of the motion of the Lorentz electron.

  5. Multi-nucleon transfer: a probe to investigate the reaction mechanism around the barrier

    International Nuclear Information System (INIS)

    Mandal, Samit K.

    2014-01-01

    The investigation of multi-nucleon transfer mechanism offers valuable information on the pairing interactions that enhance the transfer of nucleon pairs across heavy ions involved in the reaction. These reactions are also a useful tool to study exotic nuclei far from the stability line, which can be explored with the new generation radioactive beam facility. In this talk, multi-nucleon transfer reaction mechanisms between heavy ions and their effect on the reaction dynamics around the coulomb barrier energies have been discussed. Experimental results will be presented with a semi classical description of multi nucleon transfer reaction calculation. One and two nucleon transfer cross sections reproduced using a quantum mechanical coupled channel calculations will also be discussed. A feasibility of investigation of multi-nucleon transfer mechanism to explore the pairing correlation at moderate spin states with radioactive beams will be discussed. (author)

  6. A mechanistic study on the reaction pathways leading to benzene and naphthalene in cellulose vapor phase cracking

    International Nuclear Information System (INIS)

    Norinaga, Koyo; Yang, Huamei; Tanaka, Ryota; Appari, Srinivas; Iwanaga, Keita; Takashima, Yuka; Kudo, Shinji; Shoji, Tetsuya; Hayashi, Jun-ichiro

    2014-01-01

    The reaction pathways leading to aromatic hydrocarbons such as benzene and naphthalene in gas-phase reactions of multi-component mixtures derived from cellulose fast pyrolysis were studied both experimentally and numerically. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase cracking of the nascent pyrolysates at temperature ranging from 400 to 900 °C, residence time from 0.2 to 4.3 s, and at 241 kPa. The products of alkyne and diene were identified from the primary pyrolysis of cellulose even at low temperature range 500–600 °C. These products include acetylene, propyne, propadiene, vinylacetylene, and cyclopentadiene. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step-like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C 3 alkyne and diene are primary precursors of benzene at 650 °C, while combination of ethylene and vinylacetylene produces benzene dominantly at 850 °C. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene. Furan and acrolein are likely important alkyne precursors in cellulose pyrolysis at low temperature, whereas dehydrogenations of olefins are major route to alkyne at high temperatures. - Highlights: • Analytical pyrolysis experiments provided data for kinetic modeling. • Detailed chemical kinetic model was used and evaluated. • Alkyne and diene were important intermediates for aromatic hydrocarbon formation. • Reaction pathways leading to aromatic hydrocarbons were proposed

  7. Reaction 12C(16O,α)24Mg leading to nuclear molecular resonances

    International Nuclear Information System (INIS)

    Nagatani, K.; Shimoda, T.; Tanner, D.; Tribble, R.; Yamaya, T.

    1979-01-01

    The reactions 12 C( 16 O,α) 24 Mg and 13 C( 16 O,α) 25 Mg were investigated at an incident energy of 145 MeV. In the reaction with the 12 C target, broad peaks are observed at forward angles which correspond to the molecular resonance states of the 12 C+ 12 C system, while the spectra with 13 C target show only a smooth continuum

  8. Reaction mechanisms in the radiolysis of peptides, polypeptides and proteins II reactions at side-chain loci in model systems

    International Nuclear Information System (INIS)

    Garrison, W.M.

    1983-11-01

    The major emphasis in radiation biology at the molecular level has been on the nucleic acid component of the nucleic acid-protein complex because of its primary genetic importance. But there is increasing evidence that radiation damage to the protein component also has important biological implications. Damage to capsid protein now appears to be a major factor in the radiation inactivation of phage and other viruses. And, there is increasing evidence that radiation-chemical change in the protein component of chromation leads to changes in the stability of the repressor-operator complexes involved in gene expression. Knowledge of the radiation chemistry of protein is also of importance in other fields such as the application of radiation sterilization to foods and drugs. Recent findings that a class of compounds, the α,α'-diaminodicarboxylic acids, not normally present in food proteins, are formed in protein radiolysis is of particular significance since certain of their peptide derivatives have been showing to exhibit immunological activity. The purpose of this review is to bring together and to correlate our present knowledge of products and mechanisms in the radiolysis of peptides, polypeptides and proteins both aqueous and solid-state. In part 1 we presented a discussion of the radiation-induced reactions of the peptide main-chain in model peptide and polypeptide systems. Here in part 2 the emphasis is on the competing radiation chemistry at side-chain loci of peptide derivatives of aliphatic, aromatic-unsaturated and sulfur-containing amino acids in similar systems. Information obtained with the various experimental techniques of product analysis, competition kinetics, spin-trapping, pulse radiolysis, and ESR spectroscopy are included

  9. Mechanism to preserve phrenic nerve function during photosensitization reaction: drug uptake and photosensitization reaction effect on electric propagation

    Science.gov (United States)

    Takahashi, Haruka; Hamada, Risa; Ogawa, Emiyu; Arai, Tsunenori

    2018-02-01

    To study a mechanism of phrenic nerve preservation phenomena during a photosensitization reaction, we investigated an uptake of talaporfin sodium and photosensitization reaction effect on an electric propagation. Right phrenic nerve was completely preserved after superior vena cava isolations using the photosensitization reaction in canine animal experiments, in spite of adjacent myocardium was electrically blocked. We predicted that low drug uptake and/or low photosensitization reaction effect on the nerve might be a mechanism of that phenomena. To investigate uptake to various nerve tissue, a healthy extracted crayfish ventral nerve cord and an extracted porcine phrenic nerve were immersed in 20 μg/ml talaporfin sodium solution for 0-240 min. The mean talaporfin sodium fluorescence brightness increased depending on the immersion time. This brightness saturated around the immersion time of 120 min. We found that talaporfin sodium uptake inside the perineurium which directly related to the electric propagation function was lower than that of outside in the porcine phrenic nerve. To investigate photosensitization reaction effect on electric propagation, the crayfish nerve was immersed into the same solution for 15 min and irradiated by a 663 nm laser light with 120 mW/cm2. Since we found the action potential disappeared when the irradiation time was 25-65 s, we consider that the crayfish nerve does not tolerant to the photosensitization reaction on electric propagation function at atmospheric pressure. From these results, we think that the low uptake of talaporfin sodium inside the perineurium and low oxygen partial pressure of nerve might be the possible mechanism to preserve phrenic nerve in vivo.

  10. Mechanical and thermo-mechanical response of a lead-core bearing device subjected to different loading conditions

    Directory of Open Access Journals (Sweden)

    Zhelyazov Todor

    2018-01-01

    Full Text Available The contribution is focused on the numerical modelling, simulation and analysis of a lead-core bearing device for passive seismic isolation. An accurate finite element model of a lead-core bearing device is presented. The model is designed to analyse both mechanical and thermo-mechanical responses of the seismic isolator to different loading conditions. Specifically, the mechanical behaviour in a typical identification test is simulated. The response of the lead-core bearing device to circular sinusoidal paths is analysed. The obtained shear displacement – shear force relationship is compared to experimental data found in literature sources. The hypothesis that heating of the lead-core during cyclic loading affects the degrading phenomena in the bearing device is taken into account. Constitutive laws are defined for each material: lead, rubber and steel. Both predefined constitutive laws (in the used general–purpose finite element code and semi-analytical procedures aimed at a more accurate modelling of the constitutive relations are tested. The results obtained by finite element analysis are to be further used to calibrate a macroscopic model of the lead-core bearing device seen as a single-degree-of-freedom mechanical system.

  11. Errors in Postural Preparation Lead to Increased Choice Reaction Times for Step Initiation in Older Adults

    Science.gov (United States)

    Nutt, John G.; Horak, Fay B.

    2011-01-01

    Background. This study asked whether older adults were more likely than younger adults to err in the initial direction of their anticipatory postural adjustment (APA) prior to a step (indicating a motor program error), whether initial motor program errors accounted for reaction time differences for step initiation, and whether initial motor program errors were linked to inhibitory failure. Methods. In a stepping task with choice reaction time and simple reaction time conditions, we measured forces under the feet to quantify APA onset and step latency and we used body kinematics to quantify forward movement of center of mass and length of first step. Results. Trials with APA errors were almost three times as common for older adults as for younger adults, and they were nine times more likely in choice reaction time trials than in simple reaction time trials. In trials with APA errors, step latency was delayed, correlation between APA onset and step latency was diminished, and forward motion of the center of mass prior to the step was increased. Participants with more APA errors tended to have worse Stroop interference scores, regardless of age. Conclusions. The results support the hypothesis that findings of slow choice reaction time step initiation in older adults are attributable to inclusion of trials with incorrect initial motor preparation and that these errors are caused by deficits in response inhibition. By extension, the results also suggest that mixing of trials with correct and incorrect initial motor preparation might explain apparent choice reaction time slowing with age in upper limb tasks. PMID:21498431

  12. PHYSIOLOGICAL REACTION OF COMMON OSIER (SALIX VIMINIALIS L. VAR. JORR TO THE PRESENCE OF LEAD IN THE SUBSOIL

    Directory of Open Access Journals (Sweden)

    Katarzyna Malinowska

    2015-02-01

    Full Text Available The effect of lead ions of the concentrations within the range of 15–1000 mg∙dm-3 on the physiological reaction of common osier var. Jorr was examined. The content of assimilation pigments, the rate the CO2 assimilation, transpiration, the indices of relative water content and the deficit of water saturation and the content of lead in the nutrient solution. The studied physiological parameters in common osier var. Jorr were differentiated by the rate of lead ions in the nutrient solution. The Jorr variety of common osier was characterised by good values of the determined physiological parameters under stressful conditions at a large accumulation of lead. This suggests that it shows quite a high tolerance to the stress caused by contamination of the subsoil with lead.

  13. Nuclear and hadronic reaction mechanisms producing spin asymmetry

    Indian Academy of Sciences (India)

    We briefly review concept of the quark recombination (QRC) model and a general success of the model. To solve the existing problem, so called anomalous spin observables, in the high energy hyperon spin phenomena, we propose a mechanism; the primarily produced quarks, which are predominantly and quarks, ...

  14. Reaction kinetics and mechanism of magnetic field effects in cryptochrome

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Schulten, Klaus

    2012-01-01

    Creatures as varied as mammals, fish, insects, reptiles, and birds have an intriguing sixth sense that allows them to orient themselves in the Earth's magnetic field. Despite decades of study, the physical basis of this magnetic sense remains elusive. A likely mechanism is furnished by magnetically...

  15. Ambiguities in the reaction mechanism for (e,e'N)

    International Nuclear Information System (INIS)

    Forest, T. de Jr.

    1984-01-01

    The primary motivation for performing quasi-elastic (e,e'N) experiments revolves around the plane wave impulse approximation (PWIA) description of this reaction. Since the PWIA is an approximation, corrections are necessary in practice in order to extract the desired nuclear structure. Unless one understands the physics behind these corrections this introduces ambiguities. In fact the PWIA itself is an ambiguous prescription since a 'free' off-shell cross section is not a well-defined concept. It is these ambiguities which are discussed in this talk. Most of the paper is devoted to the ambiguities associated with the electromagnetic interaction. The author concentrates on four topics: (1) the interaction of the electron with the nucleus in general; (2) ambiguities in the application of the impulse approximation; (3) the sigma-omega model; and (4) the Coulomb sum rule. (Auth.)

  16. The influence of the “cage effect” on the mechanism of reversible bimolecular multistage chemical reactions in solutions

    International Nuclear Information System (INIS)

    Doktorov, Alexander B.

    2015-01-01

    Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants

  17. The influence of the "cage effect" on the mechanism of reversible bimolecular multistage chemical reactions in solutions.

    Science.gov (United States)

    Doktorov, Alexander B

    2015-08-21

    Manifestations of the "cage effect" at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a "cage complex." Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the "cage effect" leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

  18. The influence of the “cage effect” on the mechanism of reversible bimolecular multistage chemical reactions in solutions

    Energy Technology Data Exchange (ETDEWEB)

    Doktorov, Alexander B., E-mail: doktorov@kinetics.nsc.ru [Voevodsky Institute of Chemical Kinetics & Combustion, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia and Novosibirsk State University, Novosibirsk 630090 (Russian Federation)

    2015-08-21

    Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

  19. Analysis of reaction products formed in the gas phase reaction of E,E-2,4-hexadienal with atmospheric oxidants: Reaction mechanisms and atmospheric implications

    Science.gov (United States)

    Colmenar, I.; Martin, P.; Cabañas, B.; Salgado, S.; Martinez, E.

    2018-03-01

    An analysis of reaction products for the reaction of E,E-2,4-hexadienal with chlorine atoms (Cl) and OH and NO3 radicals has been carried out at the first time with the aim of obtaining a better understanding of the tropospheric reactivity of α,β-unsaturated carbonyl compounds. Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography-Mass Spectrometry with a Time of Flight detector (GC-TOFMS) were used to carry out the qualitative and/or quantitative analyses. Reaction products in gas and particulate phase were observed from the reactions of E,E-2,4- hexadienal with all oxidants. E/Z-Butenedial and maleic anhydride were the main products identified in gas phase. E-butenedial calculated molar yield ranging from 4 to 10%. A significant amount of multifunctional compounds (chloro and hydroxy carbonyls) was identified. These compounds could be formed in particulate phase explaining the ∼90% of unaccounted carbon in gas phase. The reaction with Cl atoms in the presence of NOx with a long reaction time gave Peroxy Acetyl Nitrate (PAN) as an additional product, which is known for being an important specie in the generation of the photochemical smog. Nitrated compounds were the major organic products from the reaction with the NO3 radical. Based on the identified products, the reaction mechanisms have been proposed. In these mechanisms a double bond addition of the atmospheric oxidant at C4/C5 of E,E-2,4-hexadienal is the first step for tropospheric degradation.

  20. Insights into the Reaction Mechanism of Aromatic Ring Cleavage by Homogentisate Dioxygenase: A Quantum Mechanical/Molecular Mechanical Study.

    Science.gov (United States)

    Qi, Yue; Lu, Jiarui; Lai, Wenzhen

    2016-05-26

    To elucidate the reaction mechanism of the ring cleavage of homogentisate by homogentisate dioxygenase, quantum mechanical/molecular mechanical (QM/MM) calculations were carried out by using two systems in different protonation states of the substrate C2 hydroxyl group. When the substrate C2 hydroxyl group is ionized (the ionized pathway), the superoxo attack on the substrate is the rate-limiting step in the catalytic cycle, with a barrier of 15.9 kcal/mol. Glu396 was found to play an important role in stabilizing the bridge species and its O-O cleavage product by donating a proton via a hydrogen-bonded water molecule. When the substrate C2 hydroxyl group is not ionized (the nonionized pathway), the O-O bond cleavage of the bridge species is the rate-limiting step, with a barrier of 15.3 kcal/mol. The QM/MM-optimized geometries for the dioxygen and alkylperoxo complexes using the nonionized model (for the C2 hydroxyl group) are in agreement with the experimental crystal structures, suggesting that the C2 hydroxyl group is more likely to be nonionized.

  1. Combined quantum mechanical and molecular mechanical reaction pathway calculation for aromatic hydroxylation by p-hydroxybenzoate-3-hydroxylase

    NARCIS (Netherlands)

    Ridder, L.; Mulholland, A.; Rietjens, I.M.C.M.; Vervoort, J.

    1999-01-01

    The reaction pathway for the aromatic 3-hydroxylation of p-hydroxybenzoate by the reactive C4a-hydroperoxyflavin cofactor intermediate in p-hydroxybenzoate hydroxylase (PHBH) has been investigated by a combined quantum mechanical and molecular mechanical (QM/MM) method. A structural model for the

  2. Computational comparison of quantum-mechanical models for multistep direct reactions

    International Nuclear Information System (INIS)

    Koning, A.J.; Akkermans, J.M.

    1993-01-01

    We have carried out a computational comparison of all existing quantum-mechanical models for multistep direct (MSD) reactions. The various MSD models, including the so-called Feshbach-Kerman-Koonin, Tamura-Udagawa-Lenske and Nishioka-Yoshida-Weidenmueller models, have been implemented in a single computer system. All model calculations thus use the same set of parameters and the same numerical techniques; only one adjustable parameter is employed. The computational results have been compared with experimental energy spectra and angular distributions for several nuclear reactions, namely, 90 Zr(p,p') at 80 MeV, 209 Bi(p,p') at 62 MeV, and 93 Nb(n,n') at 25.7 MeV. In addition, the results have been compared with the Kalbach systematics and with semiclassical exciton model calculations. All quantum MSD models provide a good fit to the experimental data. In addition, they reproduce the systematics very well and are clearly better than semiclassical model calculations. We furthermore show that the calculated predictions do not differ very strongly between the various quantum MSD models, leading to the conclusion that the simplest MSD model (the Feshbach-Kerman-Koonin model) is adequate for the analysis of experimental data

  3. A Postulated Mechanism That Leads to Materialization and Dematerialization of Matter and to Antigravity.

    Science.gov (United States)

    Bearden, Thomas E.

    This document presents a discussion of the postulated mechanism that leads to the materialization and dematerialization of matter and to antigravity. The mechanism also explains why an orbital electron does not radiate energy, in contradiction to classical electromagnetic theory. One of the paradoxes of special relativity is explained. A new model…

  4. Lead inhibition of DNA-binding mechanism of Cys(2)His(2) zinc finger proteins.

    Science.gov (United States)

    Hanas, J S; Rodgers, J S; Bantle, J A; Cheng, Y G

    1999-11-01

    The association of lead with chromatin in cells suggests that deleterious metal effects may in part be mediated through alterations in gene function. To elucidate if and how lead may alter DNA binding of cysteine-rich zinc finger proteins, lead ions were analyzed for their ability to alter the DNA binding mechanism of the Cys(2)His(2) zinc finger protein transcription factor IIIA (TFIIIA). As assayed by DNase I protection, the interaction of TFIIIA with the 50-bp internal control region of the 5S ribosomal gene was partially inhibited by 5 microM lead ions and completely inhibited by 10 to 20 microM lead ions. Preincubation of free TFIIIA with lead resulted in DNA-binding inhibition, whereas preincubation of a TFIIIA/5S RNA complex with lead did not result in DNA-binding inhibition. Because 5S RNA binds TFIIIA zinc fingers, this result is consistent with an inhibition mechanism via lead binding to zinc fingers. The complete loss of DNase I protection on the 5S gene indicates the mechanism of inhibition minimally involves the N-terminal fingers of TFIIIA. Inhibition was not readily reversible and occurred in the presence of an excess of beta-mercaptoethanol. Inhibition kinetics were fast, progressing to completion in approximately 5 min. Millimolar concentrations of sulfhydryl-specific arsenic ions were not inhibitory for TFIIIA binding. Micromolar concentrations of lead inhibited DNA binding by Sp1, another Cys(2)His(2) finger protein, but not by the nonfinger protein AP2. Inhibition of Cys(2)His(2) zinc finger transcription factors by lead ions at concentrations near those known to have deleterious physiological effects points to new molecular mechanisms for lead toxicity in promoting disease.

  5. Heterogeneous reaction mechanisms and kinetics relevant to the CVD of semiconductor materials

    Energy Technology Data Exchange (ETDEWEB)

    Creighton, J.R.; Coltrin, M.E.

    1994-03-01

    This report documents the state of the art in experimental and theoretical techniques for determining reaction mechanisms and chemical kinetics of heterogeneous reactions relevant to the chemical vapor deposition of semiconductor materials. It summarizes the most common ultra-high vacuum experimental techniques that are used and the types of rate information available from each. Several case studies of specific chemical systems relevant to the microelectronics industry are described. Theoretical methods for calculating heterogeneous reaction rate constants are also summarized.

  6. Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review.

    Science.gov (United States)

    He, Jie; Yang, Xiaofang; Men, Bin; Wang, Dongsheng

    2016-01-01

    The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals (OH) from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH. Hence, it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology. Due to the complex reaction system, the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating, and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies. Iron-based materials usually possess high catalytic activity, low cost, negligible toxicity and easy recovery, and are a superior type of heterogeneous Fenton catalysts. Therefore, this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials. OH, hydroperoxyl radicals/superoxide anions (HO2/O2(-)) and high-valent iron are the three main types of reactive oxygen species (ROS), with different oxidation reactivity and selectivity. Based on the mechanisms of ROS generation, the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron, the heterogeneous catalysis mechanism, and the heterogeneous reaction-induced homogeneous mechanism. Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed. Finally, related future research directions are also suggested. Copyright © 2015. Published by Elsevier B.V.

  7. A facile and expedient one-pot three-component reaction leading to ...

    Indian Academy of Sciences (India)

    A three-component reaction between triphenylphosphine, a dialkyl acetylenedicarboxylate and phthalazin-1(2H)-ones that affords novel organic phosphorane derivatives in good to excellent yields is reported. FTIR, 1H, 13C and 31P NMR and elemental analyses have been utilized to characterize the synthesized ...

  8. Development of a skeletal multi-component fuel reaction mechanism based on decoupling methodology

    International Nuclear Information System (INIS)

    Mohan, Balaji; Tay, Kun Lin; Yang, Wenming; Chua, Kian Jon

    2015-01-01

    Highlights: • A compact multi-component skeletal reaction mechanism was developed. • Combined bio-diesel and PRF mechanism was proposed. • The mechanism consists of 68 species and 183 reactions. • Well validated against ignition delay times, flame speed and engine results. - Abstract: A new coupled bio-diesel surrogate and primary reference fuel (PRF) oxidation skeletal mechanism has been developed. The bio-diesel surrogate sub-mechanism consists of oxidation sub-mechanisms of Methyl decanoate (MD), Methyl 9-decenoate (MD9D) and n-Heptane fuel components. The MD and MD9D are chosen to represent the saturated and unsaturated methyl esters respectively in bio-diesel fuels. Then, a reduced iso-Octane oxidation sub-mechanism is added to the bio-diesel surrogate sub-mechanism. Then, all the sub-mechanisms are integrated to a reduced C_2–C_3 mechanism, detailed H_2/CO/C_1 mechanism and reduced NO_x mechanism based on decoupling methodology. The final mechanism consisted of 68 species and 183 reactions. The mechanism was well validated with shock-tube ignition delay times, laminar flame speed and 3D engine simulations.

  9. Effect of compound nuclear reaction mechanism in 12C(6Li,d) reaction at sub-Coulomb energy

    Science.gov (United States)

    Mondal, Ashok; Adhikari, S.; Basu, C.

    2017-09-01

    The angular distribution of the 12C(6Li,d) reaction populating the 6.92 and 7.12 MeV states of 16O at sub-Coulomb energy (Ecm=3 MeV) are analysed in the framework of the Distorted Wave Born Approximation (DWBA). Recent results on excitation function measurements and backward angle angular distributions derive ANC for both the states on the basis of an alpha transfer mechanism. In the present work, we show that considering both forward and backward angle data in the analysis, the 7.12 MeV state at sub-Coulomb energy is populated from Compound nuclear process rather than transfer process. The 6.92 MeV state is however produced from direct reaction mechanism.

  10. Reaction mechanisms in 24.3 MeV/nucleon 238U induced reactions through a comprehensive study of fission

    International Nuclear Information System (INIS)

    Chbihi, A.; Galin; Guerreau, D.; Lewitowicz, M.; Morjean, M.; Pouthas, J.; Piasecki, E.; Kordyasz, A.; Iwanicki, J.; Jastrzebski, J.; Pienkowski, L.; Crema, E.; Gatty, B.; Jacquet, D.; Muchorowska, M.

    1994-01-01

    Nuclear reaction mechanisms for system characterized by very different asymmetries (U+C, Si, Ni, Au) have been investigated at 24.3 MeV/nucleon, using as observables both the fission products and the neutron multiplicity. It is clearly observed that the fusion process-whatever its completeness- can only occur with rather light target nuclei, indicating the persistence of potential energy effects much above the interaction barrier. (authors). 22 refs., 1 fig

  11. Study of the mechanism of Pb + Au reaction at 29 A.MeV; Etude du mecanisme de la reaction Pb + Au a 29 A.MeV

    Energy Technology Data Exchange (ETDEWEB)

    Aboufirassi, M

    1994-07-01

    The aim of this thesis is to demonstrate the binary character of Pb + Au reaction at 29 A.MeV and to study the decay modes of very excited nuclei produced. The experiment set up was performed at the GANIL in the scattering chamber NAUTILUS. It was composed by multi detectors of fragments (Z {>=}8) and multi detectors of light charged particles. (Z<8). The analysis of events which lead to detection of more then 80 % of both total charge and total parallel momentum proved that two body final state is still present at this incident energy. This mechanism is similar to the mechanism of heavy ion reaction at low bombarding energy. We have shown that complete damping occurred leading to excitation energy as high as 6 Me V/u. The decay modes of deep inelastic products are evaporation residue or binary fission or multifragmentation. Analysing the fission products, we have estimated the aligned spin of deep inelastic products (45 h). Finally, the study of light charged particles detected with fission fragments has demonstrated that these particles are emitted essentially before fission. The temperature value of hot nuclei emitted at foreword angle is deduced of light particle spectra. (author). 59 refs.

  12. Development and validation of a reduced combined biodiesel–diesel reaction mechanism

    DEFF Research Database (Denmark)

    Ng, Hoon Kiat; Gan, Suyin; Ng, Jo-Han

    2013-01-01

    In this study, a compact combined biodiesel–diesel (CBD) reaction mechanism for diesel engine simulations is proposed through the combination of three component mechanisms using a chemical class-based approach. The proposed mechanism comprises the reaction mechanisms of methyl crotonate (MC...... to characterise the combustion of fossil diesel. Here, the MC and MB mechanisms are reduced before integrating with a compact n-heptane mechanism. CHEMKIN-PRO is used as the solver for the zero-dimensional, closed homogenous reactor with a constant volume in this study. In the first phase, the mechanisms of MC...... ranging from initial temperatures of 750–1350 K, pressures of 40–60 bar and equivalence ratios of 0.4–1.5. The mechanism is generally found to accurately predict the timing and duration of ID for the combustion of each surrogate fuel. This model is also shown to be feasible for use with multidimensional...

  13. Probing the reaction mechanism of IspH protein by x-ray structure analysis

    KAUST Repository

    Gräwert, Tobias

    2009-12-28

    Isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP) represent the two central intermediates in the biosynthesis of isoprenoids. The recently discovereddeoxyxylulose 5-phosphate pathway generates a mixture of IPP and DMAPP in its final step by reductive dehydroxylation of 1-hydroxy-2-methyl- 2-butenyl 4-diphosphate. This conversion is catalyzed by IspH protein comprising a central iron-sulfur cluster as electron transfer cofactor in the active site. The five crystal structures of IspH in complex with substrate, converted substrate, products and PPi reported in this article provide unique insights into the mechanism of this enzyme. While IspH protein crystallizes with substrate bound to a [4Fe-4S] cluster, crystals of IspH in complex with IPP, DMAPP or inorganic pyrophosphate feature [3Fe-4S] clusters. The IspH:substrate complex reveals a hairpin conformation of the ligand with the C(1) hydroxyl group coordinated to the unique site in a [4Fe-4S] cluster of aconitase type. The resulting alkoxide complex is coupled to a hydrogen-bonding network, which serves as proton reservoir via a Thr167 proton relay. Prolonged x-ray irradiation leads to cleavage of the C(1)-O bond (initiated by reducing photo electrons). The data suggest a reaction mechanism involving a combination of Lewis-acid activation and proton coupled electron transfer. The resulting allyl radical intermediate can acquire a second electron via the iron-sulfur cluster. The reaction may be terminated by the transfer of a proton from the β-phosphate of the substrate to C(1) (affording DMAPP) or C(3) (affording IPP).

  14. Probing the reaction mechanism of IspH protein by x-ray structure analysis

    KAUST Repository

    Grä wert, Tobias; Span, Ingrid; Eisenreich, Wolfgang; Rohdich, Felix; Eppinger, Jö rg; Bacher, Adelbert; Groll, Michael

    2009-01-01

    Isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP) represent the two central intermediates in the biosynthesis of isoprenoids. The recently discovereddeoxyxylulose 5-phosphate pathway generates a mixture of IPP and DMAPP in its final step by reductive dehydroxylation of 1-hydroxy-2-methyl- 2-butenyl 4-diphosphate. This conversion is catalyzed by IspH protein comprising a central iron-sulfur cluster as electron transfer cofactor in the active site. The five crystal structures of IspH in complex with substrate, converted substrate, products and PPi reported in this article provide unique insights into the mechanism of this enzyme. While IspH protein crystallizes with substrate bound to a [4Fe-4S] cluster, crystals of IspH in complex with IPP, DMAPP or inorganic pyrophosphate feature [3Fe-4S] clusters. The IspH:substrate complex reveals a hairpin conformation of the ligand with the C(1) hydroxyl group coordinated to the unique site in a [4Fe-4S] cluster of aconitase type. The resulting alkoxide complex is coupled to a hydrogen-bonding network, which serves as proton reservoir via a Thr167 proton relay. Prolonged x-ray irradiation leads to cleavage of the C(1)-O bond (initiated by reducing photo electrons). The data suggest a reaction mechanism involving a combination of Lewis-acid activation and proton coupled electron transfer. The resulting allyl radical intermediate can acquire a second electron via the iron-sulfur cluster. The reaction may be terminated by the transfer of a proton from the β-phosphate of the substrate to C(1) (affording DMAPP) or C(3) (affording IPP).

  15. Dissipative effects in fission investigated with proton-on-lead reactions

    Directory of Open Access Journals (Sweden)

    Rodríguez-Sánchez J. L.

    2016-01-01

    Full Text Available The complete kinematic measurement of the two fission fragments permitted us to investigate dissipative effects at large deformations, between the saddle-point and the corresponding scission configurations. Up to now, this kind of study has only been performed with fusionfission reactions using a limited number of observables, such as the mass distribution of the fission fragments or the neutron multiplicities. However, the large angular momenta gained by the compound nucleus could affect the conclusions drawn from such experiments. In this work, the use of spallation reactions, where the fissioning systems are produced with low angular momentum, small deformations and high excitation energies, favors the study of dissipation, and allowed us to define new observables, such as postscission neutron multiplicities and the neutron excess of the final fission fragments as a function of the atomic number of the fissioning system. These new observables are used to investigate the dissipation at large deformations.

  16. High spin states excited by the (p, t) reaction on lead isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Kumabe, I.; Hyakutake, M. [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering; Yuasa, K.; Yamagata, T.; Kishimoto, S.; Ikegami, H.; Muraoka, M [eds.

    1980-01-01

    In order to find high spin states the sup(204, 206, 208)Pb (p, t) reactions have been investigated with RCNP isochronous cyclotron and a high resolution magnetic spectrograph ''RAIDEN''. The experimental angular distributions were analyzed by DWBA calculations, and the lowest 10/sup +/, 12/sup +/ (i sub(13/2))/sup 2/ and 11/sup -/ (i sub(13/2), h sub(9/2)) states in /sup 202/Pb, /sup 204/Pb and /sup 206/Pb were established.

  17. Derivation of the reduced reaction mechanisms of ozone depletion events in the Arctic spring by using concentration sensitivity analysis and principal component analysis

    Directory of Open Access Journals (Sweden)

    L. Cao

    2016-12-01

    Full Text Available The ozone depletion events (ODEs in the springtime Arctic have been investigated since the 1980s. It is found that the depletion of ozone is highly associated with an auto-catalytic reaction cycle, which involves mostly the bromine-containing compounds. Moreover, bromide stored in various substrates in the Arctic such as the underlying surface covered by ice and snow can be also activated by the absorbed HOBr. Subsequently, this leads to an explosive increase of the bromine amount in the troposphere, which is called the “bromine explosion mechanism”. In the present study, a reaction scheme representing the chemistry of ozone depletion and halogen release is processed with two different mechanism reduction approaches, namely, the concentration sensitivity analysis and the principal component analysis. In the concentration sensitivity analysis, the interdependence of the mixing ratios of ozone and principal bromine species on the rate of each reaction in the ODE mechanism is identified. Furthermore, the most influential reactions in different time periods of ODEs are also revealed. By removing 11 reactions with the maximum absolute values of sensitivities lower than 10 %, a reduced reaction mechanism of ODEs is derived. The onsets of each time period of ODEs in simulations using the original reaction mechanism and the reduced reaction mechanism are identical while the maximum deviation of the mixing ratio of principal bromine species between different mechanisms is found to be less than 1 %. By performing the principal component analysis on an array of the sensitivity matrices, the dependence of a particular species concentration on a combination of the reaction rates in the mechanism is revealed. Redundant reactions are indicated by principal components corresponding to small eigenvalues and insignificant elements in principal components with large eigenvalues. Through this investigation, aside from the 11 reactions identified as

  18. Electrocatalysis of anodic oxygen-transfer reactions at modified lead dioxide electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Hsiao, Yun-Lin.

    1990-09-21

    The electrocatalytic activities were compared for pure and chloride-doped beta-PbO{sub 2} (Cl-PbO{sub 2}) films on gold and platinum substrates. Rate constants were increased significantly for oxidations of Mn{sup 2+}, toluene, benzyl alcohol, dimethylsulphoxide (DMSO) and benzaldehyde in acidic media by the incorporation of Cl{sup {minus}} into the oxide films. These reactions are concluded to occur by the electrocatalytic transfer of oxygen from H{sub 2}O to the reaction products. Results of x-ray diffraction studies indicate the Cl-PbO{sub 2} film continues to have the slightly distorted rutile structure of pure beta-PbO{sub 2}. The observed electrocatalytic phenomena are concluded to be the beneficial consequence of surface defects generated when Cl{sup {minus}} serves for charge compensation within the surface matrix and, thereby, increases the number of surface sites capable of adsorbing hydroxyl radicals which are transferred in the electrocatalytic O-transfer reactions. 91 refs., 44 figs., 10 tabs.

  19. Mechanical and fatigue properties of martensitic Fe-13Cr steel in contact with lead and lead-bismuth melts

    Energy Technology Data Exchange (ETDEWEB)

    Yaskiv, O.I., E-mail: oleh.yaskiv@ipm.lviv.ua; Fedirko, V.M.

    2014-01-15

    Highlights: •We investigated the influence of Pb and Pb-Bi melts on mechanical properties of Fe-13Cr steel at high temperatures. •We revealed the temperature interval of liquid metal embrittlement of Fe-13Cr steel. •Pb-Bi has more negative impact as compared with Pb for both plasticity and fatigue. -- Abstract: The influence of stagnant liquid-metal environments (Pb and Pb-Bi) on mechanical (strength and plasticity) and fatigue properties (low cycle fatigue) of martensitic Fe-13Cr steel in temperature interval of 250–600 °S have been investigated. Heavy liquid metals facilitate decreasing in ultimate strength by 10–20% against that in vacuum. The increase of temperature enhances this effect. Fe-13Cr steel is susceptible to liquid-metal embrittlement in the temperature interval of 350–450 °S, which manifests itself more substantially in lead-bismuth eutectic. The decrease of plasticity in Pb is 11% at 450 °S and in Pb-Bi is 30% in temperature interval 350–400 °S. Liquid metal environments significantly reduce fatigue life of Fe-13Cr steel. Pb-Bi has a more negative impact. In particular, with increasing total strain amplitude (up to 1.0%), the decrease in the cycle number to fracture by more than two orders of magnitude occurs.

  20. Mechanism and kinetics of LiX(X=H, D, T) + H2O reaction

    International Nuclear Information System (INIS)

    Lei Hongjie; Duan Hao; Xing Pifeng; Tang Yongjian

    2011-01-01

    The reaction mechanism of LiX(X=H, D, T) with H 2 O was investigated at MP2/6-311G (d) level using ab initio quantum chemistry in Gaussian 03 software. The equilibrium geometries, harmonic frequencies and energy of various stationary points on the potential energy surfaces were calculated in the lowest singlet states. Considering the quantum correction, the reaction rate constants were calculated using classical transition state theory. The results show the reaction of LiH (LiD, LiT) with H 2 O was considerably dependent on temperature that it is lower, the reaction rate constants are smaller. (authors)

  1. Reaction mechanism of oxygen atoms with unsaturated hydrocarbons by the crossed molecular beams method

    Energy Technology Data Exchange (ETDEWEB)

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

    1982-04-01

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

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

    Science.gov (United States)

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

    1982-04-01

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

  3. Determining the reaction in kinematic pairs of certain mechanisms using a digital computer

    Energy Technology Data Exchange (ETDEWEB)

    Chifchieva, V N

    1980-01-01

    In Dorr classifiers, walking excavators, conveyors, sieves and other mechanisms, one finds a triad with a sliding pair. An algorithm is proposed for determining reactions in the kinematic connections of a triad with one, two or three sliding pairs. The algorithm is suitable for use in digital computers. It is based on the transfer function method, and has several advantages over the technnique of determining reactions in kinematic pairs of V. Zinovyev. A concrete example is given of calculating reactions in the connections of a crank and lever mechanism of a walking excavator.

  4. 2013 Gordon Research Conference, Inorganic reaction mechanisms, Galveston, TX, March 3-8 2013

    Energy Technology Data Exchange (ETDEWEB)

    Abu-Omar, Mahdi M. [Purdue Univ., West Lafayette, IN (United States)

    2012-12-08

    The 2013 Gordon Conference on Inorganic Reaction Mechanisms will present cutting-edge research on the molecular aspects of inorganic reactions involving elements from throughout the periodic table and state-of-the art techniques that are used in the elucidation of reaction mechanisms. The Conference will feature a wide range of topics, such as homogeneous and heterogeneous catalysis, metallobiochemistry, electron-transfer in energy reactions, polymerization, nitrogen fixation, green chemistry, oxidation, solar conversion, alkane functionalization, organotransition metal chemistry, and computational chemistry. The talks will cover themes of current interest including energy, materials, and bioinorganic chemistry. Sections cover: Electron-Transfer in Energy Reactions; Catalytic Polymerization and Oxidation Chemistry; Kinetics and Spectroscopy of Heterogeneous Catalysts; Metal-Organic Chemistry and its Application in Synthesis; Green Energy Conversion;Organometallic Chemistry and Activation of Small Molecules; Advances in Kinetics Modeling and Green Chemistry; Metals in Biology and Disease; Frontiers in Catalytic Bond Activation and Cleavage.

  5. Mechanical performances of lead-free solder joint connections with applications in the aerospace domain

    Directory of Open Access Journals (Sweden)

    Georgiana PADURARU

    2016-03-01

    Full Text Available The paper presents some theoretical and experimental aspects regarding the tribological performances of lead-free solder joint connections, with application in the aerospace domain. In order to highlight the mechanical and tribological properties of solder joint in correlation with different pad finishes, there were made some mechanical determinations using a dedicated Share Test System. The theoretical model highlights the link between the experimental results and the influence of gravitational acceleration on the mechanical and functional integrity of the electronic assemblies that works in vibration environment. The paper novelty is provided by the interdisciplinary experiment that offers results that can be used in the mechanical, tribological, electronical and aerospace domains.

  6. Cross sections of (p, xn) reactions in the isotopes of lead and bismuth

    Energy Technology Data Exchange (ETDEWEB)

    Bell, R E [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada); Skarsgard, H M [Atomic Energy Research Establishment, Reactor Research Div., Harwell (United Kingdom)

    1956-07-01

    Measurements have been made by the activation method of cross sections of (p, xn) reactions in Bi{sup 209}, Pb{sup 206}, Pb{sup 207}, and Pb{sup 208}. The present results cover x = 3 to 7 in Bi{sup 209}, 2 to 6 in Pb{sup 206}, 2 to 4 in Pb{sup 207}, and 3 and 4 in Pb{sup 208}, over a total proton energy range from 12 to 85 Mev. The absolute accuracy is about 15%. Each cross section plotted as a function of proton energy rises above its threshold to a peak whose height is of the order of one barn, and then falls again to a low and fairly constant value. The results from x = 3 to 7 are consistent with a compound nucleus plus prompt nucleon-nucleon cascade model using reasonable nuclear parameters, but the experimental (p, 2n) cross section appears to be almost double the value so predicted. Since (p, xn) reactions are dominant in the energy range 10 to 40 Mev., their sum approximates the total reaction cross section; the experimental sum fluctuates around the smooth curve computed for the compound nucleus model with r{sub 0} = 1.3 X 10{sup -13} cm. The fluctuations are similar to, but more marked than, those in the total neutron cross section of heavy elements in the same energy range. A more detailed theoretical discussion of these results is given by Jackson in the paper immediately following. (author)

  7. Reaction of winter oilseed rape varieties to elevated concentrations of lead

    Directory of Open Access Journals (Sweden)

    Oreščanin Bojana

    2012-01-01

    Full Text Available Remediation methods allow the removal of metals from contaminated soil, and phytoremediation a technology for cleaning contaminated soil and waste material by plants, is becoming increasingly used. Brassica napus L., as one of the main oilcrops and high-biomass producing species, is becoming more and more interesting for the use in phytoextraction as it is proved to be tolerant to higher concentrations of heavy metals. The aim of this study was to examine the specific responses of three commercial winter rapeseed varieties, Banaćanka, Slavica and Kata, to the increased concentrations of lead in vitro. Significant reduction in root length of plants treated with lead was observed only in the variety Slavica, indicating susceptibility of this variety to the increased concentrations of this heavy metal. As in variety Kata a significant reduction in the length of the above-ground part due to the treatment with lead was detected, it could be concluded that the variety Banaćanka is the most tolerant to the applied concentrations of lead since there were no significant changes in the growth and biomass accumulation in all treatments except one, and could be recommended for further use in phytoremediation studies. [Projekat Ministarstva nauke Republike Srbije, br. TR31025 i br. III43007

  8. Exchange reaction between hydrogen and deuterium. II - Proposal for an heterogeneous initiation mechanism of gaseous phase reactions

    Energy Technology Data Exchange (ETDEWEB)

    Marteau, Chantal; Gaillard-Cusin, Francoise; James, Henri [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

    1978-05-01

    Investigation of experimental data related to evolution period exhibited by H/sub 2/-D/sub 2/ exchange process requires to take into account the variation against time of every atomic species -adsorbed or not- implied in the reaction mechanism. The formation of first chain carriers involves: - chemisorption of either gaseous reactant on the surface active centres (..sigma..), e.g.: ..sigma.. + 1/2 H/sub 2/ reversible ..sigma..H; - consecutive generation of atomic species through hetero-homogeneous transfer between chemisorbed species (..sigma..H) and gaseous molecules: ..sigma..H+H/sub 2/..--> sigma..+H/sub 2/+H/sup 0/, ..sigma..H+D/sub 2/..--> sigma..+HD+D/sup 0/. Therefore, it can be shown that the heterogeneous initiation process of a gas phase reaction identifies to a chain linear mechanism. Such an heterogeneous sequence conditions the further proceeding of the homogeneous chain reaction; both evolutions being kinematically connected. Rate constant of hydrogen adsorption on silica glass: ksub(a1) approximately 10/sup 14/ exp(-47/RT)Isup(0,5).molesup(-0,5).S/sup -1/ has been evaluated.

  9. Microstructure And Mechanical Properties Of Lead Oxide- Thermoplastic Elas Tomer Composite

    International Nuclear Information System (INIS)

    Sudirman; Handayani, Ari; Darwinto, Tri; Teguh, Yulius S.P.P.; Sunarni, Anik; Marlijanti, Isni

    2000-01-01

    Research on microstructure and mechanical properties of lead oxide-thermoplastic elastomer composite with Pb 3 O 4 as lead oxide. Thermoplastic elastomer synthesized from natural rubber as the elastomer and methyl metacrilate as the thermoplastic and irradiated simultaneously with optimum gamma ray. Thermoplastic elastomer (NR-PMMA) grind in a laboplastomill and Pb 3 O 4 was added in varied amount of 10%. 30%. 40% and 50%wt.The results showed that mechanical properties (tensile strength and elongation break) decreased as the Pb 3 O 4 composition increased. Microstructure from SEM observation showed that Pb 3 O 4 distributed evenly and having function as filler in composite

  10. Production of He-, Ne-, Ar-, Kr-, and Xe-isotopes by proton-induced reactions on lead

    International Nuclear Information System (INIS)

    Leya, I.; Michel, R.

    2003-01-01

    We measured integral thin target cross sections for the proton-induced production of He-, Ne-, Ar-, Kr-, and Xe-isotopes from lead from the respective reaction thresholds up to 2.6 GeV. The production of noble gas isotopes in lead by proton-induced reactions is of special importance for design studies of accelerator driven systems and energy amplifiers. In order to minimise the influences of secondary particles on the production of residual nuclides a new Mini-Stack approach was used instead of the well-known stacked-foil techniques for all experiments with proton energies above 200 MeV. With some exceptions our database for the proton-induced production of noble gas isotopes from lead is consistent and nearly complete. In contradistinction to the production of He from Al and Fe, where the cross sections obtained by thin-target irradiation experiments are up to a factor of 2 higher than the NESSI data, both datasets agree for the He production from lead. (orig.)

  11. Insights into the π-p → ηn reaction mechanism

    International Nuclear Information System (INIS)

    Durand, J.; Julia-Diaz, B.; Julia-Diaz, B.; Julia-Diaz, B.; Lee, T.S.H.; Sato, T.; Lee, T.S.H.; Sato, T.

    2009-01-01

    A dynamical coupled-channels formalism is used to investigate the eta-meson production mechanism on the proton induced by pions, in the total center-of-mass energy region from threshold up to 2 GeV. We show how and why studying exclusively total cross section data might turn out to be misleading in pinning down the reaction mechanism. (authors)

  12. Formation of amorphous Ti-50at.%Pt by solid state reactions during mechanical alloying

    CSIR Research Space (South Africa)

    Mahlatji, ML

    2013-10-01

    Full Text Available Mechanical alloying of an equiatomic mixture of crystalline elemental powders of Ti and Pt in a high-energy ball mill results in formation of an amorphous alloy by solid-state reactions. Mechanical alloying was carried out in an argon atmosphere...

  13. Effects of reaction conditions on the emission behaviors of arsenic, cadmium and lead during sewage sludge pyrolysis.

    Science.gov (United States)

    Han, Hengda; Hu, Song; Syed-Hassan, Syed Shatir A; Xiao, Yiming; Wang, Yi; Xu, Jun; Jiang, Long; Su, Sheng; Xiang, Jun

    2017-07-01

    Sewage sludge is an important class of bioresources whose energy content could be exploited using pyrolysis technology. However, some harmful trace elements in sewage sludge can escape easily to the gas phase during pyrolysis, increasing the potential of carcinogenic material emissions to the atmosphere. This study investigates emission characteristics of arsenic, cadmium and lead under different pyrolysis conditions for three different sewage sludge samples. The increased temperature (within 723-1123K) significantly promoted the cadmium and lead emissions, but its influence on arsenic emission was not pronounced. The releasing rate order of the three trace elements is volatile arsenic compounds>cadmium>lead in the beginning of pyrolysis. Fast heating rates promoted the emission of trace elements for the sludge containing the highest amount of ash, but exhibited an opposite effect for other studied samples. Overall, the high ash sludge released the least trace elements almost under all reaction conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Fracture Mechanics Analyses of the Slip-Side Joggle Regions of Wing-Leading-Edge Panels

    Science.gov (United States)

    Raju, Ivatury S.; Knight, Norman F., Jr.; Song, Kyongchan; Phillips, Dawn R.

    2011-01-01

    The Space Shuttle wing-leading edge consists of panels that are made of reinforced carbon-carbon. Coating spallation was observed near the slip-side region of the panels that experience extreme heating. To understand this phenomenon, a root-cause investigation was conducted. As part of that investigation, fracture mechanics analyses of the slip-side joggle regions of the hot panels were conducted. This paper presents an overview of the fracture mechanics analyses.

  15. Interest of uranium complexes for the mechanism study of the McMurry reaction

    International Nuclear Information System (INIS)

    Maury, O.

    1997-01-01

    The reducing coupling reactions of ketones in diols and olefins are generally carried out with titanium or samarium compounds. In this work uranium complexes have been used. They have allowed to study the chemical reaction mechanism. This thesis is divided into three parts: 1) the reduction mechanism of uranium tetrachloride by cyclic voltametry has been studied at first. It has been shown that this reduction is followed by a transfer reaction of chlorides between the reduced specie of the higher electronic density and UCl . 2) In the second part is described: the synthesis, the crystal structure, the reactivity of the chemical agents, the stereochemistry of diols and alkenes formation and the pinacolisation reaction catalysis. 3) In the last part, the limits of the McMurry reaction are given by the study of the aromatic ketones pinacolisation reaction by-products. The obtained results show that the complexes of the metals which present a high reducing and oxo-philic (Ti, Sm, U..) character react in a similar way with the carbonyl compounds. If the uranium compounds are less used than those of the titanium in the field of the organic synthesis applications, they are precious auxiliaries and excellent models for reactions mechanisms study and for the synthesis methods optimization. (O.M.)

  16. Synergetic mechanism of methanol–steam reforming reaction in a catalytic reactor with electric discharges

    International Nuclear Information System (INIS)

    Kim, Taegyu; Jo, Sungkwon; Song, Young-Hoon; Lee, Dae Hoon

    2014-01-01

    Highlights: • Methanol–steam reforming was performed on Cu catalysts under an electric discharge. • Discharge had a synergetic effect on the catalytic reaction for methanol conversion. • Discharge lowered the temperature for catalyst activation or light off. • Discharge controlled the yield and selectivity of species in a reforming process. • Adsorption triggered by a discharge was a possible mechanism for a synergetic effect. - Abstract: Methanol–steam reforming was performed on Cu/ZnO/Al 2 O 3 catalysts under an electric discharge. The discharge occurred between the electrodes where the catalysts were packed. The electric discharge was characterized by the discharge voltage and electric power to generate the discharge. The existence of a discharge had a synergetic effect on the catalytic reaction for methanol conversion. The electric discharge provided modified reaction paths resulting in a lower temperature for catalyst activation or light off. The discharge partially controlled the yield and selectivity of species in a reforming process. The aspect of control was examined in view of the reaction kinetics. The possible mechanisms for the synergetic effect between the catalytic reaction and electric discharge on methanol–steam reforming were addressed. A discrete reaction path, particularly adsorption triggered by an electric discharge, was suggested to be the most likely mechanism for the synergetic effect. These results are expected to provide a guide for understanding the plasma–catalyst hybrid reaction

  17. Mechanism of degradation and discoloration reaction of L-ascorbic acid

    International Nuclear Information System (INIS)

    Kurata, Tadao

    1976-01-01

    The mechanisms of decomposition and coloration reaction of L-ascorbic acid are reviewed. At the initial stage of the decomposition, it can be classified roughly into oxidative and non-oxidative processes of decomposition. ASA forms furfural by being heated and decomposed in strong acid. The mechanism of the production of furfural at varying pH in acidic region was discussed. Furfural was produced through the enol form of 3-deoxy-L-pentosulose(3DP). 3DP seemed to be produced by two different routes: the one route consists of successive reactions from ASA through lactone ring-opening, dehydration, decarboxylation, to 3DP, and the other consists of reactions from the 3-keto form of ASA, through lactone ring-opening, decarboxylation, and dehydration, to the enol form of 3DP. ASA is easily reduced and decomposed through dehydro-ASA(DHA) by the presence of an oxidizing agent. The decomposition of DHA is discussed in cases of the systems of DHA alone, DHA and α-aminoacid, and DHA and amine. DHA was decomposed by the same reaction scheme as the decomposition of ASA and yielded 2-furoic acid. In the presence of an amino acid, DHA was decomposed by the Strecker decomposition, and yielded a red compound and a radical. In the presence of an amine, the discoloration reaction seemed to take place through radical reaction mechanism. The coloration reaction of ASA occurs in an acidic medium, and is accelerated by the oxidative process of decomposition. (Nishino, S.)

  18. Thermo-mechanical tests on W7-X current lead flanges

    International Nuclear Information System (INIS)

    Dhard, Chandra Prakash; Rummel, Thomas; Zacharias, Daniel; Bykov, Victor; Moennich, Thomas; Buscher, Klaus-Peter

    2013-01-01

    Highlights: • There are significant mechanical loads on the cryostat and radial flanges for W7-X current leads. • These are due to evacuation of W7-X cryostat, cool-down of cold mass, electro-magnetic forces and self weight of leads. • The actual mechanical loads were reduced to simplify the experimental set-up. • The tests were carried out on mock-up flanges test assembly at ambient temperature and at 77 K. • The thermo-mechanical tests on W7-X current lead flanges validate the design and joints of these flanges to the leads. -- Abstract: Fourteen pieces of high temperature superconducting current leads (CL) arranged in seven pairs, will be installed on the outer vessel of Wendelstein 7-X (W7-X) stellarator. In order to support the CL, it is provided with two glass fiber reinforce plastic (GFRP) flanges, namely, the lower cryostat flange (CF) remaining at room temperature and upper radial flange (RF) at about 5 K. Both the flanges i.e. CF and RF experience high mechanical loads with respect to the CL, due to the evacuation of W7-X cryostat, cool-down of cold mass including the CL, electro-magnetic forces due to current and plasma operations and self weight of CL. In order to check the integrity of these flanges for such mechanical loads, thermo-mechanical tests were carried out on these flanges at room temperatures and at liquid nitrogen (LN2) temperatures. The details of test set-up, results and modeling are described in the paper

  19. Reduction of very large reaction mechanisms using methods based on simulation error minimization

    Energy Technology Data Exchange (ETDEWEB)

    Nagy, Tibor; Turanyi, Tamas [Institute of Chemistry, Eoetvoes University (ELTE), P.O. Box 32, H-1518 Budapest (Hungary)

    2009-02-15

    A new species reduction method called the Simulation Error Minimization Connectivity Method (SEM-CM) was developed. According to the SEM-CM algorithm, a mechanism building procedure is started from the important species. Strongly connected sets of species, identified on the basis of the normalized Jacobian, are added and several consistent mechanisms are produced. The combustion model is simulated with each of these mechanisms and the mechanism causing the smallest error (i.e. deviation from the model that uses the full mechanism), considering the important species only, is selected. Then, in several steps other strongly connected sets of species are added, the size of the mechanism is gradually increased and the procedure is terminated when the error becomes smaller than the required threshold. A new method for the elimination of redundant reactions is also presented, which is called the Principal Component Analysis of Matrix F with Simulation Error Minimization (SEM-PCAF). According to this method, several reduced mechanisms are produced by using various PCAF thresholds. The reduced mechanism having the least CPU time requirement among the ones having almost the smallest error is selected. Application of SEM-CM and SEM-PCAF together provides a very efficient way to eliminate redundant species and reactions from large mechanisms. The suggested approach was tested on a mechanism containing 6874 irreversible reactions of 345 species that describes methane partial oxidation to high conversion. The aim is to accurately reproduce the concentration-time profiles of 12 major species with less than 5% error at the conditions of an industrial application. The reduced mechanism consists of 246 reactions of 47 species and its simulation is 116 times faster than using the full mechanism. The SEM-CM was found to be more effective than the classic Connectivity Method, and also than the DRG, two-stage DRG, DRGASA, basic DRGEP and extended DRGEP methods. (author)

  20. Revealing the reaction mechanisms of Li–O2 batteries using environmental transmission electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Langli; Liu, Bin; Song, Shidong; Xu, Wu; Zhang, Ji-Guang; Wang, Chongmin

    2017-03-27

    The capacity, Coulombic efficiency, rate, and cyclability of a Li-O2 battery critically depend on the electrode reaction mechanism and the structure/morphology of the reaction product as well as their spatial and temporal evolution1-8, which are all further complicated by the choice of different electrolyte. For the case of aprotic cell, the discharge product, Li2O2, is formed through solution and surface mechanisms9,10, but little is known on the formation mechanism of the perplexing morphology of the reaction product11-15. For the case of Li-O2 battery using solid electrolyte, neither electrode reaction mechanism nor the nature of the reaction production is known. Herein, we reveal the full cycle reaction pathway for Li-O2 batteries and its correlation with the nature of the reaction product. Using an aberration-corrected environmental TEM under oxygen environment, we captured, for the first time, the morphology and phase evolution on the carbon nanotube (CNT) cathode of a working solid-state Li-O2 nano-battery16 and directly correlated these features with electrochemical reaction. We found that the oxygen reduction reaction on CNTs initially produces LiO2, which subsequently evolves to Li2O2 and O2 through disproportionation reaction. Surprisingly it is just the releasing of O2 that inflates the particles to a hollow structure with a Li2O outer surface layer and Li2O2 inner-shell, demonstrating that, in general, accommodation of the released O2 coupled with the Li+ ion diffusion and electron transport paths across both spatial and temporal scales critically governs the morphology of the discharging/charging product in Li-O2 system. We anticipate that the direct observation of Li-O2 reaction mechanisms and their correlation with the morphology of the reaction product set foundation for quantitative understanding/modeling of the electrochemical processes in the Li-O2 system, enabling rational design of both solid-state and aprotic Li-O2 batteries.

  1. Structure of Hordeum vulgare NADPH-dependent thioredoxin reductase 2. Unwinding the reaction mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Kirkensgaard, Kristine G. [Carlsberg Laboratory (Denmark); Enzyme and Protein Chemistry, Department of Systems BioIogy, Technical University of Denmark (Denmark); Hägglund, Per; Finnie, Christine; Svensson, Birte [Enzyme and Protein Chemistry, Department of Systems BioIogy, Technical University of Denmark (Denmark); Henriksen, Anette, E-mail: anette@crc.dk [Carlsberg Laboratory (Denmark)

    2009-09-01

    The first crystal structure of a cereal NTR, a protein involved in seed development and germination, has been determined. The structure is in a conformation that excludes NADPH binding and indicates that a domain reorientation facilitated by Trx binding precedes NADPH binding in the reaction mechanism. Thioredoxins (Trxs) are protein disulfide reductases that regulate the intracellular redox environment and are important for seed germination in plants. Trxs are in turn regulated by NADPH-dependent thioredoxin reductases (NTRs), which provide reducing equivalents to Trx using NADPH to recycle Trxs to the active form. Here, the first crystal structure of a cereal NTR, HvNTR2 from Hordeum vulgare (barley), is presented, which is also the first structure of a monocot plant NTR. The structure was determined at 2.6 Å resolution and refined to an R{sub cryst} of 19.0% and an R{sub free} of 23.8%. The dimeric protein is structurally similar to the structures of AtNTR-B from Arabidopsis thaliana and other known low-molecular-weight NTRs. However, the relative position of the two NTR cofactor-binding domains, the FAD and the NADPH domains, is not the same. The NADPH domain is rotated by 25° and bent by a 38% closure relative to the FAD domain in comparison with AtNTR-B. The structure may represent an intermediate between the two conformations described previously: the flavin-oxidizing (FO) and the flavin-reducing (FR) conformations. Here, analysis of interdomain contacts as well as phylogenetic studies lead to the proposal of a new reaction scheme in which NTR–Trx interactions mediate the FO to FR transformation.

  2. Structure of Hordeum vulgare NADPH-dependent thioredoxin reductase 2. Unwinding the reaction mechanism

    International Nuclear Information System (INIS)

    Kirkensgaard, Kristine G.; Hägglund, Per; Finnie, Christine; Svensson, Birte; Henriksen, Anette

    2009-01-01

    The first crystal structure of a cereal NTR, a protein involved in seed development and germination, has been determined. The structure is in a conformation that excludes NADPH binding and indicates that a domain reorientation facilitated by Trx binding precedes NADPH binding in the reaction mechanism. Thioredoxins (Trxs) are protein disulfide reductases that regulate the intracellular redox environment and are important for seed germination in plants. Trxs are in turn regulated by NADPH-dependent thioredoxin reductases (NTRs), which provide reducing equivalents to Trx using NADPH to recycle Trxs to the active form. Here, the first crystal structure of a cereal NTR, HvNTR2 from Hordeum vulgare (barley), is presented, which is also the first structure of a monocot plant NTR. The structure was determined at 2.6 Å resolution and refined to an R cryst of 19.0% and an R free of 23.8%. The dimeric protein is structurally similar to the structures of AtNTR-B from Arabidopsis thaliana and other known low-molecular-weight NTRs. However, the relative position of the two NTR cofactor-binding domains, the FAD and the NADPH domains, is not the same. The NADPH domain is rotated by 25° and bent by a 38% closure relative to the FAD domain in comparison with AtNTR-B. The structure may represent an intermediate between the two conformations described previously: the flavin-oxidizing (FO) and the flavin-reducing (FR) conformations. Here, analysis of interdomain contacts as well as phylogenetic studies lead to the proposal of a new reaction scheme in which NTR–Trx interactions mediate the FO to FR transformation

  3. Modeling the mechanism of glycosylation reactions between ethanol, 1,2-ethanediol and methoxymethanol.

    Science.gov (United States)

    Azofra, Luis Miguel; Alkorta, Ibon; Toro-Labbé, Alejandro; Elguero, José

    2013-09-07

    The mechanism of the S(N)2 model glycosylation reaction between ethanol, 1,2-ethanediol and methoxymethanol has been studied theoretically at the B3LYP/6-311+G(d,p) computational level. Three different types of reactions have been explored: (i) the exchange of hydroxyl groups between these model systems; (ii) the basic catalysis reactions by combination of the substrates as glycosyl donors (neutral species) and acceptors (enolate species); and (iii) the effect on the reaction profile of an explicit H2O molecule in the reactions considered in (ii). The reaction force, the electronic chemical potential and the reaction electronic flux have been characterized for the reaction path in each case. Energy calculations show that methoxymethanol is the worst glycosyl donor model among the ones studied here, while 1,2-ethanediol is the best, having the lowest activation barrier of 74.7 kJ mol(-1) for the reaction between this one and the ethanolate as the glycosyl acceptor model. In general, the presence of direct interactions between the atoms involved in the penta-coordinated TS increases the activation energies of the processes.

  4. Computational organic chemistry: bridging theory and experiment in establishing the mechanisms of chemical reactions.

    Science.gov (United States)

    Cheng, Gui-Juan; Zhang, Xinhao; Chung, Lung Wa; Xu, Liping; Wu, Yun-Dong

    2015-02-11

    Understanding the mechanisms of chemical reactions, especially catalysis, has been an important and active area of computational organic chemistry, and close collaborations between experimentalists and theorists represent a growing trend. This Perspective provides examples of such productive collaborations. The understanding of various reaction mechanisms and the insight gained from these studies are emphasized. The applications of various experimental techniques in elucidation of reaction details as well as the development of various computational techniques to meet the demand of emerging synthetic methods, e.g., C-H activation, organocatalysis, and single electron transfer, are presented along with some conventional developments of mechanistic aspects. Examples of applications are selected to demonstrate the advantages and limitations of these techniques. Some challenges in the mechanistic studies and predictions of reactions are also analyzed.

  5. Reaction mechanisms and rate constants of waste degradation in landfill bioreactor systems with enzymatic-enhancement.

    Science.gov (United States)

    Jayasinghe, P A; Hettiaratchi, J P A; Mehrotra, A K; Kumar, S

    2014-06-01

    Augmenting leachate before recirculation with peroxidase enzymes is a novel method to increase the available carbon, and therefore the food supply to microorganisms at the declining phase of the anaerobic landfill bioreactor operation. In order to optimize the enzyme-catalyzed leachate recirculation process, it is necessary to identify the reaction mechanisms and determine rate constants. This paper presents a kinetic model developed to ascertain the reaction mechanisms and determine the rate constants for enzyme catalyzed anaerobic waste degradation. The maximum rate of reaction (Vmax) for MnP enzyme-catalyzed reactors was 0.076 g(TOC)/g(DS).day. The catalytic turnover number (k(cat)) of the MnP enzyme-catalyzed was 506.7 per day while the rate constant (k) of the un-catalyzed reaction was 0.012 per day. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. A chemometric method to identify enzymatic reactions leading to the transition from glycolytic oscillations to waves

    Science.gov (United States)

    Zimányi, László; Khoroshyy, Petro; Mair, Thomas

    2010-06-01

    In the present work we demonstrate that FTIR-spectroscopy is a powerful tool for the time resolved and noninvasive measurement of multi-substrate/product interactions in complex metabolic networks as exemplified by the oscillating glycolysis in a yeast extract. Based on a spectral library constructed from the pure glycolytic intermediates, chemometric analysis of the complex spectra allowed us the identification of many of these intermediates. Singular value decomposition and multiple level wavelet decomposition were used to separate drifting substances from oscillating ones. This enabled us to identify slow and fast variables of glycolytic oscillations. Most importantly, we can attribute a qualitative change in the positive feedback regulation of the autocatalytic reaction to the transition from homogeneous oscillations to travelling waves. During the oscillatory phase the enzyme phosphofructokinase is mainly activated by its own product ADP, whereas the transition to waves is accompanied with a shift of the positive feedback from ADP to AMP. This indicates that the overall energetic state of the yeast extract determines the transition between spatially homogeneous oscillations and travelling waves.

  7. Prediction of Tetraoxygen Reaction Mechanism with Sulfur Atom on the Singlet Potential Energy Surface

    Directory of Open Access Journals (Sweden)

    Ashraf Khademzadeh

    2014-01-01

    Full Text Available The mechanism of S+O4 (D2h reaction has been investigated at the B3LYP/6-311+G(3df and CCSD levels on the singlet potential energy surface. One stable complex has been found for the S+O4 (D2h reaction, IN1, on the singlet potential energy surface. For the title reaction, we obtained four kinds of products at the B3LYP level, which have enough thermodynamic stability. The results reveal that the product P3 is spontaneous and exothermic with −188.042 and −179.147 kcal/mol in Gibbs free energy and enthalpy of reaction, respectively. Because P1 adduct is produced after passing two low energy level transition states, kinetically, it is the most favorable adduct in the 1S+1O4 (D2h atmospheric reactions.

  8. Kinetics and mechanism of the gas phase reaction of Cl atoms with iodobenzene

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Ponomarev, DA; Nielsen, OJ

    2001-01-01

    Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms with iodobenzene (C6H5I) in 20-700 Torr of N-2, air, or O-2 diluent at 296 K. The reaction proceeds with a rate constant k(Cl + QH(5)I) = (3.3 +/- 0.7) x 10(-11) cm(3) molecule(-1) s(-1) to give...

  9. Li-ion Battery Separators, Mechanical Integrity and Failure Mechanisms Leading to Soft and Hard Internal Shorts.

    Science.gov (United States)

    Zhang, Xiaowei; Sahraei, Elham; Wang, Kai

    2016-09-01

    Separator integrity is an important factor in preventing internal short circuit in lithium-ion batteries. Local penetration tests (nail or conical punch) often produce presumably sporadic results, where in exactly similar cell and test set-ups one cell goes to thermal runaway while the other shows minimal reactions. We conducted an experimental study of the separators under mechanical loading, and discovered two distinct deformation and failure mechanisms, which could explain the difference in short circuit characteristics of otherwise similar tests. Additionally, by investigation of failure modes, we provided a hypothesis about the process of formation of local "soft short circuits" in cells with undetectable failure. Finally, we proposed a criterion for predicting onset of soft short from experimental data.

  10. Inelastic collisions of heavy ions and their reaction mechanisms; Collisions inelastiques d'ions lourds et mecanismes de reaction

    Energy Technology Data Exchange (ETDEWEB)

    Scarpaci, J.A

    2004-06-01

    This work is dedicated to the study of inelastic collisions of heavy ions. Most experiments took place in Ganil facility. The 2 first chapters introduce the notion of inelastic scattering of heavy ions. The third chapter deals with target excitation, giant monopolar or dipolar or quadrupolar resonances ant the multi-phonon concept and presents relevant experimental results from the Ca{sup 40} + Ca{sup 40} nuclear reaction at 50 MeV/A. The fourth chapter is dedicated to nuclear processes involved in inelastic collisions: pick-up break-up mechanisms, the angular distribution of emitted protons and the towing mode. These notions are applied to the reaction Zr{sup 90}(Ar{sup 40}, Ar{sup 40}'). The fifth chapter presents the solving of the time dependent Schroedinger equation (TDSE) applied to the wave function of a particle plunged in a variable potential. TDSE solving is applied to the break-up of Be{sup 11}. These calculations have been validated by comparing them with experimental results from the nuclear reaction Ti{sup 48}(Be{sup 11}, Be{sup 10} + n + {gamma}) that is described in the chapter 6. The last chapter presents the advantages of inelastic scattering considered as a tool to study exotic nuclei.

  11. Understanding organometallic reaction mechanisms and catalysis experimental and computational tools computational and experimental tools

    CERN Document Server

    Ananikov, Valentin P

    2014-01-01

    Exploring and highlighting the new horizons in the studies of reaction mechanisms that open joint application of experimental studies and theoretical calculations is the goal of this book. The latest insights and developments in the mechanistic studies of organometallic reactions and catalytic processes are presented and reviewed. The book adopts a unique approach, exemplifying how to use experiments, spectroscopy measurements, and computational methods to reveal reaction pathways and molecular structures of catalysts, rather than concentrating solely on one discipline. The result is a deeper

  12. Complex Reaction Kinetics in Chemistry: A Unified Picture Suggested by Mechanics in Physics

    Directory of Open Access Journals (Sweden)

    Elena Agliari

    2018-01-01

    Full Text Available Complex biochemical pathways can be reduced to chains of elementary reactions, which can be described in terms of chemical kinetics. Among the elementary reactions so far extensively investigated, we recall the Michaelis-Menten and the Hill positive-cooperative kinetics, which apply to molecular binding and are characterized by the absence and the presence, respectively, of cooperative interactions between binding sites. However, there is evidence of reactions displaying a more complex pattern: these follow the positive-cooperative scenario at small substrate concentration, yet negative-cooperative effects emerge as the substrate concentration is increased. Here, we analyze the formal analogy between the mathematical backbone of (classical reaction kinetics in Chemistry and that of (classical mechanics in Physics. We first show that standard cooperative kinetics can be framed in terms of classical mechanics, where the emerging phenomenology can be obtained by applying the principle of least action of classical mechanics. Further, since the saturation function plays in Chemistry the same role played by velocity in Physics, we show that a relativistic scaffold naturally accounts for the kinetics of the above-mentioned complex reactions. The proposed formalism yields to a unique, consistent picture for cooperative-like reactions and to a stronger mathematical control.

  13. Ontology aided modeling of organic reaction mechanisms with flexible and fragment based XML markup procedures.

    Science.gov (United States)

    Sankar, Punnaivanam; Aghila, Gnanasekaran

    2007-01-01

    The mechanism models for primary organic reactions encoding the structural fragments undergoing substitution, addition, elimination, and rearrangements are developed. In the proposed models, each and every structural component of mechanistic pathways is represented with flexible and fragment based markup technique in XML syntax. A significant feature of the system is the encoding of the electron movements along with the other components like charges, partial charges, half bonded species, lone pair electrons, free radicals, reaction arrows, etc. needed for a complete representation of reaction mechanism. The rendering of reaction schemes described with the proposed methodology is achieved with a concise XML extension language interoperating with the structure markup. The reaction scheme is visualized as 2D graphics in a browser by converting them into SVG documents enabling the desired layouts normally perceived by the chemists conventionally. An automatic representation of the complex patterns of the reaction mechanism is achieved by reusing the knowledge in chemical ontologies and developing artificial intelligence components in terms of axioms.

  14. Chemical reaction of hexagonal boron nitride and graphite nanoclusters in mechanical milling systems

    Energy Technology Data Exchange (ETDEWEB)

    Muramatsu, Y.; Grush, M.; Callcott, T.A. [Univ. of Tennessee, Knoxville, TN (United States)] [and others

    1997-04-01

    Synthesis of boron-carbon-nitride (BCN) hybrid alloys has been attempted extensively by many researchers because the BCN alloys are considered an extremely hard material called {open_quotes}super diamond,{close_quotes} and the industrial application for wear-resistant materials is promising. A mechanical alloying (MA) method of hexagonal boron nitride (h-BN) with graphite has recently been studied to explore the industrial synthesis of the BCN alloys. To develop the MA method for the BCN alloy synthesis, it is necessary to confirm the chemical reaction processes in the mechanical milling systems and to identify the reaction products. Therefore, the authors have attempted to confirm the chemical reaction process of the h-BN and graphite in mechanical milling systems using x-ray absorption near edge structure (XANES) methods.

  15. Chemical reaction of hexagonal boron nitride and graphite nanoclusters in mechanical milling systems

    International Nuclear Information System (INIS)

    Muramatsu, Y.; Grush, M.; Callcott, T.A.

    1997-01-01

    Synthesis of boron-carbon-nitride (BCN) hybrid alloys has been attempted extensively by many researchers because the BCN alloys are considered an extremely hard material called open-quotes super diamond,close quotes and the industrial application for wear-resistant materials is promising. A mechanical alloying (MA) method of hexagonal boron nitride (h-BN) with graphite has recently been studied to explore the industrial synthesis of the BCN alloys. To develop the MA method for the BCN alloy synthesis, it is necessary to confirm the chemical reaction processes in the mechanical milling systems and to identify the reaction products. Therefore, the authors have attempted to confirm the chemical reaction process of the h-BN and graphite in mechanical milling systems using x-ray absorption near edge structure (XANES) methods

  16. Behavioural evidence for separate mechanisms of audiovisual temporal binding as a function of leading sensory modality.

    Science.gov (United States)

    Cecere, Roberto; Gross, Joachim; Thut, Gregor

    2016-06-01

    The ability to integrate auditory and visual information is critical for effective perception and interaction with the environment, and is thought to be abnormal in some clinical populations. Several studies have investigated the time window over which audiovisual events are integrated, also called the temporal binding window, and revealed asymmetries depending on the order of audiovisual input (i.e. the leading sense). When judging audiovisual simultaneity, the binding window appears narrower and non-malleable for auditory-leading stimulus pairs and wider and trainable for visual-leading pairs. Here we specifically examined the level of independence of binding mechanisms when auditory-before-visual vs. visual-before-auditory input is bound. Three groups of healthy participants practiced audiovisual simultaneity detection with feedback, selectively training on auditory-leading stimulus pairs (group 1), visual-leading stimulus pairs (group 2) or both (group 3). Subsequently, we tested for learning transfer (crossover) from trained stimulus pairs to non-trained pairs with opposite audiovisual input. Our data confirmed the known asymmetry in size and trainability for auditory-visual vs. visual-auditory binding windows. More importantly, practicing one type of audiovisual integration (e.g. auditory-visual) did not affect the other type (e.g. visual-auditory), even if trainable by within-condition practice. Together, these results provide crucial evidence that audiovisual temporal binding for auditory-leading vs. visual-leading stimulus pairs are independent, possibly tapping into different circuits for audiovisual integration due to engagement of different multisensory sampling mechanisms depending on leading sense. Our results have implications for informing the study of multisensory interactions in healthy participants and clinical populations with dysfunctional multisensory integration. © 2016 The Authors. European Journal of Neuroscience published by Federation

  17. Investigation of the CH3Cl + CN(-) reaction in water: Multilevel quantum mechanics/molecular mechanics study.

    Science.gov (United States)

    Xu, Yulong; Zhang, Jingxue; Wang, Dunyou

    2015-06-28

    The CH3Cl + CN(-) reaction in water was studied using a multilevel quantum mechanics/molecular mechanics (MM) method with the multilevels, electrostatic potential, density functional theory (DFT) and coupled-cluster single double triple (CCSD(T)), for the solute region. The detailed, back-side attack SN2 reaction mechanism was mapped along the reaction pathway. The potentials of mean force were calculated under both the DFT and CCSD(T) levels for the reaction region. The CCSD(T)/MM level of theory presents a free energy activation barrier height at 20.3 kcal/mol, which agrees very well with the experiment value at 21.6 kcal/mol. The results show that the aqueous solution has a dominant role in shaping the potential of mean force. The solvation effect and the polarization effect together increase the activation barrier height by ∼11.4 kcal/mol: the solvation effect plays a major role by providing about 75% of the contribution, while polarization effect only contributes 25% to the activation barrier height. Our calculated potential of mean force under the CCSD(T)/MM also has a good agreement with the one estimated using data from previous gas-phase studies.

  18. Urban gardens: Lead exposure, recontamination mechanisms, and implications for remediation design

    International Nuclear Information System (INIS)

    Clark, Heather F.; Hausladen, Debra M.; Brabander, Daniel J.

    2008-01-01

    Environmental lead contamination is prevalent in urban areas where soil represents a significant sink and pathway of exposure. This study characterizes the speciation of lead that is relevant to local recontamination and to human exposure in the backyard gardens of Roxbury and Dorchester, MA, USA. One hundred forty-one backyard gardens were tested by X-ray fluorescence, and 81% of gardens have lead levels above the US EPA action limit of 400 μg/g. Raised gardening beds are the in situ exposure reduction method used in the communities to promote urban gardening. Raised beds were tested for lead and the results showed that the lead concentration increased from an initial range of 150±40 μg/g to an average of 336 μg/g over 4 years. The percent distribution of lead in the fine grain soil (<100 μm) and the trace metal signature of the raised beds support the conclusion that the mechanism of recontamination is wind-transported particles. Scanning electron microscopy and sequential extraction were used to characterize the speciation of lead, and the trace metal signature of the fine grain soil in both gardens and raised gardening beds is characteristic of lead-based paint. This study demonstrates that raised beds are a limited exposure reduction method and require maintenance to achieve exposure reduction goals. An exposure model was developed based on a suite of parameters that combine relevant values from the literature with site-specific quantification of exposure pathways. This model suggests that consumption of homegrown produce accounts for only 3% of children's daily exposure of lead while ingestion of fine grained soil (<100 μm) accounts for 82% of the daily exposure. This study indicates that urban lead remediation on a yard-by-yard scale requires constant maintenance and that remediation may need to occur on a neighborhood-wide scale

  19. Partial strands synthesizing leads to inevitable aborting and complicated products in consecutive polymerase chain reactions (PCRs)

    Institute of Scientific and Technical Information of China (English)

    LUO Rui; ZHANG DaMing

    2007-01-01

    Various abnormal phenomena have been observed during PCR so far. The present study performed a series of consecutive PCRs (including many rounds of re-amplification continuously) and found that the abortion of re-amplification was inevitable as long as a variety of complicated product appeared.The aborting stages varied, according to the lengths of targets. Longer targets reached the abortion earlier than the shorter ones, marked by appearance of the complex that was immobile in electrophoresis. Denatured gel-electrophoresis revealed that the complex was mainly made up of shorter or partially synthesized strands, together with small amounts of full-length ones. Able to be digested by S1 nuclease but unable by restriction endonucleases (REs), the complex was proved to consist of both single regions and double-helix regions that kept the complex stable thermodynamically. Simulations gave evidence that partial strands, even at lower concentration, could disturb re-amplification effectively and lead to the abortion of re-amplifications finally. It was pointed out that the partial strands formed chiefly via polymerase's infidelity, and hence the solution to lighten the abnormality was also proposed.

  20. Partial strands synthesizing leads to inevitable aborting and complicated products in consecutive polymerase chain reactions (PCRs)

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Various abnormal phenomena have been observed during PCR so far. The present study performed a series of consecutive PCRs (including many rounds of re-amplification continuously) and found that the abortion of re-amplification was inevitable as long as a variety of complicated product appeared. The aborting stages varied, according to the lengths of targets. Longer targets reached the abortion earlier than the shorter ones, marked by appearance of the complex that was immobile in electropho-resis. Denatured gel-electrophoresis revealed that the complex was mainly made up of shorter or partially synthesized strands, together with small amounts of full-length ones. Able to be digested by S1 nuclease but unable by restriction endonucleases (REs), the complex was proved to consist of both single regions and double-helix regions that kept the complex stable thermodynamically. Simulations gave evidence that partial strands, even at lower concentration, could disturb re-amplification effec- tively and lead to the abortion of re-amplifications finally. It was pointed out that the partial strands formed chiefly via polymerase’s infidelity, and hence the solution to lighten the abnormality was also proposed.

  1. WNT and DKK Determine Hair Follicle Spacing Through a Reaction-Diffusion Mechanism

    Science.gov (United States)

    Sick, Stefanie; Reinker, Stefan; Timmer, Jens; Schlake, Thomas

    2006-12-01

    Mathematical reaction-diffusion models have been suggested to describe formation of animal pigmentation patterns and distribution of epidermal appendages. However, the crucial signals and in vivo mechanisms are still elusive. Here we identify WNT and its inhibitor DKK as primary determinants of murine hair follicle spacing, using a combined experimental and computational modeling approach. Transgenic DKK overexpression reduces overall appendage density. Moderate suppression of endogenous WNT signaling forces follicles to form clusters during an otherwise normal morphogenetic program. These results confirm predictions of a WNT/DKK-specific mathematical model and provide in vivo corroboration of the reaction-diffusion mechanism for epidermal appendage formation.

  2. Identification of mechanisms in heavy ion reactions by measurement of angular correlations

    International Nuclear Information System (INIS)

    Carlin Filho, N.

    1987-01-01

    The identification of reaction mechanisms in light heavy-ion collisions has been performed within the framework of the three body kinematics, by means of angular correlation measurements. The 16 O+ 27 Al, 16 +O+ 28 Si and 10 B+ 27 Al reactions were investigated at Laboratory bombarding energies of 64 MeV, 64 and 48 MeV, respectively. Contributions of transfer-reemission and projectile sequential decay mechanisms were identified by the analysis of the relative kinetic energy of the final state components, excitation energies of the system at the intermediate stages, and also by means of fits to theoretical predictions for the angular correlations. (author) [pt

  3. Kinetic and mechanism formation reaction of complex compound Cu with di-n-buthildithiocarbamate (dbdtc) ligand

    Science.gov (United States)

    Haryani, S.; Kurniawan, C.; Kasmui

    2018-04-01

    Synthesis of complex compound is one field of research which intensively studied. Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metal separation science, and have potential use as chemotherapeutic, pesticides, and as additives to lubricants. However, the information about is reaction kinetic and mechanism are very much lacking. The research and analyzes results show that reaction synthesis ligand DBDTC and complex compounds Cu-DBDTC. Optimum reaction condition of formation of complex compounds Cu with DBDTC at pH=3, [DBDTC] = 4.10-3 M, and the time of reaction 5 minutes. Based the analysis varian reaction of complex compounds at pH 3 and 4, diffrence significance at the other pH: 5; 5,5; 6; 6,5 ; 7; and 8. The various of mole with reactants comosition difference sigbificance, those the time reaction for 5 and 6 minutes diffrence by significance with the other time, it is 3,4,8, and 10 minutes. The great product to at condition pH 6, the time optimum at 5 minutes and molar ratio of logam: ligand = 1:2. The reaction kinetic equation of complex compound Cu with chelathing ligand DBDTC is V=0.917106 [Cu2+]0.87921 [DBDTC]2.03021. Based on the kinetic data, and formed complex compounds estimation, the mechanism explaining by 2 stages. In the first stage formation of [Cu(DBDTC)], and then [Cu(DBDTC)2] with the last structure geomethry planar rectangle. The result of this research will be more useful if an effort is being done in reaction mechanism by chemical computation method for obtain intermediate, and for constant “k” in same stage, k1.k2. and compound complex constanta (β).

  4. Soft tissue deformation modelling through neural dynamics-based reaction-diffusion mechanics.

    Science.gov (United States)

    Zhang, Jinao; Zhong, Yongmin; Gu, Chengfan

    2018-05-30

    Soft tissue deformation modelling forms the basis of development of surgical simulation, surgical planning and robotic-assisted minimally invasive surgery. This paper presents a new methodology for modelling of soft tissue deformation based on reaction-diffusion mechanics via neural dynamics. The potential energy stored in soft tissues due to a mechanical load to deform tissues away from their rest state is treated as the equivalent transmembrane potential energy, and it is distributed in the tissue masses in the manner of reaction-diffusion propagation of nonlinear electrical waves. The reaction-diffusion propagation of mechanical potential energy and nonrigid mechanics of motion are combined to model soft tissue deformation and its dynamics, both of which are further formulated as the dynamics of cellular neural networks to achieve real-time computational performance. The proposed methodology is implemented with a haptic device for interactive soft tissue deformation with force feedback. Experimental results demonstrate that the proposed methodology exhibits nonlinear force-displacement relationship for nonlinear soft tissue deformation. Homogeneous, anisotropic and heterogeneous soft tissue material properties can be modelled through the inherent physical properties of mass points. Graphical abstract Soft tissue deformation modelling with haptic feedback via neural dynamics-based reaction-diffusion mechanics.

  5. Measurement of activation reaction rate distributions in a lead assembly bombarded with 500-MeV protons

    CERN Document Server

    Takada, H; Sasa, T; Tsujimoto, K; Yasuda, H

    2000-01-01

    Reaction rate distributions of various activation detectors such as the /sup nat/Ni(n, x)/sup 58/Co, /sup 197/Au(n,2n)/sup 196/Au, and /sup 197/Au(n,4n)/sup 194/Au reactions were measured to study the production and the transport of spallation neutrons in a lead assembly bombarded with protons of 500 MeV. The measured data were analyzed with the nucleon-meson transport code NMTC/JAERI combined with the MCNP4A code using the nuclide production cross sections based on the JENDL Dosimetry File and those calculated with the ALICE-F code. It was found that the NMTC/JAERI-MCNP4A calculations agreed well with the experiments for the low-energy-threshold reaction of /sup nat/Ni(n, x)/sup 58/Co. With the increase of threshold energy, however, the calculation underestimated the experiments, especially above 20 MeV. The reason for the disagreement can be attributed to the underestimation of the neutron yield in the tens of mega-electron-volt regions by the NMTC/JAERI code. (32 refs).

  6. Characterization of Reactants Reaction Mechanisms and Reaction Products Leading to Extreme Acid Rain and Acid Aerosol Conditions in Southern California

    OpenAIRE

    Hoffmann, Michael R.; Morgan, J. J.; Jacob, D. J.; Munger, J. W.; Waldman, J. M.

    1983-01-01

    Analyses of fogwater collected by inertial impaction in the Los Angeles basin and the San Joaquin Valley indicated unusually high concentrations of major and minor ions. The dominant ions measured were NO_3^-, SO_4^(2-), NH_4^+ and H^+ Nitrate exceeded sulfate on an equivalent basis by a factor of 2.5 in the central and coastal regions of the Los Angeles basin, but was approximately equal in the eastern Los Angeles basin and the San Joaquin Valley. Maximum observed values for NH_4^+, NO_3^- a...

  7. 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.

  8. 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

  9. Hybrid Quantum Mechanics/Molecular Mechanics Solvation Scheme for Computing Free Energies of Reactions at Metal-Water Interfaces.

    Science.gov (United States)

    Faheem, Muhammad; Heyden, Andreas

    2014-08-12

    We report the development of a quantum mechanics/molecular mechanics free energy perturbation (QM/MM-FEP) method for modeling chemical reactions at metal-water interfaces. This novel solvation scheme combines planewave density function theory (DFT), periodic electrostatic embedded cluster method (PEECM) calculations using Gaussian-type orbitals, and classical molecular dynamics (MD) simulations to obtain a free energy description of a complex metal-water system. We derive a potential of mean force (PMF) of the reaction system within the QM/MM framework. A fixed-size, finite ensemble of MM conformations is used to permit precise evaluation of the PMF of QM coordinates and its gradient defined within this ensemble. Local conformations of adsorbed reaction moieties are optimized using sequential MD-sampling and QM-optimization steps. An approximate reaction coordinate is constructed using a number of interpolated states and the free energy difference between adjacent states is calculated using the QM/MM-FEP method. By avoiding on-the-fly QM calculations and by circumventing the challenges associated with statistical averaging during MD sampling, a computational speedup of multiple orders of magnitude is realized. The method is systematically validated against the results of ab initio QM calculations and demonstrated for C-C cleavage in double-dehydrogenated ethylene glycol on a Pt (111) model surface.

  10. Modified reaction mechanism of aerated n-dodecane liquid flowing over heated metal tubes

    Science.gov (United States)

    Reddy, K. T.; Cernansky, N. P.; Cohen, R. S.

    1988-01-01

    The degradation mechanism of the n-dodecane was studied using a modified jet fuel thermal oxidation tester containing a sample withdrawal system as a reaction vessel. The reaction products were identified using gas chromatography and mass spectorometry. The soluble products were found to consist mainly of C5-C10 n-alkanes and 1-alkenes, C7-C10 aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, dodecyl hydroperoxide (ROOH) decomposition products, and C24 alkane isomers. The data from the experiments agreed with those of Hazlett et al. (1977). It was found that alkyl peroxide radical reactions dominate in the autooxidation temperature regime (at T not above 300 C); the dominant path is for the alkyl peroxyl radical to react bimolecularly with fuel to yield primarily alkyl hydroperoxides. The alkyl peroxide radical also undergoes self-termination and unimolecular isomerization and decomposition reactions, to yield smaller amounts of C12 alcohol plus ketone products and tetrahydrofuran derivatives, respectively.

  11. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

    International Nuclear Information System (INIS)

    Osborn, David L.

    2017-01-01

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low temperature combustion and the oxidation of volatile organic compounds in earth’s atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization make characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, while master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

  12. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

    Science.gov (United States)

    Osborn, David L.

    2017-05-01

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low-temperature combustion and in the oxidation of volatile organic compounds in Earth's atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization makes characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, and master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

  13. Formation of degradation compounds from lignocellulosic biomass in the biorefinery: sugar reaction mechanisms

    DEFF Research Database (Denmark)

    Rasmussen, Helena; Sørensen, Hanne R.; Meyer, Anne S.

    2014-01-01

    , several aldehydes and ketones and many different organic acids and aromatic compounds may be generated during hydrothermal treatment of lignocellulosic biomass. The reaction mechanisms are of interest because the very same compounds that are possible inhibitors for biomass processing enzymes......The degradation compounds formed during pretreatment when lignocellulosic biomass is processed to ethanol or other biorefinery products include furans, phenolics, organic acids, as well as mono- and oligomeric pentoses and hexoses. Depending on the reaction conditions glucose can be converted to 5......-(hydroxymethyl)-2-furaldehyde (HMF) and/or levulinic acid, formic acid and different phenolics at elevated temperatures. Correspondingly, xylose can follow different reaction mechanisms resulting in the formation of furan-2-carbaldehyde (furfural) and/or various C-1 and C-4 compounds. At least four routes...

  14. Chemical dynamics in the gas phase: Time-dependent quantum mechanics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gray, S.K. [Argonne National Laboratory, IL (United States)

    1993-12-01

    A major goal of this research is to obtain an understanding of the molecular reaction dynamics of three and four atom chemical reactions using numerically accurate quantum dynamics. This work involves: (i) the development and/or improvement of accurate quantum mechanical methods for the calculation and analysis of the properties of chemical reactions (e.g., rate constants and product distributions), and (ii) the determination of accurate dynamical results for selected chemical systems, which allow one to compare directly with experiment, determine the reliability of the underlying potential energy surfaces, and test the validity of approximate theories. This research emphasizes the use of recently developed time-dependent quantum mechanical methods, i.e. wave packet methods.

  15. Expanding the Enzyme Universe: Accessing Non-Natural Reactions by Mechanism-Guided Directed Evolution

    Science.gov (United States)

    Renata, Hans; Wang, Z. Jane

    2015-01-01

    High selectivities and exquisite control over reaction outcomes entice chemists to use biocatalysts in organic synthesis. However, many useful reactions are not accessible because they are not in nature’s known repertoire. We will use this review to outline an evolutionary approach to engineering enzymes to catalyze reactions not found in nature. We begin with examples of how nature has discovered new catalytic functions and how such evolutionary progressions have been recapitulated in the laboratory starting from extant enzymes. We then examine non-native enzyme activities that have been discovered and exploited for chemical synthesis, emphasizing reactions that do not have natural counterparts. The new functions have mechanistic parallels to the native reaction mechanisms that often manifest as catalytic promiscuity and the ability to convert from one function to the other with minimal mutation. We present examples of how non-natural activities have been improved by directed evolution, mimicking the process used by nature to create new catalysts. Examples of new enzyme functions include epoxide opening reactions with non-natural nucleophiles catalyzed by a laboratory-evolved halohydrin dehalogenase, cyclopropanation and other carbene transfer reactions catalyzed by cytochrome P450 variants, and non-natural modes of cyclization by a modified terpene synthase. Lastly, we describe discoveries of non-native catalytic functions that may provide future opportunities for expanding the enzyme universe. PMID:25649694

  16. A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface

    Science.gov (United States)

    Yang, Yang; Dai, Changqing; Fisher, Adrian; Shen, Yanchun; Cheng, Daojian

    2017-09-01

    Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O2 dissociation, OOH dissociation, and H2O2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of \\text{O}2* hydrogenation reaction is much lower than that of \\text{O}2* dissociation, indicating that \\text{O}2* hydrogenation reaction is more appropriate at the first step than \\text{O}2* dissociation. In the following, H2O2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H2O2 could be generated as a detectable product due to the high activation energy of H2O2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H2O2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e - ORR process. And the elementary step of first H2O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e - reduction pathway. Our DFT calculations show that H2O2 can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of H2O2.

  17. The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Skulason, Egill; Siahrostami, Samira

    2010-01-01

    We study the oxygen reduction reaction (ORR) mechanism on a Pt(1 1 1) surface using density functional theory calculations We find that at low overpotentials the surface is covered with a half dissociated water layer We estimate the barrier for proton transfer to this surface and the barrier...

  18. Inheritance of the bark reaction resistance mechanism in Pinus monticola infected by Cronartium ribicola

    Science.gov (United States)

    Ray J. Hoff

    1986-01-01

    Necrotic reactions in branch or main stems of western white pine (Pinus monticola Dougl.) caused by infection by the blister rust fungus (Cronartium ribicola J. C. Fisch. ex Rabenh.) are a major mechanism of resistance. Overall, 26 percent of the seedlings eliminated the fungus via this defense system. Heritability based upon crossing family groups averaged 33 percent...

  19. Hydrodeoxygenation by deuterium gas--a powerful way to provide insight into the reaction mechanisms.

    Science.gov (United States)

    Ben, Haoxi; Ferguson, Glen A; Mu, Wei; Pu, Yunqiao; Huang, Fang; Jarvis, Mark; Biddy, Mary; Deng, Yulin; Ragauskas, Arthur J

    2013-11-28

    This study demonstrates the use of isotopic labelling and NMR to study the HDO process. As far as we know, this is the first reported effort to trace the incorporation of hydrogen in the HDO process of lignin pyrolysis oil thereby providing key fundamental insight into its reaction mechanism.

  20. Mechanism and kinetics of the electrocatalytic reaction responsible for the high cost of hydrogen fuel cells.

    Science.gov (United States)

    Cheng, Tao; Goddard, William A; An, Qi; Xiao, Hai; Merinov, Boris; Morozov, Sergey

    2017-01-25

    The sluggish oxygen reduction reaction (ORR) is a major impediment to the economic use of hydrogen fuel cells in transportation. In this work, we report the full ORR reaction mechanism for Pt(111) based on Quantum Mechanics (QM) based Reactive metadynamics (RμD) simulations including explicit water to obtain free energy reaction barriers at 298 K. The lowest energy pathway for 4 e - water formation is: first, *OOH formation; second, *OOH reduction to H 2 O and O*; third, O* hydrolysis using surface water to produce two *OH and finally *OH hydration to water. Water formation is the rate-determining step (RDS) for potentials above 0.87 Volt, the normal operating range. Considering the Eley-Rideal (ER) mechanism involving protons from the solvent, we predict the free energy reaction barrier at 298 K for water formation to be 0.25 eV for an external potential below U = 0.87 V and 0.41 eV at U = 1.23 V, in good agreement with experimental values of 0.22 eV and 0.44 eV, respectively. With the mechanism now fully understood, we can use this now validated methodology to examine the changes upon alloying and surface modifications to increase the rate by reducing the barrier for water formation.

  1. The relationship of microstructure and temperature to fracture mechanics parameters in reaction bonded silicon nitride

    International Nuclear Information System (INIS)

    Jennings, H.M.; Dalgleish, B.J.; Pratt, P.L.

    1978-01-01

    The development of physical properties in reaction bonded silicon nitride has been investigated over a range of temperatures and correlated with microstructure. Fracture mechanics parameters, elastic moduli, strength and critical defect size have been determined. The nitrided microstructure is shown to be directly related to these observed properties and these basic relationships can be used to produce material with improved properties. (orig.) [de

  2. Comparison of a two-body threshold (π,2π) reaction mechanism with the usual one-body mechanism in the deuteron

    International Nuclear Information System (INIS)

    Rockmore, R.

    1984-01-01

    A two-body threshold (π +- ,π +- π -+ ) reaction mechanism is suggested in direct analogy with pion absorption. The mechanism involves boson rescattering via Δ excitation. The relative importance of this mechanism and the ordinary one-body mechanism in nuclei is studied in the particular case of S-wave deuteron targets. The contribution of the two-body mechanism to the threshold reaction cross section is found to be less than 1% of the simple one-body estimate

  3. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  4. Automated Prediction of Catalytic Mechanism and Rate Law Using Graph-Based Reaction Path Sampling.

    Science.gov (United States)

    Habershon, Scott

    2016-04-12

    In a recent article [ J. Chem. Phys. 2015 , 143 , 094106 ], we introduced a novel graph-based sampling scheme which can be used to generate chemical reaction paths in many-atom systems in an efficient and highly automated manner. The main goal of this work is to demonstrate how this approach, when combined with direct kinetic modeling, can be used to determine the mechanism and phenomenological rate law of a complex catalytic cycle, namely cobalt-catalyzed hydroformylation of ethene. Our graph-based sampling scheme generates 31 unique chemical products and 32 unique chemical reaction pathways; these sampled structures and reaction paths enable automated construction of a kinetic network model of the catalytic system when combined with density functional theory (DFT) calculations of free energies and resultant transition-state theory rate constants. Direct simulations of this kinetic network across a range of initial reactant concentrations enables determination of both the reaction mechanism and the associated rate law in an automated fashion, without the need for either presupposing a mechanism or making steady-state approximations in kinetic analysis. Most importantly, we find that the reaction mechanism which emerges from these simulations is exactly that originally proposed by Heck and Breslow; furthermore, the simulated rate law is also consistent with previous experimental and computational studies, exhibiting a complex dependence on carbon monoxide pressure. While the inherent errors of using DFT simulations to model chemical reactivity limit the quantitative accuracy of our calculated rates, this work confirms that our automated simulation strategy enables direct analysis of catalytic mechanisms from first principles.

  5. 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

  6. Cardiac implantable electronic device lead extraction using the lead-locking device system: keeping it simple, safe, and inexpensive with mechanical tools and local anesthesia.

    Science.gov (United States)

    Manolis, Antonis S; Georgiopoulos, Georgios; Metaxa, Sofia; Koulouris, Spyridon; Tsiachris, Dimitris

    2017-10-01

    We have previously reported our successful approach for percutaneous cardiac implantable electronic device (CIED) lead extraction using inexpensive tools, which we have continued over the years. Herein we report the results of the systematic use of a unique stylet, the lead-locking device (LLD), which securely locks the entire lead lumen, aided with non-powered telescoping sheaths in 54 patients to extract 98 CIED leads. This prospective observational clinical study included 38 men and 16 women aged 68.9±13.1 years undergoing lead extraction for device infection (n=46), lead malfunction (n=5), or prior to defibrillator implant (n=3). Leads were in place for 6.7±4.3 years. Infections were more commonly due to Staphylococcus species (n=40). There were 78 pacing (31 ventricular, 37 atrial, 4 VDD, and 6 coronary sinus leads) and 20 defibrillating leads. Using simple traction (6 leads) and the LLD stylets (92 leads) aided with telescoping sheaths (15 patients), 96 (98%) leads in 52 (96.3%) patients were successfully removed, with all but one leads removed using a subclavian approach; in 1 patient, the right femoral approach was also required. In 2 patients, distal fragments from one ventricular pacing and one defibrillating lead could not be removed. Finally, lead removal was completely (52/54) (96.3%) or partially (2/54) (3.7%) successful in 54 patients for 96 of 98 leads (98%) without major complications. Percutaneous lead extraction can be successful with mechanical tools using the LLD locking stylet aided with non-powered telescoping sheaths through a simplified, safe, and inexpensive procedure using local anesthesia.

  7. The Reaction Mechanism and Rate Constants in the Radiolysis of Fe2+-Cu2+ Solutions

    DEFF Research Database (Denmark)

    Bjergbakke, Erling; Sehested, Knud; Rasmussen, O. Lang

    1976-01-01

    Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some ...... 10^{8}$ and $1.3\\times 10^{8}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$ in pH 2.1 H2 SO4 and HClO4, respectively.......Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some...... of the reactions have been determined at different pH's. $k_{{\\rm Cu}^{+}+{\\rm O}_{2}}=4.6\\times 10^{5}$ and $1.0\\times 10^{6}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}^{+}+{\\rm Fe}^{3+}}=5.5\\times 10^{6}$ and $1.3\\times 10^{7}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}({\\rm III)}+{\\rm Fe}^{2+}}=3.3\\times...

  8. Survivability and Fusibility in Reactions Leading to Heavy Nuclei in the Vicinity of the N=126 Closed Shell

    International Nuclear Information System (INIS)

    Sagaidak, R. N.

    2009-01-01

    Nuclear fission is well suited to study the dynamic properties and dissipative processes in cold and moderately excited nuclei. It is also a unique tool to explore level density and shell effects at an extreme deformation. Despite the significant progress in the fission studies, the isospin dependence of fission properties and, in particular, of fission barrier heights still remains an open problem. Theoretical fission model parameters are tuned by using the experimental nuclear and fission data close to stability [1]. The models provide a reasonable description of the fission barriers close to the stability line. However, large deviations are observed between predictions of different models for the fission barriers of very neutron-deficient and neutron-rich nuclei. These discrepancies (by as much as 20-30 MeV, see, e.g. [2]) become especially important in the r-process calculations for extremely neutron-rich nuclei, whose fission barriers determine the termination of the r-process by fission [3]. Unfortunately, such neutron-rich nuclei will probably not become accessible in the nearest experiments. Therefore, fission properties of exotic nuclei and especially their isospin dependence can be investigated in alternative regions of the Nuclide Chart, which are accessible for such studies now. Fusion-evaporation cross sections for heavy fissile nuclei obtained in heavy ion induced reactions as well as their fission cross sections are mainly determined by statistical properties of decaying compound nuclei (CN) and first of all by the fission-barrier heights of nuclei involved in the de-excitation chains leading to observable evaporation residues (ER). At the same time, the ER production and fission in nearly symmetric projectile-target fusion reactions leading to the most neutron-deficient CN could be strongly suppressed due to the quasi-fission (QF) effect [4], as observed recently in the 4 8C a induced reactions leading to Ra [5] and Pb [6] CN. The production of

  9. Numerical comparison of hydrogen-air reaction mechanisms for unsteady shockinduced combustion applications

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, P. Pradeep; Kim, Kui Soon; Oh, Se Jong; Choi, Jeong Yeol [Pusan National University, Busan (Korea, Republic of)

    2015-03-15

    An unsteady shock-induced combustion (SIC) is characterized by the regularly oscillating combustion phenomenon behind the shock wave supported by the blunt projectile flying around the speed of Chapman-Jouguet detonation wave. The SIC is the coupling phenomenon between the hypersonic flow and the chemical kinetics, but the effects of chemical kinetics have been rarely reported. We compared hydrogen-air reaction mechanisms for the shock-induced combustion to demonstrate the importance of considering the reaction mechanisms for such complex flows. Seven hydrogen-air reaction mechanisms were considered, those available publically and used in other researches. As a first step in the comparison of the hydrogen combustion, ignition delay time of hydrogen-oxygen mixtures was compared at various initial conditions. Laminar premixed flame speed was also compared with available experimental data and at high pressure conditions. In addition, half-reaction length of ZND (Zeldovich-Neumann-Doering) detonation structure accounts for the length scale in SIC phenomena. Oscillation frequency of the SIC is compared by running the time-accurate 3rd-order Navier-Stokes CFD code fully coupled with the detailed chemistry by using four levels of grid resolutions.

  10. Numerical comparison of hydrogen-air reaction mechanisms for unsteady shockinduced combustion applications

    International Nuclear Information System (INIS)

    Kumar, P. Pradeep; Kim, Kui Soon; Oh, Se Jong; Choi, Jeong Yeol

    2015-01-01

    An unsteady shock-induced combustion (SIC) is characterized by the regularly oscillating combustion phenomenon behind the shock wave supported by the blunt projectile flying around the speed of Chapman-Jouguet detonation wave. The SIC is the coupling phenomenon between the hypersonic flow and the chemical kinetics, but the effects of chemical kinetics have been rarely reported. We compared hydrogen-air reaction mechanisms for the shock-induced combustion to demonstrate the importance of considering the reaction mechanisms for such complex flows. Seven hydrogen-air reaction mechanisms were considered, those available publically and used in other researches. As a first step in the comparison of the hydrogen combustion, ignition delay time of hydrogen-oxygen mixtures was compared at various initial conditions. Laminar premixed flame speed was also compared with available experimental data and at high pressure conditions. In addition, half-reaction length of ZND (Zeldovich-Neumann-Doering) detonation structure accounts for the length scale in SIC phenomena. Oscillation frequency of the SIC is compared by running the time-accurate 3rd-order Navier-Stokes CFD code fully coupled with the detailed chemistry by using four levels of grid resolutions.

  11. Reconstitution of a eukaryotic replisome reveals suppression mechanisms that define leading/lagging strand operation

    Science.gov (United States)

    Georgescu, Roxana E; Schauer, Grant D; Yao, Nina Y; Langston, Lance D; Yurieva, Olga; Zhang, Dan; Finkelstein, Jeff; O'Donnell, Mike E

    2015-01-01

    We have reconstituted a eukaryotic leading/lagging strand replisome comprising 31 distinct polypeptides. This study identifies a process unprecedented in bacterial replisomes. While bacteria and phage simply recruit polymerases to the fork, we find that suppression mechanisms are used to position the distinct eukaryotic polymerases on their respective strands. Hence, Pol ε is active with CMG on the leading strand, but it is unable to function on the lagging strand, even when Pol δ is not present. Conversely, Pol δ-PCNA is the only enzyme capable of extending Okazaki fragments in the presence of Pols ε and α. We have shown earlier that Pol δ-PCNA is suppressed on the leading strand with CMG (Georgescu et al., 2014). We propose that CMG, the 11-subunit helicase, is responsible for one or both of these suppression mechanisms that spatially control polymerase occupancy at the fork. DOI: http://dx.doi.org/10.7554/eLife.04988.001 PMID:25871847

  12. Mechanism of the electrochemical hydrogen reaction on smooth tungsten carbide and tungsten electrodes

    International Nuclear Information System (INIS)

    Wiesener, K.; Winkler, E.; Schneider, W.

    1985-01-01

    The course of the electrochemical hydrogen reaction on smooth tungsten-carbide electrodes in hydrogen saturated 2.25 M H 2 SO 4 follows a electrochemical sorption-desorption mechanism in the potential range of -0.4 to +0.1 V. At potentials greater than +0.1 V the hydrogen oxidation is controlled by a preliminary chemical sorption step. Concluding from the similar behaviour of tungsten-carbide and tungsten electrodes after cathodic pretreatment, different tungsten oxides should be involved in the course of the hydrogen reaction on tungsten carbide electrodes. (author)

  13. Mechanisms of reactions of organoaluminium compounds with alkenes and alkynes catalyzed by Zr complexes

    International Nuclear Information System (INIS)

    Parfenova, L V; Khalilov, Leonard M; Dzhemilev, Usein M

    2012-01-01

    The results of studies dealing with mechanisms of hydro-, carbo- and cycloalumination of alkenes and alkynes catalyzed by zirconium complexes are generalized and systematized for the first time. Data about the structures of intermediates responsible for the formation of the target compounds are presented and the available data on the effect of the structure of organoaluminium compounds and the electronic and steric factors determining the catalytic activity of metal complexes in these reactions are considered in detail. Much attention is paid to studies of the influence of reaction conditions on the chemo-, regio- and stereoselectivity of the Zr-containing complex catalysts. The bibliography includes 217 references.

  14. Biogenesis of Triterpene Dimers from Orthoquinones Related to Quinonemethides: Theoretical Study on the Reaction Mechanism

    Directory of Open Access Journals (Sweden)

    Mariana Quesadas-Rojas

    2016-11-01

    Full Text Available The biogenetic origin of triterpene dimers from the Celastraceae family has been proposed as assisted hetero-Diels-Alder reaction (HDA. In this work, computational calculation of HDA between natural quinonemethides (tingenone and isopristimerol and hypothetical orthoquinones has been performed at the M06-2X/6-31G(d level of theory. We have located all the HDA transition states supporting the biogenetic route via HDA cycloadditions. We found that all reactions take place through a concerted inverse electron demand and asynchronous mechanism. The enzymatic assistance for dimer formation was analyzed in terms of the calculated transition state energy barrier.

  15. Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

    International Nuclear Information System (INIS)

    Li, Xifeng; Cai, Zhongli; Katsumura, Yosuke

    2000-01-01

    The interaction of caffeic acid with e aq - , (CH 3 ) 2 (OH) CCH 2 · , CO 2 ·- , H · , ·OH and N 3 · radicals were studied by γ-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/·OH adducts, semi-quinone radicals of caffeic ions, and the stable products from the reactions were derived. The rate constants were determined. The attacked sites and the most favorable structures of the transient radicals were predicted. Reaction mechanisms were proposed. (author)

  16. Study of reaction mechanism for 12C(14N, 6Li) by angular correlation measurement

    International Nuclear Information System (INIS)

    Goldberg, V.Z.; Golovkov, M.S.; Rogatchev, G.V.; Barrov, S.P.; Zurmuhle, R.W.; Liu, Z.; Benton, D.R.; Miao, Y.; Lee, C.; Wimer, N.G.; Murgatroyd, J.T.; Li, X.

    1999-01-01

    An angular correlation for the reaction 12 C ( 14 N, 6 Li) 20 Ne* (α) populating the 8.78 MeV (6 + ) level in 20 Ne is measured at 48 MeV incident 14 N energy. 6 Li is registered for 0-degree geometry in coincidence with α particles from the 20 Ne excited state decay. The results shows that 20% was the upper limit for the contribution of compound nucleus formation. Possible main direct mechanisms of the reaction are discussed [ru

  17. Mechanism of NH{sub 3} desorption during the reaction of H{sub 2} with nitrogen containing carbonaceous materials

    Energy Technology Data Exchange (ETDEWEB)

    Juan F. Espinal; Thanh N. Truong; Fanor Mondragon [University of Antioquia, Medellin (Colombia). Institute of Chemistry

    2005-07-01

    The continued increase in demand for natural gas has stimulated the interest in coal conversion to methane as synthetic natural gas by hydropyrolysis of coal (pyrolysis in a H{sub 2} atmosphere). Because the produced raw gas contains considerable amounts of gaseous N-containing products that have to be removed before delivering to final users, the information on distribution of coal-N is important for designing purification processes. It has been reported in the literature that NH{sub 3} is the main nitrogen containing gas that is released during the hydropyrolysis process. Other gases such as HCN and N{sub 2} are also released but in a much smaller amount. To the best of our knowledge, the mechanism for NH{sub 3} desorption during hydrogen reaction with carbonaceous materials has not been studied. We carried out a molecular modeling study using Density Functional Theory in order to get an insight of the mechanism and thermodynamics for NH{sub 3} evolution using pyridinic nitrogen as a model of N-containing carbonaceous material. We propose a mechanism that involves consecutive hydrogenation steps that lead to C-N bond breakage and NH{sub 3} desorption to the gas phase. It was found that the first hydrogenation reaction is highly exothermic. However, further hydrogenations are endothermic. Several pathways for NH{sub 3} evolution were proposed and most of them show high exothermicity. 17 refs., 2 figs.

  18. Lead levels in some biological samples of auto-mechanics in Abeokuta, Nigeria.

    Science.gov (United States)

    Babalola, O O; Ojo, L O; Aderemi, M O

    2005-12-01

    Lead levels were determined in the blood, scalp hair and fingernails of 38, all male auto-mechanics (aged 18-45 years) from Abeokuta, South-western Nigeria. The subjects were classified into four sub-groups based on the period of exposure namely: 1-5, 6-10, 11-15, and >16 years. Thirty-two occupationally unexposed subjects (mainly office workers) served as the control. The weight, height and body mass indexes of all subjects were noted, in addition to other information obtained through structured questionnaire. The mean values of blood lead (BPb), hair lead (HPb) and fingernail lead (NPb) of the occupationally exposed subjects (n=38) were 48.50 +/- 9.08 microg/dL, 17.75 +/- 5.16 microg/g, and 5.92 +/- 3.30 microg/g respectively, while the corresponding mean values for these parameters in the control subjects (n = 32) were 33.(,5 +/- 10.09 microg/dL, 14.30 +/- 5.90 microg/g and 5.31 +/- 2.77 microg/g respectively. The differences in BPb and HPb levels of the two groups were statistically significant (P <0.05 and P <0.01 respectively), while that of NPb was not significant. The levels of lead in the biological samples appeared to have no relationship with the number of years on the job. From these results, it was obvious that the higher levels of lead in the biological samples of test subjects, compared with those of the controls were from environmental sources.

  19. Mechanism of formation and spatial distribution of lead atoms in quartz tube atomizers

    Science.gov (United States)

    Johansson, M.; Baxter, D. C.; Ohlsson, K. E. A.; Frech, W.

    1997-05-01

    The cross-sectional and longitudinal spatial distributions of lead atoms in a quartz tube (QT) atomizers coupled to a gas chromatograph have been investigated. A uniform analyte atom distribution over the cross-section was found in a QT having an inner diameter (i.d.) of 7 mm, whereas a 10 mm i.d. QT showed an inhomogeneous distribution. These results accentuate the importance of using QTs with i.d.s below 10 mm to fulfil the prerequirement of the Beer—Lambert law to avoid bent calibration curves. The influence of the make up gas on the formation of lead atoms from alkyllead compounds has been studied, and carbon monoxide was found equally efficient in promoting free atom formation as hydrogen. This suggests that hydrogen radicals are not essential for mediating the atomization of alkyllead in QT atomizers at ˜ 1200 K. Furthermore, thermodynamic equilibrium calculations describing the investigated system were performed supporting the experimental results. Based on the presented data, a mechanism for free lead atom formation in continuously heated QT atomizers is proposed; thermal atomization occurs under thermodynamic equilibrium conditions in a reducing gas. The longitudinal atom distribution has been further investigated applying other make up gases, N 2 and He. These results show the effect of the influx of atmospheric oxygen on the free lead atom formation. Calculations of the partial pressure of oxygen in the atomizer gas phase assuming thermodynamic equilibrium have been undertaken using a convective-diffusional model.

  20. Microwave emission from lead zirconate titanate induced by impulsive mechanical load

    Energy Technology Data Exchange (ETDEWEB)

    Aman, A., E-mail: alexander.aman@ovgu.de [Department of Engineering, Brandenburg University of Applied Science, 14470 Brandenburg an derHavel (Germany); Packaging Group, Institute of Micro- and Sensorsytems, Otto-von-Guericke University, Universitätsplatz 2, 39106 Magdeburg (Germany); Majcherek, S. [Packaging Group, Institute of Micro- and Sensorsytems, Otto-von-Guericke University, Universitätsplatz 2, 39106 Magdeburg (Germany); Hirsch, S. [Department of Engineering, Brandenburg University of Applied Science, 14470 Brandenburg an derHavel (Germany); Schmidt, B. [Chair of Micorsystem Technology, Institute of Micro- and Sensorsytems, Otto-von-Guericke University, Universitätsplatz 2, 39106 Magdeburg (Germany)

    2015-10-28

    This paper focuses on microwave emission from Lead zirconate titanate Pb [Zr{sub x}Ti{sub 1−x}] O{sub 3} (PZT) induced by mechanical stressing. The mechanical stress was initiated by impact of a sharp tungsten indenter on the upper surface of PZT ceramic. The sequences of microwave and current impulses, which flew from indenter to electric ground, were detected simultaneously. The voltage between the upper and lower surface of ceramic was measured to obtain the behavior of mechanical force acting on ceramic during the impact. It was found that the amplitude, form, and frequency of measured microwave impulses were different by compression and restitution phase of impact. Two different mechanisms of electron emission, responsible for microwave impulse generation, were proposed based on the dissimilar impulse behavior. The field emission from tungsten indenter is dominant during compression, whereas ferroemission dominates during restitution phase. Indeed, it was observed that the direction of the current flow, i.e., sign of current impulses is changed by transitions from compression to restitution phase of impact. The observed dissimilar behavior of microwave impulses, caused by increasing and decreasing applied force, can be used to calculate the contact time and behavior of mechanical force during mechanical impact on ceramic surface. It is shown that the generation of microwave impulses exhibits high reproducibility, impulse intensity, a low damping factor, and high mechanical failure resistance. Based on these microwave emission properties of PZT, the development of new type of stress sensor with spatial resolution of few microns becomes possible.

  1. Mechanisms of collective cell movement lacking a leading or free front edge in vivo.

    Science.gov (United States)

    Uechi, Hiroyuki; Kuranaga, Erina

    2017-08-01

    Collective cell movement is one of the strategies for achieving the complex shapes of tissues and organs. In this process, multiple cells within a group held together by cell-cell adhesion acquire mobility and move together in the same direction. In some well-studied models of collective cell movement, the mobility depends strongly on traction generated at the leading edge by cells located at the front. However, recent advances in live-imaging techniques have led to the discovery of other types of collective cell movement lacking a leading edge or even a free edge at the front, in a diverse array of morphological events, including tubule elongation, epithelial sheet extension, and tissue rotation. We herein review some of the developmental events that are organized by collective cell movement and attempt to elucidate the underlying cellular and molecular mechanisms, which include membrane protrusions, guidance cues, cell intercalation, and planer cell polarity, or chirality pathways.

  2. Lead toxicity in rice: effects, mechanisms, and mitigation strategies--a mini review.

    Science.gov (United States)

    Ashraf, Umair; Kanu, Adam Sheka; Mo, Zhaowen; Hussain, Saddam; Anjum, Shakeel Ahmad; Khan, Imran; Abbas, Rana Nadeem; Tang, Xiangru

    2015-12-01

    Lead (Pb) is a major environmental pollutant that affects plant morpho-physiological and biochemical attributes. Its higher levels in the environment are not only toxic to human beings but also harmful for plants and soil microbes. We have reviewed the uptake, translocation, and accumulation mechanisms of Pb and its toxic effects on germination, growth, yield, nutrient relation, photosynthesis, respiration, oxidative damage, and antioxidant defense system of rice. Lead toxicity hampers rice germination, root/shoot length, growth, and final yield. It reduces nutrient uptake through roots, disrupts chloroplastic ultrastructure and cell membrane permeability, induces alterations in leaves respiratory activities, produces reactive oxygen species (ROS), and triggers some enzyme and non-enzymatic antioxidants (as defense to oxidative damage). In the end, biochar amendments and phytoremediation technologies have been proposed as soil remediation approaches for Pb tainted soils.

  3. Effect of trace elements on the interface reactions between two lead-free solders and copper or nickel substrates

    Directory of Open Access Journals (Sweden)

    Soares D.

    2007-01-01

    Full Text Available Traditional Sn-Pb solder alloys are being replaced, because of environmental and health concerns about lead toxicity. Among some alternative alloy systems, the Sn-Zn and Sn-Cu base alloy systems have been studied and reveal promising properties. The reliability of a solder joint is affected by the solder/substrate interaction and the nature of the layers formed at the interface. The solder/substrate reactions, for Sn-Zn and Sn-Cu base solder alloys, were evaluated in what concerns the morphology and chemical composition of the interface layers. The effect of the addition of P, at low levels, on the chemical composition of the layers present at the interface was studied. The phases formed at the interface between the Cu or Ni substrate and a molten lead-free solder at 250ºC, were studied for different stage times and alloy compositions. The melting temperatures, of the studied alloys, were determined by Differential Scanning Calorimetry (DSC. Identification of equilibrium phases formed at the interface layer, and the evaluation of their chemical composition were performed by Scanning Electron Microscopy (SEM/EDS. Different interface characteristics were obtained, namely for the alloys containing Zn. The obtained IML layer thickness was compared, for both types of alloy systems.

  4. [Adsorption kinetics and mechanism of lead (II) on polyamine-functionalized mesoporous activated carbon].

    Science.gov (United States)

    Li, Kun-Quan; Wang, Yan-Jin; Yang, Mei-Rong; Zhu, Zhi-Qiang; Zheng, Zheng

    2014-08-01

    Bagasse mesoporous carbon was prepared by microwave assisted H3 PO4 activation. Amido and imido groups were modified with ethanediamine on the channels' surface of mesoporous carbon through nitric oxidation and amide reaction. The influence of Pb(II) concentration, adsorption time on Pb(II) adsorption on the ethanediamine-modified mesoporous carbon (AC-EDA) was investigated. The adsorption kinetics and mechanism were also discussed. The results showed that AC-EDA had a great performance for Pb(II) adsorption, and more than 70% of Pb(II) was adsorbed in 5 minutes. The adsorption amount of Pb(II) on the carbon increased with the increase of solution pH in acidic conditions. It was found that AC-EDA had different binding energies on different adsorption sites for Pb(II) separation. The Pb(II) adsorption process on AC-EDA was controlled by intra-particle diffusion in the first 3 min, and then film diffusion played the important pole on the adsorption. The adsorption amount increased with the increase of temperature, indicating the adsorption was an endothermic reaction. The high adsorption energy (> 11 kJ x mol(-1)) implied that the) adsorption was a chemical adsorption. The XPS of AC-EDA before and after Pb(II) adsorption showed that the polyamine group was involved in the adsorption, and should be a main factor of the high efficient adsorption.

  5. Development of the Automatic Modeling System for Reaction Mechanisms Using REX+JGG

    Science.gov (United States)

    Takahashi, Takahiro; Kawai, Kohei; Nakai, Hiroyuki; Ema, Yoshinori

    The identification of appropriate reaction models is very helpful for developing chemical vapor deposition (CVD) processes. In this study, we developed an automatic modeling system that analyzes experimental data on the cross- sectional shapes of films deposited on substrates with nanometer- or micrometer-sized trenches. The system then identifies a suitable reaction model to describe the film deposition. The inference engine used by the system to model the reaction mechanism was designed using real-coded genetic algorithms (RCGAs): a generation alternation model named "just generation gap" (JGG) and a real-coded crossover named "real-coded ensemble crossover" (REX). We studied the effect of REX+JGG on the system's performance, and found that the system with REX+JGG was the most accurate and reliable at model identification among the algorithms that we studied.

  6. [Mechanism of reaction catalyzed by RNA-ligase from bacteriophage T4].

    Science.gov (United States)

    Zagrebel'nyĭ, S N; Zernov, Iu P

    1987-01-01

    The dissociation constants of the complexes of RNA-ligase with acceptors, donors and the adenylylated donor A(5')ppAp have been determined on the basis of the inhibition of ATP-pyrophosphate exchange reaction. The dissociation constants of the complexes of the enzyme with "poor" acceptors (oligouridilates) have been shown to be slightly different from those with "good" acceptors (oligoadenylates). The dependence of the reaction velocity of the formation of ligation products on the concentration of acceptors (pA)4, (pU)4 and the adenylylated donor A(5)ppAp has been studied. On the basis of the data obtained the conclusion about the random addition mechanism has been drawn. The reaction takes place in the steady-state conditions in the case of (pA)4 and in the equilibrium conditions--in the case of (pU)4.

  7. A Density Functional Theory Study on the Reaction Mechanism of Terpinolene with O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hahkjoon [Duksung Women' s University, Seoul (Korea, Republic of)

    2016-02-15

    The energies of chemical species involved in the early stage of the reaction of terpinolene with ozone were calculated to understand the oxidation mechanism of terpinolene with atmospheric O{sub 2} and NO determined experimentally. All the quantum calculations for geometry optimization and frequency calculations in this study were carried out using B3LYP with the 6-31G(d,p) basis (Gaussian 03 software package). In conclusion, quantum chemical calculations were performed to obtain the relative energies and energy barriers for the early stage of the reaction pathways of terpinolene with ozone. The branching ratio for pathways 3 and 4 determined experimentally is in qualitative agreement with the current calculations. The results of these calculations are important for assessing the relative stabilities of the intermediates in the reaction of terpinolene with ozone although detailed RRKM calculations are still needed to fully understand the branching ratios of the final products.

  8. Replisome-mediated Translesion Synthesis and Leading Strand Template Lesion Skipping Are Competing Bypass Mechanisms*

    Science.gov (United States)

    Gabbai, Carolina B.; Yeeles, Joseph T. P.; Marians, Kenneth J.

    2014-01-01

    A number of different enzymatic pathways have evolved to ensure that DNA replication can proceed past template base damage. These pathways include lesion skipping by the replisome, replication fork regression followed by either correction of the damage and origin-independent replication restart or homologous recombination-mediated restart of replication downstream of the lesion, and bypass of the damage by a translesion synthesis DNA polymerase. We report here that of two translesion synthesis polymerases tested, only DNA polymerase IV, not DNA polymerase II, could engage productively with the Escherichia coli replisome to bypass leading strand template damage, despite the fact that both enzymes are shown to be interacting with the replicase. Inactivation of the 3′ → 5′ proofreading exonuclease of DNA polymerase II did not enable bypass. Bypass by DNA polymerase IV required its ability to interact with the β clamp and act as a translesion polymerase but did not require its “little finger” domain, a secondary region of interaction with the β clamp. Bypass by DNA polymerase IV came at the expense of the inherent leading strand lesion skipping activity of the replisome, indicating that they are competing reactions. PMID:25301949

  9. Fatigue responses of lead zirconate titanate stacks under semibipolar electric cycling with mechanical preload

    Science.gov (United States)

    Wang, Hong; Cooper, Thomas A.; Lin, Hua-Tay; Wereszczak, Andrew A.

    2010-10-01

    Lead zirconate titanate (PZT) stacks that had an interdigital internal electrode configuration were tested to more than 108 cycles. A 100 Hz semibipolar sine wave with a field range of +4.5/-0.9 kV/mm was used in cycling with a concurrently-applied 20 MPa preload. Significant reductions in piezoelectric and dielectric responses were observed during the cycling depending on the measuring condition. Extensive partial discharges were also observed. These surface events resulted in the erosion of external electrode and the exposure of internal electrodes. Sections prepared by sequential polishing technique revealed a variety of damage mechanisms including delaminations, pores, and etch grooves. The scale of damage was correlated with the degree of fatigue-induced reduction in piezoelectric and dielectric responses. The results from this study demonstrate the feasibility of using a semibipolar mode to drive a PZT stack under a mechanical preload and illustrate the potential fatigue and damages of the stack in service.

  10. INFRASTRUCTURAL MECHANISMS LEADING TOWARD PRO-ACCOUNTABLE CARE ORGANISATION ORIENTATION: A SURVEY OF HOSPITAL MANAGERS

    Science.gov (United States)

    Wan, Thomas T.H.; Masri, Maysoun Dimachkie; Ortiz, Judith

    2013-01-01

    Organisations across the country are transforming the way they deliver care, in ways similar to the accountable care organisation (ACO) model supported by Medicare. ACOs modalities are varying in size, type, and financing structure. Little is known about how specific infrastructural mechanisms influence hospital managers’ pro-ACO orientation. Using an electronic-survey of hospital managers, this study explores how pro-ACO orientation, as a latent construct, is captured from the perceptions of hospital managers; and identify infrastructural mechanisms leading to the formation of pro-ACO orientation. Of the total hospital respondents, 58% are moving toward the establishment of ACOs; 56% are planning to join in the next two years; 48% are considering joining ACOs; while 25% had already participated in ACOs during 2012. Urban hospitals are more likely than rural hospitals to be engaged in ACO development. The health provider network size is one of the strongest indicators in predicting pro-ACO orientation. PMID:25374609

  11. Fracture Mechanics Analyses of Reinforced Carbon-Carbon Wing-Leading-Edge Panels

    Science.gov (United States)

    Raju, Ivatury S.; Phillips, Dawn R.; Knight, Norman F., Jr.; Song, Kyongchan

    2010-01-01

    Fracture mechanics analyses of subsurface defects within the joggle regions of the Space Shuttle wing-leading-edge RCC panels are performed. A 2D plane strain idealized joggle finite element model is developed to study the fracture behavior of the panels for three distinct loading conditions - lift-off and ascent, on-orbit, and entry. For lift-off and ascent, an estimated bounding aerodynamic pressure load is used for the analyses, while for on-orbit and entry, thermo-mechanical analyses are performed using the extreme cold and hot temperatures experienced by the panels. In addition, a best estimate for the material stress-free temperature is used in the thermo-mechanical analyses. In the finite element models, the substrate and coating are modeled separately as two distinct materials. Subsurface defects are introduced at the coating-substrate interface and within the substrate. The objective of the fracture mechanics analyses is to evaluate the defect driving forces, which are characterized by the strain energy release rates, and determine if defects can become unstable for each of the loading conditions.

  12. Investigation of corrosion, water reaction, polonium evaporation and bismuth resource in liquid metal lead-bismuth technology

    Energy Technology Data Exchange (ETDEWEB)

    Takano, Hideki; Takizuka, Takakazu [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Kitano, Teruaki [Mitsui Shipbuilding and Engineering Co. Ltd., Tokyo (Japan)

    2000-10-01

    Lead-bismuth is the first candidate material for liquid metal target find coolant of fueled blanket system in accelerator-driven system (ADS) studied at JAERI. Advantages of the lead-bismuth utilization are non-active material, very low capture cross section, low melting point of 125degC and high boiling point of 1670degC, and beside coolant void reactivity become negative. But problems are due to the high corrosivity to most of the structural materials and the corrosive data are scarcity. In this report, corrosivity, reaction with water, thermal-hydraulics, chemical toxicity etc. are studied by investigating some facilities utilized and researched really for lead or lead-bismuth. And, furthermore, polonium evaporation rate and bismuth resource are investigated. Main results obtained are as follows: (1) In a refinery, there are enough employment experience for liquid Pb-Bi in period of about 17 years and not corrosion for the thermal conductive materials (1Cr-0.5Mo steel) used under the condition of natural convection with temperature around 400degC. (2) In Russia, extensive experience in the use as Russian submarines and in R and D during about 50 years are available. And as a result, it will be able to lead approximately zero corrosion for Cr-Si materials by adjusting oxygen film with oxygen concentration control between 10{sup -7} to 10{sup -5}% mass. However, the corrosion data are not enough systematically collected involving them in radiation dose field. (3) In liquid-dropping experiment, it is shown that interaction between water and high temperature liquid Pb-Bi is reduced steeply with rising of atmosphere pressure. But, in order to design the second circuit removal model of ADS, the interaction should be evaluated by water continuous injection experiment. (4) Polonium forms PbPo in Pb-Bi, and the evaporation rate become less three factor than that of Po, and furthermore, the rate decreases in the atmosphere. The effects of Po on employee and environment

  13. Biochemical mechanism of phytoremediation process of lead and cadmium pollution with Mucor circinelloides and Trichoderma asperellum.

    Science.gov (United States)

    Zhang, Xu; Li, Xinxin; Yang, Huanhuan; Cui, Zhaojie

    2018-08-15

    This study focused on the bioremediation mechanisms of lead (0, 100, 500, 1000 mg kg -1 ) and cadmium (0,10,50,100 mg kg -1 ) contaminated soil using two indigenous fungi selected from mine tailings as the phytostimulation of Arabidopsis thaliana. The two fungal strains were characterized as Mucor circinelloides (MC) and Trichoderma asperellum (TA) by internal transcribed spacer sequencing at the genetic levels. Our research revealed that Cadmium was more toxic to plant growth than lead and meanwhile, MC and TA can strengthen A. thaliana tolerance to cadmium and lead with 40.19-117.50% higher root length and 58.31-154.14% shoot fresh weight of plant compared to non-inoculation. In this study, TA exhibited a higher potential to the inactivation of cadmium; however, MC was more effective in lead passivation. There was a direct correlation between the type of fungi, heavy metal content, heavy metal type and oxidative damage in plant. Both lead and cadmium induced oxidative damage as indicated by increased superoxide dismutase and catalase activities, while the antioxidant levels were significantly higher in fungal inoculated plants compared with those non-inoculated. The analysis of soil enzyme activity and taxonomic richness uncovered that the dominant structures of soil microbial community were altered by exogenous microbial agents. MC enhanced higher microbial diversity and soil enzyme activity than TA. The two indigenous fungi lessened several limiting factors with respect to phytoremediation technology, such as soil chemistry, contamination level and transformation, and metal solubility. Copyright © 2018 Elsevier Inc. All rights reserved.

  14. Prediction of Mechanism and Thermochemical Properties of O3 + H2S Atmospheric Reaction

    Directory of Open Access Journals (Sweden)

    Morteza Vahedpour

    2013-01-01

    Full Text Available Ozone and hydrogen sulfide reaction mechanism including a complex was studied at the B3LYP/6-311++G(3df,3pd and CCSD/6-311++G(3df,3pd//B3LYP/6-311++G(3df,3pd levels of computation. The interaction between sulfur atom of hydrogen sulfide and terminal oxygen atom of ozone produces a stable H2S-O3 complex with no barrier. With the decomposition of this complex, four possible product channels have been found. Intrinsic reaction coordinate, topological analyses of atom in molecule, and vibrational frequency calculation have been used to confirm the suggested mechanism. Thermodynamic data at T = 298.15 K and the atmospheric pressure have been calculated. The results show that the production of H2O + SO2 is the main reaction channel with ΔG° = −645.84 kJ/mol. Rate constants of H2S + O3 reaction show two product channels, SO2 + H2O and HSO + HOO, which compete with each other based on the temperature.

  15. Mechanism of nuclear dissipation in fission and heavy-ion reactions

    International Nuclear Information System (INIS)

    Nix, J.R.; Sierk, A.J.

    1986-01-01

    Recent advances in the theoretical understanding of nuclear dissipation at intermediate excitation energies are reviewed, with particular emphasis on a new surface-plus-window mechanism that involves interactions of either one or two nucleons with the moving nuclear surface and also, for dumbbell-like shapes encountered in fission and heavy-ion reactions, the transfer of nucleons through the window separating the two portions of the system. This novel dissipation mechanism provides a unified macroscopic description of such diverse phenomena as widths of isoscalar giant quadrupole and giant octupole resonances, mean fission-fragment kinetic energies and excitation energies, dynamical thresholds for compound-nucleus formation, enhancement in neutron emission prior to fission, and widths of mass and charge distributions in deep-inelastic heavy-ion reactions. 41 refs., 8 figs

  16. Elucidation of reaction mechanism for m -cresol hydrodeoxygenation over Fe based catalysts: A kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Yongchun; Wang, Yong

    2017-09-01

    Fe based catalysts are promising for hydrodeoxygenation (HDO) of lignin derived phenolics due to their high selectivity for aromatics. In this work, the reaction mechanism of m-cresol HDO on Fe catalysts and the kinetic consequence with Pd addition were elucidated by examining the effect of H2, H2O and m-cresol pressures on toluene formation rate on Fe and PdFe catalysts. A direct CO bond cleavage mechanism is proposed for HDO catalysis on both Fe and PdFe catalysts, while Pd provides a facilitated reaction pathway at the PdFe interface and therefore promotes the catalysis on Fe without changing the high selectivity towards aromatics.

  17. Light particle emission as a probe of reaction mechanism and nuclear excitation

    International Nuclear Information System (INIS)

    Guerreau, D.

    1989-01-01

    The central part of these lectures will be dealing with the problem of energy dissipation. A good understanding of the mechanisms for the dissipation requires to study both peripheral and central collisions or, in other words, to look at the impact paramenter dependence. This should also provide valuable information on the time scale. In order to probe the reaction mechanism and nuclear excitation, one of the most powerful tool is unquestionably the observation of light particle emission, including neutrons and charged particles. Several examples will be discussed related to peripheral collisions (the fate of transfer reactions, the excitation energy generation, the production of projectile-like fragments) as well as inner collisions for which extensive studies have demonstrated the strength of intermediate energy heavy ions for the production of very hot nuclei and detailed study of their decay properties

  18. Drift mechanism of mass transfer on heterogeneous reaction in crystalline silicon substrate

    Energy Technology Data Exchange (ETDEWEB)

    Kukushkin, S.A. [Institute of Problems of Mechanical Engineering, Russian Academy of Science, St Petersburg, 199178 (Russian Federation); St. Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101 (Russian Federation); Osipov, A.V., E-mail: Andrey.V.Osipov@gmail.com [Institute of Problems of Mechanical Engineering, Russian Academy of Science, St Petersburg, 199178 (Russian Federation); St. Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101 (Russian Federation)

    2017-05-01

    This work aims to study the pressure dependence of the thickness of the epitaxial silicon carbide film growing from crystalline silicon due to the heterogeneous reaction with gaseous carbon monoxide. It turned out that this dependence exhibits the clear maximum. On further pressure increasing the film thickness decreases. The theoretical model has been developed which explains such a character of the dependence by the fact that the gaseous silicon monoxide reaction product inhibits the drift of the gaseous reagent through the channels of a crystal lattice, thus decreasing their hydraulic diameter. In the proposed hydraulic model, the dependences of the film thickness both on the gas pressure and time have been calculated. It was shown that not only the qualitative but also quantitative correspondence between theoretical and experimental results takes place. As one would expect, due to the Einstein relation, at short growth times the drift model coincides with the diffusion one. Consequences of this drift mechanism of epitaxial film growing are discussed. - Graphical abstract: This work aims to study the pressure dependence of the thickness of the epitaxial silicon carbide film growing from crystalline silicon due to the heterogeneous reaction with gaseous carbon monoxide. It turned out that this dependence exhibits the clear maximum. On further pressure increasing the film thickness decreases. The theoretical model has been developed which explains such a character of the dependence by the fact that the gaseous silicon monoxide reaction product inhibits the drift of the gaseous reagent through the channels of a crystal lattice, thus decreasing their hydraulic diameter. - Highlights: • It is established that the greater pressure, the smaller is the reaction rate. • The reaction product prevents penetration of the reagent into a reaction zone. • For description the hydraulic model of crystal lattice channels is developed. • Theoretical results for polytropic

  19. Investigation of organometallic reaction mechanisms with one and two dimensional vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James Francis [Univ. of California, Berkeley, CA (United States)

    2008-12-01

    One and two dimensional time-resolved vibrational spectroscopy has been used to investigate the elementary reactions of several prototypical organometallic complexes in room temperature solution. The electron transfer and ligand substitution reactions of photogenerated 17-electron organometallic radicals CpW(CO)3 and CpFe(CO)2 have been examined with one dimensional spectroscopy on the picosecond through microsecond time-scales, revealing the importance of caging effects and odd-electron intermediates in these reactions. Similarly, an investigation of the photophysics of the simple Fischer carbene complex Cr(CO)5[CMe(OMe)] showed that this class of molecule undergoes an unusual molecular rearrangement on the picosecond time-scale, briefly forming a metal-ketene complex. Although time-resolved spectroscopy has long been used for these types of photoinitiated reactions, the advent of two dimensional vibrational spectroscopy (2D-IR) opens the possibility to examine the ultrafast dynamics of molecules under thermal equilibrium conditions. Using this method, the picosecond fluxional rearrangements of the model metal carbonyl Fe(CO)5 have been examined, revealing the mechanism, time-scale, and transition state of the fluxional reaction. The success of this experiment demonstrates that 2D-IR is a powerful technique to examine the thermally-driven, ultrafast rearrangements of organometallic molecules in solution.

  20. Reaction mechanism for the free-edge oxidation of soot by O 2

    KAUST Repository

    Raj, Abhijeet; da Silva, Gabriel; Chung, Suk-Ho

    2012-01-01

    The reaction pathways for the oxidation by O 2 of polycyclic aromatic hydrocarbons present in soot particles are investigated using density functional theory at B3LYP/6-311++G(d,p) level of theory. For this, pyrene radical (4-pyrenyl) is chosen as the model molecule, as most soot models present in the literature employ the reactions involving the conversion of 4-pyrenyl to 4-phenanthryl by O 2 and OH to account for soot oxidation. Several routes for the formation of CO and CO 2 are proposed. The addition of O 2 on a radical site to form a peroxyl radical is found to be barrierless and exothermic with reaction energy of 188kJ/mol. For the oxidation reaction to proceed further, three pathways are suggested, each of which involve the activation energies of 104, 167 and 115kJ/mol relative to the peroxyl radical. The effect of the presence of H atom on a carbon atom neighboring the radical site on the energetics of carbon oxidation is assessed. Those intermediate species formed during oxidation with seven-membered rings or with a phenolic group are found to be highly stable. The rate constants evaluated using transition state theory in the temperature range of 300-3000K for the reactions involved in the mechanism are provided. © 2012 The Combustion Institute.

  1. A Density Functional Theory Study on the Reaction Mechanism of α-Phellandrene with NO_3

    International Nuclear Information System (INIS)

    Kim, Hahk Joon; Park, Ji Ho

    2015-01-01

    In this study, we investigated the relative energies of the chemical species involved in the reaction of α-phellandrene with NO_3 under ambient nighttime conditions to understand the reaction pathway and identify the final products using quantum chemical calculations. The expected main oxidation products are nitrosocabonyl compounds. Although the formation of an oxirane compound is plausible, the reaction might proceed further to produce an aromatic compound. To fully understand α-phellandrene oxidation by NO_3, further study of the detailed reaction mechanism of the formation of an aromatic compound detected by the experiment is needed. Oxidations by OH radical and O_3 are major loss processes for tropospheric monoterpenes during the day. NO_3 radical, which is rapidly photolyzed by sunlight, is a dominant trophospheric oxidant at night because they react rapidly with monoterpens. Some volatile organic compounds produced by the reaction with atmospheric constituents are responsible for the formation of secondary organic aerosols that serve as cloud condensation nuclei inducing a cloud climate effect in the troposphere

  2. Reaction mechanism for the free-edge oxidation of soot by O 2

    KAUST Repository

    Raj, Abhijeet

    2012-11-01

    The reaction pathways for the oxidation by O 2 of polycyclic aromatic hydrocarbons present in soot particles are investigated using density functional theory at B3LYP/6-311++G(d,p) level of theory. For this, pyrene radical (4-pyrenyl) is chosen as the model molecule, as most soot models present in the literature employ the reactions involving the conversion of 4-pyrenyl to 4-phenanthryl by O 2 and OH to account for soot oxidation. Several routes for the formation of CO and CO 2 are proposed. The addition of O 2 on a radical site to form a peroxyl radical is found to be barrierless and exothermic with reaction energy of 188kJ/mol. For the oxidation reaction to proceed further, three pathways are suggested, each of which involve the activation energies of 104, 167 and 115kJ/mol relative to the peroxyl radical. The effect of the presence of H atom on a carbon atom neighboring the radical site on the energetics of carbon oxidation is assessed. Those intermediate species formed during oxidation with seven-membered rings or with a phenolic group are found to be highly stable. The rate constants evaluated using transition state theory in the temperature range of 300-3000K for the reactions involved in the mechanism are provided. © 2012 The Combustion Institute.

  3. Reaction kinetics and mechanisms of organosilicon fungicide flusilazole with sulfate and hydroxyl radicals.

    Science.gov (United States)

    Mercado, D Fabio; Bracco, Larisa L B; Arques, Antonio; Gonzalez, Mónica C; Caregnato, Paula

    2018-01-01

    Flusilazole is an organosilane fungicide used for treatments in agriculture and horticulture for control of diseases. The reaction kinetics and mechanism of flusilazole with sulfate and hydroxyl radicals were studied. The rate constant of the radicals with the fungicide were determined by laser flash photolysis of peroxodisulfate and hydrogen peroxide. The results were 2.0 × 10 9 s -1 M -1 for the reaction of the fungicide with HO and 4.6 × 10 8  s -1  M -1 for the same reaction with SO 4 - radicals. The absorption spectra of organic intermediates detected by laser flash photolysis of S 2 O 8 2- with flusilazole, were identified as α-aminoalkyl and siloxyl radicals and agree very well with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. In the continuous photolysis experiments, performed by photo-Fenton reaction of the fungicide, the main degradation products were: (bis(4-fluorophenyl)-hydroxy-methylsilane) and the non-toxic silicic acid, diethyl bis(trimethylsilyl) ester, in ten and twenty minutes of reaction, respectively. Copyright © 2017. Published by Elsevier Ltd.

  4. Modeling of the Reaction Mechanism of Enzymatic Radical C–C Coupling by Benzylsuccinate Synthase

    Directory of Open Access Journals (Sweden)

    Maciej Szaleniec

    2016-04-01

    Full Text Available Molecular modeling techniques and density functional theory calculations were performed to study the mechanism of enzymatic radical C–C coupling catalyzed by benzylsuccinate synthase (BSS. BSS has been identified as a glycyl radical enzyme that catalyzes the enantiospecific fumarate addition to toluene initiating its anaerobic metabolism in the denitrifying bacterium Thauera aromatica, and this reaction represents the general mechanism of toluene degradation in all known anaerobic degraders. In this work docking calculations, classical molecular dynamics (MD simulations, and DFT+D2 cluster modeling was employed to address the following questions: (i What mechanistic details of the BSS reaction yield the most probable molecular model? (ii What is the molecular basis of enantiospecificity of BSS? (iii Is the proposed mechanism consistent with experimental observations, such as an inversion of the stereochemistry of the benzylic protons, syn addition of toluene to fumarate, exclusive production of (R-benzylsuccinate as a product and a kinetic isotope effect (KIE ranging between 2 and 4? The quantum mechanics (QM modeling confirms that the previously proposed hypothetical mechanism is the most probable among several variants considered, although C–H activation and not C–C coupling turns out to be the rate limiting step. The enantiospecificity of the enzyme seems to be enforced by a thermodynamic preference for binding of fumarate in the pro(R orientation and reverse preference of benzyl radical attack on fumarate in pro(S pathway which results with prohibitively high energy barrier of the radical quenching. Finally, the proposed mechanism agrees with most of the experimental observations, although the calculated intrinsic KIE from the model (6.5 is still higher than the experimentally observed values (4.0 which suggests that both C–H activation and radical quenching may jointly be involved in the kinetic control of the reaction.

  5. A coupled mechanical and chemical damage model for concrete affected by alkali–silica reaction

    Energy Technology Data Exchange (ETDEWEB)

    Pignatelli, Rossella, E-mail: rossellapignatelli@gmail.com [Department of Civil and Environmental Engineering, Politecnico di Milano, Piazza L. da Vinci 32, 20133 Milano (Italy); Lombardi Ingegneria S.r.l., Via Giotto 36, 20145 Milano (Italy); Comi, Claudia, E-mail: comi@stru.polimi.it [Department of Civil and Environmental Engineering, Politecnico di Milano, Piazza L. da Vinci 32, 20133 Milano (Italy); Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu [Department of Civil and Environmental Engineering, University of California, Berkeley, CA 94720 (United States)

    2013-11-15

    To model the complex degradation phenomena occurring in concrete affected by alkali–silica reaction (ASR), we formulate a poro-mechanical model with two isotropic internal variables: the chemical and the mechanical damage. The chemical damage, related to the evolution of the reaction, is caused by the pressure generated by the expanding ASR gel on the solid concrete skeleton. The mechanical damage describes the strength and stiffness degradation induced by the external loads. As suggested by experimental results, degradation due to ASR is considered to be localized around reactive sites. The effect of the degree of saturation and of the temperature on the reaction development is also modeled. The chemical damage evolution is calibrated using the value of the gel pressure estimated by applying the electrical diffuse double-layer theory to experimental values of the surface charge density in ASR gel specimens reported in the literature. The chemo-damage model is first validated by simulating expansion tests on reactive specimens and beams; the coupled chemo-mechanical damage model is then employed to simulate compression and flexure tests results also taken from the literature. -- Highlights: •Concrete degradation due to ASR in variable environmental conditions is modeled. •Two isotropic internal variables – chemical and mechanical damage – are introduced. •The value of the swelling pressure is estimated by the diffuse double layer theory. •A simplified scheme is proposed to relate macro- and microscopic properties. •The chemo-mechanical damage model is validated by simulating tests in literature.

  6. Thermal decomposition of a molecular material {N(n-C4H94[FeIIFeIII(C2O43]}∞ leading to ferrite: A reaction kinetics study

    Directory of Open Access Journals (Sweden)

    Bhattacharjee Ashis

    2013-01-01

    Full Text Available A multi-step thermal decomposition of a molecular precursor, {N(n-C4H94[FeIIFeIII(C2O43}∞ has been studied using non-isothermal thermogravimetry (TG measurements in the temperature range 300 to ~800 K at multiple heating rates (5, 10 and 20 K min-1. The thermal decomposition of the oxalate-based complex proceeds stepwise through a series of intermediate reactions. Two different isoconversional methods, namely, improved iterative method and model-free method are employed to evaluate the kinetic parameters: activation energy and rate of reaction, and the most probable reaction mechanism of thermal decomposition is also determined. The different reaction pathways leading to different steps in the TG profile have also been explored which are supplemented by earlier experimental observations of the present authors.

  7. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Jorge, Nelly Lidia [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain); Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Romero, Jorge Marcelo [Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Grand, Andre [INAC, SCIB, Laboratoire ' Lesions des Acides Nucleiques' , UMR CEA-UJF E3, CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble cedex 9 (France); Hernandez-Laguna, Alfonso, E-mail: ahlaguna@ugr.es [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain)

    2012-01-17

    Highlights: Black-Right-Pointing-Pointer Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. Black-Right-Pointing-Pointer Gas chromatography and computational potential energy surfaces were performed. Black-Right-Pointing-Pointer A mechanism in steps looked like the most probable mechanism. Black-Right-Pointing-Pointer A spin-orbit coupling appeared at the singlet and triple diradical open structures. Black-Right-Pointing-Pointer A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 {+-} 0.8 kcal/mol and 5.2 Multiplication-Sign 10{sup 13} s{sup -1}, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G{sup Asterisk-Operator Asterisk-Operator} level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  8. Concerted and stepwise mechanisms in cycloaddition reactions: potential surfaces and isotope effects

    International Nuclear Information System (INIS)

    Houk, K.N.; Yi Li; Storer, Joey; Raimondi, Laura; Beno, Brett

    1994-01-01

    CASSCF/6-31G * calculations have been performed on concerted and stepwise Diels-Alder reactions of butadiene with ethene, the dimerization of butadiene, and the dimerization of cyclobutadiene. The relative energies of concerted and stepwise mechanisms are compared, and the factors influencing these ''energies of concert'' are discussed. The comparison of calculated isotope effects to experimental data provides support for theoretical results. (Author)

  9. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    International Nuclear Information System (INIS)

    Jorge, Nelly Lidia; Romero, Jorge Marcelo; Grand, André; Hernández-Laguna, Alfonso

    2012-01-01

    Highlights: ► Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. ► Gas chromatography and computational potential energy surfaces were performed. ► A mechanism in steps looked like the most probable mechanism. ► A spin–orbit coupling appeared at the singlet and triple diradical open structures. ► A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463–503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 ± 0.8 kcal/mol and 5.2 × 10 13 s −1 , respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G ∗∗ level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin–orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  10. 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

  11. Mechanism of catalytic action of oxide systems in reactions of aldehyde oxidation to carboxylic acids

    International Nuclear Information System (INIS)

    Andrushkevich, T.V.

    1997-01-01

    Mechanism of selective action of oxide catalysts (on the base of V 2 O 4 , MoO 3 ) of aldehyde oxidation to acids is considered, reaction acrolein oxidation to acrylic acid is taken as an example. Multistage mechanism of the process is established; it involves consequent transformation of coordination-bonded aldehyde into carbonyl-bonded aldehyde and symmetric carboxylate. Principles of active surface construction are formulated, they take into account the activity of stabilization center of concrete intermediate compound and bond energy of oxygen with surface. (author)

  12. 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

  13. Thermal runaway reaction hazards and mechanisms of hydroxylamine with acid/base contaminants

    International Nuclear Information System (INIS)

    Wei Chunyang; Saraf, Sanjeev R.; Rogers, William J.; Sam Mannan, M.

    2004-01-01

    Hydroxylamine (HA) has been involved in two incidents since 1999 because of its thermal instability and incompatibility. In this study, thermal runaway reactions of hydroxylamine with various concentrations of KOH and HCl were studied using the reactive system screening tool (RSST) and automatic pressure tracking adiabatic calorimeter (APTAC). The thermokinetic data, such as onset temperature, heat of reaction, maximum self-heat rate, maximum pressure rate, and non-condensable gas pressure, were compared with those of hydroxylamine solution without added impurity. Our study shows that the thermal decomposition behavior of hydroxylamine is affected by the presence of acid/base, and mixing of hydroxylamine with acid/base may cause thermal decomposition at lower temperatures. Different decomposition pathways can be initiated by hydrogen ion and hydroxide ion. The decomposition mechanisms of hydroxylamine in alkaline and acidic solutions are proposed based on the products, information from the literature, and quantum mechanical calculations. The experimental results are discussed in terms of the proposed reaction mechanisms

  14. The oxidative response and viable reaction mechanism of the textile dyes by fenton reagent

    International Nuclear Information System (INIS)

    Masooda, Q.; Hijira, T.; Sitara, M.; Sehar, M.; Sundus, A.; Mohsin, A.

    2017-01-01

    The mechanism of the degradation of the Reactive Red 239 and Reactive Blue 19 by Fenton reagent was studied by advanced oxidation process in aqueous medium. The spectroscopic technique was adopted for the measurements of dye concentration. Moreover they were determined at 540 nm and 590 nm, respectively. Kinetics of the reaction was studied under the effect of concentration of reactive dyes, concentration of oxidant were followed under pseudo first order condition and found to influence the catalytic mechanism. The pH of the medium, vibrant response of several cations and anions and influence of ionic strength on the reaction kinetics were also monitored. Physical evidences for the degradation and mineralization of the dyes were evaluated by Lime water test, Ring Test and TLC test also confirmed the degradation of dye. Inhibitory effects of dyes were observed by CO3-, HCO3-, HPO42-, Cl-, I- Al3+ and Na+. Thermodynamic activation parameters in the oxidation reaction were studied and mode of mechanism was suggested on the basic of these parameters. This study explored the safe and eco friendly degradation of the textile dyes under Pseudo first order rate constant. It was observed that Fenton assisted degradation of the dyes under controlled conditions was found to be favorable for the treatment of textile wastewater. Moreover compared to other chemical methods it is effective and harmless to the environment. (author)

  15. Close correlation between the reaction mechanism and inner structure of loosely halo-nuclei

    International Nuclear Information System (INIS)

    Liu Jianye; Tianshui Normal Univ., Tianshui; National Laboratory of Heavy Ion Accelerator of Lanzhou, Lanzhou; Guo Wenjun; Ren Zhongzhou; National Laboratory of Heavy Ion Accelerator of Lanzhou, Lanzhou; Xing Yongzhong; National Laboratory of Heavy Ion Accelerator of Lanzhou, Lanzhou

    2006-01-01

    It was based on the comparisons of the variance properties of fragment multiplicities FM's and nuclear stoppings R's for the neutron-halo colliding system with those of FZ's and R's for the proton-halo colliding system with the increases of beam energy in more detail, the closely correlations between the reaction mechanism and the inner structures of halo-nuclei is found. From above comparisons it is found that the variance properties of fragment multiplicities and nuclear stopping with the increases of beam energy are quite different for the neutron-halo and proton halo colliding systems, such as the effects of loosely bound neutron-halo structure on the fragment multiplicities and nuclear stopping are obviously larger than those for the proton-halo colliding system. This is due to that the structures of halo-neutron nucleus 11 Li is more loosely than that of the proton-halo nucleus 23 Al. In this case, the fragment multiplicity and nuclear stopping of halo nuclei may be used as a possible probe for studying the reaction mechanism and the correlation between the reaction mechanism and the inner structure of halo-nuclei. (authors)

  16. Pion-transfer (n,d) and (d, 3He) reactions leading to deeply bound pionic atoms

    International Nuclear Information System (INIS)

    Toki, H.; Hirenzaki, S.; Yamazaki, T.

    1990-11-01

    Theoretical studies are given on the (n,d) and (d, 3 He) reactions leading to deeply bound pionic atoms in heavy nuclei of configuration [(nl) π ·j n -1 ]J. The cross sections for various pionic and neutron-hole configurations in the case of a 208 Pb target are calculated at incident energies 300-1000 MeV/u by using the effective number approach and the eikonal approximation for distortion. The effective number with a pion in the 1s or 2p state and a neutron hole in the i 13/2 orbit peaks around the same incident energy (T n =600 MeV) as the elementary cross section n+n→d+π - , where the momentum transfer matches the angular-momentum transfer of L=5∼7. The DWIA cross section for (n,d) producing a pion in the 1s or 2p orbit at T n =600 MeV is found to be around 42 or 75 μb/sr, respectively. At T n =350 MeV, where the momentum transfer is small, quasi-substitutional states of configurations [(2p) π (3p 1/2 ) n -1 ]L=0 and [(2p) π (3p 3/2 ) n -1 ]L=0 are preferentially populated with cross sections of 190 and 380 μb/sr, respectively. The (d, 3 He) cross sections are estimated to be an order of magnitude smaller than the (n,d) cross sections. Thus, the (n,d) and (d, 3 He) reactions are found to be suited for the production of deeply bound pionic atoms. (author)

  17. Leading survey and research report for fiscal 1999. Survey and research on chemical reaction simulator technology; 1999 nendo kagaku hanno simulator gijutsu no chosa kenkyu hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2000-03-01

    Although various chemical reactions are made use of at scenes of chemical industry for the acquisition of desired chemicals, the control of reaction process governing factors, such as temperature, pressure, catalysts, solutions, etc., is found to be carried out only on the empirical basis. At the present time, rational or optimum reaction designs are not to be prepared in a short period of time in the presence of the widespread shortage of knowledge about chemical reactions and of the shortage of understanding of chemical reactions at the micro level. Leading survey and research are conducted for the development of a 'chemical reaction simulator' technology to enable the acquisition of optimum reaction designing guidelines in a short period of time. Using the simulator, a chemical of his choice is inputted by a researcher engaged in the study of an real chemical reaction and then various techniques of computer science are mobilized for the preparation of a huge number of feasible reaction routes, and high-precision simulations are conducted for the feasible reaction routes. The results achieved this fiscal year are reported. The purpose of this research and its ripple effect on new product industry creation are stated. Then the positioning, mission, and concept of such a chemical reaction simulator are described. Finally, the result of research and survey of knowledge databases and the result of research and survey of computational chemistry are stated. (NEDO)

  18. Leading survey and research report for fiscal 1999. Survey and research on chemical reaction simulator technology; 1999 nendo kagaku hanno simulator gijutsu no chosa kenkyu hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2000-03-01

    Although various chemical reactions are made use of at scenes of chemical industry for the acquisition of desired chemicals, the control of reaction process governing factors, such as temperature, pressure, catalysts, solutions, etc., is found to be carried out only on the empirical basis. At the present time, rational or optimum reaction designs are not to be prepared in a short period of time in the presence of the widespread shortage of knowledge about chemical reactions and of the shortage of understanding of chemical reactions at the micro level. Leading survey and research are conducted for the development of a 'chemical reaction simulator' technology to enable the acquisition of optimum reaction designing guidelines in a short period of time. Using the simulator, a chemical of his choice is inputted by a researcher engaged in the study of an real chemical reaction and then various techniques of computer science are mobilized for the preparation of a huge number of feasible reaction routes, and high-precision simulations are conducted for the feasible reaction routes. The results achieved this fiscal year are reported. The purpose of this research and its ripple effect on new product industry creation are stated. Then the positioning, mission, and concept of such a chemical reaction simulator are described. Finally, the result of research and survey of knowledge databases and the result of research and survey of computational chemistry are stated. (NEDO)

  19. Iodinated Contrast Media and the Alleged "Iodine Allergy": An Inexact Diagnosis Leading to Inferior Radiologic Management and Adverse Drug Reactions.

    Science.gov (United States)

    Böhm, Ingrid; Nairz, Knud; Morelli, John N; Keller, Patricia Silva Hasembank; Heverhagen, Johannes T

    2017-04-01

    Purpose  To test the hypothesis that the incomplete diagnosis "iodine allergy" is a possibly dangerous concept for patients under routine radiologic conditions. Materials and Methods  300 patients with a history of an "iodine allergy" were retrospectively screened and compared with two age-, sex-, and procedure-matched groups of patients either diagnosed with a nonspecific "iodine contrast medium (ICM) allergy" or an allergy to a specific ICM agent. For all groups, the clinical symptoms of the most recent past adverse drug reaction (ADR), prophylactic actions taken for subsequent imaging, and ultimate outcome were recorded and analyzed. Results  The diagnosis "iodine allergy" was not otherwise specified in 84.3 % patients. For this group, in most cases, the symptoms of the previous ADRs were not documented. In contrast, the type of ADR was undocumented in only a minority of patients in the comparison groups. In the group of patients with an "iodine allergy" the percentage of unenhanced CT scans was greater than within the other two groups (36.7 % vs. 28.7 %/18.6 %). ADRs following prophylactic measures were only observed in the "iodine allergy" group (OR of 9.24 95 % CI 1.16 - 73.45; p contrast media containing covalently bound iodine.. · There is a clear correlation between the exactness of the diagnosis - from the alleged "iodine allergy" to "contrast media allergy" to naming the exact culprit CM - and the quality of documentation of the symptoms.. · Management of patients diagnosed with "iodine allergy" was associated with uncertainty leading to unenhanced scans and sometimes unnecessary prophylactic actions.. · The term "iodine allergy" should be omitted, because it is potentially dangerous and can decrease the quality of radiology exams.. Citation Format · Böhm Ingrid, Nairz Knud, Morelli John N et al. Iodinated Contrast Media and the Alleged "Iodine Allergy": An Inexact Diagnosis Leading to Inferior Radiologic Management and

  20. Mechanism of action of electrochemically active carbons on the processes that take place at the negative plates of lead-acid batteries

    Energy Technology Data Exchange (ETDEWEB)

    Pavlov, D.; Rogachev, T.; Nikolov, P.; Petkova, G. [Institute of Electrochemistry and Energy Systems, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, bl. 10, Sofia 1113 (Bulgaria)

    2009-06-01

    It is known that negative plates of lead-acid batteries have low charge acceptance when cycled at high rates and progressively accumulate lead sulphate on high-rate partial-state-of-charge (HRPSoC) operation in hybrid-electric vehicle (HEV) applications. Addition of some carbon or graphite forms to the negative paste mix improves the charge efficiency and slows down sulfation of the negative plates. The present investigation aims to elucidate the contribution of electrochemically active carbon (EAC) additives to the mechanism of the electrochemical reactions of charge of the negative plates. Test cells are assembled with four types of EAC added to the negative paste mix in five different concentrations. Through analysis of the structure of NAM (including specific surface and pore radius measurements) and of the electrochemical parameters of the test cells on HRPSoC cycling, it is established that the electrochemical reaction of charge Pb{sup 2+} + 2e{sup -} {yields} Pb proceeds at 300-400 mV lower over-potentials on negative plates doped with EAC additives as compared to the charge potentials of cells with no carbon additives. Hence, electrochemically active carbons have a highly catalytic effect on the charge reaction and are directly involved in it. Consequently, the reversibility of the charge/discharge processes is improved, which eventually leads to longer battery cycle life. Thus, charging of the negative plates proceeds via a parallel mechanism on the surfaces of both Pb and EAC particles, at a higher rate on the EAC phase. Cells with EAC in NAM have the longest cycle life when their NAM specific surface is up to 4 m{sup 2} g{sup -1} against 0.5 m{sup 2} g{sup -1} for the lead surface. The proposed parallel mechanism of charge is verified experimentally on model Pb/EAC/PbSO{sub 4} and Pb/EAC electrodes. During the charge and discharge cycles of the HRPSoC test, the EAC particles are involved in dynamic adsorption/desorption on the lead sulfate and lead

  1. Kinetics and mechanism of oxygen reduction reaction at CoPd system synthesized on XC72

    International Nuclear Information System (INIS)

    Tarasevich, M.R.; Chalykh, A.E.; Bogdanovskaya, V.A.; Kuznetsova, L.N.; Kapustina, N.A.; Efremov, B.N.; Ehrenburg, M.R.; Reznikova, L.A.

    2006-01-01

    Studies are presented of the kinetics and mechanism of oxygen electroreduction reaction on CoPd catalysts synthesized on carbon black XC72. As shown both in model conditions and in the tests within the cathodes of hydrogen-oxygen fuel cells with proton conducting electrolyte, CoPd/C system features a higher activity, as compared to Co/C. The highest activity in the oxygen reduction reaction is demonstrated by the catalysts with the Pd:Co atomic ratio being 7:3 and 4:1. The structural studies (XPS and XRD, and also the data of CO desorption measurements) evidence the CoPd alloy formation, which is reflected in the negative shift of the bonding energy maximum as compared to Pd/C and in the appearance of the additional CO desorption maximums on the voltammograms. It is found by means of structural research that CoPd alloy is formed in the course of the catalyst synthesis which features a higher catalytic activity of the binary systems. Besides, CoPd/C catalyst is more stable in respect to corrosion than Pd supported on carbon black. The measurements on the rotating disc electrode and rotating ring-disc electrode evidence that CoPd/C system provides the predominant oxygen reduction to water in the practically important range of potentials (E > 0.7 V). The proximity of kinetic parameters of the oxygen reduction reaction on CoPd/C and Pt/C catalysts points to the similar reaction mechanism. The slow step of the reaction is the addition of the first electron to the adsorbed and previously protonated O 2 molecule. The assumptions are offered about the reasons causing the higher activity and selectivity of the binary catalyst towards oxygen reduction to water, as compared to Co/C. The studies of the most active catalysts within the fuel cell cathodes are performed

  2. (3He,α) reaction mechanism at high energy and neutron inner shell structure

    International Nuclear Information System (INIS)

    Wiele, J. van de.

    1980-01-01

    The ( 3 He,α) reaction on 12 C, 16 O, 28 Si, 58 Ni, 90 Zr, 118 Sn, 124 Sn and 208 Pb targets has been studied at Esub( 3 He) = 217 MeV (or 205 MeV) in order to investigate the reaction mechanism at high energy and large momentum transfer. The reaction yields large cross sections at very forward angles and strongly enhances the largest orbital momentum transfer. The angular distribution shapes are well reproduced in the frame-work of the Z-R- D.W.B.A. analysis if we use a unique empirical α-potential: Vsub(α)(Esub(α)) = Vsub( 3 He)(3/4 Esub(α)) + Vsub(n)(1/4 Esub(α)). The excitation energy spectra have been measured up to 100 MeV in the residual light and medium nuclei and up to about 16 MeV in heavy nuclei. In addition to the well-known low-lying levels, peaks or broad structures are observed for each nucleus at higher excitation energies. They are attributed to pick up from inner shells: 1s( 11 C and 15 O), 1p( 27 Si), 1d5/2 + 1p( 57 Ni), 1f7/2( 89 Zr) 1g9/2 117 Sn, 123 Sn and 1h11/2( 207 Pb). Selectivity and localization of direct and indirect pick up ( 3 He,α) reactions were studied. Finite range calculations show that this reaction is not very sensitive to the details of the range from function but only to D 0 coefficient and range R. A microscopic α-nucleus optical potential calculated with n-n dependent and independent density forces is able to reproduce both elastic scattering and pick up reaction angular distributions [fr

  3. Elimination Reactions of (E)-2,4,6-Trinitrobenzaldehyde O-benzoyloximes Promoted by R2NH in MeCN. Change of Reaction Mechanism

    International Nuclear Information System (INIS)

    Cho, Bong Rae; Pyun, Sang Yong

    2010-01-01

    We have studied the nitrile-forming elimination reactions from 1 promoted by R 2 NH in MeCN. The reaction proceeded by (E1cb) irr mechanism. Change of the β-aryl group from 2,4-dinitrophenyl to a more strongly electron-withdrawing 2,4,6-trinitrophenyl increased the reaction rate by 470-fold, shifted the transition state toward more reactant-like, and changed the reaction mechanism from E2 to (E1cb) irr . To the best of our knowledge, this is the first example of nitrile-forming elimination reaction that proceeds by the (E1cb) irr mechanism in MeCN. Noteworthy is the carbanion stabilizing ability of the 2,4,6-trinitrophenyl group in aprotic solvent. Nitrile-forming elimination reactions of (E)-benzaldoxime derivatives have been extensively investigated under various conditions. The reactions proceeded by the E2 mechanism in MeCN despite the fact that the reactants have syn stereochemistry, poor leaving, and sp 2 hybridized β-carbon atom, all of which favor E1cb- or E1cb-like transition state. Moreover, the transition state structures were relatively insensitive to the variation of the reactant structures. The results have been attributed to the poor anion solvating ability of MeCN, which favors E2 transition state with maximum charge dispersal. For eliminations from strongly activated (E)-2,4-(NO 2 ) 2 C 6 H 3 CH=NOC(O)C 6 H 4 X, a change in the reaction mechanism from E2 to (E1cb) irr was observed as the base-solvent was changed from R 2 NH in MeCN to R 2 NH/R 2 NH 2 + in 70 mol % MeCN(aq). A combination of a strong electron-withdrawing β-aryl group and anion-solvating protic solvent was required for the mechanistic change

  4. Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

    Science.gov (United States)

    Hynes, A. J.; Wine, P. H.

    1997-01-01

    scheme to extract kinetic information about the adduct reations with O2 and branching ratios for OH regeneration. A plausible mechanism for OH regeneration in (2) involves OH addition to the nitrogen atom followed by O2 addition to the cyano carbon atom, isomeriazation and decomposition to D2CO + DOCN + OH. Our results suggest that the OH + CH3CN reaction occurs via a complex mechanism involving both bimolecular and termolecular pathways, analogous to the mechanisms for the the important atmospheric reactions of OH with CO and HNO3.

  5. Advances in quantum and molecular mechanical (QM/MM) simulations for organic and enzymatic reactions.

    Science.gov (United States)

    Acevedo, Orlando; Jorgensen, William L

    2010-01-19

    Application of combined quantum and molecular mechanical (QM/MM) methods focuses on predicting activation barriers and the structures of stationary points for organic and enzymatic reactions. Characterization of the factors that stabilize transition structures in solution and in enzyme active sites provides a basis for design and optimization of catalysts. Continued technological advances allowed for expansion from prototypical cases to mechanistic studies featuring detailed enzyme and condensed-phase environments with full integration of the QM calculations and configurational sampling. This required improved algorithms featuring fast QM methods, advances in computing changes in free energies including free-energy perturbation (FEP) calculations, and enhanced configurational sampling. In particular, the present Account highlights development of the PDDG/PM3 semi-empirical QM method, computation of multi-dimensional potentials of mean force (PMF), incorporation of on-the-fly QM in Monte Carlo (MC) simulations, and a polynomial quadrature method for efficient modeling of proton-transfer reactions. The utility of this QM/MM/MC/FEP methodology is illustrated for a variety of organic reactions including substitution, decarboxylation, elimination, and pericyclic reactions. A comparison to experimental kinetic results on medium effects has verified the accuracy of the QM/MM approach in the full range of solvents from hydrocarbons to water to ionic liquids. Corresponding results from ab initio and density functional theory (DFT) methods with continuum-based treatments of solvation reveal deficiencies, particularly for protic solvents. Also summarized in this Account are three specific QM/MM applications to biomolecular systems: (1) a recent study that clarified the mechanism for the reaction of 2-pyrone derivatives catalyzed by macrophomate synthase as a tandem Michael-aldol sequence rather than a Diels-Alder reaction, (2) elucidation of the mechanism of action of fatty

  6. Diversion of the melanin synthetic pathway by dopamine product scavengers: A quantum chemical modeling of the reaction mechanisms

    Directory of Open Access Journals (Sweden)

    T. B. Demissie

    2017-01-01

    Full Text Available We report the stability and reactivity of the oxidation products as well as L-cysteine and N-acetylcysteine adducts of dopamine studied using quantum chemical calculations. The overall reactions studied were subdivided into four reaction channels. The first reaction channel is the oxidation of dopamine to form dopaminoquinone. The second reaction channel leads to melanin formation through subsequent reactions. The third and fourth reaction channels are reactions leading to the formation of dopaminoquinone adducts which are aimed to divert the synthesis of melanin. The results indicate that L-cysteine and N-acetylcysteine undergo chemical reactions mainly at C5 position of dopaminoquinone. The analyses of the thermodynamic energies indicate that L-cysteine and N-acetylcysteine covalently bind to dopaminoquinone by competing with the internal cyclization reaction of dopaminoquinone which leads to the synthesis of melanin. The analysis of the results, based on the reaction free energies, is also supported by the investigation of the natural bond orbitals of the reactants and products.

  7. Theoretical Research on the Mechanism of the Dimerization Reactions of Alkyl Ketene

    Directory of Open Access Journals (Sweden)

    Zhiguo Zhang

    2013-01-01

    Full Text Available A quantum chemical method was employed to investigate the mechanism of dimerization reactions of alkyl ketene. All the geometric configurations of the stationary points on the reactions path were optimized with Gaussian03 employing density functional theory at the B3LYP/6-311G++(d, p level by energy gradient technique. The transition states were also investigated through synchronous transit method, and its reasonability was confirmed by using frequency analysis and intrinsic reaction coordinate analysis. The results can be summed up as follows: according to the frontier orbital theory, the dimerization reaction (3 to generate four-membered carbon cyclic product P3 is forbidden. Two different dimerization processes of alkyl ketene are all concerted but nonsynchronous, taking place through twisted four-membered cyclic transition states. The activation energies were calculated to be 34.54 and 61.73 kJ/mol, respectively for the two ketene dimerization processes. Calculation results satisfactorily explained the experimental facts.

  8. Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

    Science.gov (United States)

    Ahlborg, Nadia L.; Zhu, Dongming

    2013-01-01

    The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

  9. Characteristics and mechanism of explosive reactions of Purex solvents with Nitric Acid at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Miyata, Teijiro [Radiation Application Development Association, Tokai, Ibaraki (Japan); Takada, Junichi; Koike, Tadao; Tsukamoto, Michio; Watanabe, Koji [Department of Fuel Cycle Safety Research, Nuclear Safety Research Center, Tokai Research Establishment, Japan Atomic Energy Research Institute, Tokai, Ibaraki (Japan); Ida, Masaaki [JGC PLANTECH CO., LTD (Japan); Nakagiri, Naotaka [JGC Corp., Tokyo (Japan); Nishio, Gunji [Research Organization for Information Science and Technology, Tokai, Ibaraki (Japan)

    2000-03-01

    This investigation was undertaken to make clear the energetic properties and mechanism of explosive decomposition of Purex solvent systems (TBP/n-Dodecane/HNO{sub 3}) by Nitric Acid at elevated temperatures using a calorimetric technique (DSC, ARC) and a chromatographic technique (GC, GC/MS). The measurement of exothermic events of solvent-HNO{sub 3} reactions using DSC with a stainless steel sealed cell showed distinct two peaks with maxima at around 170 and 320degC, respectively. The peak at around 170degC was mainly attributed to the reactions of dealkylation products (n-butyl nitrate) of TBP and the solvent with nitric acid, and the peak at around 320degC was attributed to the exothermic decomposition of nitrated dodecanes formed in the foregoing exothermic reaction of dodecane with nitric acid. By using the data obtained in ARC experiments, activation energies of 123.2 and 152.5 kJ/mol were determined for the exothermic reaction of TBP with nitric acid and for the exothermic pyrolysis of n-butyl nitrate, respectively. Some possible pathways were considered for the explosive decomposition of TBP by nitric acid at elevated temperatures. (author)

  10. Memorable Experiences with Sad Music—Reasons, Reactions and Mechanisms of Three Types of Experiences

    Science.gov (United States)

    Peltola, Henna-Riikka

    2016-01-01

    Reactions to memorable experiences of sad music were studied by means of a survey administered to a convenience (N = 1577), representative (N = 445), and quota sample (N = 414). The survey explored the reasons, mechanisms, and emotions of such experiences. Memorable experiences linked with sad music typically occurred in relation to extremely familiar music, caused intense and pleasurable experiences, which were accompanied by physiological reactions and positive mood changes in about a third of the participants. A consistent structure of reasons and emotions for these experiences was identified through exploratory and confirmatory factor analyses across the samples. Three types of sadness experiences were established, one that was genuinely negative (Grief-Stricken Sorrow) and two that were positive (Comforting Sorrow and Sweet Sorrow). Each type of emotion exhibited certain individual differences and had distinct profiles in terms of the underlying reasons, mechanisms, and elicited reactions. The prevalence of these broad types of emotional experiences suggested that positive experiences are the most frequent, but negative experiences were not uncommon in any of the samples. The findings have implications for measuring emotions induced by music and fiction in general, and call attention to the non-pleasurable aspects of these experiences. PMID:27300268

  11. Mechanisms leading to increased risk of preterm birth in growth-restricted guinea pig pregnancies.

    Science.gov (United States)

    Palliser, Hannah K; Kelleher, Meredith A; Welsh, Toni N; Zakar, Tamas; Hirst, Jonathan J

    2014-02-01

    Intrauterine growth restriction (IUGR) is a risk factor for preterm labor; however, the mechanisms of the relationship remain unknown. Prostaglandin (PG), key stimulants of labor, availability is regulated by the synthetic enzymes, prostaglandin endoperoxidases 1 and 2 (PTGS1 and 2), and the metabolizing enzyme, 15-hydroxyprostaglandin dehydrogenase (HPGD). We hypothesized that IUGR increases susceptibility to preterm labor due to the changing balance of synthetic and metabolizing enzymes and hence greater PG availability. We have tested this hypothesis using a surgically induced IUGR model in guinea pigs, which results in significantly shorter gestation. Myometrium, amnion, chorion, and placentas were collected from sham operated or IUGR pregnancies, and PTGS1 and HPGD protein expression were quantified throughout late gestation (>62 days) and labor. The PTGS1 expression was significantly upregulated in the myometrium of IUGR animals, and chorionic HPGD expression was markedly decreased (P production over metabolism in IUGR pregnancies leads to a greater susceptibility to preterm birth.

  12. An introduction to the mechanisms leading to density-wave instabilities in BWRs

    International Nuclear Information System (INIS)

    March-Leuba, Jose

    2004-01-01

    This paper presents a review of the physical mechanisms that lead to density-wave instabilities in boiling water reactors (BWRs). The goal of this paper is not to present new information; but ideas that are generally known and accepted in the field of BWR stability. The number of people working in the field of BWR stability has grown over the past years to a significant number; nevertheless, the field is still small enough so that personal communication is an effective way of conveying information. The unfortunate consequence is that this field has a large component of ''art'' as opposed to science.'' This paper attempts to summarize these basic ideas for the reader. (author)

  13. Reaction mechanism for the symmetric breakup of 24Mg following an interaction with 12C

    International Nuclear Information System (INIS)

    Gyapong, G.J.; Watson, D.L.; Catford, W.N.; Clarke, N.M.; Bennett, S.J.; Freer, M.; Fulton, B.R.; Jones, C.D.; Leddy, M.; Murgatroyd, J.T.; Rae, W.D.M.; Simmons, P.

    1994-01-01

    Data on the yield of the symmetric breakup of 24 Mg as a function of beam energy are presented and compared with detailed calculations of the energy dependence. The 24 Mg states seen in symmetric breakup agree with previously observed breakup states having spin and parities J π =4 + ,(6 + ),8 + . The data allow the variations of yield for indivual states to be judged, as the beam energy is varied. The variation in the yield of the 4 + states is compared in detail with calculations assuming several possible compound nuclear or direct reaction mechanisms. It is concluded that a massive ( 12 C) transfer or a simple statistical compound process are unlikely mechanisms, but that each of several other mechanisms is consistent with the data. ((orig.))

  14. Reaction Mechanisms and HCCI Combustion Processes of Mixtures of n-Heptane and the Butanols

    Directory of Open Access Journals (Sweden)

    Hu eWang

    2015-03-01

    Full Text Available A reduced primary reference fuel (PRF-Alcohol-Di-tert-butyl Peroxide (DTBP mechanism with 108 species and 435 reactions, including sub-mechanisms of PRF, methanol, ethanol, DTBP and the four butanol isomers, is proposed for homogeneous charge compression ignition (HCCI engine combustion simulations of butanol isomers/n-heptane mixtures. HCCI experiments fuelled with butanol isomer/n-heptane mixtures on two different engines are conducted for the validation of proposed mechanism. The mechanism has been validated against shock tube ignition delays, laminar flame speeds, species profiles in premixed flames and engine HCCI combustion data, and good agreements with experimental results are demonstrated under various validation conditions. It is found that although the reactivity of neat tert-butanol is the lowest, mixtures of tert-butanol/n-heptane exhibit the highest reactivity among the butanol isomer/n-heptane mixtures if the n-heptane blending ratio exceeds 20% (mole. Kinetic analysis shows that the highest C-H bond energy in the tert-butanol molecule is partially responsible for this phenomenon. It is also found that the reaction tC4H9OH+CH3O2 =tC4H9O+CH3O2H plays important role and eventually produces the OH radical to promote the ignition and combustion. The proposed mechanism is able to capture HCCI combustion processes of the butanol/n-heptane mixtures under different operating conditions. In addition, the trend that tert-butanol /n-heptane has the highest reactivity is also captured in HCCI combustion simulations. The results indicate that the current mechanism can be used for HCCI engine predictions of PRF and alcohol fuels.

  15. Comparison of the key mechanisms leading to rollovers in Liquefied Natural Gas using Computational Fluid Dynamics

    Science.gov (United States)

    Hubert, Antoine; Dadonau, Maksim; Dembele, Siaka; Denissenko, Petr; Wen, Jennifer

    2017-11-01

    Growing demand for the LNG fosters growth of the number of production sites with varying composition and density. Combining different sources of LNG may result in a stably stratified system, in which heat and mass transfer between the layers is limited. Heating of the LNG due to wall thermal conductivity leads to formation of convection cells confined within the layers. While the upper layer can release the extra energy via preferential methane boil-off, the bottom layer cannot and hence becomes superheated. Gradual density equilibration reduces stratification and may eventually lead to a sudden mixing event called ``rollover'', accompanied by violent evaporation of the superheated LNG. Three phenomena are potentially responsible for density equilibration. The first is the growing difference in thermal expansion of the layers due to the reduced ability of the bottom layer to reject heat. The second is the penetration of the heated near-wall boundary layer into the upper layer. The third is the ``entrainment mixing'' occurring at the contact surface between the two layers. The present study uses CFD to compare these mechanisms. Boussinesq approximation and an extended version of the k- ɛ model is used. The code is validated by comparison with a large-scale LNG rollover experiment.

  16. Space Shuttle Orbiter Wing-Leading-Edge Panel Thermo-Mechanical Analysis for Entry Conditions

    Science.gov (United States)

    Knight, Norman F., Jr.; Song, Kyongchan; Raju, Ivatury S.

    2010-01-01

    Linear elastic, thermo-mechanical stress analyses of the Space Shuttle Orbiter wing-leading-edge panels is presented for entry heating conditions. The wing-leading-edge panels are made from reinforced carbon-carbon and serve as a part of the overall thermal protection system. Three-dimensional finite element models are described for three configurations: integrated configuration, an independent single-panel configuration, and a local lower-apex joggle segment. Entry temperature conditions are imposed and the through-the-thickness response is examined. From the integrated model, it was concluded that individual panels can be analyzed independently since minimal interaction between adjacent components occurred. From the independent single-panel model, it was concluded that increased through-the-thickness stress levels developed all along the chord of a panel s slip-side joggle region, and hence isolated local joggle sections will exhibit the same trend. From the local joggle models, it was concluded that two-dimensional plane-strain models can be used to study the influence of subsurface defects along the slip-side joggle region of these panels.

  17. Fracture Mechanics Analyses of the Slip-Side Joggle Regions of Wing-Leading Edge Panels

    Science.gov (United States)

    Raju, Ivatury S.; Knight, Norman F., Jr.; Song, Kyongchan; Phillips, Dawn R.

    2010-01-01

    The Space Shuttle Orbiter wing comprises of 22 leading edge panels on each side of the wing. These panels are part of the thermal protection system that protects the Orbiter wings from extreme heating that take place on the reentry in to the earth atmosphere. On some panels that experience extreme heating, liberation of silicon carbon (SiC) coating was observed on the slip side regions of the panels. Global structural and local fracture mechanics analyses were performed on these panels as a part of the root cause investigation of this coating liberation anomaly. The wing-leading-edge reinforced carbon-carbon (RCC) panels, Panel 9, T-seal 10, and Panel 10, are shown in Figure 1 and the progression of the stress analysis models is presented in Figure 2. The global structural analyses showed minimal interaction between adjacent panels and the T-seal that bridges the gap between the panels. A bounding uniform temperature is applied to a representative panel and the resulting stress distribution is examined. For this loading condition, the interlaminar normal stresses showed negligible variation in the chord direction and increased values in the vicinity of the slip-side joggle shoulder. As such, a representative span wise slice on the panel can be taken and the cross section can be analyzed using plane strain analysis.

  18. Dual strain mechanisms in a lead-free morphotropic phase boundary ferroelectric

    DEFF Research Database (Denmark)

    Walker, Julian; Simons, Hugh; Alikin, Denis O

    2016-01-01

    Electromechanical properties such as d33 and strain are significantly enhanced at morphotropic phase boundaries (MPBs) between two or more different crystal structures. Many actuators, sensors and MEMS devices are therefore systems with MPBs, usually between polar phases in lead (Pb)-based ferroe......Electromechanical properties such as d33 and strain are significantly enhanced at morphotropic phase boundaries (MPBs) between two or more different crystal structures. Many actuators, sensors and MEMS devices are therefore systems with MPBs, usually between polar phases in lead (Pb......)-based ferroelectric ceramics. In the search for Pb-free alternatives, systems with MPBs between polar and non-polar phases have recently been theorized as having great promise. While such an MPB was identified in rare-earth (RE) modified bismuth ferrite (BFO) thin films, synthesis challenges have prevented its...... realization in ceramics. Overcoming these, we demonstrate a comparable electromechanical response to Pb-based materials at the polar-to-non-polar MPB in Sm modified BFO. This arises from 'dual' strain mechanisms: ferroelectric/ferroelastic switching and a previously unreported electric-field induced...

  19. Multi-level quantum mechanics theories and molecular mechanics study of the double-inversion mechanism of the F- + CH3I reaction in aqueous solution.

    Science.gov (United States)

    Liu, Peng; Zhang, Jingxue; Wang, Dunyou

    2017-06-07

    A double-inversion mechanism of the F - + CH 3 I reaction was discovered in aqueous solution using combined multi-level quantum mechanics theories and molecular mechanics. The stationary points along the reaction path show very different structures to the ones in the gas phase due to the interactions between the solvent and solute, especially strong hydrogen bonds. An intermediate complex, a minimum on the potential of mean force, was found to serve as a connecting-link between the abstraction-induced inversion transition state and the Walden-inversion transition state. The potentials of mean force were calculated with both the DFT/MM and CCSD(T)/MM levels of theory. Our calculated free energy barrier of the abstraction-induced inversion is 69.5 kcal mol -1 at the CCSD(T)/MM level of theory, which agrees with the one at 72.9 kcal mol -1 calculated using the Born solvation model and gas-phase data; and our calculated free energy barrier of the Walden inversion is 24.2 kcal mol -1 , which agrees very well with the experimental value at 25.2 kcal mol -1 in aqueous solution. The calculations show that the aqueous solution makes significant contributions to the potentials of mean force and exerts a big impact on the molecular-level evolution along the reaction pathway.

  20. Genetic mechanisms leading to primary amenorrhea in balanced X-autosome translocations.

    Science.gov (United States)

    Moysés-Oliveira, Mariana; Guilherme, Roberta Dos Santos; Dantas, Anelisa Gollo; Ueta, Renata; Perez, Ana Beatriz; Haidar, Mauro; Canonaco, Rosane; Meloni, Vera Ayres; Kosyakova, Nadezda; Liehr, Thomas; Carvalheira, Gianna Maria; Melaragno, Maria Isabel

    2015-05-01

    To map the X-chromosome and autosome breakpoints in women with balanced X-autosome translocations and primary amenorrhea, searching candidate genomic loci for female infertility. Retrospective and case-control study. University-based research laboratory. Three women with balanced X-autosome translocation and primary amenorrhea. Conventional cytogenetic methods, genomic array, array painting, fluorescence in situ hybridization, and quantitative reverse transcription-polymerase chain reaction. Karyotype, copy number variation, breakpoint mapping, and gene expression levels. All patients presented with breakpoints in the Xq13q21 region. In two patients, the X-chromosome breakpoint disrupted coding sequences (KIAA2022 and ZDHHC15 genes). Although both gene disruptions caused absence of transcription in peripheral blood, there is no evidence that supports the involvement of these genes with ovarian function. The ZDHHC15 gene belongs to a conserved syntenic region that encompasses the FGF16 gene, which plays a role in female germ line development. The break in the FGF16 syntenic block may have disrupted the interaction between the FGF16 promoter and its cis-regulatory element. In the third patient, although both breakpoints are intergenic, a gene that plays a role in the DAX1 pathway (FHL2 gene) flanks distally the autosome breakpoint. The FHL2 gene may be subject to position effect due to the attachment of an autosome segment in Xq21 region. The etiology of primary amenorrhea in balanced X-autosome translocation patients may underlie more complex mechanisms than interruption of specific X-linked candidate genes, such as position effect. The fine mapping of the rearrangement breakpoints may be a tool for identifying genetic pathogenic mechanisms for primary amenorrhea. Copyright © 2015 American Society for Reproductive Medicine. Published by Elsevier Inc. All rights reserved.

  1. 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

  2. Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xifeng; Cai, Zhongli; Katsumura, Yosuke [Tokyo Univ., Tokai, Ibaraki (Japan). Nuclear Engineering Research Lab

    2000-03-01

    The interaction of caffeic acid with e{sub aq}{sup -}, (CH{sub 3}){sub 2}(OH) CCH{sub 2}{sup {center_dot}}, CO{sub 2}{sup {center_dot}}{sup -}, H{sup {center_dot}}, {center_dot}OH and N{sub 3}{sup {center_dot}} radicals were studied by {gamma}-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/{center_dot}OH adducts, semi-quinone radicals of caffeic ions, and the stable products from the reactions were derived. The rate constants were determined. The attacked sites and the most favorable structures of the transient radicals were predicted. Reaction mechanisms were proposed. (author)

  3. Reaction Mechanism of Tar Evolution in Biomass Steam Gasification for Hydrogen Production

    International Nuclear Information System (INIS)

    Shingo Katayama; Masahiro Suzuki; Atsushi Tsutsumi

    2006-01-01

    Reaction mechanism of tar evolution in steam gasification of biomass was investigated with a continuous cross-flow moving bed type differential reactor, in which tar and gases can be fractionated according to reaction time. We estimated that time profile of tar and gas evolution in the gasification of cellulose, xylan, and lignin, and compared it with experimental product time profile of real biomass gasification. The experimental tar evolution rate is different from estimated tar evolution rate. The estimated tar evolution rate has a peak at 20 s. On the other hand, the experimental tar evolution rate at 20 s is little, and tar at initial stage includes more water-soluble and water-insoluble compounds. It can be concluded that in the real biomass steam gasification the evolution of tar from cellulose and lignin component was found to be precipitated by that from hemi-cellulose component. (authors)

  4. Heterogeneous kinetics, products, and mechanisms of ferulic acid particles in the reaction with NO3 radicals

    Science.gov (United States)

    Liu, Changgeng; Zhang, Peng; Wen, Xiaoying; Wu, Bin

    2017-03-01

    Methoxyphenols, as an important component of wood burning, are produced by lignin pyrolysis and considered to be the potential tracers for wood smoke emissions. In this work, the heterogeneous reaction between ferulic acid particles and NO3 radicals was investigated. Six products including oxalic acid, 4-vinylguaiacol, vanillin, 5-nitrovanillin, 5-nitroferulic acid, and caffeic acid were confirmed by gas chromatography-mass spectrometry (GC-MS). In addition, the reaction mechanisms were proposed and the main pathways were NO3 electrophilic addition to olefin and the meta-position to the hydroxyl group. The uptake coefficient of NO3 radicals on ferulic acid particles was 0.17 ± 0.02 and the effective rate constant under experimental conditions was (1.71 ± 0.08) × 10-12 cm3 molecule-1 s-1. The results indicate that ferulic acid degradation by NO3 can be an important sink at night.

  5. Anaerobic reductive dechlorination of tetrachloroethene: how can dual Carbon-Chlorine isotopic measurements help elucidating the underlying reaction mechanism?

    Science.gov (United States)

    Badin, Alice; Buttet, Géraldine; Maillard, Julien; Holliger, Christof; Hunkeler, Daniel

    2014-05-01

    Chlorinated ethenes (CEs) such as tetrachloroethene (PCE) are common persistent groundwater contaminants. Among clean-up strategies applied to sites affected by such pollution, bioremediation has been considered with a growing interest as it represents a cost-effective, environmental friendly approach. This technique however sometimes leads to an incomplete and slow biodegradation of CEs resulting in an accumulation of toxic metabolites. Understanding the reaction mechanisms underlying anaerobic reductive dechlorination would thus help assessing PCE biodegradation in polluted sites. Stable isotope analysis can provide insight into reaction mechanisms. For chlorinated hydrocarbons, carbon (C) and chlorine (Cl) isotope data (δ13C and δ37Cl) tend to show a linear correlation with a slope (m ≡ ɛC/ɛCl) characteristic of the reaction mechanism [1]. This study hence aims at exploring the potential of a dual C-Cl isotope approach in the determination of the reaction mechanisms involved in PCE reductive dechlorination. C and Cl isotope fractionation were investigated during anaerobic PCE dechlorination by two bacterial consortia containing members of the Sulfurospirillum genus. The specificity in these consortia resides in the fact that they each conduct PCE reductive dechlorination catalysed by one different reductive dehalogenase, i.e. PceADCE which yields trichloroethene (TCE) and cis-dichloroethene (cDCE), and PceATCE which yields TCE only. The bulk C isotope enrichment factors were -3.6±0.3 o for PceATCE and -0.7±0.1o for PceADCE. The bulk Cl isotope enrichment factors were -1.3±0.2 o for PceATCE and -0.9±0.1 o for PceADCE. When applying the dual isotope approach, two m values of 2.7±0.1 and 0.7±0.2 were obtained for the reductive dehalogenases PceATCE and PceADCE, respectively. These results suggest that PCE can be degraded according to two different mechanisms. Furthermore, despite their highly similar protein sequences, each reductive dehalogenase seems

  6. Plant polyphenols mobilize nuclear copper in human peripheral lymphocytes leading to oxidatively generated DNA breakage: implications for an anticancer mechanism.

    Science.gov (United States)

    Shamim, Uzma; Hanif, Sarmad; Ullah, M F; Azmi, Asfar S; Bhat, Showket H; Hadi, S M

    2008-08-01

    It was earlier proposed that an important anti-cancer mechanism of plant polyphenols may involve mobilization of endogenous copper ions, possibly chromatin-bound copper and the consequent pro-oxidant action. This paper shows that plant polyphenols are able to mobilize nuclear copper in human lymphocytes, leading to degradation of cellular DNA. A cellular system of lymphocytes isolated from human peripheral blood and comet assay was used for this purpose. Incubation of lymphocytes with neocuproine (a cell membrane permeable copper chelator) inhibited DNA degradation in intact lymphocytes. Bathocuproine, which is unable to permeate through the cell membrane, did not cause such inhibition. This study has further shown that polyphenols are able to degrade DNA in cell nuclei and that such DNA degradation is inhibited by neocuproine as well as bathocuproine (both of which are able to permeate the nuclear pore complex), suggesting that nuclear copper is mobilized in this reaction. Pre-incubation of lymphocyte nuclei with polyphenols indicates that it is capable of traversing the nuclear membrane. This study has also shown that polyphenols generate oxidative stress in lymphocyte nuclei which is inhibited by scavengers of reactive oxygen species (ROS) and neocuproine. These results indicate that the generation of ROS occurs through mobilization of nuclear copper resulting in oxidatively generated DNA breakage.

  7. A general reaction mechanism for carbapenem hydrolysis by mononuclear and binuclear metallo-β-lactamases.

    Science.gov (United States)

    Lisa, María-Natalia; Palacios, Antonela R; Aitha, Mahesh; González, Mariano M; Moreno, Diego M; Crowder, Michael W; Bonomo, Robert A; Spencer, James; Tierney, David L; Llarrull, Leticia I; Vila, Alejandro J

    2017-09-14

    Carbapenem-resistant Enterobacteriaceae threaten human health, since carbapenems are last resort drugs for infections by such organisms. Metallo-β-lactamases (MβLs) are the main mechanism of resistance against carbapenems. Clinically approved inhibitors of MBLs are currently unavailable as design has been limited by the incomplete knowledge of their mechanism. Here, we report a biochemical and biophysical study of carbapenem hydrolysis by the B1 enzymes NDM-1 and BcII in the bi-Zn(II) form, the mono-Zn(II) B2 Sfh-I and the mono-Zn(II) B3 GOB-18. These MβLs hydrolyse carbapenems via a similar mechanism, with accumulation of the same anionic intermediates. We characterize the Michaelis complex formed by mono-Zn(II) enzymes, and we identify all intermediate species, enabling us to propose a chemical mechanism for mono and binuclear MβLs. This common mechanism open avenues for rationally designed inhibitors of all MβLs, notwithstanding the profound differences between these enzymes' active site structure, β-lactam specificity and metal content.Carbapenem-resistant bacteria pose a major health threat by expressing metallo-β-lactamases (MβLs), enzymes able to hydrolyse these life-saving drugs. Here the authors use biophysical and computational methods and show that different MβLs share the same reaction mechanism, suggesting new strategies for drug design.

  8. From Sound to Significance: Exploring the Mechanisms Underlying Emotional Reactions to Music.

    Science.gov (United States)

    Juslin, Patrik N; Barradas, Gonçalo; Eerola, Tuomas

    2015-01-01

    A common approach to studying emotional reactions to music is to attempt to obtain direct links between musical surface features such as tempo and a listener's responses. However, such an analysis ultimately fails to explain why emotions are aroused in the listener. In this article we explore an alternative approach, which aims to account for musical emotions in terms of a set of psychological mechanisms that are activated by different types of information in a musical event. This approach was tested in 4 experiments that manipulated 4 mechanisms (brain stem reflex, contagion, episodic memory, musical expectancy) by selecting existing musical pieces that featured information relevant for each mechanism. The excerpts were played to 60 listeners, who were asked to rate their felt emotions on 15 scales. Skin conductance levels and facial expressions were measured, and listeners reported subjective impressions of relevance to specific mechanisms. Results indicated that the target mechanism conditions evoked emotions largely as predicted by a multimechanism framework and that mostly similar effects occurred across the experiments that included different pieces of music. We conclude that a satisfactory account of musical emotions requires consideration of how musical features and responses are mediated by a range of underlying mechanisms.

  9. A first principles study of the mechanical, electronic, and vibrational properties of lead oxide

    Science.gov (United States)

    Zhuravlev, Yu. N.; Korabel'nikov, D. V.

    2017-11-01

    The first principles study of the crystal structure, chemical bonds, elastic and mechanical properties, electron energy band structure and density, and normal long-wave vibrations of nine phases of lead monoxide, dioxide, and tetraoxide has been performed under normal and external pressure within the framework of density functional theory (DFT) with the Perdew-Becke-Ernzerhof (PBE) gradient exchange-correlation functional and its hybrid version with a 25-% Hartree-Fock (HF) exchange contribution in the basis of localized atom orbitals. The behavior of physical parameters has been studied using the cold four- and threeparameter equations of state. The parameters of the crystal structures are in satisfactory agreement with experimental data, and elastic constants indicate their mechanical stability and anisotropy in the elastic properties. The elasticity, shear, and Young moduli, hardness, acoustic velocities, and Debye temperature of dioxide on the one hand and monoxide and tetraoxide on the other hand appreciably differ from each other. The difference between electron properties may be explained by the character of hybridization in the upper filled and lower empty energy bands as evident from the density of states. In monoxide, the indirect band gap width decreases with increasing pressure at a rate of 0.16 eV/GPa, and the direct band gap width increases at a rate of 0.13 eV/GPa. To identify crystalline phases, the frequencies and intensities of long-wave modes active in IR and Raman spectra have been calculated.

  10. Presynaptic mechanisms of lead neurotoxicity: effects on vesicular release, vesicle clustering and mitochondria number.

    Science.gov (United States)

    Zhang, Xiao-Lei; Guariglia, Sara R; McGlothan, Jennifer L; Stansfield, Kirstie H; Stanton, Patric K; Guilarte, Tomás R

    2015-01-01

    Childhood lead (Pb2+) intoxication is a global public health problem and accounts for 0.6% of the global burden of disease associated with intellectual disabilities. Despite the recognition that childhood Pb2+ intoxication contributes significantly to intellectual disabilities, there is a fundamental lack of knowledge on presynaptic mechanisms by which Pb2+ disrupts synaptic function. In this study, using a well-characterized rodent model of developmental Pb2+ neurotoxicity, we show that Pb2+ exposure markedly inhibits presynaptic vesicular release in hippocampal Schaffer collateral-CA1 synapses in young adult rats. This effect was associated with ultrastructural changes which revealed a reduction in vesicle number in the readily releasable/docked vesicle pool, disperse vesicle clusters in the resting pool, and a reduced number of presynaptic terminals with multiple mitochondria with no change in presynaptic calcium influx. These studies provide fundamental knowledge on mechanisms by which Pb2+ produces profound inhibition of presynaptic vesicular release that contribute to deficits in synaptic plasticity and intellectual development.

  11. Mechanism of inhibition of human secretory phospholipase A2 by flavonoids: rationale for lead design

    Science.gov (United States)

    Lättig, Jens; Böhl, Markus; Fischer, Petra; Tischer, Sandra; Tietböhl, Claudia; Menschikowski, Mario; Gutzeit, Herwig O.; Metz, Peter; Pisabarro, M. Teresa

    2007-08-01

    The human secretory phospholipase A2 group IIA (PLA2-IIA) is a lipolytic enzyme. Its inhibition leads to a decrease in eicosanoids levels and, thereby, to reduced inflammation. Therefore, PLA2-IIA is of high pharmacological interest in treatment of chronic diseases such as asthma and rheumatoid arthritis. Quercetin and naringenin, amongst other flavonoids, are known for their anti-inflammatory activity by modulation of enzymes of the arachidonic acid cascade. However, the mechanism by which flavonoids inhibit Phospholipase A2 (PLA2) remained unclear so far. Flavonoids are widely produced in plant tissues and, thereby, suitable targets for pharmaceutical extractions and chemical syntheses. Our work focuses on understanding the binding modes of flavonoids to PLA2, their inhibition mechanism and the rationale to modify them to obtain potent and specific inhibitors. Our computational and experimental studies focused on a set of 24 compounds including natural flavonoids and naringenin-based derivatives. Experimental results on PLA2-inhibition showed good inhibitory activity for quercetin, kaempferol, and galangin, but relatively poor for naringenin. Several naringenin derivatives were synthesized and tested for affinity and inhibitory activity improvement. 6-(1,1-dimethylallyl)naringenin revealed comparable PLA2 inhibition to quercetin-like compounds. We characterized the binding mode of these compounds and the determinants for their affinity, selectivity, and inhibitory potency. Based on our results, we suggest C(6) as the most promising position of the flavonoid scaffold to introduce chemical modifications to improve affinity, selectivity, and inhibition of PLA2-IIA by flavonoids.

  12. Mechanisms of emission of particles charged in 6Li + 6Li and 6Li + 10B reactions at low energies

    International Nuclear Information System (INIS)

    Quebert, Jean

    1964-01-01

    The lithium 6 nucleus is a projectile of interest to study nuclear reactions at low energy due to the possibility to obtain high heats of reaction, and to its structure which can play an important role in the projectile-target interaction. This research thesis focused on the study of two low-energy reactions provoked by lithium projectiles. These reactions are studied within the framework of the theoretical model of aggregates. The first part presents the experimental conditions of both reactions, reports the development and analysis of nuclear plates, and the transformation of a given type of particle histogram into a spectrum in the mass centre system. The next parts report the study of the 6 Li + 6 Li reaction (previous results, kinematic analysis, spectrum of secondary particles, theoretical analysis of results) and of the 6 Li + 10 B reaction (previous results, experimental results, study of the continuous spectrum of alpha particle, reaction mechanisms)

  13. Exchange reaction between hydrogen and deuterium. I. Importance of surface reactions in the steady-state mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Marteau, C; Gaillard-Cusin, F; James, H [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

    1978-05-01

    Investigation of heterogeneous initiation process of gas phase linear chain reactions is carried out through the study of H/sub 2/-D/sub 2/ exchange reaction. Experimental data under study concern mainly the stationary rate of HD formation and the prestationary proceeding. Steady-state method accounts for the first one of these data; it allows to clearly compare the wall process part to the part played by the homogeneous chain reaction towards HD formation. Activation energy of exchange elementary step between chemisorbed hydrogen (on silica) and gaseous deuterium has been evaluated: Esub(e1)=52+-1 Kcal/mole.

  14. Kinetics modeling and reaction mechanism of ferrate(VI) oxidation of benzotriazoles.

    Science.gov (United States)

    Yang, Bin; Ying, Guang-Guo; Zhang, Li-Juan; Zhou, Li-Jun; Liu, Shan; Fang, Yi-Xiang

    2011-03-01

    Benzotriazoles (BTs) are high production volume chemicals with broad application in various industrial processes and in households, and have been found to be omnipresent in aquatic environments. We investigated oxidation of five benzotriazoles (BT: 1H-benzotriazole; 5MBT: 5-methyl-1H-benzotriazole; DMBT: 5,6-dimethyl-1H-benzotriazole hydrate; 5CBT: 5-chloro-1H-benzotriazole; HBT: 1-hydroxybenzotriazole) by aqueous ferrate (Fe(VI)) to determine reaction kinetics as a function of pH (6.0-10.0), and interpreted the reaction mechanism of Fe(VI) with BTs by using a linear free-energy relationship. The pK(a) values of BT and DMBT were also determined using UV-Visible spectroscopic method in order to calculate the species-specific rate constants, and they were 8.37 ± 0.0 and 8.98 ± 0.08 respectively. Each of BTs reacted moderately with Fe(VI) with the k(app) ranged from 7.2 to 103.8 M(-1)s(-1) at pH 7.0 and 24 ± 1 °C. When the molar ratio of Fe(VI) and BTs increased up to 30:1, the removal rate of BTs reached about >95% in buffered milli-Q water or secondary wastewater effluent. The electrophilic oxidation mechanism of the above reaction was illustrated by using a linear free-energy relationship between pH-dependence of species-specific rate constants and substituent effects (σ(p)). Fe(VI) reacts initially with BTs by electrophilic attack at the 1,2,3-triazole moiety of BT, 5MBT, DMBT and 5CBT, and at the N-OH bond of HBT. Moreover, for BT, 5MBT, DMBT and 5CBT, the reactions with the species HFeO(4)(-) predominantly controled the reaction rates. For HBT, the species H(2)FeO(4) with dissociated HBT played a major role in the reaction. The results showed that Fe(VI) has the ability to degrade benzotriazoles in water. Copyright © 2011 Elsevier Ltd. All rights reserved.

  15. Studying mechanism of radical reactions: From radiation to nitroxides as research tools

    Science.gov (United States)

    Maimon, Eric; Samuni, Uri; Goldstein, Sara

    2018-02-01

    Radicals are part of the chemistry of life, and ionizing radiation chemistry serves as an indispensable research tool for elucidation of the mechanism(s) underlying their reactions. The ever-increasing understanding of their involvement in diverse physiological and pathological processes has expanded the search for compounds that can diminish radical-induced damage. This review surveys the areas of research focusing on radical reactions and particularly with stable cyclic nitroxide radicals, which demonstrate unique antioxidative activities. Unlike common antioxidants that are progressively depleted under oxidative stress and yield secondary radicals, nitroxides are efficient radical scavengers yielding in most cases their respective oxoammonium cations, which are readily reduced back in the tissue to the nitroxide thus continuously being recycled. Nitroxides, which not only protect enzymes, cells, and laboratory animals from diverse kinds of biological injury, but also modify the catalytic activity of heme enzymes, could be utilized in chemical and biological systems serving as a research tool for elucidating mechanisms underlying complex chemical and biochemical processes.

  16. Asymmetric effect of mechanical stress on the forward and reverse reaction catalyzed by an enzyme.

    Directory of Open Access Journals (Sweden)

    Collin Joseph

    Full Text Available The concept of modulating enzymatic activity by exerting a mechanical stress on the enzyme has been established in previous work. Mechanical perturbation is also a tool for probing conformational motion accompanying the enzymatic cycle. Here we report measurements of the forward and reverse kinetics of the enzyme Guanylate Kinase from yeast (Saccharomyces cerevisiae. The enzyme is held in a state of stress using the DNA spring method. The observation that mechanical stress has different effects on the forward and reverse reaction kinetics suggests that forward and reverse reactions follow different paths, on average, in the enzyme's conformational space. Comparing the kinetics of the stressed and unstressed enzyme we also show that the maximum speed of the enzyme is comparable to the predictions of the relaxation model of enzyme action, where we use the independently determined dissipation coefficient [Formula: see text] for the enzyme's conformational motion. The present experiments provide a mean to explore enzyme kinetics beyond the static energy landscape picture of transition state theory.

  17. Improved removal performance and mechanism investigation of papermaking wastewater treatment using manganese enhanced Fenton reaction.

    Science.gov (United States)

    Wang, Yingcai; Wang, Can; Shi, Shuai; Fang, Shuai

    2018-06-01

    The effects of Mn(II) on Fenton system to treat papermaking wastewater and the mechanism of Mn(II) enhanced Fenton reaction were investigated in this study. The chemical oxygen demand (COD) removal efficiency was enhanced in the presence of Mn(II), which increased by 19% compared with that of the Fenton system alone. The pseudo-first order reaction kinetic rate constant of Mn(II)/Fenton system was 2.11 times higher than that of Fenton system. 67%-81% COD were removed with the increasing Mn(II) concentration from 0 to 0.8 g/L. COD removal efficiency was also enhanced in a wider pH range (3-7), which indicated the operation parameters of Fenton technology could be broadened to a milder condition. The study of the mechanism showed that Mn(II) participated in the oxidation and coagulation stages in Fenton system. In the oxidation stage, Mn(II) promotes the production of HO 2 •/ O 2 • - , then HO 2 •/ O 2 • - reacts with Fe(III) to accelerate the formation of Fe(II), and finally accelerates the production of HO•. Meantime MnMnO 3 and Fe(OH) 3 forms in the coagulation stage, facilitating the removal of suspended substances and a large amount of COD, which enhances the overall COD removal of papermaking wastewater. This study provided a detailed mechanism to improve practical applications of Fenton technology.

  18. A Mechanism of Unidirectional Transformation, Leading to Antibiotic Resistance, Occurs within Nasopharyngeal Pneumococcal Biofilm Consortia.

    Science.gov (United States)

    Lattar, Santiago M; Wu, Xueqing; Brophy, Jennifer; Sakai, Fuminori; Klugman, Keith P; Vidal, Jorge E

    2018-05-15

    Streptococcus pneumoniae acquires genes for resistance to antibiotics such as streptomycin (Str) or trimethoprim (Tmp) by recombination via transformation of DNA released by other pneumococci and closely related species. Using naturally transformable pneumococci, including strain D39 serotype 2 (S2) and TIGR4 (S4), we studied whether pneumococcal nasopharyngeal transformation was symmetrical, asymmetrical, or unidirectional. Incubation of S2 Tet and S4 Str in a bioreactor simulating the human nasopharynx led to the generation of Spn Tet/Str recombinants. Double-resistant pneumococci emerged soon after 4 h postinoculation at a recombination frequency (rF) of 2.5 × 10 -4 while peaking after 8 h at a rF of 1.1 × 10 -3 Acquisition of antibiotic resistance genes by transformation was confirmed by treatment with DNase I. A high-throughput serotyping method demonstrated that all double-resistant pneumococci belonged to one serotype lineage (S2 Tet/Str ) and therefore that unidirectional transformation had occurred. Neither heterolysis nor availability of DNA for transformation was a factor for unidirectional transformation given that the density of each strain and extracellular DNA (eDNA) released from both strains were similar. Unidirectional transformation occurred regardless of the antibiotic-resistant gene carried by donors or acquired by recipients and regardless of whether competence-stimulating peptide-receptor cross talk was allowed. Moreover, unidirectional transformation occurred when two donor strains (e.g., S4 Str and S19F Tmp ) were incubated together, leading to S19F Str/Tmp but at a rF 3 orders of magnitude lower (4.9 × 10 -6 ). We finally demonstrated that the mechanism leading to unidirectional transformation was due to inhibition of transformation of the donor by the recipient. IMPORTANCE Pneumococcal transformation in the human nasopharynx may lead to the acquisition of antibiotic resistance genes or genes encoding new capsular variants

  19. Reaction mechanism of sterol hydroxylation by steroid C25 dehydrogenase - Homology model, reactivity and isoenzymatic diversity.

    Science.gov (United States)

    Rugor, Agnieszka; Wójcik-Augustyn, Anna; Niedzialkowska, Ewa; Mordalski, Stefan; Staroń, Jakub; Bojarski, Andrzej; Szaleniec, Maciej

    2017-08-01

    Steroid C25 dehydrogenase (S25DH) is a molybdenum-containing oxidoreductase isolated from the anaerobic Sterolibacterium denitrificans Chol-1S. S25DH is classified as 'EBDH-like' enzyme (EBDH, ethylbenzene dehydrogenase) and catalyzes the introduction of an OH group to the C25 atom of a sterol aliphatic side-chain. Due to its regioselectivity, S25DH is proposed as a catalyst in production of pharmaceuticals: calcifediol or 25-hydroxycholesterol. The aim of presented research was to obtain structural model of catalytic subunit α and investigate the reaction mechanism of the O 2 -independent tertiary carbon atom activation. Based on homology modeling and theoretical calculations, a S25DH α subunit model was for the first time characterized and compared to other S25DH-like isoforms. The molecular dynamics simulations of the enzyme-substrate complexes revealed two stable binding modes of a substrate, which are stabilized predominantly by van der Waals forces in the hydrophobic substrate channel. However, H-bond interactions involving polar residues with C3=O/C3-OH in the steroid ring appear to be responsible for positioning the substrate. These results may explain the experimental kinetic results which showed that 3-ketosterols are hydroxylated 5-10-fold faster than 3-hydroxysterols. The reaction mechanism was studied using QM:MM and QM-only cluster models. The postulated mechanism involves homolytic CH cleavage by the MoO ligand, giving rise to a radical intermediate with product obtained in an OH rebound process. The hypothesis was supported by kinetic isotopic effect (KIE) experiments involving 25,26,26,26-[ 2 H]-cholesterol (4.5) and the theoretically predicted intrinsic KIE (7.0-7.2). Finally, we have demonstrated that the recombinant S25DH-like isoform catalyzes the same reaction as S25DH. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Reaction mechanism of CO oxidation on Cu2O(111): A density functional study

    Science.gov (United States)

    Sun, Bao-Zhen; Chen, Wen-Kai; Xu, Yi-Jun

    2010-10-01

    The possible reaction mechanisms for CO oxidation on the perfect Cu2O(111) surface have been investigated by performing periodic density functional theoretical calculations. We find that Cu2O(111) is able to facilitate the CO oxidation with different mechanisms. Four possible mechanisms are explored (denoted as MER1, MER2, MLH1, and MLH2, respectively): MER1 is CO(gas)+O2(ads)-->CO2(gas) MER2 is CO(gas)+O2(ads)-->CO3(ads)-->O(ads)+CO2(gas) MLH1 refers to CO(ads)+O2(ads)-->O(ads)+CO2(ads) and MLH2 refers to CO(ads)+O2(ads)-->OOCO(ads)-->O(ads)+CO2(ads). Our transition state calculations clearly reveal that MER1 and MLH2 are both viable; but MER1 mechanism preferentially operates, in which only a moderate energy barrier (60.22 kJ/mol) needs to be overcome. When CO oxidation takes place along MER2 path, it is facile for CO3 formation, but is difficult for its decomposition, thereby CO3 species can stably exist on Cu2O(111). Of course, the reaction of CO with lattice O of Cu2O(111) is also considered. However, the calculated barrier is 600.00 kJ/mol, which is too large to make the path feasible. So, we believe that on Cu2O(111), CO reacts with adsorbed O, rather than lattice O, to form CO2. This is different from the usual Mars-van Krevene mechanism. The present results enrich our understanding of the catalytic oxidation of CO by copper-based and metal-oxide catalysts.

  1. Oxidative Dehydrogenation on Nanocarbon: Insights into the Reaction Mechanism and Kinetics via in Situ Experimental Methods.

    Science.gov (United States)

    Qi, Wei; Yan, Pengqiang; Su, Dang Sheng

    2018-03-20

    possibility for the fair comparisons of different nanocarbon catalysts and the consequent structure-function relation regularity. Surface modification and heteroatom doping are proved as the most effective strategies to adjust the catalytic property (activity and product selectivity etc.) of the nanocarbon catalysts. Nanocarbon is actually a proper candidate platform helping us to understand the classical catalytic reaction mechanism better, since there is no lattice oxygen and all the catalytic process happens on nanocarbon surface. This Account also exhibits the importance of the in situ structural characterizations for heterogeneous nanocarbon catalysis. The research strategy and methods proposed for carbon catalysts may also shed light on other complicated catalytic systems or fields concerning the applications of nonmetallic materials, such as energy storage and environment protection etc.

  2. Kinetics and mechanism of the reaction of recombination of vinyl and hydroxyl radicals

    Science.gov (United States)

    Knyazev, Vadim D.

    2017-10-01

    The recombination of the vinyl (C2H3) and the hydroxyl (OH) radicals was studied computationally using quantum chemistry and master equation/RRKM. The reaction mechanism includes the initial addition, several isomerization steps, and decomposition via seven different channels. The spectrum of products demonstrates temperature dependence in the 300-3000 K range. At low temperatures (below 1600 K), CH3 + HCO products are dominant but at elevated temperatures vinoxy radical (CH2CHO) and hydrogen atom become more important. The acetyl (CH3CO) + H products and formation of vinylidene (CH2C:) and water products are minor but non-negligible.

  3. Study of the properties of leading protons and antiprotons produced in p-barp exclusive reactions at 32 GeV/c

    International Nuclear Information System (INIS)

    Bogolyubskii, M.Y.; Boos, E.G.; Borovikov, A.A.

    1986-01-01

    We study the properties of leading protons and antiprotons from nondiffractive events in p-barp exclusive reactions at 32 GeV/c. It is found that the relative leading of protons and antiprotons does not depend on the final-state multiplicity and that the longitudinal momenta of leading hadrons are not correlated, but a significant part of the transverse momentum of a leading hadron is compensated by the transverse momentum of another hadron. It is shown that these experimental data are well described by the statistical model of independent particle emission but contradict the Lund string-fragmentation model

  4. Amino-Functionalized Multiwalled Carbon Nanotubes Lead to Successful Ring-Opening Polymerization of Poly(ε-caprolactone): Enhanced Interfacial Bonding and Optimized Mechanical Properties.

    Science.gov (United States)

    Roumeli, Eleftheria; Papageorgiou, Dimitrios G; Tsanaktsis, Vasilios; Terzopoulou, Zoe; Chrissafis, Konstantinos; Avgeropoulos, Apostolos; Bikiaris, Dimitrios N

    2015-06-03

    In this work, the synthesis, structural characteristics, interfacial bonding, and mechanical properties of poly(ε-caprolactone) (PCL) nanocomposites with small amounts (0.5, 1.0, and 2.5 wt %) of amino-functionalized multiwalled carbon nanotubes (f-MWCNTs) prepared by ring-opening polymerization (ROP) are reported. This method allows the creation of a covalent-bonding zone on the surface of nanotubes, which leads to efficient debundling and therefore satisfactory dispersion and effective load transfer in the nanocomposites. The high covalent grafting extent combined with the higher crystallinity provide the basis for a significant enhancement of the mechanical properties, which was detected in the composites with up to 1 wt % f-MWCNTs. Increasing filler concentration encourages intrinsic aggregation forces, which allow only minor grafting efficiency and poorer dispersion and hence inferior mechanical performance. f-MWCNTs also cause a significant improvement on the polymerization reaction of PCL. Indeed, the in situ polymerization kinetics studies reveal a significant decrease in the reaction temperature, by a factor of 30-40 °C, combined with accelerated the reaction kinetics during initiation and propagation and a drastically reduced effective activation energy.

  5. Determination of the shapes and sizes of the regions in which in hadron-nucleus collisions reactions leading to the nucleon emission, particle production, and fragment evaporation occur

    International Nuclear Information System (INIS)

    Strugalski, Z.

    1985-01-01

    Shapes and sizes of the regions in target-nuclei in which reactions leading to the nucleon emission, particle production and fragment evaporation occur are determined. The region of nucleon emission is of cylindrical shape, with the diameter as large as two nucleon diameters, centered on the incident hadron course. The reactions leading to the particle production happen predominantly along the incident hadron course in nuclear matter. The fragment evaporation goes from the surface layer of the part of the target-nucleus damaged in nucleon emission process

  6. Spectroscopic factors measurement of the five first energy levels of lead 208 nucleus using the 208Pb(e,e'p207Tl* huge pulse transfer reaction

    International Nuclear Information System (INIS)

    Medaglia, R.

    1999-08-01

    In this work, the spectral functions and the spectroscopic factors of the first five energy levels of the lead 208 nucleus have been measured using the 208 Pb(e,e'p) 207 Tl * reaction. The aim is to characterize the effect of the nuclear environment on pulse and energy distributions of protons. In order to minimize the ejected proton-residual nucleus interactions in the final state, the measurement has been performed at 750 and 570 MeV/c pulse transfers, and thus for proton kinetic energies of 263 MeV and 161 MeV, contrarily to a previous measurement performed at 100 MeV. A kinematics with a transverse electromagnetic coupling, instead of a longitudinal one, has been used because of the important coupling dependence observed for medium nuclei. The experiment has been carried out at the NIKHEF electron accelerator and smoothing ring. The pulse distributions of the first five energy levels for a proton pulse range of 0 to 300 MeV/c have been extracted from the (e,e'p) cross sections. An integration of model-dependent distributions gives the spectroscopic factors which indicate the number of protons of each level. These data rae compared to models that include both the proton interactions in the final state and the coulomb distortions. The Pavie model reproduces well the observed distributions and the transfer dependence, while the Ohio model does not. The spectroscopic factors obtained with the Pavie model are the same for both transfers and are 20% higher as an average than the previous experiment performed at 450 MeV/c. However, they are 30% below the shell model. The uncertain estimation of the reaction mechanisms does not allow to consider this reduction as being due exclusively to nuclear structure effects. (J.S.)

  7. Dissipative structure of mechanically stimulated reaction; Kikaiteki reiki hanno ni okeru san`itsu kozo

    Energy Technology Data Exchange (ETDEWEB)

    Hida, M. [Okayama Univ., Okayama (Japan). Faculty of Engineering

    1994-12-20

    Recently various studies have been conducted concerning the state changes of materials obtained through mechanical alloying (MA) or mechano-chemical (MC) processing. What is noticeable is the quasi-steady state of almost all the materials obtained through various processes including MA and MC, and that the super cooling, supersaturating and high residue distortion realized under unbalanced conditions have not been clarified. In other words, the tracing capability to the external binding conditions is low. In this report, the appearance of the high temperature phase and high pressure phase obtained through MA or MC processing, the forming of amorphous, the mesomerism of the amorphous materials, the interesting phenomena generated by combination between the mechanical disturbance and chemical reactions were discussed with concrete examples, and a steady dissipative organization theory was approached from the viewpoint of dissipative structure development which is equal to the forming process of the quasi-steady phase. 34 refs., 2 figs.

  8. Surface/subsurface observation and removal mechanisms of ground reaction bonded silicon carbide

    Science.gov (United States)

    Yao, Wang; Zhang, Yu-Min; Han, Jie-cai; Zhang, Yun-long; Zhang, Jian-han; Zhou, Yu-feng; Han, Yuan-yuan

    2006-01-01

    Reaction Bonded Silicon Carbide (RBSiC) has long been recognized as a promising material for optical applications because of its unique combination of favorable properties and low-cost fabrication. Grinding of silicon carbide is difficult because of its high hardness and brittleness. Grinding often induces surface and subsurface damage, residual stress and other types of damage, which have great influence on the ceramic components for optical application. In this paper, surface integrity, subsurface damage and material removal mechanisms of RBSiC ground using diamond grinding wheel on creep-feed surface grinding machine are investigated. The surface and subsurface are studied with scanning electron microscopy (SEM) and optical microscopy. The effects of grinding conditions on surface and subsurface damage are discussed. This research links the surface roughness, surface and subsurface cracks to grinding parameters and provides valuable insights into the material removal mechanism and the dependence of grind induced damage on grinding conditions.

  9. Conversion of glucose into 5-hydroxymethylfurfural in different solvents and catalysts: Reaction kinetics and mechanism

    Directory of Open Access Journals (Sweden)

    Cunshan Zhou

    2017-06-01

    Full Text Available Synthesis of 5-hydroxymethylfurfural (HMF from glucose was done in H2O, dimethylsulfoxide (DMSO and 1-butyl-3-methylimidazolium chloride ([Bmim]Cl catalyzed by metal (III chloride (FeCl3·6H2O, CrCl3·6H2O and AlCl3. The effects of solvent/catalyst system and temperature/time on the performance of the reaction are studied. HMF yield in the different solvents follows a decreasing order as DMSO > [Bmim]Cl > H2O. The highest HMF yield is achieved by CrCl3·6H2O, followed by AlCl3 and then FeCl3·6H2O. An optimal temperature/time is found at 393 K or 403 K and a time between 30 min and 480 min. Under the optimal reaction conditions, HMF yields of 54.43% and 52.86% are obtained in DMSO with CrCl3·6H2O at 403 K and 480 min and AlCl3 at 393 K and 240 min, respectively. The mechanism of the halide chlorides catalyzed glucose conversion reaction is proposed. The kinetic model is established to describe the HMF formation and the experimental data conform to the model.

  10. THEORETICAL RESEARCH ON THE MULTI-CHANNEL REACTION MECHANISM AND KINETICS OF HNCS WITH OH-

    Directory of Open Access Journals (Sweden)

    Li-Jie Hou

    Full Text Available We presented a theoretical study on the detailed reaction mechanism and kinetics of the HNCS molecule with the OH-. The barrierless minimum energy path and the most favorable entrance channel have been determined by study the thermodynamic and kinetic characters of the channel with low energy barrier. The B3LYP/6-311++G** method was employed for all the geometrical optimizations and a multi-level extrapolation method based on the G3 energies was employed for further energy refinements. In addition, the analysis of the combining interaction between hydroxide ion and HNCS was performed by natural bond orbitals (NBO analysis. The calculation results indicated that the reaction of OH- with HNCS had four channels, and the channel of H-atom in HNCS direct extraction to OH- (OH-+HNCS→IM1→TS3→IM4→P2(SCN- +H2O in singlet state was the main channel with the low potential energy and high equilibrium constant and reaction rate constant. SCN- and H2O were main products.

  11. Automatic analysis and reduction of reaction mechanisms for complex fuel combustion

    Energy Technology Data Exchange (ETDEWEB)

    Nilsson, Daniel

    2001-05-01

    This work concentrates on automatic procedures for simplifying chemical models for realistic fuels using skeletal mechanism construction and Quasi Steady-State Approximation (QSSA) applied to detailed reaction mechanisms. To automate the selection of species for removal or approximation, different indices for species ranking have thus been proposed. Reaction flow rates are combined with sensitivity information for targeting a certain quantity, and used to determine a level of redundancy for automatic skeletal mechanism construction by exclusion of redundant species. For QSSA reduction, a measure of species lifetime can be used for species ranking as-is, weighted by concentrations or molecular transport timescales, and/or combined with species sensitivity. Maximum values of the indices are accumulated over ranges of parameters, (e.g. fuel-air ratio and octane number), and species with low accumulated index values are selected for removal or steady-state approximation. In the case of QSSA, a model with a certain degree of reduction is automatically implemented as FORTRAN code by setting a certain index limit. The code calculates source terms of explicitly handled species from reaction rates and the steady-state concentrations by internal iteration. Homogeneous-reactor and one-dimensional laminar-flame models were used as test cases. A staged combustor fuelled by ethylene with monomethylamine addition is modelled by two homogeneous reactors in sequence, i.e. a PSR (Perfectly Stirred Reactor) followed by a PFR (Plug Flow Reactor). A modified PFR model was applied for simulation of a Homogeneous Charge Compression Ignition (HCCI) engine fuelled with four-component natural gas, whereas a two-zone model was required for a knocking Spark Ignition (SI) engine powered by Primary Reference Fuel (PRF). Finally, a laminar one-dimensional model was used to simulate premixed flames burning methane and an aeroturbine kerosene surrogate consisting of n-decane and toluene. In

  12. Status on DEMO Helium Cooled Lithium Lead breeding blanket thermo-mechanical analyses

    Energy Technology Data Exchange (ETDEWEB)

    Aubert, J., E-mail: julien.aubert@cea.fr [CEA-Saclay, DEN, DM2S, F-91191 Gif-sur-Yvette (France); Aiello, G.; Jaboulay, J.-C. [CEA-Saclay, DEN, DM2S, F-91191 Gif-sur-Yvette (France); Kiss, B. [Institute of Nuclear Techniques, Budapest University of Technology and Economics, Budapest (Hungary); Morin, A. [CEA-Saclay, DEN, DM2S, F-91191 Gif-sur-Yvette (France)

    2016-11-01

    Highlights: • CEA with the support of Wigner-RCP and IPP-CR, is in charge of the design of the HCLL blanket for DEMO. The DEMO HCLL breeding blanket design capitalizes on the experience acquired on the HCLL Test Blanket Module designed for ITER. Design improvements are being implemented to adapt the design to DEMO specifications and performance objectives. • Thermal and mechanical analyses have been carried out in order to justify the design of the HCLL breeding blanket showing promising results for tie rods modules’ attachments system and relatively good behavior of the box in case of LOCA when comparing to RCC-MRx criteria. • CFD thermal analyses on generic breeding unit have enabled the consolidation of the results obtained with previous FEM design analyses. - Abstract: The EUROfusion Consortium develops a design of a fusion power demonstrator (DEMO) in the framework of the European “Horizon 2020” innovation and research program. One of the key components in the fusion reactor is the breeding blanket surrounding the plasma, ensuring tritium self-sufficiency, heat removal for conversion into electricity, and neutron shielding. The Helium Cooled Lithium Lead (HCLL) blanket is one of the concepts which is investigated for DEMO. It is made of a Eurofer structure and uses the eutectic liquid lithium–lead as tritium breeder and neutron multiplier, and helium gas as coolant. Within the EUROfusion organization, CEA with the support of Wigner-RCP and IPP-CR, is in charge of the design of the HCLL blanket for DEMO. This paper presents the status of the thermal and mechanical analyses carried out on the HCLL breeding blanket in order to justify the design. CFD thermal analyses on generic breeding unit including stiffening plates and cooling plates have been performed with ANSYS in order to consolidate results obtained with previous FEM design analyses. Moreover in order to expand the justification of the HCLL Breeding blanket design, the most loaded area of

  13. Electrical Transport Mechanisms and Photoconduction in Undoped Crystalline Flash-Evaporated Lead Iodide Thin Films

    Science.gov (United States)

    Al-Daraghmeh, Tariq M.; Saleh, Mahmoud H.; Ahmad, Mais Jamil A.; Bulos, Basim N.; Shehadeh, Khawla M.; Jafar, Mousa M. Abdul-Gader

    2018-03-01

    The flash-evaporation technique was utilized to fabricate undoped 1.35-μm and 1.2-μm thick lead iodide films at substrate temperatures T_{{s}} = 150 °C and 200°C, respectively. The films were deposited onto a coplanar comb-like copper (Cu-) electrode pattern, previously coated on glass substrates to form lateral metal-semiconductor-metal (MSM-) structures. The as-measured constant- temperature direct-current (dc)-voltage ( I( {V;T} ) - V ) curves of the obtained lateral coplanar Cu-PbI2-Cu samples (film plus electrode) displayed remarkable ohmic behavior at all temperatures ( T = 18 - 90°C). Their dc electrical resistance R_{{dc}} (T ) revealed a single thermally-activated conduction mechanism over the temperature range with activation energy E_{{act}} ≈ 0.90 - 0.98 {eV} , slightly less than half of room-temperature bandgap energy E_{{g}} ( ≈ 2.3 {eV} ) of undoped 2H-polytype PbI2 single crystals. The undoped flash-evaporated {PbI}_{{x}} thin films were homogeneous and almost stoichiometric ( x ≈ 1.87 ), in contrast to findings on lead iodide films prepared by other methods, and were highly crystalline hexagonal 2H-polytypic structure with c-axis perpendicular to the surface of substrates maintained at T_{s} ≳ 150°C. Photoconductivity measurements made on these lateral Cu-PbI2-Cu-structures under on-off visible-light illumination reveal a feeble photoresponse for long wavelengths ( λ > 570 {nm} ), but a strong response to blue light of photon energy E_{{ph}} ≈ 2.73 {eV} ( > E_{{g}} ), due to photogenerated electron-hole (e-h) pairs via direct band-to-band electronic transitions. The constant-temperature/dc voltage current-time I( {T,V} ) - t curves of the studied lateral PbI2 MSM-structures at low ambient temperatures ( T < 50°C), after cutting off the blue-light illumination, exhibit two trapping mechanisms with different relaxation times. These strongly depend on V and T , with thermally generated charge carriers in the PbI2 mask photogenerated

  14. Role of hydrogen bonds in the reaction mechanism of chalcone isomerase.

    Science.gov (United States)

    Jez, Joseph M; Bowman, Marianne E; Noel, Joseph P

    2002-04-23

    In flavonoid, isoflavonoid, and anthocyanin biosynthesis, chalcone isomerase (CHI) catalyzes the intramolecular cyclization of chalcones into (S)-flavanones with a second-order rate constant that approaches the diffusion-controlled limit. The three-dimensional structures of alfalfa CHI complexed with different flavanones indicate that two sets of hydrogen bonds may possess critical roles in catalysis. The first set of interactions includes two conserved amino acids (Thr48 and Tyr106) that mediate a hydrogen bond network with two active site water molecules. The second set of hydrogen bonds occurs between the flavanone 7-hydroxyl group and two active site residues (Asn113 and Thr190). Comparison of the steady-state kinetic parameters of wild-type and mutant CHIs demonstrates that efficient cyclization of various chalcones into their respective flavanones requires both sets of contacts. For example, the T48A, T48S, Y106F, N113A, and T190A mutants exhibit 1550-, 3-, 30-, 7-, and 6-fold reductions in k(cat) and 2-3-fold changes in K(m) with 4,2',4'-trihydroxychalcone as a substrate. Kinetic comparisons of the pH-dependence of the reactions catalyzed by wild-type and mutant enzymes indicate that the active site hydrogen bonds contributed by these four residues do not significantly alter the pK(a) of the intramolecular cyclization reaction. Determinations of solvent kinetic isotope and solvent viscosity effects for wild-type and mutant enzymes reveal a change from a diffusion-controlled reaction to one limited by chemistry in the T48A and Y106F mutants. The X-ray crystal structures of the T48A and Y106F mutants support the assertion that the observed kinetic effects result from the loss of key hydrogen bonds at the CHI active site. Our results are consistent with a reaction mechanism for CHI in which Thr48 polarizes the ketone of the substrate and Tyr106 stabilizes a key catalytic water molecule. Hydrogen bonds contributed by Asn113 and Thr190 provide additional

  15. Reaction pathway and oxidation mechanisms of dibutyl phthalate by persulfate activated with zero-valent iron

    Energy Technology Data Exchange (ETDEWEB)

    Li, Huanxuan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); Wan, Jinquan, E-mail: ppjqwan@scut.edu.cn [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Ma, Yongwen [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Wang, Yan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China)

    2016-08-15

    This study investigated reaction pathway and oxidation mechanisms of dibutyl phthalate (DBP) by persulfate (PS) activated with zero-valent iron (ZVI). The DBP degradation was studied at three pH values (acidic, neutral and basic) in the presence of different organic scavengers. Using a chemical probe method, both sulfate radical (SO{sub 4}·{sup −}) and hydroxyl radical (·OH) were found to be primary oxidants at pH 3.0 and pH 7.0, respectively while ·OH was the major specie to oxidize DBP at pH 11.0. A similar result was found in an experiment of Electron Spin Resonance spin-trapping where in addition to ·OH, superoxide radical (O{sub 2}·{sup −}) was detected at pH 11.0. The transformation of degradation products including dimethyl phthalate (DMP), diethyl phthalate (DEP), phthalic anhydride, and acetophenone exhibited diverse variation during the reaction processes. The phthalic anhydride concentration appeared to be maximum at all pHs. Another eleven intermediate products were also found at pH 3.0 by GC–MS and HPLC analysis, and their degradation mechanisms and pathways were proposed. It was suggested that dealkylation, hydroxylation, decarboxylation and hydrogen extraction were the dominant degradation mechanisms of DBP at pH 3.0. - Highlights: • Both SO{sub 4}{sup −}· and ·OH were found to be the major active species at pH 3.0 and pH 7.0. • ·OH and ·O2– were the primary oxidants pH 11.0. • The intermediate products were investigated as well as the degradation pathway. • Dealkylation, hydroxylation, decarboxylation, H-extraction were the major mechanisms.

  16. Study of transfer reactions (α,t), (α,3He) in the f-p shell: mechanism and spectroscopic use

    International Nuclear Information System (INIS)

    Roussel, P.

    1968-05-01

    We describe an experimental study of (α,t), (α, 3 He) reactions at 44 MeV using a solid-state identifier, on the target-nuclei 54 Fe and 58,60,62,64 Ni. A critical study of optical model and of disturbed wave analysis has been performed. We show the complementarity of different transfer-reactions, the ambiguity of spectroscopic factors, the importance of the problem of the reaction mechanism. (author) [fr

  17. Ionoregulatory disruption as the acute toxic mechanism for lead in the rainbow trout (Oncorhynchus mykiss)

    International Nuclear Information System (INIS)

    Rogers, J.T.; Richards, J.G.; Wood, C.M.

    2003-01-01

    The mechanism for acute toxicity of lead (Pb) in rainbow trout (Oncorhynchus mykiss) was investigated at Pb concentrations close to the 96 h LC50 of 1.0 mg dissolved Pb l -1 (0.8-1.4, 95% C.I.) determined in dechlorinated Hamilton city tap water (from Lake Ontario, hardness=140 mg l -1 CaCO 3 ). Tissue Pb accumulation associated with death was highest in the gill, followed by kidney and liver. Significant ionoregulatory impacts were observed in adult rainbow trout (200-300 g) fitted with indwelling dorsal aortic catheters and exposed to 1.1±0.04 mg dissolved Pb l -1 . Decreased plasma [Ca 2+ ], [Na + ] and [Cl - ] occurred after 48 h of exposure through to 120 h, with increases in plasma [Mg 2+ ], ammonia, and cortisol. No marked changes in PaO 2 , PaCO 2 , pH, glucose, or hematological parameters were evident. Branchial Na + /K + ATPase activity in juvenile trout exposed to concentrations close to the 96 h LC50 was inhibited by approximately 40% after 48 h of Pb exposure. Calcium ion flux measurements using 45 Ca as a radiotracer showed 65% inhibition of Ca 2+ influx after 0, 12, 24 or 48 h exposure to the 96 h LC50 concentration of Pb. There was also significant inhibition (40-50%) of both Na + and Cl - uptake, measured with 22 Na and 36 Cl simultaneously. We conclude that the mechanism of acute toxicity for Pb in rainbow trout occurs by ionoregulatory disruption rather than respiratory or acid/base distress at Pb concentrations close to the 96 h LC50 in moderately hard water

  18. Ionoregulatory disruption as the acute toxic mechanism for lead in the rainbow trout (Oncorhynchus mykiss)

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, J.T.; Richards, J.G.; Wood, C.M

    2003-07-16

    The mechanism for acute toxicity of lead (Pb) in rainbow trout (Oncorhynchus mykiss) was investigated at Pb concentrations close to the 96 h LC50 of 1.0 mg dissolved Pb l{sup -1} (0.8-1.4, 95% C.I.) determined in dechlorinated Hamilton city tap water (from Lake Ontario, hardness=140 mg l{sup -1} CaCO{sub 3}). Tissue Pb accumulation associated with death was highest in the gill, followed by kidney and liver. Significant ionoregulatory impacts were observed in adult rainbow trout (200-300 g) fitted with indwelling dorsal aortic catheters and exposed to 1.1{+-}0.04 mg dissolved Pb l{sup -1}. Decreased plasma [Ca{sup 2+}], [Na{sup +}] and [Cl{sup -}] occurred after 48 h of exposure through to 120 h, with increases in plasma [Mg{sup 2+}], ammonia, and cortisol. No marked changes in PaO{sub 2}, PaCO{sub 2}, pH, glucose, or hematological parameters were evident. Branchial Na{sup +}/K{sup +} ATPase activity in juvenile trout exposed to concentrations close to the 96 h LC50 was inhibited by approximately 40% after 48 h of Pb exposure. Calcium ion flux measurements using {sup 45}Ca as a radiotracer showed 65% inhibition of Ca{sup 2+} influx after 0, 12, 24 or 48 h exposure to the 96 h LC50 concentration of Pb. There was also significant inhibition (40-50%) of both Na{sup +} and Cl{sup -} uptake, measured with {sup 22}Na and {sup 36}Cl simultaneously. We conclude that the mechanism of acute toxicity for Pb in rainbow trout occurs by ionoregulatory disruption rather than respiratory or acid/base distress at Pb concentrations close to the 96 h LC50 in moderately hard water.

  19. Insights into the Diels-Alder Reaction between 3-Vinylindoles and Methyleneindolinone without and with the Assistance of Hydrogen-Bonding Catalyst Bisthiourea: Mechanism, Origin of Stereoselectivity, and Role of Catalyst.

    Science.gov (United States)

    Yan, Chao-Xian; Yang, Fan; Yang, Xing; Zhou, Da-Gang; Zhou, Pan-Pan

    2017-03-17

    The Diels-Alder reaction between 3-vinylindoles and methyleneindolinone can proceed both under catalyst-free conditions and with bisthiourea as the catalyst. The reaction with bisthiourea is much faster and results in higher stereoselectivity of the product. The reaction mechanism, origin of stereoselectivity, and role of the catalyst were elaborated based on quantum mechanical calculations and theoretical methods of reactivity indices, NCI, QTAIM, and distortion/interaction models. In the uncatalyzed reaction, the two C-C bonds that are formed undergo conversion from noncovalent to covalent bonding via a concerted asynchronous mechanism. The weak intermolecular interactions formed in the transition state play important roles. The difference between the interaction and distortion energies is responsible for the stereoselectivity. In the catalyzed reaction, bisthiourea induces both the diene and dienophile to approach it via weak intermolecular interactions, which greatly lowers the energy barrier of the reaction and leads to the product with excellent stereoselectivity. The possible pathways of this reaction were explored, which suggested that the formation of the two C-C bonds goes through either a stepwise or concerted asynchronous mechanism. These results detail the reaction mechanism and shed light on both the significant role of the bisthiourea catalyst and the origin of stereoselectivity for this type of Diels-Alder reaction and related ones.

  20. Theoretical study on the mechanism of the reaction of FOX-7 with OH and NO2 radicals: bimolecular reactions with low barrier during the decomposition of FOX-7

    Science.gov (United States)

    Zhang, Ji-Dong; Zhang, Li-Li

    2017-12-01

    The decomposition of 1,1-diamino-2,2-dinitroethene (FOX-7) attracts great interests, while the studies on bimolecular reactions during the decomposition of FOX-7 are scarce. This study for the first time investigated the bimolecular reactions of OH and NO2 radicals, which are pyrolysis products of ammonium perchlorate (an efficient oxidant usually used in solid propellant), with FOX-7 by computational chemistry methods. The molecular geometries and energies were calculated using the (U)B3LYP/6-31++G(d,p) method. The rate constants of the reactions were calculated by canonical variational transition state theory. We found three mechanisms (H-abstraction, OH addition to C and N atom) for the reaction of OH + FOX-7 and two mechanisms (O abstraction and H abstraction) for the reaction of NO2 + FOX-7. OH radical can abstract H atom or add to C atom of FOX-7 with barriers near to zero, which means OH radical can effectively degrade FOX-7. The O abstraction channel of the reaction of NO2 + FOX-7 results in the formation of NO3 radical, which has never been detected experimentally during the decomposition of FOX-7.

  1. Rationalizing the mechanism of HMDS degradation in air and effective control of the reaction byproducts

    Science.gov (United States)

    Seguin, Kevin; Dallas, Andrew J.; Weineck, Gerald

    2008-03-01

    The concern over molecular contamination on the surfaces of optics continues to grow. Most recently, this concern has focused on siloxane contamination resulting from hexamethyldisilazane (HMDS) which is commonly used as a wafer treatment to improve photoresist adhesion onto wafers. From this process, HMDS vapor can be found within FABs and process tools where it has been linked to issues related to lens hazing. This type of surface contamination is significantly detrimental to the imaging process and is generally corrected by extensive surface cleaning or even lens replacement. Additionally, this type of repair also requires adjustment of the optical axis, thereby contributing to an extended downtime. HMDS is known to be very sensitive to the presence of water and is therefore believed to degrade in humid airstreams. This research focuses on rationalizing the reaction mechanisms of HMDS in dry and humid airstreams and in the presence of several adsorbent surfaces. It is shown that HMDS hydrolyzes in humid air to trimethylsilanol (TMS) and ammonia (NH 3). Furthermore, it is shown that TMS can dimerize in air, or on specific types of adsorption media, to form hexamethyldisiloxane (HMDSO). Additionally, we report on the relative impact of these reaction mechanisms on the removal of both HMDS and its hydrolysis products (TMS, HMDSO and NH 3).

  2. Viewing loved faces inhibits defense reactions: a health-promotion mechanism?

    Directory of Open Access Journals (Sweden)

    Pedro Guerra

    Full Text Available We have known for decades that social support is associated with positive health outcomes. And yet, the neurophysiological mechanisms underlying this association remain poorly understood. The link between social support and positive health outcomes is likely to depend on the neurophysiological regulatory mechanisms underlying reward and defensive reactions. The present study examines the hypothesis that emotional social support (love provides safety cues that activate the appetitive reward system and simultaneously inhibit defense reactions. Using the startle probe paradigm, 54 undergraduate students (24 men viewed black and white photographs of loved (romantic partner, father, mother, and best friend, neutral (unknown, and unpleasant (mutilated faces. Eye-blink startle, zygomatic major activity, heart rate, and skin conductance responses to the faces, together with subjective ratings of valence, arousal, and dominance, were obtained. Viewing loved faces induced a marked inhibition of the eye-blink startle response accompanied by a pattern of zygomatic, heart rate, skin conductance, and subjective changes indicative of an intense positive emotional response. Effects were similar for men and women, but the startle inhibition and the zygomatic response were larger in female participants. A comparison between the faces of the romantic partner and the parent who shares the partner's gender further suggests that this effect is not attributable to familiarity or arousal. We conclude that this inhibitory capacity may contribute to the health benefits associated with social support.

  3. Viewing loved faces inhibits defense reactions: a health-promotion mechanism?

    Science.gov (United States)

    Guerra, Pedro; Sánchez-Adam, Alicia; Anllo-Vento, Lourdes; Ramírez, Isabel; Vila, Jaime

    2012-01-01

    We have known for decades that social support is associated with positive health outcomes. And yet, the neurophysiological mechanisms underlying this association remain poorly understood. The link between social support and positive health outcomes is likely to depend on the neurophysiological regulatory mechanisms underlying reward and defensive reactions. The present study examines the hypothesis that emotional social support (love) provides safety cues that activate the appetitive reward system and simultaneously inhibit defense reactions. Using the startle probe paradigm, 54 undergraduate students (24 men) viewed black and white photographs of loved (romantic partner, father, mother, and best friend), neutral (unknown), and unpleasant (mutilated) faces. Eye-blink startle, zygomatic major activity, heart rate, and skin conductance responses to the faces, together with subjective ratings of valence, arousal, and dominance, were obtained. Viewing loved faces induced a marked inhibition of the eye-blink startle response accompanied by a pattern of zygomatic, heart rate, skin conductance, and subjective changes indicative of an intense positive emotional response. Effects were similar for men and women, but the startle inhibition and the zygomatic response were larger in female participants. A comparison between the faces of the romantic partner and the parent who shares the partner's gender further suggests that this effect is not attributable to familiarity or arousal. We conclude that this inhibitory capacity may contribute to the health benefits associated with social support.

  4. Reaction mechanisms and kinetics of the iminovinylidene radical with NO: Ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Hsiao, Ming-Kai; Chung, Yi-Hua; Hung, Yu-Ming; Chen, Hui-Lung, E-mail: chl3@faculty.pccu.edu.tw [Department of Chemistry and Institute of Applied Chemistry, Chinese Culture University, Taipei 111, Taiwan (China)

    2014-05-28

    The nitric oxide (NO) is a notorious compound for polluting environment. Recent year, removing nitric oxide from the atmosphere becomes a focus of the investigation. In our work, we study the iminovinylidene (HNCC) radical reacted with NO molecule. The mechanism and kinetic for reaction of the HNCC radical with the NO molecule is investigated via considering the possible channels of the N and O atoms of NO attacking the N and C atoms of the HNCC based on the high level ab initio molecular orbital calculations in conjunction with variational TST and RRKM calculations. The species involved have been optimized at the B3LYP/6-311++G(3df,2p) level and their single-point energies are refined by the CCSD(T)/aug-cc-PVQZ//B3LYP/6-311++G(3df,2p) method. The calculated potential energy surfaces indicated that energetically the most favorable channel for the HNCC + NO reaction was predicted to be the formation of HNC+CNO (P8) product via the addition reaction of the C atom of HNCC radical and the N atom of NO with the head to head orientation. To rationalize the scenario of the calculated results, we also employ the Fukui functions and HSAB theory to seek for a possible explanation. In addition, the reaction rate constants were calculated using VariFlex code, and the results show that the total rate coefficient, k{sub total}, at Ar pressure 760 Torr can be represented with an equation: k{sub total} = 6.433 × 10{sup −11} T {sup 0.100} exp(0.275 kcal mol{sup −1}/RT) at T = 298–3000 K, in units of cm{sup 3} molecule{sup −1} s{sup −1}.

  5. Ablation characteristics and reaction mechanism of insulation materials under slag deposition condition

    Science.gov (United States)

    Guan, Yiwen; Li, Jiang; Liu, Yang

    2017-07-01

    Current understanding of the physical and chemical processes involved in the ablation of insulation materials by highly aluminized solid propellants is limited. The study on the heat transfer and ablation principle of ethylene propylene diene monomer (EPDM) materials under slag deposition condition is essential for future design or modification of large solid rocket motors (SRMs) for launch application. In this paper, the alumina liquid flow pattern and the deposition principle in full-scale SRM engines are discussed. The interaction mechanism between the alumina droplets and the wall are analyzed. Then, an experimental method was developed to simulate the insulation material ablation under slag deposition condition. Experimental study was conducted based on a laboratory-scale device. Meanwhile, from the analysis of the cross-sectional morphology and chemical composition of the charring layer after ablation, the reaction mechanism of the charring layer under deposition condition was discussed, and the main reaction equation was derived. The numerical simulation and experimental results show the following. (i) The alumina droplet flow in the deposition section of the laboratory-scale device is similar to that of a full-scale SRM. (ii) The charring layer of the EPDM insulator displays a porous tight/loose structure under high-temperature slag deposition condition. (iii) A seven-step carbothermal reduction in the alumina is derived and established under high-pressure and high-temperature environment in the SRM combustion chamber. (iv) The analysis using thermodynamic software indicates that the reaction of the alumina and charring layer initially forms Al4C3 during the operation. Then, Al element and Al2OC compound are subsequently produced with the reduction in the release of gas CO as well with continuous environmental heating.

  6. Exploring Reaction Mechanism on Generalized Force Modified Potential Energy Surfaces (G-FMPES) for Diels-Alder Reaction

    Science.gov (United States)

    Jha, Sanjiv; Brown, Katie; Subramanian, Gopinath

    We apply a recent formulation for searching minimum energy reaction path (MERP) and saddle point to atomic systems subjected to an external force. We demonstrate the effect of a loading modality resembling hydrostatic pressure on the trans to cis conformational change of 1,3-butadiene, and the simplest Diels-Alder reaction between ethylene and 1,3-butadiene. The calculated MERP and saddle points on the generalized force modified potential energy surface (G-FMPES) are compared with the corresponding quantities on an unmodified potential energy surface. Our study is performed using electronic structure calculations at the HF/6-31G** level as implemented in the AIMS-MOLPRO code. Our calculations suggest that the added compressive pressure lowers the energy of cis butadiene. The activation energy barrier for the concerted Diels-Alder reaction is found to decrease progressively with increasing compressive pressure.

  7. Mechanisms before Reactions: A Mechanistic Approach to the Organic Chemistry Curriculum Based on Patterns of Electron Flow

    Science.gov (United States)

    Flynn, Alison B.; Ogilvie, William W.

    2015-01-01

    A significant redesign of the introductory organic chemistry curriculum at the authors' institution is described. There are two aspects that differ greatly from a typical functional group approach. First, organic reaction mechanisms and the electron-pushing formalism are taught before students have learned a single reaction. The conservation of…

  8. Planning and leading of the technological processes by mechanical working with microsoft project

    Science.gov (United States)

    Nae, I.; Grigore, N.

    2016-08-01

    Nowadays, fabrication systems and methods are being modified; new processing technologies come up, flow sheets develop a minimum number of phases, the flexibility of the technologies grows up, new methods and instruments of monitoring and leading the processing operations also come up. The technological course (route, entry, scheme, guiding) referring to the series of the operation, putting and execution phases of a mark in order to obtain the final product from the blank is represented by a sequence of activities realized by a logic manner, on a well determined schedule, with a determined budget and resources. Also, a project can be defined as a series of specific activities, methodical structured which they aim to finish a specific objective, within a fixed schedule and budget. Within the homogeneity between the project and the technological course, this research is presenting the defining of the technological course of mechanical chip removing process using Microsoft Project. Under these circumstances, this research highlights the advantages of this method: the celerity using of other technological alternatives in order to pick the optimal process, the job scheduling being constrained by any kinds, the standardization of some processing technological operations.

  9. Conceptual design of the blanket mechanical attachment for the helium-cooled lithium-lead reactor

    International Nuclear Information System (INIS)

    Barrera, G.; Branas, B.; Lucas, J.; Doncel, J.; Medrano, M.; Garcia, A.; Giancarli, L.; Ibarra, A.; Li Puma, A.; Maisonnier, D.; Sardain, P.

    2008-01-01

    The conceptual design of a new type of fusion reactor based on the helium-cooled lithium-lead (HCLL) blanket has been performed within the European Power Plant Conceptual Studies. As part of this activity, a new attachment system suitable for the HCLL blanket modules had to be developed. This attachment is composed of two parts. The first one is the connection between module and the first part of a shield, called high temperature shield, which operates at a temperature around 500 deg. C, close to that of the blanket module. This connection must be made at the lateral walls, in order to avoid openings through the first wall and breeding zone thus avoiding complex design and fabrication issues of the module. The second connection is the one between the high temperature shield and a second shield called low temperature shield, which has a temperature during reactor operation around 150 deg. C. The design of this connection is complex because it must allow the large differential thermal expansion (up to 30 mm) between the two components. Design proposals for both connections are presented, together with the results of finite element mechanical analyses which demonstrate the feasibility to support the blanket and shield modules during normal and accidental operation conditions

  10. Study and understanding of the ageing mechanisms in lead-calcium alloys

    International Nuclear Information System (INIS)

    Rossi, F.

    2006-12-01

    The data available in the literature about ageing and over-ageing of lead-calcium alloys are often incomplete and inconsistent. It is undoubtedly due to the experimental difficulties encountered to observe the structure transformations which are numerous. As a result there is a certain confusion among the results of the different authors. Moreover, small variations in the process parameters and chemical composition may have some influence on the alloy behaviour. This work enabled us to obtain a set of TTT diagrams, more realistic and accurate than the ones available in the literature. Experimental techniques developed (particularly the preservation of the cold chain with is essential for the guaranty of the results repeatability), enabled particularly the study of the first transformations and better control the five stages of ageing and over-ageing. Our work have enabled to determine precisely the kinetics and the mechanisms of the transformations. This work constitutes a thorough analysis of the ageing and over-ageing of theses alloys. (author)

  11. Highly Efficient Lead Distribution by Magnetic Sewage Sludge Biochar: Sorption Mechanisms and Bench Applications.

    Science.gov (United States)

    Ifthikar, Jerosha; Wang, Jia; Wang, Qiliang; Wang, Ting; Wang, Huabin; Khan, Aimal; Jawad, Ali; Sun, Tingting; Jiao, Xiang; Chen, Zhuqi

    2017-08-01

    Highly efficient magnetic sewage sludge biochar (MSSBC) discloses feasible fabrication process with lower production cost, superior adsorption capacity, usage of waste sewage sludge as resource, selected by external magnetic field and exceptional regeneration property. 2gL -1 MSSBC exhibited a high adsorption capacity of 249.00mgg -1 in 200ppmPb(II) and the lead-MSSBC equilibrium was achieved within one hour, owing to the existence of the copious active sites. The adsorption kinetics was well described by the pseudo-second-order model while the adsorption isotherm could be fitted by Langmuir model. Mechanism study demonstrated the adsorption involved electrostatic attraction, ion exchange, inner-sphere complexation and formation of co-precipitates at the surface of MSSBC. Additionally, adsorption performance maintained remarkable in a broad pH window. These outcomes demonstrated the promising waste resource utilization by a feasible approach that turns the solid waste of sewage sludge into biochar adsorbent with auspicious applications in elimination of Pb(II) from wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Mechanism of Water Droplet Breakup Near the Leading Edge of an Airfoil

    Science.gov (United States)

    Vargas, Mario; Sor, Suthyvann; Magarino, Adelaida, Garcia

    2012-01-01

    This work presents results of an experimental study on droplet deformation and breakup near the leading edge of an airfoil. The experiment was conducted in the rotating rig test cell at the Instituto Nacional de Tecnica Aeroespacial (INTA) in Madrid, Spain. The airfoil model was placed at the end of the rotating arm and a monosize droplet generator produced droplets that fell from above, perpendicular to the path of the airfoil. The interaction between the droplets and the airfoil was captured with high speed imaging and allowed observation of droplet deformation and breakup as the droplet approached the airfoil near the stagnation line. Image processing software was used to measure the position of the droplet centroid, equivalent diameter, perimeter, area, and the major and minor axes of an ellipse superimposed over the deforming droplet. The horizontal and vertical displacement of each droplet against time was also measured, and the velocity, acceleration, Weber number, Bond number, Reynolds number, and the drag coefficients were calculated along the path of the droplet to the beginning of breakup. Droplet deformation is defined and studied against main parameters. The high speed imaging allowed observation of the actual mechanism of breakup and identification of the sequence of configurations from the initiation of the breakup to the disintegration of the droplet. Results and comparisons are presented for droplets of diameters in the range of 500 to 1800 microns, and airfoil velocities of 70 and 90 m/sec.

  13. EFFECT OF FLUORINE AND CHLORINE IONS ON THE REACTION SINTERING OF MECHANICALLY ACTIVATED ZIRCON-ALUMINA MIXTURE

    Directory of Open Access Journals (Sweden)

    R. Zamani Foroshani

    2015-09-01

    Full Text Available The aim of this work was to study the effect of fluorine and chlorine ions on the formation of mullite during the reaction sintering of mechanically activated zircon-alumina powder mixture. The results showed that mechanical activation of zirconalumina powder mixture for 20 h led to grain refinement and partial amorphization. In the presence of fluorine and chlorine ions, complete formation of mullite in the mechanically activated sample occurred after 2 h of reaction sintering at 1300oC and 1400oC, respectively. In the sample lacking fluorine and chlorine ions, mullitization was not completed even after 2 h of reaction sintering at 1400oC. It was concluded that presence of fluorine and chlorine ions enhance the dissociation of zircon and formation of mullite during the reaction sintering of mechanically activated zircon-alumina mixture.

  14. Studies of the pulse charge of lead-acid batteries for PV applications. Part I. Factors influencing the mechanism of the pulse charge of the positive plate

    Energy Technology Data Exchange (ETDEWEB)

    Kirchev, A.; Perrin, M.; Lemaire, E.; Karoui, F.; Mattera, F. [Commissariat de l' Energie Atomique, Institut National de l' Energie Solaire, INES-RDI, Parc Technologique de Savoie Technolac, 50 Avenue du Lac Leman, 73377 Le Bourget du Lac Cedex (France)

    2008-02-15

    The mechanism of the positive plate charge in pulse regime was studied in model lead-acid cells with one positive and two negative plates (8 Ah each) and Ag/Ag{sub 2}SO{sub 4} reference electrodes. The results showed that the evolution of the electrode potential is much slower on the positive plate than on the negative plate. Regardless of this fact, the calculated capacitive current of charge and self-discharge of the electrochemical double layer (EDL) during the 'ON' and 'OFF' half-periods of the pulse current square waves is comparable with the charge current amplitude. The result is due to the high values of the EDL on the surface of the lead dioxide active material. The influence of different factors like state of charge, state of health, pulse frequency, current amplitude and open circuit stay before the polarization was discussed. The previously determined optimal frequency of 1 Hz was associated with a maximum in the average double layer current on frequency dependence. The average double layer current is also maximal at SOC between 75 and 100%. The exchange of the constant current polarization with pulse polarization does not change substantially the mechanism and the overvoltage of the oxygen evolution reaction on the positive plate. The mechanism of the self-discharge of the EDL was also estimated analyzing long-time PPP transients (up to 2 h). It was found that when the PPP is lower than 1.2 V the preferred mechanism of EDL self-discharge is by coupling with the lead sulphate oxidation reaction. At higher values of PPP the EDL self-discharge happens via oxygen evolution. The high faradic efficiency of the pulse charge is due to the chemical oxidation of the Pb(II) ions by the O atoms and OH radicals formed at the oxygen evolution both during the 'ON' and 'OFF' periods. (author)

  15. Chemical dynamics simulations of X- + CH3Y → XCH3 + Y- gas-phase S(N)2 nucleophilic substitution reactions. Nonstatistical dynamics and nontraditional reaction mechanisms.

    Science.gov (United States)

    Manikandan, Paranjothy; Zhang, Jiaxu; Hase, William L

    2012-03-29

    Extensive classical chemical dynamics simulations of gas-phase X(-) + CH(3)Y → XCH(3) + Y(-) S(N)2 nucleophilic substitution reactions are reviewed and discussed and compared with experimental measurements and predictions of theoretical models. The primary emphasis is on reactions for which X and Y are halogen atoms. Both reactions with the traditional potential energy surface (PES), which include pre- and postreaction potential energy minima and a central barrier, and reactions with nontraditional PESs are considered. These S(N)2 reactions exhibit important nonstatistical atomic-level dynamics. The X(-) + CH(3)Y → X(-)---CH(3)Y association rate constant is less than the capture model as a result of inefficient energy transfer from X(-)+ CH(3)Y relative translation to CH(3)Y rotation and vibration. There is weak coupling between the low-frequency intermolecular modes of the X(-)---CH(3)Y complex and higher frequency CH(3)Y intramolecular modes, resulting in non-RRKM kinetics for X(-)---CH(3)Y unimolecular decomposition. Recrossings of the [X--CH(3)--Y](-) central barrier is important. As a result of the above dynamics, the relative translational energy and temperature dependencies of the S(N)2 rate constants are not accurately given by statistical theory. The nonstatistical dynamics results in nonstatistical partitioning of the available energy to XCH(3) +Y(-) reaction products. Besides the indirect, complex forming atomic-level mechanism for the S(N)2 reaction, direct mechanisms promoted by X(-) + CH(3)Y relative translational or CH(3)Y vibrational excitation are possible, e.g., the roundabout mechanism.

  16. Non-ionic iodinated contrast media related immediate reactions: A mechanism study of 27 patients.

    Science.gov (United States)

    Zhai, Liqin; Guo, Xiangjie; Zhang, Haoyue; Jin, Qianqian; Zeng, Qiang; Tang, Xiaoxian; Gao, Cairong

    2017-01-01

    The underlying mechanism of non-ionic iodinated contrast media-related immediate reactions was evaluated in this study. Patients presenting at least grade II immediate reactions after non-ionic iodinated contrast media injection were enrolled. Basophil activation was evaluated by flow cytometry. The plasma concentration of human terminal complement complex SC5b-9, as well as concentrations of serum chymase, tryptase, human mast cell carboxypeptidase A3, human prostaglandin D2, and total IgE were measured by enzyme-linked immunosorbent assay. The basophil activation percentage was significantly higher in the study group than in the control group (17.94±21.06% vs 3.45±1.49%). The plasma concentration of human terminal complement complex SC5b-9 and concentrations of serum chymase, human mast cell carboxypeptidase A3, prostaglandin D2, tryptase, and total IgE were also significantly increased (236.99±318.21 vs 49.70±30.41ng/mL, 0.41±0.49 vs 0.09±0.06ng/mL, 1.17±0.67 vs 0.30±0.17ng/mL, 203.52±137.27 vs 102.28±48.72pg/mL, 3.81±0.22 vs 2.70±0.16ng/mL, 102.00±51.84 vs 19.97±2.75ng/mL, respectively). Both mast cells and basophils were activated in non-ionic iodinated contrast media to mediate immediate hypersensitivity, and mast cells may be involved. Different mechanisms, including IgE-dependent, complement-dependent, and direct membrane effects, contributed to mast cell and basophil activation. Individual patients may use a single or combined mechanism involving single or combined mast cells and basophils. Immediate reactions following non-ionic iodinated contrast media injection may be a mechanically heterogenous disease. Copyright © 2016. Published by Elsevier B.V.

  17. Removal of selenite by zero-valent iron combined with ultrasound: Se(IV) concentration changes, Se(VI) generation, and reaction mechanism.

    Science.gov (United States)

    Fu, Fenglian; Lu, Jianwei; Cheng, Zihang; Tang, Bing

    2016-03-01

    In this paper, the performance and application of zero-valent iron (ZVI) assisted by ultrasonic irradiation for the removal of selenite (Se(IV)) in wastewater was evaluated and reaction mechanism of Se(IV) with ZVI in such systems was investigated. A series of batch experiments were conducted to determine the effects of ultrasound power, pH, ZVI concentration, N2 and air on Se(IV) removal. ZVI before and after reaction with Se(IV) was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Results indicated that ultrasound can lead to a significant synergy in the removal of Se(IV) by ZVI because ultrasound can promote the generation of OH and accelerate the advanced Fenton process. The primary reaction products of ZVI and Se(IV) were Se(0), ferrihydrite, and Fe2O3. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Evidence for leading mesons in anti p sup 4 He reactions at 0. 6 GeV c sup -1 incident momentum

    Energy Technology Data Exchange (ETDEWEB)

    Balestra, F.; Bossolasco, S.; Bussa, M.P.; Busso, L.; Fava, L.; Ferrero, L.; Grasso, A.; Maggiora, A.; Panzieri, D.; Piragino, G.; Piragino, R.; Tosello, F. (Ist. di Fisica Generale ' A. Avogadro' , Univ. of Turin (Italy) INFN, Sezione di Torino (Italy)); Bendiscioli, G.; Filippini, V.; Rotondi, A.; Salvini, P.; Venaglioni, A.; Zenoni, A. (Dipt. di Fisica Nucleare e Teoria, Univ. of Pavia (Italy) INFN, Sezione di Pavia (Italy)); Batusov, Yu.; Bunyatov, S.A.; Falomkin, I.V.; Nichitiu, F.; Pontecorvo, G.B.; Rozhdestvensky, A.M.; Sapozhnikov, M.G.; Tretyak, V.I. (Joint Inst. of Nuclear Research, Dubna (USSR)); Guaraldo, C. (Lab. Nazionali di Frascati dell' INFN (Italy)); Lodi Rizzini, E. (Dipt. di Automazione Industriale, Univ. of Brescia (Italy) INFN, Sezione di Pavia (Italy)); Haatuft, A.; Halsteinslid, A.; Myklebost, K.; Olsen, J.M. (Physics Dept., Univ. of Bergen (Norway)); Breivik, F.O.; Danielsen, K.M.; Jacobsen, T.; Soerensen, S.O. (Inst. of Physics, Univ. of Oslo (Norway))

    1991-01-01

    Leading mesons are seen in anti p {sup 4}He {yields} neutral strange particles at 0.6 GeV c{sup -1} incident momentum. These results differ somewhat from our previous results from anti p Ne-reactions. The concept of an ''effective target'' is useless. (orig.).

  19. An oxidative cross-coupling reaction of 4-hydroxydithiocoumarin and amines/thiols using a combination of I2 and TBHP: access to lead molecules for biomedical applications.

    Science.gov (United States)

    Mahato, Karuna; Arora, Neha; Ray Bagdi, Prasanta; Gattu, Radhakrishna; Ghosh, Siddhartha Sankar; Khan, Abu T

    2018-02-06

    A metal-free I 2 /TBHP induced highly atom economic and operationally simple oxidative cross-coupling reaction has been developed for the direct synthesis of sulfenamides/sulfanes/disulfides from the reaction of 4-hydroxydithiocoumarin and amines/thiols. The novelties of the present protocol are unprecedented S-C bond formation in addition to S-N and S-S bonds, shorter reaction time, mild and environmentally benign reaction conditions, functional group tolerance and moderate to excellent yields. Moreover, the four newly synthesized compounds namely 4q, 6d, 6e and 7a exhibit anti-proliferative activity against the breast cancer cell line MCF7, and may be lead molecules for future drug development.

  20. Lead extraction from waste funnel cathode-ray tubes glasses by reaction with silicon carbide and titanium nitride

    International Nuclear Information System (INIS)

    Yot, Pascal G.; Mear, Francois O.

    2009-01-01

    As a possibility to clean waste CRT glass, treatment of lead-containing glass with a reducing agent, SiC or TiN, leads to a porous material containing metallic lead, Pb(0), located on the surface of the pore, and unreduced lead, Pb(II). The influences of reducing agent content, of the time, and at last of the temperature on lead reduction were analysed. Our investigations have pointed out significant differences as a function of the used reducing agent. CRT glass heat treated with SiC lead to less Pb(0), compared to TiN as shown by X-ray diffraction, and differential scanning calorimetry (DSC). It has been also evidenced that lead reduction occurs on randomized zones inside the sample leading to macroscopic lead beads inside glassy samples. XPS and XAS measurements were also carried out to investigate the local structure of lead and have evidenced a change of role of lead inside the glassy framework in function of the used conditions.

  1. Determining Role of the Chain Mechanism in the Temperature Dependence of the Gas-Phase Rate of Combustion Reactions

    Science.gov (United States)

    Azatyan, V. V.; Bolod'yan, I. A.; Kopylov, N. P.; Kopylov, S. N.; Prokopenko, V. M.; Shebeko, Yu. N.

    2018-05-01

    It is shown that the strong dependence of the rate of gas-phase combustion reactions on temperature is determined by the high values of the reaction rate constants of free atoms and radicals. It is established that with a branched chain mechanism, a special role in the reaction rate temperature dependence is played by positive feedback between the concentrations of active intermediate species and the rate of their change. The role of the chemical mechanism in the temperature dependence of the process rate with and without inhibitors is considered.

  2. From Cycling Between Coupled Reactions to the Cross-Bridge Cycle: Mechanical Power Output as an Integral Part of Energy Metabolism

    Directory of Open Access Journals (Sweden)

    Frank Diederichs

    2012-10-01

    Full Text Available ATP delivery and its usage are achieved by cycling of respective intermediates through interconnected coupled reactions. At steady state, cycling between coupled reactions always occurs at zero resistance of the whole cycle without dissipation of free energy. The cross-bridge cycle can also be described by a system of coupled reactions: one energising reaction, which energises myosin heads by coupled ATP splitting, and one de-energising reaction, which transduces free energy from myosin heads to coupled actin movement. The whole cycle of myosin heads via cross-bridge formation and dissociation proceeds at zero resistance. Dissipation of free energy from coupled reactions occurs whenever the input potential overcomes the counteracting output potential. In addition, dissipation is produced by uncoupling. This is brought about by a load dependent shortening of the cross-bridge stroke to zero, which allows isometric force generation without mechanical power output. The occurrence of maximal efficiency is caused by uncoupling. Under coupled conditions, Hill’s equation (velocity as a function of load is fulfilled. In addition, force and shortening velocity both depend on [Ca2+]. Muscular fatigue is triggered when ATP consumption overcomes ATP delivery. As a result, the substrate of the cycle, [MgATP2−], is reduced. This leads to a switch off of cycling and ATP consumption, so that a recovery of [ATP] is possible. In this way a potentially harmful, persistent low energy state of the cell can be avoided.

  3. Histopathology and immune histochemistry of red tattoo reactions. Interface dermatitis is the lead pathology, with increase in T-lymphocytes and Langerhans cells suggesting an allergic pathomechanism.

    Science.gov (United States)

    Høgsberg, T; Thomsen, B M; Serup, J

    2015-11-01

    The majority of tattoo reactions are affiliated to red pigmented areas and often suspected to be allergic in nature. A sizeable series of biopsies of such reactions has not previously been performed. The aim of this study was to type and grade epidermal and dermal changes in tattoo reactions to red/red nuances by microscopy and immunochemistry relevant for the assessment of a possible allergic pathomechanism. Skin biopsies were taken from red tattoo reactions, graded by conventional microscopy and stained for T and B-lymphocytes, Langerhans cells, macrophages and tumour necrosis factor (TNF)-α. The study included 19 biopsies from 19 patients. The culprit colours were red/pink (n = 15) and purple/bordeaux (n = 4). Interface dermatitis was clearly the lead pathology found in 78% of samples, overlapped with granulomatous (in 32%) and pseudolymphomatous reaction patterns (in 32%). Epidermal hyperkeratosis (in 89%) was common as was leakage of red pigment across the dermo-epidermal junction, with transepidermal elimination (in 28%). The dermal cellular infiltration was dominated by T-lymphocytes (in 100%), Langerhans cells (in 95%) and macrophages (in 100%). TNF-α was common. The predominant histological pattern of chronic tattoo reactions in red/red nuances is interface dermatitis. T-lymphocytes and Langerhans cells are increased suggesting an allergic pathomechanism. TNF-α may contribute to reactions. In many cases, overlapping reactive patterns were identified. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  4. Structural evolution and reaction mechanism of lithium nickelate (LiNiO2 during the carbonation reaction

    Directory of Open Access Journals (Sweden)

    Daniela González-Varela

    2018-03-01

    Full Text Available Lithium nickelate (LiNiO2 was synthesized using the lithium excess method, and then characterized by X-ray diffraction, scanning electron microscopy and N2 adsorption-desorption. Finally, differential thermal and thermogravimetric analyses were performed in CO2 presence, at high temperatures. Results show that LiNiO2 is able to react with CO2 through a complex structural evolution process, where lithium atoms are released to produce Li2CO3, while some nickel atoms are rearranged on different Li1-xNi1+xO2 crystalline phases. LiNiO2-CO2 reaction kinetic parameters were determined assuming a first-order reaction, where kinetic constants tended to increase as a function of temperature. However, kinetic constant values did not follow a linear trend. This atypical behavior was attributed to LiNiO2 sintering and crystalline evolution performed as a function of temperature.

  5. High Electrocatalytic Response of a Mechanically Enhanced NbC Nanocomposite Electrode Towards Hydrogen Evolution Reaction

    KAUST Repository

    Coy, Emerson

    2017-08-22

    Resistant and efficient electrocatalysts for hydrogen evolution reaction (HER) are desired to replace scarce and commercially expensive platinum electrodes. Thin film electrodes of metal-carbides are a promising alternative due to their reduced price and similar catalytic properties. However, most of the studied structures to date neglect long lasting chemical and structural stability, focusing only on electrochemical efficiency. Herein we report on a new approach to easily deposit and control the micro/nanostructure of thin film electrodes based on niobium carbide (NbC) and their electrocatalytic response. We will show that, by improving the mechanical properties of the NbC electrodes, microstructure and mechanical resilience can be obtained whilst maintaining high electro catalytic response. We also address the influence of other parameters such as conductivity and chemical composition on the overall performance of the thin film electrodes. Finally, we show that nanocomposite NbC electrodes are promising candidates towards HER , and furthermore, that the methodology presented here is suitable to produce other transition metal carbides (TM-C) with improved catalytic and mechanical properties.

  6. Elucidation of Mechanisms and Selectivities of Metal-Catalyzed Reactions using Quantum Chemical Methodology.

    Science.gov (United States)

    Santoro, Stefano; Kalek, Marcin; Huang, Genping; Himo, Fahmi

    2016-05-17

    solving complex problems and proposing new detailed reaction mechanisms that rationalize the experimental findings. For each of the considered reactions, a consistent mechanism is presented, the experimentally observed selectivities are reproduced, and their sources are identified. Reproducing selectivities requires high accuracy in computing relative transition state energies. As demonstrated by the results summarized in this Account, this accuracy is possible with the use of the presented methodology, benefiting of course from a large extent of cancellation of systematic errors. It is argued that as the employed models become larger, the number of rotamers and isomers that have to be considered for every stationary point increases and a careful assessment of their energies is therefore necessary in order to ensure that the lowest energy conformation is located. This issue constitutes a bottleneck of the investigation in some cases and is particularly important when analyzing selectivities, since small energy differences need to be reproduced.

  7. Dissociation reactions of the 11Be one-neutron halo: the interplay between structure and reaction mechanism

    International Nuclear Information System (INIS)

    Anne, R.; Lewitowicz, M.; Saint-Laurent, M.G.; Arnell, S.E.; Jonson, B.; Nilsson, T.; Nyman, G.; Wilhelmsen Rolander, K.; Esbensen, H.; Wolski, D.

    1992-01-01

    Reactions of a radioactive 11 Be beam at 41 MeV/u have been investigated. The absolute magnitude of the differential cross-sections of the forward neutrons in the exclusive ( 10 Be + n) channel can be accounted for quantitatively in a simple model. The narrow distribution from high-Z targets turns out to arise from Coulomb dissociation whereas the broad distribution from the beryllium target is due to diffraction dissociation

  8. Quantum and Statistical Mechanics Applied to Singlet Carbenes, Pericyclic Reactions, and Condensed Phase Phenomena

    Science.gov (United States)

    Evanseck, Jeffrey Donald

    The completed research covers a broad range of theoretical applications in organic chemistry. It is divided into three chapters which covers the chemistry of singlet carbenes (Chapter 1), substituent effects in pericyclic rearrangements (Chapter 2), and the effects of solvent on the reactivity of organic reactions (Chapter 3). The selectivity between 1,2- and 1,4-intramolecular additions to restricted diene systems has been investigated. A decrease in activation energy for the intramolecular cycloaddition is noted for systems which approach the idealized geometry found with intermolecular addition of carbenes to olefins. Direct substitution at the carbene site dramatically effects the predicted activation barriers for 1,2-hydrogen shifts. An excellent correlation between the activation energy and a substituents sigma_sp {rm R}{rm o} parameters has been demonstrated. The long standing problem of orbital alignment influences on the selectivity of 1,2-hydrogen arrangements shows significant geometric distortions, yet has little influence on the rates of singlet alkylcarbene rearrangements. The exo-selectivities observed for 1,2-shifts in rigid systems are explained by torsional and steric interactions which develop in the transition structures. Substituent effects on pericyclic reactions have been computed for several conrotatory and disrotatory electrocyclizations. The six-electron disrotatory electrocyclization of 1-substituted hexatrienes displays a strong electronic component in determining stereoselectivity, despite incredible steric interference. The eight-electron conrotatory electrocyclization transition structure of 1-substituted octatetraene has an unusual helical transition structure which does not differentiate between substituent position. The effects of solvents on the acidity differences between E and Z esters has supplemented earlier ab initio quantum mechanical results on the enhanced acidity of Meldrum's acid. Monte Carlo simulations predict a

  9. On rates and mechanisms of OH and O3 reactions with isoprene-derived hydroxy nitrates.

    Science.gov (United States)

    Lee, Lance; Teng, Alex P; Wennberg, Paul O; Crounse, John D; Cohen, Ronald C

    2014-03-06

    Eight distinct hydroxy nitrates are stable products of the first step in the atmospheric oxidation of isoprene by OH. The subsequent chemical fate of these molecules affects global and regional production of ozone and aerosol as well as the location of nitrogen deposition. We synthesized and purified 3 of the 8 isoprene hydroxy nitrate isomers: (E/Z)-2-methyl-4-nitrooxybut-2-ene-1-ol and 3-methyl-2-nitrooxybut-3-ene-1-ol. Oxidation of these molecules by OH and ozone was studied using both chemical ionization mass spectrometry and thermo-dissociation laser induced fluorescence. The OH reaction rate constants at 300 K measured relative to propene at 745 Torr are (1.1 ± 0.2) × 10(-10) cm(3) molecule(-1) s(-1) for both the E and Z isomers and (4.2 ± 0.7) × 10(-11) cm(3) molecule(-1) s(-1) for the third isomer. The ozone reaction rate constants for (E/Z)-2-methyl-4-nitrooxybut-2-ene-1-ol are (2.7 ± 0.5) × 10(-17) and (2.9 ± 0.5) × 10(-17) cm(3) molecule(-1) s(-1), respectively. 3-Methyl-2-nitrooxybut-3-ene-1-ol reacts with ozone very slowly, within the range of (2.5-5) × 10(-19) cm(3) molecule(-1) s(-1). Reaction pathways, product yields, and implications for atmospheric chemistry are discussed. A condensed mechanism suitable for use in atmospheric chemistry models is presented.

  10. Global reaction mechanism for the auto-ignition of full boiling range gasoline and kerosene fuels

    Science.gov (United States)

    Vandersickel, A.; Wright, Y. M.; Boulouchos, K.

    2013-12-01

    Compact reaction schemes capable of predicting auto-ignition are a prerequisite for the development of strategies to control and optimise homogeneous charge compression ignition (HCCI) engines. In particular for full boiling range fuels exhibiting two stage ignition a tremendous demand exists in the engine development community. The present paper therefore meticulously assesses a previous 7-step reaction scheme developed to predict auto-ignition for four hydrocarbon blends and proposes an important extension of the model constant optimisation procedure, allowing for the model to capture not only ignition delays, but also the evolutions of representative intermediates and heat release rates for a variety of full boiling range fuels. Additionally, an extensive validation of the later evolutions by means of various detailed n-heptane reaction mechanisms from literature has been presented; both for perfectly homogeneous, as well as non-premixed/stratified HCCI conditions. Finally, the models potential to simulate the auto-ignition of various full boiling range fuels is demonstrated by means of experimental shock tube data for six strongly differing fuels, containing e.g. up to 46.7% cyclo-alkanes, 20% napthalenes or complex branched aromatics such as methyl- or ethyl-napthalene. The good predictive capability observed for each of the validation cases as well as the successful parameterisation for each of the six fuels, indicate that the model could, in principle, be applied to any hydrocarbon fuel, providing suitable adjustments to the model parameters are carried out. Combined with the optimisation strategy presented, the model therefore constitutes a major step towards the inclusion of real fuel kinetics into full scale HCCI engine simulations.

  11. Thermal analysis experiment for elucidating sodium-water chemical reaction mechanism in steam generator of sodium-cooled fast reactor

    International Nuclear Information System (INIS)

    Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki

    2012-01-01

    For the purpose of elucidating the mechanism of the sodium-water surface reaction in a steam generator of sodium-cooled fast reactors, kinetic study of the sodium (Na)-sodium hydroxide (NaOH) reaction has been carried out by using Differential Thermal Analysis (DTA) technique. The parameters, including melting points of Na and NaOH, phase transition temperature of NaOH, Na-NaOH reaction temperature, and decomposition temperature of sodium hydride (NaH) have been identified from DTA curves. Based on the measured reaction temperature, rate constant of sodium monoxide (Na 2 O) generation was obtained. Thermal analysis results indicated that Na 2 O generation at the secondary overall reaction should be considered during the sodium-water reaction. (author)

  12. Alternative interpretation of low-energy nuclear reaction processes with deuterated metals based on the Bose-Einstein condensation mechanism

    International Nuclear Information System (INIS)

    Yeong, E. Kim; Passell, Thomas O.

    2006-01-01

    Recently, a generalization of the Bose-Einstein condensation (BEC) mechanism has been made to a ground-state mixture of two different species of positively charged bosons in harmonic traps. The theory has been used to describe (D + Li) reactions in the low energy nuclear reaction (LENR) processes in condensed matter and predicts that the (D + Li) reaction rates can be larger than (D + D) reaction rates by as much as a factor of ∼ 50, implying that (D + Li) reactions may be occurring in addition to the (D + D) reactions. A survey of the existing data from LENR experiments is carried out to check the validity of the theoretical prediction. We conclude that there is compelling experimental evidence which support the theoretical prediction. New experimental tests of the theoretical prediction are suggested. (authors)

  13. Alternative Interpretation of Low-Energy Nuclear Reaction Processes with Deuterated Metals Based on the Bose-Einstein Condensation Mechanism

    Science.gov (United States)

    Kim, Yeong E.; Passell, Thomas O.

    2006-02-01

    Recently, a generalization of the Bose-Einstein condensation (BEC) mechanism has been made to a ground-state mixture of two different species of positively charged bosons in harmonic traps. The theory has been used to describe (D + Li) reactions in the low energy nuclear reaction (LENR) processes in condensed matter and predicts that the (D + Li) reaction rates can be larger than (D + D) reaction rates by as much as a factor of ~50, implying that (D + Li) reactions may be occuring in addition to the (D + D) reactions. A survey of the existing data from LENR experiments is carried out to check the validity of the theoretical prediction. We conclude that there is compelling experimental evidence which support the theoretical prediction. New experimental tests of the theoretical prediction are suggested.

  14. Alternative interpretation of low-energy nuclear reaction processes with deuterated metals based on the Bose-Einstein condensation mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Yeong, E. Kim [Department of Physics, Purdue University, West Lafayette, IN 47907 (United States); Passell, Thomas O. [TOP Consulting, PO Box 336, Palo Alto, CA 94302-0336 (United States)

    2006-07-01

    Recently, a generalization of the Bose-Einstein condensation (BEC) mechanism has been made to a ground-state mixture of two different species of positively charged bosons in harmonic traps. The theory has been used to describe (D + Li) reactions in the low energy nuclear reaction (LENR) processes in condensed matter and predicts that the (D + Li) reaction rates can be larger than (D + D) reaction rates by as much as a factor of {approx} 50, implying that (D + Li) reactions may be occurring in addition to the (D + D) reactions. A survey of the existing data from LENR experiments is carried out to check the validity of the theoretical prediction. We conclude that there is compelling experimental evidence which support the theoretical prediction. New experimental tests of the theoretical prediction are suggested. (authors)

  15. Kinetic calorimetry in the study of the mechanism of low-temperature chemical reactions

    Science.gov (United States)

    Barkalov, I. M.; Kiryukhin, D. P.

    Chemical reactions are always followed by a change in the reacting system enthalpy, hence, calorimetry as a method of enthalpy and heat capacity measuring is a universal and, sometimes, even the only possible way of studying chemical reaction kinetics. Throughout its long history, the calorimeter, having preserved the positions of the main method of thermodynamic studies, has conquered a new field of application: that of kinetic study of chemical reactions. The advantages and disadvantages of the kinetic calorimeter are now obvious. First, the advantages are: (1) the possibility of measuring the rate of a chemical reaction without any special requirements being imposed on the reaction medium (solid, viscous, multicomponent systems); (2) the high efficiency: a large volume of kinetic information in one experiment and a non-destructive character of changes; (3) the possibility of measuring directly in the field of ionizing radiation (γ-radiation, accelerated electrons) and light; and (4) recording of the chemical conversion directly at the time of its occurrence. The disadvantages of this method are: (1) the high inertia of standard calorimeter systems (τC⋍102-103S), which restricts the possibilities of studying fast processes; and (2) the complexity of the correct organization of the calorimeter experiment when the parameters of the process are changed (overheating in the sample, conversion of the process to explosive and auto wave regimens). One of the oldest and most universal methods of studying the mechanism of chemical reactions, calorimetry, is now passing through a period of turbulent development due to the advances in electronics and computerization. The wide variety of types of calorimeter set-ups and the large assortment of measurement schemes in the currently described methods complicate the experimental selection of the necessary instrument rather than facilitate it. The basic principles of the method, the types of calorimeters, and the measuring

  16. Effects of alpha-amylase reaction mechanisms on analysis of resistant-starch contents.

    Science.gov (United States)

    Moore, Samuel A; Ai, Yongfeng; Chang, Fengdan; Jane, Jay-lin

    2015-01-22

    This study aimed to understand differences in the resistant starch (RS) contents of native and modified starches obtained using two standard methods of RS content analysis: AOAC Method 991.43 and 2002.02. The largest differences were observed in native potato starch, cross-linked wheat distarch phosphate, and high-amylose corn starch stearic-acid complex (RS5) between using AOAC Method 991.43 with Bacillus licheniformis α-amylase (BL) and AOAC Method 2002.02 with porcine pancreatic α-amylase (PPA). To determine possible reasons for these differences, we hydrolyzed raw-starch granules with BL and PPA with equal activity at pH 6.9 and 37°C for up to 84 h and observed the starch granules displayed distinct morphological differences after the hydrolysis. Starches hydrolyzed by BL showed erosion on the surface of the granules; those hydrolyzed by PPA showed pitting on granule surfaces. These results suggested that enzyme reaction mechanisms, including the sizes of the binding sites and the reaction patterns of the two enzymes, contributed to the differences in the RS contents obtained using different methods of RS analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Reaction Mechanism and Distribution Behavior of Arsenic in the Bottom Blown Copper Smelting Process

    Directory of Open Access Journals (Sweden)

    Qinmeng Wang

    2017-08-01

    Full Text Available The control of arsenic, a toxic and carcinogenic element, is an important issue for all copper smelters. In this work, the reaction mechanism and distribution behavior of arsenic in the bottom blown copper smelting process (SKS process were investigated and compared to the flash smelting process. There are obvious differences of arsenic distribution in the SKS process and flash process, resulting from the differences of oxygen potentials, volatilizations, smelting temperatures, reaction intensities, and mass transfer processes. Under stable production conditions, the distributions of arsenic among matte, slag, and gas phases are 6%, 12%, and 82%, respectively. Less arsenic is reported in the gas phase with the flash process than with the SKS process. The main arsenic species in gas phase are AsS (g, AsO (g, and As2 (g. Arsenic exists in the slag predominantly as As2O3 (l, and in matte as As (l. High matte grade is harmful to the elimination of arsenic to gas. The changing of Fe/SiO2 has slight effects on the distributions of arsenic. In order to enhance the removal of arsenic from the SKS smelting system to the gas phase, low oxygen concentration, low ratios of oxygen/ore, and low matte grade should be chosen. In the SKS smelting process, no dust is recycled, and almost all dust is collected and further treated to eliminate arsenic and recover valuable metals by other process streams.

  18. Studies on adsorption, reaction mechanisms and kinetics for photocatalytic degradation of CHD, a pharmaceutical waste.

    Science.gov (United States)

    Sarkar, Santanu; Bhattacharjee, Chiranjib; Curcio, Stefano

    2015-11-01

    The photocatalytic degradation of chlorhexidine digluconate (CHD), a disinfectant and topical antiseptic and adsorption of CHD catalyst surface in dark condition has been studied. Moreover, the value of kinetic parameters has been measured and the effect of adsorption on photocatalysis has been investigated here. Substantial removal was observed during the photocatalysis process, whereas 40% removal was possible through the adsorption route on TiO2 surface. The parametric variation has shown that alkaline pH, ambient temperature, low initial substrate concentration, high TiO2 loading were favourable, though at a certain concentration of TiO2 loading, photocatalytic degradation efficiency was found to be maximum. The adsorption study has shown good confirmation with Langmuir isotherm and during the reaction at initial stage, it followed pseudo-first-order reaction, after that Langmuir Hinshelwood model was found to be appropriate in describing the system. The present study also confirmed that there is a significant effect of adsorption on photocatalytic degradation. The possible mechanism for adsorption and photocatalysis has been shown here and process controlling step has been identified. The influences of pH and temperature have been explained with the help of surface charge distribution of reacting particles and thermodynamic point of view respectively. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. Transparent Ethenylene-Bridged Polymethylsiloxane Aerogels: Mechanical Flexibility and Strength and Availability for Addition Reaction.

    Science.gov (United States)

    Shimizu, Taiyo; Kanamori, Kazuyoshi; Maeno, Ayaka; Kaji, Hironori; Doherty, Cara M; Nakanishi, Kazuki

    2017-05-09

    Transparent, low-density ethenylene-bridged polymethylsiloxane [Ethe-BPMS, O 2/2 (CH 3 )Si-CH═CH-Si(CH 3 )O 2/2 ] aerogels from 1,2-bis(methyldiethoxysilyl)ethene have successfully been synthesized via a sol-gel process. A two-step sol-gel process composed of hydrolysis under acidic conditions and polycondensation under basic conditions in a liquid surfactant produces a homogeneous pore structure based on cross-linked nanosized colloidal particles. Visible-light transmittance of the aerogels varies with the concentration of the base catalyst and reaches as high as 87% (at a wavelength of 550 nm for a 10 mm thick sample). Gelation and aging temperature strongly affect the deformation behavior of the resultant aerogels against uniaxial compression, and the obtained aerogels prepared at 80 °C show high elasticity after being unloaded. This highly resilient behavior is primarily derived from the rigidity of ethenylene groups, which is confirmed by a comparison with other aerogels with similar molecular structures, ethylene-bridged polymethylsiloxane and polymethylsilsesquioxane. Applicability of the addition reaction using a Diels-Alder reaction of benzocyclobutene has also been investigated, revealing that a successful addition takes place on the ethenylene linkings, which is verified using Raman and solid-state NMR spectroscopies. Insights into the effect of molecular structure on mechanical properties and the availability of surface functionalization provided in this study are important for realizing transparent aerogels with the desired functionality.

  20. The quantum-chemical investigation of N-cyclization reaction mechanism for epichlorohydrin aminolysis products

    Directory of Open Access Journals (Sweden)

    Andrey V. Tokar

    2014-12-01

    Full Text Available The mechanism of intramolecular cyclization for products of epichlorohydrin aminolysis by secondary amines has been investigated at ab initio level of theory. By comparative analysis of energetic characteristics, which obtained in vacuo as well as in acetonitrile solution with the trace quantities of water as an «active» solvation partner of reaction, it has been shown a decisive role of solvent, which occurs mainly at the expense of the polarizable effects for nonspecific solvation. Indeed, the addition to the substrate of one water molecule have decreased corresponding EACT values only 24.1 kJ/mol, while the appearance of acetonitrile surroundings have the same influence ~42.0 kJ/mol. The results of calculations are in good agreement with that data, which have been obtained for such type modeling previously.

  1. A coupled model of transport-reaction-mechanics with trapping. Part I - Small strain analysis

    Science.gov (United States)

    Salvadori, A.; McMeeking, R.; Grazioli, D.; Magri, M.

    2018-05-01

    A fully coupled model for mass and heat transport, mechanics, and chemical reactions with trapping is proposed. It is rooted in non-equilibrium rational thermodynamics and assumes that displacements and strains are small. Balance laws for mass, linear and angular momentum, energy, and entropy are stated. Thermodynamic restrictions are identified, based on an additive strain decomposition and on the definition of the Helmholtz free energy. Constitutive theory and chemical kinetics are studied in order to finally write the governing equations for the multi-physics problem. The field equations are solved numerically with the finite element method, stemming from a three-fields variational formulation. Three case-studies on vacancies redistribution in metals, hydrogen embrittlement, and the charge-discharge of active particles in Li-ion batteries demonstrate the features and the potential of the proposed model.

  2. A Reaction-Diffusion-Based Coding Rate Control Mechanism for Camera Sensor Networks

    Directory of Open Access Journals (Sweden)

    Naoki Wakamiya

    2010-08-01

    Full Text Available A wireless camera sensor network is useful for surveillance and monitoring for its visibility and easy deployment. However, it suffers from the limited capacity of wireless communication and a network is easily overflown with a considerable amount of video traffic. In this paper, we propose an autonomous video coding rate control mechanism where each camera sensor node can autonomously determine its coding rate in accordance with the location and velocity of target objects. For this purpose, we adopted a biological model, i.e., reaction-diffusion model, inspired by the similarity of biological spatial patterns and the spatial distribution of video coding rate. Through simulation and practical experiments, we verify the effectiveness of our proposal.

  3. A reaction-diffusion-based coding rate control mechanism for camera sensor networks.

    Science.gov (United States)

    Yamamoto, Hiroshi; Hyodo, Katsuya; Wakamiya, Naoki; Murata, Masayuki

    2010-01-01

    A wireless camera sensor network is useful for surveillance and monitoring for its visibility and easy deployment. However, it suffers from the limited capacity of wireless communication and a network is easily overflown with a considerable amount of video traffic. In this paper, we propose an autonomous video coding rate control mechanism where each camera sensor node can autonomously determine its coding rate in accordance with the location and velocity of target objects. For this purpose, we adopted a biological model, i.e., reaction-diffusion model, inspired by the similarity of biological spatial patterns and the spatial distribution of video coding rate. Through simulation and practical experiments, we verify the effectiveness of our proposal.

  4. Catapult mechanism for fast particle emission in fission and heavy ion reactions

    International Nuclear Information System (INIS)

    Maedler, P.

    1984-01-01

    The fission processes of slabs of nuclear matter is modelled in the Hartree-Fock time dependence approximation by adding an initial collective velocity field to the static self-consistent solution. In dependence on its amplitude either large amplitude density oscillations are excited or fission occurs. The final disintegration of the slab proceeds on a time scale 10 -22 s and is characterized by a sharp peak in the actual velocity field in the region of the ''snatching'' inner low density tails. A characteristic time later a low density lump correlated with a peak in the velocity field energies in front of the fragments. These particles are called ''catapult particles''. Recent experimental results possibly provide evidence for catapult neutrons in low-energy fission. The significance of the catapult mechanism for fast particle emission in the exit channel of heavy ion reactions is discussed

  5. Influence of alkali-silica reaction on the physical, mechanical, and structural behaviour of reinforced concrete

    DEFF Research Database (Denmark)

    Barbosa, Ricardo Antonio

    Alkali-silica reaction (ASR) is one of the major concrete deterioration mechanisms in the world. Cracking in concrete structures due to ASR has been observed worldwide. In Denmark numerous concrete structures have been built with a critical amount of ASR-reactive aggregate, mostly as porous opaline...... and porous calcareous opaline flint in the fine aggregate fraction. During the last few decades, an increasing number of bridges in Denmark have been severely damaged due to ASR. In the most severe cases, the ASR-damaged bridges have been demolished and reconstructed due to uncertainty about their residual...... following features in common: (a) significant amount of ASR cracks were observed on and inside the slabs, (b) the ASR cracks were oriented parallel to the plane of the slabs, and (c) ASR occurred in the fine aggregate fraction. In this PhD study, both the compressive strength and tensile strength of drilled...

  6. The influence of the entrance channel mass asymmetry on the reaction mechanism

    International Nuclear Information System (INIS)

    Agarwal, S.; Galin, J.; Gatty, B.; Guerreau, D.; Lefort, M.; Tarrago, X.; Babinet, R.; Girard, J.

    1980-01-01

    We have tried to investigate the influence of the entrance channel mass asymmetry on the reaction mechanisms associated with heavy ion collisions. Two systems, one very much asymmetric (O + Mo) and the other one almost symmetric (Cr + Fe), were studied in detail by measuring evaporation residues, deep inelastic collision products and fission fragments. An important fraction of the fragments observed in the Cr + Fe system exhibits all the characteristics of fission fragments. The analysis of these data seems to indicate that these fission like products are most likely emitted by a long lived composite system having not reached full statistical equilibrium for all the degrees of freedom. As a consequence, the fusion cross section for this symmetric system is too low as compared to predictions based on a critical distance approach for fusion, whereas the asymmetric system (O + Mo) is well understood in terms of the same model. (orig.)

  7. Implicit coupling of turbulent diffusion with chemical reaction mechanisms for prognostic atmospheric dispersion models

    Energy Technology Data Exchange (ETDEWEB)

    Berlowitz, D.R.

    1996-11-01

    In the last few decades the negative impact by humans on the thin atmospheric layer enveloping the earth, the basis for life on this planet, has increased steadily. In order to halt, or at least slow down this development, the knowledge and study of these anthropogenic influence has to be increased and possible remedies have to be suggested. An important tool for these studies are computer models. With their help the atmospheric system can be approximated and the various processes, which have led to the current situation can be quantified. They also serve as an instrument to assess short or medium term strategies to reduce this human impact. However, to assure efficiency as well as accuracy, a careful analysis of the numerous processes involved in the dispersion of pollutants in the atmosphere is called for. This should help to concentrate on the essentials and also prevent excessive usage of sometimes scarce computing resources. The basis of the presented work is the EUMAC Zooming Model (ETM), and particularly the component calculating the dispersion of pollutants in the atmosphere, the model MARS. The model has two main parts: an explicit solver, where the advection and the horizontal diffusion of pollutants are calculated, and an implicit solution mechanism, allowing the joint computation of the change of concentration due to chemical reactions, coupled with the respective influence of the vertical diffusion of the species. The aim of this thesis is to determine particularly the influence of the horizontal components of the turbulent diffusion on the existing implicit solver of the model. Suggestions for a more comprehensive inclusion of the full three dimensional diffusion operator in the implicit solver are made. This is achieved by an appropriate operator splitting. A selection of numerical approaches to tighten the coupling of the diffusion processes with the calculation of the applied chemical reaction mechanisms are examined. (author) figs., tabs., refs.

  8. Examples of processing problematic waste and material. A-3. Processing of lead by mechanical decontamination at UKAEA Harwell

    International Nuclear Information System (INIS)

    2006-01-01

    The UKAEA and its contractor (NNC) have decontaminated lead blocks arising from the decommissioning of a metallurgical site that comprised three concrete shielded remote handling cells and 36 lead shielded enclosures. The primary decommissioning and dismantling work entailed the dismantling of the 36 lead enclosures, which were expected to yield over 1000 t of lead shielding bricks as waste. During the initial dismantling of the lead shielded enclosures, all the lead bricks were monitored for radioactive contamination; clean items were segregated and set aside for detailed clearance and assurance checks. The contaminated blocks were sent for assessment and decontamination treatment, as necessary. The decontamination process utilized a purpose built partitioned containment tent, ventilated with a HEPA filtration system, so that the receipt, decontamination and radiological monitoring of individual items could be segregated in order to minimize any cross-contamination. The dismantled lead blocks comprised a range of standard thicknesses (2, 4, 9 and 10 in, or 3, 8, 13 and 15 cm) and incorporated a variety of chevron, concave and convex shapes, which are utilized to avoid weaknesses within the assembled shielding. The primary technical issues for the mechanical processing of the contaminated lead blocks were consideration of the individual lead brick shapes (i.e. the bricks were contoured) and the individual weight of the bricks, which had a range of 10-75 kg. The preferred option was a manual dry cutting technique using a handheld rotary industrial planer (the selected planer is normally associated with the joinery trade). The dry cutting option considered the malleability of the lead, which under certain circumstances during dry cutting could give rise to localized heating effects, leading to melted lead over the cutting surface, resulting in limited effectiveness in the removal of the contaminated layer. To mitigate this effect the planer was set to take cuts

  9. A zinc enolate of amide: Preparation and application in reformasky-like reaction leading to β-hydroxy amides

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Hyun Hee; Kim, Seung Hoi [Dept. of Chemistry, Dankook University, Cheonan (Korea, Republic of)

    2015-04-15

    One of the best known functionalized organic complexes is the β-hydroxy carbonyl compound. This unique functionality has been frequently found in naturally occurring bioactive derivatives. The cross-coupling reaction of A with aldehydes were carried out in the absence of any catalyst and completed in most cases within 1.0 h at room temperature. We have developed an efficient synthetic route for the preparation of β-hydroxy amides. The method involved the preparation of room-temperature-stable organo zinc reagents (A, B, and C) in THF and their subsequent coupling reactions with various carbonyl derivatives under mild conditions. Significantly, this approach using zinc enolate of amides could expand the scope of Reformatsky-like reactions. Further studies to elucidate this synthetic protocol are currently under way in our laboratory.

  10. Lead telluride with increased mechanical stability for cylindrical thermoelectric generators; Bleitellurid mit erhoehter mechanischer Stabilitaet fuer zylindrische thermoelektrische Generatoren

    Energy Technology Data Exchange (ETDEWEB)

    Schmitz, Andreas

    2013-04-30

    The aim of this work is to improve the mechanical stability of lead telluride (PbTe), trying to vary its mechanical properties independently from its thermoelectric properties. Thus the influence of material preparation as well as different dopants on the mechanical and thermoelectric properties of lead telluride is being analysed. When using appropriately set process parameters, milling and sintering of lead telluride increases the material's hardness. With sintering temperatures exceeding 300 C stable material of high relative density can be achieved. Milling lead telluride generates lattice defects leading to a reduction of the material's charge carrier density. These defects can be reduced by increased sintering temperatures. Contamination of the powder due to the milling process leads to bloating during thermal cycling and thus reduced density of the sintered material. In addition to that, evaporation of tellurium at elevated temperatures causes instability of the material's thermoelectric properties. Based on the experimental results obtained in this work, the best thermoelectric and mechanical properties can be obtained by sintering coarse powders at around 400 C. Within this work a concept was developed to vary the mechanical properties of lead telluride via synthesis of PbTe with electrically nondoping elements, which thus may keep the thermoelectric properties unchanged. Therefore, the mechanical and thermoelectric properties of Pb{sub 1-x}Ca{sub x}Te were investigated. Doping pure PbTe with calcium causes a significant increase of the material's hardness while only slightly decreasing the charge carrier density and thus keeping the thermoelectric properties apart from a slight reduction of the electrical conductivity nearly unchanged. The abovementioned concept is proven using sodium doped lead telluride, as it is used for thermoelectric generators: The additional doping with calcium again increases the material's hardness while its thermoelectric

  11. Lead telluride with increased mechanical stability for cylindrical thermoelectric generators; Bleitellurid mit erhoehter mechanischer Stabilitaet fuer zylindrische thermoelektrische Generatoren

    Energy Technology Data Exchange (ETDEWEB)

    Schmitz, Andreas

    2013-04-30

    The aim of this work is to improve the mechanical stability of lead telluride (PbTe), trying to vary its mechanical properties independently from its thermoelectric properties. Thus the influence of material preparation as well as different dopants on the mechanical and thermoelectric properties of lead telluride is being analysed. When using appropriately set process parameters, milling and sintering of lead telluride increases the material's hardness. With sintering temperatures exceeding 300 C stable material of high relative density can be achieved. Milling lead telluride generates lattice defects leading to a reduction of the material's charge carrier density. These defects can be reduced by increased sintering temperatures. Contamination of the powder due to the milling process leads to bloating during thermal cycling and thus reduced density of the sintered material. In addition to that, evaporation of tellurium at elevated temperatures causes instability of the material's thermoelectric properties. Based on the experimental results obtained in this work, the best thermoelectric and mechanical properties can be obtained by sintering coarse powders at around 400 C. Within this work a concept was developed to vary the mechanical properties of lead telluride via synthesis of PbTe with electrically nondoping elements, which thus may keep the thermoelectric properties unchanged. Therefore, the mechanical and thermoelectric properties of Pb{sub 1-x}Ca{sub x}Te were investigated. Doping pure PbTe with calcium causes a significant increase of the material's hardness while only slightly decreasing the charge carrier density and thus keeping the thermoelectric properties apart from a slight reduction of the electrical conductivity nearly unchanged. The abovementioned concept is proven using sodium doped lead telluride, as it is used for thermoelectric generators: The additional doping with calcium again increases the material's hardness while

  12. Mechanical and fatigue properties of martensitic 20X13 and austenitic 12X18H10T at interaction with lead nad lead-bismuth melts

    International Nuclear Information System (INIS)

    Yas'kiv, O.I.; Fedirko, V.M.

    2013-01-01

    The effect of Pb and Pb-Bi melts on mechanical properties and fatigue of Fe-13Cr and Fe-18Cr-10Ni-Ti steels in temperature interval 250...750 deg C has been investigated. It was shown that metal melts lead to increasing of strength of Fe-13Cr steel on 10...20 % as compared with vacuum and this effect increases with temperature rising. Fe-13Cr steel is prone to liquid metal embrittlement in temperature interval 350...450 deg C, particularly in Pb-Bi melt. Mechanical properties of Fe-18Cr-10Ni-Ti are not affected by metal melts. Both Pb and Pb-Bi assist in reducing of fatigue life of steels and this effect is more significant in Pb-Bi

  13. Contributions to the study of nuclear reactions mechanism induced by heavy ions on intermediate mass nuclei

    International Nuclear Information System (INIS)

    Avrigeanu, M.

    1982-01-01

    A detailed analysis is presented, based on Hauser-Feshbach statistical model calculations of the γ-ray excitation functions measured in the sup(74,76)Ge ( 12 C, xn) and sup(72,73)Ge ( 16 O,xnyp) reactions. The most usual quantities provided by the in beam γ-ray measurements such as the cross sections for the population of the final states as well as the decay scheme and the degree of alignment of these states mainly offer the means of testing models of both the reaction mechanism and nuclear properties of high excitation energies, since they concentrate information on the whole reaction process. Experimental information on sup(85,86)Sr and sup(85,86)Y, γ-decay scheme and the excitation functions for the population of the final states were obtained by sub(74,76)Ge ( 12 C,αn), n = 2-4, sup(74,76)Ge ( 14 N,xn) n = 3-5, sup(72,73)Ge ( 16 O,xnyp), x = 1-3, y=1 reactions at incident energies between 35 and 60 MW. Statistical model calculations in the Hauser-Feshbach formalism have been compared with the experimental γ-ray excitation functions. The competitive emission of neutrons, protons, alpha particles and gamma rays from the compound nucleus has been considered in the calculations. The calculations describe satisfactorily the total cross sections for the population of the 2n, 3n and 4n channels for 12 C + sup(74,76)Ge and 2n, np, 3n and 2np channels for 16 O + 72 Ge. The calculations are sensitive to the characteristics of the excited levels (such as spin values) but htis this sensitivity could be exploited with some reliability only if one makes use of a rather complete level scheme in the calculations. In the case of 2n, np, 3n and 2 np channels for 16 O+ 73 Ge one concludes on the reliability of consideration some structural aspects in the calculations

  14. Separation of reaction mechanisms at low energy. Study of the reactions: 27Al(d,p) 28Al, 24Mg(d,p) 25Mg, and 24Mg(d, α) 22Na

    International Nuclear Information System (INIS)

    Mermaz, M.

    1966-06-01

    The two sets of angular distributions of (d,p) reactions on Al and Mg, measured between 2 and 6 MeV, have given the possibility to test, in analysing the statistical fluctuations of cross-section, the validity of the separation of their mean values in two parts, one 'direct', another given by the statistical mechanism. With the same method of analysis we have studied excitation functions for several alpha groups of the reaction 24 Mg(d, α) 22 Na and given an evidence for an intermediate structure for the alpha channel leading to the 3. excited state of 22 Na. The angular distribution of the wide resonance at 15.9 MeV in 26 Al has been obtained. (author) [fr

  15. In situ X-ray diffraction study of the electrochemical reaction on lead electrodes in sulphate electrolytes

    International Nuclear Information System (INIS)

    Angerer, P.; Mann, R.; Gavrilovic, A.; Nauer, G.E.

    2009-01-01

    The anodic oxidation of pure lead in two acidic sulphate electrolytes with identical ionic strength (pH ∼ 0 and pH ∼ -0.1) was studied by in situ grazing incidence X-ray diffraction method (GIXD). Crystalline products such as lead sulphate (anglesite, PbSO 4 , orthorhombic), α- and β-lead dioxide (α-PbO 2 , orthorhombic, and β-PbO 2 , tetragonal), and tribasic lead sulphate hydrate with the stoichiometric composition 3PbO.PbSO 4 .H 2 O (triclinic) were detected at defined potentials. A method for the semi-quantitative determination of the thickness of the deposited layer from diffraction data is described. After the in situ measurement, the washed and dried working electrodes were additionally characterized ex situ by GIXD measurements at different angles of incidence. The phase litharge (lead oxide, t-PbO, tetragonal) and lead sulphate were observed at the surface of the lead substrate. The quantitative evaluation of the diffraction intensity of this measurement series enables the modelling of a qualitative depth profile of the layer generated during the electrochemical treatment. The anglesite phase is located in the uppermost layer, while the litharge phase was detected closer to the lead substrate

  16. Mechanisms for formation of organic acids in gas-phase reactions of ozone and hydroxyl radical with dialkenes and unsaturated carbonyls

    Science.gov (United States)

    Chien, Chao-Jung

    2001-07-01

    Carboxylic acids are ubiquitous throughout the troposphere and may contribute significant fractions of the free acidity in some remote areas. One of the important sources of these carboxylic acids is thought to be photochemical transformation of biogenic hydrocarbons such as isoprene. For the work reported here, atmospheric samples from University of North Carolina dual outdoor environmental chamber under simulated urban atmospheric conditions were analyzed for carboxylic acids. Both OH radicals and O3 initiated photooxidation reaction experiments were performed for isoprene, along with its structural analogs, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene, and their primary photooxidation products, methacrolein, acrolein, and methyl vinyl ketone. Among the detected carboxylic acids were formic, acetic, and several multifunctional carboxylic acids, including methacrylic, acrylic, glyoxylic, and glycolic acids. Quantification of most carboxylic acid products was also established. Formation yields of carboxylic acids from the reactions of O3 with studied compounds were determined, and time-concentration series of the reactants and carboxylic acid products were measured to facilitate mechanism formulation. While the reaction mechanisms of Criegee biradicals arising from decomposition of primary ozonides are proposed to account for the observed carboxylic acid products in the ozonolysis of unsaturated hydrocarbons, reactions of peroxy acyl radicals with HO2 and/or other peroxy radicals are thought to be responsible for the formation of carboxylic acids during the OH-initiated reactions in the presence of NOx. In this study, smog chamber simulations have also been performed for selected compounds using Morpho, a photochemical kinetic simulation software package. Explicit photochemical mechanisms with O 3 and OH radicals that lead to formation of carboxylic acids were elaborated and implemented, and the simulation results were compared with those from other chemical

  17. Proton propagation through nuclei and the quasi-free reaction mechanism studied with (e,e'p) reactions

    International Nuclear Information System (INIS)

    Dutta, D.; Abbott, D.; Amatuni, T.A.

    1997-01-01

    Jefferson Lab experiment E91-013 measured the energy dependence of proton propagation in nuclei, using the quasi-free (e, e'p) reaction. The ratios of the experimental (e, e'p) cross-sections integrated over the quasi-free region to PWIA calculations are presented as a function of momentum transfer, (0.6 2 2 ) and target nucleus (C, Fe and Au). As a first step towards a longitudinal and transverse separation of the quasi-free cross-section, a super ratio of the measured to the calculated cross-sections at forward and backward angles is presented

  18. ONE PROBABLE MECHANISM OF THE LEARNING-MEMORY DAMAGE BY LEAD: THE CHANGES OF NOS IN HIPPOCAMPUS

    Institute of Scientific and Technical Information of China (English)

    王静; 赵义; 杨章民; 张进; 李积胜; 司履生; 王一理

    2003-01-01

    Objective To study the effects of lead on the activity and expression of nitric oxide synthase (NOS) and relationship between the effects of lead on learning-memory and changes of NOS in subfields of hippocampus. Methods Y-maze test was used to study the effects of lead on ability of learning-memory; NADPH-d histochemistry and immunohistochemistry methods were used to investigate the changes of NOS in subfields of hippocampus. Results Compared with the control group, the ability of learning- memory in lead-exposed rats was significantly decreased (P<0.05); the number of NOS positive neurons in CA1 region and dentate gyrus of lead-exposed rats was significantly decreased(P<0.05), but no marked changes in CA3 region; the number of nNOS positive neurons in CA1 of lead-exposed rats was also significantly decreased(P<0.05), but no obvious changes in CA3. Conclusion Lead could damage the ability of learning-memory in rats. Lead could decrease the activity and expression of NOS in hippocampus and had different effects on NOS in different subfields of hippocampus. The changes of NOS in hippocampus induced by lead may be the mechanism of the learning-memory damage by lead.

  19. 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.

  20. Different mechanisms for lead acetate, aluminum and cadmium sulfate in rat corpus cavernosum

    International Nuclear Information System (INIS)

    Senbel, Amira M.; Saad, Evan I.; Taha, Safaa S.; Mohamed, Hosny F.

    2016-01-01

    Introduction: Some heavy metals show adverse vascular and neurological effects, however, their effect on erection is underestimated. This study aims to investigate the effect of Pb, Cd and Al on erectile function and their potential mechanism of action in rats. Methods: Measurement of intracavernosal pressure/mean arterial pressure (ICP/MAP) changes elicited by electrical stimulation of cavernous nerve in anesthetized rats treated with Pb-acetate, Al-sulfate, or Cd-sulfate acutely, and subacutely for 7 days. Serum creatinine, testosterone, TBARs, GSH levels and metal accumulation in corpus cavernosum were measured. Results: Pb, Al and Cd significantly reduced ICP/MAP in rats after acute (2,10–2,10 and 1,3 mg/kg respectively) and sub-acute (3, 3, and 1 mg/kg/day respectively) treatments. They selectively accumulated in the corpus cavernosum reaching 25.107 ± 2.081 μg/g wet weight for Pb, 1.029 ± 0.193 for Cd, 31.343 ± 1.991 for Al, compared to 7.084 ± 1.517, 0.296 ± 0.067, and 8.86 ± 1.115 as controls respectively. Serum creatinine levels were not altered. Cd and Al significantly reduced testosterone level to 0.483 ± 0.059 and 0.419 ± 0.037 ng/ml respectively compared to 0.927 ± 0.105 ng/ml as control. Aluminum elevated TBARs significantly by 27.843%. The acute anti-erectile action of Pb was blocked by non-selective NOS and GC inhibitors and potassium channel blocker. Lead also masked the potentiatory effect of L-arginine and diazoxide on ICP/MAP. No interaction with muscarinic or nicotinic modulators was observed. Conclusions: Pb, Cd and Al show anti-erectile effect independent on renal injury. They don not modulate cholinergic nor ganglionic transmission in corpus cavernosum. Pb may inhibit NO/cGMP/K + channel pathway. The effect of Cd and Al but not Pb seems to be hormonal dependent.

  1. Urban gardens: lead exposure, recontamination mechanisms, and implications for remediation design.

    Science.gov (United States)

    Clark, Heather F; Hausladen, Debra M; Brabander, Daniel J

    2008-07-01

    Environmental lead contamination is prevalent in urban areas where soil represents a significant sink and pathway of exposure. This study characterizes the speciation of lead that is relevant to local recontamination and to human exposure in the backyard gardens of Roxbury and Dorchester, MA, USA. One hundred forty-one backyard gardens were tested by X-ray fluorescence, and 81% of gardens have lead levels above the US EPA action limit of 400 microg/g. Raised gardening beds are the in situ exposure reduction method used in the communities to promote urban gardening. Raised beds were tested for lead and the results showed that the lead concentration increased from an initial range of 150+/-40 microg/g to an average of 336 microg/g over 4 years. The percent distribution of lead in the fine grain soil (lead, and the trace metal signature of the fine grain soil in both gardens and raised gardening beds is characteristic of lead-based paint. This study demonstrates that raised beds are a limited exposure reduction method and require maintenance to achieve exposure reduction goals. An exposure model was developed based on a suite of parameters that combine relevant values from the literature with site-specific quantification of exposure pathways. This model suggests that consumption of homegrown produce accounts for only 3% of children's daily exposure of lead while ingestion of fine grained soil (lead remediation on a yard-by-yard scale requires constant maintenance and that remediation may need to occur on a neighborhood-wide scale.

  2. Magnetic isotope effect and theory of atomic orbital hybridization to predict a mechanism of chemical exchange reactions.

    Science.gov (United States)

    Epov, Vladimir N

    2011-08-07

    A novel approach is suggested to investigate the mechanisms of chemical complexation reactions based on the results of Fujii with co-workers; they have experimentally observed that several metals and metalloids demonstrate mass-independent isotope fractionation during the reactions with the DC18C6 crown ether using solvent-solvent extraction. In this manuscript, the isotope fractionation caused by the magnetic isotope effect is used to understand the mechanisms of chemical exchange reactions. Due to the rule that reactions are allowed for certain electron spin states, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions. Mass-independent fractionation is suggested to take place due to the hyperfine interaction of the nuclear spin with the electron spin of the intermediate product. Moreover, the sign of the mass-independent fractionation is found to be dependent on the element and its species, which is also explained by the magnetic isotope effect. For example, highly negative mass-independent isotope fractionation of magnetic isotopes was observed for reactions of DC18C6 with SnCl(2) species and with several Ru(III) chloro-species, and highly positive for reactions of this ether with TeCl(6)(2-), and with several Cd(II) and Pd(II) species. The atomic radius of an element is also a critical parameter for the reaction with crown ether, particularly the element ions with [Kr]4d(n)5s(m) electron shell fits the best with the DC18C6 crown ring. It is demonstrated that the magnetic isotope effect in combination with the theory of orbital hybridization can help to understand the mechanism of complexation reactions. The suggested approach is also applied to explain previously published mass-independent fractionation of Hg isotopes in other types of chemical exchange reactions. This journal is © the Owner Societies 2011

  3. Influence of additives on microstructures, mechanical properties and shock-induced reaction characteristics of Al/Ni composites

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Wei; Zhang, Xianfeng, E-mail: lynx@mail.njust.edu.cn; Wu, Yang; He, Yong; Wang, Chuanting; Guo, Lei

    2015-11-05

    Granular composites containing aluminum (Al) and nickel (Ni) are typical structural energetic materials, which possess ideal combination of both mechanical properties and energy release capability. The influence of two additives, namely Teflon (PTFE) and copper (Cu), on mechanical properties and shock-induced chemical reaction (SICR) characteristics of Al/Ni material system has been investigated. Three composites, namely Al/Ni, Al/Ni/PTFE and Al/Ni/Cu with same volumetric ratio of Al powder to Ni powder, were processed by means of static pressing. Scanning electron microscopy was used to study the microstructure of the mentioned three composites. Quasi static compression tests were also conducted to determine the mechanical properties and fracture behavior of the mentioned three composites. It was shown that the additives affected both compressive strength and fracture mode of the three composites. Impact initiation experiments on the mentioned three composites were performed to determine their shock-induced chemical reaction characteristics by considering pressure histories measured in the test chamber. The experimental results showed that the additives had significant effects on critical initiation velocity, reaction rate, reaction efficiency and post-reaction behavior. - Highlights: • .Al/Ni, Al/Ni/PTFE and Al/Ni/Cu were processed by means of static pressing. • .Microstructures, mechanical properties and shock-induced reactions were studied. • .Microstructures affect both compressive strength and fracture mode. • .Impact velocity is an important factor in shock-induced chemical characteristics. • .Each additive has significant effects on energy release behavior.

  4. Influence of additives on microstructures, mechanical properties and shock-induced reaction characteristics of Al/Ni composites

    International Nuclear Information System (INIS)

    Xiong, Wei; Zhang, Xianfeng; Wu, Yang; He, Yong; Wang, Chuanting; Guo, Lei

    2015-01-01

    Granular composites containing aluminum (Al) and nickel (Ni) are typical structural energetic materials, which possess ideal combination of both mechanical properties and energy release capability. The influence of two additives, namely Teflon (PTFE) and copper (Cu), on mechanical properties and shock-induced chemical reaction (SICR) characteristics of Al/Ni material system has been investigated. Three composites, namely Al/Ni, Al/Ni/PTFE and Al/Ni/Cu with same volumetric ratio of Al powder to Ni powder, were processed by means of static pressing. Scanning electron microscopy was used to study the microstructure of the mentioned three composites. Quasi static compression tests were also conducted to determine the mechanical properties and fracture behavior of the mentioned three composites. It was shown that the additives affected both compressive strength and fracture mode of the three composites. Impact initiation experiments on the mentioned three composites were performed to determine their shock-induced chemical reaction characteristics by considering pressure histories measured in the test chamber. The experimental results showed that the additives had significant effects on critical initiation velocity, reaction rate, reaction efficiency and post-reaction behavior. - Highlights: • .Al/Ni, Al/Ni/PTFE and Al/Ni/Cu were processed by means of static pressing. • .Microstructures, mechanical properties and shock-induced reactions were studied. • .Microstructures affect both compressive strength and fracture mode. • .Impact velocity is an important factor in shock-induced chemical characteristics. • .Each additive has significant effects on energy release behavior

  5. Mechanisms Leading to Co-Existence of Gas Hydrate in Ocean Sediments [Part 1 of 2

    Energy Technology Data Exchange (ETDEWEB)

    Bryant, Steven; Juanes, Ruben

    2011-12-31

    In this project we have sought to explain the co-existence of gas and hydrate phases in sediments within the gas hydrate stability zone. We have focused on the gas/brine interface at the scale of individual grains in the sediment. The capillary forces associated with a gas/brine interface play a dominant role in many processes that occur in the pores of sediments and sedimentary rocks. The mechanical forces associated with the same interface can lead to fracture initiation and propagation in hydrate-bearing sediments. Thus the unifying theme of the research reported here is that pore scale phenomena are key to understanding large scale phenomena in hydrate-bearing sediments whenever a free gas phase is present. Our analysis of pore-scale phenomena in this project has delineated three regimes that govern processes in which the gas phase pressure is increasing: fracturing, capillary fingering and viscous fingering. These regimes are characterized by different morphology of the region invaded by the gas. On the other hand when the gas phase pressure is decreasing, the corresponding regimes are capillary fingering and compaction. In this project, we studied all these regimes except compaction. Many processes of interest in hydrate-bearing sediments can be better understood when placed in the context of the appropriate regime. For example, hydrate formation in sub-permafrost sediments falls in the capillary fingering regime, whereas gas invasion into ocean sediments is likely to fall into the fracturing regime. Our research provides insight into the mechanisms by which gas reservoirs are converted to hydrate as the base of the gas hydrate stability zone descends through the reservoir. If the reservoir was no longer being charged, then variation in grain size distribution within the reservoir explain hydrate saturation profiles such as that at Mt. Elbert, where sand-rich intervals containing little hydrate are interspersed between intervals containing large hydrate

  6. Mechanisms Leading to Co-Existence of Gas Hydrate in Ocean Sediments [Part 2 of 2

    Energy Technology Data Exchange (ETDEWEB)

    Bryant, Steven; Juanes, Ruben

    2011-12-31

    In this project we have sought to explain the co-existence of gas and hydrate phases in sediments within the gas hydrate stability zone. We have focused on the gas/brine interface at the scale of individual grains in the sediment. The capillary forces associated with a gas/brine interface play a dominant role in many processes that occur in the pores of sediments and sedimentary rocks. The mechanical forces associated with the same interface can lead to fracture initiation and propagation in hydrate-bearing sediments. Thus the unifying theme of the research reported here is that pore scale phenomena are key to understanding large scale phenomena in hydrate-bearing sediments whenever a free gas phase is present. Our analysis of pore-scale phenomena in this project has delineated three regimes that govern processes in which the gas phase pressure is increasing: fracturing, capillary fingering and viscous fingering. These regimes are characterized by different morphology of the region invaded by the gas. On the other hand when the gas phase pressure is decreasing, the corresponding regimes are capillary fingering and compaction. In this project, we studied all these regimes except compaction. Many processes of interest in hydrate-bearing sediments can be better understood when placed in the context of the appropriate regime. For example, hydrate formation in sub-permafrost sediments falls in the capillary fingering regime, whereas gas invasion into ocean sediments is likely to fall into the fracturing regime. Our research provides insight into the mechanisms by which gas reservoirs are converted to hydrate as the base of the gas hydrate stability zone descends through the reservoir. If the reservoir was no longer being charged, then variation in grain size distribution within the reservoir explain hydrate saturation profiles such as that at Mt. Elbert, where sand-rich intervals containing little hydrate are interspersed between intervals containing large hydrate

  7. Reaction and nucleation mechanisms of copper electrodeposition on disposable pencil graphite electrode

    Energy Technology Data Exchange (ETDEWEB)

    Majidi, M.R. [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, 29th Bahman Bolvard, Tabriz 51664 (Iran, Islamic Republic of)], E-mail: sr.majidi@gmail.com; Asadpour-Zeynali, K.; Hafezi, B. [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, 29th Bahman Bolvard, Tabriz 51664 (Iran, Islamic Republic of)

    2009-01-01

    The reaction and nucleation mechanism of copper electrodeposition on disposable pencil graphite electrode (PGE) in acidic sulphate solution were investigated using cyclic voltammetry (CV) and chronoamperometry (CA) techniques, respectively. Electrochemical experiments were followed by morphological studies with scanning electron microscopy (SEM). The effect of some experimental parameters, namely copper concentration, pH, scan rate, background electrolyte, deposition potential, and conditioning surface of the electrode were described. At the surface of PGE, Cu{sup 2+} ions were reduced at -250 mV vs. SCE. It was found that electrodeposition of copper is affected by rough surface of PGE. The nucleation mechanisms were examined by fitting the experimental CA data into Scharifker-Hills nucleation models. The nuclei population densities were also determined by means of two common fitting models developed for three-dimensional nucleation and growth (Scharifker-Mostany and Mirkin-Nilov-Herrman-Tarallo). It was found that deposition potential and background electrolyte affect the distribution of the deposited copper. The morphology of the deposited copper is affected by background electrolyte.

  8. Inducer expulsion in Streptococcus pyogenes: properties and mechanism of the efflux reaction

    International Nuclear Information System (INIS)

    Sutrina, S.L.; Reizer, J.; Saier, M.H Jr.

    1988-01-01

    Expulsion of preaccumulated methyl-β-D-thiogalactoside-phosphate (TMG-P) from Streptococcus pyogenes is a two-step process comprising intracellular dephosphorylation of TMG-P followed by rapid efflux of the intracellularly formed free galactoside. The present study identifies the mechanism and the order and characterizes the temperature dependency of the efflux step. Unidirectional efflux of the intracellularly formed [ 14 C]TMG was only slightly affected when measured in the presence of unlabeled TMG (25 to 400 mM) in the extracellular medium. In contrast, pronounced inhibition of net efflux was observed in the presence of relatively low concentrations (1 to 16 mM) of extracellular [ 14 C]TMG. Since net efflux was nearly arrested when the external concentration of [ 14 C]TMG approached the intracellular concentration of this sugar, we propose that a facilitated diffusion mechanism is responsible for efflux and equilibration of TMG between the intracellular and extracellular milieus. The exit reaction was markedly dependent upon temperature, exhibited a high energy of activation (23 kcal [ca. 96 kJ] per mol), and followed first-order kinetics, indicating that the permease mediating this efflux was not saturated under the conditions of expulsion employed

  9. Simulation mechanisms of low energy nuclear reaction using super flow energy external fields

    International Nuclear Information System (INIS)

    Gareev, F.A.; Zhidkova, I.E.; ); Ratis, Yu.I.

    2005-01-01

    Full text: The review of possible stimulation mechanisms of the LENR (low energy nuclear reactions) is represented. We have concluded that transamination of nuclei at low energies and excess heat are possible in the framework of the modern physical theory - the universal resonance synchronization principle and based on its different enhancement mechanisms of reaction rates are responsible for these processes. The excitation nd ionization of atom may play role as trigger for LERN. Investigation of this phenomenon requires knowledge of different branches if science: nuclear and atomic physics, chemistry and electrochemistry, condensed matter and solid state physics. The results of this research field can provide a new source of energy, substances and technologies. The puzzle of poor re-productivity of experimental data in due ti the fact LENR occurs in open systems and it is extremely sensitive to parameters of external fields and systems. Classical re-productivity principle should be reconsidered for LENR experiments. Poor re-productivity and unexpected results do not means that the experiment is wrong. Our main conclusion: LENR may be understand in terms of the modern theory without any violation of the basic physics. 2) Weak and electromagnetic interactions may show the strong influence of the surrounding conditions on the nuclear processes. 3) Universal resonance synchronization principle is a key issue to make a bridge between various scales of interactions and it is responsible for self-organization of hierarchical systems independent of substances, fields and interactions. We bring some arguments in favor of the mechanism - order based on order - declared by Schroedinger in fundamental problem of contemporary science. 4) The universal resonance synchronization principle became a fruitful interdisciplinary science of general laws of self-organized processes in different branches of physics because it is consequence of the energy conservation law and resonance

  10. Effect of the Ti/B4C mole ratio on the reaction products and reaction mechanism in an Al–Ti–B4C powder mixture

    International Nuclear Information System (INIS)

    Zhang, Jingjing; Lee, Jung-Moo; Cho, Young-Hee; Kim, Su-Hyeon; Yu, Huashun

    2014-01-01

    The effect of the Ti/B 4 C mole ratio on the fabrication behavior of Al composites is investigated using Al–Ti–B 4 C powder mixtures as reactants. The quick spontaneous infiltration (QSI) process combined with the combustion reaction and DTA analysis were used. According to the thermodynamic predictions, which are verified in the experimental results, TiB 2 is formed in all the samples whereas TiC is only formed in reactants with a Ti/B 4 C mole ratio of more than two. The C atoms from the reacted B 4 C do not move into TiC but instead they move into Al 3 BC or Al 4 C 3 when the Ti/B 4 C mole ratio is less than two. In addition, the reaction mechanism with a Ti/B 4 C mole ratio of 0.75 is investigated extensively. - Highlights: • The critical role of the Ti/B 4 C mole ratio on the reaction products of Al–Ti–B 4 C was studied using experiments. • The experimental results are also supported by thermodynamic calculations presented in this paper. • The reaction mechanism with a Ti/B 4 C mole ratio of 0.75 is investigated extensively

  11. Reaction mechanism and thermal stability study on cathode materials for rechargeable lithium ion batteries

    Science.gov (United States)

    Fang, Jin

    Olivine-type lithium iron phosphate has been a very promising cathode material since it was proposed by Padhi in 1997, low-cost, environmental friendly and stable structure ensure the commercialization of LiFePO 4. In LiFePO4, during charge and discharge process, Li ions are transferred between two phases, Li-poor LialphaFePO 4 and Li-rich Li1-betaFePO4, which implies a significant energy barrier for the new phase nucleation and interface growth, contrary to the fast reaction kinetics experimentally observed. The understanding of the lithiation and delithiation mechanism of this material has spurred a lot of research interests. Many theory models have been proposed to explain the reaction mechanism of LiFePO4, among them, the single phase model claims that the reaction goes through a metastable single phase, and the over potential required to form this single phase is about 30mV, so we studied the driving force to transport lithium ions between Lialpha FePO4 and Li1-betaFePO4 phases and compared the particle sizes effect. Experiment results shows that, the nano-sized (30nm) LiFePO4 has wider solid solution range, lower solid solution formation temperature and faster kinetics than normal LiFePO4 (150nm). Also a 20mV over potential was observed in both samples, either after relaxing the FePO4/LiFePO4 system to equilibrium or transport lithium from one side to the other side, the experiment result is corresponding to theoretical calculation; indicates the reaction might go through single-phase reaction mechanism. The energy and power density of lithium ion battery largely depend on cathode materials. Mn substituted LiFePO4 has a higher voltage than LiFePO4, which results a higher theoretical energy density. Safety issue is one of the most important criterions for batteries, since cathode materials need to maintain stable structure during hundreds of charge and discharge cycles and ranges of application conditions. We have reported that iron-rich compound o-Fe1-yMnyPO4

  12. The Atmospherically Important Reaction of Hydroxyl Radicals with Methyl Nitrate: A Theoretical Study Involving the Calculation of Reaction Mechanisms, Enthalpies, Activation Energies, and Rate Coefficients.

    Science.gov (United States)

    Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2017-09-07

    A theoretical study, involving the calculation of reaction enthalpies, activation energies, mechanisms, and rate coefficients, was made of the reaction of hydroxyl radicals with methyl nitrate, an important process for methyl nitrate removal in the earth's atmosphere. Four reaction channels were considered: formation of H 2 O + CH 2 ONO 2 , CH 3 OOH + NO 2 , CH 3 OH + NO 3 , and CH 3 O + HNO 3 . For all channels, geometry optimization and frequency calculations were performed at the M06-2X/6-31+G** level, while relative energies were improved at the UCCSD(T*)-F12/CBS level. The major channel is found to be the H abstraction channel, to give the products H 2 O + CH 2 ONO 2 . The reaction enthalpy (ΔH 298 K RX ) of this channel is computed as -17.90 kcal mol -1 . Although the other reaction channels are also exothermic, their reaction barriers are high (>24 kcal mol -1 ), and therefore these reactions do not contribute to the overall rate coefficient in the temperature range considered (200-400 K). Pathways via three transition states were identified for the H abstraction channel. Rate coefficients were calculated for these pathways at various levels of variational transition state theory including tunneling. The results obtained are used to distinguish between two sets of experimental rate coefficients, measured in the temperature range of 200-400 K, one of which is approximately an order of magnitude greater than the other. This comparison, as well as the temperature dependence of the computed rate coefficients, shows that the lower experimental values are favored. The implications of the results to atmospheric chemistry are discussed.

  13. Electro-mechanical response of a 3D nerve bundle model to mechanical loads leading to axonal injury.

    Science.gov (United States)

    Cinelli, I; Destrade, M; Duffy, M; McHugh, P

    2018-03-01

    Traumatic brain injuries and damage are major causes of death and disability. We propose a 3D fully coupled electro-mechanical model of a nerve bundle to investigate the electrophysiological impairments due to trauma at the cellular level. The coupling is based on a thermal analogy of the neural electrical activity by using the finite element software Abaqus CAE 6.13-3. The model includes a real-time coupling, modulated threshold for spiking activation, and independent alteration of the electrical properties for each 3-layer fibre within a nerve bundle as a function of strain. Results of the coupled electro-mechanical model are validated with previously published experimental results of damaged axons. Here, the cases of compression and tension are simulated to induce (mild, moderate, and severe) damage at the nerve membrane of a nerve bundle, made of 4 fibres. Changes in strain, stress distribution, and neural activity are investigated for myelinated and unmyelinated nerve fibres, by considering the cases of an intact and of a traumatised nerve membrane. A fully coupled electro-mechanical modelling approach is established to provide insights into crucial aspects of neural activity at the cellular level due to traumatic brain injury. One of the key findings is the 3D distribution of residual stresses and strains at the membrane of each fibre due to mechanically induced electrophysiological impairments, and its impact on signal transmission. Copyright © 2017 John Wiley & Sons, Ltd.

  14. Possibilities and scope of the double isotope effect method in the elucidation of mechanisms of enzyme catalyzed reactions

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, H L; Medina, R [Technische Univ. Muenchen, Freising (Germany, F.R.). Lehrstuhl fuer Allgemeine Chemie und Biochemie

    1991-01-01

    Kinetic isotope effects on enzyme catalyzed reactions are indicative for the first irreversible in a sequence of individual steps. Hints on the relative velocities of other steps can only be obtained from the partitioning factor R and its dependence on external reaction conditions. In general, the experimental data needed are obtained from isotope abundance measurements in a defined position of the substrate or product as a function of turnover. This method does not reveal events dealing with neighbour atoms or preceding the main isotope sensitive step. In the method presented here, the analytical measurement is extended to the second atom involved in a bond fission of formation (Double Isotope Effect Method). It is shown that the additional results obtained support the identification of the main isotopically sensitive step and its relative contribution to the overall reaction rate, the identification of other kinetically significant steps and the differentiation between stepwise and concerted reaction mechanisms. The method and its advantages are demonstrated on reactions comprising C-N-bond splitting (urease and arginase reaction), C-C-bound fission (reactions catalyzed by pyruvate-dehydrogenase, pyruvate-formiate-lyase and lactate-oxidase), C-O-bound formation (ribulose-bisphosphate-oxygenase reaction), and N-O-bond fission (nitrate- and nitrite-reductase reactions). (orig.).

  15. Mechanically activated SHS reaction in the Fe-Al system: in-situ time resolved diffraction using synchrotron radiation

    International Nuclear Information System (INIS)

    Gaffet, E.; Charlot, F.; Klein, D.; Bernard, F.; Niepce, J.C.

    1998-01-01

    The mechanical activation self propagating high temperature synthesis (M.A.S.H.S.) processing is a new way to produce nanocrystalline iron aluminide intermetallic compounds. This process is maily the combination of two steps; in the one hand, a mechanical activation where the Fe - Al powder mixture was milled during a short time at given energy and frequency of shocks and in the other hand, a self propagating high temperature synthesis (S.H.S.) reaction, for which the exothermicity of the Fe + Al reaction is used. This fast propagated MASHS reaction has been in-situ investigated using the time resolved X-ray diffraction (TRXRD) using a X-ray synchrotron beam and an infrared thermography camera, allowing the coupling of the materials structure and the temperature field. The effects of the initial mean compositions, of the milling conditions as well as of the compaction parameters on the MASHS reaction are reported. (orig.)

  16. Lead generation strategy as a multichannel mechanism of growth of a modern enterprise

    Directory of Open Access Journals (Sweden)

    Łukowski Wojciech

    2016-09-01

    Full Text Available Lead generation strategy describes the marketing process of involvement and capture of interest in a product or service which is aimed at developing sales plans and, as a consequence, soliciting new clients. Lead generation is becoming an increasingly popular demand-generating strategy, which – through its multichannelled dissemination of the generated message – gives it a much greater reach. Lead generation assists organisations in achieving a greater brand awareness, building relationships and attracting more potential clients to fill their sales pipeline. The primary purpose of this publication is identifying the possibilities that the implementation of lead generation strategies provides to modern enterprises. It discusses the key aspects of this issue, demonstrating how the significance of organisations change, how their value effectively increases as a result of the implementation of tools furnished by processes that form an integral part of lead generation. The article defines the factors and processes that affect the effective course of actions undertaken within lead generation campaigns.

  17. Leading coordinate analysis of reaction pathways in proton chain transfer: Application to a two-proton transfer model for the green fluorescent protein

    International Nuclear Information System (INIS)

    Wang Sufan; Smith, Sean C.

    2006-01-01

    The 'leading coordinate' approach to computing an approximate reaction pathway, with subsequent determination of the true minimum energy profile, is applied to a two-proton chain transfer model based on the chromophore and its surrounding moieties within the green fluorescent protein (GFP). Using an ab initio quantum chemical method, a number of different relaxed energy profiles are found for several plausible guesses at leading coordinates. The results obtained for different trial leading coordinates are rationalized through the calculation of a two-dimensional relaxed potential energy surface (PES) for the system. Analysis of the 2-D relaxed PES reveals that two of the trial pathways are entirely spurious, while two others contain useful information and can be used to furnish starting points for successful saddle-point searches. Implications for selection of trial leading coordinates in this class of proton chain transfer reactions are discussed, and a simple diagnostic function is proposed for revealing whether or not a relaxed pathway based on a trial leading coordinate is likely to furnish useful information

  18. Theoretical investigation of the mechanism of tritiated methane dehydrogenation reaction using nickel-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Liang; Li, Jiamao; Deng, Bing; Yang, Yong; Wang, Heyi [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Li, Weiyi [School of Physics and Chemistry, Xihua University, Chengdu 610065 (China); Li, Shuo, E-mail: lishuo@cqut.edu.cn [School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054 (China); Tan, Zhaoyi, E-mail: tanzhaoyi@caep.cn [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)

    2015-06-15

    Graphical abstract: - Highlights: • Four-step dehydrogenation of CT{sub 4} catalyzed by Ni to form Ni–C by releasing T{sub 2}. • The process of Ni + CT{sub 4} → NiCT{sub 2} + T{sub 2} is more achievable than that of NiCT{sub 2} → NiC + T{sub 2}. • TNiCT → T{sub 2}NiC step is the RDS with the rate constant of k = 2.8 × 10{sup 13} exp(−313,136/RT). • The hydrogen isotope effect value of k{sub H}/k{sub T} is 2.94, and k{sub D}/k{sub T} is 1.39. • CH{sub 4} and CD{sub 4} dehydrogenations are likely to occur, accompanied by the CT{sub 4} cracking. - Abstract: The mechanism of tritiated methane dehydrogenation reaction catalyzed by nickel-based catalyst was investigated in detail by density functional theory (DFT) at the B3LYP/[6-311++G(d, p), SDD] level. The computational results indicated that the dehydrogenation of tritiated methane is endothermic. The decomposition of tritiated methane catalyzed by Ni to form Ni-based carbon (Ni–C) after a four-step dehydrogenation companied with releasing tritium. After the first and second dehydrogenation steps, Ni + CT{sub 4} formed NiCT{sub 2}. After the third and fourth dehydrogenation steps, NiCT{sub 2} formed NiC. The first and second steps of dehydrogenation occurred on both the singlet and triplet states, and the lowest energy route is Ni + CT{sub 4} → {sup 1}COM → {sup 1}TS1 → {sup 3}IM1 → {sup 3}TS2 → {sup 3}IM2. The third and fourth steps of dehydrogenation occurred on both the singlet and quintet states, and the minimum energy reaction pathway appeared to be IM3 → {sup 1}TS4 → {sup 5}IM4 → {sup 5}TS5 → {sup 5}IM5 → {sup 5}pro + T{sub 2}. The fourth step of dehydrogenation TNiCT → T{sub 2}NiC was the rate-determining step of the entire reaction with the rate constant of k{sub 2} = 2.8 × 10{sup 13} exp(−313,136/RT) (in cm{sup 3} mol{sup −1} s{sup −1}), and its activation energy barrier was calculated to be 51.8 kcal/mol. The Ni-catalyzed CH{sub 4} and CD{sub 4} cracking

  19. Study of a new mechanism of reaction between heavy ions: the quasi-fission

    International Nuclear Information System (INIS)

    Ngo, Christian.

    1975-01-01

    A new type of deep inelastic reaction between two heavy ions (quasi-fission) has been discovered and studied when the product Z 1 Z 2 between the two ion atomic numbers is greater than or approximately equal to 1500. This mechanism is mainly binary, the total kinetic energy of the products is the one expected for a binary fission giving the same products, most of the products have masses very close to the initial masses, the angular distribution of the light products is peaked slightly forwards the projectile grazing angle (when the bombarding energy is not too much above the interaction barrier), at last, the total cross section for this process is a large part of the total reaction cross section. These results have been interpreted on the one hand using a static model and on the other hand using a dynamic model. An interaction potential between the two heavy ions has been derived using the energy density formalism within the framework of the sudden approximation. It has been shown that the nuclear part satisfies a scaling law which allows to factorize it in one term which depends on the two ion masses and another term which is independent of the system (universal function). Using the critical distance notion, the static calculations reproduce the quasi-fission cross sections. With regards to the dynamical calculations, the previously described potential has been introduced within the framework of Deubler and Dietrich's model. It is a classical dynamical calculation including dissipative terms. The vibration degrees of freedom of each ion have been explicitely taken into account. This calculation nicely reproduces both the energy loss in the relative motion, the focusing effect of the angular distribution, and the quasi-fission cross sections [fr

  20. The Reaction Mechanism of Claisen Rearrangement Obtained by Transition State Spectroscopy and Single Direct-Dynamics Trajectory

    Directory of Open Access Journals (Sweden)

    Takayoshi Kobayashi

    2013-02-01

    Full Text Available Chemical bond breaking and formation during chemical reactions can be observed using “transition state spectroscopy”. Comparing the measurement result of the transition state spectroscopy with the simulation result of single direct-dynamics trajectory, we have elucidated the reaction dynamics of Claisen rearrangement of allyl vinyl ether. Observed the reaction of the neat sample liquid, we have estimated the time constants of transformation from straight-chain structure to aromatic-like six-membered ring structure forming the C1-C6 bond. The result clarifies that the reaction proceeds via three steps taking longer time than expected from the gas phase calculation. This finding provides new hypothesis and discussions, helping the development of the field of reaction mechanism analysis.

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

    Science.gov (United States)

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

    2013-01-01

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

  2. Influence of the initial grain size of silicon on microstructure and mechanical properties of reaction-sintered silicon nitride

    International Nuclear Information System (INIS)

    Heinrich, J.

    1977-01-01

    The influence of the initial grain size of the silicon powder on the microstructure and the resulting mechanical properties are studied. The smaller the grain size of the silicon powders used, the higher will be the degree of reaction at the beginning of the nitridation reaction and the higher the amount of α-modification in the fully nitridated samples. Moreover, the nitrification time can be considerably shortened when fine-grained silicon powders ( [de

  3. Asymmetric Horner-Wadsworth-Emmons Reactions with meso-Dialdehydes: Scope, Mechanism, and Synthetic Applications

    DEFF Research Database (Denmark)

    Rein, Tobias; Vares, Lauri; Kawasaki, Ikuo

    1999-01-01

    Asymmetric Homer-Wadsworth-Emmons reactions between chiral phosphonate reagents and various meso-dialdehydes have been investigated. A mechanistic model useful for rationalizing the experimentally observed stereoselectivities is presented. Furthermore; strategies for applying these reactions...

  4. First-principles quantum mechanical investigations: Catalytic reactions of furfural on Pd(111) and at the water/Pd(111) interface

    Science.gov (United States)

    Xue, Wenhua

    Bio-oils have drawn more and more attention from scientists as a promising new clean, cheap energy source. One of the most interesting relevant issues is the effect of catalysts on the catalytic reactions that are used for producing bio-oils. Furfural, as a very important intermediate during these reactions, has attracted significant studies. However, the effect of catalysts, including particularly the liquid/solid interface formed by a metal catalyst and liquid water, in the catalytic reactions involving furfural still remains elusive. In this research, we performed ab initio molecular dynamics simulations and first-principles density-functional theory calculations to investigate the atomic-scale mechanisms of catalytic hydrogenation of furfural on the palladium surface and at the liquid/state interface formed by the palladium surface and liquid water. We studied all the possible mechanisms that lead to formation of furfuryl alcohol (FOL), formation of tetrahydrofurfural (THFAL), and formation of tetrahydrofurfurfuryl alcohol (THFOL). We found that liquid water plays a significant role in the hydrogenation reactions. During the reaction in the presence of water and the palladium catalyst, in particular, water directly participates in the hydrogenation of the aldehyde group of furfural and facilitates the formation of FOL by reducing the activation energy. Our calculations show that water provides hydrogen for the hydrogenation of the aldehyde group, and at the same time, a pre-existing hydrogen atom, which is resulted from dissociation of molecular hydrogen (experimentally, molecular hydrogen is always supplied for hydrogenation) on the palladium surface, is bonded to water, making the water molecule intact in structure. In the absence of water, on the other hand, formation of FOL and THFAL on the palladium surface involves almost the same energy barriers, suggesting a comparable selectivity. Overall, as water reduces the activation energy for the formation of FOL

  5. Quantitative comparison of catalytic mechanisms and overall reactions in convergently evolved enzymes: implications for classification of enzyme function.

    Science.gov (United States)

    Almonacid, Daniel E; Yera, Emmanuel R; Mitchell, John B O; Babbitt, Patricia C

    2010-03-12

    Functionally analogous enzymes are those that catalyze similar reactions on similar substrates but do not share common ancestry, providing a window on the different structural strategies nature has used to evolve required catalysts. Identification and use of this information to improve reaction classification and computational annotation of enzymes newly discovered in the genome projects would benefit from systematic determination of reaction similarities. Here, we quantified similarity in bond changes for overall reactions and catalytic mechanisms for 95 pairs of functionally analogous enzymes (non-homologous enzymes with identical first three numbers of their EC codes) from the MACiE database. Similarity of overall reactions was computed by comparing the sets of bond changes in the transformations from substrates to products. For similarity of mechanisms, sets of bond changes occurring in each mechanistic step were compared; these similarities were then used to guide global and local alignments of mechanistic steps. Using this metric, only 44% of pairs of functionally analogous enzymes in the dataset had significantly similar overall reactions. For these enzymes, convergence to the same mechanism occurred in 33% of cases, with most pairs having at least one identical mechanistic step. Using our metric, overall reaction similarity serves as an upper bound for mechanistic similarity in functional analogs. For example, the four carbon-oxygen lyases acting on phosphates (EC 4.2.3) show neither significant overall reaction similarity nor significant mechanistic similarity. By contrast, the three carboxylic-ester hydrolases (EC 3.1.1) catalyze overall reactions with identical bond changes and have converged to almost identical mechanisms. The large proportion of enzyme pairs that do not show significant overall reaction similarity (56%) suggests that at least for the functionally analogous enzymes studied here, more stringent criteria could be used to refine

  6. Quantitative comparison of catalytic mechanisms and overall reactions in convergently evolved enzymes: implications for classification of enzyme function.

    Directory of Open Access Journals (Sweden)

    Daniel E Almonacid

    2010-03-01

    Full Text Available Functionally analogous enzymes are those that catalyze similar reactions on similar substrates but do not share common ancestry, providing a window on the different structural strategies nature has used to evolve required catalysts. Identification and use of this information to improve reaction classification and computational annotation of enzymes newly discovered in the genome projects would benefit from systematic determination of reaction similarities. Here, we quantified similarity in bond changes for overall reactions and catalytic mechanisms for 95 pairs of functionally analogous enzymes (non-homologous enzymes with identical first three numbers of their EC codes from the MACiE database. Similarity of overall reactions was computed by comparing the sets of bond changes in the transformations from substrates to products. For similarity of mechanisms, sets of bond changes occurring in each mechanistic step were compared; these similarities were then used to guide global and local alignments of mechanistic steps. Using this metric, only 44% of pairs of functionally analogous enzymes in the dataset had significantly similar overall reactions. For these enzymes, convergence to the same mechanism occurred in 33% of cases, with most pairs having at least one identical mechanistic step. Using our metric, overall reaction similarity serves as an upper bound for mechanistic similarity in functional analogs. For example, the four carbon-oxygen lyases acting on phosphates (EC 4.2.3 show neither significant overall reaction similarity nor significant mechanistic similarity. By contrast, the three carboxylic-ester hydrolases (EC 3.1.1 catalyze overall reactions with identical bond changes and have converged to almost identical mechanisms. The large proportion of enzyme pairs that do not show significant overall reaction similarity (56% suggests that at least for the functionally analogous enzymes studied here, more stringent criteria could be used to

  7. Fixation and reduction of uranium by natural organic matter: reaction mechanisms and kinetics

    International Nuclear Information System (INIS)

    Nakashima, S.; Perruchot, A.; Trichet, J.; Disnar, J.R.

    1987-01-01

    The reactivity of lignite towards soluble uranyl species in an aqueous medium is experimentally investigated as a function of temperature (between 20 0 C and 400 0 C). The fixation process starts near 45 0 C, with reduction beginning around 120 0 C. The fixation process leads to the formation of chemically and thermally stable organo-uranyl species. The reduction of free uranyl species is accompanied by a stoichiometric (2:1) liberation of protons into the medium. These protons originate from the organic matter which thus undergoes dehydrogenation. The general evolution of the carbonaceous residue in the course of this reaction shows that alcoholic and aliphatic hydrocarbon groups are responsible for the reduction. This chemical dehydrogenation could explain the low hydrogen content of natural organic materials associated with uraniferous deposits. The kinetics of the reduction step have been studied at 180 0 C, 190 0 C and 200 0 C. The kinetic parameters determined over this temperature range, and the extrapolation made to 20 0 C, show that reduction can be a crucial process in the geochemical behaviour of uranium especially in the thermal conditions in which sedimentary basins evolve [fr

  8. The Role of Various Stressors in the Trigger Mechanism of Raynaud's Disease (Hemorheological and Vascular Reactions

    Directory of Open Access Journals (Sweden)

    Mantskava M.M.

    2014-05-01

    Full Text Available The emergence and spread of stress reactions are provided by the blood circulation system. In its turn, the adequacy of blood circulation depends on the hemorheological and vascular mechanisms. The changeability of their properties appears to be the basis of the increasing of stress stages. From the viewpoint of biophysical reactions, any change and movement occur with the expenditure and accumulation of energy. Higher level of adaptation energy waste and secondary level take place, when a small stressor entails a small expenditure. There is a maximum possible rate of adaptive energy consumption and at this maximum the organism cannot cope with any additional stimulus. At the same time adaptive and stress diseases develop. Let’s consider the duration and manifestation of Raynaud's disease from the perspective of adaptation diseases and diseases of the third grade, which appears to be the cause of the double stress effect - cold and emotional- physical and psychic. Total of 97 patients with Raynaud's disease were examined. For a new vision of the problem it was necessary to find out how the streessors of various nature impact the hemoreheological status and vascular resistance. For this purpose all the patients were examined for a resistance index of resistive arteries of the hand and the indices of erythrocyte aggregation and deformability. The patients were divided into four subgroups. The first subgroup – the patients after chilblain, the second subgroup – the patients with psychic strerssor, the third subgroup – the patients with prolonged chronic stress, and the fourth subgroup – the patients without the differentiation of the stressors. According to the obtained results, it is obvious that at cold and emotional stress (I and II subgroups the hemorheological and vascular parameters are changed. However, this change (hemorheological and vascular is more pronounced at chronic emotional stress (III subgroup as compared both to the

  9. Research and development regarding the retaining mechanism of lead ions in industrial wastewaters using natural matter with remarkable properties

    Science.gov (United States)

    Pop, A.; Iepure, G.

    2017-05-01

    The paper shows the studying of the retaining mechanism of lead ions in industrial wastewaters through static and dynamic ion exchange mechanisms. In the experimental determinations of the lead metallic ion retention, metallurgical industry wastewaters have been used on samples of volcanic zeolite tuff (from Barsana, Maramures), samples that show a high concentration of lead ions and an acidic pH. The results showed that both the static and the dynamic ion exchanges ended with good results and they were consistent with other studies conducted on clinoptilolite zeolite tuff. Knowing that the industrial sector is an important source of environment pollution and degradation and being aware of what a serious threat the heavy metal pollution is, due to their high toxicity and stability, the experiment may find applicability in different aspects, both in the Maramures mining basing as well as in the worldwide controlling and directing of the polluting processes.

  10. A mechanism of leading-edge protrusion in the absence of Arp2/3 complex.

    Science.gov (United States)

    Suraneni, Praveen; Fogelson, Ben; Rubinstein, Boris; Noguera, Philippe; Volkmann, Niels; Hanein, Dorit; Mogilner, Alex; Li, Rong

    2015-03-01

    Cells employ protrusive leading edges to navigate and promote their migration in diverse physiological environments. Classical models of leading-edge protrusion rely on a treadmilling dendritic actin network that undergoes continuous assembly nucleated by the Arp2/3 complex, forming ruffling lamellipodia. Recent work demonstrated, however, that, in the absence of the Arp2/3 complex, fibroblast cells adopt a leading edge with filopodia-like protrusions (FLPs) and maintain an ability to move, albeit with altered responses to different environmental signals. We show that formin-family actin nucleators are required for the extension of FLPs but are insufficient to produce a continuous leading edge in fibroblasts lacking Arp2/3 complex. Myosin II is concentrated in arc-like regions of the leading edge in between FLPs, and its activity is required for coordinated advancement of these regions with formin-generated FLPs. We propose that actomyosin contraction acting against membrane tension advances the web of arcs between FLPs. Predictions of this model are verified experimentally. The dependence of myosin II in leading-edge advancement helps explain the previously reported defect in directional movement in the Arpc3-null fibroblasts. We provide further evidence that this defect is cell autonomous during chemotaxis. © 2015 Suraneni et al. This article is distributed by The American Society for Cell Biology under license from the author(s). Two months after publication it is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).

  11. Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl- attack on CH3Cl.

    Science.gov (United States)

    Kuechler, Erich R; York, Darrin M

    2014-02-07

    The nucleophilic attack of a chloride ion on methyl chloride is an important prototype SN2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resulting free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.

  12. Does the Fit Between Competitive Strategy and Administrative Mechanisms Lead to Superior Performance?

    OpenAIRE

    Barth, Henrik

    2000-01-01

    At least two different administrative mechanisms are available for the small business manager to develop and pursue a competitive strategy. One refers to managerial skills needed to implement and follow the competitive strategy chosen by the firm. The other refers to the design of organisation structure i.e. how job tasks are divided, grouped and coordinated. This paper argues that the fit between the competitive strategy followed by a firm and the utilisation of the administrative mechanisms...

  13. The Mechanical and Reaction Behavior of PTFE/Al/Fe2O3 under Impact and Quasi-Static Compression

    Directory of Open Access Journals (Sweden)

    Jun-yi Huang

    2017-01-01

    Full Text Available Quasi-static compression and drop-weight test were used to characterize the mechanical and reaction behavior of PTFE/Al/Fe2O3 composites. Two kinds of PTFE/Al/Fe2O3 composites were prepared with different mass of PTFE, and the reaction phenomenon and stress-strain curves were recorded; the residuals after reaction were analyzed by X-ray diffraction (XRD. The results showed that, under quasi-static compression condition, the strength of the materials is increased (from 37.1 Mpa to 77.2 Mpa with the increase of PTFE, and the reaction phenomenon occurred only in materials with high PTFE content. XRD analysis showed that the reaction between Al and Fe2O3 was not triggered with identical experimental conditions. In drop-weight tests, PTFE/Al/Fe2O3 specimens with low PTFE content were found to be more insensitive by high-speed photography, and a High Temperature Metal Slag Spray (HTMSS phenomenon was observed in both kinds of PTFE/Al/Fe2O3 composites, indicating the existence of thermite reaction, which was confirmed by XRD. In PTFE/Al/Fe2O3 system, the reaction between PTFE and Al precedes the reaction between Al and Fe2O3.

  14. Ageing mechanisms in chickpea seeds: Relationship of sugar hydrolysis and lipid peroxidation with Amadori and Millard reactions

    Directory of Open Access Journals (Sweden)

    mahdi shaaban

    2017-05-01

    Full Text Available This experiment was performed in order to study on ageing mechanisms of chickpea seeds (Cicer arietinum L. in natural storage and accelerated ageing conditions in seed laboratory of Gorgan Agricultural Science and Natural Resources, Gorgan, Iran at 2015. Experiment was in completely randomized design arrangement with four replications. Treatments were 2 and 4 years natural storage and 1-5 days of accelerated ageing with control treatment. The results showed that with increasing of natural storage and accelerated ageing duration, germination percentage was decreased. Increasing of ageing duration decreased soluble sugars, non-reducing sugars and soluble proteins but lipid peroxidation, reducing sugars, protein carbonylation and Amadori and Millard reaction were increased. In natural storage condition lipid peroxidation was more than sugar hydrolysis but in accelerated ageing condition sugar hydrolysis was more than lipid peroxidation. These results show that the main reason of Amadori and Millard reaction in chickpea seeds in natural storage condition is lipid peroxidation and in accelerated ageing condition is sugar hydrolysis. Also, the results showed that Amadori reaction in natural storage condition was more than Amadori reaction and in accelerated ageing condition Millard reaction was more than Amadori reaction. The results of the present study showed that sever Millard reaction after Amadori reaction induced higher damage on seed and results to more decrease of seed viability and reduce of seed germination percentage in accelerated ageing than natural storage.

  15. A mathematical analysis of Prx2-STAT3 disulfide exchange rate constants for a bimolecular reaction mechanism.

    Science.gov (United States)

    Langford, Troy F; Deen, William M; Sikes, Hadley D

    2018-03-22

    Appreciation of peroxiredoxins as the major regulators of H 2 O 2 concentrations in human cells has led to a new understanding of redox signaling. In addition to their status as the primary reducers of H 2 O 2 to water, the oxidized peroxiredoxin byproduct of this reaction has recently been shown capable of participation in H 2 O 2 -mediated signaling pathways through disulfide exchange reactions with the transcription factor STAT3. The dynamics of peroxidase-transcription factor disulfide exchange reactions have not yet been considered in detail with respect to how these reactions fit into the larger network of competing reactions in human cells. In this study, we used a kinetic model of oxidation and reduction reactions related to H 2 O 2 metabolism in the cytosol of human cells to study the dynamics of peroxiredoxin-2 mediated oxidation of the redox-regulated transcription factor STAT3. In combination with previously reported experimental data, the model was used to estimate the rate coefficient of a biomolecular reaction between Prx2 and STAT3 for two sets of assumptions that constitute lower and upper bound cases. Using these estimates, we calculated the relative rates of the reaction of oxidized peroxiredoxin-2 and STAT3 and other competing reactions in the cytosol. These calculations revealed that peroxiredoxin-2-mediated oxidation of STAT3 likely occurs at a much slower rate than competing reactions in the cytosol. This analysis suggests the existence of more complex mechanisms, potentially involving currently unknown protein-protein recognition partners, which facilitate disulfide exchange reactions between peroxiredoxin-2 and STAT3. Copyright © 2018 Elsevier Inc. All rights reserved.

  16. Temporal predictive mechanisms modulate motor reaction time during initiation and inhibition of speech and hand movement.

    Science.gov (United States)

    Johari, Karim; Behroozmand, Roozbeh

    2017-08-01

    Skilled movement is mediated by motor commands executed with extremely fine temporal precision. The question of how the brain incorporates temporal information to perform motor actions has remained unanswered. This study investigated the effect of stimulus temporal predictability on response timing of speech and hand movement. Subjects performed a randomized vowel vocalization or button press task in two counterbalanced blocks in response to temporally-predictable and unpredictable visual cues. Results indicated that speech and hand reaction time was decreased for predictable compared with unpredictable stimuli. This finding suggests that a temporal predictive code is established to capture temporal dynamics of sensory cues in order to produce faster movements in responses to predictable stimuli. In addition, results revealed a main effect of modality, indicating faster hand movement compared with speech. We suggest that this effect is accounted for by the inherent complexity of speech production compared with hand movement. Lastly, we found that movement inhibition was faster than initiation for both hand and speech, suggesting that movement initiation requires a longer processing time to coordinate activities across multiple regions in the brain. These findings provide new insights into the mechanisms of temporal information processing during initiation and inhibition of speech and hand movement. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Fundamental mechanisms and reactions in non-catalytic subcritical hydrothermal processes: A review.

    Science.gov (United States)

    Yousefifar, Azadeh; Baroutian, Saeid; Farid, Mohammed M; Gapes, Daniel J; Young, Brent R

    2017-10-15

    The management and disposal of solid waste is of increasing concern across the globe. Hydrothermal processing of sludge has been suggested as a promising solution to deal with the considerable amounts of sludge produced worldwide. Such a process not only degrades organic compounds and reduces waste volume, but also provides an opportunity to recover valuable substances. Hydrothermal processing comprises two main sub-processes: wet oxidation (WO) and thermal hydrolysis (TH), in which the formation of various free radicals results in the production of different intermediates. Volatile fatty acids (VFAs), especially acetic acid, are usually the main intermediates which remain as a by-product of the process. This paper aims to review the fundamental mechanism for hydrothermal processing of sludge, and the formation of different free radicals and intermediates therein. In addition, the proposed kinetic models for the two processes (WO and TH) from the literature are reviewed and the advantages and disadvantages of each model are outlined. The effect of mass transfer as a critical component of the design and development of the processes, which has been neglected in most of these proposed models, is also reviewed, and the effect of influencing parameters on the processes' controlling step (reaction or mass transfer) is discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Fragment molecular orbital study on electron tunneling mechanisms in bacterial photosynthetic reaction center.

    Science.gov (United States)

    Kitoh-Nishioka, Hirotaka; Ando, Koji

    2012-11-01

    The tunneling mechanisms of electron transfers (ETs) in photosynthetic reaction center of Blastochloris viridis are studied by the ab initio fragment molecular orbital (FMO) method combined with the generalized Mulliken-Hush (GMH) and the bridge Green function (GF) calculations of the electronic coupling T(DA) and the tunneling current method for the ET pathway analysis at the fragment-based resolution. For the ET from batctriopheophytin (H(L)) to menaquinone (MQ), a major tunneling current through Trp M250 and a minor back flow via Ala M215, Ala M216, and His M217 are quantified. For the ET from MQ to ubiquinone, the major tunneling pathway via the nonheme Fe(2+) and His L190 is identified as well as minor pathway via His M217 and small back flows involving His L230, Glu M232, and His M264. At the given molecular structure from X-ray experiment, the spin state of the Fe(2+) ion, its replacement by Zn(2+), or its removal are found to affect the T(DA) value by factors within 2.2. The calculated T(DA) values, together with experimentally estimated values of the driving force and the reorganization energy, give the ET rates in reasonable agreement with experiments.

  19. Optimal Ordering Policy and Coordination Mechanism of a Supply Chain with Controllable Lead-Time-Dependent Demand Forecast

    Directory of Open Access Journals (Sweden)

    Hua-Ming Song

    2011-01-01

    Full Text Available This paper investigates the ordering decisions and coordination mechanism for a distributed short-life-cycle supply chain. The objective is to maximize the whole supply chain's expected profit and meanwhile make the supply chain participants achieve a Pareto improvement. We treat lead time as a controllable variable, thus the demand forecast is dependent on lead time: the shorter lead time, the better forecast. Moreover, optimal decision-making models for lead time and order quantity are formulated and compared in the decentralized and centralized cases. Besides, a three-parameter contract is proposed to coordinate the supply chain and alleviate the double margin in the decentralized scenario. In addition, based on the analysis of the models, we develop an algorithmic procedure to find the optimal ordering decisions. Finally, a numerical example is also presented to illustrate the results.

  20. Fusability and survivability in reactions leading to heavy nuclei in the vicinity of the N = 126 shell

    International Nuclear Information System (INIS)

    Sagajdak, R.N.

    2008-01-01

    The production of heavy nuclei from Rn to Th around the N = 126 neutron shell in complete fusion reactions of nuclei has been considered in a systematic way in the framework of the conventional barrier-passing fusion model coupled with the Standard Statistical Model (SSM). Available data on the excitation functions for fusion and production of evaporation residues obtained in very asymmetric combinations are described with these models rather well. In the interaction of massive projectiles with heavy target nuclei quasi-fission effects appear in the entrance reaction channel. The quantity of the fusion probability introduced empirically has been used to reproduce excitation functions with the same SSM parameters (fission barriers) as those obtained in the analysis of very asymmetric combinations. A lack of stabilization against fission around N = 126 for Th nuclei was earlier explained with a reduced collective contribution to the level density in spherical nuclei. However, the present analysis shows severe inhibition for fusion, i.e., the drop in production cross sections of Th nuclei in the vicinity of N = 126 is mainly caused by entrance channel effects. The macroscopic component of fission barriers for nuclei involved in a deexcitation cascade has been derived and compared with the theoretical model predictions and available data