WorldWideScience

Sample records for 4alpha reaction mechanism

  1. Neck fragmentation reaction mechanism

    CERN Document Server

    Baran, V; Di Toro, M

    2004-01-01

    Based on a microscopic transport model, we study the origin of nonstatistical Intermediate Mass Fragment ($IMF$) production in semicentral heavy ion collisions at the Fermi energies. We show that a fast, dynamical $IMF$ formation process, the {\\it neck fragmentation mechanism}, can explain the experimentally observed features: deviations from Viola systematics and anisotropic, narrow angular distributions. It may be regarded as the continuation of the multifragmentation mechanism towards intermediate impact parameters. Its relation to other dynamical mechanisms, the induced fission and the abrasion of the spectator zones, that can also contribute to mid-rapidity $IMF$ production, is discussed. The dependence on beam energy and centrality of the collision is carefully analysed. The competition between volume and surface instabilities makes this mechanism very sensitive to the in-medium nucleon-nucleon interactions, from the cross sections for hard collisions to the compressibility and other Equation of State (...

  2. Inorganic Reaction Mechanisms Part II: Homogeneous Catalysis

    Science.gov (United States)

    Cooke, D. O.

    1976-01-01

    Suggests several mechanisms for catalysis by metal ion complexes. Discusses the principal factors of importance in these catalysis reactions and suggests reactions suitable for laboratory study. (MLH)

  3. Direct mechanism in solar nuclear reactions

    OpenAIRE

    Oberhummer, H; Staudt, G.

    1994-01-01

    A short overview of the direct reaction mechanism and the models used for the analysis of such processes is given. Nuclear reactions proceeding through the direct mechanism and involved in solar hydrogen burning are discussed. The significance of these nuclear reactions with respect to the solar neutrino problem is investigated.

  4. Is EC class predictable from reaction mechanism?

    OpenAIRE

    Nath Neetika; Mitchell John BO

    2012-01-01

    We thank the Scottish Universities Life Sciences Alliance (SULSA) and the Scottish Overseas Research Student Awards Scheme of the Scottish Funding Council (SFC) for financial support. Background: We investigate the relationships between the EC (Enzyme Commission) class, the associated chemical reaction, and the reaction mechanism by building predictive models using Support Vector Machine (SVM), Random Forest (RF) and k-Nearest Neighbours (kNN). We consider two ways of encoding the reaction...

  5. Heuristics-Guided Exploration of Reaction Mechanisms

    CERN Document Server

    Bergeler, Maike; Proppe, Jonny; Reiher, Markus

    2015-01-01

    For the investigation of chemical reaction networks, the efficient and accurate determination of all relevant intermediates and elementary reactions is inevitable. The complexity of such a network may grow rapidly, in particular if reactive species are involved that might cause a myriad of side reactions. Without automation, a complete investigation of complex reaction mechanisms is tedious and possibly unfeasible. Therefore, only the expected dominant reaction paths of a chemical reaction network (e.g., a catalytic cycle or an enzymatic cascade) are usually explored in practice. Here, we present a computational protocol that constructs such networks in a parallelized and automated manner. Molecular structures of reactive complexes are generated based on heuristic rules and subsequently optimized by electronic-structure methods. Pairs of reactive complexes related by an elementary reaction are then automatically detected and subjected to an automated search for the connecting transition state. The results are...

  6. Reaction mechanism of -acylhydroxamate with cysteine proteases

    Indian Academy of Sciences (India)

    R Shankar; P Kolandaivel

    2007-09-01

    The gas-phase reaction mechanism of -acylhydroxamate with cysteine proteases has been investigated using ab initio and density functional theory. On the irreversible process, after breakdown of tetrahedral intermediate (INT1), small 1-2 anionotropic has been formed and rearranged to give stable by-products sulfenamide (P1) and thiocarbamate (P2) with considerable energy loss. While, on the reversible part of this reaction mechanism, intermediate (INT2) breaks down on oxidation, to form a stable product (P3). Topological and AIM analyses have been performed for hydrogen bonded complex in this reaction profile. Intrinsic reaction coordinates [IRC, minimum-energy path (MEP)] calculation connects the transition state between R-INT1, INT1-P1 and INT1-P2. The products P1, P2 and P3 are energetically more stable than the reactant and hence the reaction enthalpy is found to be exothermic.

  7. 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...

  8. Is EC class predictable from reaction mechanism?

    Directory of Open Access Journals (Sweden)

    Nath Neetika

    2012-04-01

    Full Text Available Abstract Background We investigate the relationships between the EC (Enzyme Commission class, the associated chemical reaction, and the reaction mechanism by building predictive models using Support Vector Machine (SVM, Random Forest (RF and k-Nearest Neighbours (kNN. We consider two ways of encoding the reaction mechanism in descriptors, and also three approaches that encode only the overall chemical reaction. Both cross-validation and also an external test set are used. Results The three descriptor sets encoding overall chemical transformation perform better than the two descriptions of mechanism. SVM and RF models perform comparably well; kNN is less successful. Oxidoreductases and hydrolases are relatively well predicted by all types of descriptor; isomerases are well predicted by overall reaction descriptors but not by mechanistic ones. Conclusions Our results suggest that pairs of similar enzyme reactions tend to proceed by different mechanisms. Oxidoreductases, hydrolases, and to some extent isomerases and ligases, have clear chemical signatures, making them easier to predict than transferases and lyases. We find evidence that isomerases as a class are notably mechanistically diverse and that their one shared property, of substrate and product being isomers, can arise in various unrelated ways. The performance of the different machine learning algorithms is in line with many cheminformatics applications, with SVM and RF being roughly equally effective. kNN is less successful, given the role that non-local information plays in successful classification. We note also that, despite a lack of clarity in the literature, EC number prediction is not a single problem; the challenge of predicting protein function from available sequence data is quite different from assigning an EC classification from a cheminformatics representation of a reaction.

  9. 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.

  10. Modulation of the transient receptor potential vanilloid channel TRPV4 by 4alpha-phorbol esters: a structure-activity study

    DEFF Research Database (Denmark)

    Klausen, Thomas Kjaer; Pagani, Alberto; Minassi, Alberto;

    2009-01-01

    The mechanism of activation of the transient receptor potential vanilloid 4 (TRPV4) channel by 4alpha-phorbol esters was investigated by combining information from chemical modification of 4alpha-phorbol-didecanoate (4alpha-PDD, 2a), site-directed mutagenesis, Ca(2+) imaging, and electrophysiolog...... of TRPV4 activation by small molecules and obtain information for the rational design of structurally simpler ligands for this ion channel....

  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. Angular correlation measurements for 4-{alpha} decaying states in {sup 16}O

    Energy Technology Data Exchange (ETDEWEB)

    Wuosmaa, A.H.; Back, B.B.; Betts, R.R. [and others

    1995-08-01

    Previous measurements of the {sup 12}C({sup 12}C,{sup 8}Be){sup 16}O{sup *}(4 {alpha}) reaction identified discrete levels in {sup 16}O which decay by breakup into 4 {alpha} particles through a number of different decay sequences, including {sup 16}O{sup *} {yields} {sup 8}Be + {sup 8}Be and {alpha} + {sup 12}C (O{sub 2}{sup +}). These states are observed in a range of excitation energies where resonances are observed in inelastic {alpha} + {sup 12}C scattering leading to the {sup 8}Be + {sup 8}Be and {alpha} + {sup 12}C final states. These resonances were associated with 4 {alpha}-particle chain configurations in {sup 16}O. Should the states populated in the {sup 12}C + {sup 12}C reaction possess this same extended structure, it would serve as an important piece of evidence supporting the idea that even more deformed structures are formed in the {sup 24}Mg compound system. In order to more firmly make this association, it is important to determine the spins of the states populated in the {sup 12}C + {sup 12}C reaction.

  13. New methods for quantum mechanical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, W.H. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley Lab., CA (United States)

    1996-12-01

    Quantum mechanical methods are developed to describe the dynamics of bimolecular chemical reactions. We focus on developing approaches for directly calculating the desired quantity of interest. Methods for the calculation of single matrix elements of the scattering matrix (S-matrix) and initial state-selected reaction probabilities are presented. This is accomplished by the use of absorbing boundary conditions (ABC) to obtain a localized (L{sup 2}) representation of the outgoing wave scattering Green`s function. This approach enables the efficient calculation of only a single column of the S-matrix with a proportionate savings in effort over the calculation of the entire S-matrix. Applying this method to the calculation of the initial (or final) state-selected reaction probability, a more averaged quantity, requires even less effort than the state-to-state S-matrix elements. It is shown how the same representation of the Green`s function can be effectively applied to the calculation of negative ion photodetachment intensities. Photodetachment spectroscopy of the anion ABC{sup -} can be a very useful method for obtaining detailed information about the neutral ABC potential energy surface, particularly if the ABC{sup -} geometry is similar to the transition state of the neutral ABC. Total and arrangement-selected photodetachment spectra are calculated for the H{sub 3}O{sup -} system, providing information about the potential energy surface for the OH + H{sub 2} reaction when compared with experimental results. Finally, we present methods for the direct calculation of the thermal rate constant from the flux-position and flux-flux correlation functions. The spirit of transition state theory is invoked by concentrating on the short time dynamics in the area around the transition state that determine reactivity. These methods are made efficient by evaluating the required quantum mechanical trace in the basis of eigenstates of the Boltzmannized flux operator.

  14. [Reaction mechanism studies of heavy ion induced nuclear reactions

    International Nuclear Information System (INIS)

    This report contains papers that discuss: Target Dependence of Complex Fragment Emission in 47-MeV/u La-Induced Reactions; Deconvolution of Time-of-Flight Data to Improve Mass Identification; and Study of the Reaction of La + Al at E/A = 50 MeV with Landau-Vlasov Dynamics

  15. Knockout Reaction Mechanism for 6He+%Knockout Reaction Mechanism for 6He+

    Institute of Scientific and Technical Information of China (English)

    吕林辉; 叶沿林; 曹中鑫; 肖军; 江栋兴; 郑涛; 华辉; 李智焕; 葛俞成; 李湘庆; 楼建玲; 李阔昂; 李奇特; 乔锐; 游海波; 陈瑞九

    2012-01-01

    A knockout reaction experiment was carried out by using the 6He beam at 82.5 MeV/nucleon impinging on CH2 and C targets. The a core fragments at forward angles were detected in coincidence with the recoiled protons at larger angles. From this exclusive measure- ment the valence nucleon knockout mechanism and the core knockout mechanism are separated. This study provides a basis for the exclusive spectroscopic investigation of the exotic nuclei.

  16. 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. PMID:26456602

  17. Molecular analysis of a Clostridium butyricum NCIMB 7423 gene encoding 4-alpha-glucanotransferase and characterization of the recombinant enzyme produced in Escherichia coli.

    Science.gov (United States)

    Goda, S K; Eissa, O; Akhtar, M; Minton, N P

    1997-10-01

    An Escherichia coli clone was detected in a Clostridium butyricum NCIMB 7423 plasmid library capable of degrading soluble amylose. Deletion subcloning of its recombinant plasmid indicated that the gene(s) responsible for amylose degradation was localized on a 1.8 kb NspHI-Scal fragment. This region was sequenced in its entirety and shown to encompass a large ORF capable of encoding a protein with a calculated molecular mass of 57,184 Da. Although the deduced amino acid sequence showed only weak similarity with known amylases, significant sequences identity was apparent with the 4-alpha-glucano-transferase enzymes of Streptococcus pneumoniae (46.9%), potato (42.9%) and E. coli (16.2%). The clostridial gene (designated maIQ) was followed by a second ORF which, through its homology to the equivalent enzymes of E. coli and S. pneumoniae, was deduced to encode maltodextrin phosphorylase (MaIP). The translation stop codon of MaIQ overlapped the translation start codon of the putative maIP gene, suggesting that the two genes may be both transcriptionally and translationally coupled. 4-alpha-Glucanotransferase catalyses a disproportionation reaction in which single or multiple glucose units from oligosaccharides are transferred to the 4-hydroxyl group of acceptor sugars. Characterization of the recombinant C. butyricum enzyme demonstrated that glucose, maltose and maltotriose could act as acceptor, whereas of the three only maltotriose could act as donor. The enzyme therefore shares properties with the E. coli MaIQ protein, but differs significantly from the glucanotransferase of Thermotoga maritima, which is unable to use maltotriose as donor or glucose as acceptor. Physiologically, the concerted action of 4-alpha-glucanotransferase and maltodextrin phosphorylase provides C. butyricum with a mechanism of utilizing amylose/maltodextrins with little drain on cellular ATP reserves. PMID:9353929

  18. Deducing Reaction Mechanism: A Guide for Students, Researchers, and Instructors

    Science.gov (United States)

    Meek, Simon J.; Pitman, Catherine L.; Miller, Alexander J. M.

    2016-01-01

    An introductory guide to deducing the mechanism of chemical reactions is presented. Following a typical workflow for probing reaction mechanism, the guide introduces a wide range of kinetic and mechanistic tools. In addition to serving as a broad introduction to mechanistic analysis for students and researchers, the guide has also been used by…

  19. Multiple post-translational modifications in hepatocyte nuclear factor 4{alpha}

    Energy Technology Data Exchange (ETDEWEB)

    Yokoyama, Atsushi; Katsura, Shogo; Ito, Ryo; Hashiba, Waka; Sekine, Hiroki; Fujiki, Ryoji [Institute of Molecular and Cellular Biosciences, University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan); Kato, Shigeaki, E-mail: uskato@mail.ecc.u-tokyo.ac.jp [Institute of Molecular and Cellular Biosciences, University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan)

    2011-07-15

    Highlights: {yields} We performed comprehensive PTM analysis for HNF4{alpha} protein. {yields} We identified 8 PTMs in HNF4{alpha} protein including newly identified PTMs. {yields} Among them, we found acetylation at lysine 458 was one of the prime PTMs for HNF4{alpha} function. {yields} Acetylation at lysine 458 was inhibitory for HNF4{alpha} transcription function. {yields} This modification fluctuated in response to extracellular condition. -- Abstract: To investigate the role of post-translational modifications (PTMs) in the hepatocyte nuclear factor 4{alpha} (HNF4{alpha})-mediated transcription, we took a comprehensive survey of PTMs in HNF4{alpha} protein by massspectrometry and identified totally 8 PTM sites including newly identified ubiquitilation and acetylation sites. To assess the impact of identified PTMs in HNF4{alpha}-function, we introduced point mutations at the identified PTM sites and, tested transcriptional activity of the HNF4{alpha}. Among the point-mutations, an acetylation site at lysine 458 was found significant in the HNF4{alpha}-mediated transcriptional control. An acetylation negative mutant at lysine 458 showed an increased transcriptional activity by about 2-fold, while an acetylation mimic mutant had a lowered transcriptional activation. Furthermore, this acetylation appeared to be fluctuated in response to extracellular nutrient conditions. Thus, by applying an comprehensive analysis of PTMs, multiple PTMs were newly identified in HNF4{alpha} and unexpected role of an HNF4{alpha} acetylation could be uncovered.

  20. Photochemical Reactions of Cyclohexanone: Mechanisms and Dynamics.

    Science.gov (United States)

    Shemesh, Dorit; Nizkorodov, Sergey A; Gerber, R Benny

    2016-09-15

    Photochemistry of carbonyl compounds is of major importance in atmospheric and organic chemistry. The photochemistry of cyclohexanone is studied here using on-the-fly molecular dynamics simulations on a semiempirical multireference configuration interaction potential-energy surface to predict the distribution of photoproducts and time scales for their formation. Rich photochemistry is predicted to occur on a picosecond time scale following the photoexcitation of cyclohexanone to the first singlet excited state. The main findings include: (1) Reaction channels found experimentally are confirmed by the theoretical simulations, and a new reaction channel is predicted. (2) The majority (87%) of the reactive trajectories start with a ring opening via C-Cα bond cleavage, supporting observations of previous studies. (3) Mechanistic details, time scales, and yields are predicted for all reaction channels. These benchmark results shed light on the photochemistry of isolated carbonyl compounds in the atmosphere and can be extended in the future to photochemistry of more complex atmospherically relevant carbonyl compounds in both gaseous and condensed-phase environments.

  1. Chemical kinetic reaction mechanism for the combustion of propane

    Science.gov (United States)

    Jachimowski, C. J.

    1984-01-01

    A detailed chemical kinetic reaction mechanism for the combustion of propane is presented and discussed. The mechanism consists of 27 chemical species and 83 elementary chemical reactions. Ignition and combustion data as determined in shock tube studies were used to evaluate the mechanism. Numerical simulation of the shock tube experiments showed that the kinetic behavior predicted by the mechanism for stoichiometric mixtures is in good agrement with the experimental results over the entire temperature range examined (1150-2600K). Sensitivity and theoretical studies carried out using the mechanism revealed that hydrocarbon reactions which are involved in the formation of the HO2 radical and the H2O2 molecule are very important in the mechanism and that the observed nonlinear behavior of ignition delay time with decreasing temperature can be interpreted in terms of the increased importance of the HO2 and H2O2 reactions at the lower temperatures.

  2. Mechanism of cis-prenyltransferase reaction probed by substrate analogues

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Yen-Pin; Liu, Hon-Ge [Institute of Biochemical Sciences, National Taiwan University, Taipei 106, Taiwan, ROC (China); Teng, Kuo-Hsun [Institute of Biological Chemistry, Academia Sinica, Taipei 115, Taiwan, ROC (China); Liang, Po-Huang, E-mail: phliang@gate.sinica.edu.tw [Institute of Biochemical Sciences, National Taiwan University, Taipei 106, Taiwan, ROC (China); Institute of Biological Chemistry, Academia Sinica, Taipei 115, Taiwan, ROC (China)

    2010-10-01

    Research highlights: {yields} The extremely slow trans-OPPS reaction using 2-Fluoro-FPP supports the sequential mechanism with the carbocation intermediate. {yields} The similar UPPS reaction rate under single turnover supports the concerted mechanism, without the carbocation intermediate. {yields} The secondary kinetic isotope effect also supports associate transition state for UPPS reaction, without the carbocation intermediate. -- Abstract: Undecaprenyl pyrophosphate synthase (UPPS) is a cis-type prenyltransferases which catalyzes condensation reactions of farnesyl diphosphate (FPP) with eight isopentenyl pyrophosphate (IPP) units to generate C{sub 55} product. In this study, we used two analogues of FPP, 2-fluoro-FPP and [1,1-{sup 2}H{sub 2}]FPP, to probe the reaction mechanism of Escherichia coli UPPS. The reaction rate of 2-fluoro-FPP with IPP under single-turnover condition is similar to that of FPP, consistent with the mechanism without forming a farnesyl carbocation intermediate. Moreover, the deuterium secondary KIE of 0.985 {+-} 0.022 measured for UPPS reaction using [1,1-{sup 2}H{sub 2}]FPP supports the associative transition state. Unlike the sequential mechanism used by trans-prenyltransferases, our data demonstrate E. coli UPPS utilizes the concerted mechanism.

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

    International Nuclear Information System (INIS)

    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 CO2 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/CO2 flow rate confirms the production of CO and CO2 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 char

  4. 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.

  5. 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. PMID:27225077

  6. Synthesis of 7-Ethyl-10-hydroxycamptothecin and Proposed Reaction Mechanism

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The improved 3-step preparation of a key antitumor agent, 7-ethyl-10-hydroxycamptothecin(SN-38), which consists of ethylation, oxidation and photo-chemical rearrangement, is described. The proposed reaction mechanism is also discussed.

  7. Reaction Mechanism of the Multi-channel Decomposition Reactions of 1-Pentenyl Free Radicals

    Institute of Scientific and Technical Information of China (English)

    CHENG,Xue-Li; ZHAO,Yan-Yun; LI,Feng; LI,Li-Qing; TAO,Xiu-Jun

    2008-01-01

    The reactions of 1-pentenyl decomposition system have been studied extensively at the B3LYP/6-311++G** level with Gaussion 98 package. The potential energy surface with zero-point energy correction was drawn. All reaction channels were fully investigated with the vibrational mode analysis, frontier orbital analysis and electron population analysis to confirm the transition states and reveal the reaction mechanism.

  8. Nitrile reaction in high-temperature water: Kinetics and mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Izzo, B.; Harrell, C.L.; Klein, M.T. [Univ. of Delaware, Newark, DE (United States). Dept. of Chemical Engineering

    1997-08-01

    The reaction pathways, kinetics and mechanisms underlying the hydrolysis of aliphatic and aromatic nitriles in high-temperature water (HTW) were investigated. The reaction products were the associated amides and carboxylic acids. Autocatalytic kinetics were observed and confirmed by experiment and analysis of the physical chemistry of the HTW reaction environment. A model incorporating two autocatalytic steps captured the observed kinetics well, and the associated optimized rate constants highlighted the key differences in the reaction chemistry of aliphatic and aromatic nitriles. The rate behavior of nitrile hydrolysis at these conditions has tangible consequences regarding optimal processing strategies.

  9. Density Functional Study on the Mechanism of Amadori Rearrangement Reaction

    Institute of Scientific and Technical Information of China (English)

    BAO Xiu-Xiu; CHEN Zu-Qin; XIE Hu-Jun

    2011-01-01

    The reaction mechanism of amadori rearrangement in the initial stage of Maillard reaction has been investigated by means of density functional theory calculations in the gaseous phase and aqueous solution. Cyclic ribose and glycine were taken as the model in the amadori rearrangement. Reaction mechanisms have been proposed, and possibility for the formation of different compounds has been evaluated through calculating the relative energy changes for different steps of the reaction by following the total mass balance. The calculations reveal that the amadori rearrangement initialized via the intramolecular rearrangement, transferring one proton from N(3) to O(4) atom. In the next step, the second proton is also transferred from N(3) to O(4) atom,corresponding to the cleavage of C(4)-O(4) bond and the release of one water molecule. Then another proton is transferred from N(3) to C(5) atom via TS3 with the reaction barrier of 58.3kcal.mol-1 after tunneling the effect correction calculated at the B3LYP/6-31+G(d) level of theory,and this step is rate limiting for the whole catalytic cycle. Ultimately, the product is generated via keto-enolic tautomerization. Present calculation 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.

  10. 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.

  11. 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)

  12. Atherton–Todd reaction: mechanism, scope and applications

    Directory of Open Access Journals (Sweden)

    Stéphanie S. Le Corre

    2014-05-01

    Full Text Available Initially, the Atherton–Todd (AT reaction was applied for the synthesis of phosphoramidates by reacting dialkyl phosphite with a primary amine in the presence of carbon tetrachloride. These reaction conditions were subsequently modified with the aim to optimize them and the reaction was extended to different nucleophiles. The mechanism of this reaction led to controversial reports over the past years and is adequately discussed. We also present the scope of the AT reaction. Finally, we investigate the AT reaction by means of exemplary applications, which mainly concern three topics. First, we discuss the activation of a phenol group as a phosphate which allows for subsequent transformations such as cross coupling and reduction. Next, we examine the AT reaction applied to produce fire retardant compounds. In the last section, we investigate the use of the AT reaction for the production of compounds employed for biological applications. The selected examples to illustrate the applications of the Atherton–Todd reaction mainly cover the past 15 years.

  13. The catalytic reaction mechanism of drosophilid alcohol dehydrogenases

    Directory of Open Access Journals (Sweden)

    Imin Wushur

    2015-03-01

    Full Text Available The present review describes the current knowledge about the reaction mechanism of drosophilid alcohol dehydrogenases (DADH, a member of the short chain dehydrogenase/reductase (SDR superfamily. Included is the binding order of the substrates to the enzyme, rate limiting steps, stereochemistry of the reaction, active site topology, role of important amino acids and water molecules in the reaction and pH dependence of kinetic coefficients. We focus on the contribution from steady state kinetics where alternative substrates, dead end and product inhibitors, isotopes and mutated DADHs have been used as well as on the contributions from X-ray crystallography, NMR and theoretical calculations. Furthermore, we also raise some open questions in order to fully understand the reaction mechanism of this enzyme.

  14. On the Reaction Mechanism of Br2 with OCS

    Institute of Scientific and Technical Information of China (English)

    Hai Tao YU; Hua ZHONG; Ming Xia LI; Hong Gang FU; Jia Zhong SUN

    2005-01-01

    The reaction mechanism of photochemical reaction between Br2 ( 1 ∑ ) and OCS ( 1 ∑ ) is predicted by means of theoretical methods. The calculated results indicate that the direct addition of Br2 to the CS bond of OCS molecule is more favorable in energy than the direct addition of Br2to the CO bond. Furthermore, the intermediate isomer syn-BrC(O)SBr is more stable thermodynamically and kinetically than anti-BrC(O)SBr. The original resultant anti-BrC(O)SBr formed in the most favorable reaction channel can easily isomerize into the final product syn-BrC(O)SBr with only 31.72 kJ/mol reaction barrier height. The suggested mechanism is in good agreement with previous experimental study.

  15. Theoretical Study on the Dark Oxidation Reaction Mechanism of Ethers

    Institute of Scientific and Technical Information of China (English)

    WANG Gui-Xiu; ZHU Rong-Xiu; ZHANG Dong-Ju; LIU Cheng-Bu

    2006-01-01

    The dark oxidation reactions of ethers including aether, isopropyl ether, phenyl isopropyl ether, and benzyl isopropyl ether have been studied by using density functional theory calculations. The structures of initial contact charge transfer complexes (CCTCs), transition states and caged radical intermediates have been located at the B3LYP/6-31G (d) level. The bonding nature of ethers with triplet O2 in CCTCs has been analyzed, and the detailed mechanism of dark oxidation reactions of ether is presented clearly.

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

    International Nuclear Information System (INIS)

    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. Thermal degradation reaction mechanism of xylose: A DFT study

    Science.gov (United States)

    Huang, Jinbao; He, Chao; Wu, Longqin; Tong, Hong

    2016-08-01

    The thermal degradation reaction mechanism of xylose as hemicellulose model compound was investigated by using density functional theory methods M062X with the 6-31++G(d,p) basis set. Eight possible pyrolytic reaction pathways were proposed and the standard kinetic and thermodynamic parameters in all reaction pathways were calculated at different temperatures. In reaction pathway (1), xylose is first transformed into acyclic containing-carbonyl isomer, and then the isomer further decomposes through four possible pyrolysis pathways (1-1)-(1-4). Pathways (2) and (3) depict an immediate ring-opening process through the simultaneous breaking of C-O and C-C bonds. Pathways (4)-(7) describe the pyrolysis processes of various anhydro-xyloses through a direct ring-opening process. Pathway (8) gives the evolutionary process of pyranones. The calculation results show that reaction pathways (1), (2) and (5) are the major reaction channels and reaction pathways (3), (4), and (6)-(8) are the competitive reaction channels in pyrolysis of xylose. The major products of xylose pyrolysis are low molecular products such as 2-furaldehyde, glycolaldehyde, acetaldehyde, methylglyoxal and acetone, and the main competitive products are formaldehyde, formic acid, acetic acid, CO2, CH4, acetol, pyranone, and so on.

  18. Reaction mechanism study of 7Li(7Li, 6He) reaction at above Coulomb barrier energies

    Indian Academy of Sciences (India)

    V V Parkar; V Jha; S Santra; B J Roy; K Ramachandran; A Shrivastava; K Mahata; A Chatterjee; S Kailas

    2009-02-01

    The elastic scattering and the 6He angular distributions were measured in 7Li + 7Li reaction at two energies, lab = 20 and 25 MeV. FRDWBA calculations have been performed to explain the measured 6He data. The calculations were very sensitive to the choice of the optical model potentials in entrance and exit channels. The one-step proton transfer was found to be the dominant reaction mechanism in 6He production.

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

    Science.gov (United States)

    Li, Wenjin; Ma, Ao

    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 C7eq → C7ax 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.

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

    Science.gov (United States)

    Li, Wenjin; Ma, Ao

    2016-03-01

    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 C7eq → C7ax 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. Physical Mechanism of Nuclear Reactions at Low Energies

    CERN Document Server

    Oleinik, V P; Arepjev, Yu.D

    2002-01-01

    The physical mechanism of nuclear reactions at low energies caused by spatial extension of electron is considered. Nuclear reactions of this type represent intra-electronic processes, more precisely, the processes occurring inside the area of basic localization of electron. Distinctive characteristics of these processes are defined by interaction of the own field produced by electrically charged matter of electron with free nuclei. Heavy nucleus, appearing inside the area of basic localization of electron, is inevitably deformed because of interaction of protons with the adjoining layers of electronic cloud, which may cause nuclear fission. If there occur "inside" electron two or greater number of light nuclei, an attractive force appears between the nuclei which may result in the fusion of nuclei. The intra-electronic mechanism of nuclear reactions is of a universal character. For its realization it is necessary to have merely a sufficiently intensive stream of free electrons, i.e. heavy electric current, an...

  2. Reaction of niobium with hexane and methanol by mechanical grinding

    International Nuclear Information System (INIS)

    In mechanical alloying (MA) processing, alcohol, acetone and other organic solvents are often added as dispersants in order that powders will not stick to a vessel. It has been however considered that these organic solvents are simply additives. Enough attention has not been paid to the role or reaction of these dispersants. Recently, it was found that these organic solvents could react with some metals. For example, the authors reported that NbC is obtained by a reaction between Nb and methanol in the preparation of Al3Nb intermetallics by the MA method. Niobium hydrides are obtained by milling of Nb powders in hydrocarbon. In this paper, the authors discuss the reaction between Nb powder and hexane (C6H14) or methanol (CH3OH) during mechanical grinding (MG) processing

  3. Hydroxylation Reaction Mechanism for Nitrosodimethylamine by Oxygen Atom

    Institute of Scientific and Technical Information of China (English)

    LI Lan; LIN Xiao-yan; LI Zong-he

    2011-01-01

    The hydroxylation reaction mechanism of nitrosodimethylamine(NDMA)by oxygen atom was theoretically investigated at the B3LYP/6-31G** level.It has been found that the path of the oxydation of the C-H bond is easier than the path involving a Singlet/Triplet crossing.The study of the potential surface shows that both solvent effect at B3LYP/6-31G** level and different method at more credible MP2/6-311G** level in the gas phase have no effect on the hydroxylation reaction mechanism.The oxidation hydroxylation process of NDMA by O is exothermic reaction and easy to occur.

  4. The mechanism of electronic excitation in the bacterial bioluminescent reaction

    International Nuclear Information System (INIS)

    The current state of the problem of formation of the electron-excited product in the chemiluminescent reaction that underlies the bacterial luminescence is analysed. Various schemes of chemical transformations capable of producing a bacterial bioluminescence emitter are presented. The problem of excitation of secondary emitters is considered; two possible mechanisms of their excitation are analysed.

  5. 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

  6. Benzoxazinone-Mediated Triazine Degradation: A Proposed Reaction Mechanism.

    Science.gov (United States)

    Willett, C D; Lerch, R N; Lin, C-H; Goyne, K W; Leigh, N D; Roberts, C A

    2016-06-22

    The role of benzoxazinones (Bx, 2-hydroxy-2H-1,4-benzoxazin-3(4H)-one) in triazine resistance in plants has been studied for over half a century. In this research, fundamental parameters of the reaction between DIBOA-Glc (2-β-d-glucopyranosyloxy-4-hydroxy-1,4-benzoxazin-3-one) and atrazine (ATR, 6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine) were examined. Through a series of experiments employing a variety of chromatographic and spectroscopic techniques, the DIBOA-Glc/ATR reaction was characterized in terms of reactant and product kinetics, stoichiometry, identification of a reaction intermediate, and reaction products formed. Results of these experiments demonstrated that the reaction mechanism proceeds via nucleophilic attack of the hydroxamic acid moiety of DIBOA-Glc at the C-2 position of the triazine ring to form hydroxyatrazine (HA, 2-hydroxy-4-ethylamino-6-isopropylamino-s-triazine), with associated degradation of DIBOA-Glc. Degradation of reactants followed first-order kinetics with a noncatalytic role of DIBOA-Glc. A reaction intermediate was identified as a DIBOA-Glc-HA conjugate, indicating a 1:1 DIBOA-Glc:ATR stoichiometry. Reaction products included HA and Cl(-), but definitive identification of DIBOA-Glc reaction product(s) was not attained. With these reaction parameters elucidated, DIBOA-Glc can be evaluated in terms of its potential for a myriad of applications, including its use to address the problem of widespread ATR contamination of soil and water resources. PMID:27215133

  7. DFT study on mechanism of the classical Biginelli reaction

    Institute of Scientific and Technical Information of China (English)

    Jin Guang Ma; Ji Ming Zhang; Hai Hui Jiang; Wan Yong Ma; Jian Hua Zhou

    2008-01-01

    The condensation of benzaldehyde, urea, and ethyl acetoacetate according to the procedure described by Biginelli was investigated at the B3LYP/6-31G(d), B3LYP/6-31+G(d,p), and B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p) levels to explore the reaction mechanism. According to the mechanism proposed by Kappe, structures of five intermediates were optimized and four transition states were found. The calculation results proved that the mechanism proposed by Kappe is right.

  8. Nuclear reaction mechanisms. Progress report, June 1975--May 1976

    Energy Technology Data Exchange (ETDEWEB)

    Blann, M.

    1976-01-01

    Research under the subject contract has been directed along two major lines: (1) development and exploration of pre-equilibrium statistical models; (2) experimental measurement and theoretical investigation of heavy ion reaction mechanisms, with emphasis on the limits on compound nucleus formation. Much of the work under this contract has been published and a list of publications is part of this report. This work is not otherwise summarized herein. New unpublished results on heavy ion reactions are briefly summarized, as are results of precompound ..cap alpha.. emission. Colloquia and addresses are also summarized. Separate abstracts appear in ERA for six of the papers in this report.

  9. 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.

  10. Facilitating effects of berberine on rat pancreatic islets through modulating hepatic nuclear factor 4 alpha expression and glucokinase activity

    Institute of Scientific and Technical Information of China (English)

    Zhi-Quan Wang; Fu-Er Lu; San-Hua Leng; Xin-Sheng Fang; Guang Chen; Zeng-Si Wang; Li-Ping Dong; Zhong-Qing Yan

    2008-01-01

    AIM: To observe the effect of berberine on insulin secretion in rat pancreatic islets and to explore its possible molecular mechanism.METHODS: Primary rat islets were isolated from male Sprague-Dawley rats by collagenase digestion and treated with different concentrations (1, 3, 10 and 30 μmol/L) of berberine or 1 μmol/L Glibenclamide (GB) for 24 h. Glucose-stimulated insulin secretion (GSIS) assay was conducted and insulin was determined by radioimmunoassay. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (NTT) assay was performed to evaluate cytotoxicity. The mRNA level of hepatic nuclear factor 4 alpha (HNF4α) was determined by reverse transcription polymerase chain reaction (RT-PCR). Indirect immunofluorescence staining and Western blot analysis were employed to detect protein expression of HNF4α in the islets. Glucokinase (GK) activity was measured by spectrophotometric method.RESULTS: Berberine enhanced GSIS rather than basal insulin secretion dose-dependently in rat islets and showed no significant cytotoxicity on islet cells at the concentration of 10 μmol/L. Both mRNA and protein expressions of HNF4α were up-regulated by berberine in a dose-dependent manner, and GK activity was also increased accordingly. However, GB demonstrated no regulatory effects on HNF4α expression or GK activity.CONCLUSION: Berberine can enhance GSIS in rat islets, and probably exerts the insulinotropic effect via a pathway involving HNF4α and GK, which is distinct from sulphonylureas (SUs).

  11. Kinetics and reaction mechanism of hydroxyl radical reaction with methyl formate

    Energy Technology Data Exchange (ETDEWEB)

    Good, D.A.; Hanson, J.; Francisco, J.S.; Li, Z.; Jeong, G.R.

    1999-12-16

    Ab initio molecular orbital theory has been used to examine the kinetics and mechanism for the reaction of hydroxyl radical with methyl formate. From the ab initio parameters the room temperature rate constant is calculated and found to be in good agreement with the experimental determination. It is found that 86% of the reaction proceeds via abstraction of the carbonyl hydrogen from methyl formate by hydroxyl radical, resulting in the formation of CH{sub 3}OCO radical. CH{sub 3}OCO is expected to oxidize to formaldehyde and carbon dioxide under tropospheric conditions.

  12. Reactions of a stable dialkylsilylene and their mechanisms

    Indian Academy of Sciences (India)

    Mitsuo Kira

    2012-11-01

    Various reactions for a stable dialkylsilylene, 2,2,5,5-tetrakis(trimethylsilyl)silacyclopentane-1,1-diyl (1), are summarized and their mechanisms are discussed. Silylene 1 isomerizes to the corresponding silaethene via the 1,2-trimethylsilyl migration. Reduction of 1 with alkali metals affords the corresponding radical anion 1.− with a relatively small 29Si hfs constant (2.99 mT) and a large g-factor (g = 2.0077) compared with those for trivalent silyl radicals. Photo-excitation of 1 generates the corresponding singlet excited state (11*) with the lifetime of 80.5 ns. The excited state reacts with C=C double bond compounds including benzene, naphthalene, and ()- and ()-2-butenes. Although the thermal reactions of 1 with haloalkanes occur via radical mechanisms, the insertion into O-H, Si-H and Si-Cl bonds proceeds concertedly via the threemembered cyclic transition states. The reaction of 1 with H2SiCl2 gives the Si-Cl insertion product exclusively, while the quantitative insertion to Si-H bond occurs when Me2SiHCl is used as a substrate. The origin of the rather unusual Si-H/Si-Cl selectivity is elucidated using DFT calculations. Silylene 1 adds to C=C, C≡C, and C=O bonds to afford the corresponding silacycles as stable compounds. The importance of the carbonyl silaylides during the reactions of silylenes with aldehydes and ketones is emphasized.

  13. Reaction Kinetics and Mechanism of Magnetic Field Effects in Cryptochrome

    OpenAIRE

    Ilia A Solov'yov; 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 sensitive radical pair reactions occurring in the retina, the light-sensitive part of animal eyes. A photoreceptor, cryptochrome, has been suggested to endow birds with magnetoreceptive abilities...

  14. Chemical reactions modulated by mechanical stress: extended Bell theory.

    Science.gov (United States)

    Konda, Sai Sriharsha M; Brantley, Johnathan N; Bielawski, Christopher W; Makarov, Dmitrii E

    2011-10-28

    A number of recent studies have shown that mechanical stress can significantly lower or raise the activation barrier of a chemical reaction. Within a common approximation due to Bell [Science 200, 618 (1978)], this barrier is linearly dependent on the applied force. A simple extension of Bell's theory that includes higher order corrections in the force predicts that the force-induced change in the activation energy will be given by -FΔR - ΔχF(2)∕2. Here, ΔR is the change of the distance between the atoms, at which the force F is applied, from the reactant to the transition state, and Δχ is the corresponding change in the mechanical compliance of the molecule. Application of this formula to the electrocyclic ring-opening of cis and trans 1,2-dimethylbenzocyclobutene shows that this extension of Bell's theory essentially recovers the force dependence of the barrier, while the original Bell formula exhibits significant errors. Because the extended Bell theory avoids explicit inclusion of the mechanical stress or strain in electronic structure calculations, it allows a computationally efficient characterization of the effect of mechanical forces on chemical processes. That is, the mechanical susceptibility of any reaction pathway is described in terms of two parameters, ΔR and Δχ, both readily computable at zero force.

  15. Characterization of the proposed 4-{\\alpha} cluster state candidate in 16O

    CERN Document Server

    Li, K C W; Adsley, P; Papka, P; Smit, F D; Brümmer, J W; Diget, C Aa; Freer, M; Harakeh, M N; Kokalova, Tz; Nemulodi, F; Pellegri, L; Rebeiro, B; Swartz, J A; Triambak, S; van Zyl, J J; Wheldon, C

    2016-01-01

    The $\\mathrm{^{16}O}(\\alpha, \\alpha^{\\prime})$ reaction was studied at $\\theta_{lab} = 0^\\circ$ at an incident energy of $\\textrm{E}_{lab}$ = 200 MeV using the K600 magnetic spectrometer at iThemba LABS. Proton and $\\alpha$-decay from the natural parity states were observed in a large-acceptance silicon-strip detector array at backward angles. The coincident charged particle measurements were used to characterize the decay channels of the $0_{6}^{+}$ state in $\\mathrm{^{16}O}$ located at $E_{x} = 15.097(5)$ MeV. This state is identified by several theoretical cluster calculations to be a good candidate for the 4-$\\alpha$ cluster state. The results of this work suggest the presence of a previously unidentified resonance at $E_{x}\\approx15$ MeV that does not exhibit a $0^{+}$ character. This unresolved resonance may have contaminated previous observations of the $0_{6}^{+}$ state.

  16. Reaction route graphs. III. Non-minimal kinetic mechanisms.

    Science.gov (United States)

    Fishtik, Ilie; Callaghan, Caitlin A; Datta, Ravindra

    2005-02-24

    The concept of reaction route (RR) graphs introduced recently by us for kinetic mechanisms that produce minimal graphs is extended to the problem of non-minimal kinetic mechanisms for the case of a single overall reaction (OR). A RR graph is said to be minimal if all of the stoichiometric numbers in all direct RRs of the mechanism are equal to +/-1 and non-minimal if at least one stoichiometric number in a direct RR is non-unity, e.g., equal to +/-2. For a given mechanism, four unique topological characteristics of RR graphs are defined and enumerated, namely, direct full routes (FRs), empty routes (ERs), intermediate nodes (INs), and terminal nodes (TNs). These are further utilized to construct the RR graphs. One algorithm involves viewing each IN as a central node in a RR sub-graph. As a result, the construction and enumeration of RR graphs are reduced to the problem of balancing the peripheral nodes in the RR sub-graphs according to the list of FRs, ERs, INs, and TNs. An alternate method involves using an independent set of RRs to draw the RR graph while satisfying the INs and TNs. Three examples are presented to illustrate the application of non-minimal RR graph theory.

  17. Mapping of HNF4alpha target genes in intestinal epithelial cells

    DEFF Research Database (Denmark)

    Boyd, Mette; Bressendorff, Simon; Moller, Jette;

    2009-01-01

    . The HNF4alpha ChIP-chip data was matched with gene expression and histone H3 acetylation status of the promoters in order to identify HNF4alpha binding to actively transcribed genes with an open chromatin structure. RESULTS: 1,541 genes were identified as potential HNF4alpha targets, many of which have...... not previously been described as being regulated by HNF4alpha. The 1,541 genes contributed significantly to gene ontology (GO) pathways categorized by lipid and amino acid transport and metabolism. An analysis of the homeodomain transcription factor Cdx-2 (CDX2), the disaccharidase trehalase (TREH...... a transcription factor network also including HNF1alpha, all of which are transcription factors involved in intestinal development and gene expression....

  18. Insight into the Mechanism of the Michael Reaction.

    Science.gov (United States)

    Giraldo, Carolina; Gómez, Sara; Weinhold, Frank; Restrepo, Albeiro

    2016-07-01

    The mechanism for the nucleophilic addition step of the Michael reaction between methanethiol as a model Michael donor and several α-substituted methyl acrylates (X=F, Cl, Me, H, CN, NO2 ) as model Michael acceptors is described in detail. We suggest a novel way to condense electrophilic Fukui functions at specific atoms in terms of the contributions from the atomic orbitals to the LUMO or, more generally, to the orbital controlling the reaction. This procedure correctly associates activation energies to local electrophilic Fukui indices for the cases treated in this work. The calculated reaction barriers strongly depend on the nature of the substituent. As a general rule, activation energies are governed by structural changes, although electronic factors are significant for electron-withdrawing groups. Nucleophilic addition to Michael receptors is best described as a highly nonsynchronous process, in which the geometry of the transition state comprises a nonplanar six-membered ring. Formation of the S⋅⋅⋅C bond, which defines the interaction between the reactants, progresses ahead of all other primitive processes in the early stages of the transformation. In view of our results, we postulate that highly complex chemical reactions, as is the case for the nucleophilic addition step studied herein, that involve cleavage/formation of a total of six bonds, lower their activation energies by favoring nonsynchronicity, that is, for these types of systems, primitive changes should advance at different rates.

  19. Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks

    Energy Technology Data Exchange (ETDEWEB)

    Ziaul Huque

    2007-08-31

    This is the final technical report for the project titled 'Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks'. The aim of the project was to develop an efficient chemistry model for combustion simulations. The reduced chemistry model was developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) was used via a new network topology known as Non-linear Principal Components Analysis (NPCA). A commonly used Multilayer Perceptron Neural Network (MLP-NN) was modified to implement NPCA-NN. The training rate of NPCA-NN was improved with the GEneralized Regression Neural Network (GRNN) based on kernel smoothing techniques. Kernel smoothing provides a simple way of finding structure in data set without the imposition of a parametric model. The trajectory data of the reaction mechanism was generated based on the optimization techniques of genetic algorithm (GA). The NPCA-NN algorithm was then used for the reduction of Dimethyl Ether (DME) mechanism. DME is a recently discovered fuel made from natural gas, (and other feedstock such as coal, biomass, and urban wastes) which can be used in compression ignition engines as a substitute for diesel. An in-house two-dimensional Computational Fluid Dynamics (CFD) code was developed based on Meshfree technique and time marching solution algorithm. The project also provided valuable research experience to two graduate students.

  20. Roles of interfacial reaction on mechanical properties of solder interfaces

    Science.gov (United States)

    Liu, Pilin

    This study investigated roles of interfacial reaction in fracture and fatigue of solder interconnects. The interfacial reaction phases in the as-reflowed and after aging were examined by cross-sectional transmission electron microscopy (TEM) while interfacial mechanical properties were determined from a flexural peel fracture mechanics technique. Because of their widespread uses in microelectronic packaging, SnPb solder interfaces, and Bi-containing Pb-free solder interfaces were chosen as the subjects of this study. In the interfacial reaction study, we observed a complicated micro structural evolution during solid-state aging of electroless-Ni(P)/SnPb solder interconnects. In as-reflowed condition, the interfacial reaction produced Ni3Sn 4 and P-rich layers. Following overaging, the interfacial microstructure degenerated into a complex multilayer structure consisting of multiple layers of Ni-Sn compounds and transformed Ni-P phases. In SnPb solder interfacial system, fatigue study showed that the overaging of the high P electroless Ni-P/SnPb interconnects resulted in a sharp reduction in the fatigue resistance of the interface in the high crack growth rate regime. Fracture mechanism analysis indicated that the sharp drop in fatigue resistance was triggered by the brittle fracture of the Ni3Sn2 intermetallic phase developed at the overaged interface. The fatigue behavior was strongly dependent on P concentration in electroless Ni. Kirkendall voids were found in the interfacial region after aging, but they did not cause premature fracture of the solder interfaces. In Bi-containing solder interfacial system, we found that Bi segregated to the Cu-intermetallic interface during aging in SnBi/Cu interconnect. This caused serious embrittlement of Sn-Bi/Cu interface. Further aging induced numerous voids along the Cu3Sn/Cu interface. These interfacial voids were different from Kirkendall voids. Their formation was explained on basis of vacancy condensation at the

  1. 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...... absorption and electron-spin-resonance observations together with known facts on avian magnetoreception. The reaction cycle permits one to predict magnetic field effects on cryptochrome activation and deactivation. The suggested analysis method gives insight into structural and dynamic design features...... required for optimal detection of the geomagnetic field by cryptochrome and suggests further experimental and theoretical studies....

  2. Computational analysis of the mechanism of chemical reactions in terms of reaction phases: hidden intermediates and hidden transition States.

    Science.gov (United States)

    Kraka, Elfi; Cremer, Dieter

    2010-05-18

    Computational approaches to understanding chemical reaction mechanisms generally begin by establishing the relative energies of the starting materials, transition state, and products, that is, the stationary points on the potential energy surface of the reaction complex. Examining the intervening species via the intrinsic reaction coordinate (IRC) offers further insight into the fate of the reactants by delineating, step-by-step, the energetics involved along the reaction path between the stationary states. For a detailed analysis of the mechanism and dynamics of a chemical reaction, the reaction path Hamiltonian (RPH) and the united reaction valley approach (URVA) are an efficient combination. The chemical conversion of the reaction complex is reflected by the changes in the reaction path direction t(s) and reaction path curvature k(s), both expressed as a function of the path length s. This information can be used to partition the reaction path, and by this the reaction mechanism, of a chemical reaction into reaction phases describing chemically relevant changes of the reaction complex: (i) a contact phase characterized by van der Waals interactions, (ii) a preparation phase, in which the reactants prepare for the chemical processes, (iii) one or more transition state phases, in which the chemical processes of bond cleavage and bond formation take place, (iv) a product adjustment phase, and (v) a separation phase. In this Account, we examine mechanistic analysis with URVA in detail, focusing on recent theoretical insights (with a variety of reaction types) from our laboratories. Through the utilization of the concept of localized adiabatic vibrational modes that are associated with the internal coordinates, q(n)(s), of the reaction complex, the chemical character of each reaction phase can be identified via the adiabatic curvature coupling coefficients, A(n,s)(s). These quantities reveal whether a local adiabatic vibrational mode supports (A(n,s) > 0) or resists

  3. A New Formulation of the Lindemann Mechanism of Unimolecular Reactions

    Institute of Scientific and Technical Information of China (English)

    钱人元

    2003-01-01

    A new formulation of the Lindemann mechanism of unimolecular reactions in gaseous phase is presented, without the use of steady state hypothesis. It is hereby shown that the nature of applicability of steady state hypothesis in the regime of high reactant gas pressure is different from that in the regime of low gas pressure. In the former case it is an equilibrium approximation, while in the latter case it is a highly reactive intermediate approximation in no connection with a steady state. Furthermore for the latter case it is shown that in the classical formulation of Lindemann mecbRnism the use of steady state hypothesis is an ad hoc assumption. A highly reactive intermediate in the sense that its concentration is very small during the whole course of reaction is a necessary condition for the applicability of very reactive intermediate approximation. When the two distinctive nature of the applicability of steady state hypothesis is mlxed-up, wrong or useless conclusion may be arrived at. The only possible case of realizing a true steady state in a complex reaction is pointed out.

  4. 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.

  5. Heavy ion reactions: an experimental vista. [Review, angular momentum, compound-nucleus decay, reaction mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Stokstad, R.G.

    1977-01-01

    Examples of recent experiments in the areas of fusion and deep-inelastic scattering are presented and discussed. Emphasis is placed on the importance of individual nucleons in the fusion process, the effects of high angular momentum, and the understanding of compound nuclear decay. Experiments on deep inelastic scattering are entering a new stage in which important parameters of the reaction mechanism are now open to investigation. Primarily through coincidence measurements, direct information on the angular momentum transferred in a collision and on the time scale of decay is being obtained.

  6. Study on the Reaction Mechanism of Naphthalene with Oxalyl Chloride

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The reaction of naphthalene with oxalyl chloride in the presence of anhydrous AlCl3 was investigated. The homolog of dinaphthyl methanone can be obtained mainly from this reaction. Naphthalene conversion does not have evident correlation with the amount of AlCl3. The results show that the reaction proceeds via carbon cation electrophilic substitution reaction-free radical substitution reaction pathway.

  7. 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.

  8. Reaction mechanisms and staggering in S+Ni collisions

    Energy Technology Data Exchange (ETDEWEB)

    D' Agostino, M., E-mail: dagostino@bo.infn.it [Dipartimento di Fisica dell' Universita and INFN, Bologna (Italy); Bruno, M. [Dipartimento di Fisica dell' Universita and INFN, Bologna (Italy); Gulminelli, F. [LPC (IN2P3-CNRS/Ensicaen et Universite), F-14076 Caen cedex (France); Morelli, L. [Dipartimento di Fisica dell' Universita and INFN, Bologna (Italy); Baiocco, G. [Dipartimento di Fisica dell' Universita and INFN, Bologna (Italy); LPC (IN2P3-CNRS/Ensicaen et Universite), F-14076 Caen cedex (France); Bardelli, L. [INFN, Firenze (Italy); INFN, Catania (Italy); Barlini, S. [INFN, Firenze (Italy); Cannata, F. [Dipartimento di Fisica dell' Universita and INFN, Bologna (Italy); Casini, G. [INFN, Firenze (Italy); Geraci, E. [Dipartimento di Fisica dell' Universita, Catania (Italy); INFN, Catania (Italy); Gramegna, F.; Kravchuk, V.L. [INFN, Laboratori Nazionali di Legnaro (Italy); Marchi, T. [INFN, Laboratori Nazionali di Legnaro (Italy); Dipartimento di Fisica dell' Universita, Padova (Italy); Moroni, A. [INFN, Milano (Italy); Ordine, A. [INFN, Napoli (Italy); Raduta, Ad.R. [NIPNE, Bucharest-Magurele, POB-MG6 (Romania)

    2011-07-01

    The reactions {sup 32}S+{sup 58}Ni and {sup 32}S+{sup 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.

  9. Reaction mechanisms and staggering in S+Ni collisions

    Science.gov (United States)

    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.

    2011-07-01

    The reactions S32+Ni58 and S32+Ni64 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.

  10. Mechanical reaction-diffusion model for bacterial population dynamics

    CERN Document Server

    Ngamsaad, Waipot

    2015-01-01

    The effect of mechanical interaction between cells on the spreading of bacterial population was investigated in one-dimensional space. A nonlinear reaction-diffusion equation has been formulated as a model for this dynamics. In this model, the bacterial cells are treated as the rod-like particles that interact, when contacting each other, through the hard-core repulsion. The repulsion introduces the exclusion process that causes the fast diffusion in bacterial population at high density. The propagation of the bacterial density as the traveling wave front in long time behavior has been analyzed. The analytical result reveals that the front speed is enhanced by the exclusion process---and its value depends on the packing fraction of cell. The numerical solutions of the model have been solved to confirm this prediction.

  11. Preparation by a Rheological Phase Reaction Method and Thermal Decomposition Reaction Mechanism of Nickelous Salicylate Tetrahydrate

    Institute of Scientific and Technical Information of China (English)

    Wang Jin-long; Yuan Liang-jie; Yang Yi-yong; Sun Ju-tang; Zhang Ke-li

    2003-01-01

    The single crystal nickel salicylate tetrahydrate was prepared with the rheological phase reaction method from nickelous hydroxide and salicylic acid. The crystal structure was determined. It is monoclinic, space group P21 /n, a =0.67874(3), b=0. 515 91(2), c=2. 313 30(9) nm, β=90.9286(17)°, V=0. 809 94(6) nm3, Z=2, ρcalcd =0. 065 0[I >2a(I)]. The thermal decomposition mechanism in an inert atmosphere was investigated via TG, DTG and DTA. The thermal decomposition products were characterized with IR and micro-powder X-ray diffraction method. A new coordination polymer (NiC6 H4O)n as an intermediate product and nanoscale metal nickel were obtained in the ranges of 364-429 ℃ and 429-680 ℃, respectively.

  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...

  13. Monosaccharide templates for de novo designed 4-alpha-helix bundle proteins: template effects in carboproteins

    DEFF Research Database (Denmark)

    Brask, Jesper; Dideriksen, J.M.; Nielsen, John;

    2003-01-01

    De novo design and total chemical synthesis of proteins provide powerful approaches to critically test our understanding of protein folding, structure, and stability. The 4-alpha-helix bundle is a frequently studied structure in which four amphiphilic alpha-helical peptide strands form a hydropho......)) and melting points in chemical and thermal denaturation experiments....

  14. HNF4alpha and CDH1 are associated with ulcerative colitis in a Dutch cohort

    NARCIS (Netherlands)

    Sommeren, S. van; Visschedijk, M.C.; Festen, E.A.; Jong, D.J. de; Ponsioen, C.Y.; Wijmenga, C.; Weersma, R.K.

    2011-01-01

    BACKGROUND: Inflammatory bowel diseases (IBDs), consisting of ulcerative colitis (UC) and Crohn's disease (CD), are complex disorders with multiple genes contributing to disease pathogenesis. A recent genome-wide association scan identified three novel susceptibility loci for UC: HNF4alpha, CDH1, an

  15. HNF4 alpha and CDH1 Are Associated with Ulcerative Colitis in a Dutch Cohort

    NARCIS (Netherlands)

    van Sommeren, Suzanne; Visschedijk, Marijn C.; Festen, Eleonora A. M.; de Jong, Dirk J.; Ponsioen, Cyriel Y.; Wijmenga, Cisca; Weersma, Rinse K.

    2011-01-01

    Background: Inflammatory bowel diseases (IBDs), consisting of ulcerative colitis (UC) and Crohn's disease (CD), are complex disorders with multiple genes contributing to disease pathogenesis. A recent genome-wide association scan identified three novel susceptibility loci for UC: HNF4 alpha, CDH1, a

  16. Crystallization and melt behaviour of isotactic poly((4-alpha,alpha-dimethyl-benzyl)phenyl methacrylate)

    NARCIS (Netherlands)

    vanEkenstein, GORA; Tan, YY

    1997-01-01

    The crystallization and melting behaviour of practically 100% isotactic poly((4-alpha,alpha-dimethylbenzyl) phenyl methacrylate) has been studied by d.s.c. and light microscopy. Crystallization from the melt seemed to be non-spherulitic. The maximum crystallization rate, which could only be determin

  17. Theoretical Study on the Mechanism of Sonogashira Coupling Reaction

    Institute of Scientific and Technical Information of China (English)

    CHEN Li-Ping; HONG San-Guo; HOU Hao-Qing

    2008-01-01

    The mechanism of palladium-catalyzed Sonogashira cross-coupling reaction has been studied theoretically by DFT (density functional theory) calculations. The model system studied consists of Pd(PH3)2 as the starting catalyst complex, phenyl bromide as the substrate and acetylene as the terminal alkyne, without regarding to the co-catalyst and base. Mechanistically and energetically plausible catalytic cycles for the cross-coupling have been identified. The DFT analysis shows that the catalytic cycle occurs in three stages: oxidative addition of phenyl bromide to the palladium center, alkynylation of palladium(II) intermediate, and reductive elimination to phenylacetylene. In the oxidative addition, the neutral and anionic pathways have been investigated, which could both give rise to cis-configured palladium(II) diphosphine intermediate. Starting from the palladium(II) diphosphine intermediate, the only identifiable pathway in alkynylation involves the dissociation of Br group and the formation of square-planar palladium(II) intermediate, in which the phenyl and alkynyl groups are oriented cis to each other. Due to the close proximity of phenyl and alkynyl groups, the reductive elimination of phenylacetylene proceeds smoothly.

  18. The mechanism and kinetics of epoxy-amine reactions

    International Nuclear Information System (INIS)

    Full text.Silane coupling agents have an important role at the interface for improving the performance of composite materials based on polymer matrices reinforced with glass fibers or mineral fillers. The silanes are also used in some adhesive formulations or as substrate primers, giving higher strength of adhesives joints. In these interface or interphase problems, most of the data in the literature concerns the final properties of the composite materials, such as strength or young's modulus; there is very little information about the chemical properties of the interphase. The aim of this study is to try to provide some of this basic data. The coupling agent studied here is the γ-aminopropyltriethoxysilane (γ-APS) or A1100. It is the most commonly used coupling agents. During composite processing, it is frequently reacted with an epoxy prepolymer based on diglycidylether of bisphenol A. We have studied these reactions from a fundamental point of view and not in industrial conditions. First we compared the kinetics results of different analytical techniques. Secondly, we compared the reactivities of the epoxy in DGEBA and the amino-hydrogen functions in coupling agent to those of model reagents like phenylglycidylether and hexylamine. the third part consists of validating a kinetic mechanism and calculating the rate constants, activation energy and reactivity ratios

  19. Novel P2 promoter-derived HNF4{alpha} isoforms with different N-terminus generated by alternate exon insertion

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Jianmin, E-mail: jmhuang@partners.org [Pediatric Endocrine Unit, MassGeneral Hospital for Children and Harvard Medical School, Boston, Massachusetts, 02114-2696 (United States); Levitsky, Lynne L. [Pediatric Endocrine Unit, MassGeneral Hospital for Children and Harvard Medical School, Boston, Massachusetts, 02114-2696 (United States); Rhoads, David B., E-mail: rhoads@helix.mgh.harvard.edu [Pediatric Endocrine Unit, MassGeneral Hospital for Children and Harvard Medical School, Boston, Massachusetts, 02114-2696 (United States)

    2009-04-15

    Hepatocyte nuclear factor 4{alpha} (HNF4{alpha}) is a critical transcription factor for pancreas and liver development and functions in islet {beta} cells to maintain glucose homeostasis. Mutations in the human HNF4A gene lead to maturity onset diabetes of the young (MODY1) and polymorphisms are associated with increased risk for type 2 diabetes mellitus (T2DM). Expression of six HNF4{alpha} variants, three each from two developmentally regulated promoters, has been firmly established. We have now detected a new set of HNF4{alpha} variants designated HNF4{alpha}10-12 expressed from distal promoter P2. These variants, generated by inclusion of previously undetected exon 1E (human = 222 nt, rodent = 136 nt) following exon 1D have an altered N-terminus but identical remaining reading frame. HNF4{alpha}10-{alpha}12 are expressed in pancreatic islets (and liver) and exhibit transactivation potentials similar to the corresponding {alpha}7-{alpha}9 isoforms. DNA-binding analyses implied much higher protein levels of HNF4{alpha}10-{alpha}12 in liver than expected from the RT-PCR data. Our results provide evidence for a more complex expression pattern of HNF4{alpha} than previously appreciated. We recommend inclusion of exon 1E and nearby DNA sequences in screening for HNF4{alpha} mutations and polymorphisms in genetic analyses of MODY1 and T2DM.

  20. Structure and reaction mechanism of basil eugenol synthase.

    Directory of Open Access Journals (Sweden)

    Gordon V Louie

    Full Text Available Phenylpropenes, a large group of plant volatile compounds that serve in multiple roles in defense and pollinator attraction, contain a propenyl side chain. Eugenol synthase (EGS catalyzes the reductive displacement of acetate from the propenyl side chain of the substrate coniferyl acetate to produce the allyl-phenylpropene eugenol. We report here the structure determination of EGS from basil (Ocimum basilicum by protein x-ray crystallography. EGS is structurally related to the short-chain dehydrogenase/reductases (SDRs, and in particular, enzymes in the isoflavone-reductase-like subfamily. The structure of a ternary complex of EGS bound to the cofactor NADP(H and a mixed competitive inhibitor EMDF ((7S,8S-ethyl (7,8-methylene-dihydroferulate provides a detailed view of the binding interactions within the EGS active site and a starting point for mutagenic examination of the unusual reductive mechanism of EGS. The key interactions between EMDF and the EGS-holoenzyme include stacking of the phenyl ring of EMDF against the cofactor's nicotinamide ring and a water-mediated hydrogen-bonding interaction between the EMDF 4-hydroxy group and the side-chain amino moiety of a conserved lysine residue, Lys132. The C4 carbon of nicotinamide resides immediately adjacent to the site of hydride addition, the C7 carbon of cinnamyl acetate substrates. The inhibitor-bound EGS structure suggests a two-step reaction mechanism involving the formation of a quinone-methide prior to reduction. The formation of this intermediate is promoted by a hydrogen-bonding network that favors deprotonation of the substrate's 4-hydroxyl group and disfavors binding of the acetate moiety, akin to a push-pull catalytic mechanism. Notably, the catalytic involvement in EGS of the conserved Lys132 in preparing the phenolic substrate for quinone methide formation through the proton-relay network appears to be an adaptation of the analogous role in hydrogen bonding played by the equivalent

  1. 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

  2. Mechanisms in adverse reactions to food. The nose

    DEFF Research Database (Denmark)

    Høst, A

    1995-01-01

    Rhinitis is a common symptom in food allergic patients, but rhinitis is rarely the only symptom. Rhinitis due to adverse reactions to preservatives and colorants is very rare. In anaphylactic systemic reactions to foods the rhinitis symptoms are caused by inflammatory mediators transported...... by the circulation. In non-anaphylactic reactions, the nasal inflammation and symptoms are probably induced by interaction with food allergens transported to the nasal mucosa via the blood circulation....

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

    OpenAIRE

    Zhaoyong Liu; Zhongdong Zhang; Pusheng Liu; Jianing Zhai; Chaohe Yang

    2015-01-01

    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 pa...

  4. Preparation by a Rheological Phase Reaction Method and Thermal Decomposition Reaction Mechanism of Nickelous Salicylate Tetrahydrate

    Institute of Scientific and Technical Information of China (English)

    WangJin-long; YuanLiang-jie; YangYi-yong; SunJu-tang; ZhangKe-li

    2003-01-01

    The single crystal nickel salicylate tetrahydrate was prepared with the rheological phase reaction method from nickelous hydroxide and salicylic acid. The crystal structure was determinecL It is monoclinic, space group P21/n, α=0.678 74(3), b=0. 515 91(2), c=2. 313 30(9) nm, β=90.9286(17)°,V=0. 809 94(6) nm3, Z=2, ρcalod =1. 661 g· cm-3. Final R indices: R=0. 027 9 and ωR=0.065 0[Ⅰ>2σ(Ⅰ)]. The thermal decomposition mechanism in an inert atmosphere was investigated via TG, DTG and DTA. The thermal decomposition products were characterized with IR and micro-powder X-ray diffraction method. A new coordination polymer ( NiC6 H4 O)n as an intermediate product and nanoscale metal nickel were obtained in the ranges of 364-429℃ and 429-680℃, respectively.

  5. The mechanisms of delayed onset type adverse reactions to oseltamivir.

    Science.gov (United States)

    Hama, Rokuro

    2016-09-01

    Oseltamivir is recommended for the treatment and prophylaxis of influenza in persons at higher risk for influenza complications such as individuals with diabetes, neuropsychiatric illnesses, and respiratory, cardiac, renal, hepatic or haematological diseases. However, a recent Cochrane review reported that reduction of antibody production, renal disorders, hyperglycaemia, psychiatric disorders, and QT prolongation may be related to oseltamivir use. The underlying mechanisms are reviewed. There is decisive evidence that administration of a clinically compatible dose of oseltamivir in mice challenged by a respiratory syncytial virus (RSV) that lacks a neuraminidase gene showed symptom-relieving effects and inhibition of viral clearance. These effects were accompanied by decreased level of T cell surface sialoglycosphingolipid (ganglioside) GM1 that is regulated by the endogenous neuraminidase in response to viral challenge. Clinical and non-clinical evidence supports the view that the usual dose of oseltamivir suppresses pro-inflammatory cytokines such as interferon-gamma, interleukin-6, and tumour necrosis factor-alpha almost completely with partial suppression of viral shedding in human influenza virus infection experiment. Animal toxicity tests support the clinical evidence with regard to renal and cardiac disorders (bradycardia and QT prolongation) and do not disprove the metabolic effect. Reduction of antibody production and cytokine induction and renal, metabolic, cardiac, and prolonged psychiatric disorders after oseltamivir use may be related to inhibition of the host's endogenous neuraminidase. While the usual clinical dose of zanamivir may not have this effect, a higher dose or prolonged administration of zanamivir and other neuraminidase inhibitors may induce similar delayed reactions, including reduction of the antibody and/or cytokine production. PMID:27251370

  6. Theoretical studies on reaction mechanisms of unstable nuclei

    International Nuclear Information System (INIS)

    Recent studies on reactions of unstable nuclei by means of the continuum-discretized coupled-channels method (CDCC) are briefly reviewed. The topics covered are: four-body breakup processes for 6He induced reaction, microscopic description of projectile breakup processes, and new approach to inclusive breakup processes. (author)

  7. Mechanism of reaction synthesis of Li-B alloys

    Institute of Scientific and Technical Information of China (English)

    LIU; Zhijian; (刘志坚); QU; Xuanhui; (曲选辉); LI; Zhiyou; (李志友); HUANG; Baiyun; (黄伯云)

    2003-01-01

    A model for reaction synthesis of Li-B alloys has been presented. Results show that the first exothermal reaction can be divided into three stages. The first stage is an instantaneous reaction on the boundary between boron particles and lithium melting, in which the caloric released is inversely proportional to the particle size of the boron powder. The second stage is a reaction between the unreacted boron and the lithium that diffuses through the product LiB3 on the surface of the boron particle. This process can be described by Johnston model. The third stage is dissolution of the product LiB3 to Li liquid, which takes place at temperature up to 420℃. At the same time, the second exothermal reaction begins, which consists of nucleation and growth of the last Li-B compound. It can be divided into two substages, i.e. the nucleation pregnant stage and the exploded reaction stage. When the concentration of the particle nucleated is high enough, an exploding reaction takes place. The lower the temperature, the longer the time needed for the exploding reaction. By the model presented, the experimental phenomena in the synthesis are explained.

  8. Theoretical Study on Reaction Mechanism of Aluminum-Water System

    Institute of Scientific and Technical Information of China (English)

    Yun-lan Sun; Yan Tian; Shu-fen Li

    2008-01-01

    A theoretical study on the reaction of aluminum with water in the gas phase was performed using the hybrid density functional B3LYP and QCISD(T) methods with the 6-311+G(d,p) and the 6-311++G(d,p) basis sets. The results show that there are three possible reaction pathways that involve four isomers, seven transition structures, and two possible products for the reaction of aluminum with water. The two most favorable reaction pathways were found, whose intermediates and products agreed quite well with experimental results. The enthalpy and Gibbs free energy change of the reaction between AI and H2O at 298 and 2000 K were calculated. Some results are also in good agreement with the previous calculations or experimental results.

  9. 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.

  10. Variation near the hepatocyte nuclear factor (HNF)-4alpha gene associates with type 2 diabetes in the Danish population

    DEFF Research Database (Denmark)

    Hansen, S K; Rose, C S; Glümer, C;

    2005-01-01

    The hepatocyte nuclear factor (HNF)-4alpha is an orphan nuclear receptor, which plays crucial roles in regulating hepatic gluconeogenesis and insulin secretion. The gene encoding HNF-4alpha (HNF4A) is located on chromosome 20q12-q13 in a region that in several studies has shown linkage with type 2...

  11. Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism.

    Science.gov (United States)

    Demissie, Taye B; Garabato, Brady D; Ruud, Kenneth; Kozlowski, Pawel M

    2016-09-12

    The methylation of Hg(II) (SCH3 )2 by corrinoid-based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical, in contrast to previously proposed reaction mechanisms. This reaction mechanism is a consequence of relativistic effects that lower the energies of the mercury 6p1/2 and 6p3/2 orbitals, making them energetically accessible for chemical bonding. In the absence of spin-orbit coupling, the predicted reaction mechanism is qualitatively different. This is the first example of relativity being decisive for the nature of an observed enzymatic reaction mechanism. PMID:27510509

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

    International Nuclear Information System (INIS)

    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

  13. Generation Mechanism of Deferoxamine Radical by Tyrosine-Tyrosinase Reaction.

    Science.gov (United States)

    Tada, Mika; Niwano, Yoshimi; Kohno, Masahiro

    2015-01-01

    Nitroxide radical formations of deferoxamine mesylate (DFX) that is used clinically to treat iron-overload patients was examined by a tyrosine-tyrosinase reaction system as models of the H-atom transfer or proton-coupled electron transfer. When DFX was exposed to the tyrosine-tyrosinase reaction, nine-line ESR spectrum (g = 2.0063, hfcc; aN = 0.78 mT, aH(2) = 0.63 mT) was detected, indicating that the oxidation of DFX leads to a nitroxide radical. The signal intensity of the DFX radical increased dependently on the concentrations of tyrosine and tyrosinase. The amounts of DMPO-OH spin adducts via the tyrosine-tyrosinase reaction declined with DFX. Furthermore, mass spectra of an extra removed from the tyrosine-tyrosinase reaction mixture showed that the enzyme reactions might not be degradations of DFX. Therefore, there might be two types of DFX reaction passways, which could be through an internal electron transfer from tyrosine and hydrogen absorptions by ·OH directly.

  14. The Kabachnik–Fields Reaction: Mechanism and Synthetic Use

    Directory of Open Access Journals (Sweden)

    György Keglevich

    2012-11-01

    Full Text Available The Kabachnik–Fields (phospha-Mannich reaction involving the condensation of primary or secondary amines, oxo compounds (aldehydes and ketones and >P(OH species, especially dialkyl phosphites, represents a good choice for the synthesis of α-aminophosphonates that are of significant importance due to their biological activity. In general, these three-component reactions may take place via an imine or an α-hydroxy-phosphonate intermediate. The monitoring of a few Kabachnik–Fields reactions by in situ Fourier transform IR spectroscopy has indicated the involvement of the imine intermediate that was also justified by theoretical calculations. The Kabachnik–Fields reaction was extended to >P(OH species, comprising cyclic phosphites, acyclic and cyclic H-phosphinates, as well as secondary phosphine oxides. On the other hand, heterocyclic amines were also used to prepare new α-amino phosphonic, phosphinic and phosphine oxide derivatives. In most cases, the synthesis under solvent-free microwave (MW conditions is the method of choice. It was proved that, in the cases studied by us, there was no need for the use of any catalyst. Moreover, it can be said that sophisticated and environmentally unfriendly catalysts suggested are completely unnecessary under MW conditions. Finally, the double Kabachnik–Fields reaction has made available bis(phosphonomethylamines, bis(phosphinoxidomethylamines and related species. The bis(phosphinoxidomethylamines serve as precursors for bisphosphines that furnish ring platinum complexes on reaction with dichlorodibenzonitriloplatinum.

  15. How NO{sub 2} affects the reaction mechanism of the SCR reaction

    Energy Technology Data Exchange (ETDEWEB)

    Koebel, M.; Madia, G.; Raimondo, F.; Wokaun, A.

    2003-03-01

    The rate of the selective catalytic reduction (SCR) of NO with N-containing reducing agents may be considerably enhanced by converting part of the NO into NO{sub 2}. The reaction using an equimolar mixture of NO and NO{sub 2} is known as 'fast SCR reaction' and the rate enhancement is most pronounced at low temperatures (T<300{sup o}C). In the present work the possible role of NO{sub 2} on catalysts based on TiO{sub 2}-WO{sub 3}-V{sub 2}O{sub 5} was investigated by in-situ Raman spectroscopy. The experiments suggest that the V{sup +4} species formed during the reduction of NO with ammonia are reoxidized faster by NO{sub 2} than by oxygen, resulting in an increased reaction rate of the fast SCR reaction. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    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. Molecular Mechanism by which One Enzyme Catalyzes Two Reactions

    Science.gov (United States)

    Nishimasu, Hiroshi; Fushinobu, Shinya; Wakagi, Takayoshi

    Unlike ordinary enzymes, fructose-1,6-bisphosphate (FBP) aldolase/phosphatase (FBPA/P) catalyzes two distinct reactions : (1) the aldol condensation of dihydroxyacetone phosphate (DHAP) and glyceraldehyde-3-phosphate to FBP, and (2) the dephosphorylation of FBP to fructose-6-phosphate. We solved the crystal structures of FBPA/P in complex with DHAP (its aldolase form) and FBP (its phosphatase form). The crystal structures revealed that FBPA/P exhibits the dual activities through a dramatic conformational change in the active-site architecture. Our findings expand the conventional concept that one enzyme catalyzes one reaction.

  18. An ab initio molecular dynamics study of the roaming mechanism of the H2+HOC+ reaction

    Science.gov (United States)

    Yu, Hua-Gen

    2011-08-01

    We report here a direct ab initio molecular dynamics study of the p-/o-H2+HOC+ reaction on the basis of the accurate SAC-MP2 potential energy surface. The quasi-classical trajectory method was employed. This work largely focuses on the study of reaction mechanisms. A roaming mechanism was identified for this molecular ion-molecule reaction. The driving forces behind the roaming mechanism were thoroughly investigated by using a trajectory dynamics approach. In addition, the thermal rate coefficients of the H2+HOC+ reaction were calculated in the temperature range [25, 300] K and are in good agreement with experiments.

  19. 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...

  20. Heavy-ion reaction mechanisms studied with the spin spectrometer

    International Nuclear Information System (INIS)

    Experimental data and statistical-model calculations for xn and αxn products of the reaction 20Ne + 146Nd at 136 MeV are shown to be in generally good agreement, indicating that equilibrium processes are dominant. Preliminary results on the heavy-ion ejectiles from 19F + 159Tb are presented

  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, 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)

  3. 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 t...

  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. Assessment of deuteron-induced reaction mechanisms at low and medium energies

    OpenAIRE

    Avrigeanu V.; Avrigeanu M.

    2010-01-01

    An extended analysis of the nuclear reaction mechanisms involved in the deuterons interaction with 63,65Cu is presented. First, the available elastic-scattering data analysis provided us the optical potential for reaction cross sections calculations. An increased effort has been devoted to the breakup mechanism, both the elastic breakup and the breakup fusion contributions to the different activation cross sections being carefully considered. Next, the direct reaction contributions throu...

  6. Fasting induces basolateral uptake transporters of the SLC family in the liver via HNF4alpha and PGC1alpha.

    Science.gov (United States)

    Dietrich, Christoph G; Martin, Ina V; Porn, Anne C; Voigt, Sebastian; Gartung, Carsten; Trautwein, Christian; Geier, Andreas

    2007-09-01

    Fasting induces numerous adaptive changes in metabolism by several central signaling pathways, the most important represented by the HNF4alpha/PGC-1alpha-pathway. Because HNF4alpha has been identified as central regulator of basolateral bile acid transporters and a previous study reports increased basolateral bile acid uptake into the liver during fasting, we hypothesized that HNF4alpha is involved in fasting-induced bile acid uptake via upregulation of basolateral bile acid transporters. In rats, mRNA of Ntcp, Oatp1, and Oatp2 were significantly increased after 48 h of fasting. Protein expression as determined by Western blot showed significant increases for all three transporters 72 h after the onset of fasting. Whereas binding activity of HNF1alpha in electrophoretic mobility shift assays remained unchanged, HNF4alpha binding activity to the Ntcp promoter was increased significantly. In line with this result, we found significantly increased mRNA expression of HNF4alpha and PGC-1alpha. Functional studies in HepG2 cells revealed an increased endogenous NTCP mRNA expression upon cotransfection with either HNF4alpha, PGC-1alpha, or a combination of both. We conclude that upregulation of the basolateral bile acid transporters Ntcp, Oatp1, and Oatp2 in fasted rats is mediated via the HNF4alpha/PGC-1alpha pathway.

  7. Fasting induces basolateral uptake transporters of the SLC family in the liver via HNF4alpha and PGC1alpha.

    Science.gov (United States)

    Dietrich, Christoph G; Martin, Ina V; Porn, Anne C; Voigt, Sebastian; Gartung, Carsten; Trautwein, Christian; Geier, Andreas

    2007-09-01

    Fasting induces numerous adaptive changes in metabolism by several central signaling pathways, the most important represented by the HNF4alpha/PGC-1alpha-pathway. Because HNF4alpha has been identified as central regulator of basolateral bile acid transporters and a previous study reports increased basolateral bile acid uptake into the liver during fasting, we hypothesized that HNF4alpha is involved in fasting-induced bile acid uptake via upregulation of basolateral bile acid transporters. In rats, mRNA of Ntcp, Oatp1, and Oatp2 were significantly increased after 48 h of fasting. Protein expression as determined by Western blot showed significant increases for all three transporters 72 h after the onset of fasting. Whereas binding activity of HNF1alpha in electrophoretic mobility shift assays remained unchanged, HNF4alpha binding activity to the Ntcp promoter was increased significantly. In line with this result, we found significantly increased mRNA expression of HNF4alpha and PGC-1alpha. Functional studies in HepG2 cells revealed an increased endogenous NTCP mRNA expression upon cotransfection with either HNF4alpha, PGC-1alpha, or a combination of both. We conclude that upregulation of the basolateral bile acid transporters Ntcp, Oatp1, and Oatp2 in fasted rats is mediated via the HNF4alpha/PGC-1alpha pathway. PMID:17640976

  8. Reaction Mechanism of O‘—sialon—ZrO2 Composite by Using Reaction Nitridation Mathod

    Institute of Scientific and Technical Information of China (English)

    LIHongxia; JIBaokun; 等

    1997-01-01

    O'-sialon-ZrO2 composite based on the cheap commercial available zircon and silicon as raw materials can be achieved by using reac-tion nitridation method,More attention was given to the nitriding process and the effect of additives on it .The experimental results show that there are two nitridation paths:one is the direct nitridation of silicon powder and the other is through the reaction between the medi-um compound ZrSi2 and the nitrogen.The effects of addition of calcia and the incorpora-tion of BN on the nitriding reaction were also investigated,the primitive experimental results demonstrated that both of calcia and BN could deteriorate the nitriding degree.

  9. 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.

  10. Production mechanism of superheavy nuclei in massive fusion reactions

    Institute of Scientific and Technical Information of China (English)

    FENG Zhao-Qing; JIN Gen-Ming; LI Jun-Qing; Werner Scheid

    2009-01-01

    Within the concept of the dinuclear system (DNS), a dynamical model is proposed for describing the formation of superheavy nuclei in complete fusion reactions by incorporating the coupling of the relative motion to the nucleon transfer process. The capture of two heavy colliding nuclei, the formation of the compound nucleus and the de-excitation process are calculated by using an empirical coupled channel model, solving a set of microscopically derived master equations numerically and applying statistical theory, respectively.Fusion-fission reactions and evaporation residue excitation functions of synthesizing superheavy nuclei (SHN) are investigated systematically and compared them with available experimental data. The possible factors that affecting the production cross sections of SHN are discussed in this workshop.

  11. Prevention of growth of human lung carcinoma cells and induction of apoptosis by a novel phenoxazinone, 2-amino-4,4alpha-dihydro-4alpha,7-dimethyl-3H-phenoxazine-3-one.

    Science.gov (United States)

    Abe, A; Yamane, M; Tomoda, A

    2001-04-01

    Anti-tumor effects of a novel phenoxazinone, 2-amino-4,4-dihydro-4alpha,7-dimethyl-3H-phenoxazine-3-one (Phx), which was synthesized by the reaction of 2-amino-5-methylphenol with bovine hemoglobin, were studied in terms of suppression of the proliferation of human lung carcinoma cells and apoptosis induction. When Phx was added to cultures of the human lung carcinoma cell lines A549 (adenocarcinoma) and H226 (squamous carcinoma), it caused the growth inhibition and the death of these cells. Phx also fragmented the DNA of these cells to oligonucleosomal-sized fragments, which is characteristic of the apoptosis, dependent on the dose and exposure time. The cellular death caused by the administration of Phx was partially reversed by the addition of Z-VAD-fmk, a caspase family inhibitor. Present results suggest that Phx demonstrates anti-cancer activity against human lung carcinoma cell lines A549 and H226, by inhibiting growth and inducing apoptosis. PMID:11335795

  12. Quantum-mechanical description of initial stage of fusion reaction

    International Nuclear Information System (INIS)

    Within the formalism of the reduced density matrix the process of capture of projectile by a target at energies near the Coulomb barrier is considered. The influence of dissipation and fluctuations is taken self-consistently into account. Using the calculated probabilities of the capture, averaged in all mutual orientations of the deformed colliding nuclei, the evaporation residue cross-sections are calculated for the asymmetric fusion reactions

  13. 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.

  14. Elucidation of Reaction Mechanisms Far from Thermodynamic Equilibrium.

    Science.gov (United States)

    Nagao, Raphael

    2016-04-01

    Far from equilibrium: This thesis provides a deep mechanistic analysis of the electrooxidation of methanol when the system is kept far from the thermodynamic equilibrium. Under an oscillatory regime, interesting characteristics between the elementary reaction steps were observed. We were able to elucidate the effect of the intrinsic drift in a potential time-series responsible for spontaneous transition of temporal patterns and the carbon dioxide decoupling from direct and indirect pathways. PMID:27308227

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

    NARCIS (Netherlands)

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

    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

  16. Kinetics and mechanism of the reaction of uranium hexafluoride and tritium

    Science.gov (United States)

    Maienschein, Jon L.; Sunderland, William E.

    1985-03-01

    Using infrared analysis, we found that the reaction rate of gaseous uranium hexafluoride and tritium is determined solely by the rate at which energy from the radioactive decay of tritium is absorbed in the reaction mixture. Because uranium hexafluoride and tritium absorb β-energy with different efficiencies, the reaction rate is somewhat dependent on the initial reactant concentrations. Reaction products include uranium subfluorides and tritium fluoride. A radiochemistry model has been developed that includes β-energy production and absorption in the gas phase to allow calculation of the reaction yield per ion pair formed. With this model it was found that the reaction mechanism does not include lengthy chain propagation steps-only about 10 uranium hexafluoride molecules are consumed for each ion-pair formed in the gas phase. Many possible reaction steps are suggested that could contribute to the observed overall mechanism.

  17. Program Helps To Determine Chemical-Reaction Mechanisms

    Science.gov (United States)

    Bittker, D. A.; Radhakrishnan, K.

    1995-01-01

    General Chemical Kinetics and Sensitivity Analysis (LSENS) computer code developed for use in solving complex, homogeneous, gas-phase, chemical-kinetics problems. Provides for efficient and accurate chemical-kinetics computations and provides for sensitivity analysis for variety of problems, including problems involving honisothermal conditions. Incorporates mathematical models for static system, steady one-dimensional inviscid flow, reaction behind incident shock wave (with boundary-layer correction), and perfectly stirred reactor. Computations of equilibrium properties performed for following assigned states: enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. Written in FORTRAN 77 with exception of NAMELIST extensions used for input.

  18. THE MECHANISM OF THE ABDERHALDEN REACTION : STUDIES ON IMMUNITY. I.

    Science.gov (United States)

    Bronfenbrenner, J

    1915-03-01

    1. The Abderhalden reaction is specific. 2. The properties of serum on which it depends develop in experimental animals simultaneously with antibodies during the process of immunization. 3. It is impossible to observe by direct methods the presence of digesting ferments in the blood of immune animals. 4. The Abderhalden test may be resolved into two phases. A dialyzable substance appears in the second phase and is the result of the autodigestion of serum. 5. The autodigestion of serum in the Abderhalden test is due to the removal of antitrypsin from the serum by the sensitized substratum.

  19. Theoretical Studies of the Reaction Mechanisms of CH3S + NO2

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The potential energy surface for the CH3S + NO2 reaction has been studied using the ab initio G3 (MP2) method. A variety of possible complexes and saddle points along the minimum energy reaction paths have been characterized at UMP2 (full)/6-31G(d) level. The calculations reveal dominating reaction mechanisms of the title reaction: CH3S + NO2 firstly produce intermediate CH3SONO, then break up into CH3SO + NO. The results are valuable to understand the atmospheric sulfur compounds oxidation mechanism.

  20. Reaction mechanism and kinetics of the NCN +NO reaction: Comparison of theory and experiment

    Science.gov (United States)

    Huang, Chih-Liang; Tseng, Shiang Yang; Wang, Tzu Yi; Wang, Niann S.; Xu, Z. F.; Lin, M. C.

    2005-05-01

    The rate constants for the NCN +NO reaction have been measured by laser photolysis/laser-induced fluorescence technique in the temperature range of 254-353K in the presence of He (40-600Torr) and N2 (30-528Torr) buffer gases. The NCN radical was produced from the photodissociation of NCN3 at 193nm and monitored with a dye laser at 329.01nm. The reaction was found to be strongly positive-pressure dependent with negative-temperature dependence, as was reported previously. The experimental data could be reasonably accounted for by dual-channel Rice-Ramsperger-Kassel-Marcus calculations based on the predicted potential-energy surface using the modified Gaussian-2 method. The reaction is predicted to occur via weak intermediates, cis- and trans-NCNNO, in the A″2 state which crosses with the A'2 state containing more stable cis- and trans-NCNNO isomers. The high barriers for the fragmentation of these isomers and their trapping in the A'2 state by collisional stabilization give rise to the observed positive-pressure dependence and negative-temperature effect. The predicted energy barrier for the fragmentation of the cis-NCNNO (A'2) to CN +N2O also allows us to quantitatively account for the rate constant previously measured for the reverse process CN +N2O→NCN+NO.

  1. Nuclear and hadronic reaction mechanisms producing spin asymmetry

    Indian Academy of Sciences (India)

    Ken-Ichi Kubo

    2001-08-01

    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, 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 hyperon productions, are also discussed and well understood by the presently proposed mechanism. Recently, a further difficulty was observed in an exclusive K+ production and we will indicate a possible diagram for resolving it.

  2. Contribution of quantum effects to the mechanism of positronium reactions

    International Nuclear Information System (INIS)

    Quantum-mechanical effects in the mechanism of positronium spin conversion by FeCl2 in water-glycerol mixtures have been demonstrated by measurements of the rate constant of the process as a function of viscosity over the range 0.7-466 cP. Apparently these effects are due to the tunnelling of the positronium atom (Ps) as a whole from some trap to the corresponding level of the complex [Ps...Fe2+]. Similar effects have not been observed for oxidation of Ps by K2Cr2O7. (orig.)

  3. Photocatalytic oxidation of paracetamol: dominant reactants, intermediates, and reaction mechanisms.

    Science.gov (United States)

    Yang, Liming; Yu, Liya E; Ray, Madhumita B

    2009-01-15

    The role of primary active species (ecb(-), hvb(+), *OH, HO2*, O2*(-), and H2O2) during photocatalytic degradation of paracetamol (acetaminophen) using TiO2 catalyst was systematically investigated. Hydroxyl radicals (*OH) are responsible for the major degradation of paracetamol with a second-order rate constant (1.7 x 10(9) M(-1) s(-1)) for an *OH-paracetamol reaction. A total of 13 intermediates was identified and classified into four categories: (i) aromatic compounds, (ii) carboxylic acids, (iii) nitrogen-containing straight chain compounds, and (iv) inorganic species (ammonium and nitrate ions). Concentration profiles of identified intermediates indicate that paracetamol initially undergoes hydroxylation through *OH addition onto the aromatic ring at ortho (predominantly), meta, and para positions with respect to the -OH position of paracetamol. This initial *OH hydroxylation is followed by further oxidation generating carboxylic acids. Subsequent mineralization of smaller intermediates eventually increases ammonium and nitrate concentration in the system. PMID:19238980

  4. Free Energies of Chemical Reactions in Solution and in Enzymes with Ab Initio Quantum Mechanics/Molecular Mechanics Methods

    Science.gov (United States)

    Hu, Hao; Yang, Weitao

    2008-05-01

    Combined quantum mechanics/molecular mechanics (QM/MM) methods provide an accurate and efficient energetic description of complex chemical and biological systems, leading to significant advances in the understanding of chemical reactions in solution and in enzymes. Here we review progress in QM/MM methodology and applications, focusing on ab initio QM-based approaches. Ab initio QM/MM methods capitalize on the accuracy and reliability of the associated quantum-mechanical approaches, however, at a much higher computational cost compared with semiempirical quantum-mechanical approaches. Thus reaction-path and activation free-energy calculations based on ab initio QM/MM methods encounter unique challenges in simulation timescales and phase-space sampling. This review features recent developments overcoming these challenges and enabling accurate free-energy determination for reaction processes in solution and in enzymes, along with applications.

  5. Recent insight into the mechanism of proton-induced composite particle emission in inclusive reactions

    Science.gov (United States)

    Cowley, A. A.; Dimitrova, S. S.; Zemlyanaya, E. V.; Lukyanov, K. V.; van Zyl, J. J.

    2016-01-01

    Recent results for the inclusive reaction 93Nb(p,α) between incident energies of 65 and 160 MeV are shown to be consistent with a competition between knockout and pickup. The pre-equilibrium statistical multistep process terminates in either mechanism. The incident-energy dependence of the reaction reflects the dynamics of the participating reaction components. It is consequently not surprising to observe knockout to dominate at the lower and highest incident energies, with pickup very prominent in between.

  6. Oxygen Atom Exchange Mechanism in Reaction of OH Radical with AsO

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Oxygen atom exchange reaction mechanism in the reaction of OH radicals with AsO was investigated by means of the density functional theory (DFT) with 6-311++G(3df,3pd) and 6-311++G(d,p) basis sets. The calculated results suggest that the reaction between OH and AsO should make the oxygen atoms exchange rapidly because the barrier to isomerization is significantly less than the HO-AsO bond dissociation energy.

  7. Degradation of quinoline by wet oxidation - kinetic aspects and reaction mechanisms

    DEFF Research Database (Denmark)

    Thomsen, A.B.

    1998-01-01

    of succinic acid is suggested to be a result of a coupling reaction of the acetic acid radical A reaction mechanism is suggested for the degradation of quinoline: it involves hydroxyl radicals and the possible interaction with autoclave walls is discussed. (C) 1998 Elsevier Science Ltd. All rights reserved....

  8. 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

    and microorganisms may be valuable biobased chemicals. Hence a new potential for industrial scale synthesis of chemicals has emerged. A better understanding of the reaction mechanisms and the impact of the reaction conditions on the product formation is thus a prerequisite for designing better biomass processing...

  9. Theoretical study on the reaction mechanism of CN radical with ketene

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The bimolecular single collision reaction potential energy surface of CN radical with ketene (CH2CO) was investigated by means of B3LYP and QCISD(T) methods. The calculated results indicate that there are three possible channels in the reaction. The first is an attack reaction by the carbon atom of CN at the carbon atom of the methylene of CH2CO to form the intermediate NCCH2CO followed by a rupture reaction of the C-C bond combined with -CO group to the products CH2CN+CO. The second is a direct addition reaction between CN and CH2CO to form the intermediate CH2C(O)CN followed by its isomerization into NCCH2CO via a CN-shift reaction, and subsequently, NCCH2CO dissociates into CH2CN+CO through a CO-loss reaction. The last is a direct hydrogen abstraction reaction of CH2CO by CN radical. Because of the existence of a 15.44 kJ/mol reaction barrier and higher energy of reaction products, the path can be ruled out as an important channel in the reaction kinetics. The present theoretical computation results, which give an available suggestion on the reaction mechanism, are in good agreement with previous experimental studies.

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

    International Nuclear Information System (INIS)

    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. 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.

  12. 2013 INORGANIC REACTION MECHANISMS GORDON RESEARCH CONFERENCE (MARCH 3-8, 2013 - HOTEL GALVEZ, GALVESTON TX)

    Energy Technology Data Exchange (ETDEWEB)

    Abu-Omar, Mahdi M.

    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.

  13. Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

    Energy Technology Data Exchange (ETDEWEB)

    Vahteristo, K.

    2010-07-01

    This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene, 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene, 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters, 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene. The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis

  14. Genetic evidence that HNF-1alpha-dependent transcriptional control of HNF-4alpha is essential for human pancreatic beta cell function

    DEFF Research Database (Denmark)

    Hansen, Sara K; Párrizas, Marcelina; Jensen, Maria L;

    2002-01-01

    Mutations in the genes encoding hepatocyte nuclear factor 4alpha (HNF-4alpha) and HNF-1alpha impair insulin secretion and cause maturity onset diabetes of the young (MODY). HNF-4alpha is known to be an essential positive regulator of HNF-1alpha. More recent data demonstrates that HNF-4alpha......, and consequently in reduced HNF-1alpha-dependent activation. These findings provide genetic evidence that HNF-1alpha serves as an upstream regulator of HNF-4alpha and interacts directly with the P2 promoter in human pancreatic cells. Furthermore, they indicate that this regulation is essential to maintain normal...

  15. Theoretical Study on the Mechanism of CF2 Reaction with CH2O

    Institute of Scientific and Technical Information of China (English)

    LI Zhi-Feng; Lü Ling-Ling; ZHU Yuan-Cheng; LIU Xin-Wen

    2008-01-01

    The insertion reaction mechanism of CF2 with CH2O was investigated at the B3LYP/6-311G(d)//MP2/6-311G(d) level.The geometric conformations at each stationary point in reaction potential surface were fully optimized and the transition states were verified by intrinsic reaction coordinate (IRC) and frequency analysis.The energies of all reactants were calculated with CCSD(T)/6-311G(d)//G2MP2 methods.Results indicated that the P1 reaction route with difuoroaldehyde as product is the dominant reaction pathway, which exhibits nucleophilic character.According to NBO analysis, the starting point of insertion reaction is the interaction between carbene LP(C3) and formaldehyde (*(C1-O2).Besides, the thermodynamic and dynamic properties of dominated reaction (1) at different temperature were studied with statistic thermo- dynamic method and Eyring transition state theory adjusted by Wigner means, from which the proper temperature (500~1200 K) of reaction (1) could be estimated.Finally, the thermo- dynamic and dynamic properties of insertion reaction mechanisms (CF2, CX2 (X = Cl, Br) with CH2O) were compared and discussed.

  16. Reaction mechanism for the thermal decomposition of BCl3/CH4/H2 gas mixtures.

    Science.gov (United States)

    Reinisch, Guillaume; Vignoles, Gérard L; Leyssale, Jean-Marc

    2011-10-27

    This paper presents an ab initio study of the B/C/Cl/H gas phase mechanism, featuring 10 addition-elimination reactions involving BH(i)Cl(j) (i + j ≤ 3) species and a first description of the chemical interaction between the carbon-containing and boron-containing subsystems through the three reactions BCl(3) + CH(4) ⇌ BCl(2)CH(3) + HCl, BHCl(2) + CH(4) ⇌ BCl(2)CH(3) + H(2), and BCl(2) + CH(4) ⇌ BHCl(2) + CH(3). A reaction mechanism is then proposed and used to perform some illustrative equilibrium and kinetic calculations in the context of chemical vapor deposition (CVD) of boron carbide. Our results show that the new addition-elimination reaction paths play a crucial role by lowering considerably the activation barrier with respect to previous theoretical evaluations; they also confirm that BCl(2)CH(3) is an important species in the mechanism.

  17. Hepatocyte nuclear factor 4 alpha is a key factor related to depression and physiological homeostasis in the mouse brain.

    Directory of Open Access Journals (Sweden)

    Kyosuke Yamanishi

    Full Text Available Major depressive disorder (MDD is a common psychiatric disorder that involves marked disabilities in global functioning, anorexia, and severe medical comorbidities. MDD is associated with not only psychological and sociocultural problems, but also pervasive physical dysfunctions such as metabolic, neurobiological and immunological abnormalities. Nevertheless, the mechanisms underlying the interactions between these factors have yet to be determined in detail. The aim of the present study was to identify the molecular mechanisms responsible for the interactions between MDD and dysregulation of physiological homeostasis, including immunological function as well as lipid metabolism, coagulation, and hormonal activity in the brain. We generated depression-like behavior in mice using chronic mild stress (CMS as a model of depression. We compared the gene expression profiles in the prefrontal cortex (PFC of CMS and control mice using microarrays. We subsequently categorized genes using two web-based bioinformatics applications: Ingenuity Pathway Analysis and The Database for Annotation, Visualization, and Integrated Discovery. We then confirmed significant group-differences by analyzing mRNA and protein expression levels not only in the PFC, but also in the thalamus and hippocampus. These web tools revealed that hepatocyte nuclear factor 4 alpha (Hnf4a may exert direct effects on various genes specifically associated with amine synthesis, such as genes involved in serotonin metabolism and related immunological functions. Moreover, these genes may influence lipid metabolism, coagulation, and hormonal activity. We also confirmed the significant effects of Hnf4a on both mRNA and protein expression levels in the brain. These results suggest that Hnf4a may have a critical influence on physiological homeostasis under depressive states, and may be associated with the mechanisms responsible for the interactions between MDD and the dysregulation of

  18. Degradation mechanisms of geosmin and 2-MIB during UV photolysis and UV/chlorine reactions.

    Science.gov (United States)

    Kim, Tae-Kyoung; Moon, Bo-Ram; Kim, Taeyeon; Kim, Moon-Kyung; Zoh, Kyung-Duk

    2016-11-01

    We conducted chlorination, UV photolysis, and UV/chlorin reactions to investigate the intermediate formation and degradation mechanisms of geosmin and 2-methylisoborneol (2-MIB) in water. Chlorination hardly removed geosmin and 2-MIB, while the UV/chlorine reaction at 254 nm completely removed geosmin and 2-MIB within 40 min and 1 h, respectively, with lesser removals of both compounds during UV photolysis. The kinetics during both UV photolysis and UV/chlorine reactions followed a pseudo first-order reaction. Chloroform was found as a chlorinated intermediate during the UV/chlorine reaction of both geosmin and 2-MIB. The pH affected both the degradation and chloroform production during the UV/chlorine reaction. The open ring and dehydration intermediates identified during UV/chlorine reactions were 1,4-dimethyl-adamantane, and 1,3-dimethyl-adamantane from geosmin, 2-methylenebornane, and 2-methyl-2-bornene from 2-MIB, respectively. Additionally, 2-methyl-3-pentanol, 2,4-dimethyl-1-heptene, 4-methyl-2-heptanone, and 1,1-dichloro-2,4-dimethyl-1-heptane were newly identified intermediates from UV/chlorine reactions of both geosmin and 2-MIB. These intermediates were degraded as the reaction progressed. We proposed possible degradation pathways during the UV photolysis and UV/chlorine reactions of both compounds using the identified intermediates.

  19. The mechanism of the (p,α) reaction: pick-up or knock-out

    International Nuclear Information System (INIS)

    Several early studies of the (p,α) reaction to discrete states of the final nucleus indicated that it proceeds mainly by the pick-up mechanism, whereas more recent experiments provide qualitative arguments in favour of the knock-out mechanism. This paper reports calculations showing that the angular distributions and analysing powers of the sup(90,92)Zr(p,α)sup(87,89)Y and 118Sn(p,α)115In reactions can be equally well fitted by distorted wave calculations using either mechanism. (author)

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

    International Nuclear Information System (INIS)

    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.)

  1. Quantum mechanical investigations on the role of neutral and negatively charged enamine intermediates in organocatalyzed reactions

    Energy Technology Data Exchange (ETDEWEB)

    Hubin, Pierre O., E-mail: pierre.hubin@unamur.be [Laboratoire de Physico-Chimie Informatique (PCI), Unité de Chimie Physique Théorique et Structurale, University of Namur, 61 rue de Bruxelles, 5000 Namur (Belgium); Jacquemin, Denis [Laboratoire CEISAM – UMR CNRS 6230, Université de Nantes, 2 rue de la Houssinière, BP92208, 44322 Nantes Cedex 3 (France); Institut Universitaire de France 103, Boulevard St Michel, 75005 Paris Cedex 5 (France); Leherte, Laurence; Vercauteren, Daniel P. [Laboratoire de Physico-Chimie Informatique (PCI), Unité de Chimie Physique Théorique et Structurale, University of Namur, 61 rue de Bruxelles, 5000 Namur (Belgium)

    2014-04-15

    Highlights: • M06-2X functional is suitable to model key steps of proline-catalyzed reactions. • Investigation of the proline-catalyzed aldol reaction mechanism. • Influence of water molecules on the C–C bond formation step. • Mechanism for the reaction of proline-derived enamines with benzhydrylium cations. - Abstract: The proline-catalyzed aldol reaction is the seminal example of asymmetric organocatalysis. Previous theoretical and experimental studies aimed at identifying its mechanism in order to rationalize the outcome of this reaction. Here, we focus on key steps with modern first principle methods, i.e. the M06-2X hybrid exchange–correlation functional combined to the solvation density model to account for environmental effects. In particular, different pathways leading to the formation of neutral and negatively charged enamine intermediates are investigated, and their reactivity towards two electrophiles, i.e. an aldehyde and a benzhydrylium cation, are compared. Regarding the self-aldol reaction, our calculations confirm that the neutral enamine intermediate is more reactive than the negatively charged one. For the reaction with benzhydrylium cations however, the negatively charged enamine intermediate is more reactive.

  2. Quantum mechanical investigations on the role of neutral and negatively charged enamine intermediates in organocatalyzed reactions

    International Nuclear Information System (INIS)

    Highlights: • M06-2X functional is suitable to model key steps of proline-catalyzed reactions. • Investigation of the proline-catalyzed aldol reaction mechanism. • Influence of water molecules on the C–C bond formation step. • Mechanism for the reaction of proline-derived enamines with benzhydrylium cations. - Abstract: The proline-catalyzed aldol reaction is the seminal example of asymmetric organocatalysis. Previous theoretical and experimental studies aimed at identifying its mechanism in order to rationalize the outcome of this reaction. Here, we focus on key steps with modern first principle methods, i.e. the M06-2X hybrid exchange–correlation functional combined to the solvation density model to account for environmental effects. In particular, different pathways leading to the formation of neutral and negatively charged enamine intermediates are investigated, and their reactivity towards two electrophiles, i.e. an aldehyde and a benzhydrylium cation, are compared. Regarding the self-aldol reaction, our calculations confirm that the neutral enamine intermediate is more reactive than the negatively charged one. For the reaction with benzhydrylium cations however, the negatively charged enamine intermediate is more reactive

  3. DFT studies on cobalt-catalyzed cyclotrimerization reactions: the mechanism and origin of reaction improvement under microwave irradiation.

    Science.gov (United States)

    Rodriguez, Antonio M; Cebrián, Cristina; Prieto, Pilar; García, José Ignacio; de la Hoz, Antonio; Díaz-Ortiz, Ángel

    2012-05-14

    A DFT computational mechanistic study of the [2+2+2] cyclotrimerization of a diyne with benzonitrile, catalyzed by a cobalt complex, has been carried out. Three alternative catalytic cycles have been examined together with the precatalytic step (responsible for the induction period). The favored mechanism takes place by means of an intramolecular metal-assisted [4+2] cycloaddition. The beneficial role of microwave activation has been studied. It is concluded that microwave irradiation can decrease the catalytic induction period through thermal effects and can also increase the triplet lifetime and promote the reaction, thus improving the final yield.

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

    International Nuclear Information System (INIS)

    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. These equations can be formulated for any important set of asymptotic channels. 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. 1 figure

  5. Mechanism and kinetics of the NOCO reaction on Rh

    Science.gov (United States)

    Zhdanov, V. P.; Kasemo, B.

    During the past 15 years, the NOCO reaction on Rh has attracted considerable attention of the researchers working in academic and applied surface science. The practical importance of this reaction is connected with its relevance for environmental chemistry. From the point of view of academic studies, the NOCO reaction on Rh is of interest because it represents one of the simplest examples from the class of catalytic reactions occurring via decomposition of adsorbed species. At present, the detailed kinetic data for this reaction are available both for single-crystal and supported Rh, at ultrahigh vacuum (UHV) conditions and also at realistic pressures. For this reason, the NOCO reaction on Rh has become one of the major testing platforms for a microscopic, surface-science based approach to heterogeneous catalysis. The present review shows how far the progress in this field has come. In particular, the review describes in detail the evolution of the ideas for the mechanism of the reaction and also presents the data for the elementary reaction steps, obtained primarily on Rh(1 1 1) at UHV conditions. Then, the possibility of using these data for simulation of the reaction kinetics at moderate pressures, P NO ⋍ P CO ⋍ 0.01 bar, is discussed. The technological aspects of application of Rh in the automotive exhaust systems are surveyed as well, but only briefly.

  6. Effect of nuclear-reaction mechanisms on the population of excited nuclear states and isomeric ratios

    Science.gov (United States)

    Skobelev, N. K.

    2016-07-01

    Experimental data on the cross sections for channels of fusion and transfer reactions induced by beams of radioactive halo nuclei and clustered and stable loosely bound nuclei were analyzed, and the results of this analysis were summarized. The interplay of the excitation of single-particle states in reaction-product nuclei and direct reaction channels was established for transfer reactions. Respective experiments were performed in stable (6Li) and radioactive (6He) beams of the DRIBs accelerator complex at the Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, and in deuteron and 3He beams of the U-120M cyclotron at the Nuclear Physics Institute, Academy Sciences of Czech Republic (Řež and Prague, Czech Republic). Data on subbarrier and near-barrier fusion reactions involving clustered and loosely bound light nuclei (6Li and 3He) can be described quite reliably within simple evaporation models with allowance for different reaction Q-values and couple channels. In reactions involving halo nuclei, their structure manifests itself most strongly in the region of energies below the Coulomb barrier. Neutron transfer occurs with a high probability in the interactions of all loosely bound nuclei with light and heavy stable nuclei at positive Q-values. The cross sections for such reactions and the respective isomeric ratios differ drastically for nucleon stripping and nucleon pickup mechanisms. This is due to the difference in the population probabilities for excited single-particle states.

  7. Density functional theory study on the insertion reaction mechanism of dibromocarbene with formaldehyde

    Institute of Scientific and Technical Information of China (English)

    LI ZhiFeng; L(U) LingLing; KANG JingWan; LU XiaoQuan

    2007-01-01

    The insertion reaction mechanism of CBr2 with CH3CH2O has been studied by using the B3LYP/6-311G(d) and CCSD(T)/6-311G(d) at single point. The geometries of reactions, transition state and products were completely optimized. All the transition state is verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The results show that reaction (1) is the dominant reaction path, which proceeds via two steps: i) two reactants form an intermediate (IM1), which is an exothermal reaction of 8.62 kJ·mol-1 without energy barrier; ii) P1 is obtained via the TS1 and the H-shift, in which the energy barrier is 44.53 kJ·mol-1. The statistical thermodynamics and Eyring transition state theory with Wigner correction are used to study the thermodynamic and kinetic characters of this reaction in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature ranges from 200 to 1900 K at 1.0 atm, in which the reaction has a bigger spontaneity capability, equilibrium constant (K) and higher rate constant (k).

  8. 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.

  9. Theoretical Studies on Reaction Mechanisms of HNCS with NH (X3∑)

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The reaction mechanisms of HNCS with NH(X3∑) were theoretically investigated. The minimum energy paths (MEP) of the reaction were calculated by using the density functional theory(DFT) at the B3LYP/6-311 + + G** level. The equilibrium structural parameters, the harmonic vibrational frequencies, the total energies, and the zeropoint energies(ZPE) of all the species were calculated. The single-point energies along the MEP were further refined at the QCISD(T)/6-311 + + G** level. It was found that the mechanisms of the HNCS + NH(X3∑) reaction involve two channels producing the HNC + HNS and the N2H2 + CS products. Channel 1 plays a dominant role and the HNC + HNS are the main products. The reaction is exothermic.

  10. Formation reaction mechanisms of hydroxide anions from Mg(OH)2 layers

    International Nuclear Information System (INIS)

    Highlights: • Mg(OH)2 hydroxide anion migrates to the surface thus producing an adsorbed free hydroxide anion. • Orbital contributions from adsorbed free hydroxide anion dominate the shape of total DOS in the region near the Fermi level. • The hydroxide anion formation reaction in Mg(OH)2 from Mg(OH)2 dissociation is slower than the formation from H2O dissociation. • Formation of hydroxide anions in a layered hydroxide would involve reaction of H2O molecules with layer hydroxide anions. - Abstract: DFT calculations with periodic boundary conditions were used to study two formation reaction mechanisms of adsorbed free hydroxide anions on the surface of the brucite, Mg(OH)2. In the first mechanism, we investigated the migration of a hydroxide anion present in the structure of Mg(OH)2 to the layer surface. In the second, a mechanism composed of three elementary reactions was examined for the reaction of H2O molecules with the brucite layer surface. The result in both mechanisms is the formation of hydroxide anions and a hydroxide vacancy in the positively charged Mg(OH)2 layer. The global reaction is the same in both cases and the computed Gibbs free energy variation equals 37.5 kcal/mol at room temperature. The reaction barrier for the formation of hydroxide anion on Mg(OH)2 surface from H2O dissociation (27.6 kcal/mol) is lower than the reaction barrier for the formation of hydroxide anions from Mg(OH)2 dissociation (43.2 kcal/mol)

  11. Structural snapshots of the SCR reaction mechanism on Cu-SSZ-13.

    Science.gov (United States)

    Günter, Tobias; Carvalho, Hudson W P; Doronkin, Dmitry E; Sheppard, Thomas; Glatzel, Pieter; Atkins, Andrew J; Rudolph, Julian; Jacob, Christoph R; Casapu, Maria; Grunwaldt, Jan-Dierk

    2015-06-01

    The structure of copper sites in Cu-SSZ-13 during NH3-SCR was unravelled by a combination of novel operando X-ray spectroscopic techniques. Strong adsorption of NH3 on Cu, its reaction with weakly adsorbed NO from the gas phase, and slow re-oxidation of Cu(I) were proven. Thereby the SCR reaction mechanism is significantly different to that observed for Fe-ZSM-5. PMID:25951966

  12. Unraveling the reaction mechanisms governing methanol-to-olefins catalysis by theory and experiment.

    Science.gov (United States)

    Hemelsoet, Karen; Van der Mynsbrugge, Jeroen; De Wispelaere, Kristof; Waroquier, Michel; Van Speybroeck, Veronique

    2013-06-01

    The conversion of methanol to olefins (MTO) over a heterogeneous nanoporous catalyst material is a highly complex process involving a cascade of elementary reactions. The elucidation of the reaction mechanisms leading to either the desired production of ethene and/or propene or undesired deactivation has challenged researchers for many decades. Clearly, catalyst choice, in particular topology and acidity, as well as the specific process conditions determine the overall MTO activity and selectivity; however, the subtle balances between these factors remain not fully understood. In this review, an overview of proposed reaction mechanisms for the MTO process is given, focusing on the archetypal MTO catalysts, H-ZSM-5 and H-SAPO-34. The presence of organic species, that is, the so-called hydrocarbon pool, in the inorganic framework forms the starting point for the majority of the mechanistic routes. The combination of theory and experiment enables a detailed description of reaction mechanisms and corresponding reaction intermediates. The identification of such intermediates occurs by different spectroscopic techniques, for which theory and experiment also complement each other. Depending on the catalyst topology, reaction mechanisms proposed thus far involve aromatic or aliphatic intermediates. Ab initio simulations taking into account the zeolitic environment can nowadays be used to obtain reliable reaction barriers and chemical kinetics of individual reactions. As a result, computational chemistry and by extension computational spectroscopy have matured to the level at which reliable theoretical data can be obtained, supplying information that is very hard to acquire experimentally. Special emphasis is given to theoretical developments that open new perspectives and possibilities that aid to unravel a process as complex as methanol conversion over an acidic porous material.

  13. Structural snapshots of the SCR reaction mechanism on Cu-SSZ-13.

    Science.gov (United States)

    Günter, Tobias; Carvalho, Hudson W P; Doronkin, Dmitry E; Sheppard, Thomas; Glatzel, Pieter; Atkins, Andrew J; Rudolph, Julian; Jacob, Christoph R; Casapu, Maria; Grunwaldt, Jan-Dierk

    2015-06-01

    The structure of copper sites in Cu-SSZ-13 during NH3-SCR was unravelled by a combination of novel operando X-ray spectroscopic techniques. Strong adsorption of NH3 on Cu, its reaction with weakly adsorbed NO from the gas phase, and slow re-oxidation of Cu(I) were proven. Thereby the SCR reaction mechanism is significantly different to that observed for Fe-ZSM-5.

  14. Catalytic conversion reactions in nanoporous systems with concentration-dependent selectivity: Statistical mechanical modeling

    Science.gov (United States)

    García, Andrés; Wang, Jing; Windus, Theresa L.; Sadow, Aaron D.; Evans, James W.

    2016-05-01

    Statistical mechanical modeling is developed to describe a catalytic conversion reaction A →Bc or Bt with concentration-dependent selectivity of the products, Bc or Bt, where reaction occurs inside catalytic particles traversed by narrow linear nanopores. The associated restricted diffusive transport, which in the extreme case is described by single-file diffusion, naturally induces strong concentration gradients. Furthermore, by comparing kinetic Monte Carlo simulation results with analytic treatments, selectivity is shown to be impacted by strong spatial correlations induced by restricted diffusivity in the presence of reaction and also by a subtle clustering of reactants, A .

  15. Recent insight into the mechanism of proton-induced composite particle emission in inclusive reactions

    Directory of Open Access Journals (Sweden)

    Cowley A.A.

    2016-01-01

    Full Text Available Recent results for the inclusive reaction 93Nb(p,α between incident energies of 65 and 160 MeV are shown to be consistent with a competition between knockout and pickup. The pre-equilibrium statistical multistep process terminates in either mechanism. The incident-energy dependence of the reaction reflects the dynamics of the participating reaction components. It is consequently not surprising to observe knockout to dominate at the lower and highest incident energies, with pickup very prominent in between.

  16. Theoretical Study on the Mechanism of the Gas-phase Reaction of Sc+ with Propargyl Alcohol

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yi-Ping; CHEN Hong-Yan; CHENG Wei-Xian; FENG Yu; YANG Li-Jun

    2008-01-01

    In order to elucidate the reaction mechanisms of reaction Sc+ with propargyl alcohol(PPA),the triplet potential energy surface for the reactions has been theoretically investigated using a DFT method.The geometries for the reactants,intermediates,transition states and products were completely optimized at B3LYP/DZVP level.The single point energy of each stationary point was calculated at MP4/(6-311+G** for C,H,O and Lanl2dz for Sc+)level.All the transition states were verified by the vibrational analysis and the internal reaction coordinate(IRC)calculations.The present results show that the reaction takes an insertion-elimination mechanism both along the O-H and C-O bond activation branches,but the C-O bond activation is much more favorable in energy than the O-H bond activation.All theoretical results not only support the existing conclusions inferred from early experiment,but also complement the pathway and mechanism for this reaction.

  17. 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.

  18. The Mechanisms of Oxygen Reduction and Evolution Reactions in Nonaqueous Lithium-Oxygen Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Ruiguo; Walter, Eric D.; Xu, Wu; Nasybulin, Eduard N.; Bhattacharya, Priyanka; Bowden, Mark E.; Engelhard, Mark H.; Zhang, Jiguang

    2014-09-01

    The oxygen reduction/evolution reaction (ORR/OER) mechanisms in nonaqueous Li-O2 batteries have been investigated by using electron paramagnetic resonance spectroscopy in this work. We identified the superoxide radical anion (O2•-) as an intermediate in the ORR process using 5,5-dimethyl-pyrroline N-oxide as a spin trap, while no O2•- in OER was detected during the charge process. These findings provide insightful understanding on the fundamental oxygen reaction mechanisms in rechargeable nonaqueous Li-O2 batteries.

  19. Ab initio Mechanism Study on the Reaction of Chlorine Atom with Formic Acid

    Institute of Scientific and Technical Information of China (English)

    于海涛; 付宏刚; 等

    2003-01-01

    The potential energy surface(PES) for the reaction of Cl atom with HCOOH is predicted using ab initio molecular orbital calculation methods at UQCIDS(T,full)6-311++G(3df,2p)//UMP2(full)/6-311+G(d,P) level of theory with zero-point vibrational energy (ZPVE) correction.The calculated results show that the reaction mechanism of Cl atom with formic acid is a C-site hydrogen abstraction reaction from cis-HOC(H)O molecule by Cl atom with a 3.73kJ/mol reaction barrier height,leading to the formation of cis-HOCO radical which will reacts with Cl atom or other molecules in such a reaction system.Because the reaction barrier height of O-site hydrogen abstraction reaction from cis-HOC(H)O molecule by Cl atom which leads to the formation of HCO2 radical is 67.95kJ/mol,it is a secondary reaction channel in experiment,This is in good agreement with the prediction based on the previous experiments.

  20. Reaction mechanism of the reverse water-gas shift reaction using first-row middle transition metal catalysts L'M (M = Fe, Mn, Co): a computational study.

    Science.gov (United States)

    Liu, Cong; Cundari, Thomas R; Wilson, Angela K

    2011-09-19

    The mechanism of the reverse water-gas shift reaction (CO(2) + H(2) → CO + H(2)O) was investigated using the 3d transition metal complexes L'M (M = Fe, Mn, and Co, L' = parent β-diketiminate). The thermodynamics and reaction barriers of the elementary reaction pathways were studied with the B3LYP density functional and two different basis sets: 6-311+G(d) and aug-cc-pVTZ. Plausible reactants, intermediates, transition states, and products were modeled, with different conformers and multiplicities for each identified. Different reaction pathways and side reactions were also considered. Reaction Gibbs free energies and activation energies for all steps were determined for each transition metal. Calculations indicate that the most desirable mechanism involves mostly monometallic complexes. Among the three catalysts modeled, the Mn complex shows the most favorable catalytic properties. Considering the individual reaction barriers, the Fe complex shows the lowest barrier for activation of CO(2). PMID:21838224

  1. Reaction Mechanism of Glutamate Carboxypeptidase II Revealed by Mutagenesis, X-ray Crystallography, and Computational Methods

    Energy Technology Data Exchange (ETDEWEB)

    Klusak, Vojtech; Barinka, Cyril; Plechanovova, Anna; Mlcochova, Petra; Konvalinka, Jan; Rulisek, Lubomir; Lubkowski, Jacek; (Charles U); (ASCR-ICP); (NCI)

    2009-05-29

    Glutamate carboxypeptidase II (GCPII, EC 3.4.17.21) is a zinc-dependent exopeptidase and an important therapeutic target for neurodegeneration and prostate cancer. The hydrolysis of N-acetyl-l-aspartyl-l-glutamate (N-Ac-Asp-Glu), the natural dipeptidic substrate of the GCPII, is intimately involved in cellular signaling within the mammalian nervous system, but the exact mechanism of this reaction has not yet been determined. To investigate peptide hydrolysis by GCPII in detail, we constructed a mutant of human GCPII [GCPII(E424A)], in which Glu424, a putative proton shuttle residue, is substituted with alanine. Kinetic analysis of GCPII(E424A) using N-Ac-Asp-Glu as substrate revealed a complete loss of catalytic activity, suggesting the direct involvement of Glu424 in peptide hydrolysis. Additionally, we determined the crystal structure of GCPII(E424A) in complex with N-Ac-Asp-Glu at 1.70 {angstrom} resolution. The presence of the intact substrate in the GCPII(E424A) binding cavity substantiates our kinetic data and allows a detailed analysis of GCPII/N-Ac-Asp-Glu interactions. The experimental data are complemented by the combined quantum mechanics/molecular mechanics calculations (QM/MM) which enabled us to characterize the transition states, including the associated reaction barriers, and provided detailed information concerning the GCPII reaction mechanism. The best estimate of the reaction barrier was calculated to be {Delta}G {approx} 22({+-}5) kcal{center_dot}mol{sup -1}, which is in a good agreement with the experimentally observed reaction rate constant (k{sub cat} {approx} 1 s{sup -1}). Combined together, our results provide a detailed and consistent picture of the reaction mechanism of this highly interesting enzyme at the atomic level.

  2. New Perspectives for Studies of Reaction Mechanisms at Low-Medium Energies

    Science.gov (United States)

    Gramegna, F.; Mastinu, P. F.; Vannucci, L.; Boscolo Marchi, E.; Cherubini, R.; Moroni, A.; Bracco, A.; Camera, F.; Million, B.; Wieland, O.; Benzoni, G.; Leoni, S.; Airoldi, A.; Sacchi, R.; Galbusera, E.; Giussani, A.; Ottolenghi, A.; Gadioli, E.; Ballarini, F.; Maj, A.; Brekiesz, M.; Kmiecik, M.; Barlini, S.; Lanchais, A.; Bruno, M.; D'Agostino, M.; Geraci, E.; Vannini, G.; Ordine, A.; Casini, G.; Nannini, A.; Chiari, M.; Abbondanno, U.; Milazzo, P. M.; Margagliotti, G. V.; Bonasera, A.

    2003-04-01

    Many open questions regarding the study of reaction mechanisms with heavy ions have still to be solved, even in the energetic range between 5 and 20 MeV/u, which is covered by the accelerating system Tandem XTU--Linac ALPI of the Laboratori Nazionali of Legnaro. Using complex apparatuses like GARFIELD, coupled with different ancillary detectors, it is possible to perform exclusive measurements, which should be capable of giving new important information, in order to better understand both nuclear structure problems, like for example the study of the mechanisms underlying the Giant Dipole Resonance Damping, and reaction mechanisms phenomena, like the characterization of those mechanisms which are responsible for the many-fragment emission. Preliminary results and future plans to be performed with the GARFIELD facility have been described.

  3. New Perpspectives for Studies of Reaction Mechanisms at Low Medium Energies

    Science.gov (United States)

    Gramegna, F.; Mastinu, P. F.; Vannucci, L.; Marchi, E. Boscolo; Cherubini, R.; Moroni, A.; Bracco, A.; Camera, F.; Million, B.; Wieland, O.; Benzoni, G.; Leoni, S.; Airoldi, A.; Sacchi, R.; Galbusera, E.; Giussani, A.; Ottolenghi, A.; Gadioli, E.; Ballarini, F.; Maj, A.; Brekiesz, M.; Kmiecik, M.; Barlini, S.; Lanchais, A.; Bruno, M.; D'Agostino, M.; Geraci, E.; Vannini, G.; Ordine, A.; Casini, G.; Nannini, A.; Chiari, M.; Abbondanno, U.; Milazzo, P. M.; Margagliotti, G. V.; Bonasera, A.

    2003-07-01

    In the energetic range between 5 and 20 MeV/n, which is covered by the accelerating system Tandem XTU - Linac ALPI of the Laboratori Nazionali of Legnaro, many open questions regarding the study of reaction mechanisms with heavy ions have still to be solved. Using complex apparatuses like GARFIELD coupled with different ancillary detectors, it is possible to perform exclusive measurements, which are necessary to get new important information. This will bring to a better understanding both on nuclear structure problems, like for example the study of the mechanisms underlying the Giant Dipole Resonance Damping, and on reaction mechanisms phenomena, like the characterization of those mechanisms, which are responsible for the many-fragment emission. Preliminary results and plans to be performed with the GARFIELD facility have been described.

  4. 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.

  5. Reaction Mechanism of Thiophene on Vanadium Oxides under FCC Operating Conditions

    Institute of Scientific and Technical Information of China (English)

    Wang Peng; Zheng Aiguo; Tian Huiping; Long Jun

    2004-01-01

    The reaction mechanism of thiophene on vanadium oxides under FCC operating conditions had been preliminary studied using in-situ FT-IR analysis of thiophene and atmospheric pressure continuous fixed-bed reaction, followed by characterization via pyridine adsorption-temperature programmed desorption method, and FT-IR and XPS spectra. The research had discovered that, under 500C thiophene could undergo the redox reaction with V2O5, while being converted into CO, CO2 as well as SO2 with its conversion rate reaching 41.2%. At the same time the oxidation number of vanadium decreased. The existence of a few Bronsted acid centers on V2O5 could lead to an increase of H2S yield among the products derived from the reaction with thiophene.

  6. Reaction mechanism of 3-chlorophenol with OH, H in aqueous solution.

    Science.gov (United States)

    Zhu, Jie; Chen, Ye-Fei; Dong, Wen-Bo; Pan, Xun-Xi; Hou, Hui-Qi

    2003-01-01

    The reaction mechanism of 3-chlorophenol with OH, H in aqueous solution was studied by transient technology. The 3-chlorophenol aqueous solutions have been saturated with air or N2 previously. Under alkaline condition, the reaction of OH radical with 3-chlorophenol produces 3-chlorinated phenoxyl radical, with the absorption peaks at 400 nm and 417 nm. Under neutral condition, the reaction of OH radical with 3-chlorophenol produces OH-adduct with the maximal absorption at about 340 nm. And in acid solution, the reaction of H with 3-chlorophenol produces H-adduct with the maximal absorption at about 320 nm. 3-chlorophenol is compared with 4-and 2-chlorophenols from the free radical pathways. The results show that the positions of chlorine on the aromatic ring strongly influence the dehalogenation and degradation process.

  7. Reaction mechanism of 3-chlorophenol with OH, H in aqueous solution

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The reaction mechanism of 3-chlorophenol with OH, H inaqueous solution was studied by transient technology. The3-chlorophenol aqueous solutions have been saturated with air or N2previously. Under alkaline condition, the reaction of OH radicalwith 3-chlorophenol produces 3-chlorinated phenoxyl radical, withthe absorption peaks at 400 nm and 417 nm. Under neutral condition,the reaction of OH radical with 3-chlorophenol produces OH-adductwith the maximal absorption at about 340 nm. And in acid solution,the reaction of H with 3-chlorophenol produces H-adduct with themaximal absorption at about 320 nm. 3-chlorophenol is compared with4- and 2-chlorophenols from the free radical pathways. The resultsshow that the positions of chlorine on the aromatic ring stronglyinfluence the dehalogenation and degradation process.

  8. A DFT Study Toward the Reaction Mechanisms of TNT With Hydroxyl Radicals for Advanced Oxidation Processes.

    Science.gov (United States)

    He, Xi; Zeng, Qun; Zhou, Yang; Zeng, Qingxuan; Wei, Xianfeng; Zhang, Chaoyang

    2016-05-26

    The degradation pathway of environmental contaminant 2,4,6-trinitrotoluene (TNT) was investigated computationally at the SMD(Pauling)/M06-2X/6-311+G(d,p) level of theory. The dominant decomposition pathway of TNT → 4,6-dinitro-o-cresol → 4,6-dinitro-2-hydroxybenzylalcohol → 4,6-dinitro-2-hydroxybenzaldehyde was provided, and the corresponding predicted products and their distributions are in a good agreement with available experimental data on TNT degradation by Fenton reaction. It was shown that the mechanism of addition-elimination is crucial for this stage of the reaction. The reaction of H atom abstraction is a minor competing pathway. The details on transition states, intermediate radicals, and free energy surfaces for all proposed reactions are given and make up for a lack of experimental knowledge. PMID:27135259

  9. Mechanisms of branching reactions in melanin formation - Ab initio quantum engineering approach -

    Science.gov (United States)

    Kishida, Ryo; Menez Aspera, Susan; Kasai, Hideaki

    Melanin, a pigment found in animals, consists of two types of oligomeric unit: eumelanin and pheomelanin. The color of the skin, the hair, and the eyes is controlled by the ratio of eumelanin/pheomelanin production. Especially, dopachrome and dopaquinone are the precursor molecules of melanin which directly affect the composition of melanin through their branching reactions. Dopachrome is converted into two possible monomers of eumelanin. Dopaquinone can undergo both eumelanin and pheomelanin synthesis. To understand the mechanisms and controlling factors that govern the conversions, reactions of the two molecules are investigated using density functional theory-based first-principles calculations. Our results deepen mechanistic understanding of the reactions and open possibilities to design properties and functions of melanin. In this talk, we will discuss about the competitions of the branching reactions.

  10. Kinetics and Mechanism of the Reaction of Ozone with Double Bonds

    Science.gov (United States)

    Razumovskii, S. D.; Zaikov, Gennadii E.

    1980-12-01

    Analysis of the results of recent studies has shown that the reaction of ozone with the double bonds of organic compounds apparently takes place not by a synchronous addition mechanism but through a reversible stage involving the formation of an intermediate complex of ozone with the double bond. The subsequent stages of the reaction involve the formation of a primary ozonide, its decomposition into two fragments, their combination, and a number of other transformations. The properties of the intermediate products, the relationship between the structure of the original alkenes and their reactivity towards ozone, the influence of the nature of the solvent on the direction and rate of the reaction, and the practical application of the reaction of ozone with double bonds in research and chemical technology have been examined. The bibliography contains 205 references.

  11. Theoretical Study on the Mechanism of the Cycloaddition Reaction between Stannylene and Ethylene or Formaldehyde

    Institute of Scientific and Technical Information of China (English)

    卢秀慧; 翟利民; 王沂轩

    2001-01-01

    The mechanism of the cycloaddition reaction of singlet stannylene and ethylene or formaldehyde has been studied by using density functional theory, The geometrical parameters, h-armonic vibrational frequencies and energies of stationary points for potential energy surface are calculated by RB3LYP/3-21G* method. The results show that the two reaction proceesses are both two steps: (1) stannylene and ethylene or formaldehyde form an energy-rich intermediate complex respectively, which is an exothermal reaction with no barrier;(2) two intermediate complexes isomerize to the product, respectively, with the barriers of these two reactions being 52.97and 45.15 kJ/mol at RB3LYP/3-21G* level.

  12. Hybrid direct carbon fuel cells and their reaction mechanisms - a review

    DEFF Research Database (Denmark)

    Deleebeeck, Lisa; Kammer Hansen, Kent

    2014-01-01

    with carbon capture and storage (CCS) due to the high purity of CO2 emitted in the exhaust gas. Direct carbon (or coal) fuel cells (DCFCs) are directly fed with solid carbon to the anode chamber. The fuel cell converts the carbon at the anode and the oxygen at the cathode into electricity, heat and reaction...... is discussed on the fuel cell stack and system levels. The range of DCFC types can be roughly broken down into four fuel cell types: aqueous hydroxide, molten hydroxide, molten carbonate and solid oxide fuel cells. Emphasis is placed on the electrochemical reactions occurring at the anode and the proposed...... mechanism(s) of these reactions for molten carbonate, solid oxide and hybrid direct carbon fuel cells. Additionally, the criteria of choosing the ‘best’ DCFC technology is explored, including system design (continuous supply of solid fuel), performance (power density, efficiency), environmental burden...

  13. 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.

  14. Kinetics and Mechanism of the Exothermic First-stage Decomposition Reaction of Dinitroglycoluril

    Institute of Scientific and Technical Information of China (English)

    ZHAO,Feng-Qi(赵凤起); HU,Rong-Zu(胡荣祖); CHEN,Pei(陈沛); LUO,Yang(罗阳); GAO,Sheng-Li(高胜利); SONG,Ji-Rong(宋纪蓉); SHI,Qi-Zhen(史启祯)

    2004-01-01

    Under linear temperature increase condition, the thermal behavior, mechanism and kinetic parameters of the exothermic decomposition reaction of the title compound have been studied by means of DSC and IR. The initial stage of the mechanism was proposed. The empirical kinetic model function in differential form, apparent activation energy and pre-exponential constant of the exothermic decomposition reaction are α 0.526, 207.0 kJ·mol-1 and 1018.49 s-1, respectively. The critical temperature of thermal explosion of the compound is 252.87 ℃. The values of △S≠, △H≠ and △G≠ of the reaction are 128.4 J·mol-1·K-1, 218.9 kJ·mol-1 and 152.7 kJ·mol-1, respectively.

  15. The Mechanism of the Eeffect of Mineral Admixtures on the Expansion of Aalkali-silica Reaction

    Institute of Scientific and Technical Information of China (English)

    WANG Aiqin; Niu Jishou; ZHANG Chengzhi

    2008-01-01

    On the base of the influence rule of silica fume, slag and fly ash on alkali-silica reaction under the condition of 70℃, the mechanism of the effect of mineral admixtures on alkali-silica reaction is studied further in the paper. The results show that the effects of mineral admixtures on alkali-silica reaction are mainly chemistry effect and surface physichemistry effect. Under suitable condition, the chemistry effect may make alkali-silica reaction to be inhibited effectively, but the physichemistry effect only make alkali-silica reaction to be delayed. The chemistry effect and the physichemistry effect of minerals admixture are relative to the content of Ca(OH)2 in system. Under the condition that there is a large quantity of Ca(OH)2, mineral admixture cannot inhibit alkali-silica reaction effectively. Only when Ca(OH)2 in the system is very less, it is possible that mineral admixture inhibits alkali-silica reaction effectively.

  16. Mechanisms of oxygen reduction reactions for carbon alloy catalysts via first principles molecular dynamics

    International Nuclear Information System (INIS)

    Carbon alloy catalysts (CACs) are one of promising candidates for platinum-substitute cathode catalysts for polymer electrolyte fuel cells. We have investigated possible mechanisms of oxygen reduction reactions (ORRs) for CACs via first-principles-based molecular dynamics simulations. In this contribution, we review possible ORRs at likely catalytic sites of CACs suggested from our simulations. (author)

  17. Effect of CO2-induced reactions on the mechanical behaviour of fractured wellbore cement

    NARCIS (Netherlands)

    Wolterbeek, Timotheus K.T.; Hangx, Suzanne J.T.; Spiers, Christopher J.

    2016-01-01

    Geomechanical damage, such as fracturing of wellbore cement, can severely impact well integrity in CO2 storage fields. Chemical reactions between the cement and CO2-bearing fluids may subsequently alter the cement’s mechanical properties, either enhancing or inhibiting damage accumulation during ong

  18. 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 for ...

  19. Hydrogen-air detonation cells computed using skeletal and reduced reaction mechanisms

    Science.gov (United States)

    Kessler, David; Taylor, Brian; Gamezo, Vadim; Oran, Elaine

    2011-11-01

    The multidimensional instability of gas-phase detonations results in a complex dynamic structure at the detonation front that leaves behind characteristic cellular patterns as it propagates. In fuel-air mixtures with high effective activation energies, such as hydrogen and air, these detonation cells can become irregular and modelling this behavior using reduced chemical reaction mechanisms can be challenging. Using complex reaction mechanisms, however, can be computationally overwhelming for problems of practical interest. We compare the reaction front structures and dynamic behavior of two-dimensional detonations in a stoichiometric hydrogen-air mixture computed using a 12-step skeletal mechanism and several reduced mechanisms, including a calibrated one-step model. We pay particular attention to how transverse instabilities that form in this high-activation-energy mixture are affected by the details of the chemistry model. We then discuss how to adjust the parameters in reduced reaction models to better describe irregular triple point behavior. NAS/NRC Postdoctoral Research Associate.

  20. Ego Defenses and Reaction to Stress: A Validation Study of the Defense Mechanisms Inventory

    Science.gov (United States)

    Gleser, Goldine C.; Sacks, Marilyn

    1973-01-01

    This study investigated the relationship between scores on the Defense Mechanisms Inventory and reaction to an experimental conflict situation in which Ss (85 undergraduate college students) were led to believe that their performance was deficient on a new test of scholastic ability. The pattern of defenses predicted residual posttest estimates of…

  1. Reaction mechanism and influence factors analysis for calcium sulfide generation in the process of phosphogypsum decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Liping, E-mail: lpma2522@hotmail.com [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650093 (China); Niu, Xuekui; Hou, Juan; Zheng, Shaocong; Xu, Wenjuan [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650093 (China)

    2011-11-10

    Highlights: Black-Right-Pointing-Pointer Reusing phosphogypsum is to decompose and recycle Ca and sulfur. Black-Right-Pointing-Pointer FactSage6.1 software was used to simulate the decomposition reactions. Black-Right-Pointing-Pointer Experiments had been taken with high sulfur concentration coal as reducing agent. Black-Right-Pointing-Pointer The reaction mechanism of CaS generation had been analysis, 1100 Degree-Sign C could be the best temperature for PG decomposition. - Abstract: FactSage6.1 software simulation and experiments had been used to analysis the reaction mechanism and influence factors for CaS generation during the process of phosphogypsum decomposition. Thermodynamic calculation showed that the reaction for CaS generation was very complex and CaS was generated mainly through solid-solid reaction and gas-solid reaction. The proper CO and CO{sub 2} have benefit for improving the decomposition effects of phosphogypsum and reducing the generation of CaS at 1100 Degree-Sign C. Using high sulfur concentration coal as reducer, the proper reaction conditions to control the generation of CaS were: the coal particle size was between 60 mesh and 100 mesh, reaction temperature was above 1100 Degree-Sign C and the heating rate was 5 Degree-Sign C/min. Experimental and theoretical calculation indicated that the concentration of CaS was only ten percents in the solid product at 1100 Degree-Sign C, which is favorable for the further cement producing using solid production.

  2. Theoretical Study on the Reaction Mechanism of F2+2HBr=2HF+Br2

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    The gas phase reaction mechanism of F2 + 2HBr = 2HF + Br2 has been investigated by (U)MP2 at 6-311G** level, and a series of four-center and three-center transition states have been obtained. The reaction mechanism was achieved by comparing the activation energy of seven reaction paths, i.e. the dissociation energy of F2 is less than the activation energy of the bimolecular elementary reaction F2 + HBr → HF + BrF. Thus it is theoretically proved that the title reaction occurs more easily inthe free radical reaction with three medium steps.

  3. Hepatitis C virus suppresses Hepatocyte Nuclear Factor 4 alpha, a key regulator of hepatocellular carcinoma.

    Science.gov (United States)

    Vallianou, Ioanna; Dafou, Dimitra; Vassilaki, Niki; Mavromara, Penelope; Hadzopoulou-Cladaras, Margarita

    2016-09-01

    Hepatitis C Virus (HCV) infection presents with a disturbed lipid profile and can evolve to hepatic steatosis and hepatocellular carcinoma (HCC). Hepatocyte Nuclear Factor 4 alpha (HNF4α) is the most abundant transcription factor in the liver, a key regulator of hepatic lipid metabolism and a critical determinant of Epithelial to Mesenchymal Transition and hepatic development. We have previously shown that transient inhibition of HNF4α initiates transformation of immortalized hepatocytes through a feedback loop consisting of miR-24, IL6 receptor (IL6R), STAT3, miR-124 and miR-629, suggesting a central role of HNF4α in HCC. However, the role of HNF4α in Hepatitis C Virus (HCV)-related hepatocarcinoma has not been evaluated and remains controversial. In this study, we provide strong evidence suggesting that HCV downregulates HNF4α expression at both transcriptional and translational levels. The observed decrease of HNF4α expression correlated with the downregulation of its downstream targets, HNF1α and MTP. Ectopic overexpression of HCV proteins also exhibited an inhibitory effect on HNF4α levels. The inhibition of HNF4α expression by HCV appeared to be mediated at transcriptional level as HCV proteins suppressed HNF4α gene promoter activity. HCV also up-regulated IL6R, activated STAT3 protein phosphorylation and altered the expression of acute phase genes. Furthermore, as HCV triggered the loss of HNF4α a consequent change of miR-24, miR-629 or miR-124 was observed. Our findings demonstrated that HCV-related HCC could be mediated through HNF4α-microRNA deregulation implying a possible role of HNF4α in HCV hepatocarcinogenesis. HCV inhibition of HNF4α could be sustained to promote HCC. PMID:27477312

  4. Cluster reaction of [Ag8]-/[Cu8]- with chlorine: Evidence for the harpoon mechanism?

    Science.gov (United States)

    Luo, Zhixun; Berkdemir, Cüneyt; Smith, Jordan C.; Castleman, A. W.

    2013-09-01

    To examine the question whether the harpoon mechanism can account for the reactive behavior of microscopic charged systems, we have investigated the reactivity of coinage metal clusters in gas phase. Our studies reveal that the reactivity between [Cu8]-/[Ag8]- and chlorine gas is consistent with the harpoon mechanism. An increased reactive cross section is noted through our theoretical estimation based on two methods, ascribed to a long-range transfer of valence electrons from the [Cu8]-/[Ag8]- cluster to chlorine. Insights into this reactivity will be of interest to other researchers working on obtaining a better understanding of the reaction mechanisms of such superatomic species.

  5. A theoretical study of the mechanism of the addition reaction between carbene and azacyclopropane

    Directory of Open Access Journals (Sweden)

    XIAOJUN TAN

    2010-05-01

    Full Text Available The mechanism of the addition reaction between carbene and azacyclopropane was investigated using the second-order Moller–Plesset perturbation theory (MP2. By using the 6-311+G* basis set, geometry optimization, vibrational analysis and the energy properties of the involved stationary points on the potential energy surface were calculated. From the surface energy profile, it can be predicted that there are two reaction mechanisms. The first one (1 is carbene attack at the N atom of azacyclopropane to form an intermediate, 1a (IM1a, which is a barrier-free exothermic reaction. Then, IM1a can isomerize to IM1b via a transition state 1a (TS1a, in which the potential barrier is 30.0 kJ/mol. Subsequently, IM1b isomerizes to a product (Pro1 via TS1b with a potential barrier of 39.3 kJ/mol. The other one (2 is carbene attack at the C atom of azacyclopropane, firstly to form IM2 via TS2a, the potential barrier is 35.4 kJ/mol. Then IM2 isomerizes to a product (Pro2 via TS2b with a potential barrier of 35.1 kJ/mol. Correspondingly, the reaction energy for the reactions (1 and (2 is –478.3 and –509.9 kJ/mol, respectively. Additionally, the orbital interactions are also discussed for the leading intermediate.

  6. Pharmacoepidemiological characterization of drug-induced adverse reaction clusters towards understanding of their mechanisms.

    Science.gov (United States)

    Mizutani, Sayaka; Noro, Yousuke; Kotera, Masaaki; Goto, Susumu

    2014-06-01

    A big challenge in pharmacology is the understanding of the underlying mechanisms that cause drug-induced adverse reactions (ADRs), which are in some cases similar to each other regardless of different drug indications, and are in other cases different regardless of same drug indications. The FDA Adverse Event Reporting System (FAERS) provides a valuable resource for pharmacoepidemiology, the study of the uses and the effects of drugs in large human population. However, FAERS is a spontaneous reporting system that inevitably contains noise that deviates the application of conventional clustering approaches. By performing a biclustering analysis on the FAERS data we identified 163 biclusters of drug-induced adverse reactions, counting for 691 ADRs and 240 drugs in total, where the number of ADR occurrences are consistently high across the associated drugs. Medically similar ADRs are derived from several distinct indications for use in the majority (145/163=88%) of the biclusters, which enabled us to interpret the underlying mechanisms that lead to similar ADRs. Furthermore, we compared the biclusters that contain same drugs but different ADRs, finding the cases where the populations of the patients were different in terms of age, sex, and body weight. We applied a biclustering approach to catalogue the relationship between drugs and adverse reactions from a large FAERS data set, and demonstrated a systematic way to uncover the cases different drug administrations resulted in similar adverse reactions, and the same drug can cause different reactions dependent on the patients' conditions. PMID:24534381

  7. Quantitative interpretation to the chain mechanism of free radical reactions in cyclohexane pyrolysis

    Institute of Scientific and Technical Information of China (English)

    Yingxian Zhao; Bo Shen; Feng Wei

    2011-01-01

    Pyrolysis of cyclohexane was conducted with a plug flow tube reactor in the temperature range of 873-973 K.Based on the experimental data,the mechanism and kinetic model of cyclohexane pyrolysis reaction were proposed.The kinetic analysis shows that overall conversion of cyclohexane is a first order reaction,of which the rate constant increased from 0.0086 to 0.0225 to 0.0623 s- 1 with the increase of temperature from 873 to 923 to 973 K,and the apparent activation energy was determined to be 155.0+1.0 kJ.mo1-1.The mechanism suggests that the cyclohexane is consumed by four processes:the homolysis of C-C bond (Path Ⅰ),the homolysis of C-H bond (Path Ⅱ) in reaction chain initiation,the H-abstraction of various radicals from the feed molecules in reaction chain propagation (Path Ⅲ),and the process associated with coke formation (Path Ⅳ).The reaction path probability (RPP) ratio of Xpath Ⅰ ∶ Xpath Ⅱ∶ XPath Ⅲ ∶ XPath Ⅳ was 0.5420 ∶ 0.0045 ∶ 0.3897 ∶ 0.0638 at 873 K,and 0.4336 ∶ 0.0061 ∶ 0.4885 ∶ 0.0718 at 973 K,respectively.

  8. Pulse radiolysis study on the mechanisms of reactions of CCl3OO· radical with quercetin, rutin and epigallocatechin gallate

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The mechanisms of reactions between CCl3OO· radical and quercetin, rutin and epigallocatechin gallate (EGCG) have been studied using pulse radiolytic technique. It is suggested that the electron transfer reaction is the main reaction between CCl3OO· radical and rutin, EGCG, but there are two main pathways for the reaction of CCl3OO· radical with quercetin, one is the electron transfer reaction, the other is addition reaction. The reaction rate constants were determined. It is proved that quercetin and rutin are better CCl3OO· radical scavengers than EGCG.

  9. Centripetal Acceleration Reaction: An Effective and Robust Mechanism for Flapping Flight in Insects.

    Directory of Open Access Journals (Sweden)

    Chao Zhang

    Full Text Available Despite intense study by physicists and biologists, we do not fully understand the unsteady aerodynamics that relate insect wing morphology and kinematics to lift generation. Here, we formulate a force partitioning method (FPM and implement it within a computational fluid dynamic model to provide an unambiguous and physically insightful division of aerodynamic force into components associated with wing kinematics, vorticity, and viscosity. Application of the FPM to hawkmoth and fruit fly flight shows that the leading-edge vortex is the dominant mechanism for lift generation for both these insects and contributes between 72-85% of the net lift. However, there is another, previously unidentified mechanism, the centripetal acceleration reaction, which generates up to 17% of the net lift. The centripetal acceleration reaction is similar to the classical inviscid added-mass in that it depends only on the kinematics (i.e. accelerations of the body, but is different in that it requires the satisfaction of the no-slip condition, and a combination of tangential motion and rotation of the wing surface. Furthermore, the classical added-mass force is identically zero for cyclic motion but this is not true of the centripetal acceleration reaction. Furthermore, unlike the lift due to vorticity, centripetal acceleration reaction lift is insensitive to Reynolds number and to environmental flow perturbations, making it an important contributor to insect flight stability and miniaturization. This force mechanism also has broad implications for flow-induced deformation and vibration, underwater locomotion and flows involving bubbles and droplets.

  10. Theoretical investigation on H abstraction reaction mechanisms and rate constants of Isoflurane with the OH radical

    Science.gov (United States)

    Ren, Hongjiang; Li, Xiaojun

    2015-12-01

    The mechanism of H abstraction reactions for Isoflurane with the OH radical was investigated using density functional theory and G3(MP2) duel theory methods. The geometrical structures of all the species were fully optimised at B3LYP/6-311++G** level of theory. Thermochemistry data were obtained by utilising the high accurate model chemistry method G3(MP2) combined with the standard statistical thermodynamic calculations. Gibbs free energies were used for the reaction channels analysis. All the reaction channels were confirmed throughout the intrinsic reaction coordinate analysis. The results show that two channels were obtained, which correspond to P(1) and P(2) with the respective activation barriers of 63.03 and 54.82 kJ/mol. The rate constants for the two channels over a wide temperature range of 298.15-2000 K were predicted and the calculated data are in agreement with the experimental one. The results show that P(2) is the dominant reaction channel under 800 K and above 800 K, it can be found that P(1) will be more preferable reaction channel.

  11. ARTICLES: Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde

    Science.gov (United States)

    Lu, Xiu-hui; Li, Yong-qing; Xu, Yue-hua; Han, Jun-feng; Shi, Le-yi

    2010-06-01

    Mechanism of the cycloadditional reaction between singlet dichloro-germylidene and formaldehyde has been investigated with MP2/6-31G* method, including geometry optimization, vibrational analysis and energies for the involved stationary points on the potential energy surface. Prom the potential energy profile, we predict that the cycloaddition reaction between singlet dichloro-germylidene and formaldehyde has two competitive dominant reaction pathways, going with the formation of two side products (INT3 and INT4), simultaneously. Both of the two competitive reactions consist of two steps, two reactants firstly form a three-membered ring intermediate INT1 and a twisted four-membered ring intermediate INT2, respectively, both of which are barrier-free exothermic reactions of 41.5 and 72.3 kJ/mol; then INT1 isomerizes to a four-membered ring product P1 via transition state TS1, and INT2 isomerizes to a chlorine-transfer product P2 via transition state TS2, with the barriers of 2.9 and 0.3 kJ/mol, respectively. Simultaneously, P1 and INT2 further react with formaldehyde to form INT3 and INT4, respectively, which are also barrier-free exothermic reaction of 74.9 and 88.1 kJ/mol.

  12. Alkali-Silica Reaction Inhibited by LiOH and Its Mechanism

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A high alkali reactive aggregate-zeolitization perlite was used to test the long-term effectiveness of LiOH in inhibiting alkali-silica reaction.In this paper,the rigorous conditions were designed that the mortar bars had been cured at 80℃ for 3 years after autoclaved 24 hours at 150℃.Under this condition,LiOH was able to inhibit the alkali-silica reaction long-term effectiveness.Not only the relationship between the molar ratio of n(Li)/(Na) and the alkali contents in systems was established, but also the governing mechanism of such effects was also studied by SEM.

  13. Reaction mechanism in high Nb containing TiAl alloy by elemental powder metallurgy

    Institute of Scientific and Technical Information of China (English)

    WANG Yan-hang; LIN Jun-pin; HE Yue-hui; WANG Yan-li; LIN Zhi; CHEN Guo-liang

    2006-01-01

    High Nb containing TiAl alloy was fabricated in argon atmosphere by reactive hot pressing process. Reaction mechanism was investigated by means of microstructural analyses and thermodynamic calculations. The results show that it is feasible to prepare high Nb containing TiAl alloy with fine lamellar colonies by reactive hot pressing process. The reaction between Ti and Al powders is dominant in Ti-Al-Nb system. Nb powders dissolve into the Ti-Al matrix by diffusion. Pore nests are formed in situ after Nb powders diffusion. The hot pressing atmosphere is optimized by thermodynamic calculations. Vacuum or argon protective atmosphere should be adopted.

  14. Theoretical Studies on the Reaction Mechanism of 1-Chloroethane with Hydroxyl Radical

    Institute of Scientific and Technical Information of China (English)

    WANG Bing-Xing; WANG Li

    2007-01-01

    The reaction mechanism of 1-chloroethane with hydroxyl radical has been investigated by using density functional theory (DFT) B3LYP/6-31G (d, p) method. All bond dissociation enthalpies were computed at the same theoretical level. It was found that hydrogen abstraction pathway is the most favorable. There are two hydrogen abstraction pathways with activation barriers of 0.630 and 4.988 kJ/mol, respectively, while chlorine abstraction pathway was not found. It was observed that activation energies have a more reasonable correlation with the reaction enthalpy changes (ΔHr) than with bond dissociation enthalpies (BDE).

  15. Nucleophilic Substitution Reaction of p-Dinitrobenzene by a Carbanion: Evidence for Electron Transfer Mechanism

    Institute of Scientific and Technical Information of China (English)

    LIU,You-Cheng(刘有成); ZHANG,Kai-Dong(张凯东); L(U),Jian-Ming(吕建明); WU,Long-min(吴隆民); LIU,Zhong-Li(刘中立)

    2002-01-01

    On the basis of investigation of cyclic voltmmnetry, EPR spectroscopy and competition experunebts, the nucleophilic substitution reaction of p-dinitrobenzene with the sodium salt of ethyl α-cyanoacetate carbanion in dimethyl sulfoxide giving ethyl α-cyano- α- (p-nitrophenyl) acetate is shown to take place via the intermediacy of dinitrobenzene radical anion. The reaction rate goes faster than that between p-nitrohalobenzenes and the same sodium salt of ethyl α-cyanoacetate carbanion. There is an evidence for a single electron transfer mechanism.

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

    International Nuclear Information System (INIS)

    The interaction of caffeic acid with eaq-, (CH3)2(OH) CCH2·, CO2·-, H·, ·OH and N3· 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)

  17. Ab initio MO study of reaction mechanism for carbonyl migration of Co complex

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Ab initio method under the effective core potential (ECP) approximation is employed to study the reaction mechanism of carbonyl migration of the cycle of olefin hydroformylation catalyzed by a carbonyl cobalt HCo(CO)3 at Hartree-Fock (HF) level. The structures of the reactant, transition state and product for the reaction are determined. The energy of each stationary point is corrected at MP2/LAN2DZ//LANL2DZ+ZPE (zero-point energy) level. The calculated activation barrier is 28.89 kJ/mol.

  18. Kinetic Reaction Mechanism of Sinapic Acid Scavenging NO2 and OH Radicals: A Theoretical Study

    Science.gov (United States)

    Lu, Yang; Wang, AiHua; Shi, Peng; Zhang, Hui; Li, ZeSheng

    2016-01-01

    The mechanism and kinetics underlying reactions between the naturally-occurring antioxidant sinapic acid (SA) and the very damaging ·NO2 and ·OH were investigated through the density functional theory (DFT). Two most possible reaction mechanisms were studied: hydrogen atom transfer (HAT) and radical adduct formation (RAF). Different reaction channels of neutral and anionic sinapic acid (SA-) scavenging radicals in both atmosphere and water medium were traced independently, and the thermodynamic and kinetic parameters were calculated. We find the most active site of SA/SA- scavenging ·NO2 and ·OH is the –OH group in benzene ring by HAT mechanism, while the RAF mechanism for SA/SA- scavenging ·NO2 seems thermodynamically unfavorable. In water phase, at 298 K, the total rate constants of SA eliminating ·NO2 and ·OH are 1.30×108 and 9.20×109 M-1 S-1 respectively, indicating that sinapic acid is an efficient scavenger for both ·NO2 and ·OH. PMID:27622460

  19. Modeling a halogen dance reaction mechanism: A density functional theory study.

    Science.gov (United States)

    Jones, Leighton; Whitaker, Benjamin J

    2016-07-01

    Since the discovery of the halogen dance (HD) reaction more than 60 years ago, numerous insights into the mechanism have been unveiled. To date however, the reaction has not been investigated from a theoretical perspective. Density functional theory (DFT) was used to model the potential energy surface linking the starting reagents to the lithiated products for each step in the mechanism using a thiophene substrate. It was found that the lithium-halogen exchange mechanism is critical to understand the HD mechanism in detail and yielded the knowledge that SN 2 transition states (TS) are favored over the four-center type for the lithium-bromine exchange steps. The overall driving force for the HD is thermodynamics, while the kinetic factors tightly control the reaction path through temperature. The SN 2 lithium-bromide TS are barrierless, except the second, which is the limiting step. Finally, the model for the HD is discovered to be a pseudo-clock type, due to a highly favorable bromide catalysis step and the reformation of 2-bromothiophene. © 2016 Wiley Periodicals, Inc. PMID:27075112

  20. Mechanism of electron transfer reaction of ternary dipicolinatochromium(III) complex involving oxalate as secondary ligand

    Indian Academy of Sciences (India)

    Hassan Amroun Ewais; Iqbal Mohamed Ibrhium Ismail

    2013-09-01

    Mechanism of electron transfer reaction of ternary Mechanism of the oxidation of [CrIII(DPA)(OX)(H2O)]− (DPA = dipicolinate and OX = oxalate) by periodate in aqueous acidic medium has been studied spectrophotometrically over the pH range of 4.45-5.57 at different temperatures. The reaction is first order with respect to both [IO$^{−}_{4}$] and the complex concentration, and it obeys the following rate law: $$d[{\\text Cr}^{\\text{VI}}]/dt = k_6K_4K_6[{\\text IO}^−_4][{\\text{Cr}}^{\\text{III}}]_{\\text{T}}/\\{([H^+] + K_4) + (K_5[H+] + K_6K_4)[{\\text{IO}}^{−}_{4}]\\}.$$ The rate of the reaction increases with increasing pH due to the deprotonation equilibria of the complex. The experimental rate law is consistent with a mechanism in which the deprotonated form [CrIII(DPA)(OX)(OH)]2− is more reactive than the conjugated acid. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO$^{−}_{4}$ to chromium(III). Thermodynamic activation parameters were calculated using the transition state theory equation.dipicolinatochromium(III) complex involving oxalate as secondary ligand

  1. Reactions of the OOH radical with guanine: Mechanisms of formation of 8-oxoguanine and other products

    Science.gov (United States)

    Kumar, Nagendra; Shukla, P. K.; Mishra, P. C.

    2010-09-01

    The mutagenic product 8-oxoguanine (8-oxoGua) is formed due to intermediacy of peroxyl (OOR) radicals in lipid peroxidation and protein oxidation-induced DNA damage. The mechanisms of these reactions are not yet understood properly. Therefore, in the present study, the mechanisms of formation of 8-oxoGua and other related products due to the reaction of the guanine base of DNA with the hydroperoxyl radical (OOH) were investigated theoretically employing the B3LYP and BHandHLYP hybrid functionals of density functional theory and the polarizable continuum model for solvation. It is found that the reaction of the OOH radical with guanine can occur following seven different mechanisms leading to the formation of various products including 8-oxoGua, its radicals, 5-hydroxy-8-oxoguanine and CO 2. The mechanism that yields 8-oxoGua as an intermediate and 5-hydroxy-8-oxoGua as the final product was found to be energetically most favorable.

  2. Mechanisms of the reaction between polyhalogenated nitrobutadienes and electron-deficient anilines: computational modeling.

    Science.gov (United States)

    Sari, Ozlem; Erdem, Safiye Sağ; Kaufmann, Dieter E

    2014-03-01

    Nitro-substituted polyhalogenated butadienes are valuable synthetic precursors for polyfunctionalized bioactive heterocyclic compounds. Recently, a new reaction between 2-nitroperchloro-1,3-butadiene and electron-deficient anilines producing the Z stereoisomers of a variety of allylidene arylhydrazines has been reported. Although the formation of a chlorinated nitrile oxide intermediate was proved by trapping it with appropriate alkenes via 1,3-dipolar cycloaddition, the details of the overall mechanism remained unclear. The elucidation of the mechanism is important for a better understanding of polyhalogenated nitrobutadiene chemistry. We proposed six reaction paths for the formation of allylidene arylhydrazine, starting from 2-nitroperchloro-1,3-butadiene and para-nitro aniline, and generated the potential energy profiles with the DFT/B3LYP/6-31+G(d,p) method. To include the solvent effect, single-point energy calculations were carried out at the B3LYP/6-31+G(d,p) level by the polarizable continuum model with tetrahydrofuran, as used in the experimental study. The Gibbs activation energies of the rate-determining steps of each mechanism were defined. Taking into account the downhill nature of the overall potential energy profile, Paths 5 and 6 which proceed via extrusion of p-nitrophenylisocyanate and the formation of chlorinated nitrile oxide were chosen as plausible mechanisms. Results also provide insights into the chemistry of nitrile oxides, oximes, oxazete, and nitroso compounds as well as S(N)Vin reactions. PMID:24533665

  3. 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.

  4. The Kabachnik-Fields reaction: synthetic potential and the problem of the mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Cherkasov, Rafael A; Galkin, Vladimir I [Department of Chemistry, Kazan State University, Kazan (Russian Federation)

    1998-10-31

    The published data of the last decade concerning the mechanism of the Kabachnik-Fields reaction and its significance for the chemistry of organophosphorus compounds as a method for the synthesis of {alpha}-amino phosphonates and their numerous functionally substituted derivatives and analogues, such as phosphinates and phosphine oxides, are generalised and systematised. The review discusses the classical version of the Kabachnik-Fields reaction, its modifications with the use of phosphorus chlorides, neutral esters and inorganic phosphorus acids, as well as chemical processes simulating separate steps of the reaction, viz., hydrophosphorylation of imines and amination of {alpha}-hydroxy phosphonates. Data on the practical application of {alpha}-amino phosphonates are presented. The bibliography includes 253 references.

  5. Mechanisms and Kinetics of Radical Reaction of O(1D,3P) + HCN System

    Institute of Scientific and Technical Information of China (English)

    HUANG Yu-Cheng; DU Jin-Yan; JU Xue-Hai; YE Shi-Yong; ZHOU Tao

    2008-01-01

    The reaction of HCN with O(1D, 3P) radical has been investigated by density functional theory (DFT) and ab initio methods. The stationary points on the reaction paths(reactants, intermediates and products) were optimized at the (U)B3LYP/aug-cc-pVTZ level.Single-point calculations were performed at the (U)QCISD(T)/aug-cc-pVTZ level for the optimized structures and all the total energies were corrected by zero-point energy. It is shown that there exist three competing mechanisms of oxygen attacking nitrogen O→N, oxygen attacking carbon O→C and oxygen attacking hydrogen O→H. The rate constants were obtained via Eyring transition-state theory in the temperature range of 600~2000 K. The linear relationship between lnk and 1/T was presented. The results show that path 1 is the main reaction channel and the product of NCO + H is predominant.

  6. Quantum Chemical Study on the Reaction Mechanism of OBrO Radical with OH Radical

    Institute of Scientific and Technical Information of China (English)

    ZhAO,Min(赵岷); ZHAO,Yan-Ling(赵艳玲); LIU,Peng-Jun(刘朋军); CHANG,Ying-Fei(常鹰飞); PAN,Xiu-Mei(潘秀梅); SU,Zhong-Min(苏忠民); WANG,Rong-Shun(王荣顺)

    2004-01-01

    The reaction mechanism of OBrO with OH has been studied using the B3LYP/6-31 l+G(d,p) and the high-level electron-correlation CCSD(T)/6-311 +G(d,p) at single-point. The results show that the title reaction could probably proceed by four possible schemes, generating HOBr+O2, HBr+O3, BrO+HO2 and HOBrO2 products, respectively. The main channel is the one to yield HOBr+ O2. The whole reaction involves the formation of three-membered, four-membered and five-membered rings, followed by the complicated processes of association,H-shift, Br-shift and dissociation. All routes are exothermic.

  7. A Theoretical Study on the Mechanism of the Cycloaddition Reaction between Alkylidenestannylene and Ethylene

    Institute of Scientific and Technical Information of China (English)

    LU Xiu-Hui; YU Hai-Bin; WU Wei-Rong

    2005-01-01

    The mechanism of a cycloaddition reaction between singlet alkylidenestannylene and ethylene has been investigated with MP2/3-21G* and B3LYP/3-21G* methods, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. Energies for the involved conformations were calculated by CCSD(T)//MP2/3-21G* and CCSD(T)//B3LYP/3-21G* methods, respectively. The results show that the dominant reaction pathway of the cycloaddition is that an intermediate (INT) is firstly formed between the two reactants through a barrier-free exothermic reaction of 39.7 kJ/mol, and the intermediate then isomerizes to a four-membered ring product (P2.1) via a transition state TS2.1 with a barrier of 66.8 kJ/mol.

  8. Theoretical Study on the Mechanism of the Cycloaddition Reaction between Alkylidene Carbene and Ethylene

    Institute of Scientific and Technical Information of China (English)

    LU,Xiu-Hui(卢秀慧); ZHAI,Li-Min(翟利民); WU,Wei-Rong(武卫荣)

    2004-01-01

    The mechanism of cycloaddition reaction between singlet alkylidene carbene and ethylene has been investigated with second-order Moller-Plesset perturbation theory (MP2). By using 6-31G* basis , geometry optimization, vibrational analysis and energetics have been calculated for the involved stationary points on the potential energy surface. The results show that the title reaction has two major competition channels. An energy-rich intermediate (INT) is firstly formed between alkylidene carbene and ethylene through a barrier-free exothermic reaction of 63.62 kJ/mol, and the intermediate then isomerizes to a three-membered ring product (P1) and a four-memberd ring product (P2) via transition state TS1 and TS2, in which energy barriers are 47.00 and 51.02 kJ/mol, respectively. P1 is the main product.

  9. Reaction mechanism for methanol oxidation on Au(1 1 1): A density functional theory study

    Science.gov (United States)

    Liu, Shuping; Jin, Peng; Zhang, Donghui; Hao, Ce; Yang, Xueming

    2013-01-01

    The microscopic reaction mechanism for methanol oxidation on Au(1 1 1) surface has been thoroughly investigated by means of density functional theory (DFT) computations. The adsorption geometries and energies were obtained for all the adsorbates, including the reactants, the products, and various possible intermediates on the metal. According to different oxygen conditions, we propose two possible reaction pathways for methanol oxidation on Au(1 1 1): (1) HCHO esterification: the intermediate formaldehyde and methoxy couple to yield methyl formate at low oxygen coverage or without the presence of oxygen atoms; (2) HCHO oxidation: the formaldehyde is oxidized to form formate at high oxygen coverage, which further dissociates to give CO2. Our study emphasizes the critical role of oxygen coverage during the methanol oxidation reaction, and can perfectly explain the difference in product distributions observed in previous experiments.

  10. Dehydriding reaction kinetic mechanism of MgH2-Nb2O5 by Chou model

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Chou model was used to investigate the dehydriding reaction kinetic mechanism of MgH2-Nb2O5 hydrogen storage materials at 573 K.A new conception,"characteristic absorption/desorption time(yc)"was introduced to characterize the reaction rate.The fitting results show that for the hydrogen desorbing mechanism.the surface penetration iS the rate.controlling step.The mechanism remains the same even when the original particle size of Nb2O5 is before ball milling(BM)or when the BM time changes.And tc indicates that the desorption rate of MgH2-Nb2O5 will be faster than that of MgH2-Nb2O5 by BM.The dehydriding reaction rate of MgH2-Nb2O5(micro particle)BMed for 50 h is 4.76 times faster than that of the MgH2-Nb2O5(micro particle)BMed for 0.25 h,while the dehydriding reaction rate of MgH2-Nb2O5(nano particle)BMed for 50 h is only 1.1 8 times as that of the MgH2-Nb2O5 (nano particle)BMed for 0.25 h.The dehydriding reaction rate of the BMed MgH2-Nb2O5(nano particle)is 1-9 times faster than that of the BMed MgH2-Nb2O5(micro particle).

  11. Eclogite-melt/peridotite reaction: Experimental constrains on the destruction mechanism of the North China Craton

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    To study the mechanism of melt-peridotite reaction pertinent to the destruction of the North China Craton (NCC) lithosphere, a series of experiments were performed at a pressure of 2.0 GPa and temperatures from 1250 to 1400°C using Bixiling eclogite and Damaping peridotite as starting materials. The experimental results show that the reaction between eclogite melt and peridotite causes dissolution of olivine and orthopyroxene and precipitation of clinopyroxene in the melt. The experimental run products, characterized by a lherzolite/pyroxenite/garnet-pyroxenite sequence, are consistent with the mantle xenoliths in the Neogene Hannuoba basalt of the NCC found by Liu et al. (2005). It suggests that the mafic lower continental crust was probably recycled into the mantle during the Mesozoic Era. In the experiments conducted at 1300 and 1350°C, the resulting melts have a high Mg# andesite signature, indicating that the melt-peridotite reaction may have played a major role in the generation of high Mg# andesite. Our experimental results support the hypothesis that melts derived from foundered eclogite in the asthenosphere will consume the lithospheric peridotites. Therefore, melt-peridotite reaction is an important mechanism for the destruction/thinning of the lithosphere.

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

    International Nuclear Information System (INIS)

    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

  13. Studies on Mechanism of Hoesch Reaction with Mass Spectrometry and Its Improvement

    Institute of Scientific and Technical Information of China (English)

    LI,Shao-Bai; ZHENG,Hong-Yan

    2004-01-01

    @@ It has been about ninety years since Hoesch reaction was first discovered in 1915. To our knowledge, although several authors[1,2] have studied the mechanism of Hoesch reaction, it has not been explained clearly. Here we represent an investigation on the mechanism with isotopic mass spectrometry. The effects of isotopes on mass spectra were illustrated obviously. FAB spectrum contained intermediate molecular ions at m/z 336 (M+, 19.3), 338 (M+, 18.2), 340 (M+, 12.3),etc and the peak 364 had already arose. This isotopic cluster demonstrated the positive ion 4 (M+, 336) was in existence (isotopes of Zn: 64, 66, 67, 68, 70). A possible intermediate molecular structure of the signal at m/z 364 could be assigned to 3 (M+, 364). Ions peaks of a possible intermediate negative ions suggested the structure 7.

  14. New Insights into Reaction Mechanisms of Ethanol Steam Reforming on Co-ZrO2

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Junming; Karim, Ayman M.; Mei, Donghai; Engelhard, Mark H.; Bao, Xinhe; Wang, Yong

    2015-01-01

    The reaction pathway of ethanol steam reforming on Co-ZrO2 has been identified and the active sites associated with each step are proposed. Ethanol is converted to acetaldehyde and then to acetone, followed by acetone steam reforming. More than 90% carbon was found to follow this reaction pathway. N2-Sorption, X-ray Diffraction (XRD), Temperature Programmed Reduction (TPR), in situ X-ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy, as well as theoretical Density Functional Theory (DFT) calculations have been employed to identify the structure and functionality of the catalysts, which was further used to correlate their performance in ESR. It was found that metallic cobalt is mainly responsible for the acetone steam reforming reactions; while, CoO and basic sites on the support play a key role in converting ethanol to acetone via dehydrogenation and condensation/ketonization reaction pathways. The current work provides fundamental understanding of the ethanol steam reforming reaction mechanisms on Co-ZrO2 catalysts and sheds light on the rational design of selective and durable ethanol steam reforming catalysts.

  15. 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.

  16. Quantum and Molecular Mechanical (QM/MM) Monte Carlo Techniques for Modeling Condensed-Phase Reactions.

    Science.gov (United States)

    Acevedo, Orlando; Jorgensen, Wiliiam L

    2014-09-01

    A recent review (Acc. Chem. Res. 2010, 43:142-151) examined our use and development of a combined quantum and molecular mechanical (QM/MM) technique for modelling organic and enzymatic reactions. Advances included the PDDG/PM3 semiempirical QM (SQM) method, computation of multi-dimensional potentials of mean force (PMF), incorporation of on-the-fly QM in Monte Carlo simulations, and a polynomial quadrature method for rapidly treating proton-transfer reactions. The current article serves as a follow up on our progress. Highlights include new reactions, alternative SQM methods, a polarizable OPLS force field, and novel solvent environments, e.g., "on water" and room temperature ionic liquids. The methodology is strikingly accurate across a wide range of condensed-phase and antibody-catalyzed reactions including substitution, decarboxylation, elimination, isomerization, and pericyclic classes. Comparisons are made to systems treated with continuum-based solvents and ab initio or density functional theory (DFT) methods. Overall, the QM/MM methodology provides detailed characterization of reaction paths, proper configurational sampling, several advantages over implicit solvent models, and a reasonable computational cost. PMID:25431625

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

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James Francis

    2008-12-16

    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){sub 3} and CpFe(CO){sub 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){sub 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){sub 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.

  18. 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.

  19. 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.

  20. Stochastic innovation as a mechanism by which catalysts might self-assemble into chemical reaction networks

    OpenAIRE

    Bradford, Justin A; Dill, Ken A.

    2007-01-01

    We develop a computer model for how two different chemical catalysts in solution, A and B, could be driven to form AB complexes, based on the concentration gradients of a substrate or product that they share in common. If A's product is B's substrate, B will be attracted to A, mediated by a common resource that is not otherwise plentiful in the environment. By this simple physicochemical mechanism, chemical reactions could spontaneously associate to become chained together in solution. Accord...

  1. DFT studies on the SCR reaction mechanism of nitrogen monoxide with propylene catalyzed by copper oxide

    Institute of Scientific and Technical Information of China (English)

    TIAN Ying; XU Jing; ZHAO Jing-xiang

    2007-01-01

    The SCR reaction mechanism of NO with C3H6catalyzed by CuO was studied by the method of Density Functional Theory (DFT) at the B3LYP/LanL2DZ levels. The optimized geometries of the stationary points on the potential surface were obtained and the transition state was confirmed by IRC and vibration analysis. The activation energy was calculated being 34. 26 kJ/mol. It was shown that propylene reacted firstly with Cu forming intermediate, and then nitrogen monoxide immediately reacted with the intermediate to be reduced. It was proved to be a direct interaction mechanism.

  2. Mechanism and Kinetics Analysis of NO/SO2/N2/O2 Dissociation Reactions in Non-Thermal Plasma

    Institute of Scientific and Technical Information of China (English)

    WANG Xinliang; LI Tingting; WEI Dongxiang; WEI Yanli; GU Fan

    2008-01-01

    The kinetics mechanism of the dissociation reactions in a NO/SO2/N2/O2 system was investigated in consideration of energetic electrons' impacts on a non-thermal plasma. A model was derived from the Boltzmann equation and molecule collision theory to predict the dissociation reaction rate coefficients. Upon comparison with available literature, the model was confirmed to be acceptably accurate in general. Several reaction rate coefficients of the NO/SO2/N2/O2 dissociation system were derived according to the Arrhenius formula. The activation energies of each plasma reaction were calculated by quantum chemistry methods. The relation between the dissociation reaction rate coefficient and electron temperature was established to describe the importance of each reaction and to predict relevant processes of gaseous chemical reactions. The sensitivity of the mechanism of NO/SO2/N2/O2 dissociation reaction in a non-thermal plasma was also analysed.

  3. Diffusive coupling can discriminate between similar reaction mechanisms in an allosteric enzyme system

    Directory of Open Access Journals (Sweden)

    Nicola Ernesto M

    2010-11-01

    Full Text Available Abstract Background A central question for the understanding of biological reaction networks is how a particular dynamic behavior, such as bistability or oscillations, is realized at the molecular level. So far this question has been mainly addressed in well-mixed reaction systems which are conveniently described by ordinary differential equations. However, much less is known about how molecular details of a reaction mechanism can affect the dynamics in diffusively coupled systems because the resulting partial differential equations are much more difficult to analyze. Results Motivated by recent experiments we compare two closely related mechanisms for the product activation of allosteric enzymes with respect to their ability to induce different types of reaction-diffusion waves and stationary Turing patterns. The analysis is facilitated by mapping each model to an associated complex Ginzburg-Landau equation. We show that a sequential activation mechanism, as implemented in the model of Monod, Wyman and Changeux (MWC, can generate inward rotating spiral waves which were recently observed as glycolytic activity waves in yeast extracts. In contrast, in the limiting case of a simple Hill activation, the formation of inward propagating waves is suppressed by a Turing instability. The occurrence of this unusual wave dynamics is not related to the magnitude of the enzyme cooperativity (as it is true for the occurrence of oscillations, but to the sensitivity with respect to changes of the activator concentration. Also, the MWC mechanism generates wave patterns that are more stable against long wave length perturbations. Conclusions This analysis demonstrates that amplitude equations, which describe the spatio-temporal dynamics near an instability, represent a valuable tool to investigate the molecular effects of reaction mechanisms on pattern formation in spatially extended systems. Using this approach we have shown that the occurrence of inward

  4. An ab initio molecular dynamics study of the roaming mechanism of the H{sub 2}+HOC{sup +} reaction

    Energy Technology Data Exchange (ETDEWEB)

    Yu Huagen, E-mail: hgy@bnl.gov [Department of Chemistry, Brookhaven National Laboratory, Upton, NY 11973 (United States)

    2011-08-01

    We report here a direct ab initio molecular dynamics study of the p-/o-H{sub 2}+HOC{sup +} reaction on the basis of the accurate SAC-MP2 potential energy surface. The quasi-classical trajectory method was employed. This work largely focuses on the study of reaction mechanisms. A roaming mechanism was identified for this molecular ion-molecule reaction. The driving forces behind the roaming mechanism were thoroughly investigated by using a trajectory dynamics approach. In addition, the thermal rate coefficients of the H{sub 2}+HOC{sup +} reaction were calculated in the temperature range [25, 300] K and are in good agreement with experiments.

  5. Comparison of automatically generated reaction mechanism for oxidation of simple hydrocarbons in IC engine

    Directory of Open Access Journals (Sweden)

    Muhammad Mansha

    2011-10-01

    Full Text Available In this work, a detailed kinetic reaction mechanism, consisting of 208 reactions and 79 species, has been developed todescribe the oxidation of simple hydrocarbon fuel (natural gas in IC engine. The performance of the proposed mechanismis tested using simulation, tool CHEMKIN 4.1.1, and experimental measurements. The simulation results of the proposedreaction scheme were compared with those of reference mechanisms (GRI v3.0 and Konnov 0.5 version as well as experimentaldata. Based upon simulation results, it can be concluded that the proposed mechanism shows good concordanceswith GR I3.0 mechanism especially in the prediction of temperature, pressure, and major product species (H2O, CO2 profilesat stoichiometric conditions (= 1.0. Although, there are some discrepancies among each predicted profile, the proposeddetailed mechanism is good to describe the oxidation of natural gas in IC engine. The experimental data also showed favorableresults for prediction of major product species (CO2, H2O & CO at various engine operating speeds in idle mode.

  6. Palladium-atom catalyzed formic acid decomposition and the switch of reaction mechanism with temperature.

    Science.gov (United States)

    He, Nan; Li, Zhen Hua

    2016-04-21

    Formic acid decomposition (FAD) reaction has been an innovative way for hydrogen energy. Noble metal catalysts, especially palladium-containing nanoparticles, supported or unsupported, perform well in this reaction. Herein, we considered the simplest model, wherein one Pd atom is used as the FAD catalyst. With high-level theoretical calculations of CCSD(T)/CBS quality, we investigated all possible FAD pathways. The results show that FAD catalyzed by one Pd atom follows a different mechanism compared with that catalyzed by surfaces or larger clusters. At the initial stage of the reaction, FAD follows a dehydration route and is quickly poisoned by CO due to the formation of very stable PdCO. PdCO then becomes the actual catalyst for FAD at temperatures approximately below 1050 K. Beyond 1050 K, there is a switch of catalyst from PdCO to Pd atom. The results also show that dehydration is always favoured over dehydrogenation on either the Pd-atom or PdCO catalyst. On the Pd-atom catalyst, neither dehydrogenation nor dehydration follows the formate mechanism. In contrast, on the PdCO catalyst, dehydrogenation follows the formate mechanism, whereas dehydration does not. We also systematically investigated the performance of 24 density functional theory methods. We found that the performance of the double hybrid mPW2PLYP functional is the best, followed by the B3LYP, B3PW91, N12SX, M11, and B2PLYP functionals.

  7. Effect of CO2-induced reactions on the mechanical behaviour of fractured wellbore cement

    Science.gov (United States)

    Wolterbeek, Timotheus; Hangx, Suzanne; Spiers, Christopher

    2016-04-01

    Geomechanical damage, such as fracturing of wellbore cement, can severely impact well integrity in CO2 storage fields. Chemical reactions between the cement and CO2-bearing fluids may subsequently alter the cement's mechanical properties, either enhancing or inhibiting damage accumulation during ongoing changes in wellbore temperature and stress-state. To evaluate the potential for such effects, we performed triaxial compression tests on Class G Portland cement, conducted at down-hole temperature (80 ° C) and effective confining pressures ranging from 1 to 25 MPa. After deformation, samples displaying failure on localised shear fractures were reacted with CO2-H2O, and then subjected to a second triaxial test to assess changes in mechanical properties. Using results from the first phase of deformation, baseline yield and failure criteria were constructed for virgin cement. These delineate stress conditions where unreacted cement is most prone to dilatational (permeability-enhancing) failure. Once shear-fractures formed, later reaction with CO2 did not produce further geomechanical weakening. Instead, after six weeks of reaction, we observed up to 83% recovery of peak-strength and increased frictional strength (15-40%) in the post-failure regime, due to calcium carbonate precipitation in the fractures. As such, our results suggest more or less complete mechanical healing on timescales of the order of months.

  8. Analysis of Vibration Mode for H2+F→HF+H Reaction Mechanism: Density functional Theory Calculation

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Three density functional theory methods (DFT) have been used to investigate the H2+F?HF+H reaction comparing with the Hartree-Fock method and Moller-Plesset (MP2) perturbation theory method. Through the analysis of the vibrational mode and vibrational frequency in the reaction process, the reaction mechanism has been discussed. The activation energy, the reorganization energy and rate constant of the ET reaction are calculated at semi-quantitative level.

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

    International Nuclear Information System (INIS)

    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 O2 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

  10. Quantum Mechanical and Molecular Dynamics Studies of the Reaction Mechanism of the Nucleophilic Substitution at the Si Atom.

    Science.gov (United States)

    Matsubara, Toshiaki; Ito, Tomoyoshi

    2016-05-01

    The mechanism of the nucleophilic substitution at the Si atom, SiH3Cl + Cl*(-) → SiH3Cl* + Cl(-), is examined by both quantum mechanical (QM) and molecular dynamics (MD) methods. This reaction proceeds by two steps with the inversion or retention of the configuration passing through an intermediate with the trigonal bipyramid (TBP) structure, although the conventional SN2 reaction at the C atom proceeds by one step with the inversion of the configuration passing through a transition state with the TBP structure. We followed by the QM calculations all the possible paths of the substitution reaction that undergo the TBP intermediates with the cis and trans forms produced by the frontside and backside attacks of Cl(-). As a result, it was thought that TBPcis1 produced with a high probability is readily transformed to the energetically more stable TBPtrans. This fact was also shown by the MD simulations. In order to obtain more information concerning the trajectory of Cl(-) on the dissociation from TBPtrans, which we cannot clarify on the basis of the energy profile determined by the QM method, the MD simulations with and without the water solvent were conducted and analyzed in detail. The QM-MD simulations without the water solvent revealed that the dissociation of Cl(-) from TBPtrans occurs without passing through TBPcis1'. The ONIOM-MD simulations with the water solvent further suggested that the thermal fluctuation of the water solvent significantly affects the oscillation of the kinetic and potential energies of the substrate to facilitate the isomerization of the TBP intermediate from the cis form to the trans form and the subsequent dissociation of Cl(-) from TBPtrans. PMID:27046773

  11. Products and mechanism of the reaction of ozone with phospholipids in unilamellar phospholipid vesicles

    Energy Technology Data Exchange (ETDEWEB)

    Santrock, J.; Gorski, R.A.; O' Gara, J.F. (Biomedical Science Department, General Motors Research Laboratories, Warren, MI (United States))

    1992-01-01

    While considerable effort has been expended on determining the health effects of exposure to typical urban concentrations of O3, little is known about the chemical events responsible for toxicity. Phospholipids containing unsaturated fatty acids in the cell membranes of lung cells are likely reaction sites for inhaled ozone (O3). In this study, we examined the reaction of O3 with 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) in unilamellar phospholipid vesicles. Reaction of ozone with the carbon-carbon double bond of POPC yielded an aldehyde and a hydroxy hydroperoxide. The hydroxy hydroperoxide eliminated H2O2 to yield a second aldehyde. Upon further ozonolysis, the aldehydes were oxidized to the corresponding carboxylic acids. A material balance showed that no other reaction consumed POPC and O3 or produced these products. As a mechanistic probe, we measured incorporation of oxygen-18 from 18O3 into aldehyde, carboxylic acid, and H2O2. Approximately 50% of the aldehyde oxygen atoms were derived from O3. Oxygen in H2O2 was derived solely from O3, where both oxygen atoms in a molecule of H2O2 were from the same molecule of O3. One of the carboxylic acid oxygen atoms was derived from the precursor aldehyde, while the other was derived from O3. These results support the following mechanism. Cleavage of the carbon-carbon double bond of POPC by O3 yields a carbonyl oxide and an aldehyde. Reaction of H2O with the carbonyl oxide yields a hydroxy hydroperoxide, preventing formation ozonide by reaction of the carbonyl oxide and aldehyde. Elimination of H2O2 from the hydroxy hydroperoxide yields a second aldehyde. Oxidation of the aldehydes by O3 yields carboxylic acids.

  12. Studies of reaction mechanism in 12C + 12C system at intermediate energy of 28.7 MeV/N

    International Nuclear Information System (INIS)

    The reaction mechanism in 12C + 12C system at intermediate energy of about 30 MeV/nucleon was studied. The contribution of various reaction mechanisms (inelastic scattering, transfer reactions, compound nucleus reactions, sequential decay following inelastic excitation and transfer) to the total reaction cross section were found. The analysis of inclusive and coincidence spectra shows that sequential fragmentation processes dominate

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

    International Nuclear Information System (INIS)

    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

  14. Study on the mechanism of coal liquefaction reaction and a new process concept

    Institute of Scientific and Technical Information of China (English)

    SHI Shi-dong; LI Wen-bo; WANG Yong; GUO Zhi; LI Ke-jian

    2008-01-01

    The coal hydrogenation reaction process is simply considered as three steps. In the first step, the smaller molecules associated with coal structure units are released as some gases and water in the condition of solvent and heating. In this step, some weaker bonds of the coal structure units are ruptured to form free radicals. The radicals are stabi-lized by hydrogen atoms from donor solvent and/or H2. In the second step, chain reaction occurs quickly. In the process of chain reaction, the covalent bonds of coal structure units are attacked by the radicals to form some asphaltenes. In the third step, asphaltenes are hydrogenated form more liquids and some gases. In coal liquefaction, the second step of coal hydrogenation reaction should be controlled to avoid integration of radicals, and the third step of coal hydrogenation should be accelerated to increase the coal conversion and the oil yield. A new concept of coal liquefaction process named as China direct coal lique-faction (CDCL) process is presented based on the mechanism study of coal liquefaction.

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

    Science.gov (United States)

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

    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.

  16. Gravitropisms and reaction woods of forest trees - evolution, functions and mechanisms.

    Science.gov (United States)

    Groover, Andrew

    2016-08-01

    Contents 790 I. 790 II. 792 III. 795 IV. 797 V. 798 VI. 800 VII. 800 800 References 800 SUMMARY: The woody stems of trees perceive gravity to determine their orientation, and can produce reaction woods to reinforce or change their position. Together, graviperception and reaction woods play fundamental roles in tree architecture, posture control, and reorientation of stems displaced by wind or other environmental forces. Angiosperms and gymnosperms have evolved strikingly different types of reaction wood. Tension wood of angiosperms creates strong tensile force to pull stems upward, while compression wood of gymnosperms creates compressive force to push stems upward. In this review, the general features and evolution of tension wood and compression wood are presented, along with descriptions of how gravitropisms and reaction woods contribute to the survival and morphology of trees. An overview is presented of the molecular and genetic mechanisms underlying graviperception, initial graviresponse and the regulation of tension wood development in the model angiosperm, Populus. Critical research questions and new approaches are discussed.

  17. 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.

  18. Toward Understanding the Roaming Mechanism in H + MgH → Mg + HH Reaction.

    Science.gov (United States)

    Mauguière, Frédéric A L; Collins, Peter; Stamatiadis, Stamatis; Li, Anyang; Ezra, Gregory S; Farantos, Stavros C; Kramer, Zeb C; Carpenter, Barry K; Wiggins, Stephen; Guo, Hua

    2016-07-14

    The roaming mechanism in the reaction H + MgH →Mg + HH is investigated by classical and quantum dynamics employing an accurate ab initio three-dimensional ground electronic state potential energy surface. The reaction dynamics are explored by running trajectories initialized on a four-dimensional dividing surface anchored on three-dimensional normally hyperbolic invariant manifold associated with a family of unstable orbiting periodic orbits in the entrance channel of the reaction (H + MgH). By locating periodic orbits localized in the HMgH well or involving H orbiting around the MgH diatom, and following their continuation with the total energy, regions in phase space where reactive or nonreactive trajectories may be trapped are found. In this way roaming reaction pathways are deduced in phase space. Patterns similar to periodic orbits projected into configuration space are found for the quantum bound and resonance eigenstates. Roaming is attributed to the capture of the trajectories in the neighborhood of certain periodic orbits. The complex forming trajectories in the HMgH well can either return to the radical channel or "roam" to the MgHH minimum from where the molecule may react. PMID:26918375

  19. Memorable Experiences with Sad Music-Reasons, Reactions and Mechanisms of Three Types of Experiences.

    Science.gov (United States)

    Eerola, Tuomas; 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

  20. Memorable Experiences with Sad Music-Reasons, Reactions and Mechanisms of Three Types of Experiences.

    Directory of Open Access Journals (Sweden)

    Tuomas Eerola

    Full Text Available 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.

  1. 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

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

    International Nuclear Information System (INIS)

    Data on the yield of the symmetric breakup of 24Mg as a function of beam energy are presented and compared with detailed calculations of the energy dependence. The 24Mg states seen in symmetric breakup agree with previously observed breakup states having spin and parities Jπ=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 (12C) transfer or a simple statistical compound process are unlikely mechanisms, but that each of several other mechanisms is consistent with the data. ((orig.))

  3. 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.

  4. Reaction mechanisms in transport theories: a test of the nuclear effective interaction

    CERN Document Server

    Colonna, M; Di Toro, M; Frecus, B; Zhang, Y X

    2012-01-01

    We review recent results concerning collective excitations in neutron-rich systems and reactions between charge asymmetric systems at Fermi energies. Solving numerically self-consistent transport equations for neutrons and protons with specific initial conditions, we explore the structure of the different dipole vibrations in the $^{132}Sn$ system and investigate their dependence on the symmetry energy. We evidence the existence of a distinctive collective mode, that can be associated with the Pygmy Dipole Resonance, with an energy well below the standard Giant Dipole Resonance and isoscalar-like character, i.e. very weakly dependent on the isovector part of the nuclear effective interaction. At variance, the corresponding strength is rather sensitive to the behavior of the symmetry energy below saturation, which rules the number of excess neutrons in the nuclear surface. In reactions between charge asymmetric systems at Fermi energies, we investigate the interplay between dissipation mechanisms and isospin e...

  5. Reaction Mechanisms in Petroleum: From Experimentation to Upgrading and Geological Conditions

    CERN Document Server

    Lannuzel, Frédéric; Bounaceur, Roda; Marquaire, Paul-Marie; Michels, Raymond

    2009-01-01

    Among the numerous questions that arise concerning the exploitation of petroleum from unconventional reservoirs, lie the questions of the composition of hydrocarbons present in deep seated HP-HT reservoirs or produced during in-situ upgrading steps of heavy oils and oil shales. Our research shows that experimental hydrocarbon cracking results obtained in the laboratory cannot be extrapolated to geological reservoir conditions in a simple manner. Our demonstration is based on two examples: 1) the role of the hydrocarbon mixture composition on reaction kinetics (the "mixing effect") and the effects of pressure (both in relationship to temperature and time). The extrapolation of experimental data to geological conditions requires investigation of the free-radical reaction mechanisms through a computed kinetic model. We propose a model that takes into account 52 reactants as of today, and which can be continuously improved by addition of new reactants as research proceeds. This model is complete and detailed enou...

  6. Reaction mechanism studies on isoquinoline with hydroxyl radical in aqueous solutions

    Institute of Scientific and Technical Information of China (English)

    ZHU Dazhang; WANG Shilong; SUN Xiaoyu; NI Yarning; YAO Side

    2007-01-01

    The reaction mechanism between isoquinoline and .OH radical in aqueous dilute solutions under different conditions was studied by pulse radiolysis. The main chara-cteristic peaks in these transient absorption spectra were attributed and the growth-decay trends of several transient species were investigated. Under neutral or alkaline condi-tions, the reaction of-OH radical and isoquinoline produces OH-adducts with respective rate constants of 3.4 × 109 and 6.6× 109 mol-1.dm3·s-1 while under acidic conditions, the isoquinoline was firstly protonated and then -OH added to the benzene ring and produced protonated isoquinoline OH-adducts with a rate constant of 3.9× 109 mol-1.dm3·s-1.With a better understanding on radiolysis ofisoquinoline, this study is of help for its degradation and for environmental protection.

  7. 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. PMID:26442337

  8. Loss of hepatocyte-nuclear-factor-4alpha affects colonic ion transport and causes chronic inflammation resembling inflammatory bowel disease in mice.

    Directory of Open Access Journals (Sweden)

    Mathieu Darsigny

    Full Text Available BACKGROUND: Hnf4alpha, an epithelial specific transcriptional regulator, is decreased in inflammatory bowel disease and protects against chemically-induced colitis in mice. However, the precise role of this factor in maintaining normal inflammatory homeostasis of the intestine remains unclear. The aim of this study was to evaluate the sole role of epithelial Hnf4alpha in the maintenance of gut inflammatory homeostasis in mice. METHODOLOGY/PRINCIPAL FINDINGS: We show here that specific epithelial deletion of Hnf4alpha in mice causes spontaneous chronic intestinal inflammation leading to focal areas of crypt dropout, increased cytokines and chemokines secretion, immune cell infiltrates and crypt hyperplasia. A gene profiling analysis in diseased Hnf4alpha null colon confirms profound genetic changes in cell death and proliferative behaviour related to cancer. Among the genes involved in the immune protection through epithelial barrier function, we identify the ion transporter claudin-15 to be down-modulated early in the colon of Hnf4alpha mutants. This coincides with a significant decrease of mucosal ion transport but not of barrier permeability in young animals prior to the manifestation of the disease. We confirm that claudin-15 is a direct Hnf4alpha gene target in the intestinal epithelial context and is down-modulated in mouse experimental colitis and inflammatory bowel disease. CONCLUSION: Our results highlight the critical role of Hnf4alpha to maintain intestinal inflammatory homeostasis during mouse adult life and uncover a novel function for Hnf4alpha in the regulation of claudin-15 expression. This establishes Hnf4alpha as a mediator of ion epithelial transport, an important process for the maintenance of gut inflammatory homeostasis.

  9. Mechanisms of emission of particles charged in 6Li + 6Li and 6Li + 10B reactions at low energies

    International Nuclear Information System (INIS)

    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 6Li + 6Li reaction (previous results, kinematic analysis, spectrum of secondary particles, theoretical analysis of results) and of the 6Li + 10B reaction (previous results, experimental results, study of the continuous spectrum of alpha particle, reaction mechanisms)

  10. Reaction pathway and oxidation mechanisms of dibutyl phthalate by persulfate activated with zero-valent iron.

    Science.gov (United States)

    Li, Huanxuan; Wan, Jinquan; Ma, Yongwen; Wang, Yan

    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 (SO4(-)) and hydroxyl radical (·OH) were found to be primary oxidants at pH3.0 and pH7.0, respectively while ·OH was the major specie to oxidize DBP at pH11.0. A similar result was found in an experiment of Electron Spin Resonance spin-trapping where in addition to OH, superoxide radical (O2(-)) was detected at pH11.0. 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 pH3.0 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 pH3.0. PMID:27125682

  11. Reaction mechanism of cobalt-substituted homoprotocatechuate 2,3-dioxygenase: a QM/MM study.

    Science.gov (United States)

    Cao, Lili; Dong, Geng; Lai, Wenzhen

    2015-04-01

    The reaction mechanisms of cobalt-substituted homoprotocatechuate 2,3-dioxygenase (Co-HPCD) with electron-rich substrate homoprotocatechuate (HPCA) and electron-poor substrate 4-nitrocatechol (4NC) were investigated by quantum mechanical/molecular mechanical (QM/MM) calculations. Our results demonstrated that the Co-O2 adducts has doublet ground state with a Co(III)-O2(•-) character when 4NC was used as the substrate, in good agreement with the EPR spectroscopic experiment. The reactive oxygen species is the doublet Co(III)-O2(•-) for Co-HPCD/4NC and the quartet SQ(•↑)-Co(II)-O2(•-↓) species for Co-HPCD/HPCA, indicating that the substrate plays important roles in the dioxygen activation by Co-HPCD. B3LYP was found to overestimate the rate-limiting barriers in Co-HPCD. TPSSh predicts barriers of 21.5 versus 12.0 kcal/mol for Co-HPCD/4NC versus Co-HPCD/HPCA, which is consistent with the fact that the rate of the reaction is decreased when the substrate was changed from HPCA to 4NC.

  12. Substrate Oxidation by Indoleamine 2,3-Dioxygenase: EVIDENCE FOR A COMMON REACTION MECHANISM.

    Science.gov (United States)

    Booth, Elizabeth S; Basran, Jaswir; Lee, Michael; Handa, Sandeep; Raven, Emma L

    2015-12-25

    The kynurenine pathway is the major route of L-tryptophan (L-Trp) catabolism in biology, leading ultimately to the formation of NAD(+). The initial and rate-limiting step of the kynurenine pathway involves oxidation of L-Trp to N-formylkynurenine. This is an O2-dependent process and catalyzed by indoleamine 2,3-dioxygenase and tryptophan 2,3-dioxygenase. More than 60 years after these dioxygenase enzymes were first isolated (Kotake, Y., and Masayama, I. (1936) Z. Physiol. Chem. 243, 237-244), the mechanism of the reaction is not established. We examined the mechanism of substrate oxidation for a series of substituted tryptophan analogues by indoleamine 2,3-dioxygenase. We observed formation of a transient intermediate, assigned as a Compound II (ferryl) species, during oxidation of L-Trp, 1-methyl-L-Trp, and a number of other substrate analogues. The data are consistent with a common reaction mechanism for indoleamine 2,3-dioxygenase-catalyzed oxidation of tryptophan and other tryptophan analogues.

  13. Reduction of Large Detailed Chemical Kinetic Mechanisms for Autoignition Using Joint Analyses of Reaction Rates and Sensitivities

    Energy Technology Data Exchange (ETDEWEB)

    Saylam, A; Ribaucour, M; Pitz, W J; Minetti, R

    2006-11-29

    A new technique of reduction of detailed mechanisms for autoignition, which is based on two analysis methods is described. An analysis of reaction rates is coupled to an analysis of reaction sensitivity for the detection of redundant reactions. Thresholds associated with the two analyses have a great influence on the size and efficiency of the reduced mechanism. Rules of selection of the thresholds are defined. The reduction technique has been successfully applied to detailed autoignition mechanisms of two reference hydrocarbons: n-heptane and iso-octane. The efficiency of the technique and the ability of the reduced mechanisms to reproduce well the results generated by the full mechanism are discussed. A speedup of calculations by a factor of 5.9 for n-heptane mechanism and by a factor of 16.7 for iso-octane mechanism is obtained without losing accuracy of the prediction of autoignition delay times and concentrations of intermediate species.

  14. Computational approaches to the determination of active site structures and reaction mechanisms in heterogeneous catalysts.

    Science.gov (United States)

    Catlow, C R A; French, S A; Sokol, A A; Thomas, J M

    2005-04-15

    We apply quantum chemical methods to the study of active site structures and reaction mechanisms in mesoporous silica and metal oxide catalysts. Our approach is based on the use of both molecular cluster and embedded cluster (QM/MM) techniques, where the active site and molecular complex are described using density functional theory (DFT) and the embedding matrix simulated by shell model potentials. We consider three case studies: alkene epoxidation over the microporous TS-1 catalyst; methanol synthesis on ZnO and Cu/ZnO and C-H bond activation over Li-doped MgO. PMID:15901543

  15. Reaction mechanism on reduction surface of mixed conductor membrane for H2 production by coal-gas

    International Nuclear Information System (INIS)

    The reaction mechanism on surface of BaCo0.7Fe0.2Nb0.1O3-δ membrane for reforming coal-gas was studied. The effects of metal particle on membrane surface were concluded. 'Activation mechanism' was proposed to be the key for enhancing oxygen permeation of membrane; while the catalyst-bed only takes charge of the reforming reaction. Though not as important as 'activation mechanism', the 'space charge mechanism' still affects the oxygen permeation of membrane. According to these mechanisms, the new design and surface-modifying strategy of membrane reactor were proposed.

  16. First-principles modeling of catalysts: novel algorithms and reaction mechanisms

    Science.gov (United States)

    Richard, Bryan Goldsmith

    A molecular level understanding of a reaction mechanism and the computation of rates requires knowledge of the stable structures and the corresponding transition states that connect them. Temperature, pressure, and environment effects must be included to bridge the 'materials gap' so one can reasonably compare ab initio (first-principles, i.e., having no empirical parameters) predictions with experimental measurements. In this thesis, a few critical problems pertaining to ab initio modeling of catalytic systems are addressed; namely, 1) the issue of building representative models of isolated metal atoms grafted on amorphous supports, 2) modeling inorganic catalytic reactions in non-ideal solutions where the solvent participates in the reaction mechanism, and 3) bridging the materials gap using ab initio thermodynamics to predict the stability of supported nanoparticles under experimental reaction conditions. In Chapter I, a background on first-principles modeling of heterogeneous and homogenous catalysts is provided. Subsequently, to address the problem of modeling catalysis by isolated metal atoms on amorphous supports, we present in Chapter II a sequential-quadratic programming algorithm that systematically predicts the structure and reactivity of isolated active sites on insulating amorphous supports. Modeling solution phase reactions is also a considerable challenge for first-principles modeling, yet when done correctly it can yield critical kinetic and mechanistic insight that can guide experimental investigations. In Chapter III, we examine the formation of peroxorhenium complexes by activation of H2O2, which is key in selective oxidation reactions catalyzed by CH3ReO3 (methyltrioxorhenium, MTO). New experiments and density functional theory (DFT) calculations were conducted to better understand the activation of H2O2 by MTO and to provide a strong experimental foundation for benchmarking computational studies involving MTO and its derivatives. It was found

  17. Theoretical Study on the Reaction Mechanism of SiCl4 with H in the Gas Phase

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The reaction mechanism of SiCl4 with H2 has been studied theoretically using Gaussian 98 program at B3LYP/6-311G* level. Three different reaction paths (a, b, c) in the gas phase were obtained. The geometries, vibrational frequencies and energies of every stagnation point in the reaction channel were calculated and the mechanisms have been confirmed. The results show that path a has an activation energy of 79.12 kcal/mol, which was considered as the main reaction path. Comparably, paths b and c have the energy barriers of 125.07 and 136.25 kcal/mol, res- pectively. The reaction rate constant was calculated by TST method over a wide temperature range of 900~1600 K, which further confirmed that path a was the main reaction channel.

  18. 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.

  19. 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

  20. Effect of atmospheric oxidative plasma treatments on polypropylenic fibers surface: Characterization and reaction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Nisticò, Roberto, E-mail: roberto.nistico@unito.it [University of Torino, Department of Chemistry and NIS Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Magnacca, Giuliana [University of Torino, Department of Chemistry and NIS Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Faga, Maria Giulia; Gautier, Giovanna [CNR-IMAMOTER, Strada delle Cacce 73, 10135 Torino (Italy); D’Angelo, Domenico; Ciancio, Emanuele [Clean-NT Lab, Environment Park S.p.A., Via Livorno 60, 10144 Torino (Italy); Lamberti, Roberta; Martorana, Selanna [Herniamesh S.r.l., Via F.lli Meliga 1/C, 10034 Chivasso (Italy)

    2013-08-15

    Atmospheric pressure plasma-dielectric barrier discharge (APP-DBD, open chamber configuration) was used to functionalize polypropylene (PP) fibers surface in order to generate oxidized-reactive groups such as hydroperoxides, alcohols and carbonyl species (i.e. ketones and others). Such a species increased the surface polarity, without causing material degradation. Three different types of plasma mixture (He, He/O{sub 2}, He/O{sub 2}/H{sub 2}O) under three different values of applied power (750, 1050, 1400 W) were investigated. The formed plasma species (O{sub 2}{sup +}, O single atom and OH radical) and their distribution were monitored via optical emission spectrometry (OES) measurements, and the plasma effects on PP surface species formation were followed by X-ray photoemission spectroscopy (XPS). Results allowed to better understand the reaction pathways between plasma phase and PP fibers. In fact, two reaction mechanisms were proposed, the first one concerning the plasma phase reactions and the second one involving material surface modifications.

  1. Computational study of the reaction mechanism and kinetics of ethyl acrylate ozonolysis in atmosphere

    Science.gov (United States)

    Sun, Yanhui; Cao, Haijie; Han, Dandan; Li, Jing; He, Maoxia; Wang, Chen

    2012-06-01

    The reaction mechanism for the ozonolysis of ethyl acrylate (EA) has been investigated at the CCSD(T)/6-31G(d)+CF//B3LYP/6-31+G(d,p) level of theory. The profile of the potential energy surface (PES) is constructed. Ozone adds to EA via a cyclic transition state to produce a highly unstable primary ozonide which can decompose readily. Over the temperature range of 200-2000 K, the total and individual rate constants are obtained by employing multichannel Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The calculated rate constants are 1.37 × 10-18 cm3 molecule-1 s-1 at 294 K and 1.65 × 10-18 cm3 molecule-1 s-1 at 298 K under the pressure of 760 Torr. The main products of the reactions are ethyl glyoxylate and formaldehyde. These results are in good agreement with the previous experimental data. Several experimental uncertain products are identified. The branching ratios of main reaction paths are also discussed at different temperatures and pressures.

  2. A Theoretical Investigation on the Reaction Mechanism of the C9H+ 12·Side-chain Decomposition

    Institute of Scientific and Technical Information of China (English)

    CHENG,Xueli; ZHAO,Yanyun; LI,Feng; ZHANG,Dongsheng

    2009-01-01

    n-Phenylpropane cation C9H+·12 serves as a prototype to investigate the reaction mechanisms of alkylbenzene cations.The decomposition reactions of C9H+·12 system have been studied extensively at the B3LYP/6-311 + + G**level with Gaussian 98 program package.All reaction channels were fully investigated with the vibrational mode analysis to confirm the transition states and with electron population analysis to discuss the electron redistribution,and to elucidate the reaction mechanism.The reaction mechanism shows that there is a non-barrier channel of C9H+·12→C7H+7+C2H·5,which is thermodynamically most favorable.

  3. Detailed Chemical Kinetic Reaction Mechanisms for Primary Reference Fuels for Diesel Cetane Number and Spark-Ignition Octane Number

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Mehl, M; Curran, H J

    2010-03-03

    For the first time, a detailed chemical kinetic reaction mechanism is developed for primary reference fuel mixtures of n-hexadecane and 2,2,4,4,6,8,8-heptamethyl nonane for diesel cetane ratings. The mechanisms are constructed using existing rules for reaction pathways and rate expressions developed previously for the primary reference fuels for gasoline octane ratings, n-heptane and iso-octane. These reaction mechanisms are validated by comparisons between computed and experimental results for shock tube ignition and for oxidation under jet-stirred reactor conditions. The combined kinetic reaction mechanism contains the submechanisms for the primary reference fuels for diesel cetane ratings and submechanisms for the primary reference fuels for gasoline octane ratings, all in one integrated large kinetic reaction mechanism. Representative applications of this mechanism to two test problems are presented, one describing fuel/air autoignition variations with changes in fuel cetane numbers, and the other describing fuel combustion in a jet-stirred reactor environment with the fuel varying from pure 2,2,4,4,6,8,8-heptamethyl nonane (Cetane number of 15) to pure n-hexadecane (Cetane number of 100). The final reaction mechanism for the primary reference fuels for diesel fuel and gasoline is available on the web.

  4. The effect of a mechanical force on quantum reaction rate: quantum Bell formula.

    Science.gov (United States)

    Makarov, Dmitrii E

    2011-11-21

    The purpose of this note is to derive a quantum-mechanical analog of Bell's formula, which describes the sensitivity of a chemical reaction to a mechanical pulling force. According to this formula, the reaction rate depends exponentially on the force f, i.e., k(f) ~ exp(f/f(c)), where the force scale f(c) is estimated as the thermal energy k(B)T divided by a distance a between the reactant and transition states along the pulling coordinate. Here I use instanton theory to show that, at low temperatures where quantum tunneling is dominant, this force scale becomes f(c) ~ ℏω/a (in the limit where frictional damping is absent) or f(c) ~ ℏτ(-1)/a (in the strong damping limit). Here ω is a characteristic vibration frequency along the pulling coordinate and τ is a characteristic relaxation time in the reactant state. That is, unlike the classical case where f(c) is unaffected by dissipation, this force scale becomes friction dependent in the quantum limit. I further derive higher-order corrections in the force dependence of the rate, describe generalizations to many degrees of freedom, and discuss connection to other quantum rate theories. PMID:22112071

  5. TDDFT Study on Different Sensing Mechanisms of Similar Cyanide Sensors Based on Michael Addition Reaction

    Institute of Scientific and Technical Information of China (English)

    Guang-yue Li; Ping Song; Guo-zhong He

    2011-01-01

    The solvents and substituents of two similar fluorescent sensors for cyanide, 7-diethylamino-3-formylcoumarin (sensor a) and 7-diethylamino-3-(2-nitrovinyl)coumarin (sensor b), are proposed to account for their distinct sensing mechanisms and experimental phenomena.The time-dependent density functional theory has been applied to investigate the ground states and the first singlet excited electronic states of the sensor as well as their possible Michael reaction products with cyanide, with a view to monitoring their geometries and photophysical properties. The theoretical study indicates that the protic water solvent could lead to final Michael addition product of sensor a in the ground state, while the aprotic acetonitrile solvent could lead to carbanion as the final product of sensor b. Furthermore,the Michael reaction product of sensor a has been proved to have a torsion structure in its first singlet excited state. Correspondingly, sensor b also has a torsion structure around the nitrovinyl moiety in its first singlet excited state, while not in its carbanion structure. This could explain the observed strong fluorescence for sensor a and the quenching fluorescencefor the sensor b upon the addition of the cyanide anions in the relevant sensing mechanisms.

  6. Gas-Phase Reactions of Methoxyphenols with NO3 Radicals: Kinetics, Products, and Mechanisms.

    Science.gov (United States)

    Zhang, Haixu; Yang, Bo; Wang, Youfeng; Shu, Jinian; Zhang, Peng; Ma, Pengkun; Li, Zhen

    2016-03-01

    Methoxyphenols, a group of important tracers for wood smoke, are emitted to the atmosphere in large quantities, but their transformations are rarely studied. In this study, the kinetics and products of the gas-phase reactions of eugenol and 4-ethylguaiacol with NO3 radicals were investigated online using a vacuum ultraviolet photoionization gas time-of-flight mass spectrometer. The rate coefficients of the gaseous reactions of eugenol and 4-ethylguaiacol with NO3 radicals were (1.6 ± 0.4) × 10(-13) and (1.1 ± 0.2) × 10(-12) cm(3) molecule(-1) s(-1) (at 298 K), indicating that the atmospheric lifetimes of the NO3 radicals were 3.5 and 0.5 h, respectively. With the aid of gas-chromatography-mass-spectrometry analysis, several types of degradation products were identified with nitro derivatives as the major products. The configurations of the nitro-product isomers and their formation mechanisms were determined via theoretical calculations. On the basis of these products, degradation pathways of the methoxyphenols with NO3 radicals were proposed. This study determines the degradation rates and mechanisms of the methoxyphenols at night and implies the significant NO3 nighttime chemistry. PMID:26845070

  7. Amorphous and crystalline polyetheretherketone: Mechanical properties and tissue reactions during a 3-year follow-up.

    Science.gov (United States)

    Nieminen, Tuomo; Kallela, Ilkka; Wuolijoki, Erkki; Kainulainen, Heikki; Hiidenheimo, Ilmari; Rantala, Immo

    2008-02-01

    The study was aimed to test the mechanical strength, structural stability, and tissue reactions of optically amorphous and crystalline polyetheretherketone (PEEK) plates during a 3-year follow-up in vivo and in vitro. The injection-moulded PEEK plates were implanted to the dorsal subcutis of 12 sheep, which were sacrificed at 6-156 weeks. Thereafter, the plates were subjected to tensile tests, and levels of crystallinity were assessed by differential scanning calorimetry (DSC). Histological evaluation was carried out using the paraffin technique. In vitro properties were examined with the tensile test and DSC at 0-156 weeks. Tissue reactions were mild and fairly similar for the amorphous and crystalline plates at corresponding points in time. The mechanical characteristics of the plates remained stable over the entire follow-up. The tensile yield load and elongation at the yield load of the crystalline plates were roughly double ( approximately 500 vs. 270 N and 2.4 vs. 1.4 mm, respectively) in comparison to the amorphous plates. The elongation at break load of the crystalline plates was smaller than that of the amorphous ones (6 vs. 10). The level of crystallinity in both the optically amorphous ( approximately 15%) and crystalline (32-34%) plates remained invariable during the follow-up. The in vitro and in vivo data coincided remarkably well. In conclusion, both optically amorphous and crystalline PEEK plates are suitable for the fixation of fractures and osteotomies. PMID:17618477

  8. On Cosmic-Ray-Driven Electron Reaction Mechanism for Ozone Hole and Chlorofluorocarbon Mechanism for Global Climate Change

    CERN Document Server

    Lu, Qing-Bin

    2012-01-01

    Numerous laboratory measurements have provided a sound physical basis for the cosmic-ray driven electron-induced reaction (CRE) mechanism of halogen-containing molecules for the ozone hole. And observed spatial and time correlations between polar ozone loss or stratospheric cooling and cosmic rays have shown strong evidence of the CRE mechanism [Q.-B. Lu, Phys. Rep. 487, 141-167(2010)]. Chlorofluorocarbons (CFCs) were also long-known greenhouse gases but were thought to play only a minor role in climate change. However, recent observations have shown evidence of the saturation in greenhouse effect of non-CFC gases. A new evaluation has shown that halocarbons alone (mainly CFCs) could account for the rise of 0.5~0.6 deg C in global surface temperature since 1950, leading to the striking conclusion that not CO2 but CFCs were the major culprit for global warming in the late half of the 20th century [Q.-B. Lu, J. Cosmology 8, 1846-1862(2010)]. Surprizingly, a recent paper [J.-W. Grooss and R. Muller, Atmos. Envir...

  9. 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.

  10. 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}.

  11. Pathophysiological mechanisms of local (pulmonary inflammatory reaction at the traumatic disease of the spinal cord

    Directory of Open Access Journals (Sweden)

    Uljanov V.Yu.

    2015-06-01

    Full Text Available Objective: to study pathophysiological mechanisms of local (pulmonary inflammatory reaction in the sharp and early periods of a traumatic disease of a spinal cord on the basis of an assessment of dynamic changes of cellular structure of a bronchial secret, an alveolar epithelium and a microbic landscape of a tracheobronchial tree at patients with the complicated damages of cervical department of a backbone. Materials and methods. Methods of cytologic, immunofermental and bacteriological researches at 40 patients with the complicated damages of cervical department of a backbone to dynamics studied the contents the neutrofil of leukocytes and alveolar macrophages in a bronchial secret, a mutsin antigene 3GE5 and surfaktant protein D in serum of blood, character of microbic flora of a tracheobronchial tree and its some biological properties. Results. Activation of local (pulmonary inflammatory reaction in the sharp and early periods of a traumatic disease of a spinal cord is characterized by increase of the contents the neutrofil of leukocytes in a bronchial secret for the 7-14th days, lymphocyts — for the 1-14th days increase in the maintenance of a mutsin antigene 3GE5 for the 14th days and SP-D —for the 1-14th days, allocation from respiratory substrata of opportunistic microorganisms in clinically significant concentration; knocking over — increase of quantity of alveolar macrophages, decrease in the maintenance of a mutsin antigene 3GE5 and SP-D for the 21-30th days and sanitation of a locus of an infection in a tracheobronchial tree. Conclusion. The pathophysiological mechanisms defining changes of cellular structure of a bronchial secret, an alveolar epithelium and a microbic landscape of a tracheobronchial tree in the sharp and early periods of a traumatic disease of a spinal cord play an important role in development of organ (pulmonary inflammatory reaction.

  12. Conversion Reaction Mechanisms in Lithium Ion Batteries: Study of the Binary Metal Fluoride Electrodes

    International Nuclear Information System (INIS)

    Materials that undergo a conversion reaction with lithium (e.g., metal fluorides MF2: M = Fe, Cu, ...) often accommodate more than one Li atom per transition-metal cation, and are promising candidates for high-capacity cathodes for lithium ion batteries. However, little is known about the mechanisms involved in the conversion process, the origins of the large polarization during electrochemical cycling, and why some materials are reversible (e.g., FeF2) while others are not (e.g., CuF2). In this study, we investigated the conversion reaction of binary metal fluorides, FeF2 and CuF2, using a series of local and bulk probes to better understand the mechanisms underlying their contrasting electrochemical behavior. X-ray pair-distribution-function and magnetization measurements were used to determine changes in short-range ordering, particle size and microstructure, while high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) were used to measure the atomic-level structure of individual particles and map the phase distribution in the initial and fully lithiated electrodes. Both FeF2 and CuF2 react with lithium via a direct conversion process with no intercalation step, but there are differences in the conversion process and final phase distribution. During the reaction of Li+ with FeF2, small metallic iron nanoparticles (2. In contrast to FeF2, no continuous Cu network was observed in the lithiated CuF2; rather, the converted Cu segregates to large particles (5-12 nm in diameter) during the first discharge, which may be partially responsible for the lack of reversibility in the CuF2 electrode.

  13. 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…

  14. A novel mechanism for the oxidation reaction of VO2+ on a graphite electrode in acidic solutions

    Science.gov (United States)

    Wang, Wenjun; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei; Zeng, Chaoliu

    2014-09-01

    With the consideration of optimizing the performance of the all-vanadium redox flow battery (VRB), the oxidation reaction mechanism of VO2+ on a rotating graphite disk electrode has been investigated by potentiodynamic polarization in sulfuric acid solutions with various pH and vanadium concentrations. Furthermore, the reaction orders of VO2+ and H+ for the oxidation reaction of VO2+ have been calculated from the polarization results and compared with the theoretical results according to the possible reaction mechanisms available in the literature. However, a new oxidation reaction mechanism has been proposed to describe the oxidation of VO2+ at last, and the theoretic reaction orders of VO2+ and H+ based on the new mechanism are consistent with the experimental results when the electrochemical reaction is the rate-limited process. Moreover, a corresponding kinetic equation has been established for the oxidation reaction of VO2+ on a spectroscopically pure graphite electrode, and can be well used to predict the polarization behavior in V (IV) acidic solutions.

  15. 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.

  16. Cell mechanics and stress: from molecular details to the 'universal cell reaction' and hormesis.

    Science.gov (United States)

    Agutter, Paul S

    2007-04-01

    The 'universal cell reaction' (UCR), a coordinated biphasic response to external (noxious and other) stimuli observed in all living cells, was described by Nasonov and his colleagues in the mid-20th century. This work has received no attention from cell biologists in the West, but the UCR merits serious consideration. Although it is non-specific, it is likely to be underpinned by precise mechanisms and, if these mechanisms were characterized and their relationship to the UCR elucidated, then our understanding of the integration of cellular function could be improved. As a step towards identifying such mechanisms, I review some recent advances in understanding cell mechanics and the stress response and I suggest potentially testable hypotheses. There is a particular need for time-course studies of cellular responses to different stimulus doses or intensities. I also suggest a correspondence with hormesis; re-investigation of the UCR using modern biophysical and molecular-biological techniques might throw light on this much-discussed phenomenon.

  17. NO-CO-O2 Reaction on a Metal Catalytic Surface using Eley-Rideal Mechanism

    Institute of Scientific and Technical Information of China (English)

    Waqar Ahmad

    2008-01-01

    Interactions among the reacting species NO, CO and O2 on metal catalytic surfaces are studied by means of Monte Carlo simulation using the Eley-Rideal (ER) mechanism. The study of this three-component system is important for understanding of the reaction kinetics by varying the relative ratios of the reactants. It is found that contrary to the conventional Langmuir-Hinshelwood (LH) thermal mechanism in which two irreversible phase transitions are obtained between active states and poisoned states, a single phase transition is observed when the ER mechanism is combined with the LH mechanism. The phase diagrams of the surface coverage and the steady state production of CO2, N2 and N2O are evaluated as a function of the partial pressures of the reactants in the gas phase. The continuous production of CO2 starts as soon as the CO pressure is switched on and the second order phase transition at the first critical point is eliminated, which is in agreement with the experimental findings.

  18. The reaction mechanism and mechanical properties of the composites fabricated in an Al-ZrO2-C system

    International Nuclear Information System (INIS)

    The in situ composites with the reinforcement volume fraction of 30 vol.% and the C/ZrO2 mole ratio of 0, 0.5 and 1.0 have been fabricated by using exothermic dispersion synthesis in an Al-ZrO2-C system. The reaction mechanism and mechanical properties of the composites have also been studied. When the reinforcement volume fraction of the composites is 30 vol.% and the C/ZrO2 mole ratio is zero, the Al first reacts with ZrO2 to produce the α-Al2O3 particles and the active Zr atoms, and then the Zr atoms react with Al to form the Al3Zr blocks, which are distributed uniformly throughout the aluminum matrix. The ultimate tensile strength and elongation of the composites at room temperature are 215.2 MPa and 3.0%, respectively. The fracture mechanism of the composite can be characterized by a crack nucleus initiating in the Al3Zr blocks and then propagating to the interface because of the poor properties of Al3Zr. With increasing the C/ZrO2 mole ratios, the ZrC is formed previous to the Al3Zr due to its lower Gibbs free energy, and its formation peak becomes bigger in the DSC curve. The amount of the Al3Zr blocks decreases, which leads to the improvement in the tensile properties of the composites. When the C/ZrO2 mole ratio is up to 1, the Al3Zr blocks have almost disappeared in the composites. The reinforcements are composed of α-Al2O3 and ZrC. At the same time, the ultimate tensile strength and elongation increase to 245.4 MPa and 8.0%, respectively. The tensile fracture surface is composed of fine ductile dimples.

  19. The Effect of Exertion and Sex on Vertical Ground Reaction Force Variables and Landing Mechanics.

    Science.gov (United States)

    Bell, David R; Pennuto, Anthony P; Trigsted, Stephanie M

    2016-06-01

    Bell, DR, Pennuto, AP, and Trigsted, SM. The effect of exertion and sex on vertical ground reaction force variables and landing mechanics. J Strength Cond Res 30(6): 1661-1669, 2016-The purpose of this investigation was to determine how exertion and sex affected a variety of vertical ground reaction force (VGRF) parameters during a jump-landing task, including peak VGRF, peak VGRF asymmetry, loading rate, and loading rate asymmetry. Additionally, we wanted to determine whether landing mechanics changed after exertion as measured by the Landing Error Scoring System (LESS). Forty recreationally active participants (20 men and 20 women) completed jump landings from a 30-cm-high box onto force plates before and after repeated bouts of an exercise circuit until a specific rating of perceived exertion was achieved. Three-way (sex × time × limb) analyses of variance were used to analyze variables pre-exertion to postexertion. No significant 3-way interactions were observed for peak VGRF (p = 0.31) or loading rate (p = 0.14). Time by sex interactions were observed for peak VGRF (p = 0.02) and loading rate (p = 0.008). Post hoc analysis revealed that men increased landing force and loading rate after exertion while women did not. Landing mechanics, as assessed by total LESS score, were worse after exertion (p errors for knee flexion landing. Women may be more resistant to exertion compared with men and use different joint controls' strategies to cope with VGRF after exertion. However, VGRF asymmetry is not affected by sex and exertion. Limiting peak VGRF and addressing landing postures, especially after exertion, should be components of injury prevention strategies. PMID:26562710

  20. A kinetic study on the potential of a hybrid reaction mechanism for prediction of NOx formation in biomass grate furnaces

    Science.gov (United States)

    Zahirović, Selma; Scharler, Robert; Kilpinen, Pia; Obernberger, Ingwald

    2011-10-01

    This paper presents the verification of a hybrid reaction mechanism (28 species, 104 reactions) by means of a kinetic study with a view to its application for the CFD-based prediction of gas phase combustion and NOx formation in biomass grate furnaces. The mechanism is based on a skeletal kinetic scheme that includes the subsets for H2, CO, NH3 and HCN oxidation derived from the detailed Kilpinen 97 reaction mechanism. To account for the CH4 breakdown two related reactions from the 4-step global mechanism for hydrocarbons oxidation by Jones and Lindstedt were adopted. The hybrid mechanism was compared to the global mechanism and validated against the detailed Kilpinen 97 mechanism. For that purpose plug flow reactor simulations at conditions relevant to biomass combustion (atmospheric pressure, 1200-1600 K) for approximations of the flue gases in a grate furnace at fuel lean and fuel rich conditions were carried out. The hybrid reaction mechanism outperformed the global one at all conditions investigated. The most striking differences obtained in predictions by the hybrid and the detailed mechanism at the residence times prior to ignition were attributed to the simplified description of the CH4 oxidation in the case of the former. The overall agreement regarding both combustion and NOx chemistry between the hybrid and the detailed mechanism was better at fuel lean conditions than at fuel rich conditions. However, also at fuel rich conditions, the agreement was improving with increasing temperature. Moreover, it was shown that an improvement in the prediction of NOx formation by the N-subset of the hybrid reaction mechanism can be achieved by replacing its C-H-O subset with that of the detailed one.

  1. Shrinkage Cracking: A mechanism for self-sustaining carbon mineralization reactions in olivine rocks

    Science.gov (United States)

    Zhu, W.; Fusseis, F.; Lisabeth, H. P.; Xing, T.; Xiao, X.; De Andrade, V. J. D.; Karato, S. I.

    2015-12-01

    The hydration and carbonation of olivine results in an up to ~44% increase in solid molar volume, which may choke off of fluid supply and passivate reactive surfaces, thus preventing further carbonation reactions. The carbonation of olivine has ben studied extensively in the laboratory. To date, observations from these experimental studies indicate that carbonation reaction rates generally decrease with time and the extent of carbonation is limited in olivine rocks. Field studies, however, show that 100% hydration and carbonation occur naturally in ultramafic rocks. The disagreement between the laboratory results under controlled conditions and the field observations underlines the lack of understanding of the mechanisms responsible for the self-sustaining carbonation interaction in nature. We developed a state-of-the-art pressurized hydrothermal cell that is transparent to X-rays to characterize the real-time evolution of pore geometry during fluid-rock interaction using in-situ synchrotron-based X-ray microtomography. Through a time series of high-resolution 3-dimensional images, we document the microstructural evolution of a porous olivine aggregate reacting with a sodium bicarbonate solution at elevated pressure and temperature conditions. We observed porosity increases, near constant rate of crystal growth, and pervasive reaction-induced fractures. Based on the nanometer scale tomography data, we propose that shrinkage cracking is the mechanism responsible for producing new reactive surface and keep the carbonation reaction self-sustaining in our experiment. Shrinkage cracks are commonly observed in drying mud ponds, cooling lava flows and ice wedge fields. Stretching of a contracting surface bonded to a substrate of nearly constant dimensions leads to a stress buildup in the surface layer. When the stress exceeds the tensile strength, polygonal cracks develop in the surface layer. In our experiments, the stretching mismatch between the surface and interior of

  2. The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxyl radical

    Directory of Open Access Journals (Sweden)

    D. Huang

    2011-08-01

    Full Text Available Aqueous phase chemical processes of organic compounds in the atmosphere have received increasing attention, partly due to their potential contribution to the formation of secondary organic aerosol (SOA. Here, we analyzed the aqueous OH-initiated oxidation of isoprene and its reaction products including carbonyl compounds and organic acids, regarding the acidity and temperature as in-cloudy conditions. We also performed a laboratory simulation to improve our understanding of the kinetics and mechanisms for the products of aqueous isoprene oxidation that are significant precursors of SOA; these included methacrolein (MACR, methyl vinyl ketone (MVK, methyl glyoxal (MG, and glyoxal (GL. We used a novel chemical titration method to monitor the concentration of isoprene in the aqueous phase. We used a box model to interpret the mechanistic differences between aqueous and gas phase OH radical-initiated isoprene oxidations. Our results were the first demonstration of the rate constant for the reaction between isoprene and OH radical in water, 1.2 ± 0.4 × 1010 M−1 s−1 at 283 K. Molar yields were determined based on consumed isoprene. Of note, the ratio of the yields of MVK (24.1 ± 0.8 % to MACR (10.9 ± 1.1% in the aqueous phase isoprene oxidation was approximately double that observed for the corresponding gas phase reaction. We hypothesized that this might be explained by a water-induced enhancement in the self-reaction of a hydroxy isoprene peroxyl radical (HOCH2C(CH3(O2CH = CH2 produced in the aqueous reaction. The observed yields for MG and GL were 11.4 ± 0.3 % and 3.8 ± 0.1 %, respectively. Model simulations indicated that several potential pathways may contribute to the formation of MG and GL. Finally, oxalic acid increased steadily throughout the course of the study, even after isoprene was consumed completely. The observed yield of oxalic acid was 26.2 ± 0

  3. Preparation of Polystyrenylphosphonous Acid of Low Polymerization Degree and Influence of Initiators upon the Free Radical Reaction Mechanism

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The polystyrenylphosphonous acid (PSPA) of low polymerization degree was prepared with one step reaction. The reaction mechanism was changed with different initiators. For the reaction with AIBN or BPO as the initiator, there are 2 or 3 series of radical reaction chains and 5 or 9 series of polystyrenyl products. The main products are PSPA without or with the fragment of the initiator H[CH(C6H5)-CH2]n-PO2H2 and C6H5CO2-[CH2CH (C6H5)]n-PO2H2 respectively.

  4. Surftherm: A program to analyze thermochemical and kinetic data in gas-phase and surface chemical reaction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Coltrin, M.E.; Moffat, H.K.

    1994-06-01

    This report documents the Surftherm program that analyzes transport coefficient, thermochemical- and kinetic rate information in complex gas-phase and surface chemical reaction mechanisms. The program is designed for use with the Chemkin (gas-phase chemistry) and Surface Chemkin (heterogeneous chemistry) programs. It was developed as a ``chemist`s companion`` in using the Chemkin packages with complex chemical reaction mechanisms. It presents in tabular form detailed information about the temperature and pressure dependence of chemical reaction rate constants and their reverse rate constants, reaction equilibrium constants, reaction thermochemistry, chemical species thermochemistry and transport properties. This report serves as a user`s manual for use of the program, explaining the required input and the output.

  5. A Theoretical Investigation on the Reaction Mechanism of the C8H+·10 Side-Chain Decomposition Processes

    Institute of Scientific and Technical Information of China (English)

    CHENG Xue-Li; ZHAO Yan-Yun; LI Feng

    2008-01-01

    The dissociation of ethylbenzene cation C8H+·10 served as a prototype to investigate the decompasition mechanisms of alkylbenzene cations.The reactions of C8H+·10 decomposition reaction system have been studied extensively at the B3L YP/6-311++G** level with Gaussion 98 package.The chain reaction of C8H+·10 dissociation is initiated by C-H bond rupture.All reaction channels were fully investigated with the vibrational mode analysis to confirm the transition states and reveal the reaction mechanism.The energetically most favorable pathway is C8H+·10→TS4→·P2+H· and the channel ieading to C8H+·10 and C2H4 is also competitive.

  6. Structures and reaction mechanisms of the two related enzymes, PurN and PurU.

    Science.gov (United States)

    Sampei, Gen-ichi; Kanagawa, Mayumi; Baba, Seiki; Shimasaki, Toshiaki; Taka, Hiroyuki; Mitsui, Shohei; Fujiwara, Shinji; Yanagida, Yuki; Kusano, Mayumi; Suzuki, Sakiko; Terao, Kayoko; Kawai, Hiroya; Fukai, Yoko; Nakagawa, Noriko; Ebihara, Akio; Kuramitsu, Seiki; Yokoyama, Shigeyuki; Kawai, Gota

    2013-12-01

    The crystal structures of glycinamide ribonucleotide transformylases (PurNs) from Aquifex aeolicus (Aa), Geobacillus kaustophilus (Gk) and Symbiobacterium toebii (St), and of formyltetrahydrofolate hydrolase (PurU) from Thermus thermophilus (Tt) were determined. The monomer structures of the determined PurN and PurU were very similar to the known structure of PurN, but oligomeric states were different; AaPurN and StPurN formed dimers, GkPurN formed monomer and PurU formed tetramer in the crystals. PurU had a regulatory ACT domain in its N-terminal side. So far several structures of PurUs have been determined, yet, the mechanisms of the catalysis and the regulation of PurU have not been elucidated. We, therefore, modelled ligand-bound structures of PurN and PurU, and performed molecular dynamics simulations to elucidate the reaction mechanisms. The evolutionary relationship of the two enzymes is discussed based on the comparisons of the structures and the catalytic mechanisms. PMID:24108189

  7. The mechanism of chemisorption of hydrogen atom on graphene: Insights from the reaction force and reaction electronic flux

    International Nuclear Information System (INIS)

    At the PBE-D3/cc-pVDZ level of theory, the hydrogen chemisorption on graphene was analyzed using the reaction force and reaction electronic flux (REF) theories in combination with electron population analysis. It was found that chemisorption energy barrier is mainly dominated by structural work (∼73%) associated to the substrate reconstruction whereas the electronic work is the greatest contribution of the reverse energy barrier (∼67%) in the desorption process. Moreover, REF shows that hydrogen chemisorption is driven by charge transfer processes through four electronic events taking place as H approaches the adsorbent surface: (a) intramolecular charge transfer in the adsorbent surface; (b) surface reconstruction; (c) substrate magnetization and adsorbent carbon atom develops a sp3 hybridization to form the σC-H bond; and (d) spontaneous intermolecular charge transfer to reach the final chemisorbed state

  8. The mechanism of chemisorption of hydrogen atom on graphene: Insights from the reaction force and reaction electronic flux

    Energy Technology Data Exchange (ETDEWEB)

    Cortés-Arriagada, Diego, E-mail: dcortesr@uc.cl; Gutiérrez-Oliva, Soledad; Herrera, Bárbara; Soto, Karla; Toro-Labbé, Alejandro [Nucleus Millennium Chemical Processes and Catalysis, Laboratorio de Química Teórica Computacional (QTC), Departamento de Química-Física, Facultad de Química, Pontificia Universidad Católica de Chile, Av. Vicuña Mackenna 4860, Macul, Santiago (Chile)

    2014-10-07

    At the PBE-D3/cc-pVDZ level of theory, the hydrogen chemisorption on graphene was analyzed using the reaction force and reaction electronic flux (REF) theories in combination with electron population analysis. It was found that chemisorption energy barrier is mainly dominated by structural work (∼73%) associated to the substrate reconstruction whereas the electronic work is the greatest contribution of the reverse energy barrier (∼67%) in the desorption process. Moreover, REF shows that hydrogen chemisorption is driven by charge transfer processes through four electronic events taking place as H approaches the adsorbent surface: (a) intramolecular charge transfer in the adsorbent surface; (b) surface reconstruction; (c) substrate magnetization and adsorbent carbon atom develops a sp{sup 3} hybridization to form the σC-H bond; and (d) spontaneous intermolecular charge transfer to reach the final chemisorbed state.

  9. 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. PMID:27082700

  10. Implications of sterically constrained n-butane oxidation reactions on the reaction mechanism and selectivity to 1-butanol

    Science.gov (United States)

    Dix, Sean T.; Gómez-Gualdrón, Diego A.; Getman, Rachel B.

    2016-11-01

    Density functional theory (DFT) is used to analyze the reaction network in n-butane oxidation to 1-butanol over a Ag/Pd alloy catalyst under steric constraints, and the implications on the ability to produce 1-butanol selectively using MOF-encapsulated catalysts are discussed. MOFs are porous crystalline solids comprised of metal nodes linked by organic molecules. Recently, they have been successfully grown around metal nanoparticle catalysts. The resulting porous networks have been shown to promote regioselective chemistry, i.e., hydrogenation of trans-1,3-hexadiene to 3-hexene, presumably by forcing the linear alkene to stand "upright" on the catalyst surface and allowing only the terminal C-H bonds to be activated. In this work, we extend this concept to alkane oxidation. Our goal is to determine if a MOF-encapsulated catalyst could be used to selectively produce 1-butanol. Reaction energies and activation barriers are presented for more than 40 reactions in the pathway for n-butane oxidation. We find that C-H bond activation proceeds through an oxygen-assisted pathway and that butanal and 1-butanol are some of the possible products.

  11. Theoretical Study of the Scattering Resonance State, Reaction Mechanism and Partial Potential Energy Surface of the F+CH4→HF +CH3 Reaction

    Institute of Scientific and Technical Information of China (English)

    Qiang WANG; Zheng Ting CAI; Da Cheng FENG

    2006-01-01

    The partial potential energy surface was constructed by ab initio method [QCISD(T)/6-311++G(2df,2pd)]for F+CH4→HF+CH3 reaction system. It not only explained the reaction mechanism brought forward by Diego Troya by means of quasiclassical trajectory (QCT) but also successfully validated Kopin Liu's experimental phenomena about the existence of the reactive resonance. The lifetime of the scattering resonance state was about 0.07 ps. All these were in agreement with the experiments.

  12. Thermochemical reaction mechanism of lead oxide with poly(vinyl chloride) in waste thermal treatment.

    Science.gov (United States)

    Wang, Si-Jia; Zhang, Hua; Shao, Li-Ming; Liu, Shu-Meng; He, Pin-Jing

    2014-12-01

    Poly(vinyl chloride) (PVC) as a widely used plastic that can promote the volatilization of heavy metals during the thermal treatment of solid waste, thus leading to environmental problems of heavy metal contamination. In this study, thermogravimetric analysis (TGA) coupled with differential scanning calorimeter, TGA coupled with Fourier transform infrared spectroscopy and lab-scale tube furnace experiments were carried out with standard PVC and PbO to explicate the thermochemical reaction mechanism of PVC with semi-volatile lead. The results showed that PVC lost weight from 225 to 230°C under both air and nitrogen with an endothermic peak, and HCl and benzene release were also detected. When PbO was present, HCl that decomposed from PVC instantly reacted with PbO via an exothermal gas-solid reaction. The product was solid-state PbCl2 at 501°C, PbCl2 melted, volatilized and transferred into flue gas or condensed into fly ash. Almost all PbCl2 volatilized above 900°C, while PbO just started to volatilize slowly at this temperature. Therefore, the chlorination effect of PVC on lead was apt to lower-temperature and rapid. Without oxygen, Pb2O was generated due to the deoxidizing by carbon, with oxygen, the amount of residual Pb in the bottom ash was significantly decreased.

  13. Removal of Cr (VI) with wheat-residue derived black carbon: Reaction mechanism and adsorption performance

    International Nuclear Information System (INIS)

    The removal of Cr (VI) from aqueous solutions using black carbon (BC) isolated from the burning residues of wheat straw was investigated as a function of pH, contact time, reaction temperature, supporting electrolyte concentration and analytical initial Cr (VI) concentration in batch studies. The effect of surface properties on the adsorption behavior of Cr (VI) was investigated with scanning electron microscope (SEM) equipped with the energy dispersive X-ray spectroscope (EDS) and Fourier transform-infrared (FTIR) spectroscopy. The removal mechanism of Cr (VI) onto the BC was investigated and the result showed that the adsorption reaction consumed a large amount of protons along the reduction of Cr (VI) to Cr (III). The oxidation of the BC took place concurrently to the chromium reduction and led to the formation of hydroxyl and carboxyl functions. An initial solution pH of 1.0 was most favorable for Cr (VI) removal. The adsorption process followed the pseudo-second order equation and Freundlich isotherm very well. The Cr (VI) adsorption was temperature-dependent and almost independent on the sodium chloride concentrations. The maximum adsorption capacity for Cr (VI) was found at 21.34 mg/g in an acidic medium, which is comparable to other low-cost adsorbents.

  14. 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.

  15. Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides.

    Science.gov (United States)

    Björkbacka, Åsa; Yang, Miao; Gasparrini, Claudia; Leygraf, Christofer; Jonsson, Mats

    2015-09-28

    One of the main challenges for the nuclear power industry today is the disposal of spent nuclear fuel. One of the most developed methods for its long term storage is the Swedish KBS-3 concept where the spent fuel is sealed inside copper canisters and placed 500 meters down in the bedrock. Gamma radiation will penetrate the canisters and be absorbed by groundwater thereby creating oxidative radiolysis products such as hydrogen peroxide (H2O2) and hydroxyl radicals (HO˙). Both H2O2 and HO˙ are able to initiate corrosion of the copper canisters. In this work the kinetics and mechanism of reactions between the stable radiolysis product, H2O2, and copper and copper oxides were studied. Also the dissolution of copper into solution after reaction with H2O2 was monitored by ICP-OES. The experiments show that both H2O2 and HO˙ are present in the systems with copper and copper oxides. Nevertheless, these species do not appear to influence the dissolution of copper to the same extent as observed in recent studies in irradiated systems. This strongly suggests that aqueous radiolysis can only account for a very minor part of the observed radiation induced corrosion of copper. PMID:26287519

  16. Surface reaction mechanisms during ozone and oxygen plasma assisted atomic layer deposition of aluminum oxide.

    Science.gov (United States)

    Rai, Vikrant R; Vandalon, Vincent; Agarwal, Sumit

    2010-09-01

    We have elucidated the reaction mechanism and the role of the reactive intermediates in the atomic layer deposition (ALD) of aluminum oxide from trimethyl aluminum in conjunction with O(3) and an O(2) plasma. In situ attenuated total reflection Fourier transform infrared spectroscopy data show that both -OH groups and carbonates are formed on the surface during the oxidation cycle. These carbonates, once formed on the surface, are stable to prolonged O(3) exposure in the same cycle. However, in the case of plasma-assisted ALD, the carbonates decompose upon prolonged O(2) plasma exposure via a series reaction kinetics of the type, A (CH(3)) --> B (carbonates) --> C (Al(2)O(3)). The ratio of -OH groups to carbonates on the surface strongly depends on the oxidizing agent, and also the duration of the oxidation cycle in plasma-assisted ALD. However, in both O(3) and O(2) plasma cycles, carbonates are a small fraction of the total number of reactive sites compared to the hydroxyl groups.

  17. Structure-Based Mechanism for Early PLP-Mediated Steps of Rabbit Cytosolic Serine Hydroxymethyltransferase Reaction

    Directory of Open Access Journals (Sweden)

    Martino L. Di Salvo

    2013-01-01

    Full Text Available Serine hydroxymethyltransferase catalyzes the reversible interconversion of L-serine and glycine with transfer of one-carbon groups to and from tetrahydrofolate. Active site residue Thr254 is known to be involved in the transaldimination reaction, a crucial step in the catalytic mechanism of all pyridoxal 5′-phosphate- (PLP- dependent enzymes, which determines binding of substrates and release of products. In order to better understand the role of Thr254, we have expressed, characterized, and determined the crystal structures of rabbit cytosolic serine hydroxymethyltransferase T254A and T254C mutant forms, in the absence and presence of substrates. These mutants accumulate a kinetically stable gem-diamine intermediate, and their crystal structures show differences in the active site with respect to wild type. The kinetic and crystallographic data acquired with mutant enzymes permit us to infer that conversion of gem-diamine to external aldimine is significantly slowed because intermediates are trapped into an anomalous position by a misorientation of the PLP ring, and a new energy barrier hampers the transaldimination reaction. This barrier likely arises from the loss of the stabilizing hydrogen bond between the hydroxymethyl group of Thr254 and the ε-amino group of active site Lys257, which stabilizes the external aldimine intermediate in wild type SHMTs.

  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.

  19. Nuclear structure and reaction mechanism effects in quasi continuum gamma decay

    International Nuclear Information System (INIS)

    In this thesis an investigation of nuclear structure and reaction mechanism effects is presented as they manifest themselves in the gamma-ray quasi-continua of residual nuclei produced in 12C induced reactions. The author has studied the nuclear structure at high angular momentum and excitation energy of two heavy nuclei (152Dy,156Dy) that have a very different structure at low angular momentum and excitation energy. In addition the effect of the quasi-continuous gamma-decay process on the feeding of the yrast states (the states with the lowest excitation energy at a certain angular momentum) in these two rare earth nuclei has been investigated. The results are discussed in terms of collective and non-collective excitation modes. The interplay between these two types of motion of the nucleons in nuclei in the same mass region and its influence on the structure of the yrast states has been investigated in a search for high-spin isomeric states. (Auth.)

  20. Studies on the Reaction Mechanism of CPP and the Factors Affecting the Yields of Ethylene and Propylene

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The reaction mechanisms of Catalytic Pyrolysis Process and the ethylene and propylene forma-tion reaction are analyzed, and ethylene and propylene are produced through both the free radical reac-tion and carbenium ion reaction. The factors affecting the yields of ethylene and propylene are discussed.The results showed that greater yields of ethylene and propylene can be obtained on ZSM-5 catalystsrather than USY and REY catalysts, and the modified ZSM-5 could improve the ethylene yield. A highertemperature is favorable for enhancement of the free radical reaction as opposed to carbenium ion reaction,and change in temperature can adjust the ratio of ethylene and propylene production. A higher steamamount could produce more ethylene and propylene and less coke, and lowering the catalyst/oil ratio isfavorable for producing ethylene.

  1. Studies on the Reaction Mechanism of CPP and the Factors Affecting the Yields of Ethylene and Propylene

    Institute of Scientific and Technical Information of China (English)

    Hou Dianguo; Wang Xieqing; Xie Chaogang; Shi Zhicheng

    2002-01-01

    The reaction mechanisms of Catalytic Pyrolysis Process and theethylene and propylene forma-tion reaction are analyzed, and ethylene and propylene are produced through both the free radical reac-tion and carbenium ion reaction. The factors affecting the yields of ethylene and propylene are discussed.The results showed that greater yields of ethylene and propylene can be obtained on ZSM-5 catalystsrather than USY and REY catalysts, and the modified ZSM-5 could improve the ethylene yield. A highertemperature is favorable for enhancement of the free radical reaction as opposed to carbenium ion reaction,and change in temperature can adjust the ratio of ethylene and propylene production. A higher steamamount could produce more ethylene and propylene and less coke, and lowering the catalyst/oil ratio isfavorable for producing ethylene.

  2. 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. PMID:22163620

  3. 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.

  4. Study on reaction mechanism of low temperature preparation of nanocrystalline LaCoO3-λ

    Institute of Scientific and Technical Information of China (English)

    SHEN Haiyun; YANG Qiuhua; LI Ning

    2008-01-01

    Perovskite-type oxide nanocrystalline LaCoO3-λ was prepared using the citrate method.The structure and morphology of the sam-pies were characterized by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM).The intermediate products were analyzed by thermal gravimetric and differential thermal analysis (TG-DTA) technology.The results showed that nanocrystaUine LaCoO3-λwith a granula of 30-50 nm had a cubic perovskite structure.The reaction mechanism of low temperature preparation was suggested as fol-lows:the metal complex was first formed by the combination of metal ion and citric acid;and then it decomposed into an aconitie acid com-plex, followed by an oxycarbonate,and finally a perovskite-type oxide.

  5. Structrue and Characteristics of Mesoporous Silica Synthesized in Acid Medium and Its Reaction Mechanism

    Institute of Scientific and Technical Information of China (English)

    LEI Jia-heng; ZHAO Jun; CHEN Yong-xi; GUO Li-ping; LIU Dan

    2004-01-01

    Structrue and pore characteristics of the mesoporous silica synthesized in acid medium were studied by means of XRD, HRTEM, BET, FT-IR, DSC-TGA, and the reaction mechanism was also investigated deeply. The results show that mesopores in the sample possess hexagonal arrays obviously, whereas the structure of silica matrix is amorphous. The results also show that the acting mode of silica and CTMA+ inside the mesopores was chemical bonding force. The structure of mesoporous silica was mainly dependent on the aggregational condition of micelle of CTMA+ as well as their liquid-crystallized status. In addition, condensation and dehydration of silicate radicals were accompanied in the process of calcination, which resulted in the mesoporous structure ordered in local range and the pore sizes largening.

  6. Alkene Cleavage Catalysed by Heme and Nonheme Enzymes: Reaction Mechanisms and Biocatalytic Applications

    Directory of Open Access Journals (Sweden)

    Francesco G. Mutti

    2012-01-01

    Full Text Available The oxidative cleavage of alkenes is classically performed by chemical methods, although they display several drawbacks. Ozonolysis requires harsh conditions (−78°C, for a safe process and reducing reagents in a molar amount, whereas the use of poisonous heavy metals such as Cr, Os, or Ru as catalysts is additionally plagued by low yield and selectivity. Conversely, heme and nonheme enzymes can catalyse the oxidative alkene cleavage at ambient temperature and atmospheric pressure in an aqueous buffer, showing excellent chemo- and regioselectivities in certain cases. This paper focuses on the alkene cleavage catalysed by iron cofactor-dependent enzymes encompassing the reaction mechanisms (in case where it is known and the application of these enzymes in biocatalysis.

  7. 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...

  8. The mechanism of bursting phenomena in Belousov-Zhabotinsky(BZ) chemical reaction with multiple time scales

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The dynamics of a typical Belousov-Zhabotinsky(BZ)reaction with multiple time scales is investigated in this paper.Different forms of periodic bursting phenomena,and specially,three types of chaotic bursters with different structures can be obtained,which are in common with the behaviors observed in experiments.The bifurcations connecting the quiescent state and the repetitive spikes are presented to account for the occurrence of the NKoscillations as well as the different forms of chaotic bursters.The mechanism of the period-adding bifurcation sequences is explored to reveal why the length of the periods in the sequences does not change continuously with the continuous variation of the parameters.

  9. Mechanism of electron transfer reaction for xanthene dye-sensitized formation of methyl viologen radical

    Energy Technology Data Exchange (ETDEWEB)

    Usui, Y.; Misawa, H.; Sakuragi, H.; Tokumaru, K.

    1987-05-01

    Sensitized reduction of methyl viologen, MV/sup 2 +/, occurs efficiently through electron transfer from triplet xanthene dyes to MV/sup 2 +/ followed by electron transfer to the resulting semioxidized dyes from a reductant like triethanolamine. Unreactive ion pair complexes between these dyes and MV/sup 2 +/ are formed (formation constant: 1.2 x 10/sup 3/ M/sup -1/ for Eosine Y and MV/sup 2 +/ in 50% aqueous ethanol solution). The quantum yield for the reduced methyl viologen radical depends on the concentrations of MV/sup 2 +/ and the amine and on the ionic strength of solution. The efficiency of the electron transfer from triplet dyes to MV/sup 2 +/ is increased by addition of alcohol, and solvent effects on the reaction mechanism are discussed. 38 references, 5 figures, 2 tables.

  10. 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).

  11. Mechanism of coupling drug transport reactions located in two different membranes

    Directory of Open Access Journals (Sweden)

    Helen I. Zgurskaya

    2015-02-01

    Full Text Available Gram- negative bacteria utilize a diverse array of multidrug transporters to pump toxic compounds out of cells. Some transporters together with periplasmic membrane fusion proteins (MFPs and outer membrane channels assemble trans-envelope complexes that expel multiple antibiotics across outer membranes of Gram-negative bacteria and into the external medium. Others further potentiate this efflux by pumping drugs across the inner membrane into the periplasm. Together these transporters create a powerful network of efflux that protect bacteria against a broad range of antimicrobial agents. This review is focused on the mechanism of coupling transport reactions located in two different membranes of Gram-negative bacteria. Using a combination of biochemical, genetic and biophysical approaches we have reconstructed the sequence of events leading to the assembly of trans-envelope drug efflux complexes and characterized the roles of periplasmic and outer membrane proteins in this process. Our recent data suggest a critical step in the activation of intermembrane efflux pumps, which is controlled by MFPs. We propose that the reaction cycles of transporters are tightly coupled to the assembly of the trans-envelope complexes. Transporters and MFPs exist in the inner membrane as dormant complexes. The activation of complexes is triggered by MFP binding to the outer membrane channel, which leads to a conformational change in the membrane proximal domain of MFP needed for stimulation of transporters. The activated MFP-transporter complex engages the outer membrane channel to expel substrates across the outer membrane. The recruitment of the channel is likely triggered by binding of effectors (substrates to MFP or MFP-transporter complexes. This model together with recent structural and functional advances in the field of drug efflux provides a fairly detailed understanding of the mechanism of drug efflux across the two membranes.

  12. Conversion Reaction Mechanisms in Lithium Ion Batteries: Study of the Binary Metal Fluoride Electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Feng; Robert, Rosa; Chernova, Natasha A.; Pereira, Nathalie; Omenya, Fredrick; Badway, Fadwa; Hua, Xiao; Ruotolo, Michael; Zhang, Ruigang; Wu, Lijun; Volkov, Vyacheslav; Su, Dong; Key, Baris; Whittingham, M. Stanley; Grey, Clare P.; Amatucci, Glenn G.; Zhu, Yimei; Graetz, Jason (Binghamton); (Rutgers); (BNL); (Cambridge); (SBU)

    2015-10-15

    Materials that undergo a conversion reaction with lithium (e.g., metal fluorides MF{sub 2}: M = Fe, Cu, ...) often accommodate more than one Li atom per transition-metal cation, and are promising candidates for high-capacity cathodes for lithium ion batteries. However, little is known about the mechanisms involved in the conversion process, the origins of the large polarization during electrochemical cycling, and why some materials are reversible (e.g., FeF{sub 2}) while others are not (e.g., CuF{sub 2}). In this study, we investigated the conversion reaction of binary metal fluorides, FeF{sub 2} and CuF{sub 2}, using a series of local and bulk probes to better understand the mechanisms underlying their contrasting electrochemical behavior. X-ray pair-distribution-function and magnetization measurements were used to determine changes in short-range ordering, particle size and microstructure, while high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) were used to measure the atomic-level structure of individual particles and map the phase distribution in the initial and fully lithiated electrodes. Both FeF{sub 2} and CuF{sub 2} react with lithium via a direct conversion process with no intercalation step, but there are differences in the conversion process and final phase distribution. During the reaction of Li{sup +} with FeF{sub 2}, small metallic iron nanoparticles (<5 nm in diameter) nucleate in close proximity to the converted LiF phase, as a result of the low diffusivity of iron. The iron nanoparticles are interconnected and form a bicontinuous network, which provides a pathway for local electron transport through the insulating LiF phase. In addition, the massive interface formed between nanoscale solid phases provides a pathway for ionic transport during the conversion process. These results offer the first experimental evidence explaining the origins of the high lithium reversibility in FeF{sub 2}. In contrast

  13. Kinetics and Reaction Mechanisms of High-Temperature Flash Oxidation of Molybdenite

    Science.gov (United States)

    Wilkomirsky, Igor; Otero, Alfonso; Balladares, Eduardo

    2010-02-01

    The kinetics and reaction mechanism of the flash oxidation of +35/-53 μm molybdenite particles in air, as well as in 25, 50, and 100 pct oxygen higher than 800 K, has been investigated using a stagnant gas reactor and a laminar flow reactor coupled to a fast-response, two-wavelength pyrometer. The changes in the morphology and in the chemical composition of partially reacted particles were also investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), differential thermal analysis (DTA), and electron microprobe. High-speed photography was also used to characterize the particle combustion phenomena. The effects of oxygen concentration and gas temperature on ignition and peak combustion temperatures were studied. The experimental results indicate that MoS2 goes through a process of ignition/combustion with the formation of gaseous MoO3 and SO2 with no evidence of formation of a molten phase, although the reacting molybdenite particles reach temperatures much higher than their melting temperature. This effect may be a result of the combustion of gaseous sulfur from partial decomposition of molybdenite to Mo2S3 under a high gas temperature and 100 pct oxygen. In some cases, the partial fragmentation and distortion of particles also takes place. The transformation can be approximated to the unreacted core model with chemical control and with activation energy of 104.0 ± 4 kJ/mol at the actual temperature of the reacting particles. The reaction was found to be first order with respect to the oxygen concentration. The rate constant calculated at the actual temperatures of the reacting particles shows a good agreement with kinetic data obtained at lower temperatures. The ignition temperature of molybdenite shows an inverse relationship with the gas temperature and oxygen content, with the lowest ignition temperature of 1120 K for 100 pct oxygen. Increasing the oxygen content from 21 to 100 pct increases the particle combustion temperature from 1600 K

  14. Isospin transport and reaction mechanism in nuclear reactions in the range 20-40 MeV/n

    Science.gov (United States)

    Barlini, S.; Piantelli, S.; Casini, G.; Olmi, A.; Bini, M.; Pasquali, G.; Poggi, G.; Stefanini, A. A.; Bougault, R.; Bonnet, E.; Borderie, B.; Chibhi, A.; Frankland, J. D.; Gruyer, D.; Lopez, O.; Le Neindre, N.; Parlog, M.; Rivet, M. F.; Vient, E.; Rosato, E.; Vigilante, M.; Bruno, M.; Marchi, T.; Morelli, L.; Cinausero, M.; Degerlier, M.; Gramegna, F.; Kozik, T.; Twarog, T.; Fabris, D.; Valdré, S.; Pastore, G.

    2015-10-01

    In recent years, many efforts have been devoted to the investigation of the isospin degree of freedom in nuclear reactions. Comparing systems involving partners with different N/Z, it has been possible to investigate the isospin transport process and its influence on the final products population. This can be then related to the symmetry energy term of the nuclear EOS. From the experimental point of view, this task requires detectors able to measure both charge and mass of the emitted products, in the widest possible range of energy and size of the fragments. With this objective, the FAZIA and GARFIELD+RCo apparatus have been used with success in some recent experiments.

  15. Isospin transport and reaction mechanism in nuclear reactions in the range 20–40 MeV/n

    Energy Technology Data Exchange (ETDEWEB)

    Barlini, S., E-mail: barlini@fi.infn.it; Piantelli, S.; Casini, G.; Olmi, A.; Bini, M.; Pasquali, G.; Poggi, G.; Stefanini, A. A.; Valdré, S.; Pastore, G. [Dipartimento di Fisica ed Astronomia dell’Università and INFN Sezione di Firenze, Firenze (Italy); Bougault, R.; Lopez, O.; Le Neindre, N.; Parlog, M.; Vient, E. [LPC, IN2P3-CNRS, ENSICAEN et Université de Caen, F-14050 Caen-Cedex (France); Bonnet, E.; Chibhi, A.; Frankland, J. D. [GANIL, CEA/DSM-CNRS/IN2P3, B.P.5027, F-14076 Caen cedex (France); Borderie, B.; Rivet, M. F. [Institut de Physique Nucléaire, CNRS/IN2P3, Université Paris-Sud 11, F-91406 Orsay cedex (France); and others

    2015-10-15

    In recent years, many efforts have been devoted to the investigation of the isospin degree of freedom in nuclear reactions. Comparing systems involving partners with different N/Z, it has been possible to investigate the isospin transport process and its influence on the final products population. This can be then related to the symmetry energy term of the nuclear EOS. From the experimental point of view, this task requires detectors able to measure both charge and mass of the emitted products, in the widest possible range of energy and size of the fragments. With this objective, the FAZIA and GARFIELD+RCo apparatus have been used with success in some recent experiments.

  16. 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.

  17. Detailed mechanism of the CH2I + O2 reaction: Yield and self-reaction of the simplest Criegee intermediate CH2OO

    Science.gov (United States)

    Ting, Wei-Lun; Chang, Chun-Hung; Lee, Yu-Fang; Matsui, Hiroyuki; Lee, Yuan-Pern; Lin, Jim-Min, Jr.

    2014-09-01

    The application of a new reaction scheme using CH2I + O2 to generate the simplest Criegee intermediate, CH2OO, has stimulated lively research; the Criegee intermediates are extremely important in atmospheric chemistry. The detailed mechanism of CH2I + O2 is hence important in understanding kinetics involving CH2OO. We employed ultraviolet absorption to probe simultaneously CH2I2, CH2OO, CH2I, and IO in the reaction system of CH2I + O2 upon photolysis at 248 nm of a flowing mixture of CH2I2, O2, and N2 (or SF6) in the pressure range 7.6-779 Torr to investigate the reaction kinetics. With a detailed mechanism to model the observed temporal profiles of CH2I, CH2OO, and IO, we found that various channels of the reaction CH2I + O2 and CH2OO + I play important roles; an additional decomposition channel of CH2I + O2 to form products other than CH2OO or ICH2OO becomes important at pressure less than 60 Torr. The pressure dependence of the derived rate coefficients of various channels of reactions of CH2I + O2 and CH2OO + I has been determined. We derived a rate coefficient also for the self-reaction of CH2OO as k = (8 ± 4) × 10-11 cm3 molecule-1 s-1 at 295 K. The yield of CH2OO from CH2I + O2 was found to have a pressure dependence on N2 and O2 smaller than in previous reports; for air under 1 atm, the yield of ˜30% is about twice of previous estimates.

  18. A computational linear elastic fracture mechanics-based model for alkali-silica reaction

    International Nuclear Information System (INIS)

    This article presents a fracture mechanics model for Alkali-Silica Reaction (ASR). The model deals with the case of a concrete made up of dense aggregates submitted to chemical attack. The chemistry and diffusion (of ions and gel) are not modelled. The focus is put on the mechanical consequences of the progressive replacement of the outer layer of the aggregate by a less dense gel. A schematic cracking pattern is assumed: a ring-shaped crack appears in the cement paste surrounding the spherical aggregate depending on the pressure build-up. The onset of cracking is determined using an incremental energy criterion. The stored elastic energy and deformation of a given configuration are determined assuming that each aggregate behaves as if it was embedded in an infinite cement paste matrix. The calculations are performed by Finite Element Analysis. We note a very different behaviour of aggregates of different sizes. Adding the contributions of different aggregate sizes leads to an estimation of the global free expansion of a concrete of given aggregate size distribution. A rate of attack is identified that leads to recover the usual sigmoid ASR expansion curve. (authors)

  19. Reaction Mechanism of Siderite Lump in Coal-Based Direct Reduction

    Science.gov (United States)

    Zhu, Deqing; Luo, Yanhong; Pan, Jian; Zhou, Xianlin

    2016-02-01

    Siderite is one of the significant iron ore resources in China and yet is difficult to upgrade by traditional beneficiation processes. A process of coal-based direct reduction-magnetic separation was successfully developed for the beneficiation of siderite. However, few studies have thoroughly investigated the mechanism of the direct reduction of siderite. In order to reveal the reaction mechanism of coal-based direct reduction of siderite lump, thermodynamics of direct reduction was investigated with coal as the reductant. The thermodynamics results indicate that coal-based direct reduction process of siderite lump at 1,050°C follows the steps as FeCO3→ Fe3O4→ FeO → Fe, which is verified by chemical titration analysis, X-ray diffraction and scanning electron microscope. The microstructure of siderite sample varies with different reduction stages and some 45% porosity induced by thermal decomposition of siderite is conductive to subsequent reduction. The conversion of FeO to Fe is the main reduction rate-controlling step. The reduced product with the metallic iron size over 30 μm can be effectively beneficiated by wet magnetic separation after grinding. The obvious layered structure of reduced product is due to different heat transfer resistance, CO and CO2 concentration.

  20. Reaction Mechanism Underlying Atomic Layer Deposition of Antimony Telluride Thin Films.

    Science.gov (United States)

    Han, Byeol; Kim, Yu-Jin; Park, Jae-Min; Yusup, Luchana L; Ishii, Hana; Lansalot-Matras, Clement; Lee, Won-Jun

    2016-05-01

    The mechanism underlying the deposition of SbTe films by alternating exposures to Sb(NMe2)3 and Te(GeMe3)2 was investigated. Sb(NMe2)3 and Te(GeMe3)2 were selected because they have very high vapor pressure and are free of Si, Cl, and O atoms in the molecules. The mechanism of deposition was proposed by density functional theory (DFT) calculation and was verified by in-situ quartz crystal microbalance (QCM) analysis. DFT calculation expected the ligand-exchange reactions between the Sb and Te precursors to form Me2NGeMe3 as the byproduct. QCM analysis indicated that a single -NMe2 group in Sb(NMe2)3 reacts with -TeGeMe3 on the surface to form an Sb2Te3 film, and that a small fraction of Sb is incorporated into the film by the thermal decomposition of Sb(NMe2)3. The Te(GeMe3)2 molecules were thermally stable up to 120 degrees C, while the Sb(NMe2)3 molecules decomposed at temperatures of 60 degrees C and higher. Sb-rich SbTe films with different Sb contents were prepared by controlling the partial decomposition of Sb(NMe2)3 molecules, which was enhanced by increasing the pulse time of the precursor. PMID:27483847

  1. O2 activation by binuclear Cu sites: Noncoupled versus exchange coupled reaction mechanisms

    Science.gov (United States)

    Chen, Peng; Solomon, Edward I.

    2004-09-01

    Binuclear Cu proteins play vital roles in O2 binding and activation in biology and can be classified into coupled and noncoupled binuclear sites based on the magnetic interaction between the two Cu centers. Coupled binuclear Cu proteins include hemocyanin, tyrosinase, and catechol oxidase. These proteins have two Cu centers strongly magnetically coupled through direct bridging ligands that provide a mechanism for the 2-electron reduction of O2 to a µ-2:2 side-on peroxide bridged species. This side-on bridged peroxo-CuII2 species is activated for electrophilic attack on the phenolic ring of substrates. Noncoupled binuclear Cu proteins include peptidylglycine -hydroxylating monooxygenase and dopamine -monooxygenase. These proteins have binuclear Cu active sites that are distant, that exhibit no exchange interaction, and that activate O2 at a single Cu center to generate a reactive CuII/O2 species for H-atom abstraction from the C-H bond of substrates. O2 intermediates in the coupled binuclear Cu enzymes can be trapped and studied spectroscopically. Possible intermediates in noncoupled binuclear Cu proteins can be defined through correlation to mononuclear CuII/O2 model complexes. The different intermediates in these two classes of binuclear Cu proteins exhibit different reactivities that correlate with their different electronic structures and exchange coupling interactions between the binuclear Cu centers. These studies provide insight into the role of exchange coupling between the Cu centers in their reaction mechanisms.

  2. [The reactions of hypersensitivity: the mechanisms of development, clinical manifestations, principles of diagnostic (a lecture)].

    Science.gov (United States)

    Tukavkina, S Yu; Kharseyeva, G G

    2014-05-01

    The article considers the principles of modern classification of hypersensitivity, pathogenic mechanisms of formation of its various types resulting in development of typical clinical symptoms and syndromes. The knowledge and comprehension of these issues is important for physicians of different specializations since it permits to properly make out and formulate diagnosis and timely send patient for examination and treatment to such specialist as allergist-immunologist. The particular attention was paid to description of pathogenesis of diseases and syndromes underlaid by IgE-mediated type of hypersensitivity since their share is highest and clinical manifestations frequently require emergency medical care. The diagnostic of allergic diseases is to be implemented sequentially (step-by-step) and include common clinical and special (specific) methods. In case of choosing of extent of specialized allergological examination the diagnostic significance of techniques and their safety is to be taken into account concerning condition of patient. The diagnosis is objectively formulated only by complex of examination results. It is worth to remember about possibility of development of syndromes similar to IgE-mediated allergy by their clinical manifestations but belonging to non-allergic type of hypersensitivity. It is important to know main causes, mechanisms and ways of formation of such reactions previously named as anaphylactoid ones. PMID:25338461

  3. Simulation mechanisms of low energy nuclear reaction using super flow energy external fields

    International Nuclear Information System (INIS)

    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

  4. Surface damage of metallic implants due to mechanical loading and chemical reactions

    Science.gov (United States)

    Ryu, Jaejoong

    indicate that surface roughness undergoes continuous evolution during alternating contact loading and exposure to etchant. Surface roughness evolution is governed by the residual stress induced due to contact loading. Two different stress-assisted dissolution driven instabilities in roughness evolution have been identified. In order to investigate stressed surface damage by electrochemical reaction during active contact loading, in the first stage, surface failure due to sliding contact was investigated as a function of different residual stress states from compressive to tensile. Residual stress is usually developed during manufacturing process or former mechanical interactions playing an important role on service life of the surface. The wear mechanism of fatigue contact in the presence of residual stresses was explored by analytical model of fatigue crack growth by utilizing modified delamination wear theory with surface layer spalling model. Fatigue stress intensity factors (DeltaKI) loaded by contact stress and combined residual stress implied that buckling of subsurface crack with compressive residual stress opens crack-tip and consequently increase wear rate during sliding contact. As for the experimental verification of the modified delamination model, cyclic sliding contact experiment on metallic implant materials in ambient was conducted by utilizing atomic force microscope (AFM) and four-point-bending set up by which well characterized pre-stress was established on rectangular specimen. In addition, complex mechanism of corrosion on the damaged surface illustrated strong stress-dependent effects on wear rate in repassivating environment and dissolution rates in reactive environment.

  5. 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)

    The effect of the Ti/B4C mole ratio on the fabrication behavior of Al composites is investigated using Al–Ti–B4C 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, TiB2 is formed in all the samples whereas TiC is only formed in reactants with a Ti/B4C mole ratio of more than two. The C atoms from the reacted B4C do not move into TiC but instead they move into Al3BC or Al4C3 when the Ti/B4C mole ratio is less than two. In addition, the reaction mechanism with a Ti/B4C mole ratio of 0.75 is investigated extensively. - Highlights: • The critical role of the Ti/B4C mole ratio on the reaction products of Al–Ti–B4C was studied using experiments. • The experimental results are also supported by thermodynamic calculations presented in this paper. • The reaction mechanism with a Ti/B4C mole ratio of 0.75 is investigated extensively

  6. Studies of reaction mechanism in {sup 12}C + {sup 12}C system at intermediate energy of 28.7 MeV/N

    Energy Technology Data Exchange (ETDEWEB)

    Magiera, A. [Inst. of Physics, Jagiellonian Univ., Cracow (Poland)

    1996-12-31

    The reaction mechanism in {sup 12}C + {sup 12}C system at intermediate energy of about 30 MeV/nucleon was studied. The contribution of various reaction mechanisms (inelastic scattering, transfer reactions, compound nucleus reactions, sequential decay following inelastic excitation and transfer) to the total reaction cross section were found. The analysis of inclusive and coincidence spectra shows that sequential fragmentation processes dominate. 100 refs, 45 figs, 1 tab

  7. Reaction mechanisms in 24.3 MeV/nucleon {sup 238}U induced reactions through a comprehensive study of fission

    Energy Technology Data Exchange (ETDEWEB)

    Chbihi, A.; Galin; Guerreau, D.; Lewitowicz, M.; Morjean, M.; Pouthas, J. [Grand Accelerateur National d`Ions Lourds (GANIL), 14 - Caen (France); Piasecki, E.; Kordyasz, A.; Iwanicki, J.; Jastrzebski, J.; Pienkowski, L. [Warsaw Univ. (Poland); Crema, E. [Sao Paulo Univ., SP (Brazil). Inst. de Fisica; Czarnacki, W.; Kisielinski, M.; Tucholski, A. [Soltan Inst. for Nuclear Studies, Otwock-Swierk (Poland); Gatty, B.; Jacquet, D. [Paris-11 Univ., 91 - Orsay (France). Inst. de Physique Nucleaire; Jahnke, U. [Hahn-Meitner-Institut Berlin GmbH (Germany); Muchorowska, M.

    1994-12-31

    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.

  8. Reaction site and mechanism in the UV or visible light induced TiO2 photodegradation of Orange G

    Institute of Scientific and Technical Information of China (English)

    YANG Shi-ying; LOU Li-ping; WU Xiao-na; CHEN Ying-xu

    2006-01-01

    For TiO2 heterogeneous reaction, the reaction site and the detailed mechanism are interesting and controversy topics. In this paper, effects of surface fluorination of TiO2 on the photocatalytic degradation of an azo dye, Orange G(OG) under UV or visible light irradiation were investigated, and the possible reaction site and mechanism were elucidated. The adsorption of OG on TiO2 was nearly inhibited by fluoride but its UV light induced photodegradation rate was greatly increased by a factor of about 2.7, which was due to the more generated free hydroxyl radicals. It supported the views that fluoride could desorb the oxidant species from surface and that the reaction sites could move to the bulk solution. In TiO2/Vis system, the observed inhibition effects of fluorination could be interpreted by the competitive adsorption, which provided additional evidences that the visible light sensitized photodegradation of dye pollutants on the catalyst surface.

  9. Mechanically activated SHS reaction in the Fe-Al system: in-situ time resolved diffraction using synchrotron radiation

    International Nuclear Information System (INIS)

    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.)

  10. Final Report: Dominant Mechanisms of Uranium-Phosphate Reactions in Subsurface Sediments

    Energy Technology Data Exchange (ETDEWEB)

    Catalano, Jeffrey G. [Washington Univ., St. Louis, MO (United States); Giammar, Daniel E. [Washington Univ., St. Louis, MO (United States); Wang, Zheming [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-03-08

    Phosphate addition is an in situ remediation approach that may enhance the sequestration of uranium without requiring sustained reducing conditions. However, the geochemical factors that determine the dominant immobilization mechanisms upon phosphate addition are insufficiently understood to design efficient remediation strategies or accurately predict U(VI) transport. The overall objective of our project is to determine the dominant mechanisms of U(VI)-phosphate reactions in subsurface environments. Our research approach seeks to determine the U(VI)-phosphate solid that form in the presence of different groundwater cations, characterize the effects of phosphate on U(VI) adsorption and precipitation on smectite and iron oxide minerals, examples of two major reactive mineral phases in contaminated sediments, and investigate how phosphate affects U(VI) speciation and fate during water flow through sediments from contaminated sites. The research activities conducted for this project have generated a series of major findings. U(VI) phosphate solids from the autunite mineral family are the sole phases to form during precipitation, with uranyl orthophosphate not occurring despite its predicted greater stability. Calcium phosphates may take up substantial quantities of U(VI) through three different removal processes (adsorption, coprecipitation, and precipitation) but the dominance of each process varies with the pathway of reaction. Phosphate co-adsorbs with U(VI) onto smectite mineral surfaces, forming a mixed uranium-phosphate surface complex over a wide range of conditions. However, this molecular-scale association of uranium and phosphate has not effect on the overall extent of uptake. In contrast, phosphate enhanced U(VI) adsorption to iron oxide minerals at acidic pH conditions but suppresses such adsorption at neutral and alkaline pH, despite forming mixed uranium-phosphate surface complexes during adsorption. Nucleation barriers exist that inhibit U(VI) phosphate

  11. 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

  12. Low-Pressure Photolysis of 2,3-Pentanedione in Air: Quantum Yields and Reaction Mechanism.

    Science.gov (United States)

    Bouzidi, Hichem; Djehiche, Mokhtar; Gierczak, Tomasz; Morajkar, Pranay; Fittschen, Christa; Coddeville, Patrice; Tomas, Alexandre

    2015-12-24

    Dicarbonyls in the atmosphere mainly arise from secondary sources as reaction products in the degradation of a large number of volatile organic compounds (VOC). Because of their sensitivity to solar radiation, photodissociation of dicarbonyls can dominate the fate of these VOC and impact the atmospheric radical budget. The photolysis of 2,3-pentanedione (PTD) has been investigated for the first time as a function of pressure in a static reactor equipped with continuous wave cavity ring-down spectroscopy to measure the HO2 radical photostationary concentrations along with stable species. We showed that (i) Stern-Volmer plots are consistent with low OH-radical formation yields in RCO + O2 reactions, (ii) the decrease of the photodissociation rate due to pressure increase from 26 to 1000 mbar is of about 30%, (iii) similarly to other dicarbonyls, the Stern-Volmer analysis shows a curvature at the lower pressure investigated, which may be assigned to the existence of excited singlet and triplet PTD states, (iv) PTD photolysis at 66 mbar leads to CO2, CH2O and CO with yields of (1.16 ± 0.04), (0.33 ± 0.02) and (0.070 ± 0.005), respectively, with CH2O yield independent of pressure up to 132 mbar and CO yield in agreement with that obtained at atmospheric pressure by Bouzidi et al. (2014), and (v) the PTD photolysis mechanism remains unchanged between atmospheric pressure and 66 mbar. As a part of this work, the O2 broadening coefficient for the absorption line of HO2 radicals at 6638.21 cm(-1) has been determined (γO2 = 0.0289 cm(-1) atm(-1)). PMID:26608471

  13. Strongly correlated mechanisms of a photoexcited radical reaction from the anti-Hermitian contracted Schroedinger equation

    International Nuclear Information System (INIS)

    Photoexcited radical reactions are critical to processes in both nature and materials, and yet they can be challenging for electronic structure methods due to the presence of strong electron correlation. Reduced-density-matrix (RDM) methods, based on solving the anti-Hermitian contracted Schroedinger equation (ACSE) for the two-electron RDM (2-RDM), are examined for studying the strongly correlated mechanisms of these reactions with application to the electrocyclic interconversion of allyl and cyclopropyl radicals. We combine recent extensions of the ACSE to excited states [G. Gidofalvi and D. A. Mazziotti, Phys. Rev. A 80, 022507 (2009)] and arbitrary spin states [A. E. Rothman, J. J. Foley IV, and D. A. Mazziotti, Phys. Rev. A 80, 052508 (2009)]. The ACSE predicts that the ground-state ring closure of the allyl radical has a high 52.5 kcal/mol activation energy that is consistent with experimental data, while the closure of an excited allyl radical can occur by disrotatory and conrotatory pathways whose transition states are essentially barrierless. Comparisons are made with multireference second- and third-order perturbation theories and multireference configuration interaction. While predicted energy differences do not vary greatly between methods, the ACSE appears to improve these differences when they involve a strongly and a weakly correlated radical by capturing a greater share of single-reference correlation that increases the stability of the weakly correlated radicals. For example, the ACSE predicts a -39.6 kcal/mol conversion of the excited allyl radical to the ground-state cyclopropyl radical in comparison to the -32.6 to -37.3 kcal/mol conversions predicted by multireference methods. In addition, the ACSE reduces the computational scaling with the number of strongly correlated orbitals from exponential (traditional multireference methods) to quadratic. Computed ground- and excited-state 2-RDMs are nearly N-representable.

  14. Ozonation of benzotriazole and methylindole: Kinetic modeling, identification of intermediates and reaction mechanisms.

    Science.gov (United States)

    Benitez, F Javier; Acero, Juan L; Real, Francisco J; Roldán, Gloria; Rodríguez, Elena

    2015-01-23

    The ozonation of 1H-benzotriazole (BZ) and 3-methylindole (ML), two emerging contaminants that are frequently present in aquatic environments, was investigated. The experiments were performed with the contaminants (1μM) dissolved in ultrapure water. The kinetic study led to the determination of the apparent rate constants for the ozonation reactions. In the case of 1H-benzotriazole, these rate constants varied from 20.1 ± 0.4M(-1)s(-1) at pH=3 to 2143 ± 23 M(-1)s(-1) at pH=10. Due to its acidic nature (pKa=8.2), the degree of dissociation of this pollutant was determined at every pH of work, and the specific rate constants of the un-dissociated and dissociated species were evaluated, being the values of these rate constants 20.1 ± 2.0 and 2.0 ± 0.3 × 10(3)M(-1)s(-1), respectively. On the contrary, 3-methylindole does not present acidic nature, and therefore, it can be proposed an average value for its rate constant of 4.90 ± 0.7 × 10(5)M(-1)s(-1) in the whole pH range 3-10. Further experiments were performed to identify the main degradation byproducts (10 mg L(-1) of contaminants, 0.023 gh(-1) of ozone). Up to 8 intermediates formed in the ozonation of 3-methylindole were identified by LC-TOFMS, while 6 intermediates were identified in the ozonation of 1H-benzotriazole. By considering these intermediate compounds, the reaction mechanisms were proposed and discussed. Finally, evaluated rate constants allowed to predict and modeling the oxidation of these micropollutants in general aquatic systems.

  15. 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. PMID:22810049

  16. The Effect of Mechanical Vibration Stimulation of Perception Subthreshold on the Muscle Force and Muscle Reaction Time of Lower Leg

    OpenAIRE

    Kim, Huigyun; Kwak, Kiyoung; Kim, Dongwook

    2016-01-01

    The objective of this study is to investigate the effect of mechanical vibration stimulation on the muscle force and muscle reaction time of lower leg according to perception threshold and vibration frequency. A vibration stimulation with perception threshold intensity was applied on the Achilles tendon and tibialis anterior tendon. EMG measurement and analysis system were used to analyze the change of muscle force and muscle reaction time according to perception threshold and vibration frequ...

  17. Density Functional Study on the Mechanism of Collision Reaction among Protons,N2 and Water Vapor

    Institute of Scientific and Technical Information of China (English)

    SUN,Hao(孙昊); PAN,Xiu-Mei(潘秀梅); ZHAO,Min(赵岷); LIU,Peng-Jun(刘朋军); SU,Zhong-Min(苏忠民); WANG,Rong-Shun(王荣顺)

    2004-01-01

    The mechanism of collision reaction among protons, N2 and water vapor was theoretically studied using Density Functional Theory. The geometries of reactants, transition states, intermediates and products were optimized at the B3LYP/6-311 + G** level by the BERNY gradient analysis method. Transition states and intermediates have been identified by vibrational frequency analysis. The relationship among reactants, intermediates, transition states and products was affirmed by IRC calculation. The variations of energy and geometry along the IRC-determined reaction paths were described. The possible reaction pathways were represented and the optimal one was decided from the viewpoint of energy.

  18. Further theoretical insight into the reaction mechanism of the hepatitis C NS3/NS4A serine protease

    Science.gov (United States)

    Martínez-González, José Ángel; Rodríguez, Alex; Puyuelo, María Pilar; González, Miguel; Martínez, Rodrigo

    2015-01-01

    The main reactions of the hepatitis C virus NS3/NS4A serine protease are studied using the second-order Møller-Plesset ab initio method and rather large basis sets to correct the previously reported AM1/CHARMM22 potential energy surfaces. The reaction efficiencies measured for the different substrates are explained in terms of the tetrahedral intermediate formation step (the rate-limiting process). The energies of the barrier and the corresponding intermediate are so close that the possibility of a concerted mechanism is open (especially for the NS5A/5B substrate). This is in contrast to the suggested general reaction mechanism of serine proteases, where a two-step mechanism is postulated.

  19. 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

  20. Mechanism of sperm capacitation and the acrosome reaction: role of protein kinases

    Institute of Scientific and Technical Information of China (English)

    Debby Ickowicz; Maya Finkelstein; Haim Breitbart

    2012-01-01

    Mammalian sperm must undergo a series of biochemical and physiological modifications,collectively called capacitation,in the female reproductive tract prior to the acrosome reaction (AR).The mechanisms of these modifications are not well characterized though protein kinases were shown to be involved in the regulation of intracellular Ca2+ during both capacitation and the AR.In the present review,we summarize some of the signaling events that are involved in capacitation.During the capacitation process,phosphatidyl-inositol-3-kinase (P13K) is phosphorylated/activated via a protein kinase A (PKA)-dependent cascade,and downregulated by protein kinase C α (PKCα).PKCα is active at the beginning of capacitation,resulting in P13K inactivation.During capacitation,PKCα as well as PP1γ2 is degraded by a PKA-dependent mechanism,allowing the activation of P13K.The activation of PKA during capacitation depends mainly on cyclic adenosine monophosphate (cAMP) produced by the bicarbonate-dependent soluble adenylyl cyclase.This activation of PKA leads to an increase in actin polymerization,an essential process for the development of hyperactivated motility,which is necessary for successful fertilization.Actin polymerization is mediated by PIP2 in two ways:first,P(I)P2 acts as a cofactor for phospholipase D (PLD) activation,and second,as a molecule that binds and inhibits actin-severing proteins such as gelsolin.Tyrosine phosphorylation of gelsolin during capacitation by Src family kinase (SFK) is also important for its inactivation.Prior to the AR,gelsolin is released from P(I)P2 and undergoes dephosphorylation/activation,resulting in fast F-actin depolymerization,leading to the AR.

  1. Kinetics and Mechanisms of the Acid-base Reaction Between NH3 and HCOOH in Interstellar Ice Analogs

    Science.gov (United States)

    Bergner, Jennifer B.; Öberg, Karin I.; Rajappan, Mahesh; Fayolle, Edith C.

    2016-10-01

    Interstellar complex organic molecules are commonly observed during star formation, and are proposed to form through radical chemistry in icy grain mantles. Reactions between ions and neutral molecules in ices may provide an alternative cold channel to complexity, as ion-neutral reactions are thought to have low or even no-energy barriers. Here we present a study of the kinetics and mechanisms of a potential ion-generating, acid-base reaction between NH3 and HCOOH to form the salt NH{}4+HCOO-. We observe salt growth at temperatures as low as 15 K, indicating that this reaction is feasible in cold environments. The kinetics of salt growth are best fit by a two-step model involving a slow “pre-reaction” step followed by a fast reaction step. The reaction energy barrier is determined to be 70 ± 30 K with a pre-exponential factor 1.4 ± 0.4 × 10-3 s-1. The pre-reaction rate varies under different experimental conditions and likely represents a combination of diffusion and orientation of reactant molecules. For a diffusion-limited case, the pre-reaction barrier is 770 ± 110 K with a pre-exponential factor of ˜7.6 × 10-3 s-1. Acid-base chemistry of common ice constituents is thus a potential cold pathway to generating ions in interstellar ices.

  2. Kinetics and mechanisms of the acid-base reaction between NH$_3$ and HCOOH in interstellar ice analogs

    CERN Document Server

    Bergner, Jennifer B; Rajappan, Mahesh; Fayolle, Edith C

    2016-01-01

    Interstellar complex organic molecules (COMs) are commonly observed during star formation, and are proposed to form through radical chemistry in icy grain mantles. Reactions between ions and neutral molecules in ices may provide an alternative cold channel to complexity, as ion-neutral reactions are thought to have low or even no energy barriers. Here we present a study of a the kinetics and mechanisms of a potential ion-generating acid-base reaction between NH$_{3}$ and HCOOH to form the salt NH$_{4}^{+}$HCOO$^{-}$. We observe salt growth at temperatures as low as 15K, indicating that this reaction is feasible in cold environments. The kinetics of salt growth are best fit by a two-step model involving a slow "pre-reaction" step followed by a fast reaction step. The reaction energy barrier is determined to be 70 $\\pm$ 30K with a pre-exponential factor 1.4 $\\pm$ 0.4 x 10$^{-3}$ s$^{-1}$. The pre-reaction rate varies under different experimental conditions and likely represents a combination of diffusion and or...

  3. THE MECHANISM OF CURE REACTION OF 4,4'-DIAMINODIPHENYL METHANE WITH TETRAGLYCIDYL 4,4'-DIAMINODIPHENYL METHANE EPOXY

    Institute of Scientific and Technical Information of China (English)

    WANG Wei; WU Xuanzheng; QI Zongneng

    1992-01-01

    The cure reaction of tetraglycidyl 4,4'-diaminodiphenyl methane (TGDDM) epoxy resin with 4,4'-diaminodiphenyl methane (DDM) has been studied by using DSC. nstead of one exothermic peak, two exothermic peaks, indicative of a complex reaction mechanism, are shown in the DSC curve of TGDDM-DDM mixtures in nonisothermal cure experiments when the content of DDM is lower than stoichiometric ratio. The result of the kinetic analysis of the cure reaction shows that the activation energy of the lower temperature exotherm peak is about 56 kJ/mol and that of the higher temperature exotherm peak is about 136 kJ/mol. The lower temperature cure reaction peak can be attributed to the primary amine-epoxide and secondary amine-epoxide reactions, and the higher temperature cure reaction peak can be attributed to the epoxide-hydroxy reaction under catalysis of tertiary amine in the TGDDM epoxy resin. Because the network density of the cured epoxy resin is determined by these two reactions, the content of DDM has little effect on the glass transition temperature of cured epoxy resin.

  4. Quantum mechanical investigation of the atmospheric reaction CH3O2 + NO.

    Science.gov (United States)

    Lesar, Antonija; Hodoscek, Milan; Drougas, Evangelos; Kosmas, Agnie M

    2006-06-29

    The important stationary points on the potential energy surface of the reaction CH(3)O(2) + NO have been investigated using ab initio and density functional theory techniques. The optimizations were carried out at the B3LYP/6-311++G(d,p) and MP2/6-311++G(d,p) levels of theory while the energetics have been refined using the G2MP2, G3//B3LYP, and CCSD(T) methodologies. The calculations allow the proper characterization of the transition state barriers that determine the fate of the nascent association conformeric minima of methyl peroxynitrite. The main products, CH(3)O + NO(2), are formed through either rearrangement of the trans-conformer to methyl nitrate and its subsequent dissociation or via the breaking of the peroxy bond of the cis-conformer to CH(3)O + NO(2) radical pair. The important consequences of the proposed mechanism are (a) the allowance on energetic grounds for nitrate formation parallel to radical propagation under favorable external conditions and (b) the confirmation of the conformational preference of the homolytic cleavage of the peroxy bond, discussed in previous literature. PMID:16789778

  5. Reaction bonding and mechanical properties of mullite/silicon carbide composites

    International Nuclear Information System (INIS)

    Based on the RBAO technology, low-shrinkage mullite/SiC/Al2O3/ZrO2 composite were fabricated. A powder mixture of 40 vol% Al, 30 vol% Al2O3, and 30 vol% SiC was attrition milled in acetone with TZP balls which introduced a substantial ZrO2 wear debris into the mixture. The precursor powder was isopressed at 300--900 MPa and heat-treated in air by two different cycles resulting in various phase ratios in the final products. During heating, Al oxidizes to Al2O3 completely, while SiC oxidizes to SiO2 only on its surface. Fast densification (at > 1300 C) and mullite formation (at 1400 C) prevent further oxidation of the SiC particles. Because of the volume expansion associated with the oxidation of Al (28%), SiC (108%), and the mullitization (4.2%), sintering shrinkage is effectively compensated. The reaction-bonded composites exhibit low linear shrinkages and high strengths: shrinkages of 7.2%, 4.8%, and 3%, and strengths of 610, 580, and 490 MPa, corresponding to compaction pressure of 300, 600, and 900 MPa, respectively, were achieved in samples containing 49--55 vol% mullite. HIPing improved significantly the mechanical properties: a fracture strength of 490 MPa and a toughness of 4.1 MPa·m1/2 increased to 890 MPa and 6 MPa·m1/2, respectively

  6. Mechanisms of Propidium Monoazide Inhibition of Polymerase Chain Reaction and implications for Propidium Monoazide Applications

    Science.gov (United States)

    Lee, C. M.; Darrach, H.; Ponce, A.; McFarland, E.; Laymon, C.; Fingland, N. K.

    2015-12-01

    PMA-qPCR is a laboratory technique that can be used to identify viable microbes by employing the use of propidium monoazide (PMA), a DNA-intercalating dye, and quantitative polymerase chain reaction (qPCR). The current model of PMA-qPCR operates under the assumption that PMA is only capable of entering membrane-compromised cells, where it irreversibly cross-links to DNA and makes it unavailable for amplification via qPCR. However, the exact mechanism behind PMA's entry into the cell and its interaction with genetic material is not well understood. To better understand PMA's capabilities, we have examined the effect PMA has on enzyme binding and processivity using endonucleases and exonucleases. Our results suggest that the current model behind PMA-qPCR inhibition is incomplete, in that rather than precipitating the entirety of the DNA, PMA also inhibits enzyme binding and/or processivity in soluble DNA. These results have important implications for studying the viable community of microorganisms in various applications, such as environmental monitoring, planetary protection and bioburden assessment, and biohazard detection.

  7. Reaction products and mechanisms for the reaction of n-butyl vinyl ether with the oxidants OH and Cl: Atmospheric implications

    Science.gov (United States)

    Colmenar, Inmaculada; Martín, Pilar; Cabañas, Beatriz; Salgado, Sagrario; Tapia, Araceli; Martínez, Ernesto

    2015-12-01

    A reaction product study for the degradation of butyl vinyl ether (CH3(CH2)3OCHdbnd CH2) by reaction with chlorine atoms (Cl) and hydroxyl radicals (OH) has been carried out using Fourier Transform Infrared absorption spectroscopy (FTIR) and/or Gas Chromatography-Mass Spectrometry with a Time of Flight analyzer (GC-TOFMS). The rate coefficient for the reaction of butyl vinyl ether (BVE) with chlorine atoms has also been evaluated for the first time at room temperature (298 ± 2) K and atmospheric pressure (708 ± 8) Torr. The rate coefficient obtained was (9.9 ± 1.5) × 10-10 cm3 molecule-1 s-1 and this indicates the high reactivity of butyl vinyl ether with Cl atoms. However, this value may be affected by the dark reaction of BVE with Cl2. The results of a qualitative study of the Cl reaction show that the main oxidation products are butyl formate (CH3(CH2)3OC(O)H), butyl chloroacetate (CH3(CH2)3OC(O)CH2Cl and formyl chloride (HCOCl). Individual yields in the ranges ∼16-40% and 30-70% in the absence and presence of NOx, respectively, have been estimated for these products. In the OH reaction, butyl formate and formic acid were identified as the main products, with yields of around 50 and 20%, respectively. Based on the results of this work and a literature survey, the addition of OH radicals and Cl atoms at the terminal C atom of the double bond in CH3(CH2)3OCHdbnd CH2 has been proposed as the first step in the reaction mechanism for both of the studied oxidants. The tropospheric lifetime of butyl vinyl ether is very short and, as a consequence, it will be rapidly degraded and will only be involved in tropospheric chemistry at a local level. The degradation products of these reactions should be considered when evaluating the atmospheric impact.

  8. Investigation of the kinetics and mechanism of the glycerol chlorination reaction using gas chromatography–mass spectrometry

    Directory of Open Access Journals (Sweden)

    JUN WANG

    2010-01-01

    Full Text Available As a primary by-product in biodiesel production, glycerol can be used to prepare an important fine chemical, epichlorohydrin, by the glycerol chlorination reaction. Although this process has been applied in industrial production, unfortunately, less attention has been paid to the analysis and separation of the compounds in the glycerol chlorination products. In this study, a convenient and accurate method to determine the products in glycerol chlorination reaction was established and based on the results the kinetic mechanism of the reaction was investigated. The structure of main products, including 1,3--dichloropropan-2-ol, 2,3-dichloropropan-1-ol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol and glycerol was ascertained by gas chromatography–mass spectrometry and the isomers of the products were distinguished. Apidic acid was considered as the best catalyst because of its excellent catalytic effect and high boiling point. The mechanism of the glycerol chlorination reaction was proposed and a new kinetic model was developed. Kinetic equations of the process in the experimental range were obtained by data fitting and the activation energies of each tandem reaction were 30.7, 41.8, 29.4 and 49.5 kJ mol-1, respectively. This study revealed the process and mechanism of the kinetics and provides the theoretical basis for engineering problems.

  9. Adsorbate thermodynamics as a determinant of reaction mechanism: Pentamethylene sulfide on Mo(110)

    Energy Technology Data Exchange (ETDEWEB)

    Wiegand, B.C.; Friend, C.M.; Roberts, J.T. (Harvard Univ., Cambridge, MA (USA))

    The reactions of the totally unstrained, six-membered cyclic sulfide pentamethylene sulfide on Mo(110) have been investigated by using temperature-programmed reaction spectroscopy and X-ray photoelectron spectroscopy in an effort to identify the roles of ring size and strain in dictating reaction selectivity. Four gases products are detected in the temperature-programmed reaction of pentamethylene sulfide: dihydrogen at 380 and 590 K, pentane at 350 K, pentene at 345 K, and pentamethylene sulfide at 190 and 280 K. The kinetics for hydrocarbon production from pentamethylene sulfide are qualitatively different than for the four- and five-membered cyclic sulfides, trimethylene sulfide and tetrahydrothiophene.

  10. Curing reaction and mechanism of phenol-formaldehyde novolac resins for foundry

    Directory of Open Access Journals (Sweden)

    Yan Shi

    2016-05-01

    Full Text Available In this study on the curing dynamics of phenol-formaldehyde novolac resins (PFNR and hexamethylene tetramine (HMTA, two typical commercial PFNR were selected as examples and the curing reactions of the resins with HMTA were studied by differential scanning calorimetry (DSC. Based on the data calculated by the Kissinger equation and the Crane equation, a thermocuring dynamic model was established, from which the process conditions, activation energy, reaction kinetics equation and a first-order reaction of the curing reactions were derived.

  11. A Unified Approach to Mechanical Compaction, Pressure Solution, Mineral Reactions and the Temperature Distribution in Hydrocarbon Basins

    CERN Document Server

    Yang, Xin-She

    2010-01-01

    In modelling sediment compaction and mineral reactions, the rheological behaviour of sediments is typically considered as poroelastic or purely viscous. In fact, compaction due to pressure solution and mechanical processes in porous media is far more complicated. A generalised model of viscoelastic compaction and the smectite to illite mineral reaction in hydrocarbon basins is presented. A one-step dehydration model of the mineral reaction is assumed. The obtained nonlinear governing equations are solved numerically and different combinations of physical parameters are used to simulate realistic situations in typical sedimentary basins. Comparison of numerical simulations with real data has shown very good agreement with respect to both the porosity profile and the mineral reaction.

  12. Kinetic Approach to the Mechanism of Redox Reaction of Pyrocatechol Violet and Nitrite Ion in Aqueous Hydrochloric Acid

    Directory of Open Access Journals (Sweden)

    A. Adetoro

    2011-10-01

    Full Text Available The kinetics of the oxidation of Pyrocatechol violet (PCVH by nitrite ion (NO2- in aqueous acidic medium has been studied at 24±1ºC, I = 0.50 mol/dm3(NaCl, [H+] = 1.0×10-3 mol/dm3. The reaction is first order to [PCVH] and half order to [NO2-]. The redox reaction displayed a 1:1 stoichiometry and obeys the rate law: d[PCVH]/dt = (a + b[H+] [PCVH][NO2-]½. The second-order rate constant increases with increase in acid concentration and ionic strength. This system displayed positive salt effect while spectroscopic investigation and Michaelis-Menten plot showed evidence of intermediate complex formation in the course of the reaction. A plausible mechanism has been proposed for the reaction.

  13. Kinetics and Mechanism of the Thermal Decomposition Reaction of 3,3-Bis(azidomethyl)oxetane/Tetrahydrofuran Copolymer

    Institute of Scientific and Technical Information of China (English)

    LUO, Yang(罗阳); CHEN, Pei(陈沛); ZHAO, Feng-Qi(赵凤起); HU, Rong-Zu(胡劳祖); LI, Shang-Wen(李上文); GAO, Yin(高茵)

    2004-01-01

    The thermal behavior, mechanism and kinetic parameters of the exothermic decomposition reaction of 3,3-bis(azidomethyl)oxetane/tetrahydrofuran (BAMO/THF) copolymer in a temperature-programmed mode have been investigated by means of DSC, TG-DTG, fast and lower thermolysis/FTIR and TG-MS. The reaction mechanism was proposed. The apparent activation energy and pre-exponential constant of exothermic decomposition reaction of the compound at 0.1 MPa are 167.04 kJ·mol-1 and 1014.41 s-1, respectively. The corresponding critical temperatures of thermal explosion obtained from the onset temperature Te and the peak temperature Tp are 223.20 and 245.78 ℃, respectively. The kinetic equation of the exothermic decomposition process of BAMO/THF at 0.1 MPa could be expressed as:dα/dT= 1015.19 [-ln(1-α)]2/3e-2.009×104/T

  14. Toward Determining ATPase Mechanism in ABC Transporters: Development of the Reaction Path-Force Matching QM/MM Method.

    Science.gov (United States)

    Zhou, Y; Ojeda-May, P; Nagaraju, M; Pu, J

    2016-01-01

    Adenosine triphosphate (ATP)-binding cassette (ABC) transporters are ubiquitous ATP-dependent membrane proteins involved in translocations of a wide variety of substrates across cellular membranes. To understand the chemomechanical coupling mechanism as well as functional asymmetry in these systems, a quantitative description of how ABC transporters hydrolyze ATP is needed. Complementary to experimental approaches, computer simulations based on combined quantum mechanical and molecular mechanical (QM/MM) potentials have provided new insights into the catalytic mechanism in ABC transporters. Quantitatively reliable determination of the free energy requirement for enzymatic ATP hydrolysis, however, requires substantial statistical sampling on QM/MM potential. A case study shows that brute force sampling of ab initio QM/MM (AI/MM) potential energy surfaces is computationally impractical for enzyme simulations of ABC transporters. On the other hand, existing semiempirical QM/MM (SE/MM) methods, although affordable for free energy sampling, are unreliable for studying ATP hydrolysis. To close this gap, a multiscale QM/MM approach named reaction path-force matching (RP-FM) has been developed. In RP-FM, specific reaction parameters for a selected SE method are optimized against AI reference data along reaction paths by employing the force matching technique. The feasibility of the method is demonstrated for a proton transfer reaction in the gas phase and in solution. The RP-FM method may offer a general tool for simulating complex enzyme systems such as ABC transporters. PMID:27498639

  15. Toward Determining ATPase Mechanism in ABC Transporters: Development of the Reaction Path–Force Matching QM/MM Method

    Science.gov (United States)

    Zhou, Y.; Ojeda-May, P.; Nagaraju, M.; Pu, J.

    2016-01-01

    Adenosine triphosphate (ATP)-binding cassette (ABC) transporters are ubiquitous ATP-dependent membrane proteins involved in translocations of a wide variety of substrates across cellular membranes. To understand the chemomechanical coupling mechanism as well as functional asymmetry in these systems, a quantitative description of how ABC transporters hydrolyze ATP is needed. Complementary to experimental approaches, computer simulations based on combined quantum mechanical and molecular mechanical (QM/MM) potentials have provided new insights into the catalytic mechanism in ABC transporters. Quantitatively reliable determination of the free energy requirement for enzymatic ATP hydrolysis, however, requires substantial statistical sampling on QM/MM potential. A case study shows that brute force sampling of ab initio QM/MM (AI/MM) potential energy surfaces is computationally impractical for enzyme simulations of ABC transporters. On the other hand, existing semiempirical QM/MM (SE/MM) methods, although affordable for free energy sampling, are unreliable for studying ATP hydrolysis. To close this gap, a multiscale QM/MM approach named reaction path–force matching (RP–FM) has been developed. In RP–FM, specific reaction parameters for a selected SE method are optimized against AI reference data along reaction paths by employing the force matching technique. The feasibility of the method is demonstrated for a proton transfer reaction in the gas phase and in solution. The RP–FM method may offer a general tool for simulating complex enzyme systems such as ABC transporters. PMID:27498639

  16. The study of the mechanism of an electrode reaction by first- and second-order techniques A theoretical approach

    NARCIS (Netherlands)

    Sluyters, J.H.; Sluyters-Rehbach, M.; Struys, J.

    1984-01-01

    Abstract The theoretical expressions for the faradaic admittance and the faradaic demodulation voltage are rewritten, introducing the thermodynamic restrictions proposed by Reinmuth in 1972 and without any specification of the mechanism of the electrode reaction. The result is applied to general fi

  17. Reaction mechanisms and microstructures of ceramic-metal composites made by reactive metal penetration

    Energy Technology Data Exchange (ETDEWEB)

    Fahrenholtz, W.F. [Univ. of New Mexico, Albuquerque, NM (United States). Advanced Materials Lab.; Ewsuk, K.G.; Loehman, R.E. [Sandia National Labs., NM (United States)] [and others

    1996-12-31

    Ceramic-metal composites can be made by reactive penetration of molten metals into dense ceramic performs. The metal penetration is driven by a large negative Gibbs energy for reaction, which is different from the more common physical infiltration of porous media. Reactions involving Al can be written generally as (x+2)Al + (3/y)MO{sub y} {yields} Al{sub 2}O{sub 3} + M{sub 3/y}Al{sub x}, where MO{sub y} is an oxide that is wet by molten Al. In low Po{sub 2} atmospheres and at temperature above about 900{degrees}c, molten Al reduces mullite to produce Al{sub 2}O{sub 3} + M{sub 3/y}Al{sub x}, where MO is an oxide that is wet by molten Al. In low Po{sub 2} atmospheres and at temperatures above about 900{degrees}C, molten al reduces mullite to produce Al{sub 2}O{sub 3} and Si. The Al/mullite reaction has a {Delta}G{sub r}{degrees} (1200K) of -1014 kJ/mol and, if the mullite is fully dense, the theoretical volume change on reaction is less than 1%. A microstructure of mutually-interpenetrating metal and ceramic phases generally is obtained. Penetration rate increases with increasing reaction temperature from 900 to 1150{degrees}C, and the reaction layer thickness increases linearly with time. Reaction rate is a maximum at 1150{degrees}C; above that temperature the reaction slows and stops after a relatively short period of linear growth. At 1300{degrees}C and above, no reaction layer is detected by optical microscopy. Observations of the reaction front by TEM show only al and Al{sub 2}O{sub 3} after reaction at 900{degrees}C, but Si is present in increasing amounts as the reaction temperature increases to 1100{degrees}C and above. The kinetic and microstructural data suggest that the deviation from linear growth kinetics at higher reaction temperatures and longer times is due to Si build-up and saturation at the reaction front. The activation energy for short reaction times at 900 to 1150{degrees}C varies from {approximately}90 to {approximately}200 kJ/mole.

  18. Role of the direct mechanisms in the deuteron-induced surrogate reactions

    CERN Document Server

    Avrigeanu, M

    2015-01-01

    An extended analysis of the key role of direct interactions, i.e., breakup, stripping and pick-up processes, for the deuteron–induced surrogate reactions is presented. Particular comments concern the deuteron breakup which is dominant in the case of the ( d; p g ) surrogate reactions on actinides target nuclei, around the Coulomb barrier.

  19. Kinetics and Mechanism of Interfacial Reaction in a SiCf/Ti Composite

    Institute of Scientific and Technical Information of China (English)

    Guoxing ZHANG; Qiang KANG; Nanlin SHI; Geping LI; Dong LI

    2003-01-01

    In order to evaluate the interfacial reaction, a SiCf/Ti (TA1) composite was fabricated by a vacuum hot pressingmethod and then heat-treated in vacuum at 800℃ for up to 100 h. The elemental distributions of C, Si and Ti at theinterfacial reaction zone were investigated. It was found that the reaction zone occurs during the fabrication processand continuously grows at high temperature because the Si and C atoms diffuse from SiC fibers to the matrix and Tiatoms diffuse in the opposite direction. The growth of the reaction zone is diffusion controlled and the mechanismof the reaction can be described by a reactive diffusion model of solid-state growth of an AmBn layer between twoelementary substances A and B.

  20. Determining the mechanical strength of CO2-induced reaction zones in wellbore cement: is it worth it?

    Science.gov (United States)

    Hangx, Suzanne; Marcelis, Fons; van der Linden, Arjan; Liteanu, Emilia

    2015-04-01

    CO2 injection, either for long-term CO2 storage (CCS) or Enhanced Oil Recovery (EOR), strongly hinges on maintaining storage integrity. Injection and legacy wells penetrating the caprock pose one of the most likely points of leakage. In order to be able to predict the long-term integrity of such wellbores, it's important to understand their chemical, hydrological and mechanical behaviour, and how it may change due to CO2 exposure. Generally, in response to CO2/brine/cement interactions, a number of different reaction zones are observed, each with their own chemical, and hence mechanical, signature. To aid mechanical modelling efforts, assessing the risk of cement failure caused by stress and temperature changes, knowledge is required of the strength of each of these zones. We performed experiments on Class G Portland cement to investigate the chemical-mechanical coupling due to CO2-exposure. Batch reaction experiments, in the presence of CO2-rich brine, were performed under typical storage conditions (T = 65° C, PCO2 = 8 MPa) for various periods of time (1, 2, 3, 4, 5 and 6 months). After exposure, mechanical tests were performed on the observed reaction zones, using the so-called core scratching technique, to evaluate the unconfined compressive strength (UCS) as a function of exposure time. Chemical analyses (CT-imaging, SEM microscopy, EDX chemical analysis) showed the formation of three reaction zones, similarly to what has been observed in other studies. Measurements of the mechanical strength of these different zones showed highly variable results. Such variations have also been observed in other studies, using different measurement techniques. The large variability in strength measurements is most likely an inherent result of the heterogenic nature of cement, which affects the extent and location of reaction throughout the sample. This begs the question: is it worth studying the mechanical strength of reaction-induced zones in cement? Or will it suffice to

  1. Theoretical studies of the reactions of O(3p) with halogenated methyl (Ⅰ)——Reaction mechanism of the O(3p) + CH2Cl reaction

    Institute of Scientific and Technical Information of China (English)

    侯华; 王宝山; 顾月姝

    1999-01-01

    The reaction of O(3P) with CH2Cl radical has been studied using ab initio molecular orbital theory. G2 (MP2) method is used to calculate the geometrical parameters, vibrational frequencies and energies of various stationary points on the potential energy surface. The reaction mechanism is revealed. The addition of O(3P) with CH2Cl leads to the formation of an energy rich intermediate OCH2Cl which can subsequently undergo decomposition or isomerization to the final products. The calculated heat of reaction for each channel is in agreement with the experimental value. The production of H+CHClO and Cl+CH2O are predicted to be the major channels. The overall rate constants are calculated using transition state theory on the basis of ab initio data. The rate constant is pressure independent and exhibits negative temperature dependence at lower temperatures, in accordance with the experimental results.

  2. Large scale synthesis and formation mechanism of silver nanoparticles in solid-state reactions at ambient temperature

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Aiqin, E-mail: zhangaiqin@zzuli.edu.cn [State Laboratory of Surface and Interface Science and Technology, Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, Zhengzhou 450002 (China); Tian, Yakun; Xiao, Yuanhua; Sun, Yuan [State Laboratory of Surface and Interface Science and Technology, Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, Zhengzhou 450002 (China); Li, Feng [State Laboratory of Surface and Interface Science and Technology, Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, Zhengzhou 450002 (China); American Advanced Nanotechnology, Houston, TX 77459 (United States)

    2015-07-15

    Highlights: • AgNPs were prepared by solid state reaction at ambient temperature. • Only silver nitrate and ascorbic acid were needed in this reaction. • The size of the AgNPs can be tuned conveniently. • Formation mechanism of the AgNPs was investigated. - Abstract: A one-step strategy for preparing Ag nanoparticles (AgNPs) on large scale is demonstrated successfully, based on solid-state reactions at ambient temperature. The environmentally friendly synthesis can be achieved by simply grinding AgNO{sub 3} and ascorbic acid (AA) for about 30 min without adding any solvent and organic protectors. The size of AgNPs can be readily controlled by adjusting the reaction parameters such as AgNO{sub 3}/AA molar ratio and reaction time. The nanostructures of AgNPs and their formation mechanism have been also investigated with XRD, FTIR, FESEM, HRTEM and HPLC–MS. It was found that AA can reduce Ag{sup +} into Ag{sup 0} to form AgNPs directly in accompanying with its first oxidation into 2,3-diketogulonic acid (2,3-DKG) and then a series of fragmentary species of 2,3-DKG.

  3. Large scale synthesis and formation mechanism of silver nanoparticles in solid-state reactions at ambient temperature

    International Nuclear Information System (INIS)

    Highlights: • AgNPs were prepared by solid state reaction at ambient temperature. • Only silver nitrate and ascorbic acid were needed in this reaction. • The size of the AgNPs can be tuned conveniently. • Formation mechanism of the AgNPs was investigated. - Abstract: A one-step strategy for preparing Ag nanoparticles (AgNPs) on large scale is demonstrated successfully, based on solid-state reactions at ambient temperature. The environmentally friendly synthesis can be achieved by simply grinding AgNO3 and ascorbic acid (AA) for about 30 min without adding any solvent and organic protectors. The size of AgNPs can be readily controlled by adjusting the reaction parameters such as AgNO3/AA molar ratio and reaction time. The nanostructures of AgNPs and their formation mechanism have been also investigated with XRD, FTIR, FESEM, HRTEM and HPLC–MS. It was found that AA can reduce Ag+ into Ag0 to form AgNPs directly in accompanying with its first oxidation into 2,3-diketogulonic acid (2,3-DKG) and then a series of fragmentary species of 2,3-DKG

  4. Nuclear excitations and reaction mechanisms. Progress report, 1 November 1979-30 September 1980

    International Nuclear Information System (INIS)

    Among the topics investigated were the following: photon scattering and consistency condition between seagull quadrupole terms and the absorption sum rule; Raman scattering to negative-parity states; nonlocal terms due to exchange and retardation effects in charge-transfer reactions; consistency and meaning of various approximate channel coupling array equations; derivation of equations used in empirical nuclear reaction analyses; multicluster, n-particle scattering theory; converged molecular bound state calculations; consistency of approximate channel coupling array equations; derivations of equations used in empirical nuclear reaction analyses; and WKB-type approximation in angular momenta for central potentials. References to publications are given

  5. Theoretical Study of the Photochemical Reaction Mechanism of Bicyclo[4.1.0]heptane

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The photochemical reaction of bicyclo[4.1.0]heptane was studied at the complete active space SCF(CASSCF) level with a 6-31G* basis set. A multireference MP2 algorithm that has been implemented in the Gaussian program was used to correct the energetics for the dynamic correlation. Starting from the Franck-Condon excitation of bicyclo [4.1.0] heptane, the reaction is via two bonds' breakage to give rise to 1,6-heptdiene. One internal conversion(IC) and two intersystem crossing points(ISC) were located and are discussed separately. The reaction proceeds to its own characteristic product on the ground state.

  6. Study on Reaction Mechanism for Cracking FCC Gasoline on Acid Catalyst

    Institute of Scientific and Technical Information of China (English)

    Xu Youhao; Wang Xieqing

    2004-01-01

    This article is based on the experimental data on reaction of FCC naphtha in the presence of acid catalysts. The data published in the literature were reprocessed and compared with experimental data and the relationship of hydrogen and methane contained in the dry gas with the conversion rate was identified.The similarity between the route for cracking of olefin enriched FCC gasoline and the route for reaction of individual hydrocarbons was deduced, while the route for formation of ethylene in dry gas was also proposed to identify the relationship between the reaction path for formation of ethylene and the conversion rate.

  7. Exploring reaction mechanisms and their competition in 58Ni+48Ca collisions at E = 25 AMeV

    Directory of Open Access Journals (Sweden)

    Francalanza L.

    2014-03-01

    Full Text Available Latest results concerning the study of central collisions in 58Ni+48Ca reactions at Elab(Ni=25 AMeV are presented. The experimental data, collected with the CHIMERA 4π device, have been analyzed in order to investigate the competition among different reaction mechanisms for central collisions in the Fermi energy domain. The method adopted to perform the centrality selection refers to the global variable “flow angle”, that is related to the event shape in momentum space, as it is determined by the eigenvectors of the experimental kinetic-energy tensor. The main features of the reaction products were explored by using different constraints on some of the relevant observables, such as mass and velocity distributions and their correlations. Much emphasis was devoted to the competition between fusion-evaporation processes with subsequent identification of a heavy residue and a prompt multifragmentation mechanism. The reaction mechanism was simulated in the framework of transport theories (dynamical stochastic BNV calculations, followed by sequential SIMON code and further comparison with dynamical calculations from transport model (QMD, CoMD are in progress. Moreover, an extension of this study taking into account for the light particles has been envisaged.

  8. Exploring reaction mechanisms and their competition in 58Ni+48Ca collisions at E = 25 AMeV

    Science.gov (United States)

    Francalanza, L.; Abbondanno, U.; Amorini, F.; Barlini, S.; Bini, M.; Bougault, R.; Bruno, M.; Cardella, G.; Casini, G.; Colonna, M.; D'Agostino, M.; De Filippo, E.; De Sanctis, J.; Geraci, E.; Giussani, A.; Gramegna, F.; Guiot, B.; Kravchuk, V.; La Guidara, E.; Lanzalone, G.; Le Neindre, N.; Maiolino, C.; Marini, P.; Morelli, L.; Olmi, A.; Pagano, A.; Papa, M.; Piantelli, S.; Pirrone, S.; Politi, G.; Poggi, G.; Porto, F.; Russotto, P.; Rizzo, F.; Vannini, G.; Vannucci, L.

    2014-03-01

    Latest results concerning the study of central collisions in 58Ni+48Ca reactions at Elab(Ni)=25 AMeV are presented. The experimental data, collected with the CHIMERA 4π device, have been analyzed in order to investigate the competition among different reaction mechanisms for central collisions in the Fermi energy domain. The method adopted to perform the centrality selection refers to the global variable "flow angle", that is related to the event shape in momentum space, as it is determined by the eigenvectors of the experimental kinetic-energy tensor. The main features of the reaction products were explored by using different constraints on some of the relevant observables, such as mass and velocity distributions and their correlations. Much emphasis was devoted to the competition between fusion-evaporation processes with subsequent identification of a heavy residue and a prompt multifragmentation mechanism. The reaction mechanism was simulated in the framework of transport theories (dynamical stochastic BNV calculations, followed by sequential SIMON code) and further comparison with dynamical calculations from transport model (QMD, CoMD) are in progress. Moreover, an extension of this study taking into account for the light particles has been envisaged.

  9. Mechanical stimulated reaction of metal/polymer mixed powders; Kinzoku/kobunshi kongo funmatsu no kikaiteki reiki hanno

    Energy Technology Data Exchange (ETDEWEB)

    Tobita, M.; Sakakibara, A.; Takemoto, Y. [Okayama University, Okayama (Japan). Faculty of Engineering; Iwabu, H. [Kurare Co. Ltd., Osaka (Japan)

    1999-12-15

    Mechanical grinding (MG) with mechanically stimulated reaction was performed on metal/polymer mixed powders. The starting materials used in this study were the metals of Mg, Ti and Mg{sub 2}Ni powders, arid polymer of PTFE, PVC and PE powders. The MG process was investigated using XRD, IR, SEM and TEM. According to XRD results, magnesium fluoride (MgF{sub 2}, TiF{sub 2}) and chloride (MgCl{sub 2}) were detected from MG products of the Mg/PTFE, Ti/PTFE and Mg/PVC blending systems, respectively. Explosive reaction was found during MG of both Mg/PTFE and Ti/PTFE. It was also confirmed by XRD results that the production of MgF{sub 2} had already been formed just before the explosive reaction in Mg/PTFE system. It was found from IR analysis that C-C single bond in the polymers, not only both in PTFE and PVC but also in PE, changed to double bond C=C. Hydrogen produced due to decomposition of PE on blending Mg{sub 2}Ni/PE was absorbed into C-Mg{sub 2}Ni-H as amorphous solutes. These mechanically stimulated reaction was powerful method for decomposition of engineering plastics. (author)

  10. Theoretical Study of CH3CH=CH2+O(1D) Reaction:Mechanism and Kinetics

    Institute of Scientific and Technical Information of China (English)

    WU Nai-nan; LIU Hong-xia; DUAN Xue-mei; LIU Jing-yao

    2012-01-01

    The mechanism and kinetics for the reaction of propene(CH3CH=CH2) molecule with O(1D) atom were investigated theoretically.The electronic structure information of the potential energy surface(PES) was obtained at the B3LYP/6-31 l+G(d,p) level,and the single-point energies were refined by the multi-level MCG3-MPWB method.The calculated results show that O(1D) atom can attack CH3CH=CH2 via the barrierless insertion mechanism to form four energy-riched intermediates CH3C(OH)CH2(IM1),CH3CHCHOH(IM2),CH2OHCHCH2(IM3)and cycloCH2OCHCH3(IM4),respectively,on the singlet PES.The branching ratios as well as the pressure- and temperaturedependence of various product channels for this multi-well reaction were predicted by variational transition-state and Rice-Ramsperger-Kassel-Marcus(RRKM) theories.The present results will be useful to gain a deep insight into the reaction mechanism and kinetics of CH3CH=CH2+O(1D) reaction.

  11. Exploring reaction mechanisms and their competition in 58Ni + 48Ca collisions at E=25 AMeV

    International Nuclear Information System (INIS)

    Latest results concerning the study of central collisions in 58Ni+48Ca reactions at Elab(Ni)=25 AMeV are presented. The experimental data, collected with the CHIMERA 4π device, have been analyzed in order to investigate the competition among different reaction mechanisms for central collisions in the Fermi energy domain. The method adopted to perform the centrality selection refers to the global variable 'flow angle', that is related to the event shape in momentum space, as it is determined by the eigenvectors of the experimental kinetic-energy tensor. The main features of the reaction products were explored by using different constraints on some of the relevant observables, such as mass and velocity distributions and their correlations. Much emphasis was devoted to the competition between fusion-evaporation processes with subsequent identification of a heavy residue and a prompt multifragmentation mechanism. The reaction mechanism was simulated in the framework of transport theories (dynamical stochastic BNV calculations, followed by sequential SIMON code) and further comparison with dynamical calculations from transport model (QMD, CoMD) are in progress. Moreover, an extension of this study taking into account for the light particles has been envisaged. (authors)

  12. Kinetic Study on Aminolysis of 4-Nitrophenyl Isonicotinate in Acetonitrile: Effect of Amine Basicity on Reactivity and Reaction Mechanism

    International Nuclear Information System (INIS)

    A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl isonicotinate with a series of cyclic secondary amines in MeCN. The plots of kobsd vs. [amine] curve upward for the reactions with weakly basic amines (e. g., morpholine, 1-(2-hydroxyethyl)piperazine, and piperazine) but are linear for those with strongly basic amines (e. g., piperidine and 3-methylpiperidine). The curved plots for the reactions with the weakly basic amines are typical for reactions reported previously to proceed through uncatalyzed and catalyzed routes with two intermediates (e. g., a zwitterionic tetrahedral intermediate T± and its deprotonated form T-). In contrast, the linear plots for the reactions with the strongly basic amines indicate that the catalytic route (i. e., the deprotonation process to yield T- from T± by a second amine molecule) is absent. The Brφnsted-type plots for Kk2 and Kk3 (i. e., the rate constants for the uncatalyzed and catalyzed routes, respectively) exhibit excellent linear correlations with βnuc = 0.99 and 0.69, respectively. The effect of amine basicity on the reaction mechanism is discussed in detail

  13. New insight into the ZnO sulfidation reaction: mechanism and kinetics modeling of the ZnS outward growth.

    Science.gov (United States)

    Neveux, Laure; Chiche, David; Pérez-Pellitero, Javier; Favergeon, Loïc; Gay, Anne-Sophie; Pijolat, Michèle

    2013-02-01

    Zinc oxide based materials are commonly used for the final desulfurization of synthesis gas in Fischer-Tropsch based XTL processes. Although the ZnO sulfidation reaction has been widely studied, little is known about the transformation at the crystal scale, its detailed mechanism and kinetics. A model ZnO material with well-determined characteristics (particle size and shape) has been synthesized to perform this study. Characterizations of sulfided samples (using XRD, TEM and electron diffraction) have shown the formation of oriented polycrystalline ZnS nanoparticles with a predominant hexagonal form (wurtzite phase). TEM observations also have evidenced an outward development of the ZnS phase, showing zinc and oxygen diffusion from the ZnO-ZnS internal interface to the surface of the ZnS particle. The kinetics of ZnO sulfidation by H(2)S has been investigated using isothermal and isobaric thermogravimetry. Kinetic tests have been performed that show that nucleation of ZnS is instantaneous compared to the growth process. A reaction mechanism composed of eight elementary steps has been proposed to account for these results, and various possible rate laws have been determined upon approximation of the rate-determining step. Thermogravimetry experiments performed in a wide range of H(2)S and H(2)O partial pressures have shown that the ZnO sulfidation reaction rate has a nonlinear variation with H(2)S partial pressure at the same time no significant influence of water vapor on reaction kinetics has been observed. From these observations, a mixed kinetics of external interface reaction with water desorption and oxygen diffusion has been determined to control the reaction kinetics and the proposed mechanism has been validated. However, the formation of voids at the ZnO-ZnS internal interface, characterized by TEM and electron tomography, strongly slows down the reaction rate. Therefore, the impact of the decreasing ZnO-ZnS internal interface on reaction kinetics has been

  14. Kinetics and mechanism of the reaction of fluorine atoms with pentafluoropropionic acid.

    Science.gov (United States)

    Vasiliev, E S; Knyazev, V D; Karpov, G V; Morozov, I I

    2014-06-12

    The kinetics of the reaction between fluorine atoms and pentafluoropropionic acid has been studied experimentally at T = 262-343 K. The overall reaction rate constant decreases with temperature: k1(T) = 6.1 × 10(-13) exp(+1166 K)/T) cm(3) molecule(-1) s(-1). The potential energy surface of the reaction has been studied using quantum chemistry. The results were used in transition state theory calculations of the temperature dependences of the rate constants of the two channels of the reaction. The abstraction channel ultimately producing HF, C2F5, and CO2 is dominant at the experimental temperatures; the addition-elimination channel producing C2F5 and CF(O)OH becomes important above 1000 K. PMID:24819330

  15. Nuclear excitations and reaction mechanisms: Progress report: [1 August 1986-31 July 1987

    International Nuclear Information System (INIS)

    Completed and ongoing research includes various theoretical and numerical studies of few-nucleon systems; nuclear reaction models; photon scattering from nuclei, including sum rules and current conservation; and properties of the pion

  16. Reactions of the simple nitroalkanes with hydroxide ion in water. Evidence for a complex mechanism.

    Science.gov (United States)

    Li, Zhao; Cheng, Jin-Pei; Parker, Vernon D

    2011-06-21

    Conventional kinetic analysis of the reactions of nitromethane (NM), nitroethane (NE) and 2-nitropropane (2-NP) with hydroxide ion in water revealed that the reactions are complex and involve kinetically significant intermediates. Kinetic experiments at the isosbestic points where changes in reactant and product absorbance cancel indicate the evolution and decay of absorbance characteristic of the formation of reactive intermediates. The deviations from 1st-order kinetics were observed to increase with increasing extent of reaction and in the reactant order: NM < NE < 2-NP. The apparent deuterium kinetic isotope effects for proton/deuteron transfer approach unity near zero time and increased with time toward plateau values as the reaction kinetics reach steady state. It is proposed that the initially formed preassociation complexes are transformed to more intimate reactant complexes which can give products by two possible pathways. PMID:21519607

  17. Mechanism of anti-influenza virus activity of Maillard reaction products derived from Isatidis roots

    OpenAIRE

    Ke, Lijing

    2011-01-01

    The cyto-protective compositions and effects of antiviral Maillard reaction products (MRPs) derived from roots of Isatis indigotica F. were examined using biochemical and biophysical methods. The Maillard reaction was identified as the main source of compounds with antiviral activity, an observation which has led to the proposal of a new class of active compounds that protect cells from influenza virus infection. In the roots, arginine and glucose were revealed to be the predom...

  18. Generalization of the Activated Complex Theory of Reaction Rates. I. Quantum Mechanical Treatment

    Science.gov (United States)

    Marcus, R. A.

    1964-01-01

    In its usual form activated complex theory assumes a quasi-equilibrium between reactants and activated complex, a separable reaction coordinate, a Cartesian reaction coordinate, and an absence of interaction of rotation with internal motion in the complex. In the present paper a rate expression is derived without introducing the Cartesian assumption. The expression bears a formal resemblance to the usual one and reduces to it when the added assumptions of the latter are introduced.

  19. Non-equilibrium statistical mechanical approach for describing heavy ion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sventek, J.S.

    1978-11-01

    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 and pickup reactions. A model for describing the time-evolution of these reactions was 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. 61 figures, 2 tables.

  20. Graphene Facilitated Removal of Labetalol in Laccase-ABTS System: Reaction Efficiency, Pathways and Mechanism

    Science.gov (United States)

    Dong, Shipeng; Xiao, Huifang; Huang, Qingguo; Zhang, Jian; Mao, Liang; Gao, Shixiang

    2016-02-01

    The widespread occurrence of the beta-blocker labetalol causes environmental health concern. Enzymatic reactions are highly efficient and specific offering biochemical transformation of trace contaminants with short reaction time and little to none energy consumption. Our experiments indicate that labetalol can be effectively transformed by laccase-catalyzed reaction using 2, 2-Azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as a mediator, while no significant removal of labetalol can be achieved in the absence of ABTS. A total of three products were identified. It is interesting that the presence of graphene greatly increased the reaction rate while not changed the products. In the presence of 100 μg/L graphene, the pseudo-first-order reaction rate constant was increased ~50 times. We found that the enhancement of graphene is probably attributed to the formation and releasing of ABTS2+ which has a much greater reactivity towards labetalol when graphene is present. This study provides fundamental information for laccase-ABTS mediated labetalol reactions and the effect of graphene, which could eventually lead to development of novel methods to control beta-blocker contamination.

  1. Kinetics and mechanism of the reaction of gold(III chloride complexes with formic acid

    Directory of Open Access Journals (Sweden)

    Pacławski K.

    2015-01-01

    Full Text Available In this work, the results of kinetic studies of the redox reaction of gold(III chloride complexes ([AuCl4]- with formic acid, are presented. Obtained data suggest the complex character of the reaction which leads to the [AuCl2]- and [AuCl3(COOH]- ions formation as intermediates. In the pH range over 2.5, the final product of the reaction is metallic gold. From the analysis of kinetic data, the rate limiting step is found to be the gold metallic phase formation. The stage of Au(III reduction is relatively fast with the second-order rate constant equal to 61.8 M-1s-1 at temperature 50ºC. The rate of the studied reaction depends on the temperature, reactants concentration and chloride ions concentration. As a result of the data analysis, the scheme of the reaction path has been suggested. Also, the values of enthalpy and entropy of activation for the reaction have been determined.

  2. Reaction mechanism of homoprotocatechuate 2,3-dioxygenase with 4-nitrocatechol: implications for the role of substrate.

    Science.gov (United States)

    Dong, Geng; Lai, Wenzhen

    2014-02-20

    The reaction mechanism of the dioxygen activation by homoprotocatechuate 2,3-dioxygenase (HPCD) with the substrate 4-nitrocatechol was investigated by quantum mechanical/molecular mechanical calculations. Our results demonstrated that the experimentally determined side-on iron-oxygen complex in crystallo is a semiquinone substrate radical (SQ(•))-Fe(III)-hydroperoxo species, which could not act as the reactive species. In fact, the Fe(III)-superoxo species with a hydrogen bond between His200 and the proximal oxygen is the reactive oxygen species. The second-sphere His200 residue was found to play an important role in manipulating the orientation of the superoxide in the Fe-O2 adduct for the further reaction. The rate-limiting step is the attack of the superoxo group on the substrate with a barrier of 17.2 kcal/mol, in good agreement with the experimental value of 16.8 kcal/mol. The reaction mechanism was then compared with the one for HPCD with its native substrate homoprotocatechuate studied recently by the same methods, in which a hybrid SQ(•)-Fe(II)-O2(•-)/Fe(III)-O2(•-) was suggested to be the reactive species. Therefore, our studies suggested that the substrate plays important roles in the dioxygen activation by HPCD.

  3. Tyree-body mechanisms in the 3^He(e,e'p) reactions at high missing momentum

    CERN Document Server

    Laget, J M

    2004-01-01

    A particular three-body mechanism is responsible for the missing strength which has been reported in $^3$He(e,e$'$p) reactions at missing momentum above 700 MeV/c. It corresponds to the absorption of the virtual photon by a nucleon at rest which subsequently propagates on-shell and emits a meson which is reabsorbed by the pair formed by the two other nucleons. Its amplitude, which is negligible in photon induced reactions as well as in the electro-production of an on-shell meson, becomes maximal in the quasi-free kinematics (X=1). It relates the amplitude of the $^3$He(e,e$'$p)D reaction to the amplitude of $pD$ elastic scattering at backward angles.

  4. Experimental and theoretical assessment of the mechanism involved in the reaction of steroidal ketone semicarbazone with hydrogen peroxide

    Science.gov (United States)

    Sharma, Kamlesh; Mishra, Shivani B.; Mishra, Ajay K.

    2011-09-01

    3β-Acetoxy-5α-cholestan-6-one semicarbazone 1 on reaction with hydrogen peroxide affords selectively 3β-acetoxy-5α-cholestan-6-spiro-1',2',4'-triazolidine-3'-one 2. The structural assignment of the product was confirmed by spectral data and elemental analysis. A free radical mechanism of the present reaction was described successfully by calculating theoretical models of 1, A, B and 2, using DFT with B3LYP/6-31G* basis set. It was found that the reaction undergoes through the formation of two radical intermediates and the only one isomer of the product in which -NH-CO- group is cis with respect C5α-H, was selectively obtained. Frontier molecular orbital, spin electronic density, electrostatic potential and atomic charges were discussed.

  5. On the importance of steady-state isotopic techniques for the investigation of the mechanism of the reverse water-gas-shift reaction.

    Science.gov (United States)

    Tibiletti, Daniele; Goguet, Alexandre; Meunier, Frederic C; Breen, John P; Burch, Robbie

    2004-07-21

    The formation and reactivity of surface intermediates in the reverse water-gas-shift reaction on a Pt/CeO2 catalyst are critically dependent on the reaction conditions so that conclusions regarding the reaction mechanism cannot be inferred using ex operando conditions. PMID:15263955

  6. Study of the 16O(16O,12C)20Ne reaction mechanism by polarization measurements

    International Nuclear Information System (INIS)

    The 16O(16O,12C)20Ne reaction has been studied at beam energies of 68 and 90 MeV. At these energies, this reaction is selective for populating high spin states well known to have a large overlap with α+16O. The angular distributions have been analyzed with an EFR-DWBA code. Good fits are obtained and the resulting relative α particle spectroscopic factors for the 20Ne states are in good agreement with shell model predictions, and with other results from different α transfer reactions. The polarization of the 20Ne has been measured by angular correlations between 12C and 16O (product of the 20Ne decay). As expected from a semi-classical view of the transfer, a strong 20Ne polarization, on an axis perpendicular to the reaction plane has been found. This polarization remains constant on a wide span of 12C angles. Different nuclear reaction models have been tested. With selected potentials, the DWBA predicts a strong polarization in this case of a heavy ion transfer, but not as strong as the one observed in the experiment. Some possible reasons for this difference are indicated

  7. Semiempirical Predictions of Chemical Degradation Reaction Mechanisms of CL-20 as Related to Molecular Structure

    Energy Technology Data Exchange (ETDEWEB)

    Qasim, Mohammad M.; Furey, John; Fredrickson, Herbert L.; Szecsody, Jim E.; Mcgrath, Chris J.; Bajpai, Rakesh

    2004-10-01

    Quantum mechanical methods and force field molecular mechanics were used to characterize cage cyclic nitramines and to predict environmental degradation mechanisms. Due to structural similarities it is predicted that, under homologous circumstances, the major environmental RDX degradation pathways should also be effective for CL-20 and similar cyclic nitramines.

  8. Reaction Mechanisms of Synthesis of 3,4-Epoxybutyric Acid from 3-Hydroxy-{\\gamma}-Butyrolactone by Density Functional Theory

    CERN Document Server

    Yu-Chol, Jong; Yun-Hui, Ju; Kye-Ryong, Sin

    2016-01-01

    In this paper, carried out were the investigations on the synthetic reaction mechanisms of 3,4-epoxybutyric acid (EBA) from 3-hydroxy-{\\gamma}-butyrolactone (HBL) with two different activating agents, methanesulfonyl chloride (MC) or acetic acid (AA), respectively, and on the convertion of EBA to L-carnitine by density functional theory (DFT/B3LYP). The theoretical calculations showed that the two reaction mechanisms of EBA synthesis with MC or AA as an activating agent were nearly the same. If activated HBL is hydrolysed, not only ring cleavage reaction, but also reverse reaction to HBL can take place. In the case of AA as the activating agent, the activation energy ( energy barrier ) for EBA synthesis is 1.8 times larger than that with MC. It means that the synthesis of EBA with AA may make more by-products with less yield of EBA than that with MC, that can be one reason why AA gave the less yield than MC in EBA synthesis, as reported in the previous experimental study.

  9. 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

    radical and adduct formation to give the C6H5F-Cl adduct. At 296 K the rate constant for the abstraction channel is k(5a)(Cl+C6H5F) = (1.1 +/- 0.1) x 10(-17) cm(3) molecule(-1) s(-1). The C6H5F-Cl adduct undergoes rapid (k similar to 10(8) s(-1)) decomposition to reform C6H5F and Cl atoms and reaction......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...

  10. Hydrothermal synthesis of cubic α-Fe2O3 microparticles using glycine: Surface characterization, reaction mechanism and electrochemical activity

    International Nuclear Information System (INIS)

    Graphical abstract: Highlights: → We synthesize cubic α-Fe2O3 (hematite) microparticles. → Their morphological, mineralogical and surface properties are determined. → Reaction mechanism based on thermodynamics and ionic equilibrium concepts are described. → Microparticles have charge capacity of 160 mAh/g and good columbic efficiency of 94%. - Abstract: Cubic α-Fe2O3 (hematite) microparticles (side lengths = 0.3-1.3 μm) have been synthesized using glycine and ferric chloride via a simple one-step hydrothermal reaction. Their morphological, mineralogical and surface properties have been determined using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS). XRD analysis indicated that the synthesized α-Fe2O3 microparticles were minerallogically pure. An increase in hydrothermal reaction duration from 10 to 24 h increased the atomic percentages of α-Fe2O3 on the surface of the microparticles by almost 8%. The mechanism concerning reactions of species to produce this microparticles precipitate was elucidated based on thermodynamics and ionic equilibrium aspects. In the electrochemical analysis, the synthesized α-Fe2O3 microparticles (as cathode material) exhibit an approximate charge capacity of 160 mAh/g and excellent coulombic efficiency of 94%.

  11. Simulation of biodiesel combustion in a light-duty diesel engine using integrated compact biodiesel–diesel reaction mechanism

    DEFF Research Database (Denmark)

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

    2013-01-01

    This computational fluid dynamics (CFD) study is performed to investigate the combustion characteristics and emissions formation processes of biodiesel fuels in a light-duty diesel engine. A compact reaction mechanism with 80 species and 303 reactions is used to account for the effects of chemical...... kinetics. Here, the mechanism is capable of emulating biodiesel–diesel mixture of different blending levels and biodiesel produced from different feedstock. The integrated CFD-kinetic model was validated against a test matrix which covers the entire saturated–unsaturated methyl ester range typical...... of biodiesel fuels, as well as the biodiesel–diesel blending levels. The simulated cases were then validated for in-cylinder pressure profiles and peak pressure values/timings. Errors in the peak pressure values did not exceed 1%, while the variations in peak pressure timings were kept within 1.5 crank angle...

  12. FEARCF a multidimensional free energy method for investigating conformational landscapes and chemical reaction mechanisms

    Institute of Scientific and Technical Information of China (English)

    NAIDOO Kevin J.

    2012-01-01

    The development and implementation of a computational method able to produce free energies in multiple dimensions,descriptively named the free energies from adaptive reaction coordinate forces (FEARCF) method is described in this paper.While the method can be used to calculate free energies of association,conformation and reactivity here it is shown in the context of chemical reaction landscapes.A reaction free energy surface for the Claisen rearrangement of chorismate to prephenate is used as an illustration of the method's efficient convergence.FEARCF simulations are shown to achieve fiat histograms for complex multidimensional free energy volumes.The sampling efficiency by which it produces multidimensional free energies is demonstrated on the complex puckering of a pyranose ring,that is described by a three dimensional W(θ1,θ2,θ3) potential of mean force.

  13. Theoretical Studies on the Reaction Mechanism of Hydroxyl Radical with 1,1,1-Trichloroethane

    Institute of Scientific and Technical Information of China (English)

    HU Xiao-Ping; WANG Bing-Xing; GAO Ying; YANG Bing

    2011-01-01

    Ab initio and density functional theory calculations have been carried out to investigate the reaction of hydroxyl radical (OH) and 1,1,1-trichloroethane (CH3CCl3). The potential energy surface has been given according to the relative energies calculated at the MP2/cc-pVTZ level after the spin projection (PMP2). Five reaction channels were identified and the intramolecular hydrogen bonding was observed in some transition state structures. The barrier heights and reaction enthalpies calculated for all possible channels show that the hydrogen abstraction channel is predominant kinetically and thermodynamically. The contribution from other channels was predicted to be minor.

  14. Benzyl alcohol oxidation in supercritical carbon dioxide: spectroscopic insight into phase behaviour and reaction mechanism.

    Science.gov (United States)

    Caravati, Matteo; Grunwaldt, Jan-Dierk; Baiker, Alfons

    2005-01-21

    Selective oxidation of benzyl alcohol to benzaldehyde with molecular oxygen over an alumina-supported palladium catalyst was performed with high rate at about 95% selectivity in supercritical carbon dioxide. The experiments in a continuous flow fixed-bed reactor showed that the pressure has a strong influence on the reaction rate. A marked increase of the rate (turnover frequency) from 900 h(-1) to 1800 h(-1) was observed when increasing the pressure from 140 to 150 bar. Video monitoring of the bulk fluid phase behavior and the simultaneous investigation by transmission and attenuated total reflection (ATR) infrared spectroscopy at two positions of the view cell showed that the sharp increase in activity is correlated to a transition from a biphasic to a monophasic reaction mixture. In the single phase region, both oxygen and benzyl alcohol are dissolved in the supercritical CO2 phase, which leads to a reduction of the mass transport resistances (both in the external fluid film and in the catalyst pores) and thus to the high reaction rate measured in the catalytic experiments. The phase transition could be effectively and easily monitored by transmission and ATR-IR spectroscopy despite the small concentration of the dense liquid like phase. Deposition of the Pd/Al2O3 catalyst on the ATR-crystal at the bottom of the view cell allowed to gain insight into the chemical changes and mass transfer processes occurring in the solid/liquid interface region during reaction. Analyzing the shift of the upsilon2 bending mode of CO2 gave information on the fluid composition in and outside the catalyst pores. Moreover, the catalytic reaction could be investigated in situ in this spectroscopic batch reactor cell by monitoring simultaneously the reaction progress, the phase behaviour and the catalytic interface. PMID:19785149

  15. Light Particle Emission Mechanisms in Heavy-Ion Reactions at 5-20 MeV/u

    Directory of Open Access Journals (Sweden)

    Fotina O.V.

    2010-03-01

    Full Text Available Light Charged Particle emission mechanisms were studied for different mass entrance channel nuclear reactions. The 300, 400, 500 MeV 64Ni + 68Zn and 130, 250 MeV 16O + 116Sn reactions were measured at the Legnaro National Laboratory using the beams from the TANDEM-ALPI acceleration system. Light Charged Particles were measured in coincidence with Evaporation Residues and their spectra were analyzed using the global moving source fit technique. The characterization of different emission sources (evaporative, pre-equilibrium, break-up is discussed. The behavior of pre-equilibrium emission as a function of projectile energy, excitation energy and mass-asymmetry in the entrance channel was studied, evaluating the energy, mass and charge lost by the composite systems and using Griffin exciton model for the pre-equilibrium neutron emission. The present results are compared with the systematics of the asymmetric mass entrance channel reactions. The present work shows that also at the onset the pre-equilibrium emission depends not only on the projectile velocity but also on the reaction entrance channel mass-asymmetry. The first attempt of the particle spectra analysis using the Griffin exciton model is demonstrated for the case of proton emission in the 130 MeV 16O + 116Sn reaction.

  16. Theoretical study on the reaction mechanism of the gas-phase H2/CO2/Ni(3D) system.

    Science.gov (United States)

    Qin, Song; Hu, Changwei; Yang, Huaqing; Su, Zhishan

    2005-07-28

    The ground-state potential energy surface (PES) in the gas-phase H2/CO2/Ni(3D) system is investigated at the CCSD(T)//B3LYP/6-311+G(2d,2p) levels in order to explore the possible reaction mechanism of the reverse water gas shift reaction catalyzed by Ni(3D). The calculations predict that the C-O bond cleavage of CO2 assisted by co-interacted H2 is prior to the dissociation of the H2, and the most feasible reaction path for Ni(3D) + H2 + CO2 --> Ni(3D) + H2O + CO is endothermic by 12.5 kJ mol(-1) with an energy barrier of 103.9 kJ mol(-1). The rate-determining step for the overall reaction is predicted to be the hydrogen migration with water formation. The promotion effect of H2 on the cleavage of C-O bond in CO2 is also discussed and compared with the analogous reaction of Ni(3D) + CO2 --> NiO + CO, and the difference between triplet and singlet H2/CO2/Ni systems is also discussed. PMID:16833994

  17. Oxidative removal of acetaminophen using zero valent aluminum-acid system:Efficacy, influencing factors, and reaction mechanism

    Institute of Scientific and Technical Information of China (English)

    Honghua Zhang; Beipei Cao; Wanpeng Liu; Kunde Lin; Jun Feng

    2012-01-01

    Commercial available zero valent aluminum under air-equilibrated acidic conditions (ZVA1/H+/air system) demonstrated an excellent capacity to remove aqueous organic compounds.Acetaminophen (ACTM),the active ingredient of the over-the-counter drug Tylenol(R),is widely present in the aquatic environment and therefore the treatment of ACTM-contaminated water calls for further research.Herein we investigated the oxidative removal of ACTM by ZVAl/H+/air system and the reaction mechanism.In acidic solutions (pH < 3.5),ZVAl displayed an excellent capacity to remove ACTM.More than 99% of ACTM was eliminated within 16 hr in pH 1.5 reaction solutions initially containing 2.0 g/L aluminum and 2.0 mg/L ACTM at 25 ± 1℃.Higher temperature and lower pH facilitated ACTM removal.The addition of different iron species Fe0,Fe2+ and Fe3+ into ZVAl/H+/air system dramatically accelerated the reaction likely due to the enhancing transformation of H2O2 to HO·via Fenton's reaction.Furthermore,the primary intermediate h.ydroquinone and the anions formate,acetate and nitrate,were identified and a possible reaction scheme was proposed.This work suggested that ZVA1/H+/air system may be potentially employed to treat ACTM-contaminated water.

  18. Oxidation and nitration of tyrosine by ozone and nitrogen dioxide: reaction mechanisms and biological and atmospheric implications.

    Science.gov (United States)

    Sandhiya, L; Kolandaivel, P; Senthilkumar, K

    2014-04-01

    The nitration of tyrosine by atmospheric oxidants, O3 and NO2, is an important cause for the spread of allergenic diseases. In the present study, the mechanism and pathways for the reaction of tyrosine with the atmospheric oxidants O3 and NO2 are studied using DFT-M06-2X, B3LYP, and B3LYP-D methods with the 6-311+G(d,p) basis set. The energy barrier for the initial oxidation reactions is also calculated at the CCSD(T)/6-31+G(d,p) level of theory. The reaction is studied in gas, aqueous, and lipid media. The initial oxidation of tyrosine by O3 proceeds by H atom abstraction and addition reactions and leads to the formation of six different intermediates. The subsequent nitration reaction is studied for all the intermediates, and the results show that the nitration affects both the side chain and the aromatic ring of tyrosine. The rate constant of the favorable oxidation and nitration reaction is calculated using variational transition state theory over the temperature range of 278-350 K. The spectral properties of the oxidation and nitration products are calculated at the TD-M06-2X/6-311+G(d,p) level of theory. The fate of the tyrosine radical intermediate is studied by its reaction with glutathione antioxidant. This study provides an enhanced understanding of the oxidation and nitration of tyrosine by O3 and NO2 in the context of improving the air quality and reducing the allergic diseases.

  19. Kinetics and mechanisms of heterogeneous reaction of NO2 on CaCO3 surfaces under dry and wet conditions

    Directory of Open Access Journals (Sweden)

    Z. M. Chen

    2009-03-01

    Full Text Available Calcium nitrate (Ca(NO32 was observed in mineral dust and could change the hygroscopic and optical properties of mineral dust significantly due to its strong water solubility. The reaction of calcium carbonate (CaCO3 with nitric acid (HNO3 is believed the main reason for the observed Ca(NO32 in the mineral dust. In the atmosphere, the concentration of nitrogen dioxide (NO2 is orders of magnitude higher than that of HNO3; however, little is known about the reaction of NO2 with CaCO3. In this study, the heterogeneous reaction of NO2 on the surface of CaCO3 particles was investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS combined with X-ray photoelectron spectroscopy (XPS and scanning electron microscopy (SEM under wet and dry conditions. Nitrate formation was observed in both conditions, and nitrite was observed under wet conditions, indicating the reaction of NO2 on the CaCO3 surface produced nitrate and probably nitrous acid (HONO. Relative humidity (RH influenced both the initial uptake coefficient and the reaction mechanism. With RH52%, a monolayer of water formed on the surface of the CaCO3 particles, which reacted with NO2 as a first order reaction, forming HNO3 and HONO. The initial uptake coefficient γ0 was determined to be (1.66±0.38×10−7 under dry conditions and up to (0.84±0.44×10−6 under wet conditions. Considering that NO2 concentrations in the atmosphere are orders of magnitude higher than those of HNO3, the reaction of NO2 on CaCO3 particle should have similar importance as that of HNO3 in the atmosphere and could also be an important source of HONO in the atmosphere.

  20. Investigating Glutamatergic Mechanism in Attention and Impulse Control Using Rats in a Modified 5-Choice Serial Reaction Time Task

    OpenAIRE

    Abigail Benn; Emma S J Robinson

    2014-01-01

    The 5-choice serial reaction time task (5CSRTT) has been widely used to study attention and impulse control in rodents. In order to mimic cognitive impairments in psychiatry, one approach has been to use acute administration of NMDA antagonists. This disruption in glutamatergic transmission leads to impairments in accuracy, omissions, and premature responses although findings have been inconsistent. In this study, we further investigated glutamatergic mechanisms using a novel version of the 5...

  1. Studies of the genetic variability of the coding region of the hepatocyte nuclear factor-4alpha in Caucasians with maturity onset NIDDM.

    Science.gov (United States)

    Møller, A M; Urhammer, S A; Dalgaard, L T; Reneland, R; Berglund, L; Hansen, T; Clausen, J O; Lithell, H; Pedersen, O

    1997-08-01

    Mutations in the hepatocyte nuclear factor-4alpha (HNF-4alpha) gene cause the type 1 form of maturity onset diabetes of the young (MODY1). To address the question of whether genetic variability of HNF-4alpha is associated with late onset non-insulin-dependent diabetes mellitus (NIDDM) we have sequenced the coding region and intron/exon boundaries of the gene in 36 randomly recruited Danish NIDDM patients. Two nucleotide substitutions that changed the sequence of HNF-4alpha were identified: Thr/Ile130, which has been reported previously and a novel Val/Met255. The Val/Met 255 mutation was found in 4 of 477 Danish NIDDM patients and in none of 217 glucose tolerant control subjects; thus it cannot be excluded that this mutation may have an impact on NIDDM susceptibility. Among 509 NIDDM patients the allelic frequency of the Thr/Ile130 variant was 4.7% (95% confidence interval: 3.4-6.0%) compared to 1.9% (0.7-3.1%) among 239 control subjects (p = 0.008). However, in a population sample of 942 Swedish men with an average age of 70 years the allelic frequency of the variant was similar in 246 men with either impaired glucose tolerance (5.6% [2.6-8.6%]) or NIDDM (5.4% [2.7-8.1%]) as compared to 666 glucose tolerant men (5.1% [3.9-6.3%]). Also in a population sample of 369 young healthy Danes the prevalence of the codon 130 variant (4.7% [3.2-6.2%]) was similar to what was found in Swedish Caucasians. Thus, the allelic frequency of the Thr/Ile130 variant among the control subjects in the Danish case-control study deviates from the prevalence in the two other studies which is why we consider the significant association between the codon 130 variant and NIDDM an incidental finding. In glucose tolerant subjects the codon 130 variant in its heterozygous form had no major effect on glucose-induced insulin and C-peptide release although a tendency to a lower insulin secretion during an oral glucose tolerance test was seen in middle-aged subjects. In conclusion, variability in

  2. International conference: Features of nuclear excitation states and mechanisms of nuclear reactions. 51. Meeting on nuclear spectroscopy and nuclear structure. The book of abstracts

    International Nuclear Information System (INIS)

    Results of the LI Meeting on Nuclear Spectroscopy and Nuclear Structure are presented. Properties of excited states of atomic nuclei and mechanisms of nuclear reactions are considered. Studies on the theory of nucleus and fundamental interactions pertinent to experimental study of nuclei properties and mechanisms of nuclear reactions, technique and methods of experiment, application of nuclear-physical method, are provided

  3. Theoretical study on the mechanism of CH3NH2 and O3 atmospheric reaction

    Indian Academy of Sciences (India)

    Samira Valehi; Morteza Vahedpour

    2014-07-01

    Reaction pathways of methylamine with ozone on the singlet potential energy profile have been investigated at the RB3LYP/6-311++G (3df-3pd) computational level. Calculated results reveal that six kinds of products P1 (CH3NO + H2O2), P2 (CH3NH + OH + O2), P3 (NH2CH + HO2+ OH), P4 (CH2NH + H2O +O2), P5 (NH2CH2OH + O2), P6 (NH3+ CH2O +O2) are obtained through variety of transformation of one reactant complex C1. Cleavage and formation of the chemical bonds in the reaction pathways have been discussed using the structural parameters. Based on the calculations, the title reaction leads to NH3+ CH2O + O2 as thermodynamic adducts in an exothermic process by −76.28 kcal/mol in heat realizing and spontaneous reaction by −86.71 kcal/mol in standard Gibbs free energy. From a kinetic viewpoint, the production of CH3NH + OH + O2 adducts with one transition state is the most favoured path.

  4. Impact of supersonic and subsonic aircraft on ozone: Including heterogeneous chemical reaction mechanisms

    Science.gov (United States)

    Kinnison, Douglas E.; Wuebbles, Donald J.

    1994-01-01

    Preliminary calculations suggest that heterogeneous reactions are important in calculating the impact on ozone from emissions of trace gases from aircraft fleets. In this study, three heterogeneous chemical processes that occur on background sulfuric acid aerosols are included and their effects on O3, NO(x), Cl(x), HCl, N2O5, ClONO2 are calculated.

  5. Quantum statistical mechanical theory of diffusion and reaction on solid surfaces

    OpenAIRE

    Lin, S. H.; Ziv, Alan R.; Eyring, H.

    1981-01-01

    We present the derivation of the general kinetic equations of diffusion and diffusion with interaction (or chemical reaction) on solid surfaces (or in dense media) by using the density matrix method. We indicate several problems to which this formalism applies and, in particular, discuss the damping effect on diffusion.

  6. Dynamic quenching as a simple test for the mechanism of excited-state reaction

    International Nuclear Information System (INIS)

    We report on comparative studies of dynamic fluorescence quenching of 3-hydroxyflavone (3HF) and of its novel analogs by nitric oxide spin compound TEMPO. These dyes exhibit the excited-state intramolecular proton transfer (ESIPT) reaction that allows observation of two separate bands in fluorescence emission - of initially excited form and of the product of ESIPT reaction. In the frame of two-state excited-state reaction formalism, we develop the theory predicting different dependence of intensities at two bands in steady-state spectra in the cases of thermodynamic and kinetic control of ESIPT. In line with these predictions, the quenching changes strongly the distribution of intensities between these bands for 3HF but does not change it for the novel compounds whose excited states exhibit strong charge transfer character. Based on these findings, we suggest that the quenching of fluorescence by an efficient collisional quencher can be a simple and convenient method using only the steady-state experiment for distinguishing the excited-state reactions occurring under thermodynamic or under kinetic controls. This method can be used for large-scale screening of a series of compounds - potential candidates for application in fluorescence sensor and biosensor technologies

  7. Insights into the Mechanism of Type I Dehydroquinate Dehydratases from Structures of Reaction Intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Light, Samuel H.; Minasov, George; Shuvalova, Ludmilla; Duban, Mark-Eugene; Caffrey, Michael; Anderson, Wayne F.; Lavie, Arnon (NWU); (UIC)

    2012-02-27

    The biosynthetic shikimate pathway consists of seven enzymes that catalyze sequential reactions to generate chorismate, a critical branch point in the synthesis of the aromatic amino acids. The third enzyme in the pathway, dehydroquinate dehydratase (DHQD), catalyzes the dehydration of 3-dehydroquinate to 3-dehydroshikimate. We present three crystal structures of the type I DHQD from the intestinal pathogens Clostridium difficile and Salmonella enterica. Structures of the enzyme with substrate and covalent pre- and post-dehydration reaction intermediates provide snapshots of successive steps along the type I DHQD-catalyzed reaction coordinate. These structures reveal that the position of the substrate within the active site does not appreciably change upon Schiff base formation. The intermediate state structures reveal a reaction state-dependent behavior of His-143 in which the residue adopts a conformation proximal to the site of catalytic dehydration only when the leaving group is present. We speculate that His-143 is likely to assume differing catalytic roles in each of its observed conformations. One conformation of His-143 positions the residue for the formation/hydrolysis of the covalent Schiff base intermediates, whereas the other conformation positions the residue for a role in the catalytic dehydration event. The fact that the shikimate pathway is absent from humans makes the enzymes of the pathway potential targets for the development of non-toxic antimicrobials. The structures and mechanistic insight presented here may inform the design of type I DHQD enzyme inhibitors.

  8. Generalization of the Activated Complex Theory of Reaction Rates. II. Classical Mechanical Treatment

    Science.gov (United States)

    Marcus, R. A.

    1964-01-01

    In its usual classical form activated complex theory assumes a particular expression for the kinetic energy of the reacting system -- one associated with a rectilinear motion along the reaction coordinate. The derivation of the rate expression given in the present paper is based on the general kinetic energy expression.

  9. Impact of supersonic and subsonic aircraft on ozone: Including heterogeneous chemical reaction mechanisms

    International Nuclear Information System (INIS)

    Preliminary calculations suggest that heterogeneous reactions are important in calculating the impact on ozone from emissions of trace gases from aircraft fleets. In this study, three heterogeneous chemical processes that occur on background sulfuric acid aerosols are included and their effects on O3, NOx, Clx, HCl, N2O5, ClONO2 are calculated

  10. Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition.

    Science.gov (United States)

    Elliott, Simon D; Dey, Gangotri; Maimaiti, Yasheng; Ablat, Hayrensa; Filatova, Ekaterina A; Fomengia, Glen N

    2016-07-01

    Recent progress in the simulation of the chemistry of atomic layer deposition (ALD) is presented for technologically important materials such as alumina, silica, and copper metal. Self-limiting chemisorption of precursors onto substrates is studied using density functional theory so as to determine reaction pathways and aid process development. The main challenges for the future of ALD modeling are outlined.

  11. Reaction Mechanism of Al and N in Diamond Growth from a FeNiCo-C System

    Institute of Scientific and Technical Information of China (English)

    LI Shang-Sheng; LI Xiao-Lei; MA Hong-An; SU Tai-Chao; XIAO Hong-Yu; HUANG Guo-Feng; LI Yong; ZHANG Yi-Shun; JIA Xiao-Peng

    2011-01-01

    @@ It is significant to investigate the action of nitrogen getters, which are used to synthesize type-Ⅱa large diamond single crystals under high pressure and high temperature (HPHT).The reaction mechanism of A1 as a nitrogen getter and N in the HPHT alloy solvent is still indeterminate at present.In order to investigate the reaction of Al and N in the HPHT alloy solvent, Al and AlN are respectively added to the system of FeNiCo-C (wt%, abbr.FeNiCo-C) for the synthesis of diamonds at about 5.5 GPa and 1600 K.The concentration of nitrogen in the diamonds is characterized by a micro Fourier transform infrared (micro-FTIR) spectrometer.The experimental results show that c decreases when Al is added to the FeNiCo-C system.However, it increases when AlN is added.A reversible reaction confirms that Al and N can react and form AlN, simultaneously A1N can be decomposed into Al and N in the HPHT alloy solvent.Therefore the mechanism of eliminating the nitrogen of nitrogen getter Al is realized in detail.%It is significant to investigate the action of nitrogen getters, which are used to synthesize type-Iia large diamond single crystals under high pressure and high temperature (HPHT). The reaction mechanism of Al as a nitrogen getter and N in the HPHT alloy solvent is still indeterminate at present. In order to investigate the reaction of Al and N in the HPHT alloy solvent, Al and A1N are respectively added to the system of FessiNfogCoie-C (wt%, abbr. FeNiCo-C) for the synthesis of diamonds at about 5.5 Gpa and 1600K. The concentration of nitrogen in the diamonds is characterized by a micro Fourier transform infrared (micro-FTIR) spectrometer. The experimental results show that cn decreases when Al is added to the FeNiCo-C system. However, it increases when AIN is added. A reversible reaction confirms that Al and N can react and form AIN, simultaneously AIN can be decomposed into Al and N in the HPHT alloy solvent. Therefore the mechanism of eliminating the nitrogen of

  12. Mechanical Properties and Failure of Biopolymers: Atomistic Reactions to Macroscale Response.

    Science.gov (United States)

    Jung, GangSeob; Qin, Zhao; Buehler, Markus J

    2015-01-01

    The behavior of chemical bonding under various mechanical loadings is an intriguing mechanochemical property of biological materials, and the property plays a critical role in determining their deformation and failure mechanisms. Because of their astonishing mechanical properties and roles in constituting the basis of a variety of physiologically relevant materials, biological protein materials have been intensively studied. Understanding the relation between chemical bond networks (structures) and their mechanical properties offers great possibilities to enable new materials design in nanotechnology and new medical treatments for human diseases. Here we focus on how the chemical bonds in biological systems affect mechanical properties and how they change during mechanical deformation and failure. Three representative cases of biomaterials related to the human diseases are discussed in case studies, including: amyloids, intermediate filaments, and collagen, each describing mechanochemical features and how they relate to the pathological conditions at multiple scales.

  13. Expression of Putative Stem Cell Marker, Hepatocyte Nuclear Factor 4 Alpha, in Mammary Gland of Water Buffalo.

    Science.gov (United States)

    Choudhary, Ratan K; Choudhary, Shanti; Kaur, Harmanjot; Pathak, Devendra

    2016-01-01

    Buffaloes account for more than 56% of total milk production in India. Cyclic remodeling of mammary glands of human, mice, cow, sheep, and goat is determined by mammary stem cells. It is logical to assume that buffalo mammary gland will have mammary stem/progenitor cells. Thus far, no report exists on identification of buffalo mammary stem cells. Hepatocyte nuclear factor 4 alpha (HNF4A) is a candidate marker for hepatic progenitor cells and has recently been suggested as a marker of bovine mammary stem/progenitor cells. We hypothesized that ( 1 ) HNF4A identifies putative buffalo mammary stem/progenitor cells and ( 2 ) the number of HNF4A-positive cells increases during mastitis. Sixteen buffalo mammary samples were collected from a local slaughterhouse. Hematoxylin and eosin staining were performed on 5-micron thick sections and on the basis of gross examination and histomorphology of the mammary glands, physiological stages of the animals were estimated as non-lactating (n = 4), mastitis (n = 9), and prepubertal (n = 3). In total, 24048 cells were counted (5-10 microscopic fields/animal; n = 16 animals) of which, 40% cells were mammary epithelial cells (MEC) and 60% cells were the stromal cells. The percentage of MEC in non-lactating animals was higher compared to mastitic animals (47.3% vs. 37.3%), which was likely due to loss of MEC in mastitis. HNF4A staining was observed in nuclei of MEC of ducts, alveoli, and stromal cells. Basal location and low frequency of HNF4A-positive MEC (ranges from 0.4-4.5%) were consistent with stem cell characteristics. Preliminary study showed coexpression of HNF4A with MSI1 (a mammary stem cell marker in sheep), suggesting HNF4A was likely to be a putative mammary stem/progenitor cell marker in buffalo. HNF4A-positive MEC (basal and luminal; light and dark stained) tended to be higher in non-lactating than the mastitic animals (8.73 ± 1.71% vs. 4.29 ± 1.19%; P = 0.07). The first hypothesis that HNF4A identify

  14. A STUDY OF FUNDAMENTAL REACTION PATHWAYS FOR TRANSITION METAL ALKYL COMPLEXES. I. THE REACTION OF A NICKEL METHYL COMPLEX WITH ALKYNES. II. THE MECHANISM OF ALDEHYDE FORMATION IN THE REACTION OF A MOLYBDENUM HYDRIDE WITH MOLYBDENUM ALKYLS

    Energy Technology Data Exchange (ETDEWEB)

    Huggins, John Mitchell

    1980-06-01

    I. This study reports the rapid reaction under mild conditions of internal or terminal alkynes with methyl (acetyl~ acetonato) (triphenylphosphine) nickel (1) in either aromatic or ether solvents. In all cases vinylnickel products 2 are formed by insertion of the alkyne into the nickel=methyl bond. These complexes may be converted into a variety of organic products (e.g. alkenes, esters, vinyl halides) by treatment with appropriate reagents. Unsymmetrical alkynes give selectively the one regioisomer with the sterically largest substituent next to the nickel atom. In order to investigate the stereochemistry of the initial insertion, a x-ray diffraction study of the reaction of 1 with diphenylacetylene was carried out. This showed that the vinylnickel complex formed by overall trans insertion was the product of the reaction. Furthermore, subsequent slow isomerization of this complex, to a mixture of it and the corresponding cis isomer, demonstrated that this trans addition product is the kinetic product of the reaction. In studies with other alkynes, the product of trans addition was not always exclusively (or even predominantly) formed, but the ratio of the stereoisomers formed kinetically was substantially different from the thermodynamic ratio. Isotope labeling, added phosphine, and other experiments have allowed us to conclude that the mechanism of this reaction does involve initial cis addition. However, a coordinatively unsaturated vinylnickel complex is initially formed which can undergo rapid, phosphine-catalyzed cis-trans isomerization in competition with its conversion to the isolable phosphine-substituted kinetic reaction products. II. The reaction of CpMo(CO){sub 3}H (1a) with CpMo(CO){sub 3}R (2, R= CH{sub 3}, C{sub 2}H{sub 5}) at 50{degrees} C in THF gives the aldehyde RCHO and the dimers [CpMo(CO){sub 3}]{sub 2} (3a) and [CpMo(CO){sub 2}]{sub 2} (4a). Labeling one of the reactants with a methylcyclopentadienyl ligand it was possible to show that the

  15. Evaluation of Aromatic Oxidation Reactions in Seven Chemical Mechanisms with an Outdoor Chamber

    Science.gov (United States)

    Simulations using seven chemical mechanisms are intercompared against O3, NOx and hydrocarbon data from photooxidation experiments conducted at the University of North Carolina outdoor smog chamber. The mechanisms include CB4–2002, CB05, CB05-TU, a CB05 vari...

  16. Reaction Force/Torque Sensing in a Master-Slave Robot System without Mechanical Sensors

    Directory of Open Access Journals (Sweden)

    Kyoko Shibata

    2010-07-01

    Full Text Available In human-robot cooperative control systems, force feedback is often necessary in order to achieve high precision and high stability. Usually, traditional robot assistant systems implement force feedback using force/torque sensors. However, it is difficult to directly mount a mechanical force sensor on some working terminals, such as in applications of minimally invasive robotic surgery, micromanipulation, or in working environments exposed to radiation or high temperature. We propose a novel force sensing mechanism for implementing force feedback in a master-slave robot system with no mechanical sensors. The system consists of two identical electro-motors with the master motor powering the slave motor to interact with the environment. A bimanual coordinated training platform using the new force sensing mechanism was developed and the system was verified in experiments. Results confirm that the proposed mechanism is capable of achieving bilateral force sensing and mirror-image movements of two terminals in two reverse control directions.

  17. Kinetics and reaction mechanism of phenol hydroxylation catalyzed by La-Cu4FeAlCO3

    Institute of Scientific and Technical Information of China (English)

    CHEN; Chunxia; XU; Chenghua; FENG; Liangrong; SUO; Jishua

    2005-01-01

    The present work synthesizes La-Cu4FeAlCO3 catalyst under microwave irradiation and characterizes its structure using XRD and IR techniques. The results show that the obtained La-Cu4FeAlCO3 has a hydrotalcite structure. In the phenol hydroxylation with H2O2 catalyzed by La-Cu4FeAlCO3, the effects of reaction time and phenol/H2O2 molar ratio on the phenol hydroxylation, and relationships between the initial hydroxylation rate with concentration of the catalyst, phenol, H2O2 and reaction temperature are also investigated in details. It is shown the phenol conversion can reach 50.09% (mol percent) in the phenol hydroxylation catalyzed by La-Cu4FeAlCO3, under the reaction conditions of the molar ratio of phenol/H2O2 1/2, the amount ratio of phenol/catalyst 20, reaction temperature 343 K, reaction time 120 min, 10 mL distilled water as solvent. Moreover, a kinetic equation of and the activation energy of Ea=58.37 kJ/mol are obtained according to the kinetic studies. Due to the fact that the HO-Cu+-OH species are detected in La-Cu4FeAlCO3/H2O2 system by XPS, the new mechanism about the generation of hydroxyl free radicals in the phenol hydroxylation is proposed, which is supposed that HO-Cu+-OH species are transition state in this reaction.

  18. Mechanism for the growth of polycyclic aromatic hydrocarbons from the reactions of naphthalene with cyclopentadienyl and indenyl.

    Science.gov (United States)

    Xu, Fei; Shi, Xiangli; Zhang, Qingzhu; Wang, Wenxing

    2016-11-01

    Polycyclic aromatic hydrocarbons (PAHs) are globally concerned atmospheric particle-bound pollutants due to their toxicities. A mechanistic understanding of their formation from other environmental sources is of crucial importance for successful prevention of PAH. In the present work, the formation and growth mechanism of PAHs from the reactions of naphthalene with the cyclopentadienyl and indenyl radicals was investigated by using the hybrid density functional theory (DFT) at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants for the crucial elementary steps were deduced with the aid of the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution. The formation of PAHs was involved in six elementary processes including: the addition reaction, ring closure, intramolecular H-shift, C-C cleavage, intramolecular H-shift and unimolecular elimination of CH3 or H. The C-C cleavage steps were revealed as the rate determining steps due to the extremely high barrier. At high temperature conditions like the combustion and pyrolysis of many hydrocarbons, the main products are phenanthrene, 4-methyl-phenanthrene and 1-methyl-phenanthrene from the reactions of naphthalene and cyclopentadienyl, and benzo(a)anthracene, 12-methyl-phenanthrene and 7-methyl-phenanthrene from the reactions of naphthalene and indenyl radicals. The reaction of naphthalene with indenyl radical is slightly more difficult than the reaction of naphthalene with cyclopentadienyl radical because of the bigger HOMO-LUMO orbital energy difference of naphthalene with indenyl relative to that of naphthalene with cyclopentadienyl. PMID:27538266

  19. Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

    Energy Technology Data Exchange (ETDEWEB)

    Ham, Hyung Chul; Hwang, Gyeong S., E-mail: gshwang@che.utexas.edu [Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712 (United States); Manogaran, Dhivya [Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712 (United States); Lee, Kang Hee; Jin, Seon-ah; You, Dae Jong; Pak, Chanho [Energy Lab, Samsung Advanced Institute of Technology, Samsung Electronics Co., Ltd., Suwon (Korea, Republic of); Kwon, Kyungjung [Department of Energy and Mineral Resources Engineering, Sejong University, Seoul 143-747 (Korea, Republic of)

    2013-11-28

    Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd{sub 3}Co alloy catalysts toward oxygen reduction reaction (ORR) can be enhanced by adding a small amount of Ir. While Ir tends to favorably exist in the subsurface layers, the underlying Ir atoms are found to cause a substantial modification in the surface electronic structure. As a consequence, we find that the activation barriers of O/OH hydrogenation reactions are noticeably lowered, which would be mainly responsible for the enhanced ORR activity. Furthermore, our study suggests that the presence of Ir in the near-surface region can suppress Co out-diffusion from the Pd{sub 3}Co substrate, thereby improving the durability of Pd-Ir-Co catalysts. We also discuss the relative roles played by Ir and Co in enhancing the ORR activity relative to monometallic Pd catalysts.

  20. Level density and mechanism of deuteron-induced reactions on 54,58,56Fe

    Science.gov (United States)

    Ramirez, A. P. D.; Voinov, A. V.; Grimes, S. M.; Byun, Y.; Brune, C. R.; Massey, T. N.; Akhtar, S.; Dhakal, S.; Parker, C. E.

    2015-07-01

    Deuteron elastic cross sections, as well as neutron, proton, and α -particle emission spectra, from d + 54,58,56Fe reactions have been measured with deuteron beam energies of 5, 7, and 9 MeV. Optical model parameters have been tested against our experimental data. The fraction of total reaction cross section responsible for the formation of compound nuclei has been deduced from the angular distributions. The degree of discrepancy between calculated and experimental compound cross sections was found to increase with increasing neutron number. The nuclear level densities of the residual nuclei 57Co, 55Co, 57Fe, 55Fe, 52Mn, 54Mn have been deduced from the compound double differential cross sections. The Gilbert-Cameron model with Iljinov parameter systematics [A. S. Iljinov and M. V. Mebel, Nucl. Phys. A 543, 517 (1992)], 10.1016/0375-9474(92)90278-R was found to have a good agreement with our results.

  1. Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

    Science.gov (United States)

    Ham, Hyung Chul; Manogaran, Dhivya; Lee, Kang Hee; Kwon, Kyungjung; Jin, Seon-ah; You, Dae Jong; Pak, Chanho; Hwang, Gyeong S.

    2013-11-01

    Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd3Co alloy catalysts toward oxygen reduction reaction (ORR) can be enhanced by adding a small amount of Ir. While Ir tends to favorably exist in the subsurface layers, the underlying Ir atoms are found to cause a substantial modification in the surface electronic structure. As a consequence, we find that the activation barriers of O/OH hydrogenation reactions are noticeably lowered, which would be mainly responsible for the enhanced ORR activity. Furthermore, our study suggests that the presence of Ir in the near-surface region can suppress Co out-diffusion from the Pd3Co substrate, thereby improving the durability of Pd-Ir-Co catalysts. We also discuss the relative roles played by Ir and Co in enhancing the ORR activity relative to monometallic Pd catalysts.

  2. Reaction mechanisms in collisions induced by 8B beam close to the barrier

    CERN Multimedia

    The aim of the proposed experiment is to investigate on the reaction dynamics of proton-halo induced collisions at energies around the Coulomb barrier where coupling to continuum effects are expected to be important. We propose to measure $^{8}$B+$^{64}$Zn elastic scattering angular distribution together with the measurement, for the first time, of p-$^{7}$Be coincidences coming from transfer and/or break-up of $^{8}$B. The latter will allow a better understanding of the relative contribution of elastic $\\textit{vs}$ non-elastic break-up in reactions induced by extremely weakly-bound nuclei. We believe that with the availability of the post accelerated $^{8}$B beam at REX-ISOLDE we will be able to collect for the first time high quality data for the study of such an important topic.

  3. Rate constant and mechanism for the reaction of hydroxyl radical with formic acid

    Energy Technology Data Exchange (ETDEWEB)

    Jolly, G.S.; McKenney, D.J.; Singleton, D.L.; Paraskevopoulos, G.; Bossard, A.R.

    1986-11-20

    The rate constants for the reaction of OH with the monomer and dimer of formic acid have been determined at 296 K by a laser photolysis-resonance absorption technique. The OH radicals were generated by photolysis of formic acid at 222 nm with a KrCl excimer laser and were monitored by time-resolved absorption at several resonance lines of the (0,0) band of the A/sup 2/..sigma../sup +/-X/sup 2/II transition. The rate constant for the monomer was found to be 2.95 x 10/sup 11/ cm/sup 3/ mol/sup -1/ s/sup -1/. The dimer is much less reactive. Experiments with small amounts of oxygen added indicate that H atoms are formed during the reaction. The results can be interpreted as indicating significantly more abstraction of hydrogen by OH from the -OH bond than from the -CH bond of formic acid.

  4. Study of components and statistical reaction mechanism in simulation of nuclear process for optimized production of 64Cu and 67Ga medical radioisotopes using TALYS, EMPIRE and LISE++ nuclear reaction and evaporation codes

    International Nuclear Information System (INIS)

    Production of medical radioisotopes is one of the most important tasks in the field of nuclear technology. These radioactive isotopes are mainly produced through variety nuclear process. In this research, excitation functions and nuclear reaction mechanisms are studied for simulation of production of these radioisotopes in the TALYS, EMPIRE and LISE++ reaction codes, then parameters and different models of nuclear level density as one of the most important components in statistical reaction models are adjusted for optimum production of desired radioactive yields

  5. Actinide complexation kinetics: rate and mechanism of dioxoneptunium (V) reaction with chlorophosphonazo III

    International Nuclear Information System (INIS)

    Rates of complex formation and dissociation in NpO2+- Chlorophosphonazo III (2,7-bis(4-chloro-2-phosphonobenzeneazo)-1,8- dihydroxynapthalene-3,6-disulfonic acid)(CLIII) were investigated by stopped-flow spectrophotometry. Also, limited studies were made of the rates of reaction of La3+, Eu3+, Dy3+, and Fe3+ with CLIII. Rate determining step in each system is an intramolecular process, the NpO2+-CLIII reaction proceeding by a first order approach to equilibrium in the acid range from 0.1 to 1.0 M. Complex formation occurs independent of acidity, while both acid dependent and independent dissociation pathways are observed. Activation parameters for the complex formation reaction are ΔH=46.2±0.3 kJ/m and ΔS=7± J/mK (I=1.0 M); these for the acid dependent and independent dissociation pathways are ΔH=38.8±0.6 kJ/m, ΔS=-96±18 J/mK, ΔH=70.0± kJ/m, and ΔS=17±1 J/mK, respectively. An isokinetic relationship is observed between the activation parameters for CLIII complex formation with NpO2+, UO22+, Th4+, and Zr4+. Rates of CLIII complex formation reactions for Fe3+, Zr4+, NpO2+, UO22+, Th4+, La3+, Eu3+, and Dy3+ correlate with cation radius rather than charge/radius ratio

  6. Ultrahigh Vacuum Studies of the Kinetics and Reaction Mechanisms of Ozone with Surface-Bound Fullerenes

    OpenAIRE

    Davis, Erin Durke

    2011-01-01

    Acquiring in depth knowledge of the ozone oxidation of surface-bound fullerenes advances the understanding of fullerene fate in the environment, as well as the reactivity of ozone with carbonaceous nanomaterials. Recent ultrahigh vacuum studies of the reaction of gasphase ozone with surface-bound fullerenes have made it possible to observe the formation and subsequent thermal decomposition of the primary ozonide (PO). As the use of nanomaterials, such as C60, continues to incre...

  7. The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxyl radical

    OpenAIRE

    Huang, D.; X. Zhang; Chen, Z M; Zhao, Y.; X. L. Shen

    2011-01-01

    Aqueous phase chemical processes of organic compounds in the atmosphere have received increasing attention, partly due to their potential contribution to the formation of secondary organic aerosol (SOA). Here, we analyzed the aqueous OH-initiated oxidation of isoprene and its reaction products including carbonyl compounds and organic acids, regarding the acidity and temperature as in-cloudy conditions. We also performed a laboratory simulation to improve our understanding of the kinetics and ...

  8. Studies of Atmospheric Chemistry and Reaction Mechanisms Using Optical Spectroscopy and Mass Spectrometry

    OpenAIRE

    Liu, Yingdi

    2011-01-01

    This thesis mainly focuses on (1) development and applications of cavity ringdown spectroscopy (CRDS) to study atmospheric trace gases; (2) reactive intermediates in the alkene ozonolysis reactions using photoionization time-of-flight mass spectrometry (TOFMS); and (3) development of new methods using CRDS for thin film studies.Specifically, CRDS based instruments are developed to measure and characterize peroxy radicals in atmosphere. By combining the chemical amplification detection of pero...

  9. A DFT study on the mechanism of palladium-catalyzed divergent reactions of 1,6-enyne carbonates

    Indian Academy of Sciences (India)

    Xing Hui Zhang; Zhi Yuan Geng; Teng Niu; Ke Tai Wang

    2015-03-01

    The reaction mechanisms of palladium-catalyzed divergent reactions of 1,6-enyne carbonates have been investigated using DFT calculations at the B3LYP/6-31G(d,p) (LanL2DZ for Pd) level. Solvent effects on these reactions have been considered by the polarizable continuum model (PCM) for the solvent (DMF). The formation of vinylidenepyridines and vinylidenepyrrolidines were generated through 5-exo-dig cyclization or 6-endo-dig cyclization. Our calculation results suggested the following: (i) The first step of the whole cycle is the rate-determining step, which causes allenic palladium intermediate through two plausible pathways. This intermediate provides the corresponding products and releases the palladium catalyst by a subsequent hydrogen transfer and elimination process. (ii) For the catalyst CH3OPdH, the reaction could occur through two possible pathways, but 5-exo-dig cyclization is favoured over 6-endo-dig cyclization. However, when the hydrogen atom is substituted with a phenyl group, the energy barriers for 5-exo-dig cyclization or 6-endo-dig cyclization become relatively high, 18.0–28.5 kcal/mol. The computational results provide good explanation for the experimental observations.

  10. Mechanism and kinetic study on the gas-phase reactions of OH radical with carbamate insecticide isoprocarb

    Science.gov (United States)

    Zhang, Chenxi; Yang, Wenbo; Bai, Jing; Zhao, Yuyang; Gong, Chen; Sun, Xiaomin; Zhang, Qingzhu; Wang, Wenxing

    2012-12-01

    As one of the most important carbamate insecticides, isoprocarb [2-(1-methylethyl) phenyl methylcarbamate, MIPC] is widely used in agricultural and cotton spraying. The atmospheric chemical reaction mechanism and kinetics of MIPC with OH radical have been researched using the density functional theory in this paper. The study shows that OH radical is more easily added to the C atoms of aromatic ring than to carbon-oxygen double bond, while the H atom is abstracted more difficulty from -CONH- group and aromatic ring than from the -CH3- group and the -CH- group. At room temperature, the total rate constant of MIPC with OH radical is about 5.1 × 10-12 cm3 molecule-l s-l. OH radical addition reaction and H atom abstraction reaction are both important for the OH-initiated reaction of MIPC. The energy-rich adducts (MIPC-OH) and the MIPC's radical isomers are open-shell activated radicals and can be further oxidized in the atmosphere.

  11. Theoretical Studies on the Reaction Mechanisms of C3H2 (cyclopropenylidene) and O(3P) Radicals

    Institute of Scientific and Technical Information of China (English)

    XlE Xiaohua; SHEN Wei; HE Rongxing; ZHANG Jinsheng; LI Ming

    2009-01-01

    The complex potential energy surface for the reaction of C3H2 (cyclopropenylidene) with O(3p) was explored computationally using a density functional and ab initio QCISD(T) methods. The geometries of all the stationary points (transition states, intermediates and products) were fully optimized at the B3LYP/6-311++G** computa-tional level, and the single point calculation including full population analysis was performed by employing QCISD(T). Our results show that the product P1 (C2H+HCO) is the major product, while the products P2 (C2H2+ CO) and P3 (HC3O+H) are minor products, as confirmed by experiment. Product P1 could be gained through the path: R→IM1→IM2→P1, and the C3H2+O(3P) reaction was expected to be rapid. So, the C3H2+O(3p) reaction may be an efficient strategy for producing C2H using cyclopropenylidene in atmosphere. The present results can lead us to understand deeply the mechanism of the title reaction.

  12. The Effect of Mechanical Vibration Stimulation of Perception Subthreshold on the Muscle Force and Muscle Reaction Time of Lower Leg

    Science.gov (United States)

    Kim, Huigyun; Kwak, Kiyoung; Kim, Dongwook

    2016-01-01

    The objective of this study is to investigate the effect of mechanical vibration stimulation on the muscle force and muscle reaction time of lower leg according to perception threshold and vibration frequency. A vibration stimulation with perception threshold intensity was applied on the Achilles tendon and tibialis anterior tendon. EMG measurement and analysis system were used to analyze the change of muscle force and muscle reaction time according to perception threshold and vibration frequency. A root-mean-square (RMS) value was extracted using analysis software and Maximum Voluntary Contraction (MVC) and Premotor Time (PMT) were analyzed. The measurement results showed that perception threshold was different from application sites of vibration frequency. Also, the muscle force and muscle reaction time showed difference according to the presence of vibration, frequency, and intensity. This result means that the vibration stimulation causes the change on the muscle force and muscle reaction time and affects the muscles of lower leg by the characteristics of vibration stimulation. PMID:27382244

  13. The Application of Transient-State Kinetic Isotope Effects to the Resolution of Mechanisms of Enzyme-Catalyzed Reactions

    Directory of Open Access Journals (Sweden)

    Harvey F. Fisher

    2013-07-01

    Full Text Available Much of our understanding of the mechanisms of enzyme-catalyzed reactions is based on steady-state kinetic studies. Experimentally, this approach depends solely on the measurement of rates of free product appearance (d[P]/dt, a mechanistically and mathematically complex entity. Despite the ambiguity of this observed parameter, the method’s success is due in part to the elaborate rigorously derived algebraic theory on which it is based. Transient-state kinetics, on the other hand, despite its ability to observe the formation of intermediate steps in real time, has contributed relatively little to the subject due in, some measure, to the lack of such a solid mathematical basis. Here we discuss the current state of existing transient-state theory and the difficulties in its realistic application to experimental data. We describe a basic analytic theory of transient-state kinetic isotope effects in the form of three novel fundamental rules. These rules are adequate to define an extended mechanism, locating the isotope-sensitive step and identifying missing steps from experimental data. We demonstrate the application of these rules to resolved component time courses of the phenylalanine dehydrogenase reaction, extending the previously known reaction by one new prehydride transfer step and two new post hydride transfer steps. We conclude with an assessment of future directions in this area.

  14. Energy transfer mechanisms in photobiological reactions. Final report, 1 April 1960--31 March 1979. [Photodynamic processes in selected biomolecules

    Energy Technology Data Exchange (ETDEWEB)

    Spikes, J.D.

    1979-03-31

    This project was concerned primarily with studies of the mechanisms of the sensitized photooxidation of selected biomolecules using a variety of phtosensitizers. Such reactions are often termed photodynamic processes. In particular we have carried out steady-state kinetic studies, flash photolysis and spectral studies, and product formation studies of the sensitized photooxidation of the five susceptible amino acids (cycteine, histidine, methonine, tryptophan, and tyrosine) and their derivatives, as well as purines and pyrimidines. A number of studies were also carried out on the mechanisms of the photodynamic inactivation of enzymes (trypsin, ribonuclease, lysozyme). Mechanism of photosensitization were studied using a variety of sensitizers including flavins, porphyrins, and a number of synthetic dyes (substituted fluoresceins, acridines, thyazines).

  15. A mechanically coupled reaction-diffusion model for predicting the response of breast tumors to neoadjuvant chemotherapy

    Science.gov (United States)

    Weis, Jared A.; Miga, Michael I.; Arlinghaus, Lori R.; Li, Xia; Bapsi Chakravarthy, A.; Abramson, Vandana; Farley, Jaime; Yankeelov, Thomas E.

    2013-09-01

    There is currently a paucity of reliable techniques for predicting the response of breast tumors to neoadjuvant chemotherapy. The standard approach is to monitor gross changes in tumor size as measured by physical exam and/or conventional imaging, but these methods generally do not show whether a tumor is responding until the patient has received many treatment cycles. One promising approach to address this clinical need is to integrate quantitative in vivo imaging data into biomathematical models of tumor growth in order to predict eventual response based on early measurements during therapy. In this work, we illustrate a novel biomechanical mathematical modeling approach in which contrast enhanced and diffusion weighted magnetic resonance imaging data acquired before and after the first cycle of neoadjuvant therapy are used to calibrate a patient-specific response model which subsequently is used to predict patient outcome at the conclusion of therapy. We present a modification of the reaction-diffusion tumor growth model whereby mechanical coupling to the surrounding tissue stiffness is incorporated via restricted cell diffusion. We use simulations and experimental data to illustrate how incorporating tissue mechanical properties leads to qualitatively and quantitatively different tumor growth patterns than when such properties are ignored. We apply the approach to patient data in a preliminary dataset of eight patients exhibiting a varying degree of responsiveness to neoadjuvant therapy, and we show that the mechanically coupled reaction-diffusion tumor growth model, when projected forward, more accurately predicts residual tumor burden at the conclusion of therapy than the non-mechanically coupled model. The mechanically coupled model predictions exhibit a significant correlation with data observations (PCC = 0.84, p 4 fold reduction in model/data error (p = 0.02) as compared to the non-mechanically coupled model.

  16. Reaction mechanisms in the geopolymeric conversion of inorganic waste to useful products.

    Science.gov (United States)

    van Deventer, J S J; Provis, J L; Duxson, P; Lukey, G C

    2007-01-31

    High-performance materials for construction, waste immobilisation and an ever-growing range of niche applications are produced by the reaction sequence known as 'geopolymerisation'. In this process, an alkaline activating solution reacts with a solid aluminosilicate source, with solidification possible within minutes and very rapid early strength development. Geopolymers have been observed to display remarkable chemical and thermal stability, but due to their largely X-ray amorphous nature have only recently been accurately characterised. It has previously been shown that both fly ash and ground granulated blast furnace slag are highly effective as solid constituents of geopolymer reaction slurries, providing readily soluble alumina and silica that undergo a dissolution-reorientation-solidification process to form a geopolymeric material. Here a conceptual model for geopolymerisation is presented, allowing elucidation of the individual mechanistic steps involved in this complex and rapid process. The model is based on the reactions known to occur in the weathering of aluminosilicate minerals under alkaline conditions, which occur in a highly accelerated manner under the conditions required for geopolymerisation. Transformation of the waste materials to the mixture of gel and nanocrystalline/semicrystalline phases comprising the geopolymeric product is described. Presence of calcium in the solid waste materials affects the process of geopolymerisation by providing extra nucleation sites for precipitation of dissolved species, which may be used to tailor setting times and material properties if desired. Application of geopolymer technology in remediation of toxic or radioactive contaminants will depend on the ability to analyse and predict long-term durability and stability based on initial mix formulation. The model presented here provides a framework by which this will be made possible.

  17. Photodeamination Reaction Mechanism in Aminomethyl p-Cresol Derivatives: Different Reactivity of Amines and Ammonium Salts.

    Science.gov (United States)

    Škalamera, Đani; Bohne, Cornelia; Landgraf, Stephan; Basarić, Nikola

    2015-11-01

    Derivatives of p-cresol 1-4 were synthesized, and their photochemical reactivity, acid-base, and photophysical properties were investigated. The photoreactivity of amines 1 and 3 is different from that for the corresponding ammonium salts 2 and 4. All compounds have low fluorescence quantum yields because the excited states undergo deamination reactions, and for all cresols the formation of quinone methides (QMs) was observed by laser flash photolysis. The reactivity observed is a consequence of the higher acidity of the S1 states of these p-cresols and the ability for excited-state intramolecular proton transfer (ESIPT) to occur in the case of 1 and 3, but not for salts 2 and 4. In aqueous solvent, deamination depends largely on the prototropic form of the molecule. The most efficient deamination takes place when monoamine is in the zwitterionic form (pH 9-11) or diamine is in the monocationic form (pH 7-9). QM1, QM3, and QM4 react with nucleophiles, and QM1 exhibits a shorter lifetime when formed from 1 (τ in CH3CN = 5 ms) than from 2 (τ in CH3CN = 200 ms) due to the reaction with eliminated dimethylamine, which acts as a nucleophile in the case of QM1. Bifunctional QM4 undergoes two types of reactions with nucleophiles, giving adducts or new QM species. The mechanistic diversity uncovered is of significance to biological systems, such as for the use of bifunctional QMs to achieve DNA cross-linking. PMID:26461794

  18. Reaction Kinetics and Oxidation Mechanisms of the Conversion of Pyrite to Ferrous Sulphate: A Moessbauer Spectroscopy Study

    International Nuclear Information System (INIS)

    Pyrite undergoes a series of exothermic reactions during mine roasting to porous hematite. At low temperatures, the first non-refractive phase to form is ferrous sulphate and could be a cheaper alternative to hematite roasting for the mining industry. In this study, pyrite powder is heated in air at temperatures between 200 and 370 deg. C for 1 to 256 h in a temperature and time series. The rate of oxidation of pyrite to ferrous sulphate is modelled by combining the Arrhenius equation with the Weibull function to extract reliable thermodynamic data, including the energy of activation, the frequency factor and the overall order of reaction. From the thermodynamic data obtained, two possible oxidation mechanisms are recognized, depending on the bond dissociation energies of the S-S and Fe-S bonds in pyrite.

  19. Reaction Kinetics and Oxidation Mechanisms of the Conversion of Pyrite to Ferrous Sulphate: A Moessbauer Spectroscopy Study

    Energy Technology Data Exchange (ETDEWEB)

    Ferrow, Embaie A., E-mail: embaie.ferrow@geol.lu.se; Mannerstrand, Maria [Lund University, GeoBiosphere Science Centre, Department of Geology, Lithosphere Biosphere Science (Sweden); Sjoeberg, Bosse [Swedish Museum of Natural History (Sweden)

    2005-06-15

    Pyrite undergoes a series of exothermic reactions during mine roasting to porous hematite. At low temperatures, the first non-refractive phase to form is ferrous sulphate and could be a cheaper alternative to hematite roasting for the mining industry. In this study, pyrite powder is heated in air at temperatures between 200 and 370 deg. C for 1 to 256 h in a temperature and time series. The rate of oxidation of pyrite to ferrous sulphate is modelled by combining the Arrhenius equation with the Weibull function to extract reliable thermodynamic data, including the energy of activation, the frequency factor and the overall order of reaction. From the thermodynamic data obtained, two possible oxidation mechanisms are recognized, depending on the bond dissociation energies of the S-S and Fe-S bonds in pyrite.

  20. Electron spin interactions in chemistry and biology fundamentals, methods, reactions mechanisms, magnetic phenomena, structure investigation

    CERN Document Server

    Likhtenshtein, Gertz

    2016-01-01

    This book presents the versatile and pivotal role of electron spin interactions in nature. It provides the background, methodologies and tools for basic areas related to spin interactions, such as spin chemistry and biology, electron transfer, light energy conversion, photochemistry, radical reactions, magneto-chemistry and magneto-biology. The book also includes an overview of designing advanced magnetic materials, optical and spintronic devices and photo catalysts. This monograph appeals to scientists and graduate students working in the areas related to spin interactions physics, biophysics, chemistry and chemical engineering.

  1. Reaction mechanisms in massive nuclei collisions and perspectives for synthesis of heavier superheavy elements

    International Nuclear Information System (INIS)

    We discuss a hardship in synthesis of heaviest super heavy elements in massive nuclei reactions due to the hindrance to complete fusion of reacting nuclei caused on the onset of quasifission process which strongly competes with complete fusion and due to the strong increase of fission yields along the de-excitation cascade of the compound nucleus in comparison with the evaporation residue formation. The hindrance to formation of compound nucleus and evaporation residue is determined by the characteristic of the entrance channel. (authors)

  2. Nuclear excitations and reaction mechanisms: a research proposal (renewal) and report of progress

    International Nuclear Information System (INIS)

    Research progress is reported on the following subjects: (1) diamagnetism, gauge transformations and sum rules, (2) quantal motion in an electric field, (3) a theorem concerning quadrupole absorption and scattering of photons, (4) excitation of natural parity states by Raman scattering in nuclei, (5) retarded E1 transitions and isoscaler giant dipole resonances, (6) low energy photon scattering from nuclei, (7) few-body models of nuclear reactions, (8) three- and four-nucleon configuration space calculations, (9) time-dependent few-body calculations, (10) atomic and molecular structure calculations, (11) bound state approximations, (12) extended Faddeev theory, (13) configuration-space techniques, and (14) time-dependent approach to scattering problems

  3. Proposed chemical mechanisms leading to secondary organic aerosol in the reactions of aliphatic amines with hydroxyl and nitrate radicals

    Science.gov (United States)

    Price, Derek J.; Clark, Christopher H.; Tang, Xiaochen; Cocker, David R.; Purvis-Roberts, Kathleen L.; Silva, Philip J.

    2014-10-01

    The presence and importance of amines in the atmosphere, including aliphatic amines, continues to gain more attention. The atmospheric reaction mechanisms of these amines with key atmospheric radicals are important to predict both daytime and nighttime atmospheric chemistry. While previous studies have focused on the production of amine salts, this analysis looks at the importance of peroxy radical reactions to the formation of secondary organic aerosol. Atmospheric oxidation mechanisms are presented to explain the observed chemistry. A series of environmental chamber experiments were conducted in which aliphatic tertiary and secondary amines were reacted with either hydroxyl radical (OH) or nitrate radical (NO3). Chemical composition of the aerosol products was obtained with a High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a Particle Into Liquid Sampler Time of Flight Mass Spectrometer (PILS-ToF-MS), while the chemical composition of the gas-phase products was obtained with a Selected Ion Flow Tube Mass Spectrometer (SIFT-MS). A number of aerosol-phase mass spectra showed highly oxidized fragments at a much higher molecular weight (MW) than the amine precursor. It is proposed that these larger compounds are oligomers formed through peroxy radical reactions with hydrogen rearrangement. Another reaction pathway observed was the formation of amine salts. The relative importance of each pathway to the overall production of aerosol is found to be dependent on the type of amine and oxidant. For example, the oligomers were observed in the tertiary methyl amines, while the formation of amine salts was more prevalent in the secondary and tertiary ethyl amines.

  4. Multi-step reaction mechanism for F atom interactions with organosilicate glass and SiO x films

    Science.gov (United States)

    Mankelevich, Yuri A.; Voronina, Ekaterina N.; Rakhimova, Tatyana V.; Palov, Alexander P.; Lopaev, Dmitry V.; Zyryanov, Sergey M.; Baklanov, Mikhail R.

    2016-09-01

    An ab initio approach with the density functional theory (DFT) method was used to study F atom interactions with organosilicate glass (OSG)-based low-k dielectric films. Because of the complexity and significant modifications of the OSG surface structure during the interaction with radicals and etching, a variety of reactions between the surface groups and thermal F atoms can happen. For OSG film etching and damage, we propose a multi-step mechanism based on DFT static and dynamic simulations, which is consistent with the previously reported experimental observations. The important part of the proposed mechanism is the formation of pentavalent Si atoms on the OSG surface due to a quasi-chemisorption of the incident F atoms. The revealed mechanism of F atom incorporation into the OSG matrix explains the experimentally observed phenomena of fast fluorination without significant modification of the chemical structure. We demonstrate that the pentavalent Si states induce the weakening of adjacent Si–O bonds and their breaking under F atom flux. The calculated results allow us to propose a set of elementary chemical reactions of successive removal of CH3 and CH2 groups and fluorinated SiO x matrix etching.

  5. Atomistic Conversion Reaction Mechanism of WO3 in Secondary Ion Batteries of Li, Na, and Ca

    Energy Technology Data Exchange (ETDEWEB)

    He, Yang; Gu, Meng; Xiao, Hai Yan; Luo, Langli; Shao, Yuyan; Gao, Fei; Du, Yingge; Mao, Scott X.; Wang, Chong M.

    2016-05-13

    Reversible insertion and extraction of ionic species into a host lattice governs the basic operating principle for both rechargeable battery (such as lithium batteries) and electrochromic devices (such as ANA Boeing 787-8 Dreamliner electrochromic window). Intercalation and/or conversion are two fundamental chemical processes for some materials in response to the ion insertion. The interplay between these two chemical processes has never been established. It is speculated that the conversion reaction is initiated by ion intercalation. However, experimental evidence of intercalation and subsequent conversion remains unexplored. Here, using in situ HRTEM and spectroscopy, we captured the atomistic conversion reaction processes during lithium, sodium and calcium ion insertion into tungsten trioxide (WO3) single crystal model electrodes. An intercalation step right prior to conversion is explicitly revealed at atomic scale for the first time for these three ion species. Combining nanoscale diffraction and ab initio molecular dynamics simulations, it is found that, beyond intercalation, the inserted ion-oxygen bonding formation destabilized the transition-metal framework which gradually shrunk, distorted and finally collapsed to a pseudo-amorphous structure. This study provides a full atomistic picture on the transition from intercalation to conversion, which is of essential for material applications in both secondary ion batteries and electrochromic devices.

  6. Reactions of clofibric acid with oxidative and reductive radicals—Products, mechanisms, efficiency and toxic effects

    International Nuclear Information System (INIS)

    The degradation of clofibric acid induced by hydroxyl radical, hydrated electron and O2−∙/HO2∙ reactive species was studied in aqueous solutions. Clofibric acid was decomposed more effectively by hydroxyl radical than by hydrated electron or O2−∙/HO2∙. Various hydroxylated, dechlorinated and fragmentation products have been identified and quantified. A new LC–MS method was developed based on 18O isotope labeling to follow the formation of hydroxylated derivatives of clofibric acid. Possible degradation pathways have been proposed. The overall degradation was monitored by determination of sum parameters like COD, TOC and AOX. It was found that the organic chlorine degrades very effectively prior to complete mineralization. After the treatment no toxic effect was found according to Vibrio fischeri tests. However, at early stages some of the reaction products were more harmful than clofibric acid. - Highlights: • Clofibric acid is effectively degraded by OH radical. • Main primary and secondary products are hydroxylated and dihydroxylated phenyl type derivatives of clofibric acid. • In air saturated aqueous solutions O2 plays an important role in decomposition of the aromatic structure. • A new LC–MS method with 18O-labeling was developed. • Early stage reaction products are more toxic to bacteria Vibrio fischeri than clofibric acid

  7. Polyoxymetalate liquid-catalyzed polyol fuel cell and the related photoelectrochemical reaction mechanism study

    Science.gov (United States)

    Wu, Weibing; Liu, Wei; Mu, Wei; Deng, Yulin

    2016-06-01

    A novel design of liquid catalyzed fuel cell (LCFC), which uses polyoxometalates (POMs) as the photocatalyst and charge carrier has been reported previously. In this paper, the adaptability of biomass fuels (e.g., glycerol and glucose) to the LCFC and corresponding cell performance were studied in detail here. An interesting finding that greatly differs from conventional fuel cell is that high molecular weight fuels rather than small molecule fuels (e.g., methanol and ethylene glycol) are favored by the novel LCFC with respect to the power densities. The power output of LCFC strongly depends on the number and structure of hydroxyl groups in the biomass fuels. The evidence of UV-Vis and 1H NMR spectra shows that the preassociation between POM and alcohol fuels, which determines the photoelectrochemical reaction pathway of POM, is enhanced as the number of hydroxyl increases. Experimental results also demonstrate that more hydroxyl groups in the molecules lead to faster photoelectrochemical reaction between POM and fuels, higher reduction degree of POM, and further higher power output of LCFC. Our study reveals that biomass-based polyhydroxyl compounds such as starch, hemicellulose and cellulose are potential high-performance fuels for LCFC.

  8. Quantum mechanical study of the β- and δ-lyase reactions during the base excision repair process: application to FPG.

    Science.gov (United States)

    Sowlati-Hashjin, Shahin; Wetmore, Stacey D

    2015-10-14

    Bacterial FPG (or MutM) is a bifunctional DNA glycosylase that is primarily responsible for excising 8-oxoguanine (OG) from the genome by cleaving the glycosidic bond and the DNA backbone at the 3'- and 5'-phosphates of the damaged nucleoside. In the present work, quantum mechanical methods (SMD-M06-2X/6-311+G(2df,2p)//IEF-PCM-B3LYP/6-31G(d)) and a ring-opened Schiff base model that includes both the 3'- and 5'-phosphate groups are used to investigate the β- and δ-elimination reactions facilitated by FPG. Both the β- and δ-elimination reactions are shown to proceed through an E1cB mechanism that involves proton abstraction prior to the phosphate-ribose bond cleavage. Since transition states for the phosphate elimination reactions could not be characterized in the absence of leaving group protonation, our work confirms that the phosphate elimination reactions require protonation by a residue in the FPG active site, and can likely be further activated by additional active-site interactions. Furthermore, our model suggests that 5'-PO4 activation may proceed through a nearly isoenergetic direct (intramolecular) proton transfer involving the O4' proton of the deoxyribose of the damaged nucleoside. Regardless, our model predicts that both 3'- and 5'-phosphate protonation and elimination steps occur in a concerted reaction. Most importantly, our calculated barriers for the phosphate cleavage reactions reveal inherent differences between the β- and δ-elimination steps. Indeed, our calculations provide a plausible explanation for why the δ-elimination rather than the β-elimination is the rate-determining step in the BER facilitated by FPG, and why some bifunctional glycosylases (including the human counterpart, hOgg1) lack δ-lyase activity. Together, the new mechanistic features revealed by our work can be used in future large-scale modeling of the DNA-protein system to unveil the roles of key active sites residues in these relatively unexplored BER steps.

  9. Reaction mechanism of Ru(II) piano-stool complexes: umbrella sampling QM/MM MD study.

    Science.gov (United States)

    Futera, Zdeněk; Burda, Jaroslav V

    2014-07-15

    Biologically relevant interactions of piano-stool ruthenium(II) complexes with ds-DNA are studied in this article by hybrid quantum mechanics-molecular mechanics (QM/MM) computational technique. The whole reaction mechanism is divided into three phases: (i) hydration of the [Ru(II) (η(6) -benzene)(en)Cl](+) complex, (ii) monoadduct formation between the resulting aqua-Ru(II) complex and N7 position of one of the guanines in the ds-DNA oligomer, and (iii) formation of the intrastrand Ru(II) bridge (cross-link) between two adjacent guanines. Free energy profiles of all the reactions are explored by QM/MM MD umbrella sampling approach where the Ru(II) complex and two guanines represent a quantum core, which is described by density functional theory methods. The combined QM/MM scheme is realized by our own software, which was developed to couple several quantum chemical programs (in this study Gaussian 09) and Amber 11 package. Calculated free energy barriers of the both ruthenium hydration and Ru(II)-N7(G) DNA binding process are in good agreement with experimentally measured rate constants. Then, this method was used to study the possibility of cross-link formation. One feasible pathway leading to Ru(II) guanine-guanine cross-link with synchronous releasing of the benzene ligand is predicted. The cross-linking is an exergonic process with the energy barrier lower than for the monoadduct reaction of Ru(II) complex with ds-DNA. PMID:24865949

  10. Reaction mechanism of Ru(II) piano-stool complexes: umbrella sampling QM/MM MD study.

    Science.gov (United States)

    Futera, Zdeněk; Burda, Jaroslav V

    2014-07-15

    Biologically relevant interactions of piano-stool ruthenium(II) complexes with ds-DNA are studied in this article by hybrid quantum mechanics-molecular mechanics (QM/MM) computational technique. The whole reaction mechanism is divided into three phases: (i) hydration of the [Ru(II) (η(6) -benzene)(en)Cl](+) complex, (ii) monoadduct formation between the resulting aqua-Ru(II) complex and N7 position of one of the guanines in the ds-DNA oligomer, and (iii) formation of the intrastrand Ru(II) bridge (cross-link) between two adjacent guanines. Free energy profiles of all the reactions are explored by QM/MM MD umbrella sampling approach where the Ru(II) complex and two guanines represent a quantum core, which is described by density functional theory methods. The combined QM/MM scheme is realized by our own software, which was developed to couple several quantum chemical programs (in this study Gaussian 09) and Amber 11 package. Calculated free energy barriers of the both ruthenium hydration and Ru(II)-N7(G) DNA binding process are in good agreement with experimentally measured rate constants. Then, this method was used to study the possibility of cross-link formation. One feasible pathway leading to Ru(II) guanine-guanine cross-link with synchronous releasing of the benzene ligand is predicted. The cross-linking is an exergonic process with the energy barrier lower than for the monoadduct reaction of Ru(II) complex with ds-DNA.

  11. Mechanical demand and multijoint control during landing depend on orientation of the body segments relative to the reaction force.

    Science.gov (United States)

    McNitt-Gray, J L; Hester, D M; Mathiyakom, W; Munkasy, B A

    2001-11-01

    The purpose of this study was to determine how diverse momentum conditions and anatomical orientation at contact influences mechanical loading and multijoint control of the reaction force during landings. Male collegiate gymnasts (n=6) performed competition style landings (n=3) of drop jumps, front saltos, and back saltos from a platform (0.72 m) onto landing mats (0.12 m). Kinematics (200 fps), reaction forces (800 Hz) and muscle activation patterns (surface EMG, 1600 Hz) of seven lower extremity muscles were collected simultaneously. Between-task differences in segment orientation relative to the reaction force contributed to significant between-task differences in knee and hip net joint moments (NJM) during the impact phase. During the stabilization phase, ankle, knee, and hip NJMs acted to control joint flexion. Between-task differences in muscle activation patterns indicated that gymnasts scaled biarticular muscle activation to accommodate for between-task differences in NJM after contact. Activation of muscles on both sides of the joint suggests that impedance like control was used to stabilize the joints and satisfy the mechanical demand imposed on the lower extremity. Between-subject differences in the set of muscles used to control total body center of mass (TBCM) trajectory and achieve lower extremity NJMs suggests that control of multijoint movements involving impact needs to incorporate mechanical objectives at both the total body and local level. The functional consequences of such a control structure may prove to be an asset to gymnasts, particularly when required to perform a variety of landing tasks under a variety of environmental constraints.

  12. Hydrogenation of n-butyraldehyde on copper-containing catalysts. III. Isotope investigation of the reaction mechanism

    International Nuclear Information System (INIS)

    The mechanism of the hydrogenation of n-butyraldehyde on a nickel-promoted copper-zinc-aluminum-calcium catalyst at 120-200 degree C was investigated by the isotope method using deuterium. Analysis of the mass spectra and the PMR spectra of the products of the reactions of deuteration and isotope exchange show that isotope in dissociatively adsorbed form is added directly at the C=O bond of the adsorbed aldehyde, and not at the C=C bond of the enol form

  13. High-resolution nuclear magnetic resonance spectroscopy studies of polysaccharides crosslinked by sodium trimetaphosphate: a proposal for the reaction mechanism.

    Science.gov (United States)

    Lack, Stéphane; Dulong, Virginie; Picton, Luc; Le Cerf, Didier; Condamine, Eric

    2007-05-21

    An NMR spectroscopy study ((31)P, (1)H, (13)C) of the postulated crosslinking mechanism of sodium trimetaphosphate (STMP) on polysaccharides is reported using methyl alpha-D-glucopyranoside as a model. In a first step, reaction of STMP with Glc-OMe gives grafted sodium tripolyphosphate (STPP(g)). On the one hand, STTP(g) can react with a second alcohol functionality to give a crosslinked monophosphate. On the other hand, a monophosphate (grafted phosphate) could be obtained by alkaline degradation of STPP(g). NMR spectroscopy allows to detect the various species formed and to obtain the crosslinking density of STMP-polysaccharides hydrogels. PMID:17303095

  14. Apparent anti-Woodward-Hoffmann addition to a nickel bis(dithiolene) complex: the reaction mechanism involves reduced, dimetallic intermediates.

    Science.gov (United States)

    Dang, Li; Shibl, Mohamed F; Yang, Xinzheng; Harrison, Daniel J; Alak, Aiman; Lough, Alan J; Fekl, Ulrich; Brothers, Edward N; Hall, Michael B

    2013-04-01

    Nickel dithiolene complexes have been proposed as electrocatalysts for alkene purification. Recent studies of the ligand-based reactions of Ni(tfd)2 (tfd = S2C2(CF3)2) and its anion [Ni(tfd)2](-) with alkenes (ethylene and 1-hexene) showed that in the absence of the anion, the reaction proceeds most rapidly to form the intraligand adduct, which decomposes by releasing a substituted dihydrodithiin. However, the presence of the anion increases the rate of formation of the stable cis-interligand adduct, and decreases the rate of dihydrodithiin formation and decomposition. In spite of both computational and experimental studies, the mechanism, especially the role of the anion, remained somewhat elusive. We are now providing a combined experimental and computational study that addresses the mechanism and explains the role of the anion. A kinetic study (global analysis) for the reaction of 1-hexene is reported, which supports the following mechanism: (1) reversible intraligand addition, (2) oxidation of the intraligand addition product prior to decomposition, and (3) interligand adduct formation catalyzed by Ni(tfd)2(-). Density functional theory (DFT) calculations were performed on the Ni(tfd)2/Ni(tfd)2(-)/ethylene system to shed light on the selectivity of adduct formation in the absence of anion and on the mechanism in which Ni(tfd)2(-) shifts the reaction from intraligand addition to interligand addition. Computational results show that in the neutral system the free energy of activation for intraligand addition is lower than that for interligand addition, in agreement with the experimental results. The computations predict that the anion enhances the rate of the cis-interligand adduct formation by forming a dimetallic complex with the neutral complex. The [(Ni(tfd)2)2](-) dimetallic complex then coordinates ethylene and isomerizes to form a Ni,S-bound ethylene complex, which then rapidly isomerizes to the stable interligand adduct but not to the intraligand adduct

  15. Evidencing an inner-sphere mechanism for NHC-Au(I)-catalyzed carbene-transfer reactions from ethyl diazoacetate

    OpenAIRE

    Manuel R. Fructos; Juan Urbano; M. Mar Díaz-Requejo; Pérez, Pedro J

    2015-01-01

    Kinetic experiments based on the measurement of nitrogen evolution in the reaction of ethyl diazoacetate (N2CHCO2Et, EDA) and styrene or methanol catalyzed by the [IPrAu]+ core (IPr = 1,3-bis(diisopropylphenyl)imidazole-2-ylidene) have provided evidence that the transfer of the carbene group CHCO2Et to the substrate (styrene or methanol) takes place in the coordination sphere of Au(I) by means of an inner-sphere mechanism, in contrast to the generally accepted proposal of outer-sphere mechani...

  16. Study of Reaction Mechanism in the Interaction 86 MeV/A $^{12}$C with Heavy Targets

    CERN Multimedia

    2002-01-01

    Using the thin target-thin catcher techniques and the off-line analysis of the activities induced in the irradiated foils by means of singles and coincidences spectra recorded with Ge(Li) @g-rays and Si X-rays detectors, we will measure: 1) The target fragment mass and charge distribution from the interact 2) 86 MeV/A |1|2C with silver, tin and gold. 3) The target fragment average kinetic energy. 4) The target fragment angular and differential kinetic energy distributions. These measurements should allow us to better understand the heavy ion reaction mechanisms at intermediate energy.

  17. Photochemical generation of a primary vinyl cation from (E)-bromostyrene: Mechanisms of formation and reaction

    NARCIS (Netherlands)

    Gronheid, R.; Zuilhof, H.; Hellings, M.G.

    2003-01-01

    The photochemistry of (E)-bromostyrene was investigated to determine the nature of the product-forming intermediates and to clarify the mechanism of formation of vinylic cations and vinylic radicals. Both a cation- and a radical-derived product are formed, and the ionic origin of the former product

  18. Energy transfer mechanisms in photobiological reactions. Progress report, 1 August 1976--31 July 1977

    Energy Technology Data Exchange (ETDEWEB)

    Spikes, J.D.

    1977-07-31

    Progress is reported on the following studies: chemical structure of biomolecules and mechanisms of their sensitized photo-oxidation; relationships between the structure and photosensitizing efficiencies of porphyrins; effects of photodynamic treatment on mammalian tendons; and sensitized photo-oxidation of substituted uracils, methionine, other amino acids, and horse-radish peroxidase. (HLW)

  19. Synthesis of carbon C-14 labelled 2-phenyl-4-alpha-alkylaminomethyl-quinolinemethanol: a potential anti-leishmaniasis agent

    Energy Technology Data Exchange (ETDEWEB)

    Wang, T.S.T.; Fawwaz, R.A.; Heertum, R.L.van [Columbia Univ., New York, NY (United States). Coll. of Physicians and Surgeons

    1995-07-01

    Using sodium acetate, [1-{sup 14}C] as a starting material, a total of seven steps were required to synthesize the title compound. This involved acylation of ortho-dichlorobenzene to form dichloroacetophenone, [2-{sup 14}C] (I). The 2-phenyl-4-quinoline carboxylic acid, [2-{sup 14}C] (II) was prepared by the Pfitzinger reaction from (1) and dichloroisatin. Compound 11 was converted to the acid chloride (III) by reaction with SOCl{sub 2} in benzene. Grignard condensation reaction of (III) yielded 4-quinolylmethylketone, [2-{sup 14}C] (IV) which was then converted to the bromomethylketone (V). Compound V was reacted with NaBH{sub 4} to form the ethylene oxide (VI). Alkylation of the oxide yielded the title compound (VII). The overall radiochemical yield was 10.1% and the specific activity was 3.0 mCi/mmol, with a radiochemical purity of >99.5%. (author).

  20. The efficiency of self-phoretic propulsion mechanisms with surface reaction heterogeneity.

    Science.gov (United States)

    Kreissl, Patrick; Holm, Christian; de Graaf, Joost

    2016-05-28

    We consider the efficiency of self-phoretic colloidal particles (swimmers) as a function of the heterogeneity in the surface reaction rate. The set of fluid, species, and electrostatic continuity equations is solved analytically using a linearization and numerically using a finite-element method. To compare spherical swimmers of different size and with heterogeneous catalytic conversion rates, a "swimmer efficiency" functional η is introduced. It is proven that in order to obtain maximum swimmer efficiency, the reactivity has to be localized at the pole(s). Our results also shed light on the sensitivity of the propulsion speed to details of the surface reactivity, a property that is notoriously hard to measure. This insight can be utilized in the design of new self-phoretic swimmers. PMID:27250326

  1. Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures

    Science.gov (United States)

    Christopher, Phillip; Xin, Hongliang; Marimuthu, Andiappan; Linic, Suljo

    2012-12-01

    The field of heterogeneous photocatalysis has almost exclusively focused on semiconductor photocatalysts. Herein, we show that plasmonic metallic nanostructures represent a new family of photocatalysts. We demonstrate that these photocatalysts exhibit fundamentally different behaviour compared with semiconductors. First, we show that photocatalytic reaction rates on excited plasmonic metallic nanostructures exhibit a super-linear power law dependence on light intensity (rate ∝intensityn, with n > 1), at significantly lower intensity than required for super-linear behaviour on extended metal surfaces. We also demonstrate that, in sharp contrast to semiconductor photocatalysts, photocatalytic quantum efficiencies on plasmonic metallic nanostructures increase with light intensity and operating temperature. These unique characteristics of plasmonic metallic nanostructures suggest that this new family of photocatalysts could prove useful for many heterogeneous catalytic processes that cannot be activated using conventional thermal processes on metals or photocatalytic processes on semiconductors.

  2. Investigation of Surface Reaction and Degradation Mechanism of Kapton during Atomic Oxygen Exposure

    Institute of Scientific and Technical Information of China (English)

    Shuwang DUO; Meishuan LI; Yanchun ZHOU; Jingyu TONG; Gang SUN

    2003-01-01

    The erosion behavior of Kapton when exposed to atomic oxygen (AO) environment in the ground-based simulation facility was studied. The chemical and physical changes of sample surfaces after exposed to AO fluxes were investigated by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results indicated that Kapton underwent dramatically degradation, including much mass loss and change of surface morphologies; vacuum outgassing effect of Kapton was the key factor for initial mass loss in the course of atomic oxygen beam exposures. XPS analysis showed that the carbonyl group in Kapton reacted with oxygen atoms to generate CO2, then CO2 desorbed from Kapton surface. In addition, PMDA in the polyimide structure degraded due to the reaction with atomic oxygen of 5 eV.

  3. Water mediated hydrogen abstraction mechanism in the radical reaction between HOSO and NO2

    Science.gov (United States)

    Lesar, Antonija; Tušar, Simona

    2016-05-01

    The effect of water molecules on the direct hydrogen abstraction from HOSO by NO2 was investigated for the first time. Stationary points were located at the B3LYP/6-311+G(2df,2pd) and CCSD/aug-cc-pVDZ levels of theory whereas energetics was further improved by CBS-QB3 and G4 composite methods. The fractions of hydrated radical complexes were estimated in order to assess atmospheric relevance of the title reaction. The energy barrier of the water mediated process becomes negligible. The formations of post-reactive complexes from pre-reactive complexes are energetically very favorable and the processes are spontaneous suggesting that they should be very feasible under atmospheric conditions.

  4. Polymerization-induced phase separation in polyether-sulfone modified epoxy resin systems: effect of curing reaction mechanism

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Polyethersulfone (PES)-modified epoxy systems with stepwise reaction were studied throughout the entire curing process by using optical microscopes, time-resolved light scattering (TRLS), and a rheolometry instrument compared with that of chainwise polymerization. The results suggested that the phase separation process is mainly controlled by the diffusion of epoxy oligomers for stepwise mechanism system and by that of epoxy monomers for chainwise mechanism system. In case of high PES content (SPES-20%) light-scattering results showed a viscoelastic phase separation and the characteristic relaxation time of phase separation can be described well by the WLF equation. However, in the case of low PES content (SPES-14%) secondary phase separation phenomenon was observed by Optical Microscope and further demonstrated by rheological study.

  5. Mechanism for the stabilization of protein clusters above the solubility curve: the role of non-ideal chemical reactions

    CERN Document Server

    Lutsko, James F

    2016-01-01

    Dense protein clusters are known to play an important role in nucleation of protein crystals from dilute solutions. While these have generally been thought to be formed from a metastable phase, the observation of similar, if not identical, clusters above the critical point for the dilute-solution/strong-solution phase transition has thrown this into doubt. Furthermore, the observed clusters are stable for relatively long times. Because protein aggregation plays an important role in some pathologies, understanding the nature of such clusters is an important problem. One mechanism for the stabilization of such structures was proposed by Pan, Vekilov and Lubchenko and was investigated using a DDFT model which confirmed the viability of the model. Here, we revisit that model and incorporate additional physics in the form of state-dependent reaction rates. We show by a combination of numerical results and general arguments that the state-dependent rates disrupt the stability mechanism. Finally, we argue that the s...

  6. Study of the 20Ne+12C system reaction mechanisms for E(lab)20Ne=160MeV

    International Nuclear Information System (INIS)

    Coincidences between light particles (z8) are measured. The analysis of the single and coincident events shows that binary and sequentiel three body reactions, like the sequentiel break-up of the projectile, are responsible of the non relaxed part of the spectras. The relaxed component can be extracted and is compared with statistical model calculations obtained by Monte Carlo codes using the Hauser-Feshbach formalism. This prediction are consistent with the experiment for all the data. The slight discrepancies observed are reduced after a research on the parameter of the model. No evidences for incomplete fusion mechanism are observed. Even at this energy, fusion evaporation is the dominant mechanism for the system studied in this work

  7. Cure kinetics, morphologies, and mechanical properties of thermoplastic/MWCNT modified multifunctional glassy epoxies prepared via continuous reaction methods

    Science.gov (United States)

    Cheng, Xiaole

    The primary goal of this dissertation is to develop a novel continuous reactor method to prepare partially cured epoxy prepolymers for aerospace prepreg applications with the aim of replacing traditional batch reactors. Compared to batch reactors, the continuous reactor is capable of solubilizing and dispersing a broad range of additives including thermoplastic tougheners, stabilizers, nanoparticles and curatives and advancing epoxy molecular weights and viscosities while reducing energy consumption. In order to prove this concept, polyethersulfone (PES) modified 4, 4'-diaminodiphenylsulfone (44DDS)/tetraglycidyl-4, 4'-diaminodiphenylmethane (TGDDM) epoxy prepolymers were firstly prepared using both continuous reactor and batch reactor methods. Kinetic studies confirmed the chain extension reaction in the continuous reactor is similar to the batch reactor, and the molecular weights and viscosities of prepolymers were readily controlled through reaction kinetics. Atomic force microscopy (AFM) confirmed similar cured network morphologies for formulations prepared from batch and continuous reactors. Additionally tensile strength, tensile modulus and fracture toughness analyses concluded mechanical properties of cured epoxy matrices produced from both reactors were equivalent. Effects of multifunctional epoxy compositions on thermoplastics phase-separated morphologies were systematically studied using a combination of AFM with nanomechanical mapping, spectroscopic and calorimetric techniques to provide new insights to tailor cured reaction induced phase separation (CRIPS) in multifunctional epoxy blend networks. Furthermore, how resultant crosslinked glassy polymer network and phase-separated morphologies correlated with mechanical properties are discussed in detail. Multiwall carbon nanotube (MWCNT)/TGDDM epoxy prepolymers were further prepared by combining the successful strategies for advancing epoxy chemistries and dispersing nanotubes using the continuous reactor

  8. Evolution mechanism of the interfacial reaction layers in the joints of diffusion bonded Mo and Ai foils

    Institute of Scientific and Technical Information of China (English)

    LI Jinglong; ZHAO Fengkuan; YANG Weihua; XIONG Jiangtao; ZHANG Fusheng; Lü Xuechao

    2009-01-01

    Mo foil (10-20 μm in thickness) and Al foil (20-60 μm in thickness) were vacuum diffusion bonded at 600-640 ℃ under 20 MPa for 54 min-6 h. The joints were examined by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) to study the evolution mechanism of the reaction layers. The results show that Al atoms diffuse into Mo grain boundaries and form reaction products as Mo3Als, MoAl4, MoAl5 and MoAl12. The surface oxide film is eroded by the growths of the reaction products that plow into the lamellar texture of Mo grain boundaries. Mo3Al8 layer grows by "taking root" downwards and transforms into MoAl4 and MoAl5 phases upwards by absorbing Al atoms. MoAl12 layer grows up from MoAl5 layer in the same way. When the supplement of Al atoms ceases, MoAl12 transforms reversely into MoAl5 and MoAl3 into MoAl4 via the loss of Al atoms. However, MoAl4 continues to precipitate from Mo3Al8 layer. At last, there are MoAl4 and Mo3Al8 remained on the joint interface.

  9. On the reaction mechanism of the complete intermolecular O2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands.

    Science.gov (United States)

    Zapata-Rivera, Jhon; Caballol, Rosa; Calzado, Carmen J; Liakos, Dimitrios G; Neese, Frank

    2014-10-01

    The recently described intermolecular O2 transfer between the side-on Ni-O2 complex [(12-TMC)Ni-O2](+) and the manganese complex [(14-TMC)Mn](2+), where 12-TMC and 14-TMC are 12- and 14-membered macrocyclic ligands, 12-TMC=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane and 14-TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, is studied by means of DFT methods. B3LYP calculations including long-range corrections and solvent effects are performed to elucidate the mechanism. The potential energy surfaces (PESs) compatible with different electronic states of the reactants have been analyzed. The calculations confirm a two-step reaction, with a first rate-determining bimolecular step and predict the exothermic character of the global process. The relative stability of the products and the reverse barrier are in line with the fact that no reverse reaction is experimentally observed. An intermediate with a μ-η(1):η(1)-O2 coordination and two transition states are identified on the triplet PES, slightly below the corresponding stationary points of the quintet PES, suggesting an intersystem crossing before the first transition state. The calculated activation parameters and the relative energies of the two transition sates and the products are in very good agreement with the experimental data. The calculations suggest that a superoxide anion is transferred during the reaction.

  10. Effect of ferrous/ferric ions molar ratio on reaction mechanism for hydrothermal synthesis of magnetite nanoparticles

    Indian Academy of Sciences (India)

    N Mizutani; T Iwasaki; S Watano; T Yanagida; H Tanaka; T Kawai

    2008-10-01

    Magnetite nanoparticles were prepared by hydrothermal synthesis under various initial ferrous/ferric molar ratios without adding any oxidizing and reducing agents in order to clarify effects of the molar ratio on the reaction mechanism for the formation of magnetite nanoparticles. The magnetite nanoparticles prepared were characterized by a scanning electron microscope, powder X-ray diffractometer, and superconducting quantum interference device (SQUID). At the molar ratio corresponding to the stoichiometric ratio in the synthesis reaction of magnetite from ferrous hydroxide and goethite, the nucleation of magnetite crystals progressed rapidly in an initial stage of the hydrothermal synthesis, resulting in formation of the magnetite nanoparticles having a smaller size and a lower crystallinity. On the other hand, at higher molar ratios, the particle size and crystallinity increased with increasing molar ratio because using surplus ferrous hydroxide the crystallites of magnetite nanoparticles grew up slowly under hydrothermal conditions according to the Schikorr reaction. The magnetite nanoparticles prepared under various molar ratios had good magnetic properties regardless of the molar ratio.

  11. New approaches to chemical reaction mechanisms by means of radiation chemistry

    International Nuclear Information System (INIS)

    Since active species generated during radiolysis can be used as oxidative or reductive regents of various organic and inorganic compounds, radiation chemistry has been applied to wide range of research fields. We have studied charge-delocalization process in molecular systems, properties of intermediates in the excited states, mechanism of light emitting device, photo-catalyst for degradation of toxic compounds and so on by means of radiation chemistry. In the present paper, we summarize our recent research results. (author)

  12. The Al-Al3Ni Eutectic Reaction: Crystallography and Mechanism of Formation

    Science.gov (United States)

    Fan, Yangyang; Makhlouf, Makhlouf M.

    2015-09-01

    The characteristics of the Al-Al3Ni eutectic structure are examined with emphasis on its morphology and crystallography. Based on these examinations, the mechanism of formation of this technologically important eutectic is postulated. It is found that a thin shell of α-Al forms coherently around each Al3Ni fiber. The excellent thermal stability of the Al-Al3Ni eutectic may be attributed to the presence of this coherent layer.

  13. Study on the Reaction Mechanism for Carbon Dioxide Reforming of Methane over supported Nickel Catalyst

    Institute of Scientific and Technical Information of China (English)

    Ling QIAN; Zi Feng YAN

    2003-01-01

    The adsorption and dissociation of methane and carbon dioxide for reforming on nickelcatalyst were extensively investigated by TPSR and TPD experiments. It showed that thedecomposition of methane results in the formation of at least three kinds of surface carbon specieson supported nickel catalyst, while CO2 adsorbed on the catalyst weakly and only existed in onekind of adsorption state. Then the mechanism of interaction between the species dissociatedfrom CH4 and CO2 during reforming was proposed.

  14. Electrochemical oxidation of americium in nitric medium: study of reaction mechanisms

    International Nuclear Information System (INIS)

    One alternative selected by the CEA for partitioning minor actinides from aqueous solutions containing fission products is the selective extraction of oxidized americium. This is the SESAME process (Selective Extraction and Separation of Americium by Means of Electrolysis) aimed to convert americium to oxidation state (VI) and then extract it with a specific extractant of high valences. This paper presents the study of the electrochemical oxidation of americium in nitric medium which represents an important stage of the process. The reaction can be divided into two main steps: oxidation of americium (III) to americium (IV), and then of americium (IV) to americium (VI). For the first oxidation step, a ligand L is needed to stabilize the intermediate species americium (IV) which disproportionates in its free form into americium (III) and (V). Phospho-tungstate or silico-tungstate are appropriate ligands because they are stable in concentrated nitric acid and show a great affinity for metallic cations at oxidation state (IV) (Table 1 lists the stability constants of americium (IV) complexes). The presence of the lacunary poly-anion lowers the potential of the americium (IV) / americium (Ill) redox pair (see Figure 5 for the diagram of the apparent formal potential of americium versus ligand concentration). This makes it thermodynamically possible to oxidize americium (III) into americium (IV) at the anode of an electrolyzer in nitric acid. For the second oxidation step, a strong oxidant redox mediator, like silver (II), is needed to convert complexed americium at oxidation state (IV) to oxidation state (V). The AmVL complex is then hydrolyzed to yield americyle (V) aqua ion. A spectroscopic Raman study with 18O labeled species showed that the oxygen atoms of the americyle moiety came from water. This indicates that water hydrolyzes the americium (V) complex to produce americyle (V) aqua ion, AmO2+. This cation reacts with silver (Il) to give americyle (VI) ion. Figure

  15. A novel mechanism for direct real-time polymerase chain reaction that does not require DNA isolation from prokaryotic cells.

    Science.gov (United States)

    Soejima, Takashi; Xiao, Jin-Zhong; Abe, Fumiaki

    2016-01-01

    Typically, polymerase chain reaction (PCR) is performed after DNA isolation. Real-time PCR (qPCR), also known as direct qPCR in mammalian cells with weak membranes, is a common technique using crude samples subjected to preliminary boiling to elute DNA. However, applying this methodology to prokaryotic cells, which have solid cell walls, in contrast to mammalian cells which immediately burst in water, can result in poor detection. We successfully achieved PCR elongation with the addition of 1.3 cfu of Cronobacter muytjensii to a newly developed direct qPCR master mix without performing any crude DNA extraction (detection limit of 1.6 × 10(0) cfu/ml for the test sample compared with a detection limit of 1.6 × 10(3) cfu/ml primarily for crude (boiling) or classical DNA isolation). We revealed that the chromosomal DNA retained in prokaryotic cells can function as a PCR template, similarly to the mechanism in in situ PCR. Elucidating this reaction mechanism may contribute to the development of an innovative master mix for direct qPCR to detect genes in a single bacterium with solid cell walls and might lead to numerous novel findings in prokaryotic genomics research. PMID:27334801

  16. Design Paradigm Utilizing Reversible Diels-Alder Reactions to Enhance the Mechanical Properties of 3D Printed Materials.

    Science.gov (United States)

    Davidson, Joshua R; Appuhamillage, Gayan A; Thompson, Christina M; Voit, Walter; Smaldone, Ronald A

    2016-07-01

    A design paradigm is demonstrated that enables new functional 3D printed materials made by fused filament fabrication (FFF) utilizing a thermally reversible dynamic covalent Diels-Alder reaction to dramatically improve both strength and toughness via self-healing mechanisms. To achieve this, we used as a mending agent a partially cross-linked terpolymer consisting of furan-maleimide Diels-Alder (fmDA) adducts that exhibit reversibility at temperatures typically used for FFF printing. When this mending agent is blended with commercially available polylactic acid (PLA) and printed, the resulting materials demonstrate an increase in the interfilament adhesion strength along the z-axis of up to 130%, with ultimate tensile strength increasing from 10 MPa in neat PLA to 24 MPa in fmDA-enhanced PLA. Toughness in the z-axis aligned prints increases by up to 460% from 0.05 MJ/m(3) for unmodified PLA to 0.28 MJ/m(3) for the remendable PLA. Importantly, it is demonstrated that a thermally reversible cross-linking paradigm based on the furan-maleimide Diels-Alder (fmDA) reaction can be more broadly applied to engineer property enhancements and remending abilities to a host of other 3D printable materials with superior mechanical properties. PMID:27299858

  17. A novel mechanism for direct real-time polymerase chain reaction that does not require DNA isolation from prokaryotic cells.

    Science.gov (United States)

    Soejima, Takashi; Xiao, Jin-Zhong; Abe, Fumiaki

    2016-01-01

    Typically, polymerase chain reaction (PCR) is performed after DNA isolation. Real-time PCR (qPCR), also known as direct qPCR in mammalian cells with weak membranes, is a common technique using crude samples subjected to preliminary boiling to elute DNA. However, applying this methodology to prokaryotic cells, which have solid cell walls, in contrast to mammalian cells which immediately burst in water, can result in poor detection. We successfully achieved PCR elongation with the addition of 1.3 cfu of Cronobacter muytjensii to a newly developed direct qPCR master mix without performing any crude DNA extraction (detection limit of 1.6 × 10(0) cfu/ml for the test sample compared with a detection limit of 1.6 × 10(3) cfu/ml primarily for crude (boiling) or classical DNA isolation). We revealed that the chromosomal DNA retained in prokaryotic cells can function as a PCR template, similarly to the mechanism in in situ PCR. Elucidating this reaction mechanism may contribute to the development of an innovative master mix for direct qPCR to detect genes in a single bacterium with solid cell walls and might lead to numerous novel findings in prokaryotic genomics research.

  18. A Universal Damping Mechanism of Quantum Vibrations in Deep Sub-Barrier Fusion Reactions

    CERN Document Server

    Ichikawa, Takatoshi

    2015-01-01

    We demonstrate the damping of quantum octupole vibrations near the touching point when two colliding nuclei approach each other in the mass-asymmetric $^{208}$Pb + $^{16}$O system, for which the strong fusion hindrance was clearly observed. We, for the first time, apply the random-phase approximation method to the heavy-mass asymmetric di-nuclear system to calculate the transition strength $B$(E3) as a function of the center-of-mass distance. The obtained $B$(E3) strengths are substantially damped near the touching point, because the single-particle wave functions of the two nuclei strongly mix with each other and a neck is formed. The energy-weighted sums of $B$(E3) are also strongly correlated with the damping factor which is phenomenologically introduced in the standard coupled-channel calculations to reproduce the fusion hindrance. This strongly indicates that the damping of the quantum vibrations universally occurs in the deep sub-barrier fusion reactions.

  19. Chemical mechanisms and reaction rates for the initiation of hot corrosion of IN-738

    Science.gov (United States)

    Fryburg, G. C.; Kohl, F. J.; Stearns, C. A.

    1984-01-01

    Sodium-sulfate-induced hot corrosion of preoxidized IN-738 was studied at 975 C with special emphasis placed on the processes occurring during the long induction period. Thermogravimetric tests were run for predetermined periods of time, and then one set of specimens was washed with water. Chemical analysis of the wash solutions yielded information about water soluble metal salts and residual sulfate. A second set of samples was cross sectioned dry and polished in a nonaqueous medium. Element distributions within the oxide scale were obtained from electron microprobe X-ray micrographs. Evolution of SO was monitored throughout the thermogravimetric tests. Kinetic rate studies were performed for several pertinent processes; appropriate rate constants were obtained from the following chemical reactions: Cr2O3 + 2 Na2SO4(1) + 3/2 O2 yields 2 Na2CrO4(1) + 2 SO3(g)n TiO2 + Na2SO4(1) yields Na2O(TiO2)n + SO3(g)n TiO2 + Na2CrO4(1) yields Na2O(TiO2)n + CrO3(g).

  20. Pulse radiolysis study on the mechanisms of reactions of CCl3OO

    Institute of Scientific and Technical Information of China (English)

    MIAO; Jinling

    2001-01-01

    Chitosans with various degrees of deacetylation (D.D.), which were used as standard sample for FTIR determination, were prepared from completely deacetylated chitosan by homogeneous N-acetylation reaction. By combining four probable probe bands, i.e. 1655, 1560, 1380 and 1320 cm-1, eight probable reference bands, i.e. 3430, 2920, 2880, 1425, 1155, 1070, 1030 and 895 cm-1 and two baseline methods, the most suitable ratios Aprobe band/Areference band from IR spectra to determine the degree of acetylation of chitosan were evaluated from 48 combinations to be A1560/A2880, A1560/A2920 and A1655/A3430(A1560/A2880 is mostly recommended). The second baseline method, i.e. linking between adjacent two valleys, was better for measuring the absorbances of 1560 and 1655 cm-1 bands. The determination range of the D.D. (1%-100%) covered almost the whole range. The standard curves with A1560/A2880 and A1655/A3430 were also suitable for the determination of degree of substitution of other N-acylated chitosan, such as N-propionyl chitosan, N-butyryl chitosan and N-hexanoyl chitosan.

  1. [Study on the reaction mechanism of NO removal by pulse corona discharge].

    Science.gov (United States)

    Zhang, Lian-Shui; Liu, Tao; Dang, Wei; Duan, Shu-Xing

    2007-04-01

    Chemical reaction kinetics of NO removal by pulse corona discharge under the condition of normal atmospheric pressure was studied by using dispersive fluorescence spectrum and time-resomved spectrum. The fluorescence spectrum of NO pulse corona discharge was obtained. Moreover, dactylograms of NO, and those of the N+, O, N2, produced in the process of discharging were confirmed by attributing the fluorescence spectrum, and then the time behaviors of these particles were studied by analyzing these dactylograms. The results show that, the NO molecule turns to NO+ ion after colliding with high-energy electron, and then the NO+ ion breaks down to N+ and O. Subsequently, the N+ ion turns to N atom after absorbing an electron and then combines with another N atom, while the O atom turns to O2 molecule when combining with another O. From these results, the chemical kinetics model of NO removal by pulse corona discharge was proposed, which is helpful to increasing NO removal rate. PMID:17608170

  2. Decay Mechanism of 290,292114* Superheavy Nuclei Formed in 48Ca-Induced Reactions

    Science.gov (United States)

    Sandhu, Kirandeep; Sharma, Manoj K.

    2013-10-01

    We calculate the neutron-evaporation residue cross sections σ 3n , σ 4n , and σ 5n in the hot-fusion reactions 48Ca+242,244Pu →290,292114 ∗ over a wide range of compound-nucleus excitation energies (E_{{CN}}^{*} = 34-53 MeV). We work with the dynamical cluster-decay model (DCM), with a single parameter, the neck-length parameter ΔR. To calculate neutron-evaporation cross sections, we choose the superheavy proton magic Z = 126 and neutron magic N = 184. Among the 3n, 4n, and 5n production cross sections for 290, 292114∗, only the 3n decay cross sections of 292114∗ correspond to spherical fragmentation. The 4n and 5n cross sections of 292114∗ and 3n, 4n, and 5n cross sections of 290114∗ could only be fitted after the inclusion of quadrupole deformations β 2i within the optimum orientation approach. Changes in the angular momentum and N/Z ratio do not significantly influence the fragmentation paths of 290, 292114∗ superheavy nuclei. Larger barrier modification is required for the lower angular momentum states and lighter neutron clusters. The contribution of the fusion-fission component is also computed for the compound nucleus 292114∗ in the energy range E_{{CN}}^{*} = 27-47 MeV.

  3. Chlorobenzene degradation by electro-heterogeneous catalysis in aqueous solution: intermediates and reaction mechanism

    Institute of Scientific and Technical Information of China (English)

    WANG Jiade; MEI Yu; LIU Chenliang; CHEN Jianmeng

    2008-01-01

    This study was performed to investigate the variables that influence chlorobenzene (CB) degradation in aqueous solution by electro-heterogeneous catalysis. The effects of current density, pH, and electrolyte concentration on CB degradation were determined. The degradation efficiency of CB was almost 100% with an initial CB concentration of 50 mg/L, current density 15 mA/cm2, initial pH 10, electrolyte concentration 0.1 mol/L, and temperature 25℃ after 90 min of reaction. Under the same conditions, the degradation efficiency of CB was only 51% by electrochemical (EC) process, which showed that electro-heterogeneous catalysis was more efficient than EC alone. The analysis results of Purge-and-Trap chromatography-mass spectrometry (P&T/GC/MS) and ion chromatography the release of Cl-. Further oxidation of phenol and biphenyl produced p-Vinylbenzoic acid and hydroquinol. Finally, the compounds were oxidized to butenedioic acid and other small-molecule acids.

  4. A novel Si strip array to investigate reaction and decay mechanisms

    Science.gov (United States)

    Stanoiu, M.; Sümmerer, K.; Mukha, I.; Chatillon, A.; Cortina Gil, E.; Heil, M.; Hoffman, J.; Kiselev, O. A.; Kurz, N.; Ott, W.; S271 Collaboration

    2008-10-01

    The performance of a novel set-up of double-sided silicon micro-strip detectors (DSSD) developed for the GSI-R3B project (reaction studies with relativistic radioactive beams) is presented. The set-up was used in an experiment aimed at measuring the two-proton decay of 19Mg. This experiment required to record simultaneously protons and the residual nuclei with good position and energy resolution. Our experimental results show that both protons and heavy ions ranging from Z = 2 up to Z = 12 can be identified with good signal-to-noise ratio and high energy and spatial resolution. This allowed to reconstruct 2- and 3-particle vertices with high precision, opening the possibility to measure lifetimes of very short-lived nuclei and to obtain precise angular correlations of the outgoing particles. This detection system serves as a prototype for the R3B recoil detector, which will be composed of a two-layer Si strip tracker.

  5. Importance of neutron transfer channels in sub-barrier fusion reaction mechanism

    International Nuclear Information System (INIS)

    Heavy ion fusion reaction has been extensively studied for the last two decades. Fusion cross-sections show large enhancement with respect to theoretical prediction in sub-barrier energy region. It is well known that the enhancement occurs due to nuclear vibration, deformation and nucleon transfer. The influence of nuclear vibration and deformation is well described within the framework of coupled channel (CC) calculations. However, the role of neutron transfer is not yet explained. Experimental investigations have shown that large enhancement in fusion cross-sections is due to neutron transfer channels with positive Q value. But, few systems did not show any enhancement in spite of having positive Q value neutron transfer channels. Hence, Q value is not the only criteria to infer the importance of neutron transfer on fusion. In a recent article, it was stated that enhancement is related to the increase in deformation of interacting nuclei after neutron transfer. In other words, fusion will be weakly influenced by positive Q value neutron transfer channel if deformation of nuclei do not change or decrease after transfer. Moreover, it was recently reported that only valence neutrons i.e. 1n and 2n transfer channel with positive Q value has significant impact on sub-barrier fusion

  6. Synthesis and evaluation of new guanidine-thiourea organocatalyst for the nitro-Michael reaction: Theoretical studies on mechanism and enantioselectivity

    Directory of Open Access Journals (Sweden)

    Tatyana E. Shubina

    2012-09-01

    Full Text Available A new guanidine-thiourea organocatalyst has been developed and applied as bifunctional organocatalyst in the Michael addition reaction of diethyl malonate to trans-β-nitrostyrene. Extensive DFT calculations, including solvent effects and dispersion corrections, as well as ab initio calculations provide a plausible description of the reaction mechanism.

  7. Microstructures and Mechanism of Al2O3/Al Composites Fabricated by the Reaction between SiO2 and Molten Aluminum

    Institute of Scientific and Technical Information of China (English)

    CHENG Xiao-min; ZHANG Lian-meng; CHEN Tie-qun

    2003-01-01

    Al2O3/Al composite was fabricated by the reaction between SiO2 and molten aluminum.The microstructures of the composite obtained under different reaction conditions were analyzed. The formation mechanism of the composite microstructure was discussed. Results show that the reaction kinetics is influenced remarkably by the reaction temperature, reaction time and the quantity of SiO2.The morphologies of Al2O3 have different features,depending on the reaction temperature.The composite has equiaxed Al2O3 grains when materials reacted below 1200℃,and the composite is composed of a large number of fine Al2O3 grains and aluminum.The composite has a frame-shaped Al2O3 microstructure at the reaction temperature of above 1250℃.

  8. Interest of uranium complexes for the mechanism study of the McMurry reaction; Interet des complexes de l`uranium pour l`etude du mecanisme de la reaction de McMurry

    Energy Technology Data Exchange (ETDEWEB)

    Maury, O

    1997-07-04

    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.). 284 refs.

  9. Theoretical study on the reaction mechanism of (CH3)3CO(.) radical with NO

    Institute of Scientific and Technical Information of China (English)

    ZHAO; Hongmei; LIU; Kun; SUN; Chengke; LI; Zonghe

    2004-01-01

    [1]Sun, Z., Zheng, S. J., Wang, J. et al., First experimental observation on different ionic states of the tert-butoxy [(CH3)3CO' ] radical, Chem. Eur. J., 2001, 7(14): 2995-2999.[2]Wang, J., Sun, Z., Zhu, X. J. et al., First experimental observation on different ionic states of the CH3CH2O radical: a HeI photoelectron spectrum of the ethoxy CH3CH2O radical, Chem. Phys. Lett.,2001, 340: 98-102.[3]Zhu, X. J., Ge, M. F., Wang, J. et al., First experimental observation on different ionic states of both methylthio (CH3S') and methoxy (CH3O') radicals, Angew. Chem. Int. Ed., 2000, 39(11):1940-1943.[4]Ramond, T. M., Davico, G. E., Schwartz, R. L. et al., Vibronic structure of alkoxy radicals via photoelectron spectroscopy, J.Chem. Phys., 1999, 112: 1158-1169.[5]Blitz, M., Pilling, M. J., Robertson, S. H. et al., Direct studies on the decomposition of the tert-butoxy radical and its reaction with NO, Phys. Chem. Chem. Phys., 1999, 1: 73-80.[6]Lee, Y. Y., Wann, G., Lee, Y. P., Vibronic analysis of the A → X laser-induced fluorescence of jet-cooled methoxy (CH3O) radical,J. Chem. Phys., 1993, 99: 9465-9471.[7]Wiberg, K. B., Structures and charge distributions in alkoxide ions, J. Am. Chem. Soc., 1990, 112: 3379-3385.[8]Janousek, B. K., Zimmerman, A. H., Reed, K. J. et al., Electron photodetachment from aliphatic molecular anions, gas-phase electron affinities of methoxyl, tert-butoxyl, and neopentoxyl radicals, J. Am. Chem. Soc., 1978, 100: 6142-6148.[9]Griller, D., Ingold, K. U., Persistent carbon-centered radicals,Acc. Chem. Res., 1976, 9: 13-19.[10]Haire, D. L., Janzen, E. G., Synthesis and spin trapping kinetics of new alkyl substituted cyclic nitrones, Can. J. Chem., 1982, 60:1514-1522.[11]Walling, C., Kurkov, V. P., Positive halogen compounds, XV. Kinetics of the chlorination of Hydrocarbons by t-butyl hypochlorite,J. Am. Chem. Soc., 1967, 89: 4895-4901.[12]Becke, A. D., Density-functional thermochemistry, Ⅲ. The

  10. Oxygen reduction reaction induced pH-responsive chemo-mechanical hydrogel actuators.

    Science.gov (United States)

    Yu, Cunjiang; Yuan, Peixi; Erickson, Evan M; Daly, Christopher M; Rogers, John A; Nuzzo, Ralph G

    2015-10-28

    We describe and characterize elementary designs for electrochemical micro- and macro-scale chemomechanical hydrogel actuators. The actuation of a pH-sensitive cross-linked polyacrylic acid (PAA) hydrogel is driven in the model devices through the oxygen reduction reaction (ORR) occurring at the electrodes of an embedded Au mesh micro-electrochemical array. Proton consumption by the ORR at the cathode of the embedded electrochemical cell leads to the formation of a localized pH gradient that in turn drives the strain response in the composite actuators. The dynamics result from the ionization of the carboxylic acid moieties of the PAA network in the high pH region, yielding an osmotic pressure that drives a volumetric expansion due to water imbibition. This system actuates both stably and reversibly; when the electrochemically-induced ORR is halted, the localized pH gradient dissipates due to diffusive mixing, which in turn relaxes the induced strains. Two approaches to the fabrication of hydrogel actuators were examined in this work. The first method adopted a design based on small flagella (∼0.2 mm × 1.5 mm × 60 μm, width × length × height) in which the actuating PAA structures are molded atop a set of fixed electrodes mounted on a supporting substrate. These hydrogel actuators show fast, large-amplitude, and largely reversible responses in the ORR mediated chemomechanical dynamics. We also investigated larger hydrogel actuators (∼4.5 mm × 11 mm × 1 mm, width × length × height), based on an autonomous design that embeds an open mesh stretchable micro-electrode array within the hydrogel. The significant and design-dependent impacts of mass transfer on the chemomechanical dynamics are evidenced in each case, a feature examined to elucidate more efficient mesoscopic design rules for actuators of this form. PMID:26323563

  11. Studies on the reaction mechanism of the muon induced nuclear fission

    International Nuclear Information System (INIS)

    The mass and energy distribution of the fission fragments after muon induced nuclear fission allows the determination of the mean excitation energy of the fissioning nucleus after muon capture. By the systematic comparison with a mass distribution of a corresponding reaction for the first time for this an accuracy of about 1 MeV could be reached. Theoretical calculations on the excitation probability in the muon capture allow in connection with the fission probability an estimating calculation of this energy. The experimental result represents by this a test criterium for the valuation of the theoretical calculation. The measured probabilities for the occurrence of radiationless transitions in the muonic γ cascade of 237Np permit an indirect experimental determination of the barrier enhancement which causes the muon present during the fission process. The value found for this extends to 0.75+-0.1 MeV. A change of the mass distribution by the muon cannot be detected in the nuclides 235U, 237Np, and 242Pu studied here. Only the mean total kinetic energy of the fission products is reduced in these three nuclides in the prompt μ- induced fission by 1 to 2 MeV. For this result the incomplete screening of the nuclear charge during the fission process is made responsible. A mass dependence of this reduction has not been stated. Because the muon has appearently no influence on the mass splitting it can be valied as nearly ideal particle in order to study the hitherto little studied dynamics of the fission process. (orig.)

  12. Basidiomycete DyPs: Genomic diversity, structural-functional aspects, reaction mechanism and environmental significance.

    Science.gov (United States)

    Linde, Dolores; Ruiz-Dueñas, Francisco J; Fernández-Fueyo, Elena; Guallar, Victor; Hammel, Kenneth E; Pogni, Rebecca; Martínez, Angel T

    2015-05-15

    The first enzyme with dye-decolorizing peroxidase (DyP) activity was described in 1999 from an arthroconidial culture of the fungus Bjerkandera adusta. However, the first DyP sequence had been deposited three years before, as a peroxidase gene from a culture of an unidentified fungus of the family Polyporaceae (probably Irpex lacteus). Since the first description, fewer than ten basidiomycete DyPs have been purified and characterized, but a large number of sequences are available from genomes. DyPs share a general fold and heme location with chlorite dismutases and other DyP-type related proteins (such as Escherichia coli EfeB), forming the CDE superfamily. Taking into account the lack of an evolutionary relationship with the catalase-peroxidase superfamily, the observed heme pocket similarities must be considered as a convergent type of evolution to provide similar reactivity to the enzyme cofactor. Studies on the Auricularia auricula-judae DyP showed that high-turnover oxidation of anthraquinone type and other DyP substrates occurs via long-range electron transfer from an exposed tryptophan (Trp377, conserved in most basidiomycete DyPs), whose catalytic radical was identified in the H2O2-activated enzyme. The existence of accessory oxidation sites in DyP is suggested by the residual activity observed after site-directed mutagenesis of the above tryptophan. DyP degradation of substituted anthraquinone dyes (such as Reactive Blue 5) most probably proceeds via typical one-electron peroxidase oxidations and product breakdown without a DyP-catalyzed hydrolase reaction. Although various DyPs are able to break down phenolic lignin model dimers, and basidiomycete DyPs also present marginal activity on nonphenolic dimers, a significant contribution to lignin degradation is unlikely because of the low activity on high redox-potential substrates. PMID:25637654

  13. Kinetics and Mechanism of the Reaction of Coherently Synchronized Oxidation and Dehydrogenation of Cyclohexane by Hydrogen Peroxide

    Directory of Open Access Journals (Sweden)

    Aghamammadova S.

    2016-01-01

    Based on this experimental researches, the complex reaction, consisting of parallel-sequential oxidation and dehydrogenation reactions, which are coherently synchronized, proceeds during the process of cyclohexane oxidation with biomimetic catalyst. Depending on the reaction parameters it is possible to deliberately adjust the direction of oxidation reaction and reaction rate.

  14. Quantum mechanical investigation on the intermediates of alkene-ozone reaction

    International Nuclear Information System (INIS)

    The geometrical parameters, vibrational frequencies, and IR intensities for primary ozonide (POZ), secondary ozonide (SOZ) and carbonyl oxide as the intermediates of alkene-ozone reation have been predicted using high level ab initio quantum mechanical method with various basis sets. In general, the polarization function decreases bond lengths and bond angles, while the electron correlation effect increases bond lengths slightly. The electronic structure of carbonyl oxide has been predicted to be zwitterionic structure and energy difference between zwitterionic and diradical structure is evaluated to be 22.4 kcal/mol at TZ2P CISD level of theory. The experimental vibrational frequencies and IR intensities of POZ and SOZ will be compared and discussed with our high level theoretical predictions

  15. Quantum mechanical investigation on the intermediates of alkene-ozone reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Chang Duk; Kim, Seung Joon [Hannam Univ., Taejon (Korea, Republic of)

    1998-02-01

    The geometrical parameters, vibrational frequencies, and IR intensities for primary ozonide (POZ), secondary ozonide (SOZ) and carbonyl oxide as the intermediates of alkene-ozone reation have been predicted using high level ab initio quantum mechanical method with various basis sets. In general, the polarization function decreases bond lengths and bond angles, while the electron correlation effect increases bond lengths slightly. The electronic structure of carbonyl oxide has been predicted to be zwitterionic structure and energy difference between zwitterionic and diradical structure is evaluated to be 22.4 kcal/mol at TZ2P CISD level of theory. The experimental vibrational frequencies and IR intensities of POZ and SOZ will be compared and discussed with our high level theoretical predictions.

  16. Menaquinone (vitamin K2 therapy for bronchial asthma. I. Mechanism of action menaquinone on allergic reactions.

    Directory of Open Access Journals (Sweden)

    Kimura,Ikuro

    1975-02-01

    Full Text Available The mechanism of action of the drug was investigated from various points of view. The findings may be summarized as follows: 1. In the experiments of the degranulation of mesenteric mast cells of rats, menaquinone proved to significantly inhibit the degranulation either in active or passive sensitization with the reagin-like antibody. 2. Menaquinone did not inhibit the formation of the reagin-like antibody. 3. In the experiements of the degranulation of basophilic granulocytes from patients of bronchial asthma, the rate of appearance of A form basophilic cells upon addition of the antihuman IgE goat serum was not markedly but significantly inhibited in the patients treated with menaquinone for long periods, as compared with that in the control, whereas the in vitro addition of menaquinone did not exert a significant inhibitory action.

  17. n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions

    KAUST Repository

    Zhang, Siyuan

    2015-06-18

    Dimers of 2-substituted N,N\\'-dimethylbenzimidazoline radicals, (2-Y-DMBI)2 (Y=cyclohexyl (Cyc), ferrocenyl (Fc), ruthenocenyl (Rc)), have recently been reported as n-dopants for organic semiconductors. Here their structural and energetic characteristics are reported, along with the mechanisms by which they react with acceptors, A (PCBM, TIPS-pentacene), in solution. X-ray data and DFT calculations both indicate a longer C-C bond for (2-Cyc-DMBI)2 than (2-Fc-DMBI)2, yet DFT and ESR data show that the latter dissociates more readily due to stabilization of the radical by Fc. Depending on the energetics of dimer (D2) dissociation and of D2-to-A electron transfer, D2 reacts with A to form D+ and A- by either of two mechanisms, differing in whether the first step is endergonic dissociation or endergonic electron transfer. However, the D+/0.5D2 redox potentials-the effective reducing strengths of the dimers-vary little within the series (ca. -1.9V vs. FeCp2+/0) (Cp=cyclopentadienyl) due to cancelation of trends in the D+/0 potential and D2 dissociation energy. The implications of these findings for use of these dimers as n-dopants, and for future dopant design, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Kinetics and mechanism of proteinase-binding of pregnancy zone protein (PZP). Appearance of sulfhydryl groups in reactions with proteinases.

    Science.gov (United States)

    Christensen, U; Sottrup-Jensen, L; Simonsen, M

    1992-01-01

    Proteinase binding by pregnancy zone protein (PZP), an alpha-macroglobulin involves bait region cleavages, association of dimeric-PZP into tetrameric and reaction of internal gamma-glutamyl-beta-cysteinyl thiol esters of PZP with proteinase side chains. The product is an equimolar enzyme-PZP(tetramer) covalently linked complex with four free sulfhydryl groups. The kinetics of the appearances of sulfhydryl groups during the reaction of PZP with chymotrypsin has been investigated using stopped-flow and conventional mixing techniques over a broad concentration range. Thiol ester cleavages followed double exponential decays corresponding with two steps. The faster one resulted in the appearance of three sulfhydryl groups with an observed rate constant, k(obs) = k1.1 + k1.2 delta E, dependent on the excess concentration of chymotrypsin, delta E, and k1.1 = 0.03 s-1 and k1.2 = 4 x 10(4) M-1 s-1. The last sulfhydryl group appeared in a slower step, with similar concentration dependence and k2.1 approximately 0.003 s-1 and k2.2 approximately 5 x 10(3) M-1s-1. Covalent binding of the enzyme apparently was simultaneous with the faster thiol ester cleavage step. Based on these and previous results a model of the reaction mechanism of the proteinase binding reaction of PZP is proposed. It consists of four major steps: (i) Bait region cleavage of PZP-dimers by the enzyme, (ii) fast association of enzyme-PZP(dimer) species with native PZP or with another enzyme-PZP(dimer) compound resulting in release of one of the associated enzyme molecules (iii) reaction of an average of three thiol esters of the enzyme-PZP(tetramer) intermediate with the associated internal enzyme molecule or with an external one. In this step one enzyme molecule becomes covalently linked to the PZP-(tetramer), three sulfhydryl groups appear and the enzymic activity of the bound enzyme molecule decreases to the level of that of the final complex. (iv) Hydrolysis of the last thiol ester and in the presence of

  19. Converged three-dimensional quantum mechanical reaction probabilities for the F + H2 reaction on a potential energy surface with realistic entrance and exit channels and comparisons to results for three other surfaces

    Science.gov (United States)

    Lynch, Gillian C.; Halvick, Philippe; Zhao, Meishan; Truhlar, Donald G.; Yu, Chin-Hui; Kouri, Donald J.; Schwenke, David W.

    1991-01-01

    Accurate three-dimensional quantum mechanical reaction probabilities are presented for the reaction F + H2 yields HF + H on the new global potential energy surface 5SEC for total angular momentum J = 0 over a range of translational energies from 0.15 to 4.6 kcal/mol. It is found that the v-prime = 3 HF vibrational product state has a threshold as low as for v-prime = 2.

  20. Automatic reduction of the hydrocarbon reaction mechanisms in fusion edge plasmas

    International Nuclear Information System (INIS)

    For predictions of the tritium inventory in future fusion devices like ITER, the amount of eroded carbon and the hydrogen concentrations in co-deposited hydrocarbon layers have to be predicted quantitatively. Predictions about the locations of co-deposited layers are also necessary in order to design deposition diagnostics and layer removal methods. This requires a detailed physical understanding of the erosion and carbon migration processes, and computer simulations. For accurate simulation the multi-species code EIRENE would require to include over 50 participating species. Because such a calculation is computationally prohibitive current codes are being reduced, typically in an ad hoc fashion. In this work the potential of the mathematically sound method of intrinsic low dimensional manifolds (ILDM) for computational speed-up of the hydrocarbon transport problem simulation is thoroughly investigated. It is basically the Monte Carlo implementation of EIRENE that makes this task so challenging. As the method can substantially ameliorate the results in comparison to the conventional reduction mechanisms a step towards ILDM-reduced kinetics is conceived and tested. (orig.)