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Sample records for compound reaction model

  1. Reactions of Lignin Model Compounds in Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Holladay, John E.; Binder, Joseph B.; Gray, Michel J.; White, James F.; Zhang, Z. Conrad

    2009-09-15

    Lignin, a readily available form of biomass, awaits novel chemistry for converting it to valuable aromatic chemicals. Recent work has demonstrated that ionic liquids are excellent solvents for processing woody biomass and lignin. Seeking to exploit ionic liquids as media for depolymerization of lignin, we investigated reactions of lignin model compounds in these solvents. Using Brønsted acid catalysts in 1-ethyl-3-methylimidazolium triflate at moderate temperatures, we obtained up to 11.6% yield of the dealkylation product guaiacol from the model compound eugenol and cleaved phenethyl phenyl ether, a model for lignin ethers. Despite these successes, acid catalysis failed in dealkylation of the unsaturated model compound 4-ethylguaiacol and did not produce monomeric products from organosolv lignin, demonstrating that further work is required to understand the complex chemistry of lignin depolymerization.

  2. A computational study of pyrolysis reactions of lignin model compounds

    Science.gov (United States)

    Thomas Elder

    2010-01-01

    Enthalpies of reaction for the initial steps in the pyrolysis of lignin have been evaluated at the CBS-4m level of theory using fully substituted b-O-4 dilignols. Values for competing unimolecular decomposition reactions are consistent with results previously published for phenethyl phenyl ether models, but with lowered selectivity. Chain propagating reactions of free...

  3. Aromatic products from reaction of lignin model compounds with UV-alkaline peroxide

    International Nuclear Information System (INIS)

    Sun, Y.P.; Wallis, A.F.A.; Nguyen, K.L.

    1997-01-01

    A series of guaiacyl and syringyl lignin model compounds and their methylated analogues were reacted with alkaline hydrogen peroxide while irradiating with UV light at 254 nm. The aromatic products obtained were investigated by gas chromatography-mass spectrometry (GC-MS). Guaiacol, syringol and veratrol gave no detectable aromatic products. However, syringol methyl ether gave small amounts of aromatic products, resulting from ring substitution and methoxyl displacement by hydroxyl radicals. Reaction of vanillin and syringaldehyde gave the Dakin reaction products, methoxy-1,4-hydroquinones, while reaction of their methyl ethers yielded benzoic acids. Acetoguaiacone, acetosyringone and their methyl ethers afforded several hydroxylated aromatic products, but no aromatic products were identified in the reaction mixtures from guaiacylpropane and syringylpropane. In contrast, veratrylpropane gave a mixture from which 17 aromatic hydroxylated compounds were identified. It is concluded that for phenolic lignin model compounds, particularly those possessing electrondonating aromatic ring substituents, ring-cleavage reactions involving superoxide radical anions are dominant, whereas for non-phenolic lignin models, hydroxylation reactions through attack of hydroxyl radicals prevail

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

    Science.gov (United States)

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

    2012-05-01

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

  5. Fast fission phenomenon, deep inelastic reactions and compound nucleus formation described within a dynamical macroscopic model

    International Nuclear Information System (INIS)

    Gregoire, C.; Ngo, C.; Remaud, B.

    1982-01-01

    We present a dynamical model to describe dissipative heavy ion reactions. It treats explicitly the relative motion of the two ions, the mass asymmetry of the system and the projection of the isospin of each ion. The deformations, which are induced during the collision, are simulated with a time-dependent interaction potential. This is done by a time-dependent transition between a sudden interaction potential in the entrance channel and an adiabatic potential in the exit channel. The model allows us to compute the compound-nucleus cross section and multidifferential cross-sections for deep inelastic reactions. In addition, for some systems, and under certain conditions which are discussed in detail, a new dissipative heavy ion collision appears: fast-fission phenomenon which has intermediate properties between deep inelastic and compound nucleus reactions. The calculated properties concerning fast fission are compared with experimental results and reproduce some of those which could not be understood as belonging to deep inelastic or compound-nucleus reactions. (orig.)

  6. Impact of organic-mineral matter interactions on thermal reaction pathways for coal model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Buchanan, A.C. III; Britt, P.F.; Struss, J.A. [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.

    1995-07-01

    Coal is a complex, heterogeneous solid that includes interdispersed mineral matter. However, knowledge of organic-mineral matter interactions is embryonic, and the impact of these interactions on coal pyrolysis and liquefaction is incomplete. Clay minerals, for example, are known to be effective catalysts for organic reactions. Furthermore, clays such as montmorillonite have been proposed to be key catalysts in the thermal alteration of lignin into vitrinite during the coalification process. Recent studies by Hatcher and coworkers on the evolution of coalified woods using microscopy and NMR have led them to propose selective, acid-catalyzed, solid state reaction chemistry to account for retained structural integrity in the wood. However, the chemical feasibility of such reactions in relevant solids is difficult to demonstrate. The authors have begun a model compound study to gain a better molecular level understanding of the effects in the solid state of organic-mineral matter interactions relevant to both coal formation and processing. To satisfy the need for model compounds that remain nonvolatile solids at temperatures ranging to 450 C, model compounds are employed that are chemically bound to the surface of a fumed silica (Si-O-C{sub aryl}linkage). The organic structures currently under investigation are phenethyl phenyl ether (C{sub 6}H{sub 5}CH{sub 2}CH{sub 2}OC{sub 6}H{sub 5}) derivatives, which serve as models for {beta}-alkyl aryl ether units that are present in lignin and lignitic coals. The solid-state chemistry of these materials at 200--450 C in the presence of interdispersed acid catalysts such as small particle size silica-aluminas and montmorillonite clay will be reported. Initial focus will be on defining the potential impact of these interactions on coal pyrolysis and liquefaction.

  7. Reaction pathways of model compounds of biomass-derived oxygenates on Fe/Ni bimetallic surfaces

    Science.gov (United States)

    Yu, Weiting; Chen, Jingguang G.

    2015-10-01

    Controlling the activity and selectivity of converting biomass-derivatives to fuels and valuable chemicals is critical for the utilization of biomass feedstocks. There are primarily three classes of non-food competing biomass, cellulose, hemicellulose and lignin. In the current work, glycolaldehyde, furfural and acetaldehyde are studied as model compounds of the three classes of biomass-derivatives. Monometallic Ni(111) and monolayer (ML) Fe/Ni(111) bimetallic surfaces are studied for the reaction pathways of the three biomass surrogates. The ML Fe/Ni(111) surface is identified as an efficient surface for the conversion of biomass-derivatives from the combined results of density functional theory (DFT) calculations and temperature programmed desorption (TPD) experiments. A correlation is also established between the optimized adsorption geometry and experimental reaction pathways. These results should provide helpful insights in catalyst design for the upgrading and conversion of biomass.

  8. Aromatic C-Nitroso Compounds and Their Dimers: A Model for Probing the Reaction Mechanisms in Crystalline Molecular Solids

    Directory of Open Access Journals (Sweden)

    Ivana Biljan

    2017-12-01

    Full Text Available This review is focused on the dimerization and dissociation of aromatic C-nitroso compounds and their dimers, the reactions that could be used as a convenient model for studying the thermal organic solid-state reaction mechanisms. This molecular model is simple because it includes formation or breaking of only one covalent bond between two nitrogen atoms. The crystalline molecular solids of nitroso dimers (azodioxides dissociate by photolysis under the cryogenic conditions, and re-dimerize by slow warming. The thermal re-dimerization reaction is examined under the different topotactic conditions in crystals: disordering, surface defects, and phase transformations. Depending on the conditions, and on the molecular structure, aromatic C-nitroso compounds can associate to form one-dimensional polymeric structures and are able to self-assemble on gold surfaces.

  9. High-intensity ultrasound production of Maillard reaction flavor compounds in a cysteine-xylose model system.

    Science.gov (United States)

    Ong, Olivia X H; Seow, Yi-Xin; Ong, Peter K C; Zhou, Weibiao

    2015-09-01

    Application of high intensity ultrasound has shown potential in the production of Maillard reaction odor-active flavor compounds in model systems. The impact of initial pH, sonication duration, and ultrasound intensity on the production of Maillard reaction products (MRPs) by ultrasound processing in a cysteine-xylose model system were evaluated using Response Surface Methodology (RSM) with a modified mathematical model. Generation of selected MRPs, 2-methylthiophene and tetramethyl pyrazine, was optimal at an initial pH of 6.00, accompanied with 78.1 min of processing at an ultrasound intensity of 19.8 W cm(-2). However, identification of volatiles using gas chromatography-mass spectrometry (GC/MS) revealed that ultrasound-assisted Maillard reactions generated fewer sulfur-containing volatile flavor compounds as compared to conventional heat treatment of the model system. Likely reasons for this difference in flavor profile include the expulsion of H2S due to ultrasonic degassing and inefficient transmission of ultrasonic energy. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Nuclear alignment following compound nucleus reactions

    International Nuclear Information System (INIS)

    Butler, P.A.; Nolan, P.J.

    1981-01-01

    A procedure for calculating the alignment of a nuclear state populated by a compound nucleus reaction is given and used to investigate how alignment varies for different types of population mechanisms. The calculations are compared to both predictions of Gaussian models for the state population distribution and to experimental data, for a variety of types of nuclear reactions. The treatment of alignment in the analysis of γ-ray angular distribution is discussed. (orig.)

  11. Reactions of model compounds in the presence of pyrene and MoS sub 2 to simulate coprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Ting, P.-S.; Curtis, C.W.; Cronauer, D.C. (Auburn University, Auburn, AL (USA). Chemical Engineering Dept.)

    Catalytic reactions of pyrene using in situ generated MoS{sub 2} from molybdenum naphthenate and excess sulfur were evaluated in the presence of added model species, both hydrocarbons and heteroatomic species. The added hydrocarbons and heteroatomic compounds containing oxygen and sulfur had little effect on the hydrogenation of pyrene at either 400 or 425{degree}C, but quinoline at 400{degree}C reduced the hydrogenation of pyrene by half. Reactions at 425{degree}C also reduced the hydrogenation of pyrene by half regardless of the added model species. The added model species underwent different degrees of reaction: the hydrocarbons underwent little or no reaction, dibenzofuran showed little hydrodeoxygenation, dibenzothiophene yielded substantial hydrodesulfurization and quinoline was almost totally hydrodenitrogenated. The addition of quinoline at increasing concentration resulted in substantial lowering of pyrene hydrogenation and quinoline hydrodenitrogenation. Introduction of quinoline at a low concentration of 0.4 wt% gave a pyrene hydrogenation rate constant of 0.073 min{sup -1} at 400{degree}C while an increase in quinoline to 10.0 wt% yielded a rate constant of 0.020 min{sup -1}. 21 refs., 7 figs., 6 tabs.

  12. Coal chemistry. 8. Reactions of tetralin with coal and with some carbon-14-containing model compounds

    International Nuclear Information System (INIS)

    Collins, C.J.; Raaen, V.F.; Benjamin, B.M.; Maupin, P.H.; Roark, W.H.

    1979-01-01

    When coal was treated with tetralin-l- 14 C at 400 0 C, small yields of α- and β-methylnaphthalenes- 14 C were observed. In order to determine the mechanism of the reaction, tetralin was heated with 14 C-labeled 1,3-diphenylpropanes (1), with 1,3-diphenylpropene (2), and with 14 C-labeled phenetoles (3). In each case methylnaphthalenes were observed, and the origins of the methyl groups were determined with carbon-14. In addition to the methylnaphthalenes, 1 and 2 also yielded toluene and ethylbenzene (after 19 h), whereas phenetole-β- 14 C (3-β- 14 C) yielded toluene (unlabeled) plus ethyl- 14 C-benzene, benzene, phenol, and a mixture of α- and β-ethyl- 14 C-naphthalenes. Crossover experiments with labeled phenetole and unlabeled ethyl p-tolyl ether proved the intramolecularity of the reaction phenetole → toluene + ethylbenzene, thus illustrating a 1,2-phenyl shift from oxygen to carbon

  13. Reactions of hypoiodous acid with model compounds and the formation of iodoform in absence/presence of permanganate.

    Science.gov (United States)

    Zhao, Xiaodan; Ma, Jun; von Gunten, Urs

    2017-08-01

    The kinetics for the reactions of hypoiodous acid (HOI) with various phenols (phenol, 4-nitrophenol, 4-hydroxybenzoic acid), 3-oxopentanedioic acid (3-OPA) and flavone were investigated in the pH range of 6.0-11.0. The apparent second order rate constants for the reactions of HOI with phenolic compounds, 3-OPA, flavone and citric acid at pH 8.0 are 10-10 7  M -1 s -1 , (4.0 ± 0.3) × 10 3  M -1 s -1 , (2.5 ± 0.2) × 10 3  M -1 s -1 and permanganate/HOI/3-OPA and permanganate/iodide/3-OPA system at pH permanganate. For pH > 8.0, in presence of permanganate, iodoform formation is significantly inhibited and iodate formation enhanced, which is due to a faster permanganate-mediated HOI disproportionation to iodate compared to the iodination process. The production of reactive iodine in real waters containing iodide in contact with permanganate may lead to the formation of iodinated organic compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Homologation Reaction of Ketones with Diazo Compounds.

    Science.gov (United States)

    Candeias, Nuno R; Paterna, Roberta; Gois, Pedro M P

    2016-03-09

    This review covers the addition of diazo compounds to ketones to afford homologated ketones, either in the presence or in the absence of promoters or catalysts. Reactions with diazoalkanes, aryldiazomethanes, trimethylsilyldiazomethane, α-diazo esters, and disubstituted diazo compounds are covered, commenting on the complex regiochemistry of the reaction and the nature of the catalysts and promoters. The recent reports on the enantioselective version of ketone homologation reactions are gathered in one section, followed by reports on the use of cyclic ketones ring expansion in total synthesis. Although the first reports of this reaction appeared in the literature almost one century ago, the recent achievements, in particular, for the asymmetric version, forecast the development of new breakthroughs in the synthetically valuable field of diazo chemistry.

  15. The reaction of astatine with aromatic diazonium compounds

    International Nuclear Information System (INIS)

    Visser, G.W.M.; Diemer, E.L.

    1982-01-01

    Astatine reacts prefrentially with that type of aromatic diazonium salt that decomposes via a radical reaction channel (homolytic breakage of the C-N bond). The dediazonation with p-aminobenzoic acid and p-toluidine as model compounds was investigated through estatin produced in the 209 Bi(α,2n) 211 At reaction. (author)

  16. The chemistry of subcritical water reactions of a hardwood derived lignin and lignin model compounds with nitrogen, hydrogen, carbon monoxide and carbon dioxide

    Science.gov (United States)

    Hill Bembenic, Meredith A.

    collected solids from the CO reactions appeared to be the most reacted (i.e., the most changed from the unreacted lignin) according to solid state 13C-NMR analysis, and the widest variety of products (methoxy-substituted phenolic compounds) were obtained when using CO according to GC/MS analysis. Therefore, reactions with CO were completed that varied the initial reaction pressure (300, 500 and 800 psi) in order to elucidate the effects of CO pressure. Similar conversion (≈54--58%) and DCM-soluble liquid product yields (≈53--62%) were obtained for the different pressure reactions, but the reactions with an initial pressure of 500 psi had the greatest change in aromaticity from the unreacted lignin. Additional reactions between Organosolv lignin and H2O with CO (initial pressure of 500 psi) were conducted where the reaction time was varied (15, 30 and 60 min.) to determine the effect of reaction time. Longer reaction time (60 min.) appeared to inhibit conversion to low molecular weight compounds (i.e., conversion and DCM-soluble yields were lower at ≈53% and ≈28%, respectively). Solid state 13C-NMR of collected residues also showed that there are losses in carbons representative of both guaiacyl and syringyl components as reaction time increases, which may indicate that methoxy groups are being cleaved or the products are reacting with each other (i.e., repolymerization) to form high molecular weight compounds as reaction time is increased. The role of H2O and the gases during the baseline reactions and the expanded CO reactions is not intuitive based on the results, so reactions with lignin model compounds (i.e., aromatic aldehydes represented by vanillin and syringaldehyde, aromatic ketones represented by acetovanillone and acetosyringone, and aromatic ethers represented by dibenzyl ether and 2-phenethyl phenyl ether) were completed to study this. From these results, the suggested reaction pathway of Organosolv lignin reactions in subcritical H2O with and without

  17. Photocatalytic fluoroalkylation reactions of organic compounds

    OpenAIRE

    Barata Vallejo, Sebastian; Bonesi, Sergio Mauricio; Postigo, Jose Alberto

    2017-01-01

    Photocatalytic methods for fluoroalkyl-radical generation provide more convenient alternatives to the classical perfluoroalkyl-radical (Rf) production through chemical initiators, such as azo or peroxide compounds or the employment of transition metals through a thermal electron transfer (ET) initiation process. The mild photocatalytic reaction conditions tolerate a variety of functional groups and, thus, are handy to the late-stage modification of bioactive molecules. Transition metal-photoc...

  18. Phenolic compounds reduce formation of Nε-(carboxymethyl)lysine and pyrazines formed by Maillard reactions in a model bread system.

    Science.gov (United States)

    Mildner-Szkudlarz, Sylwia; Siger, Aleksander; Szwengiel, Artur; Przygoński, Krzysztof; Wojtowicz, Elżbieta; Zawirska-Wojtasiak, Renata

    2017-09-15

    This study had the objective of determining the antiglycation activity of phenolic compounds (PCs) ((+)-catechin, quercetin, gallic, ferulic, and caffeic acids) added to a model bread with regards to the inhibition of N ε -(carboxymethyl)lysine (CML) formation. PCs were found to significantly reduce CML (31.77%-87.56%), even at the lowest concentration, with the exception of ferulic acid (FA). The strongest inhibitory effect of FA (∼62%) appeared when concentration was increased to 1.0g/100g of flour. The available lysine losses (0.00%-90.51%) showed a significant correlation (0.853-0.990) with effectiveness of CML inhibition, except in the case of samples with FA. (+)-Catechin reduced CML levels the most, probably due to its structure-antioxidant activity relationship, its thermal stability (∼51% loss), and its reactivity with ε-lysine side chains (∼40.77% loss). Although the bread supplemented with PCs contained low levels of CML, this process may adversely affect bread flavor, reducing the formation of pyrazines (1.10%-80.77%). Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Dietary Compound Kaempferol Inhibits Airway Thickening Induced by Allergic Reaction in a Bovine Serum Albumin-Induced Model of Asthma.

    Science.gov (United States)

    Shin, Daekeun; Park, Sin-Hye; Choi, Yean-Jung; Kim, Yun-Ho; Antika, Lucia Dwi; Habibah, Nurina Umy; Kang, Min-Kyung; Kang, Young-Hee

    2015-12-16

    Asthma is characterized by aberrant airways including epithelial thickening, goblet cell hyperplasia, and smooth muscle hypertrophy within the airway wall. The current study examined whether kaempferol inhibited mast cell degranulation and prostaglandin (PG) release leading to the development of aberrant airways, using an in vitro model of dinitrophenylated bovine serum albumin (DNP-BSA)-sensitized rat basophilic leukemia (RBL-2H3) mast cells and an in vivo model of BSA-challenged asthmatic mice. Nontoxic kaempferol at 10-20 μM suppressed β-hexosaminidase release and cyclooxygenase 2 (COX2)-mediated production of prostaglandin D2 (PGD2) and prostaglandin F2α (PGF2α) in sensitized mast cells. Oral administration of ≤20 mg/kg kaempferol blocked bovine serum albumin (BSA) inhalation-induced epithelial cell excrescence and smooth muscle hypertrophy by attenuating the induction of COX2 and the formation of PGD2 and PGF2α, together with reducing the anti-α-smooth muscle actin (α-SMA) expression in mouse airways. Kaempferol deterred the antigen-induced mast cell activation of cytosolic phospholipase A2 (cPLA2) responsive to protein kinase Cμ (PKCμ) and extracellular signal-regulated kinase (ERK). Furthermore, the antigen-challenged activation of Syk-phospholipase Cγ (PLCγ) pathway was dampened in kaempferol-supplemented mast cells. These results demonstrated that kaempferol inhibited airway wall thickening through disturbing Syk-PLCγ signaling and PKCμ-ERK-cPLA2-COX2 signaling in antigen-exposed mast cells. Thus, kaempferol may be a potent anti-allergic compound targeting allergic asthma typical of airway hyperplasia and hypertrophy.

  20. Catalytic Upgrading of Bio-Oil by Reacting with Olefins and Alcohols over Solid Acids: Reaction Paths via Model Compound Studies

    Directory of Open Access Journals (Sweden)

    Qingwen Wang

    2013-03-01

    Full Text Available Catalytic refining of bio-oil by reacting with olefin/alcohol over solid acids can convert bio-oil to oxygen-containing fuels. Reactivities of groups of compounds typically present in bio-oil with 1-octene (or 1-butanol were studied at 120 °C/3 h over Dowex50WX2, Amberlyst15, Amberlyst36, silica sulfuric acid (SSA and Cs2.5H0.5PW12O40 supported on K10 clay (Cs2.5/K10, 30 wt. %. These compounds include phenol, water, acetic acid, acetaldehyde, hydroxyacetone, d-glucose and 2-hydroxymethylfuran. Mechanisms for the overall conversions were proposed. Other olefins (1,7-octadiene, cyclohexene, and 2,4,4-trimethylpentene and alcohols (iso-butanol with different activities were also investigated. All the olefins and alcohols used were effective but produced varying product selectivities. A complex model bio-oil, synthesized by mixing all the above-stated model compounds, was refined under similar conditions to test the catalyst’s activity. SSA shows the highest hydrothermal stability. Cs2.5/K10 lost most of its activity. A global reaction pathway is outlined. Simultaneous and competing esterification, etherfication, acetal formation, hydration, isomerization and other equilibria were involved. Synergistic interactions among reactants and products were determined. Acid-catalyzed olefin hydration removed water and drove the esterification and acetal formation equilibria toward ester and acetal products.

  1. Predicting chemically-induced skin reactions. Part I: QSAR models of skin sensitization and their application to identify potentially hazardous compounds

    Energy Technology Data Exchange (ETDEWEB)

    Alves, Vinicius M. [Laboratory of Molecular Modeling and Design, Faculty of Pharmacy, Federal University of Goiás, Goiânia, GO 74605-220 (Brazil); Laboratory for Molecular Modeling, Division of Chemical Biology and Medicinal Chemistry, Eshelman School of Pharmacy, University of North Carolina, Chapel Hill, NC 27599 (United States); Muratov, Eugene [Laboratory for Molecular Modeling, Division of Chemical Biology and Medicinal Chemistry, Eshelman School of Pharmacy, University of North Carolina, Chapel Hill, NC 27599 (United States); Laboratory of Theoretical Chemistry, A.V. Bogatsky Physical-Chemical Institute NAS of Ukraine, Odessa 65080 (Ukraine); Fourches, Denis [Laboratory for Molecular Modeling, Division of Chemical Biology and Medicinal Chemistry, Eshelman School of Pharmacy, University of North Carolina, Chapel Hill, NC 27599 (United States); Strickland, Judy; Kleinstreuer, Nicole [ILS/Contractor Supporting the NTP Interagency Center for the Evaluation of Alternative Toxicological Methods (NICEATM), P.O. Box 13501, Research Triangle Park, NC 27709 (United States); Andrade, Carolina H. [Laboratory of Molecular Modeling and Design, Faculty of Pharmacy, Federal University of Goiás, Goiânia, GO 74605-220 (Brazil); Tropsha, Alexander, E-mail: alex_tropsha@unc.edu [Laboratory for Molecular Modeling, Division of Chemical Biology and Medicinal Chemistry, Eshelman School of Pharmacy, University of North Carolina, Chapel Hill, NC 27599 (United States)

    2015-04-15

    Repetitive exposure to a chemical agent can induce an immune reaction in inherently susceptible individuals that leads to skin sensitization. Although many chemicals have been reported as skin sensitizers, there have been very few rigorously validated QSAR models with defined applicability domains (AD) that were developed using a large group of chemically diverse compounds. In this study, we have aimed to compile, curate, and integrate the largest publicly available dataset related to chemically-induced skin sensitization, use this data to generate rigorously validated and QSAR models for skin sensitization, and employ these models as a virtual screening tool for identifying putative sensitizers among environmental chemicals. We followed best practices for model building and validation implemented with our predictive QSAR workflow using Random Forest modeling technique in combination with SiRMS and Dragon descriptors. The Correct Classification Rate (CCR) for QSAR models discriminating sensitizers from non-sensitizers was 71–88% when evaluated on several external validation sets, within a broad AD, with positive (for sensitizers) and negative (for non-sensitizers) predicted rates of 85% and 79% respectively. When compared to the skin sensitization module included in the OECD QSAR Toolbox as well as to the skin sensitization model in publicly available VEGA software, our models showed a significantly higher prediction accuracy for the same sets of external compounds as evaluated by Positive Predicted Rate, Negative Predicted Rate, and CCR. These models were applied to identify putative chemical hazards in the Scorecard database of possible skin or sense organ toxicants as primary candidates for experimental validation. - Highlights: • It was compiled the largest publicly-available skin sensitization dataset. • Predictive QSAR models were developed for skin sensitization. • Developed models have higher prediction accuracy than OECD QSAR Toolbox. • Putative

  2. Predicting chemically-induced skin reactions. Part I: QSAR models of skin sensitization and their application to identify potentially hazardous compounds

    International Nuclear Information System (INIS)

    Alves, Vinicius M.; Muratov, Eugene; Fourches, Denis; Strickland, Judy; Kleinstreuer, Nicole; Andrade, Carolina H.; Tropsha, Alexander

    2015-01-01

    Repetitive exposure to a chemical agent can induce an immune reaction in inherently susceptible individuals that leads to skin sensitization. Although many chemicals have been reported as skin sensitizers, there have been very few rigorously validated QSAR models with defined applicability domains (AD) that were developed using a large group of chemically diverse compounds. In this study, we have aimed to compile, curate, and integrate the largest publicly available dataset related to chemically-induced skin sensitization, use this data to generate rigorously validated and QSAR models for skin sensitization, and employ these models as a virtual screening tool for identifying putative sensitizers among environmental chemicals. We followed best practices for model building and validation implemented with our predictive QSAR workflow using Random Forest modeling technique in combination with SiRMS and Dragon descriptors. The Correct Classification Rate (CCR) for QSAR models discriminating sensitizers from non-sensitizers was 71–88% when evaluated on several external validation sets, within a broad AD, with positive (for sensitizers) and negative (for non-sensitizers) predicted rates of 85% and 79% respectively. When compared to the skin sensitization module included in the OECD QSAR Toolbox as well as to the skin sensitization model in publicly available VEGA software, our models showed a significantly higher prediction accuracy for the same sets of external compounds as evaluated by Positive Predicted Rate, Negative Predicted Rate, and CCR. These models were applied to identify putative chemical hazards in the Scorecard database of possible skin or sense organ toxicants as primary candidates for experimental validation. - Highlights: • It was compiled the largest publicly-available skin sensitization dataset. • Predictive QSAR models were developed for skin sensitization. • Developed models have higher prediction accuracy than OECD QSAR Toolbox. • Putative

  3. Predicting chemically-induced skin reactions. Part I: QSAR models of skin sensitization and their application to identify potentially hazardous compounds

    Science.gov (United States)

    Alves, Vinicius M.; Muratov, Eugene; Fourches, Denis; Strickland, Judy; Kleinstreuer, Nicole; Andrade, Carolina H.; Tropsha, Alexander

    2015-01-01

    Repetitive exposure to a chemical agent can induce an immune reaction in inherently susceptible individuals that leads to skin sensitization. Although many chemicals have been reported as skin sensitizers, there have been very few rigorously validated QSAR models with defined applicability domains (AD) that were developed using a large group of chemically diverse compounds. In this study, we have aimed to compile, curate, and integrate the largest publicly available dataset related to chemically-induced skin sensitization, use this data to generate rigorously validated and QSAR models for skin sensitization, and employ these models as a virtual screening tool for identifying putative sensitizers among environmental chemicals. We followed best practices for model building and validation implemented with our predictive QSAR workflow using random forest modeling technique in combination with SiRMS and Dragon descriptors. The Correct Classification Rate (CCR) for QSAR models discriminating sensitizers from non-sensitizers were 71–88% when evaluated on several external validation sets, within a broad AD, with positive (for sensitizers) and negative (for non-sensitizers) predicted rates of 85% and 79% respectively. When compared to the skin sensitization module included in the OECD QSAR toolbox as well as to the skin sensitization model in publicly available VEGA software, our models showed a significantly higher prediction accuracy for the same sets of external compounds as evaluated by Positive Predicted Rate, Negative Predicted Rate, and CCR. These models were applied to identify putative chemical hazards in the ScoreCard database of possible skin or sense organ toxicants as primary candidates for experimental validation. PMID:25560674

  4. Compound semiconductor device modelling

    CERN Document Server

    Miles, Robert

    1993-01-01

    Compound semiconductor devices form the foundation of solid-state microwave and optoelectronic technologies used in many modern communication systems. In common with their low frequency counterparts, these devices are often represented using equivalent circuit models, but it is often necessary to resort to physical models in order to gain insight into the detailed operation of compound semiconductor devices. Many of the earliest physical models were indeed developed to understand the 'unusual' phenomena which occur at high frequencies. Such was the case with the Gunn and IMPATI diodes, which led to an increased interest in using numerical simulation methods. Contemporary devices often have feature sizes so small that they no longer operate within the familiar traditional framework, and hot electron or even quantum­ mechanical models are required. The need for accurate and efficient models suitable for computer aided design has increased with the demand for a wider range of integrated devices for operation at...

  5. Recent experimental results on level densities for compound reaction calculations

    International Nuclear Information System (INIS)

    Voinov, A.V.

    2012-01-01

    There is a problem related to the choice of the level density input for Hauser-Feshbach model calculations. Modern computer codes have several options to choose from but it is not clear which of them has to be used in some particular cases. Availability of many options helps to describe existing experimental data but it creates problems when it comes to predictions. Traditionally, different level density systematics are based on experimental data from neutron resonance spacing which are available for a limited spin interval and one parity only. On the other hand reaction cross section calculations use the total level density. This can create large uncertainties when converting the neutron resonance spacing to the total level density that results in sizable uncertainties in cross section calculations. It is clear now that total level densities need to be studied experimentally in a systematic manner. Such information can be obtained only from spectra of compound nuclear reactions. The question is does level densities obtained from compound nuclear reactions keep the same regularities as level densities obtained from neutron resonances- Are they consistent- We measured level densities of 59-64 Ni isotopes from proton evaporation spectra of 6,7 Li induced reactions. Experimental data are presented. Conclusions of how level density depends on the neutron number and on the degree of proximity to the closed shell ( 56 Ni) are drawn. The level density parameters have been compared with parameters obtained from the analysis of neutron resonances and from model predictions

  6. Formation of flavour compounds in the Maillard reaction

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    2006-01-01

    This paper discusses the importance of the Maillard reaction for food quality and focuses on flavour compound formation. The most important classes of Maillard flavour compounds are indicated and it is shown where they are formed in the Maillard reaction. Some emphasis is given on the kinetics of

  7. Intermolecula transfer and elimination of molecular hydrogen in thermal reactions of unsaturated organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Suria, Sabartanty [Iowa State Univ., Ames, IA (United States)

    1995-02-10

    Two reactions which are important to coal liquefaction include intermolecular transfer and the elimination of two hydrogen atoms. We have designed several model reactions to probe the viability of several hydrogen transfer and elimination pathways. This report described studies on these reactions using organic model compounds.

  8. Investigations on organogermanium compounds XII. Reactions of trialkylgermylalkalimetal compounds in hexamethylphosphoric triamide (HMPT) with some inorganic and organic compounds

    NARCIS (Netherlands)

    Bulten, E.J.; Noltes, J.G.

    1971-01-01

    Trialkylgermyl alkali metal compounds in HMPT have been found to be highly reactive nucleophiles. Reactions with some inorganic and organic compounds, such as oxygen, carbon dioxide, inorganic and orgaanic halides, aldehydes, ketones, epoxides and lactones are described. Several new

  9. Reaction of cyclic epoxide compounds with triphenylphosphine

    International Nuclear Information System (INIS)

    Kas'yan, L.I.; Stepanova, N.V.; Galafeeva, M.F.; Boldeskul, I.E.; Trachevskii, V.V.; Zefirov, N.S.

    1987-01-01

    Significant differences were found in the reactivity of a series of epoxides of cycloalkenes and methylenecycloalkanes and diepoxides in reaction with triphenylphosphine, depending both on the steric effects of the cyclic fragments and on their strain. The level of the strain can be judged indirectly from the chemical shifts of the 1 H and 13 C nuclei and the spin-spin coupling constants of the C-H bonds in the epoxide ring

  10. Modeling of Reaction Calorimeter

    OpenAIRE

    Farzad, Reza

    2014-01-01

    The purpose of this project was to model the reaction calorimeter in order to calculate the heat of absorption which is the most important parameter in this work. Reaction calorimeter is an apparatus which is used in measuring the heat of absorption of CO2 as well as the total pressure in vapor phase based on vapor-liquid equilibrium state. Mixture of monoethanolamine (MEA) and water was used as a solvent to absorb the CO2.Project was divided in to three parts in order to make the programming...

  11. Molecular modeling of inorganic compounds

    National Research Council Canada - National Science Library

    Comba, Peter; Hambley, Trevor W; Martin, Bodo

    2009-01-01

    ... mechanics to inorganic and coordination compounds. Initially, simple metal complexes were modeled, but recently the field has been extended to include organometallic compounds, catalysis and the interaction of metal ions with biological macromolecules. The application of molecular mechanics to coordination compounds is complicated by the numbe...

  12. Investigation and Modelling of Diesel Hydrotreating Reactions

    DEFF Research Database (Denmark)

    Boesen, Rasmus Risum

    on a commercial CoMo catalyst, and a simple kinetic model is presented. Hydrogenation of fused aromatic rings are known to be fast, and it is possible, that the reaction rates are limited by either internal or external mass transfer. An experiment conducted at industrial temperatures and pressure, using...... naphthalene as a model compound, have shown, that intra-particle diffusion resistance are likely to limit the reaction rate. In order to produce ULSD it is necessary to remove sulfur from some of the most refrac- tive sulfur compounds, such as sterically hindered dibenzothiophenes. Basic nitrogen com- pounds...... are known to inhibit certain hydrotreating reactions. Experimental results are pre- sented, showing the effect of 3 different nitrogen compounds, acridine, 1,4-dimethylcarabazole and 3-methylindole, on the hydrodesulfurization of a real feed and of a model compound, 4,6-dimethyldibenzothiophene. It is shown...

  13. Statistical theory of multi-step compound and direct reactions

    International Nuclear Information System (INIS)

    Feshbach, H.; Kerman, A.; Koonin, S.

    1980-01-01

    The theory of nuclear reactions is extended so as to include a statistical treatment of multi-step processes. Two types are distinguished, the multi-step compound and the multi-step direct. The wave functions for the system are grouped according to their complexity. The multi-step direct process involves explicitly those states which are open, while the multi-step compound involves those which are bound. In addition to the random phase assumption which is applied differently to the multi-step direct and to the multi-step compound cross-sections, it is assumed that the residual interaction will have non-vanishing matrix elements between states whose complexities differ by at most one unit. This is referred to as the chaining hypothesis. Explicit expressions for the double differential cross-section giving the angular distribution and energy spectrum are obtained for both reaction types. The statistical multi-step compound cross-sections are symmetric about 90 0 . The classical statistical theory of nuclear reactions is a special limiting case. The cross-section for the statistical multi-step direct reaction consists of a set of convolutions of single-step direct cross-sections. For the many step case it is possible to derive a diffusion equation in momentum space. Application is made to the reaction 181 Ta(p,n) 181 W using the statistical multi-step compound formalism

  14. Internal Displacement Reactions in Multicomponent Oxides: Part I. Line Compounds with Narrow Homogeneity Range

    OpenAIRE

    Reddy, SNS; Leonard, DN; Wiggins, LB; Jacob, KT

    2005-01-01

    As a model of an internal displacement reaction involving a ternary oxide line compound, the following reaction was studied at 1273 K as a function of time, t: $Fe+NiTiO_3 = Ni + FeTiO_3$ Both polycrystalline and single-crystal materials were used as the starting $NiTiO_3$ oxide. During the reaction, the Ni in the oxide compound is displaced by Fe and it precipitates as a \\gamma -(Ni-Fe) alloy. The reaction preserves the starting ilmenite structure. The product oxide has a consta...

  15. On the criterion for the optimum choice of a compound nucleus reaction for producing superheavy elements

    International Nuclear Information System (INIS)

    Aroumougame, R.; Gupta, R.K.

    1979-01-01

    The possible reaction partners of a cool compound nucleus reaction for the synthesis of the elements Z = 104, 106 and 108 are studied in terms of the potential energy surfaces, interaction barriers and the nuclear shapes calculated within the frame work of the Fragmentation theory based on two centre shell model. An estimate of the total reaction cross-section suggests that for larger fusion probabilities, the mass and charge asymmetries are the only essential criterion for the optimum choice of a cooler compound nuclear reaction. Larger the mass and charge asymmetries, larger is the fusion cross-section. (auth.)

  16. Nanoscale formation of new solid-state compounds by topochemical effects: The interfacial reactions ZnO with Al2O3 as a model system

    International Nuclear Information System (INIS)

    Pin, Sonia; Ghigna, Paolo; Spinolo, Giorgio; Quartarone, Eliana; Mustarelli, Piercarlo; D'Acapito, Francesco; Migliori, Andrea; Calestani, Gianluca

    2009-01-01

    The chemical reactivity of thin layers (ca. 10 nm thick) of ZnO deposited onto differently oriented Al 2 O 3 single crystals has been investigated by means of atomic force microscopy inspections and X-ray absorption spectroscopy at the Zn-K edge. The (0001) ZnO -parallel (112-bar0) sapphire interface yields the ZnAl 2 O 4 spinel and a quite stable film morphology. Instead, the (112-bar0) ZnO -parallel (11-bar02) sapphire and (0001) ZnO -parallel (0001) sapphire interfaces give origin to a new compound (or, possibly, even two new compounds), whose chemical nature is most likely that of a ZnO/Al 2 O 3 phase, with still unknown composition and crystal structure. In addition, in the last two cases, films collapse into prismatic twins of ca. 1 μm in dimension. These experimental findings demonstrate that in a solid-state reaction, the topotactical relationships between the reacting solids are of crucial importance not only in determining the kinetic and mechanisms of the process in its early stages, but even the chemical nature of the product. - Graphical abstract: EXAFS Fourier transforms and morphology of different reactive interfaces between ZnO and Al 2 O 3 .

  17. Pre-compound neutron evaporation in heavy ion fusion reactions

    International Nuclear Information System (INIS)

    Ajay Kumar; Singh, Hardev; Rajesh Kumar; Govil, I.M.; Golda, K.S.; Rakesh Kumar; Datta, S.K.; Yogi, B.K.; Viesti, G.

    2007-01-01

    In the present investigation, exclusive neutron spectra have been measured in coincidence with the observed γ-rays characteristic to the residual nuclei 53 Fe, 55 Fe and 56 Co. In this new experimental study, we have followed the strategy of forming the compound nucleus 58 Ni at the same excitation energy through two different entrance channels viz the mass symmetric reaction 31 P + 27 Al and the mass asymmetric reaction 12 C + 46 Ti

  18. Model studies on the release of aroma compounds from structured and nonstructured oil systems using proton-transfer reaction mass spectrometry.

    Science.gov (United States)

    Landy, Pascale; Pollien, Philippe; Rytz, Andreas; Leser, Martin E; Sagalowicz, Laurent; Blank, Imre; Spadone, Jean-Claude

    2007-03-07

    Relative retention, volatility, and temporal release of volatile compounds taken from aldehyde, ester, and alcohol chemical classes were studied at 70 degrees C in model systems using equilibrium static headspace analysis and real time dynamic headspace analysis. These systems were medium-chain triglycerides (MCT), sunflower oil, and two structured systems, i.e., water-in-oil emulsion and L2 phase (water-in-oil microemulsion). Hydrophilic domains of the emulsion type media retained specifically the hydrophilic compounds and alcohols. Four kinetic parameters characterizing the concentration- and time-dependent releases were extracted from the aroma release curves. Most of the kinetic parameter values were higher in structured systems than in oils particularly when using MCT. The oil nature was found to better control the dynamic release profiles than the system structures. The release parameters were well-related (i) to the volatile hydrophobicity as a function of the oil used and (ii) to the retention data in the specific case of the L2 phase due to a specific release behavior of alcohols.

  19. The reactions of anthronylidene carbene with some heterocyclic compounds

    International Nuclear Information System (INIS)

    Divisia, Bernadette

    1970-01-01

    The action of the anthronylidene carbene, generated by photochemical decomposition of 9-diazo 10-anthron, on four heterocyclic compounds (furan, thiophene, 1-methyl-pyrrole and 2,5-dihydrofuran) has been examined. Two classical carbene reactions have been observed: the addition on double bond (furan, thiophene, 1-methylpyrrole) and hydrogen atom abstraction of the heterocyclic compound (2,5-dihydrofuran). In the case of furan and thiophene, the cyclo-propanic compound resulting from the addition is spontaneously transformed into an ethylenic derivative by valence isomerization. The furan derivative undergoes a cis-trans isomerization, while the thiophene one undergoes an extra carbene attack. In the case of 1-methylpyrrole, the corresponding cyclo-propanic compound undergoes a ring cleavage, followed by a hydrogen atom migration leading to the formation of a substituted anthron. Only an allylic hydrogen atom selective abstraction of heterocyclic compound takes place in the reaction of anthronylidene carbene with 2,5-dihydrofuran. The asymmetrical coupling of radicals so obtained yields the corresponding substituted anthron. (author) [fr

  20. Bulk functionalization of graphene using diazonium compounds and amide reaction

    Science.gov (United States)

    Peng, Chang; Xiong, Yuzi; Liu, Zhibo; Zhang, Fan; Ou, Encai; Qian, Jiangtao; Xiong, Yuanqin; Xu, Weijian

    2013-09-01

    An efficient and convenient method is applied to introduce varieties of simple functionalities onto the graphene surface for the bulk preparation, which begins with pristine graphite that does not require initial oxidative damage of the graphene basal planes. Diazonium compounds functionalized reaction is demonstrated and it successfully prevented the aggregation of graphene for which providing solubility in high polar organic media or even in volatile solvents such as ethanol and acetone. This approach is complemented by the phenyl carboxylic diazonium salt functionalized graphene (PCFG) attachment of a symmetrically substituted zinc phthalocyanine (PCFG-Pc) using the amide reaction, which is used for the covalent introduction of a complex phthalocyanine molecule.

  1. Statistical methods of spin assignment in compound nuclear reactions

    International Nuclear Information System (INIS)

    Mach, H.; Johns, M.W.

    1984-01-01

    Spin assignment to nuclear levels can be obtained from standard in-beam gamma-ray spectroscopy techniques and in the case of compound nuclear reactions can be complemented by statistical methods. These are based on a correlation pattern between level spin and gamma-ray intensities feeding low-lying levels. Three types of intensity and level spin correlations are found suitable for spin assignment: shapes of the excitation functions, ratio of intensity at two beam energies or populated in two different reactions, and feeding distributions. Various empirical attempts are examined and the range of applicability of these methods as well as the limitations associated with them are given. 12 references

  2. Statistical methods of spin assignment in compound nuclear reactions

    International Nuclear Information System (INIS)

    Mach, H.; Johns, M.W.

    1985-01-01

    Spin assignment to nuclear levels can be obtained from standard in-beam gamma-ray spectroscopy techniques and in the case of compound nuclear reactions can be complemented by statistical methods. These are based on a correlation pattern between level spin and gamma-ray intensities feeding low-lying levels. Three types of intensity and level spin correlations are found suitable for spin assignment: shapes of the excitation functions, ratio of intensity at two beam energies or populated in two different reactions, and feeding distributions. Various empirical attempts are examined and the range of applicability of these methods as well as the limitations associated with them are given

  3. Reactions of α-phosphorylated carbonyl compounds with amino alcohols

    International Nuclear Information System (INIS)

    Moskva, V.V.; Sitdikova, T.Sh.; Zykova, T.V.; Alparova, M.V.; Shagvaleev, F.Sh.

    1986-01-01

    2-Aminoethanol reacts with carbonyl compounds with the formation, depending on the structure of the latter, either of a mixture of azomethines and oxazolidines, or of only azomethines. In the development of investigations on the reactivity of α-phosphorylated carbonyl compounds the authors studied the reactions of a number of amino alcohols with phosphorylated acetaldehyde and acetone. In both cases they observed the formation of compounds of enamine structure, oxazolidines and azomethines were not observed. By means of NMR spectroscopy they established clearly the formation of the E-isomeric products. The 1 H, 31 P, and 13 C NMR spectra were recorded on a WP-80 spectrometer. Chemical shifts of protons and 13 C nuclei are given relative to TMS, and phosphorus nuclei relative to orthophosphoric acid

  4. One-nucleon pickup reactions and compound-nuclear decays

    Science.gov (United States)

    Escher, J. E.; Burke, J. T.; Casperson, R. J.; Hughes, R. O.; Scielzo, N. D.

    2018-05-01

    One-nucleon transfer reactions, long used as a tool to study the structure of nuclei, are potentially valuable for determining reaction cross sections indirectly. This is significant, as many reactions of interest to astrophysics and other applications involve short-lived isotopes and cannot be measured directly. We describe a procedure for obtaining constraints for calculations of neutron capture cross sections using observables from experiments with transfer reactions. As a first step toward demonstrating the method, we outline the theory developments used to properly describe the production of the compound nucleus 88Y* via the one-nucleon pickup reaction 89Y(p,d)88Y* and test the description with data from a recent experiment. We indicate how this development can be used to extract the unknown 87Y(n,γ) cross section from 89Y(p,dγ) data. The example illustrates a more generally applicable method for determining unknown cross sections via a combination of theory and transfer (or inelastic scattering) experiments.

  5. Reaction mechanism of coal liquefaction: hydrogenolysis of model compound using synthetic pyrite as catalysts. 7. Property change of synthetic pyrite catalyst with the time after production; Sekitan ekika hanno kiko (model kagobutsu no hanno). 7. Gosei ryukatetsu shokubai no keiji henka ni tsuite

    Energy Technology Data Exchange (ETDEWEB)

    Ito, H.; Meno, H.; Uemaki, O.; Shibata, T.; Tsuji, T. [Hokkaido University, Sapporo (Japan)

    1996-10-28

    Reactions of various model compounds were investigated using synthetic pyrites for coal liquefaction. In this study, successive changes of the catalysts were investigated from the reactions of model compounds by using three different synthetic pyrites with the lapse of time after production. Benzyl phenyl ether, dibenzyl, and n-octylbenzene were used as model compounds. Reactions were conducted in an autoclave, into which sample, catalyst, decalin as solvent, and initial hydrogen pressure 10 MPa were charged. The autoclave was held at 450 or 475{degree}C of reaction temperature for 1 hour. The catalyst with a shorter lapse of time after production acted to hydrogen transfer, and inhibited the formation of condensation products due to the stabilization of decomposed fragment. It also acted to isomerization of materials by cutting alkyl side chains. When adding sulfur to the catalyst with longer lapse of time after production under these reaction conditions, it inhibited the formation of condensation products for the reaction of benzyl phenyl ether. However, it did not provide the effect for the reaction of n-octylbenzene. 5 refs., 3 figs.

  6. CoMo sulphide-catalyzed hydrodeoxygenation of lignin model compounds: An extended reaction network for the conversion of monomeric and dimeric substrates

    NARCIS (Netherlands)

    Jongerius, A.L.; Jastrzebski, R; Bruijnincx, P.C.A.; Weckhuysen, B.M.

    2012-01-01

    In the present work, extensive hydrodeoxygenation (HDO) studies with a commercial sulfided CoMo/Al2O3 catalyst were performed on a library of ligninmodel compounds at 50 bar hydrogen pressure and 300 °C in dodecane, using a batch autoclave system. The catalyst was activated under hydrogen atmosphere

  7. The quantification of free Amadori compounds and amino acids allows to model the bound Maillard reaction products formation in soybean products

    NARCIS (Netherlands)

    Troise, Antonio Dario; Wiltafsky, Markus; Fogliano, Vincenzo; Vitaglione, Paola

    2018-01-01

    The quantification of protein bound Maillard reaction products (MRPs) is still a challenge in food chemistry. Protein hydrolysis is the bottleneck step: it is time consuming and the protein degradation is not always complete. In this study, the quantitation of free amino acids and Amadori products

  8. Study on fluorescence of Maillard reaction compounds in breakfast cereals.

    Science.gov (United States)

    Delgado-Andrade, Cristina; Rufián-Henares, José A; Morales, Francisco J

    2006-09-01

    During the advanced stage of the Maillard reaction (MR) in food processing and cooking, Amadori rearrangement products undergo dehydration and fission and fluorescent substances are formed. Free and total (free + linked to the protein backbone) fluorescence (FIC) due to Maillard compounds in 60 commercial breakfast cereals was evaluated. Pronase was used for efficient release of linked fluorescent Maillard compounds from the protein backbone. Results were correlated with some heat-induced markers of the extent of the MR or sugar caramelisation during cereal processing, such as hydroxymethylfurfural, furfural, glucosilisomaltol and furosine. The effect of sample composition (dietary-fibre added, protein, etc.) on levels of FIC, expressed as fluorescence intensity (FI) per milligram of sample, is discussed. FIC is significantly correlated to the protein content of the sample and fluorescent Maillard compounds are mainly linked to the protein backbone. The ratio of total-FIC to free-FIC was 10.4-fold for corn-based, wheat-based and multicereal-based breakfast cereals but significantly higher in rice-based samples. Addition of dietary fibre or honey increased the FIC values. Data support the usefulness of FIC measurement as an unspecific heat-induced marker in breakfast cereals.

  9. Decay analysis of compound nuclei formed in reactions with exotic neutron-rich 9Li projectile and the synthesis of 217At* within the dynamical cluster-decay model

    Science.gov (United States)

    Kaur, Arshdeep; Kaushal, Pooja; Hemdeep; Gupta, Raj K.

    2018-01-01

    The decay of various compound nuclei formed via exotic neutron-rich 9Li projectile is studied within the dynamical cluster-decay model (DCM). Following the earlier work of one of us (RKG) and collaborators (M. Kaur et al. (2015) [1]), for an empirically fixed neck-length parameter ΔRemp, the only parameter in the DCM, at a given incident laboratory energy ELab, we are able to fit almost exactly the (total) fusion cross section σfus =∑x=16σxn for 9Li projectile on 208Pb and other targets, with σfus depending strongly on the target mass of the most abundant isotope and its (magic) shell structure. This result shows the predictable nature of the DCM. The neck-length parameter ΔRemp is fixed empirically for the decay of 217At* formed in 9Li + 208Pb reaction at a fixed laboratory energy ELab, and then the total fusion cross section σfus calculated for all other reactions using 9Li as a projectile on different targets. Apparently, this procedure could be used to predict σfus for 9Li-induced reactions where experimental data are not available. Furthermore, optimum choice of "cold" target-projectile combinations, forming "hot" compact configurations, are predicted for the synthesis of compound nucleus 217At* with 8Li + 209Pb as one of the target-projectile combination, or another (t , p) combination 48Ca + 169Tb, with a doubly magic 48Ca, as the best possibility.

  10. Modeling chemical reactions for drug design.

    Science.gov (United States)

    Gasteiger, Johann

    2007-01-01

    Chemical reactions are involved at many stages of the drug design process. This starts with the analysis of biochemical pathways that are controlled by enzymes that might be downregulated in certain diseases. In the lead discovery and lead optimization process compounds have to be synthesized in order to test them for their biological activity. And finally, the metabolism of a drug has to be established. A better understanding of chemical reactions could strongly help in making the drug design process more efficient. We have developed methods for quantifying the concepts an organic chemist is using in rationalizing reaction mechanisms. These methods allow a comprehensive modeling of chemical reactivity and thus are applicable to a wide variety of chemical reactions, from gas phase reactions to biochemical pathways. They are empirical in nature and therefore allow the rapid processing of large sets of structures and reactions. We will show here how methods have been developed for the prediction of acidity values and of the regioselectivity in organic reactions, for designing the synthesis of organic molecules and of combinatorial libraries, and for furthering our understanding of enzyme-catalyzed reactions and of the metabolism of drugs.

  11. Selective Oxidation of Lignin Model Compounds.

    Science.gov (United States)

    Gao, Ruili; Li, Yanding; Kim, Hoon; Mobley, Justin K; Ralph, John

    2018-05-02

    Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO 2 Cl 2 (DMSO) 2 , and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Reactions of aromatic diazonium salts with unsaturated compounds in the presence of nucleophiles

    Science.gov (United States)

    Grishchuk, B. D.; Gorbovoi, P. M.; Ganushchak, N. I.; Dombrovskii, A. V.

    1994-03-01

    The review surveys the reactions of aromatic diazonium salts with diene and monounsaturated compounds in the presence of nucleophiles. Certain further reactions of the reaction products and their application are considered. The bibliography includes 63 references.

  13. Reduction of chemical reaction models

    Science.gov (United States)

    Frenklach, Michael

    1991-01-01

    An attempt is made to reconcile the different terminologies pertaining to reduction of chemical reaction models. The approaches considered include global modeling, response modeling, detailed reduction, chemical lumping, and statistical lumping. The advantages and drawbacks of each of these methods are pointed out.

  14. The quantification of free Amadori compounds and amino acids allows to model the bound Maillard reaction products formation in soybean products.

    Science.gov (United States)

    Troise, Antonio Dario; Wiltafsky, Markus; Fogliano, Vincenzo; Vitaglione, Paola

    2018-05-01

    The quantification of protein bound Maillard reaction products (MRPs) is still a challenge in food chemistry. Protein hydrolysis is the bottleneck step: it is time consuming and the protein degradation is not always complete. In this study, the quantitation of free amino acids and Amadori products (APs) was compared to the percentage of blocked lysine by using chemometric tools. Eighty thermally treated soybean samples were analyzed by mass spectrometry to measure the concentration of free amino acids, free APs and the protein-bound markers of the Maillard reaction (furosine, Nε-(carboxymethyl)-l-lysine, Nε-(carboxyethyl)-l-lysine, total lysine). Results demonstrated that Discriminant Analysis (DA) and Correlated Component Regression (CCR) correctly estimated the percent of blocked lysine in a validation and prediction set. These findings indicate that the measure of free markers reflects the extent of protein damage in soybean samples and it suggests the possibility to obtain rapid information on the quality of the industrial processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Compound Nucleus Reactions in LENR, Analogy to Uranium Fission

    Science.gov (United States)

    Hora, Heinrich; Miley, George; Philberth, Karl

    2008-03-01

    The discovery of nuclear fission by Hahn and Strassmann was based on a very rare microanalytical result that could not initially indicate the very complicated details of this most important process. A similarity is discussed for the low energy nuclear reactions (LENRs) with analogies to the yield structure found in measurements of uranium fission. The LENR product distribution measured earlier in a reproducible way in experiments with thin film electrodes and a high density deuteron concentration in palladium has several striking similarities with the uranium fission fragment yield curve.ootnotetextG.H. Miley and J.A. Patterson, J. New Energy 1, 11 (1996); G.H. Miley et al, Proc ICCF6, p. 629 (1997).This comparison is specifically focussed to the Maruhn-Greiner local maximum of the distribution within the large-scale minimum when the fission nuclei are excited. Implications for uranium fission are discussed in comparison with LENR relative to the identification of fission a hypothetical compound nuclear reaction via a element ^306X126 with double magic numbers.

  16. Electron transfer reactions of macrocyclic compounds of cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Heckman, R.A.

    1978-08-01

    The kinetics and mechanisms of reduction of H/sub 2/O/sub 2/, Br/sub 2/, and I/sub 2/ by various macrocyclic tetraaza complexes of cobalt(II), including Vitamin B/sub 12r/, were studied. The synthetic macrocycles studied were all 14-membered rings which varied in the degree of unsaturation,substitution of methyl groups on the periphery of the ring, and substitution within the ring itself. Scavenging experiments demonstrated that the reductions of H/sub 2/O/sub 2/ produce free hydroxyl radicals only in the case of Co((14)ane)/sup 2 +/ but with none of the others. In the latter instances apparently H/sub 2/O/sub 2/ simultaneously oxidizes the metal center and the ligand. The reductions of Br/sub 2/ and I/sub 2/ produce an aquohalocobalt(III) product for all reductants (except B/sub 12r/ + Br/sub 2/, which was complicated by bromination of the corrin ring). The mechanism of halogen reduction was found to involve rate-limiting inner-sphere electron transfer from cobalt to halogen to produce a dihalide anion coordinated to the cobalt center. This intermediate subsequently decomposes in rapid reactions to halocobalt(III) and halogen atom species or reacts with another cobalt(II) center to give two molecules of halocobalt(III). The reductions of halomethylcobaloximes and related compounds and diamminecobaloxime by Cr/sup 2 +/ were also studied. The reaction was found to be biphasic in all cases with the reaction products being halomethane (for the halomethylcobaloximes), Co/sup 2 +/ (in less than 100 percent yield), a Cr(III)-dimethylglyoxime species, a small amount of free dmgH/sub 2/, and a highly-charged species containing both cobalt and chromium. The first-stage reaction occurs with a stoichiometry of 1:1 producing an intermediate with an absorption maximum at 460 nm for all starting reagents. The results were interpreted in terms of inner-sphere coordination of the cobaloxime to the Cr(II) and electron transfer through the oxime N-O bond.

  17. Modeling of fluctuating reaction networks

    International Nuclear Information System (INIS)

    Lipshtat, A.; Biham, O.

    2004-01-01

    Full Text:Various dynamical systems are organized as reaction networks, where the population size of one component affects the populations of all its neighbors. Such networks can be found in interstellar surface chemistry, cell biology, thin film growth and other systems. I cases where the populations of reactive species are large, the network can be modeled by rate equations which provide all reaction rates within mean field approximation. However, in small systems that are partitioned into sub-micron size, these populations strongly fluctuate. Under these conditions rate equations fail and the master equation is needed for modeling these reactions. However, the number of equations in the master equation grows exponentially with the number of reactive species, severely limiting its feasibility for complex networks. Here we present a method which dramatically reduces the number of equations, thus enabling the incorporation of the master equation in complex reaction networks. The method is examplified in the context of reaction network on dust grains. Its applicability for genetic networks will be discussed. 1. Efficient simulations of gas-grain chemistry in interstellar clouds. Azi Lipshtat and Ofer Biham, Phys. Rev. Lett. 93 (2004), 170601. 2. Modeling of negative autoregulated genetic networks in single cells. Azi Lipshtat, Hagai B. Perets, Nathalie Q. Balaban and Ofer Biham, Gene: evolutionary genomics (2004), In press

  18. A study on the hierarchy model of nuclear reactions

    International Nuclear Information System (INIS)

    Kitazoe, Yasuhiro; Sekiya, Tamotsu

    1975-01-01

    The application of the hierarchy model of nuclear reaction is discussed, and the hierarchy model means that the compound nucleus state is formed after several steps, at least, one step of reaction. This model was applied to the analysis of the observed cross sections of 235 U and some other elements. Neglecting exchange scattering effect, the equations for the total neutron cross section of 235 U were obtained. One of these equations describes explicitly the hierarchy of the transition from intermediate reaction state Xm into the compound nucleus state Xs, and another one describes the cross section averaged over an energy interval larger than the average level spacing of compound nucleus eigenvalues. The hierarchy of reaction mechanism was investigated in more detail, and the hierarchy model was applied to the case of unresolved energy region. It was not tried to evaluate the strength function in the mass region (A>140), since the effect of nuclear deformation was neglected in the task. (Iwase, T.)

  19. Productions of Volatile Organic Compounds (VOCs) in Surface Waters from Reactions with Atmospheric Ozone

    Science.gov (United States)

    Hopkins, Frances; Bell, Thomas; Yang, Mingxi

    2017-04-01

    Ozone (O3) is a key atmospheric oxidant, greenhouse gas and air pollutant. In marine environments, some atmospheric ozone is lost by reactions with aqueous compounds (e.g. dissolved organic material, DOM, dimethyl sulfide, DMS, and iodide) near the sea surface. These reactions also lead to formations of volatile organic compounds (VOCs). Removal of O3 by the ocean remains a large uncertainty in global and regional chemical transport models, hampering coastal air quality forecasts. To better understand the role of the ocean in controlling O3 concentrations in the coastal marine atmosphere, we designed and implemented a series of laboratory experiments whereby ambient surface seawater was bubbled with O3-enriched, VOC-free air in a custom-made glass bubble equilibration system. Gas phase concentrations of a range of VOCs were monitored continuously over the mass range m/z 33 - 137 at the outflow of the bubble equilibrator by a proton transfer reaction - mass spectrometer (PTR-MS). Gas phase O3 was also measured at the input and output of the equilibrator to monitor the uptake due to reactions with dissolved compounds in seawater. We observed consistent productions of a variety of VOCs upon reaction with O3, notably isoprene, aldehydes, and ketones. Aqueous DMS is rapidly removed from the reactions with O3. To test the importance of dissolved organic matter precursors, we added increasing (milliliter) volumes of Emiliania huxleyi culture to the equilibrator filled with aged seawater, and observed significant linear increases in gas phase concentrations of a number of VOCs. Reactions between DOM and O3 at the sea-air interface represent a potentially significant source of VOCs in marine air and a sink of atmospheric O3.

  20. Reaction between phenyl derivatives of lanthanides and carbonyl compounds

    International Nuclear Information System (INIS)

    Sigalov, A.B.; Petrov, Eh.S.; Rybakova, L.F.; Beletskaya, I.P.

    1983-01-01

    Reactions of PhLnI (Ln=Yb, Eu, Sm, Ce) with α, β-unsaturated ketons (trans-chalcone and benzalacetone) are considered as well as with 9-fluorene and benzophenone. The regioselectivity of the reaction of PhLnI addition to enones is compared with similar reactions of PhMgX and PhLi. The reaction between PhLnI and trans-chalcone proceeds regiospecifically as 1, 2-addition in contrast with reactions of PhMgI and PhLi. A new reaction of lanthanide carbinolate deoxygenation under the effect of reducers was found. The reaction product yields are presented

  1. Odd-Z Transactinide Compound Nucleus Reactions Including the Discovery of 260Bh

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, Sarah L. [Univ. of California, Berkeley, CA (United States)

    2008-01-01

    Several reactions producing odd-Z transactinide compound nuclei were studiedwith the 88-Inch Cyclotron and the Berkeley Gas-Filled Separator at the Lawrence Berkeley National Laboratory. The goal was to produce the same compound nucleus ator near the same excitation energy with similar values of angular momentum via differentnuclear reactions. In doing so, it can be determined if there is a preference in entrancechannel, because under these experimental conditions the survival portion of Swiatecki, Siwek-Wilcznska, and Wilczynski's"Fusion By Diffusion" model is nearly identical forthe two reactions. Additionally, because the same compound nucleus is produced, theexit channel is the same. Four compound nuclei were examined in this study: 258Db, 262Bh, 266Mt, and 272Rg. These nuclei were produced by using very similar heavy-ion induced-fusion reactions which differ only by one proton in the projectile or target nucleus (e.g.: 50Ti + 209Bi vs. 51V + 208Pb). Peak 1n exit channel cross sections were determined for each reaction in each pair, and three of the four pairs' cross sections were identical within statistical uncertainties. This indicates there is not an obvious preference of entrancechannel in these paired reactions. Charge equilibration immediately prior to fusionleading to a decreased fusion barrier is the likely cause of this phenomenon. In addition to this systematic study, the lightest isotope of element 107, bohrium, was discovered in the 209Bi(52Cr,n) reaction. 260Bh was found to decay by emission of a 10.16 MeV alpha particle with a half-life of 35$+19\\atop{-9}$ ms. The cross section is 59 pb at an excitation energy of 15.0 MeV. The effect of the N = 152 shell is also seen in this isotope's alpha particle energy, the first evidence of such an effect in Bh. All reactions studied are also compared to model predictions by Swiatecki

  2. Odd-Z Transactinide Compound Nucleus Reactions Including the Discovery of 260Bh

    International Nuclear Information System (INIS)

    Nelson, Sarah L; Nelson, Sarah L

    2008-01-01

    Several reactions producing odd-Z transactinide compound nuclei were studied with the 88-Inch Cyclotron and the Berkeley Gas-Filled Separator at the Lawrence Berkeley National Laboratory. The goal was to produce the same compound nucleus at or near the same excitation energy with similar values of angular momentum via different nuclear reactions. In doing so, it can be determined if there is a preference in entrance channel, because under these experimental conditions the survival portion of Swiatecki, Siwek-Wilcznska, and Wilczynski's 'Fusion By Diffusion' model is nearly identical for the two reactions. Additionally, because the same compound nucleus is produced, the exit channel is the same. Four compound nuclei were examined in this study: 258Db, 262Bh, 266Mt, and 272Rg. These nuclei were produced by using very similar heavy-ion induced-fusion reactions which differ only by one proton in the projectile or target nucleus (e.g.: 50Ti + 209Bi vs. 51V + 208Pb). Peak 1n exit channel cross sections were determined for each reaction in each pair, and three of the four pairs; cross sections were identical within statistical uncertainties. This indicates there is not an obvious preference of entrance channel in these paired reactions. Charge equilibration immediately prior to fusion leading to a decreased fusion barrier is the likely cause of this phenomenon. In addition to this systematic study, the lightest isotope of element 107, bohrium, was discovered in the 209Bi(52Cr,n) reaction. 260Bh was found to decay by emission of a 10.16 MeV alpha particle with a half-life of 35 ms. The cross section is 59 pb at an excitation energy of 15.0 MeV. The effect of the N = 152 shell is also seen in this isotope's alpha particle energy, the first evidence of such an effect in Bh. All reactions studied are also compared to model predictions by Swiatecki, Siwek-Wilcznska, and Wilczynski's 'Fusion By Diffusion' theory

  3. Modelling Students' Visualisation of Chemical Reaction

    Science.gov (United States)

    Cheng, Maurice M. W.; Gilbert, John K.

    2017-01-01

    This paper proposes a model-based notion of "submicro representations of chemical reactions". Based on three structural models of matter (the simple particle model, the atomic model and the free electron model of metals), we suggest there are two major models of reaction in school chemistry curricula: (a) reactions that are simple…

  4. Dynamical hindrance to compound nucleus formation in heavy ion reactions

    International Nuclear Information System (INIS)

    Blocki, J.; Feldmeier, H.; Swiatecki, W.J.

    1987-01-01

    A large number of dynamical trajectories corresponding to colliding nuclei, as represented by an idealized, sharp-surfaced liquid-drop model with one-body dissipation are examined. The objective was to delineate quantitatively, within this model, the behaviour of the extra-extra-push energy E XX in its dependence on the mass /or charge/ numbers of the colliding nuclei. Qualitatively, the results are as anticipated on the basis of earlier studies: the appearance of a dynamical limitation on compound nucleus formation beyond a certain threshold locus in the A 1 . A 2 plane, with the energy E XX rising smoothly but rapidly beyond the threshold. The reduction of the two-dimensional function E XX /A 1 ,A 2 / to a one-dimensional function of a mean fissility x m appears possible as a rough approximation. As expected, the mean fissility x and the entrance channel fissility x 0 . The optimum choice appears to be one in which x is given about twice the weight of x 0

  5. Integrated modelling of two xenobiotic organic compounds

    DEFF Research Database (Denmark)

    Lindblom, Erik Ulfson; Gernaey, K.V.; Henze, Mogens

    2006-01-01

    This paper presents a dynamic mathematical model that describes the fate and transport of two selected xenobiotic organic compounds (XOCs) in a simplified representation. of an integrated urban wastewater system. A simulation study, where the xenobiotics bisphenol A and pyrene are used as reference...... compounds, is carried out. Sorption and specific biological degradation processes are integrated with standardised water process models to model the fate of both compounds. Simulated mass flows of the two compounds during one dry weather day and one wet weather day are compared for realistic influent flow...... rate and concentration profiles. The wet weather day induces resuspension of stored sediments, which increases the pollutant load on the downstream system. The potential of the model to elucidate important phenomena related to origin and fate of the model compounds is demonstrated....

  6. Progress in microscopic direct reaction modeling of nucleon induced reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dupuis, M.; Bauge, E.; Hilaire, S.; Lechaftois, F.; Peru, S.; Pillet, N.; Robin, C. [CEA, DAM, DIF, Arpajon (France)

    2015-12-15

    A microscopic nuclear reaction model is applied to neutron elastic and direct inelastic scatterings, and pre-equilibrium reaction. The JLM folding model is used with nuclear structure information calculated within the quasi-particle random phase approximation implemented with the Gogny D1S interaction. The folding model for direct inelastic scattering is extended to include rearrangement corrections stemming from both isoscalar and isovector density variations occurring during a transition. The quality of the predicted (n,n), (n,n{sup '}), (n,xn) and (n,n{sup '}γ) cross sections, as well as the generality of the present microscopic approach, shows that it is a powerful tool that can help improving nuclear reactions data quality. Short- and long-term perspectives are drawn to extend the present approach to more systems, to include missing reactions mechanisms, and to consistently treat both structure and reaction problems. (orig.)

  7. Multiresponse modelling of the caramelisation reaction

    OpenAIRE

    Quintas, Mafalda; Guimarães, Carla; Baylina, João; Brandão, Teresa R. S.; Silva, Cristina L.M.

    2007-01-01

    Multiresponse modelling is a powerful tool for studying complex kinetics of reactions occurring in food products. This modelling technique uses information of reactants and products involved, allowing insightful kinetic parameters estimation and helping in clarifying reaction mechanisms. One example of a complex reaction that occurs in food processing is the caramelisation reaction. Caramelisation is the common name for a group of reactions observed when carbohydrates are exposed to high temp...

  8. Dependence of compound nucleus formation probability on K equilibration time in heavy-ion reactions

    International Nuclear Information System (INIS)

    Yadav, C.; Thomas, R.G.; Mohanty, A.K.; Kapoor, S.S.

    2014-01-01

    In the present work, we have carried out the analysis of fragment anisotropy data of various systems selected for cases Z 1 Z 2 < 1600 and Z CN < 96 so that both QF and FF are absent and the anomalous anisotropies are only due to PEF. It may also be noted that in such cases J cr (the J above which the fusion pocket vanishes) is less than J Bf = 0 (the J at which the liquid drop fission barrier vanishes) so that all J's will be contributing to PEF as well. According to PEF model, the observed angular anisotropy of fission fragments in heavy-ion induced reactions can be written as an admixture of two components: the anisotropy from compound nucleus fission (CN) and anisotropy due to non-compound nucleus fission (NCN)

  9. The nested-doorway model of multistep compound processes

    International Nuclear Information System (INIS)

    Hussein, M.S.

    1982-05-01

    The multistep compound contribution to preequilibrium reaction are discussed within the nested-doorway model. Emphasis is placed on the generalized cross-section auto-correlation function. Several of the more widely used concepts in the conventional, one-class, statistical analysis are discussed and generalized to the multiclass case. A summary of the formal results of the nested-doorway model, obtained within Feshbach's projection operator theory is given. (Author) [pt

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

    Energy Technology Data Exchange (ETDEWEB)

    Froehaug, Astrid Elisabeth

    1995-12-31

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

  11. Recent advances in the chemistry of Rh carbenoids: multicomponent reactions of diazocarbonyl compounds

    International Nuclear Information System (INIS)

    Medvedev, J J; Nikolaev, V A

    2015-01-01

    Multicomponent reactions of diazo compounds catalyzed by Rh II complexes become a powerful tool for organic synthesis. They enable three- or four-step processes to be carried out as one-pot procedures (actually as one step) with high stereoselectivity to give complex organic molecules, including biologically active compounds. This review addresses recent results in the chemistry of Rh-catalyzed multicomponent reactions of diazocarbonyl compounds with the intermediate formation of N-, O- and C=O–ylides. The diastereo- and enantioselectivity of these reactions and the possibility of using various co-catalysts to increase the efficiency of the processes under consideration are discussed. The bibliography includes 120 references

  12. Reaction of acid esters of methylenebis(phosphonous acid) with carbonyl compounds

    International Nuclear Information System (INIS)

    Novikova, Z.S.; Odinets, I.L.; Lutsenko, I.F.

    1987-01-01

    The reaction of methylenebis(phosphonites) containing two hydrophosphoryl groupings with aliphatic and aromatic aldehydes and ketones in the presence of alkali metal fluorides leads to methylenebis(α-hydroxyalkylphosphinates). The reaction of methylenebis(phosphonites) containing one hydrophosphoryl groupings with carbonyl compounds in the presence of alkali metal fluorides proceeds with the formation of a new type of heterocyclic phosphorus compound, viz., 1,2λ 3 ,4λ 5 -oxadiphospholanes. The reaction of acid esters of methylenebis(phosphonous) acid with carbonyl compounds in the presence of alkali metal alkoxides or a tertiary amine is accompanied by phosphinate-phosphonate rearrangement of the intermediately formed α-hydroxylalkylphosphinates

  13. cyclo-addition reaction of triplet carbonyl compounds to substituted ...

    Indian Academy of Sciences (India)

    Unknown

    cited state energy of the olefin must be higher than that of the ketone so that ... the first singlet and triplet1,3 (n, π*) excited state of the carbonyl compounds.3,4 ... of the oxetane via carbon–carbon and carbon–oxygen attacks. They found the ...

  14. Atmospheric Gas-Phase Reactions of Fluorinated Compounds and Alkenes

    DEFF Research Database (Denmark)

    Østerstrøm, Freja From

    Experimental studies have been performed using three different smog chamber setups to investigate the atmospheric chemistry of fluorinated compounds as well as alkenes. The three instruments were at Ford Motor Company, USA, National Center for Atmospheric Research, USA, and Copenhagen Center...

  15. The olefin metathesis reaction: reorganization and cyclization of organic compounds

    International Nuclear Information System (INIS)

    Frederico, Daniel; Brocksom, Ursula; Brocksom, Timothy John

    2005-01-01

    The olefin metathesis reaction allows the exchange of complex alkyl units between two olefins, with the formation of a new olefinic link and a sub-product olefin usually ethylene. This reaction has found extensive application in the last ten years with the development of the Grubbs and Schrock catalysts, in total synthesis of complex organic molecules, as opposed to the very important use in the petrochemical industry with relatively simple molecules. This review intends to trace a historical and mechanistic pathway from industry to academy, before illustrating the more recent advances. (author)

  16. using stereochemistry models in teaching organic compounds

    African Journals Online (AJOL)

    Preferred Customer

    The purpose of the study was to find out the effect of stereochemistry models on students' ... consistent with the names given to organic compounds. Some of ... Considering class level, what is the performance of the students in naming organic.

  17. Stochastic interest rates model in compounding | Galadima ...

    African Journals Online (AJOL)

    Stochastic interest rates model in compounding. ... in finance, real estate, insurance, accounting and other areas of business administration. The assumption that future rates are fixed and known with certainty at the beginning of an investment, ...

  18. Modelling of the Kinetics of Sulfure Compounds in Desulfurisation Processes Based on Industry Data of Plant

    Directory of Open Access Journals (Sweden)

    Krivtcova Nadezhda

    2016-01-01

    Full Text Available Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.

  19. Modelling of the Kinetics of Sulfure Compounds in Desulfurisation Processes Based on Industry Data of Plant

    OpenAIRE

    Krivtsova, Nadezhda Igorevna; Tataurshikov, A.; Kotkova, Elena

    2016-01-01

    Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.

  20. Statistical features of pre-compound processes in nuclear reactions

    International Nuclear Information System (INIS)

    Hussein, M.S.; Rego, R.A.

    1983-04-01

    Several statistical aspects of multistep compound processes are discussed. The connection between the cross-section auto-correlation function and the average number of maxima is emphasized. The restrictions imposed by the non-zero value of the energy step used in measuring the excitation fuction and the experimental error are discussed. Applications are made to the system 25 Mg( 3 He,p) 27 Al. (Author) [pt

  1. Basic features of compound and deep inelastic reactions

    International Nuclear Information System (INIS)

    Gregoire, C.

    1984-03-01

    After a general introduction and a lecture devoted to the dissipation mechanisms, we will study successively the charge equilibration, the angular momentum transfer, the mass exchanges and the compound nucleus formation with its de-excitation. The deformation degrees of freedom are considered when necessary. The self consistent treatments are not presented here and we refer for this purpose to the other lectures on this topic given during the School

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

    International Nuclear Information System (INIS)

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

    1988-05-01

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

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

    International Nuclear Information System (INIS)

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

    1988-07-01

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

  4. The use of quantum chemically derived descriptors for QSAR modelling of reductive dehalogenation of aromatic compounds

    NARCIS (Netherlands)

    Rorije E; Richter J; Peijnenburg WJGM; ECO; IHE Delft

    1994-01-01

    In this study, quantum-chemically derived parameters are developed for a limited number of halogenated aromatic compounds to model the anaerobic reductive dehalogenation reaction rate constants of these compounds. It is shown that due to the heterogeneity of the set of compounds used, no single

  5. Pyridine group assisted addition of diazo-compounds to imines in the 3-CC reaction of 2-aminopyridines, aldehydes, and diazo-compounds.

    Science.gov (United States)

    Gulevich, Anton V; Helan, Victoria; Wink, Donald J; Gevorgyan, Vladimir

    2013-02-15

    A novel three-component coupling (3-CC) reaction of 2-aminoazines, aromatic aldehydes, and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles as well as β-amino acid derivatives.

  6. Basic features of compound and deep inelastic reactions

    International Nuclear Information System (INIS)

    Gregoire, G.

    1985-01-01

    The aim of the lectures is to give, within a phenomenological standpoint of view, an idea of a few theoretical approaches which are currently used for the studies of the low-energy heavy ion collisions. In this aspect, these lectures are by no means a review of our existing knowledge of the phenomena involved during the collisions. The authors hope that they will be able to provide the students with some tools which permit to analyze the experimental results. Indeed, they believe that a good comprehension of the basic mechanisms requires an appropriate definition of collective variables. The dynamical behaviour of these collective variables gives some scenario explaining the behaviour of the corresponding observables. The coupling to the intrinsic system can be considered as responsible for the dissipative nature of the processes: deep inelastic collisions, fast fission and compound nucleus formation. After a general introduction and a lecture devoted to the dissipation mechanisms, they discuss charge equilibration, angular momentum transfer, mass exchange and compound nucleus formation with its de-excitation. The deformation degrees of freedom are considered when necessary. The self consistent treatments are not presented here

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

    Science.gov (United States)

    Haryani, S.; Kurniawan, C.; Kasmui

    2018-04-01

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

  8. Diazo Compounds as Highly Tunable Reactants in 1,3-Dipolar Cycloaddition Reactions with Cycloalkynes†

    Science.gov (United States)

    McGrath, Nicholas A.

    2012-01-01

    Diazo compounds, which can be accessed directly from azides by deimidogenation, are shown to be extremely versatile dipoles in 1,3-dipolar cycloaddition reactions with a cyclooctyne. The reactivity of a diazo compound can be much greater or much less than its azide analog, and is enhanced markedly in polar-protic solvents. These reactivities are predictable from frontier molecular orbital energies. The most reactive diazo compound exhibited the highest known second-order rate constant to date for a dipolar cycloaddition with a cycloalkyne. These data provide a new modality for effecting chemoselective reactions in a biological context. PMID:23227302

  9. Oriented heavy ions and the choice of a cool compound nucleus reaction

    International Nuclear Information System (INIS)

    Aroumougame, R.; Gupta, R.K.

    1980-01-01

    Potential energy surfaces are calculated within the mechanism of fragmentation theory with a view to selecting the target-projectile combinations for producing new elements through cool compound nucleus formation. The orientation of the colliding nuclei is also included. It is shown that both the reaction partners of a cool compound nucleus, formed in either a central or a nearly central collision, should preferably be spherical and either nearly symmetric or extremely asymmetric. For reactions with deformed nuclei, it is suggested that polarised targets should be used. The calculations are illustrated for the compound nuclei 258 104 and 260 106. (author)

  10. The Atmospheric Oxidation of Volatile Organic Compounds Through Hydrogen Shift Reactions

    DEFF Research Database (Denmark)

    Knap, Hasse Christian

    a radical is denoted as a H-shift reaction. Quantum chemical calculations were carried out to investigate the potential energy surface of the H-shift reactions and the subsequent decomposition pathways. The transition state theory including the Eckart quantum tunneling correction have been used to calculate...... the reaction rate constants of the H-shift reactions. The autoxidation of volatile organic compounds is an important oxidation mechanism that produces secondary organic aerosols (SOA) and recycles hydroxyl (OH) radicals. The autoxidation cycle produces a second generation peroxy radical (OOQOOH) through...... a series of H-shift reactions and O2 attachments. I have investigated the H-shift reactions in two OOQOOH radicals (hydroperoxy peroxy radicals and hydroperoxy acyl peroxy radicals). The H-shift reaction rate constants have been compared with the bimolecular reaction rate constants of the peroxy radicals...

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

    DEFF Research Database (Denmark)

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

    2014-01-01

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

  12. Reactions between sodium and various carbon bearing compounds

    Energy Technology Data Exchange (ETDEWEB)

    Raine, A C; Thorley, A W [UKAEA, Risley, Warrington, Cheshire (United Kingdom)

    1980-05-01

    The presence of carbon bearing materials in liquid sodium is undesirable because of their ability to carburise stainless steel components. It has been demonstrated for example that carbon taken up by stainless steels can affect their mechanical properties and that thinner sectioned material such as fuel cladding and the tubing of intermediate heat exchanger may be more sensitive to such effects. Generally speaking, there are a number of potential carbon sources in reactor systems. Some of the sources such as the graphite in neutron shield rods, boron carbide in control rods and carbide fuels are part of the reactor designs while others such as oil in mechanical pumps arid 'coupling-fluids' used to inspect plant components are associated with the respective operation arid inspection of the plant. In this paper it is intended to discuss in general terms the way these various compounds behave in liquid sodium and to assess what effect their presence will have on the materials of construction in fast reactor systems. The paper also reviews the chemistry of the environment in relation to the types of carburizing species which may exist in sodium systems.

  13. Third international workshop on compound nuclear reactions and related topics. Book of abstracts

    International Nuclear Information System (INIS)

    2012-09-01

    The conference was divided into the following sections: Fission; Surrogate reactions; Heavy ion reactions; Neutron-induced reactions; Gamma-ray strength functions; Nuclear astrophysics; Superheavy nuclei; Nuclear level density; Various nuclear reactions; Optical model simulations; and Pre-equilibrium. The publication contains 82 abstracts. (P.A.)

  14. Delineating pMDI model reactions with loblolly pine via solution-state NMR spectroscopy. Part 1, Catalyzed reactions with wood models and wood polymers

    Science.gov (United States)

    Daniel J. Yelle; John Ralph; Charles R. Frihart

    2011-01-01

    To better understand adhesive interactions with wood, reactions between model compounds of wood and a model compound of polymeric methylene diphenyl diisocyanate (pMDI) were characterized by solution-state NMR spectroscopy. For comparison, finely ground loblolly pine sapwood, milled-wood lignin and holocellulose from the same wood were isolated and derivatized with...

  15. Hydrodeoxygenation of mono- and dimeric lignin model compounds on noble metal catalysts

    NARCIS (Netherlands)

    Guvenatam, Burcu; Kursun, Osman; Heeres, Hero; Pidko, Evgeny A.; Hensen, Emiel J. M.

    2014-01-01

    The influence of reaction conditions (temperature, acidity) on the catalytic performance of supported Pt, Pd and Ru catalysts for the aqueous phase hydrodeoxygenation (HDO) of lignin model compounds was systematically investigated. Phenol conversion proceeds via hydrogenation of the aromatic ring

  16. In silico strain optimization by adding reactions to metabolic models.

    Science.gov (United States)

    Correia, Sara; Rocha, Miguel

    2012-07-24

    Nowadays, the concerns about the environment and the needs to increase the productivity at low costs, demand for the search of new ways to produce compounds with industrial interest. Based on the increasing knowledge of biological processes, through genome sequencing projects, and high-throughput experimental techniques as well as the available computational tools, the use of microorganisms has been considered as an approach to produce desirable compounds. However, this usually requires to manipulate these organisms by genetic engineering and/ or changing the enviromental conditions to make the production of these compounds possible. In many cases, it is necessary to enrich the genetic material of those microbes with hereologous pathways from other species and consequently adding the potential to produce novel compounds. This paper introduces a new plug-in for the OptFlux Metabolic Engineering platform, aimed at finding suitable sets of reactions to add to the genomes of selected microbes (wild type strain), as well as finding complementary sets of deletions, so that the mutant becomes able to overproduce compounds with industrial interest, while preserving their viability. The necessity of adding reactions to the metabolic model arises from existing gaps in the original model or motivated by the productions of new compounds by the organism. The optimization methods used are metaheuristics such as Evolutionary Algorithms and Simulated Annealing. The usefulness of this plug-in is demonstrated by a case study, regarding the production of vanillin by the bacterium E. coli.

  17. A study on superoxide dismutase activity of some model compounds.

    Science.gov (United States)

    Liao, Z; Liu, W; Liu, J; Jiang, Y; Shi, J; Liu, C

    1994-08-15

    The synthesis and characteristics of a binuclear ligand N,N,N',N'-tetrakis (2'-benzimidazolyl methyl)-1,4-diethylene amino glycol ether (EGTB) and its series of coordination compounds containing copper(II), iron(III), and manganese(II) with and without exogenous bridging ligand which was imidazolate ion (Im-), bipyridine (bpy), or 1,10-phenanthroline (phen) are reported. Depending on the redox potentials by cyclic voltammetry, the coordination compounds can act as catalysts for the dismutation of superoxide radicals (O2-). The detection of the rate constant of the reaction of superoxide ion with nitroblue tetrazolium (NBT) which is inhibited by superoxide dismutase (SOD) and its model compounds of the EGTB system has been performed by a modified illumination method. The rate constants kQ of the catalytic dismutation have been obtained.

  18. Entity models for trigger-reaction documents

    NARCIS (Netherlands)

    Khalid, M.A.; Marx, M.; Makkes, M.X.

    2008-01-01

    We define the notion of an entity model for a special kind of document popular on the web: an article followed by a list of reactions on that article, usually by many authors, usually inverse chronologically ordered. We call these documents trigger-reactions pairs. The entity model describes which

  19. Sodium-concrete reaction model development

    International Nuclear Information System (INIS)

    Nguyen, D.H.; Muhlestein, L.D.; Postma, A.K.

    1982-07-01

    Major observations have been formulated after reviewing test results for over 100 sodium-concrete reaction tests. The observations form the basis for developing a mechanistic model to predict the transient behavior of sodium-concrete reactions. The major observations are listed. Mechanisms associated with sodium and water transport to the reaction zone are identified, and represented by appropriate mathematical expressions. The model attempts to explain large-scale, long-term (100 h) test results were sodium-concrete reactions terminated even in the presence of unreacted sodium and concrete

  20. A Networks Approach to Modeling Enzymatic Reactions.

    Science.gov (United States)

    Imhof, P

    2016-01-01

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

  1. Serpentinization reaction pathways: implications for modeling approach

    Energy Technology Data Exchange (ETDEWEB)

    Janecky, D.R.

    1986-01-01

    Experimental seawater-peridotite reaction pathways to form serpentinites at 300/sup 0/C, 500 bars, can be accurately modeled using the EQ3/6 codes in conjunction with thermodynamic and kinetic data from the literature and unpublished compilations. These models provide both confirmation of experimental interpretations and more detailed insight into hydrothermal reaction processes within the oceanic crust. The accuracy of these models depends on careful evaluation of the aqueous speciation model, use of mineral compositions that closely reproduce compositions in the experiments, and definition of realistic reactive components in terms of composition, thermodynamic data, and reaction rates.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  3. Homogeneous photocatalytic reactions with organometallic and coordination compounds--perspectives for sustainable chemistry.

    Science.gov (United States)

    Hoffmann, Norbert

    2012-02-13

    Since the time of Giacomo Ciamician at the beginning of the 20th century, photochemical transformations have been recognized as contributing to sustainable chemistry. Electronic excitation significantly changes the reactivity of chemical compounds. Thus, the application of activation reagents is frequently avoided and transformations can be performed under mild conditions. Catalysis plays a central role in sustainable chemistry. Stoichiometric amounts of activation reagents are often avoided. This fact and the milder catalytic reaction conditions diminish the formation of byproducts. In the case of homogeneous catalysis, organometallic compounds are often applied. The combination of both techniques develops synergistic effects in the sense of "Green Chemistry". Herein, metal carbonyl-mediated reactions are reported. These transformations are of considerable interest for the synthesis of complex polyfunctionalized compounds. Copper(I)-catalyzed [2+2] photocycloaddition gives access to a large variety of cyclobutane derivatives. Currently, a large number of publications deal with photochemical electron-transfer-induced reactions with organometallic and coordination compounds, particularly with ruthenium complexes. Several photochemically induced oxidations can easily be performed with air or molecular oxygen when they are catalyzed with organometallic complexes. Photochemical reaction conditions also play a certain role in C-H activation with organometallic catalysts, for instance, with alkanes, although such transformations are conveniently performed with a variety of other photochemical reactions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. The nuclear reaction model code MEDICUS

    International Nuclear Information System (INIS)

    Ibishia, A.I.

    2008-01-01

    The new computer code MEDICUS has been used to calculate cross sections of nuclear reactions. The code, implemented in MATLAB 6.5, Mathematica 5, and Fortran 95 programming languages, can be run in graphical and command line mode. Graphical User Interface (GUI) has been built that allows the user to perform calculations and to plot results just by mouse clicking. The MS Windows XP and Red Hat Linux platforms are supported. MEDICUS is a modern nuclear reaction code that can compute charged particle-, photon-, and neutron-induced reactions in the energy range from thresholds to about 200 MeV. The calculation of the cross sections of nuclear reactions are done in the framework of the Exact Many-Body Nuclear Cluster Model (EMBNCM), Direct Nuclear Reactions, Pre-equilibrium Reactions, Optical Model, DWBA, and Exciton Model with Cluster Emission. The code can be used also for the calculation of nuclear cluster structure of nuclei. We have calculated nuclear cluster models for some nuclei such as 177 Lu, 90 Y, and 27 Al. It has been found that nucleus 27 Al can be represented through the two different nuclear cluster models: 25 Mg + d and 24 Na + 3 He. Cross sections in function of energy for the reaction 27 Al( 3 He,x) 22 Na, established as a production method of 22 Na, are calculated by the code MEDICUS. Theoretical calculations of cross sections are in good agreement with experimental results. Reaction mechanisms are taken into account. (author)

  5. Reaction of phosphorus ylides with carbonyl compounds in supercritical carbon dioxide

    International Nuclear Information System (INIS)

    Jeong, Kyung Il; Kim, Hak Do; Shim, Jae Jin; Ra, Choon Sup

    2004-01-01

    The condensation reaction of (benzylene)triphenylphosphoranes with carbonyl compounds in supercritical carbon dioxide was examined. Reactions of (benzylene)phosphoranes (ca. 1 mmol) with several benzaldehydes in a supercritical carbon dioxide (80 .deg. C, 2,000 psi) containing THF entrainer (5%) in a 24 mL reactor proceed smoothly to yield olefination products in fairly good to excellent yields but slower, compared to reactions in a conventional THF solvent. Generally, phosphoranes that are not substituted with a nitro group show more (Z)-selective reactions with aromatic aldehydes under scCO 2 condition than in THF. The reaction of (benzylene)triphenylphosphosphoranes with 4-t-butylcyclohexanone gave the corresponding olefin compounds with a low conversion under both the supercritical carbon dioxide and the organic THF solvent. Our preliminary study showed the Wittig reaction carries out smoothly in supercritical carbon dioxide medium and also a possible tunability of this reaction pathway by adding a entrainer. The results would be useful for devising a novel process for the environmentally friendly Wittig reaction

  6. Reaction of phosphorus ylides with carbonyl compounds in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Kyung Il; Kim, Hak Do; Shim, Jae Jin; Ra, Choon Sup [Yeungnam Univ., Gyongsan (Korea, Republic of)

    2004-02-15

    The condensation reaction of (benzylene)triphenylphosphoranes with carbonyl compounds in supercritical carbon dioxide was examined. Reactions of (benzylene)phosphoranes (ca. 1 mmol) with several benzaldehydes in a supercritical carbon dioxide (80 .deg. C, 2,000 psi) containing THF entrainer (5%) in a 24 mL reactor proceed smoothly to yield olefination products in fairly good to excellent yields but slower, compared to reactions in a conventional THF solvent. Generally, phosphoranes that are not substituted with a nitro group show more (Z)-selective reactions with aromatic aldehydes under scCO{sub 2} condition than in THF. The reaction of (benzylene)triphenylphosphosphoranes with 4-t-butylcyclohexanone gave the corresponding olefin compounds with a low conversion under both the supercritical carbon dioxide and the organic THF solvent. Our preliminary study showed the Wittig reaction carries out smoothly in supercritical carbon dioxide medium and also a possible tunability of this reaction pathway by adding a entrainer. The results would be useful for devising a novel process for the environmentally friendly Wittig reaction.

  7. Constituent models and large transverse momentum reactions

    International Nuclear Information System (INIS)

    Brodsky, S.J.

    1975-01-01

    The discussion of constituent models and large transverse momentum reactions includes the structure of hard scattering models, dimensional counting rules for large transverse momentum reactions, dimensional counting and exclusive processes, the deuteron form factor, applications to inclusive reactions, predictions for meson and photon beams, the charge-cubed test for the e/sup +-/p → e/sup +-/γX asymmetry, the quasi-elastic peak in inclusive hadronic reactions, correlations, and the multiplicity bump at large transverse momentum. Also covered are the partition method for bound state calculations, proofs of dimensional counting, minimal neutralization and quark--quark scattering, the development of the constituent interchange model, and the A dependence of high transverse momentum reactions

  8. Disjunct eddy covariance measurements of volatile organic compound fluxes using proton transfer reaction mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Taipale, R.

    2011-07-01

    Volatile organic compounds (VOCs) are emitted into the atmosphere from natural and anthropogenic sources, vegetation being the dominant source on a global scale. Some of these reactive compounds are deemed major contributors or inhibitors to aerosol particle formation and growth, thus making VOC measurements essential for current climate change research. This thesis discusses ecosystem scale VOC fluxes measured above a boreal Scots pine dominated forest in southern Finland. The flux measurements were performed using the micrometeorological disjunct eddy covariance (DEC) method combined with proton transfer reaction mass spectrometry (PTR-MS), which is an online technique for measuring VOC concentrations. The measurement, calibration, and calculation procedures developed in this work proved to be well suited to long-term VOC concentration and flux measurements with PTR-MS. A new averaging approach based on running averaged covariance functions improved the determination of the lag time between wind and concentration measurements, which is a common challenge in DEC when measuring fluxes near the detection limit. The ecosystem scale emissions of methanol, acetaldehyde, and acetone were substantial. These three oxygenated VOCs made up about half of the total emissions, with the rest comprised of monoterpenes. Contrary to the traditional assumption that monoterpene emissions from Scots pine originate mainly as evaporation from specialized storage pools, the DEC measurements indicated a significant contribution from de novo biosynthesis to the ecosystem scale monoterpene emissions. This thesis offers practical guidelines for long-term DEC measurements with PTR-MS. In particular, the new averaging approach to the lag time determination seems useful in the automation of DEC flux calculations. Seasonal variation in the monoterpene biosynthesis and the detailed structure of a revised hybrid algorithm, describing both de novo and pool emissions, should be determined in

  9. A Full Disturbance Model for Reaction Wheels

    NARCIS (Netherlands)

    Le, M.P.; Ellenbroek, Marcellinus Hermannus Maria; Seiler, R; van Put, P.; Cottaar, E.J.E.

    2014-01-01

    Reaction wheels are rotating devices used for the attitude control of spacecraft. However, reaction wheels also generate undesired disturbances in the form of vibrations, which may have an adverse effect on the pointing accuracy and stability of spacecraft (optical) payloads. A disturbance model for

  10. Multicomponent modelling of Portland cement hydration reactions

    NARCIS (Netherlands)

    Ukrainczyk, N.; Koenders, E.A.B.; Van Breugel, K.

    2012-01-01

    The prospect of cement and concrete technologies depends on more in depth understanding of cement hydration reactions. Hydration reaction models simulate the development of the microstructures that can finally be used to estimate the cement based material properties that influence performance and

  11. Spur Reaction Model of Positronium Formation

    DEFF Research Database (Denmark)

    Mogensen, O. E.

    1974-01-01

    A new model of positronium (Ps) formation is proposed. Positronium is assumed to be formed by a reaction between a positron and an electron in the positron spur. Ps formation must compete with electron‐ion recombination and electron or positron reactions with solvent molecules and scavenger...

  12. Chemical Reductive Transformations of Synthetic Organic Compounds. Probe Compound Studies and Mechanistic Modeling

    National Research Council Canada - National Science Library

    Peyton, Gary

    2001-01-01

    Advanced Oxidation Processes (AOPs) can be used to selectively remove DNT (2,4-dinitrotoluene) from a complex waste stream by adding a precursor compound such as ethanol, which forms a reducing radical upon reaction with hydroxyl radical...

  13. Pyridine Group-Assisted Addition of Diazo-Compounds to Imines in the 3-CC Reaction of 2-Aminopyridines, Aldehydes, and Diazo-Compounds

    Science.gov (United States)

    Gulevich, Anton V.; Helan, Victoria; Wink, Donald J.

    2013-01-01

    A novel three-component (3-CC) coupling reaction of 2-aminoazines, aromatic aldehydes and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles, as well as to β-amino acid derivatives. PMID:23373731

  14. Modeling of turbulent chemical reaction

    Science.gov (United States)

    Chen, J.-Y.

    1995-01-01

    Viewgraphs are presented on modeling turbulent reacting flows, regimes of turbulent combustion, regimes of premixed and regimes of non-premixed turbulent combustion, chemical closure models, flamelet model, conditional moment closure (CMC), NO(x) emissions from turbulent H2 jet flames, probability density function (PDF), departures from chemical equilibrium, mixing models for PDF methods, comparison of predicted and measured H2O mass fractions in turbulent nonpremixed jet flames, experimental evidence of preferential diffusion in turbulent jet flames, and computation of turbulent reacting flows.

  15. Organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds

    International Nuclear Information System (INIS)

    Maltsev, O V; Beletskaya, Irina P; Zlotin, Sergei G

    2011-01-01

    Recent applications of organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds: natural products, pharmaceutical agents and plant protection agents are reviewed. The key mechanisms of stereoinduction, types of organocatalysts and reagents used in these reactions are considered. The material is classified according to the type of newly formed bonds incorporating the asymmetric carbon atom, and the information for the most numerous C–C coupling reactions is systematized according to the natures of the electrophile and the nucleophile. The bibliography includes 433 references.

  16. Reactions of the nitrate radical with a series og reduced organic sulfur-compounds in air

    DEFF Research Database (Denmark)

    JENSEN, NR; HJORTH, J; LOHSE, C

    1992-01-01

    A 480 L evacuable reaction chamber, equipped with FT-IR spectroscopy on-line and ion chromatography off-line, has been used to study the gas phase reaction between the nitrate radical, NO3, and the reduced organic sulphur compounds CH3CH2SH, (CH3CH2)2S, (CH3CH2)2S2, and CH3CH2SCH3 in air. The pro......A 480 L evacuable reaction chamber, equipped with FT-IR spectroscopy on-line and ion chromatography off-line, has been used to study the gas phase reaction between the nitrate radical, NO3, and the reduced organic sulphur compounds CH3CH2SH, (CH3CH2)2S, (CH3CH2)2S2, and CH3CH2SCH3 in air......, and CH3SSCH3 lead to the conclusion that all these species, in the reaction with the NO3 radical, follow a similar degradation mechanism producing SO2, H2SO4, R-SO3H, R-CHO, and R-CH2ONO2, as the main reaction products. The inital step of the reaction of NO3 with R-S-R and R-S- H type (R = CH3, CH2CH3...

  17. Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

    Directory of Open Access Journals (Sweden)

    Masato Ohashi

    2014-09-01

    Full Text Available In this review, we summarize our recent development of palladium(0-catalyzed cross-coupling reactions of perfluoro organic compounds with organometallic reagents. The oxidative addition of a C–F bond of tetrafluoroethylene (TFE to palladium(0 was promoted by the addition of lithium iodide, affording a trifluorovinyl palladium(II iodide. Based on this finding, the first palladium-catalyzed cross-coupling reaction of TFE with diarylzinc was developed in the presence of lithium iodide, affording α,β,β-trifluorostyrene derivatives in excellent yield. This coupling reaction was expanded to the novel Pd(0/PR3-catalyzed cross-coupling reaction of TFE with arylboronates. In this reaction, the trifluorovinyl palladium(II fluoride was a key reaction intermediate that required neither an extraneous base to enhance the reactivity of organoboronates nor a Lewis acid additive to promote the oxidative addition of a C–F bond. In addition, our strategy utilizing the synergetic effect of Pd(0 and lithium iodide could be applied to the C–F bond cleavage of unreactive hexafluorobenzene (C6F6, leading to the first Pd(0-catalyzed cross-coupling reaction of C6F6 with diarylzinc compounds.

  18. Densities of accessible final states for multi-step compound reactions

    International Nuclear Information System (INIS)

    Maoming De; Guo Hua

    1993-01-01

    The densities of accessible final states for calculations of multi-step compound reactions are derived. The Pauli exclusion principle is taken into account in the calculations. The results are compared with a previous author's results and the effect of the Pauli exclusion principle is investigated. (Author)

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

    Directory of Open Access Journals (Sweden)

    Charity Robert J.

    2011-10-01

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

  20. Cluster model in reaction theory

    International Nuclear Information System (INIS)

    Adhikari, S.K.

    1979-01-01

    A recent work by Rosenberg on cluster states in reaction theory is reexamined and generalized to include energies above the threshold for breakup into four composite fragments. The problem of elastic scattering between two interacting composite fragments is reduced to an equivalent two-particle problem with an effective potential to be determined by extremum principles. For energies above the threshold for breakup into three or four composite fragments effective few-particle potentials are introduced and the problem is reduced to effective three- and four-particle problems. The equivalent three-particle equation contains effective two- and three-particle potentials. The effective potential in the equivalent four-particle equation has two-, three-, and four-body connected parts and a piece which has two independent two-body connected parts. In the equivalent three-particle problem we show how to include the effect of a weak three-body potential perturbatively. In the equivalent four-body problem an approximate simple calculational scheme is given when one neglects the four-particle potential the effect of which is presumably very small

  1. Reaction time for trimolecular reactions in compartment-based reaction-diffusion models

    Science.gov (United States)

    Li, Fei; Chen, Minghan; Erban, Radek; Cao, Yang

    2018-05-01

    Trimolecular reaction models are investigated in the compartment-based (lattice-based) framework for stochastic reaction-diffusion modeling. The formulae for the first collision time and the mean reaction time are derived for the case where three molecules are present in the solution under periodic boundary conditions. For the case of reflecting boundary conditions, similar formulae are obtained using a computer-assisted approach. The accuracy of these formulae is further verified through comparison with numerical results. The presented derivation is based on the first passage time analysis of Montroll [J. Math. Phys. 10, 753 (1969)]. Montroll's results for two-dimensional lattice-based random walks are adapted and applied to compartment-based models of trimolecular reactions, which are studied in one-dimensional or pseudo one-dimensional domains.

  2. Can Dietary Polyphenols Prevent the Formation of Toxic Compounds from Maillard Reaction?

    Science.gov (United States)

    Del Turco, Serena; Basta, Giuseppina

    2016-01-01

    Polyphenols are functional compounds in edible vegetable and food such as tea, coffee and red wine and increasing evidence demonstrates a positive link between consumption of polyphenol-rich foods and disease prevention. In this review we have focused on the current knowledge of the potential anti-glycation effects of polyphenols, particularly in regard to their influence on Maillard reaction, a non-enzymatic reaction between amino acids and reducing sugars that contributes to the production of toxic compounds, mainly reactive carbonyl species, advanced glycation end-products (AGEs) and other toxicants. The Maillard reaction occurs in the human body during hyperglycemic condition, but it is well known as browning reaction in thermally processed foods and it is responsible for flavor and toxicant formation. Dietary polyphenols can have anti-glycation effects and actively participate in Maillard reaction, mitigating the AGE formation and the heat-induced production of toxic compounds. In a time in which the role of a healthy diet in the prevention of chronic diseases is welcome and the borderline between food and medicine is becoming very thin, an improved mechanistic knowledge of how polyphenols can function to reduce harmful and unhealthy substances is mandatory.

  3. Efficient Synthesis of Spirobarbiturates and Spirothiobarbiturates Bearing Cyclopropane Rings by Rhodium(II)-Catalyzed Reactions of Cyclic Diazo Compounds

    International Nuclear Information System (INIS)

    Wang, Xue; Lee, Yong Rok

    2013-01-01

    Rhodium(II)-catalyzed reactions of cyclic diazo compounds derived from barbituric acid and thiobarbituric acid with a variety of styrene moieties were examined. These reactions provide rapid synthetic routes to the preparations of spirobarbiturates and spirothiobarbiturates bearing cyclopropane rings

  4. Efficient Synthesis of Spirobarbiturates and Spirothiobarbiturates Bearing Cyclopropane Rings by Rhodium(II)-Catalyzed Reactions of Cyclic Diazo Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xue; Lee, Yong Rok [Yeungnam Univ., Gyeongsan (Korea, Republic of)

    2013-06-15

    Rhodium(II)-catalyzed reactions of cyclic diazo compounds derived from barbituric acid and thiobarbituric acid with a variety of styrene moieties were examined. These reactions provide rapid synthetic routes to the preparations of spirobarbiturates and spirothiobarbiturates bearing cyclopropane rings.

  5. Reaction path analysis of sodium-water reaction phenomena in support of chemical reaction model development

    International Nuclear Information System (INIS)

    Kikuchi, Shin; Ohshima, Hiroyuki; Hashimoto, Kenro

    2011-01-01

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

  6. Position-specific isotope modeling of organic micropollutants transformation through different reaction pathways

    DEFF Research Database (Denmark)

    Jin, Biao; Rolle, Massimo

    2016-01-01

    The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework ...

  7. Nonlinear control of the Salnikov model reaction

    DEFF Research Database (Denmark)

    Recke, Bodil; Jørgensen, Sten Bay

    1999-01-01

    This paper explores different nonlinear control schemes, applied to a simple model reaction. The model is the Salnikov model, consisting of two ordinary differential equations. The control strategies investigated are I/O-linearisation, Exact linearisation, exact linearisation combined with LQR...

  8. Modeling Compound Flood Hazards in Coastal Embayments

    Science.gov (United States)

    Moftakhari, H.; Schubert, J. E.; AghaKouchak, A.; Luke, A.; Matthew, R.; Sanders, B. F.

    2017-12-01

    Coastal cities around the world are built on lowland topography adjacent to coastal embayments and river estuaries, where multiple factors threaten increasing flood hazards (e.g. sea level rise and river flooding). Quantitative risk assessment is required for administration of flood insurance programs and the design of cost-effective flood risk reduction measures. This demands a characterization of extreme water levels such as 100 and 500 year return period events. Furthermore, hydrodynamic flood models are routinely used to characterize localized flood level intensities (i.e., local depth and velocity) based on boundary forcing sampled from extreme value distributions. For example, extreme flood discharges in the U.S. are estimated from measured flood peaks using the Log-Pearson Type III distribution. However, configuring hydrodynamic models for coastal embayments is challenging because of compound extreme flood events: events caused by a combination of extreme sea levels, extreme river discharges, and possibly other factors such as extreme waves and precipitation causing pluvial flooding in urban developments. Here, we present an approach for flood risk assessment that coordinates multivariate extreme analysis with hydrodynamic modeling of coastal embayments. First, we evaluate the significance of correlation structure between terrestrial freshwater inflow and oceanic variables; second, this correlation structure is described using copula functions in unit joint probability domain; and third, we choose a series of compound design scenarios for hydrodynamic modeling based on their occurrence likelihood. The design scenarios include the most likely compound event (with the highest joint probability density), preferred marginal scenario and reproduced time series of ensembles based on Monte Carlo sampling of bivariate hazard domain. The comparison between resulting extreme water dynamics under the compound hazard scenarios explained above provides an insight to the

  9. Reactions of 3-Formylchromone with Active Methylene and Methyl Compounds and Some Subsequent Reactions of the Resulting Condensation Products

    Directory of Open Access Journals (Sweden)

    M. Lácova

    2005-08-01

    Full Text Available This review presents a survey of the condensations of 3-formylchromone with various active methylene and methyl compounds, e.g. malonic or barbituric acid derivatives, five-membered heterocycles, etc. The utilisation of the condensation products for the synthesis of different heterocyclic systems, which is based on the ability of the γ-pyrone ring to be opened by the nucleophilic attack is also reviewed. Finally, the applications of microwave irradiation as an unconventional method of reaction activation in the synthesis of condensation products is described and the biological activity of some chromone derivatives is noted.

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

    Science.gov (United States)

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

    2017-09-01

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

  11. Halogenating reaction activity of aromatic organic compounds during disinfection of drinking water

    International Nuclear Information System (INIS)

    Guo Gaimei; Chen Xiaodong

    2009-01-01

    The halogenating reactions of five aromatic organic compounds (AOCs) with aqueous chlorine (HOCl/OCl - ) and aqueous bromine (HOBr/OBr - ) were studied with an aim to compare the formation properties of haloacetic acids (HAAs) for the corresponding chlorination or bromination reactions of AOCs, respectively. The experiment results indicated that the HAAs substitution efficiency for the bromination reactions of AOCs was greater than that for the chlorination reactions, and the formation of HAAs had a strong dependence on the chemical structure of AOCs. The chlorination or bromination reaction activities for the AOCs with electron donating functional groups were higher than that for them with electron withdrawing functional groups. The kinetic experiments indicated that the reactions of aqueous bromine with phenol were faster than those of aqueous chlorine with phenol and the halogen consumption exhibited rapid initial and slower consumption stages for the reactions of phenol with aqueous chlorine and bromine, respectively. In addition, the HAAs production for the chlorination reaction of phenol decreased with the increase of pH. These conclusions could provide the valuable information for the effective control of the disinfection by-products during drinking water treatment operation

  12. The adsorption and reaction of halogenated volatile organic compounds (VOC's) on metal oxides. 1998 annual progress report

    International Nuclear Information System (INIS)

    Goodman, D.W.; Haw, J.F.; Lunsford, J.

    1998-01-01

    'The goal of the research is to elucidate the properties of the materials responsible for the activation of halocarbons and the nature of the intermediates formed in the dissociative adsorption of this class of compounds. This information is essential for interpreting and predicting stoichiometric and catalytic pathways for the safe destruction of halocarbon pollutants. The specific objectives are: (1) to study the adsorption and reactivity of chloromethanes and chloroethanes on metal oxides; (2) to identify the reaction intermediates using spectroscopic methods; and (3) to develop kinetic models for the reaction of these halocarbons with oxide surfaces. This report summarizes work after 20 months of a 36-month project. Emphasis has been placed understanding the surfaces phases, as well as the bulk phases that are present during the reactions of chlorinated hydrocarbons with strongly basic metal oxides. Most of the research has been carried out with carbon tetrachloride.'

  13. Gas-Solid Reaction Properties of Fluorine Compounds and Solid Adsorbents for Off-Gas Treatment from Semiconductor Facility

    Directory of Open Access Journals (Sweden)

    Shinji Yasui

    2012-01-01

    Full Text Available We have been developing a new dry-type off-gas treatment system for recycling fluorine from perfluoro compounds present in off-gases from the semiconductor industry. The feature of this system is to adsorb the fluorine compounds in the exhaust gases from the decomposition furnace by using two types of solid adsorbents: the calcium carbonate in the upper layer adsorbs HF and converts it to CaF2, and the sodium bicarbonate in the lower layer adsorbs HF and SiF4 and converts them to Na2SiF6. This paper describes the fluorine compound adsorption properties of both the solid adsorbents—calcium carbonate and the sodium compound—for the optimal design of the fixation furnace. An analysis of the gas-solid reaction rate was performed from the experimental results of the breakthrough curve by using a fixed-bed reaction model, and the reaction rate constants and adsorption capacity were obtained for achieving an optimal process design.

  14. Surface characterisation of synthetic coal chars made from model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Arenillas, A.; Pevida, C.; Rubiera, F.; Palacios, J.M.; Navarrete, R.; Denoyel, R.; Rouquerol, J.; Pis, J.J. [Instituto Nacional del Carbon, CSIC, Oviedo (Spain)

    2004-07-01

    Knowledge of surface properties is essential for understanding the reaction mechanisms involved in several coal conversion processes. However, due to the complexity and heterogeneity of coal this is rather difficult and the use of known model compounds could be a valuable tool. Single model compounds have been widely used, but they give a quite simplified picture. In this work a mixture of model compounds in a phenol-formaldehyde matrix was cured in order to create cross-linked structures. The obtained synthetic coal was pyrolysed in a fixed bed reactor, under helium atmosphere. The surface composition of the chars was evaluated by XPS, adsorption gravimetry of water vapour, temperature-programmed desorption and potentiometric titration. Texture was characterised by N{sub 2} and CO{sub 2} adsorption isotherms at 77 and 273 K, respectively, and immersion calorimetry in benzene. The results obtained from the different techniques were contrasted in order to give an overview of the surface properties (chemical and physical) of the samples studied. Chars obtained under the same operating conditions from a high volatile bituminous coal were used as a reference.

  15. Skin: Major target organ of allergic reactions to small molecular weight compounds

    International Nuclear Information System (INIS)

    Merk, Hans F.; Baron, Jens M.; Neis, Mark M.; Obrigkeit, Daniela Hoeller; Karlberg, Ann-Therese

    2007-01-01

    Skin is a major target organ for allergic reactions to small molecular weight compounds. Drug allergic reactions may be life-threatening such as in the case of anaphylactic reactions or bullous drug reactions and occur in about 5% of all hospitalized patients. Allergic contact dermatitis has an enormous influence on the social life of the patient because it is the most frequent reason for occupational skin diseases and the treatment and prevention of this disease cost approximately Euro 3 billion per year in Germany. The different proposed pathophysiological pathways leading to a drug eruption are discussed in this paper. All major enzymes which are involved in the metabolism of xenobiotica were shown to be present in skin. Evidence supporting the role of metabolism in the development of drug allergy and allergic contact dermatitis is demonstrated in the example of sulphonamides and fragrances

  16. Modeling of uncertainties in biochemical reactions.

    Science.gov (United States)

    Mišković, Ljubiša; Hatzimanikatis, Vassily

    2011-02-01

    Mathematical modeling is an indispensable tool for research and development in biotechnology and bioengineering. The formulation of kinetic models of biochemical networks depends on knowledge of the kinetic properties of the enzymes of the individual reactions. However, kinetic data acquired from experimental observations bring along uncertainties due to various experimental conditions and measurement methods. In this contribution, we propose a novel way to model the uncertainty in the enzyme kinetics and to predict quantitatively the responses of metabolic reactions to the changes in enzyme activities under uncertainty. The proposed methodology accounts explicitly for mechanistic properties of enzymes and physico-chemical and thermodynamic constraints, and is based on formalism from systems theory and metabolic control analysis. We achieve this by observing that kinetic responses of metabolic reactions depend: (i) on the distribution of the enzymes among their free form and all reactive states; (ii) on the equilibrium displacements of the overall reaction and that of the individual enzymatic steps; and (iii) on the net fluxes through the enzyme. Relying on this observation, we develop a novel, efficient Monte Carlo sampling procedure to generate all states within a metabolic reaction that satisfy imposed constrains. Thus, we derive the statistics of the expected responses of the metabolic reactions to changes in enzyme levels and activities, in the levels of metabolites, and in the values of the kinetic parameters. We present aspects of the proposed framework through an example of the fundamental three-step reversible enzymatic reaction mechanism. We demonstrate that the equilibrium displacements of the individual enzymatic steps have an important influence on kinetic responses of the enzyme. Furthermore, we derive the conditions that must be satisfied by a reversible three-step enzymatic reaction operating far away from the equilibrium in order to respond to

  17. Reactions of phenylurea compounds with aqueous chlorine: Implications for herbicide transformation during drinking water disinfection

    International Nuclear Information System (INIS)

    Chusaksri, Sarinma; Sutthivaiyakit, Somyote; Sedlak, David L.; Sutthivaiyakit, Pakawadee

    2012-01-01

    Highlights: ► Mechanism of chlorine reaction with phenylurea compounds has been studied. ► It depends on both chlorinating species and substitutents on the compounds. ► Main products were identified using LC–MS/MS and authentic standards. ► Their transformation under normal drinking water disinfection was predicted. - Abstract: Phenylurea herbicides have been known to contaminate surface waters serving as potable supplies. To access the potential for transformation of these compounds during drinking water treatment, reactions of phenylurea compounds with aqueous chlorine at different pHs were investigated. The effect of substitution at the amino-N on the rate of transformation depends upon pH. Under acidic conditions, all of the phenylurea studied except 3,4-dichloro-3′-N-methylphenylurea (3,4-DCMPU) exhibited third-order kinetics, second order with respect to chlorine and first order with respect to phenylurea, while the reactions of 3,4-DCMPU were first order with respect to both chlorine and the organic compound. Under neutral and alkaline conditions, all compounds exhibited second-order kinetics that was first order with respect to chlorine and the organic compound. Apparent second-order rate constants at 25 °C and pH 7 were 0.76 ± 0.16, 0.52 ± 0.11, 0.39 ± 0.02, 0.27 ± 0.04 and 0.23 ± 0.05 M −1 s −1 for phenylurea, 3, 4-dichlorophenylurea, 3, 4-DCMPU, metoxuron and monuron, respectively. Studies of the chlorination products, monitored by LC/MS/MS, under different pH values indicated the reaction to take place at both N atoms and also at ortho- and para- positions of the phenylurea aromatic group. The main chlorinating species were found to be different in different pH ranges. Under conditions typically encountered in drinking water treatment systems, transformation of these compounds by chlorine will be incomplete.

  18. The effect of catalytic reaction conditions on the incorporation of tritium in unsaturated compounds

    Energy Technology Data Exchange (ETDEWEB)

    Shevchenko, V P; Nagayev, I Yu; Myasoedov, N F [AN SSSR, Moscow (USSR). Inst. Molekulyarnoj Genetiki

    1989-10-01

    We have obtained multiple-tritium-labelled 5-{alpha}-androstan-3-one, dihydropicrotoxin, dimethyl-propyl-3-chloro-butyl-ammonium chloride, 2,2-di(trifluoromethyl)-3,3-dicyanobicyclohept(2,2,1)ane, dihydroalprenolol, undecanoic acid, dihydro-m,m'-di-tert.-butyl-p-coumaric acid and dihydrofusicoccin. By varying the conditions for the hydrogenation of terminal double bonds, one can considerably increase the molar radioactivity of such compounds through isotopic exchange. We discuss some tentative explanations of the effect of the labelling reaction conditions upon the synthesis of compounds with desired properties. (author).

  19. The effect of catalytic reaction conditions on the incorporation of tritium in unsaturated compounds

    International Nuclear Information System (INIS)

    Shevchenko, V.P.; Nagayev, I.Yu.; Myasoedov, N.F.

    1989-01-01

    We have obtained multiple-tritium-labelled 5-α-androstan-3-one, dihydropicrotoxin, dimethyl-propyl-3-chloro-butyl-ammonium chloride, 2,2-di(trifluoromethyl)-3,3-dicyanobicyclohept[2,2,1]ane, dihydroalprenolol, undecanoic acid, dihydro-m,m'-di-tert.-butyl-p-coumaric acid and dihydrofusicoccin. By varying the conditions for the hydrogenation of terminal double bonds, one can considerably increase the molar radioactivity of such compounds through isotopic exchange. We discuss some tentative explanations of the effect of the labelling reaction conditions upon the synthesis of compounds with desired properties. (author)

  20. Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Compounds

    Science.gov (United States)

    George, C.; Passananti, M.; Kong, L.; Shang, J.; Perrier, S.; Jianmin, C.; Donaldson, D. J.

    2016-12-01

    The atmospheric formation of organosulfur derivatives through reaction with SO2 is generally mediated by oxidants such as O3, OH; recently we have proposed a direct reaction between SO2 and unsaturated compounds as another possible pathway for organosulfate formation in the troposphere. For the first time it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds on various unsaturated compounds, and may therefore have a general environmental impact. We used different experimental strategies i.e., a coated flow tube (CFT), an aerosol flow tube (AFT) and a DRIFT (diffuse reflectance infrared Fourier transform) cell. The reaction products were analyzed by means of liquid chromatography coupled to a high resolution mass spectrometer (LC-HR-MS). We report indeed that SO2 reacts with large variety of C=C unsaturations and that even in the presence of ozone, SO2 reacts with OA leading to organosulfur products. A strong enhancement in product formation is observed under actinic illumination, increases the atmospheric significance of this chemical pathway. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could be in excess of 5%. The detection in atmospheric aerosols of organosulfur compounds with the same chemical formulae as the products identified here seems to confirm the importance of this reaction in the atmosphere.

  1. The use of lithium compounds for inhibiting alkali-aggregate reaction effects in pavement structures

    Science.gov (United States)

    Zapała-Sławeta, J.; Owsiak, Z.

    2018-05-01

    Internal corrosion of concrete caused by the reaction of reactive aggregate with sodium and potassium hydroxides from cement is a threat to the durability of concrete pavements. Traditional methods for reducing the negative effects of the reaction include the use of unreactive aggregates, low alkali cements, mineral additives or chemical admixtures, incorporated during mixing. Lowering the relative humidity of the concrete below 80% is another measure for limiting the destructive reaction. The incorporation of lithium compounds, in particular lithium nitrate and lithium hydroxide, to the concrete mix is a method of limiting alkali-silica reaction effects. The challenge is to reduce the negative effects of aggregate reactivity in members in which the reaction has occurred because the aggregate happened to be reactive. The paper presents ways of limiting the deterioration of ASR-affected concrete in road pavements and other forms of transportation infrastructure, mainly through the use of lithium compounds, i.e. lithium nitrate. Impregnation methods that allow the penetration of lithium ions into the concrete structure were characterized, as was the effectiveness of the solutions applied.

  2. Reactions of 3d-series metallocenes with organic cadmium compounds

    International Nuclear Information System (INIS)

    Razuvaev, G.A.; Mar'in, V.P.; Vyshinskaya, L.I.; Grinval'd, I.I.; Spiridonova, N.N.

    1987-01-01

    Interaction of organic cadmium compounds and 3d-series metallocenes, Cp 2 M (M=V, Cr, Mn, Ni, Co) has been studied. It is shown that direction of these reactions is determined by metallocene nature. Reactions of oxidizing addition leading to σ-complexes formation are characteristic for vanadium and chromium metallocenes. When reacting cobaltocene with R 2 Cd, R group introduction to cyclopentadienyl ring and elimination of cobalt diene complexes take place. Manganocene and nickelocene interaction goes through the stage of complex formation with transition metal - cadmium bond

  3. Modelling the Maillard reaction during the cooking of a model cheese.

    Science.gov (United States)

    Bertrand, Emmanuel; Meyer, Xuân-Mi; Machado-Maturana, Elizabeth; Berdagué, Jean-Louis; Kondjoyan, Alain

    2015-10-01

    During processing and storage of industrial processed cheese, odorous compounds are formed. Some of them are potentially unwanted for the flavour of the product. To reduce the appearance of these compounds, a methodological approach was employed. It consists of: (i) the identification of the key compounds or precursors responsible for the off-flavour observed, (ii) the monitoring of these markers during the heat treatments applied to the cheese medium, (iii) the establishment of an observable reaction scheme adapted from a literature survey to the compounds identified in the heated cheese medium (iv) the multi-responses stoichiokinetic modelling of these reaction markers. Systematic two-dimensional gas chromatography time-of-flight mass spectrometry was used for the semi-quantitation of trace compounds. Precursors were quantitated by high-performance liquid chromatography. The experimental data obtained were fitted to the model with 14 elementary linked reactions forming a multi-response observable reaction scheme. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

    International Nuclear Information System (INIS)

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

    1994-08-01

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

  5. Reactions of carbonyl compounds with α,β-unsaturated nitriles as a convenient pathway to carbo- and heterocycles

    International Nuclear Information System (INIS)

    Sharanin, Yu A; Goncharenko, M P; Litvinov, Victor P

    1998-01-01

    Published data on the methods for synthesis of carbo- and heterocyclic compounds based on reactions of α,β-unsaturated nitriles with carbonyl compounds and activated phenols are surveyed. It is demonstrated that all these reactions occur via nucleophilic addition of the carbanion generated from a carbonyl compound to the double bond of an unsaturated nitrile (the Michael reaction). The main routes of transformation of the adducts into carbo- and heterocyclic compounds are considered. The methods for regioselective preparation of fused 4H-pyrans or 1,4-dihydropyridines by varying conditions of cyclisation of Michael adducts are discussed. The bibliography includes 249 references.

  6. Investigations in anhydrous liquid ammonia. Reaction of group 2, 4, 5, 11 metal and actinoids compounds

    International Nuclear Information System (INIS)

    Woidy, Patrick

    2014-01-01

    The solubility and reactivity of metal halides, transition metal halides, and actinoid halides in liquid ammonia can lead to new starting materials for the synthesis of fluorides in low oxidation states or for nitrides via a ''low-temperature route''. In this context the ability of metal and actinoid halides to act as an acceptor for or donor of fluoride ions is also of interest. Four different systems were investigated in this study. In the first section, the synthesis and characterization of new compounds were carried out in the system CuX/NH 3 (X = F, Cl, Br, I, and CN) and lead to a ligand stabilized monovalent copper fluoride as a main result. In the second section, the solubility of uranyl compounds and uranium halides in liquid ammonia was investigated and the products were characterized. In the third section, alkali metal thorates were synthesized. Their solubility in liquid ammonia and their behavior as an acceptor for fluoride ions was investigated. In the last section, the results on the solubility behavior of transition metal halides in liquid ammonia and their coordination behavior are presented. In the first system CuX/NH 3 several new compounds, such as [Cu(NH 3 ) 3 ]X (X = Br, I or CN) were synthesized and characterized. The reactions of this compounds with fluoride ion donors (NH 4 F or Me 4 NF) led unfortunately not to the monovalent copper fluoride CuF. The comproportionation reaction of Cu and CuF 2 in liquid ammonia lead to the compounds [Cu(NH 3 ) 3 ] 2 [Cu 2 (NH 3 ) 2 ] . 4 NH 3 and [Cu(NH 3 ) 2 ]F . NH 3 . For the preparation of binary CuF, various decomposition experiments were executed on the compound [Cu(NH 3 ) 2 ]F . NH 3 which resulted in different decomposition products. In additional studies various complexes of divalent copper was investigated and with the compound [Cu(NH 3 ) 5 ]F 2 . NH 3 the solubility of fluoride containing substances in liquid ammonia could be shown. Studies of six- and tetravalent uranium

  7. X detection in heavy ion induced reactions. Application to the lifetime measurement of a compound nucleus

    International Nuclear Information System (INIS)

    Liatard, E.

    1984-01-01

    The ionization of inner electronic shells can be used to determine the lifetime of a compound nucleus formed in a nuclear reaction. The principle of the measure is based on the comparison between the unknown lifetime of the nuclear process and the known lifetime of a K-shell vacancy created during the collision. Besides testing this method, which we call the ''atomic-clok'' method with the compound nucleus 112 Te formed by the reaction 20 Ne (205 MeV) + 92 Mo, the work in this thesis basically consists of a description and a study of the problems presented by the use of X-ray spectroscopy in nuclear-decay-time measurements and Z-identification of heavy nuclear products [fr

  8. Study of kinetics and mechanism of diazo compound reactions using nuclear chemical polarization

    International Nuclear Information System (INIS)

    Gragerov, I.P.; Levit, A.F.; Kiprianova, L.A.; Buchachenko, A.L.; Sterleva, T.G.

    1975-01-01

    It has been established that at the rate-determining steps of the radical reactions in which aniline interacts with isoamyl nitrite and substituted diazo salts interact with sodium methylate, tertiary fatty amines, or phosphinic acid, no transfer of a single electron occurs. The processes of single electron transfer do not seem to play a decisive role in the kinetics of most transformations of diazo compounds. Chemical nuclear polarization is shown to be suitable for kinetic studies of fast radical processes

  9. Reaction of Diazo Compounds with Difluorocarbene: An Efficient Approach towards 1,1-Difluoroolefins.

    Science.gov (United States)

    Zhang, Zhikun; Yu, Weizhi; Wu, Chenggui; Wang, Chengpeng; Zhang, Yan; Wang, Jianbo

    2016-01-04

    A transition-metal-free difluoromethylenation of diazo compounds that proceeds under mild conditions has been developed and is based on the use of TMSCF2 Br as the difluoromethylene source and tetrabutylammonium bromide (TBAB) as the promoter. The chemoselective formal carbene dimerization reaction is achieved owing to the electronic properties and the relative stability of the difluorocarbene intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Cooperative organocatalysis of Mukaiyama-type aldol reactions by thioureas and nitro compounds

    KAUST Repository

    Bukhriakov, Konstantin; Desyatkin, Victor G.; Rodionov, Valentin

    2016-01-01

    A unique organocatalytic system for Mukaiyama-type aldol reactions based on the cooperative action of nitro compounds and thioureas has been identified. This system is compatible with a wide range of substrates and does not require low temperatures, inert atmospheres, or an aqueous workup. A catalytic mechanism based on nitro group-mediated silyl cation transfer has been proposed. © The Royal Society of Chemistry 2016.

  11. Cooperative organocatalysis of Mukaiyama-type aldol reactions by thioureas and nitro compounds

    KAUST Repository

    Bukhriakov, Konstantin

    2016-05-16

    A unique organocatalytic system for Mukaiyama-type aldol reactions based on the cooperative action of nitro compounds and thioureas has been identified. This system is compatible with a wide range of substrates and does not require low temperatures, inert atmospheres, or an aqueous workup. A catalytic mechanism based on nitro group-mediated silyl cation transfer has been proposed. © The Royal Society of Chemistry 2016.

  12. Particle-hole state densities for statistical multi-step compound reactions

    International Nuclear Information System (INIS)

    Oblozinsky, P.

    1986-01-01

    An analytical relation is derived for the density of particle-hole bound states applying the equidistant-spacing approximation and the Darwin-Fowler statistical method. The Pauli exclusion principle as well as the finite depth of the potential well are taken into account. The set of densities needed for calculations of multi-step compound reactions is completed by deriving the densities of accessible final states for escape and damping. (orig.)

  13. Iron based superconductors and related compounds synthesized by solid state metathesis and high temperature reactions

    International Nuclear Information System (INIS)

    Frankovsky, Rainer

    2013-01-01

    The results of this thesis can be divided into three major topics, which can also be seen as different approaches of solid state chemistry to reveal interesting features of known and unknown compounds and to develop alternative synthesis routes. Firstly, known compounds with related structural motifs to the superconducting iron-arsenides were investigated regarding their structural and physical properties. In case of La 3 Pd 4 Ge 4 the influence of Fe doping on the properties was studied, whereas in the series ZrMAs (M=Ti,V) the physical properties have not yet been reported at all and were investigated for the first time. Secondly, an alternative synthesis route has been developed for the synthesis of superconducting LaFeAsO 1-x F x . This solid state metathesis reaction distinctly increased the quality of the samples compared to conventionally prepared products. Furthermore, the reaction pathway was investigated and clarified, which helps to understand the processes during high temperature solid state metathesis reactions in general. Thirdly, this alternative synthesis route was expanded to other systems and new compounds like co-substituted LaFe 1-x Mn x AsO 1-y F y were prepared and thoroughly investigated. This led to a complex study of the interplay of magnetism, electronic and structural conditions and the occurrence of superconducting properties. The investigation and understanding of such complex coherences will probably be decisive for the further understanding of the superconducting mechanism in iron based superconductors.

  14. Pyrolysis mechanism of microalgae Nannochloropsis sp. based on model compounds and their interaction

    International Nuclear Information System (INIS)

    Wang, Xin; Tang, Xiaohan; Yang, Xiaoyi

    2017-01-01

    Highlights: • Pyrolysis experiments were conducted by model compounds of algal components. • Interaction affected little bio-crude yield of model compounds co-pyrolysis. • Some interaction pathways between microalgae components were recommended. • N-heterocyclic compounds were further pyrolysis products of Maillard reaction products. • Surfactant synthesis (lipid-amino acids and lipid-glucose) between algal components. - Abstract: Pyrolysis is one of important pathways to convert microalgae to liquid biofuels and key components of microalgae have different chemical composition and structure, which provides a barrier for large-scale microalgae-based liquid biofuel application. Microalgae component pyrolysis mechanism should be researched to optimal pyrolysis process parameters. In this study, single pyrolysis and co-pyrolysis of microalgal components (model compounds castor oil, soybean protein and glucose) were conducted to reveal interaction between them by thermogrametric analysis and bio-crude evaluation. Castor oil (model compound of lipid) has higher pyrolysis temperature than other model compounds and has the maximum contribution to bio-crude formation. Bio-crude from soybean protein has higher N-heterocyclic compounds as well as phenols, which could be important aromatic hydrocarbon source during biorefineries and alternative aviation biofuel production. Potential interaction pathways based on model compounds are recommended including further decomposition of Maillard reaction products (MRPs) and surfactant synthesis, which indicate that glucose played an important role on pyrolysis of microalgal protein and lipid components. The results should provide necessary information for microalgae pyrolysis process optimization and large-scale pyrolysis reactor design.

  15. Diels-Alder reactions of inert aromatic compounds within a self-assembled coordination cage.

    Science.gov (United States)

    Horiuchi, Shinnosuke; Murase, Takashi; Fujita, Makoto

    2011-07-04

    A self-assembled coordination cage serves as a nanometer-sized molecular flask to promote the Diels-Alder reactions of aromatic hydrocarbons with N-cyclohexylmaleimide. The coordination cage accelerated the Diels-Alder reaction of anthracene at the electronically unfavorable, terminal benzene ring to give a compact, cavity-restrained syn-adduct. Activation-parameter measurements for the reactions revealed considerable reduction in the entropy cost, and preorganization of the substrates is a dominant factor in the enhanced reactivity. Owing to this entropy-cost reduction, otherwise-unreactive aromatic compounds, such as naphthalenes or triphenylene, also underwent Diels-Alder reactions in a regio- and stereocontrolled fashion. In the naphthalene Diels-Alder reaction, X-ray crystallographic analysis of the guest-inclusion complex clarified the reinforced orientation and proximity of the substrate pairs before the reaction. A perylene Diels-Alder adduct was stabilized inside the cage and protected from aerial oxidation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Kinetic modeling of reactions in Foods

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    2008-01-01

    The level of quality that food maintains as it travels down the production-to-consumption path is largely determined by the chemical, biochemical, physical, and microbiological changes that take place during its processing and storage. Kinetic Modeling of Reactions in Foods demonstrates how to

  17. Prediction of adverse drug reactions using decision tree modeling.

    Science.gov (United States)

    Hammann, F; Gutmann, H; Vogt, N; Helma, C; Drewe, J

    2010-07-01

    Drug safety is of great importance to public health. The detrimental effects of drugs not only limit their application but also cause suffering in individual patients and evoke distrust of pharmacotherapy. For the purpose of identifying drugs that could be suspected of causing adverse reactions, we present a structure-activity relationship analysis of adverse drug reactions (ADRs) in the central nervous system (CNS), liver, and kidney, and also of allergic reactions, for a broad variety of drugs (n = 507) from the Swiss drug registry. Using decision tree induction, a machine learning method, we determined the chemical, physical, and structural properties of compounds that predispose them to causing ADRs. The models had high predictive accuracies (78.9-90.2%) for allergic, renal, CNS, and hepatic ADRs. We show the feasibility of predicting complex end-organ effects using simple models that involve no expensive computations and that can be used (i) in the selection of the compound during the drug discovery stage, (ii) to understand how drugs interact with the target organ systems, and (iii) for generating alerts in postmarketing drug surveillance and pharmacovigilance.

  18. Generation of semicarbazide from natural azine development in foods, followed by reaction with urea compounds.

    Science.gov (United States)

    Abernethy, Grant A

    2015-01-01

    This paper proposes a mechanism to explain the trace levels of natural semicarbazide occasionally observed in foods. The analytical derivative of semicarbazide, 2-nitrobenzaldehyde semicarbazone, is often measured as a metabolite marker to detect the widely banned antibiotic nitrofurazone. However, this marker is not specific as semicarbazide may be present in foods for several reasons other than exposure to nitrofurazone. In some cases, an entirely natural origin of semicarbazide is suspected, although up until now there was no explanation about how semicarbazide could occur naturally. In this work, semicarbazide is proposed as being generated from natural food compounds via an azine intermediate. Hydrazine, in the form of azines or hydrazones, may be generated in dilute aqueous solution from the natural food compounds ammonia, hydrogen peroxide and acetone, following known oxidation chemistry. When this mixture was prepared in the presence of ureas such as allantoin, urea, biuret or hydroxyurea, and then analysed by the standard method for the determination of semicarbazide, 2-nitrobenzaldehyde semicarbazone was detected. 2-Nitrobenzaldehyde aldazine was also found, and it may be a general marker for azines in foods. This proposal, that azine formation is central to semicarbazide development, provides a convergence of the published mechanisms for semicarbazide. The reaction starts with hydrogen peroxide, peracetic acid, atmospheric oxygen or hypochlorite; generates hydrazine either by an oxaziridine intermediate or via the chlorination of ammonia; and then either route may converge on azine formation, followed by reaction with a urea compound. Additionally, carbamate ion may speculatively generate semicarbazide by reaction with hydrazine, which might be a significant route in the case of the hypochlorite treatment of foods or food contact surfaces. Significantly, detection of 2-nitrobenzaldehyde semicarbazone may be somewhat artefactual because semicarbazide can

  19. ToxAlerts: a Web server of structural alerts for toxic chemicals and compounds with potential adverse reactions.

    Science.gov (United States)

    Sushko, Iurii; Salmina, Elena; Potemkin, Vladimir A; Poda, Gennadiy; Tetko, Igor V

    2012-08-27

    The article presents a Web-based platform for collecting and storing toxicological structural alerts from literature and for virtual screening of chemical libraries to flag potentially toxic chemicals and compounds that can cause adverse side effects. An alert is uniquely identified by a SMARTS template, a toxicological endpoint, and a publication where the alert was described. Additionally, the system allows storing complementary information such as name, comments, and mechanism of action, as well as other data. Most importantly, the platform can be easily used for fast virtual screening of large chemical datasets, focused libraries, or newly designed compounds against the toxicological alerts, providing a detailed profile of the chemicals grouped by structural alerts and endpoints. Such a facility can be used for decision making regarding whether a compound should be tested experimentally, validated with available QSAR models, or eliminated from consideration altogether. The alert-based screening can also be helpful for an easier interpretation of more complex QSAR models. The system is publicly accessible and tightly integrated with the Online Chemical Modeling Environment (OCHEM, http://ochem.eu). The system is open and expandable: any registered OCHEM user can introduce new alerts, browse, edit alerts introduced by other users, and virtually screen his/her data sets against all or selected alerts. The user sets being passed through the structural alerts can be used at OCHEM for other typical tasks: exporting in a wide variety of formats, development of QSAR models, additional filtering by other criteria, etc. The database already contains almost 600 structural alerts for such endpoints as mutagenicity, carcinogenicity, skin sensitization, compounds that undergo metabolic activation, and compounds that form reactive metabolites and, thus, can cause adverse reactions. The ToxAlerts platform is accessible on the Web at http://ochem.eu/alerts, and it is constantly

  20. Reaction-diffusion pulses: a combustion model

    International Nuclear Information System (INIS)

    Campos, Daniel; Llebot, Josep Enric; Fort, Joaquim

    2004-01-01

    We focus on a reaction-diffusion approach proposed recently for experiments on combustion processes, where the heat released by combustion follows first-order reaction kinetics. This case allows us to perform an exhaustive analytical study. Specifically, we obtain the exact expressions for the speed of the thermal pulses, their maximum temperature and the condition of self-sustenance. Finally, we propose two generalizations of the model, namely, the case of several reactants burning together, and that of time-delayed heat conduction. We find an excellent agreement between our analytical results and simulations

  1. Reaction-diffusion pulses: a combustion model

    Energy Technology Data Exchange (ETDEWEB)

    Campos, Daniel [Grup de FIsica EstadIstica, Dept. de FIsica, Universitat Autonoma de Barcelona, E-08193 Bellaterrra (Spain); Llebot, Josep Enric [Grup de FIsica EstadIstica, Dept. de FIsica, Universitat Autonoma de Barcelona, E-08193 Bellaterrra (Spain); Fort, Joaquim [Dept. de FIsica, Univ. de Girona, Campus de Montilivi, 17071 Girona, Catalonia (Spain)

    2004-07-02

    We focus on a reaction-diffusion approach proposed recently for experiments on combustion processes, where the heat released by combustion follows first-order reaction kinetics. This case allows us to perform an exhaustive analytical study. Specifically, we obtain the exact expressions for the speed of the thermal pulses, their maximum temperature and the condition of self-sustenance. Finally, we propose two generalizations of the model, namely, the case of several reactants burning together, and that of time-delayed heat conduction. We find an excellent agreement between our analytical results and simulations.

  2. Reaction Wheel Disturbance Model Extraction Software - RWDMES

    Science.gov (United States)

    Blaurock, Carl

    2009-01-01

    The RWDMES is a tool for modeling the disturbances imparted on spacecraft by spinning reaction wheels. Reaction wheels are usually the largest disturbance source on a precision pointing spacecraft, and can be the dominating source of pointing error. Accurate knowledge of the disturbance environment is critical to accurate prediction of the pointing performance. In the past, it has been difficult to extract an accurate wheel disturbance model since the forcing mechanisms are difficult to model physically, and the forcing amplitudes are filtered by the dynamics of the reaction wheel. RWDMES captures the wheel-induced disturbances using a hybrid physical/empirical model that is extracted directly from measured forcing data. The empirical models capture the tonal forces that occur at harmonics of the spin rate, and the broadband forces that arise from random effects. The empirical forcing functions are filtered by a physical model of the wheel structure that includes spin-rate-dependent moments (gyroscopic terms). The resulting hybrid model creates a highly accurate prediction of wheel-induced forces. It accounts for variation in disturbance frequency, as well as the shifts in structural amplification by the whirl modes, as the spin rate changes. This software provides a point-and-click environment for producing accurate models with minimal user effort. Where conventional approaches may take weeks to produce a model of variable quality, RWDMES can create a demonstrably high accuracy model in two hours. The software consists of a graphical user interface (GUI) that enables the user to specify all analysis parameters, to evaluate analysis results and to iteratively refine the model. Underlying algorithms automatically extract disturbance harmonics, initialize and tune harmonic models, and initialize and tune broadband noise models. The component steps are described in the RWDMES user s guide and include: converting time domain data to waterfall PSDs (power spectral

  3. Contributions of electron microscopy to the understanding of reactions on compound semiconductor surfaces

    International Nuclear Information System (INIS)

    Sands, T.

    1986-01-01

    Reacted films on compound semiconductor substrates present challenging materials characterization problems which often require the application of transmission electron microscopy (TEM) techniques. In this paper, both the problem - solving potential of the TEM techniques and the limits imposed by preparation of thin film/compound semiconductor TEM specimens are discussed. Studies of the Ni/GaAs, CuCl/aq)/CdS and Pd/GaAs reactions exemplify the role of TEM in identifying and determining the spatial distribution of interface - stabilized polymorphs and new ternary phases (e.g. tetragonal Cu/sub 2/S, Ni/sub 3/GaAs and Pd/sub x/GaAs). These examples also serve to clarify the relationship between TEM and complementary analysis techniques such as Rutherford backscattering spectrometry, Auger electron spectroscopy and glancing-angle x-ray diffraction. In particular, it is argued that a combination of (1) high-spatial-resolution information obtained by TEM and (2) an indication of the ''average'' behavior provided by data from a complementary characterization technique provide the minimum quality and quantity of data necessary to understand most reactions on compound semiconductor substrates

  4. Effects of extrusion, infrared and microwave processing on Maillard reaction products and phenolic compounds in soybean.

    Science.gov (United States)

    Zilić, Slađana; Mogol, Burçe Ataç; Akıllıoğlu, Gül; Serpen, Arda; Delić, Nenad; Gökmen, Vural

    2014-01-15

    The Maillard reaction indicators furosine, hydroxymethylfurfural (HMF), acrylamide and color were determined to evaluate heat effects induced during extrusion, infrared and microwave heating of soybean. In addition, the present paper aimed to study changes in the phenolic compounds, as well as in the overall antioxidant properties of different soybean products in relation to heating at 45-140 °C during the processes. Soybean proteins were highly sensible to Maillard reaction and furosine was rapidly formed under slight heating conditions during extrusion and infrared heating. Microwave heating at lower temperatures for a longer time yielded lower acrylamide levels in the final soybean products, as a result of its partial degradation. However, during infrared heating, acrylamide formation greatly increased with decreasing moisture content. After a short time of extrusion and infrared heating at 140 °C and microwave heating at 135 °C for 5 min, concentrations of HMF increased to 11.34, 26.21 and 34.97 µg g(-1), respectively. The heating conditions caused formation of acrylamide, HMF and furosine in high concentration. The results indicate that the complex structure of soybeans provides protection of phenolic compounds from thermal degradation, and that Maillard reaction products improved the antioxidant properties of heat-treated soybean. © 2013 Society of Chemical Industry.

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

    International Nuclear Information System (INIS)

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

    1999-01-01

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

  6. Deuterium cluster model for low energy nuclear reactions (LENR)

    Science.gov (United States)

    Miley, George; Hora, Heinrich

    2007-11-01

    For studying the possible reactions of high density deuterons on the background of a degenerate electron gas, a summary of experimental observations resulted in the possibility of reactions in pm distance and more than ksec duration similar to the K-shell electron capture [1]. The essential reason was the screening of the deuterons by a factor of 14 based on the observations. Using the bosonic properties for a cluster formation of the deuterons and a model of compound nuclear reactions [2], the measured distribution of the resulting nuclei may be explained as known from the Maruhn-Greiner theory for fission. The local maximum of the distribution at the main minimum indicates the excited states of the compound nuclei during their intermediary state. This measured local maximum may be an independent proof for the deuteron clusters at LENR. [1] H. Hora, G.H. Miley et al. Physics Letters A175, 138 (1993) [2] H. Hora and G.H. Miley, APS March Meeting 2007, Program p. 116

  7. Formation of nitrogen-containing compounds during microwave pyrolysis of microalgae: Product distribution and reaction pathways.

    Science.gov (United States)

    Huang, Feng; Tahmasebi, Arash; Maliutina, Kristina; Yu, Jianglong

    2017-12-01

    The formation of nitrogen-containing compounds in bio-oil during microwave pyrolysis of Chlorella and Spirulina microalgae has been investigated in this study. Activated carbon (AC) and magnetite (Fe 3 O 4 ) were used as microwave receptors during microwave pyrolysis experiments. It has been found that the use of Fe 3 O 4 increased the total yield of bio-oil. The use of different microwave receptors did not seem to have affected the total yield of nitrogen-containing compounds in the bio-oil. However, Fe 3 O 4 promoted the formation of nitrogen-containing aliphatics, thereby reducing the formation of nitrogen-containing aromatics. The use of AC promoted the dehydration reactions during amino acid decomposition, thereby enhancing the formation of nitrogen-containing aromatics during pyrolysis. From the gas chromatography-mass spectrometry (GC-MS) analysis results, the major high-value nitrogen-containing compounds in the pyrolysis bio-oil of Chlorella and Spirulina were identified as indole and dodecamide. The formation mechanisms of nitrogen-containing compounds were proposed and discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Study of Reaction of Curium Oxy-Compound Formation in Molten Chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Osipenko, A.G.; Mayorshin, A.A.; Bychkov, A.V. [Dimitrovgrad-10, Ulyanovsk region, 433510 (Russian Federation)

    2008-07-01

    The method of potentiometric titration using oxygen sensors with solid electrolyte membrane was applied for the study of the interaction of curium cations with oxygen anions in the molten alkali metal chlorides in the temperature range of 450-850 C degrees depending on oxy-acidity of the environment. Assumptions were made concerning ion and phase composition of the obtained high-temperature compounds and chemical reactions taking place in the melts. This scheme assumes that as the basicity of the melt increases, initially the formation of soluble curium oxychlorides takes place in the melt (presumably CmO{sup -}) that is followed by formation of solid CmOCl and finally sesquioxide Cm{sub 2}O{sub 3}. Basic thermodynamic values were calculated for the resultant curium oxy-compounds.

  9. Radiolytic oxidation of propane: computer modeling of the reaction scheme

    International Nuclear Information System (INIS)

    Gupta, A.K.; Hanrahan, R.J.

    1991-01-01

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25 o C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases. (author)

  10. EMPIRE-II statistical model code for nuclear reaction calculations

    Energy Technology Data Exchange (ETDEWEB)

    Herman, M [International Atomic Energy Agency, Vienna (Austria)

    2001-12-15

    EMPIRE II is a nuclear reaction code, comprising various nuclear models, and designed for calculations in the broad range of energies and incident particles. A projectile can be any nucleon or Heavy Ion. The energy range starts just above the resonance region, in the case of neutron projectile, and extends up to few hundreds of MeV for Heavy Ion induced reactions. The code accounts for the major nuclear reaction mechanisms, such as optical model (SCATB), Multistep Direct (ORION + TRISTAN), NVWY Multistep Compound, and the full featured Hauser-Feshbach model. Heavy Ion fusion cross section can be calculated within the simplified coupled channels approach (CCFUS). A comprehensive library of input parameters covers nuclear masses, optical model parameters, ground state deformations, discrete levels and decay schemes, level densities, fission barriers (BARFIT), moments of inertia (MOMFIT), and {gamma}-ray strength functions. Effects of the dynamic deformation of a fast rotating nucleus can be taken into account in the calculations. The results can be converted into the ENDF-VI format using the accompanying code EMPEND. The package contains the full EXFOR library of experimental data. Relevant EXFOR entries are automatically retrieved during the calculations. Plots comparing experimental results with the calculated ones can be produced using X4TOC4 and PLOTC4 codes linked to the rest of the system through bash-shell (UNIX) scripts. The graphic user interface written in Tcl/Tk is provided. (author)

  11. Production of isomers in compound and transfer reactions with 4He ions

    International Nuclear Information System (INIS)

    Karamyan, S.A.; Aksenov, N.V.; Albin, Yu.A.; Bozhikov, G.A.; Dmitriev, S.N.; Starodub, G.Ya.; Vostokin, G.K.; Carroll, J.J.

    2011-01-01

    A well-known island of nuclear isomerism appears near A = 175-180 due to the deformation alignment of single-particle orbits at high angular momentum. This sometimes results in the formation of multi-quasiparticle states with record spin that are long-lived because of 'K-hindrance', i.e., symmetry rearrangement. Production methods and spectroscopic studies of these isomers remain a challenge for modern nuclear reaction and nuclear structure physics. Activities were produced by irradiation of 176 Yb(97.6%) enriched and nat Lu targets with 35-MeV 4 He ions from the internal beam of the U200 cyclotron. Induced activities were analyzed applying methods of radiochemistry and gamma spectroscopy. Yields of compound and nucleon-transfer reactions were measured and the isomer-to-ground state ratios were deduced. Calculated results were obtained using standard procedures to reproduce the (α, xn) cross sections, and the systematic behavior of the nucleon-transfer yields was established. The isomer-to-ground state ratios for direct reactions with 4 He ions were examined, resulting in a new characterization of the reaction mechanism

  12. 1,3-Dipolar cycloaddition reactions of nitrile oxides in the synthesis of natural compounds and their analogues

    International Nuclear Information System (INIS)

    Kotyatkina, Anna I; Zhabinsky, Vladimir N; Khripach, Vladimir A

    2001-01-01

    The published data on the use of 1,3-dipolar cycloaddition reactions of nitrile oxides in the synthesis of natural compounds and their analogues are systematised and reviewed. The bibliography includes 145 references.

  13. Double generalized linear compound poisson models to insurance claims data

    DEFF Research Database (Denmark)

    Andersen, Daniel Arnfeldt; Bonat, Wagner Hugo

    2017-01-01

    This paper describes the specification, estimation and comparison of double generalized linear compound Poisson models based on the likelihood paradigm. The models are motivated by insurance applications, where the distribution of the response variable is composed by a degenerate distribution...... implementation and illustrate the application of double generalized linear compound Poisson models using a data set about car insurances....

  14. Analytical applications of oscillatory chemical reactions: determination of some pharmaceuticaly and biologically important compounds

    Directory of Open Access Journals (Sweden)

    Pejić Nataša D.

    2012-01-01

    Full Text Available Novel analytical methods for quantitive determination of analytes based on perturbations of oscillatory chemical reactions realized under open reactor conditions (continuosly fed well stirred tank reactor, CSTR, have been developed in the past twenty years. The proposed kinetic methods are generally based on the ability of the analyzed substances to change the kinetics of the chemical reactions matrix. The unambiguous correlation of quantitative characteristics of perturbations, and the amount (concentration of analyte expressed as a regression equation, or its graphics (calibration curve, enable the determination of the unknown analyte concentration. Attention is given to the development of these methods because of their simple experimental procedures, broad range of linear regression ( 10-7 10-4 mol L-1 and low limits of detection of analytes ( 10-6 10-8 mol L1, in some cases even lower than 10-12 mol L-1. Therefore, their application is very convenient for routine analysis of various inorganic and organic compounds as well as gases. This review summarizes progress made in the past 5 years on quantitative determination of pharmaceutically and biologically important compounds.

  15. Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

    International Nuclear Information System (INIS)

    Rosen, R.K.

    1989-12-01

    The trivalent uranium compound, (MeC 5 H 4 ) 3 U(thf), serves as a one- or two-electron reducing agent towards azides, RN 3 . These reactions produce either the uranium(IV) azide, (MeC 5 H 4 ) 3 UN 3 , or uranium(V) imides, (MeC 5 H 4 ) 3 UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me 3 XN 3 , the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph 3 XN 3 , the azide is produced when X = C or Sn. For Ph 3-x CH 3 N 3 , the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC 6 H 4 N 3 , only the imides are produced. The magnetic properties of uranium diimides, [(MeC 5 H 4 ) 3 U] 2 (μ-NRN), were investigated. Several uranium(III) amines, (MeC 5 H 4 ) 3 U(NH 2 R), were produced from (MeC 5 H 4 ) 3 U(thf) and RNH 2 , and NH 3 was found to be a better ligand towards (MeC 5 H 4 ) 3 U than is PMe 3

  16. Reaction kinetics and transformation of carbadox and structurally related compounds with aqueous chlorine.

    Science.gov (United States)

    Shah, Amisha D; Kim, Jae-Hong; Huang, Ching-Hua

    2006-12-01

    The potential release of carbadox (CDX), a commonly used antibacterial agent in swine husbandry, into water systems is of a concern due to its carcinogenic and genotoxic effects. Until this study, the reactivity of carbadox (possessing quinoxaline N,N'-dioxide and hydrazone moieties) toward aqueous chlorine has yetto be investigated in depth. Chemical reactivity, reaction kinetics, and transformation pathways of carbadox and structurally related compounds with free chlorine under typical water treatment conditions were determined. This study found that only CDX and desoxycarbadox (DCDX), a main metabolite of CDX with no ring N-oxide groups, react rapidly with free chlorine while other structurally related compounds including olaquindox, quindoxin, quinoxaline N-oxide, quinoxaline, and quinoline N-oxide do not. The reaction kinetics of CDX and DCDX with chlorine are highly pH dependent (e.g., the apparent second-order rate constant, kapp, for CDX ranges from 51.8 to 3.15 x 10(4) M(-1)s(-1) at pH 4-11). The high reactivity of CDX and DCDX to chlorine involves deprotonation of their hydrazone N-H moieties where initial chlorine attack results in a reactive intermediate that is further attacked by nucleophiles in the matrix to yield non-chlorinated, hydroxylated, and larger molecular weight byproducts. All of the CDX's byproducts retain their biologically active N-oxide groups, suggesting that they may remain as active antibacterial agents.

  17. No-Core Shell Model and Reactions

    International Nuclear Information System (INIS)

    Navratil, P; Ormand, W E; Caurier, E; Bertulani, C

    2005-01-01

    There has been a significant progress in ab initio approaches to the structure of light nuclei. Starting from realistic two- and three-nucleon interactions the ab initio no-core shell model (NCSM) can predict low-lying levels in p-shell nuclei. It is a challenging task to extend ab initio methods to describe nuclear reactions. In this contribution, we present a brief overview of the NCSM with examples of recent applications as well as the first steps taken toward nuclear reaction applications. In particular, we discuss cross section calculations of p+ 6 Li and 6 He+p scattering as well as a calculation of the astrophysically important 7 Be(p, γ) 8 B S-factor

  18. Comprehensive coordination chemistry. The synthesis, reactions, properties and applications of coordination compounds. V.3. Main group and early transition elements

    International Nuclear Information System (INIS)

    Wilkinson, Geoffrey; Gillard, R.D.; McCleverty, J.A.

    1987-01-01

    Comprehensive coordination chemistry reviews the synthesis reactions and properties of coordination compounds. Their uses in such diverse fields as nuclear fuels, toxicology, medicine and biology are discussed. Volume three concentrates on the main group and early transition element coordination compounds. (UK)

  19. Tunable Cascade Reaction of Aryl Diazonium Salts and Trialkylamine: Synthesis of Monofluorinated Arylhydrazones and gem-Difluorinated Azo Compounds.

    Science.gov (United States)

    Guo, Rui; Zhang, Zhengjuan; Shi, Feng; Tang, Pingping

    2016-03-04

    The first example of a mild and tunable cascade reaction of aryl diazonium salts and trialkylamine in the presence of Selectfluor to prepare monofluorinated arylhydrazones and gem-difluorinated azo compounds without metal has been explored. In the presence of H2O, the monofluorinated arylhydrazones were observed in moderate to good yield. In the absence of H2O, the gem-difluorinated azo compounds were obtained. The fluorinated arylhydrazones were utilized to synthesize fluorinated pyrazoles and other nitrogen-containing compounds.

  20. Reactions of green lizards (Lacerta viridis) to major repellent compounds secreted by Graphosoma lineatum (Heteroptera: Pentatomidae).

    Science.gov (United States)

    Gregorovičová, Martina; Černíková, Alena

    2015-06-01

    The chemical defence of Heteroptera is primarily based on repellent secretions which signal the potential toxicity of the bug to its predators. We tested the aversive reactions of green lizards (Lacerta viridis) towards the major compounds of the defensive secretion of Graphosoma lineatum, specifically: (i) a mixture of three aldehydes: (E)-hex-2-enal, (E)-oct-2-enal, (E)-dec-2-enal; (ii) a mixture of these three aldehydes and tridecane; (iii) oxoaldehyde: (E)-4-oxohex-2-enal; (iv) secretion extracted from metathoracic scent glands of G. lineatum adults and (v) hexane as a non-polar solvent. All chemicals were presented on a palatable food (Tenebrio molitor larvae). The aversive reactions of the green lizards towards the mealworms were evaluated by observing the approach latencies, attack latencies and approach-attack intervals. The green lizards exhibited a strong aversive reaction to the mixture of three aldehydes. Tridecane reduced the aversive reaction to the aldehyde mixture. Oxoaldehyde caused the weakest, but still significant, aversive reaction. The secretion from whole metathoracic scent glands also clearly had an aversive effect on the green lizards. Moreover, when a living specimen of G. lineatum or Pyrrhocoris apterus (another aposematic red-and-black prey) was presented to the green lizards before the trials with the aldehyde mixture, the aversive effect of the mixture was enhanced. In conclusion, the mixture of three aldehydes had the strong aversive effect and could signal the potential toxicity of G. lineatum to the green lizards. Copyright © 2015 Elsevier GmbH. All rights reserved.

  1. Measurement of the Residual Sodium and Reaction Compounds on a Cleaned Cold Trap

    International Nuclear Information System (INIS)

    Kim, Byung Ho; Jeong, Ji Young; Kim, Jong Man; Choi, Byung Hae; Nam, Ho Yun Nam

    2006-01-01

    The purpose of a cleaning process is to remove the residual sodium adhering to the component walls once it has been properly drained. It is necessary to clean and decontaminate a component, especially the large components of the primary coolant system; such as the intermediate heat exchangers and the primary pump. Improper and inadequate cleaning has in a number of cases resulted in problems in the storage, handling, and reuse of components. Inadequate and incomplete removal of sodium results in residues which may contain metallic sodium and alkaline compounds such as sodium hydroxide, sodium oxide, sodium carbonate, and various types of alcoholates. Reinsertion of components containing these compounds into a high-temperature sodium system can result in either a intergranular penetration characteristic of a high-oxygen sodium or an accelerated corrosion due to oxygen. Cleaning methods are needed that will avoid a deleterious local overheating, material surface degradation or deposits, a chemical, physical, or mechanical damage, and external effects. It is important to determine the levels of residual sodium that can be accepted so that those deleterious effects will not negate the reuse of the component. The purpose of this paper is to measure the amount of the sodium and the reaction compounds remaining on a component after a cleaning and prepare acceptable criteria for the reuse of components which have been subjected to a sodium cleaning

  2. A detailed chemical kinetic model for pyrolysis of the lignin model compound chroman

    Directory of Open Access Journals (Sweden)

    James Bland

    2013-12-01

    Full Text Available The pyrolysis of woody biomass, including the lignin component, is emerging as a potential technology for the production of renewable fuels and commodity chemicals. Here we describe the construction and implementation of an elementary chemical kinetic model for pyrolysis of the lignin model compound chroman and its reaction intermediate ortho-quinone methide (o-QM. The model is developed using both experimental and theoretical data, and represents a hybrid approach to kinetic modeling that has the potential to provide molecular level insight into reaction pathways and intermediates while accurately describing reaction rates and product formation. The kinetic model developed here can replicate all known aspects of chroman pyrolysis, and provides new information on elementary reaction steps. Chroman pyrolysis is found to proceed via an initial retro-Diels–Alder reaction to form o-QM + ethene (C2H4, followed by dissociation of o-QM to the C6H6 isomers benzene and fulvene (+ CO. At temperatures of around 1000–1200 K and above fulvene rapidly isomerizes to benzene, where an activation energy of around 270 kJ mol-1 is required to reproduce experimental observations. A new G3SX level energy surface for the isomerization of fulvene to benzene supports this result. Our modeling also suggests that thermal decomposition of fulvene may be important at around 950 K and above. This study demonstrates that theoretical protocols can provide a significant contribution to the development of kinetic models for biomass pyrolysis by elucidating reaction mechanisms, intermediates, and products, and also by supplying realistic rate coefficients and thermochemical properties.

  3. Utilization of biomass: Conversion of model compounds to hydrocarbons over zeolite H-ZSM-5

    DEFF Research Database (Denmark)

    Mentzel, Uffe Vie; Holm, Martin Spangsberg

    2011-01-01

    Zeolite catalyzed deoxygenation of small oxygenates present in bio-oil or selected as model compounds was performed under Methanol-to-Hydrocarbons (MTH) like reaction conditions using H-ZSM-5 as the catalyst. Co-feeding of the oxygenates with methanol generally decreases catalyst lifetime due...

  4. The Action of Chain Extenders in Nylon-6, PET, and Model Compounds

    NARCIS (Netherlands)

    Loontjens, T.; Pauwels, K.; Derks, F.; Neilen, M.; Sham, C.K.; Serné, M.

    1997-01-01

    The action of two complementary chain extenders is studied in model systems as well as in poly(ethylene terephthalate) (PET) and nylon–6. Chain extenders are low molecular weight compounds that can be used to increase the molecular weight of polymers in a short time. The reaction must preferably be

  5. Decomposition of lignin model compounds by Lewis acid catalysts in water and ethanol

    NARCIS (Netherlands)

    Guvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Emiel J. M.

    2015-01-01

    The conversion of benzyl phenyl ether, diphenyl ether, diphenyl methane and biphenyl as representative model compounds for alpha-O-4, 5-O-4, alpha(1) (methylene bridges) and 5-5' lignin linkages was investigated. We compared the use of metal chlorides and acetates. The reactions were studied in sub-

  6. Reactions of the melatonin metabolite N(1)-acetyl-5-methoxykynuramine with carbamoyl phosphate and related compounds.

    Science.gov (United States)

    Kuesel, Jana T; Hardeland, Rüdiger; Pfoertner, Henrike; Aeckerle, Nelia

    2010-01-01

    N-[2-(6-methoxyquinazolin-4-yl)-ethyl] acetamide (MQA) is a compound formed from the melatonin metabolite N(1)-acetyl-5-methoxykynuramine (AMK). We followed MQA production in reaction systems containing various putative reaction partners, in the absence and presence of hydrogen peroxide and/or copper(II). Although MQA may be formally described as a condensation product of either N(1)-acetyl-N(2)-formyl-5-methoxykynuramine (AFMK) with ammonia, or AMK with formamide, none of these combinations led to substantial quantities of MQA. However, MQA formation was observed in mixtures containing AMK, hydrogen peroxide, hydrogen carbonate and ammonia, or AMK, hydrogen peroxide, copper(II) and potentially carbamoylating agents, such as potassium cyanate or, more efficiently, carbamoyl phosphate. In the presence of hydrogen peroxide, copper(II) and carbamoyl phosphate, MQA was the major product obtained from AMK, but the omission of copper(II) mainly led to another metabolite, 3-acetamidomethyl-6-methoxycinnolinone (AMMC). This was caused by nitric oxide (NO) generated under oxidative conditions from carbamoyl phosphate, as shown by an NO spin trap. MQA formation with carbamoyl phosphate was not due to the possible decomposition product, formamide. The reaction of AMK with carbamoyl phosphate under oxidative conditions, in which inorganic phosphate and water are released and which differs from the typical process of carbamoylation via isocyanate, may be considered as a new physiological route of MQA formation.

  7. Sulfurized limonite as material for fast decomposition of organic compounds by heterogeneous Fenton reaction

    International Nuclear Information System (INIS)

    Toda, Kei; Tanaka, Toshinori; Tsuda, Yutaka; Ban, Masahiro; Koveke, Edwin P.; Koinuma, Michio; Ohira, Shin-Ichi

    2014-01-01

    Graphical abstract: - Highlights: • Used limonite degrades organic compounds by heterogeneous Fenton reaction. • Sulfurized limonite removes methylene blue color in seconds. • Recycled limonite can be used for biogas purification and wastewater treatment. - Abstract: Rapid decomposition of wastewater contaminants using sulfurized limonite (S-limonite) was investigated. Limonite is used for desulfurization of biogases, and S-limonite is obtained from desulfurization plants as solid waste. In this work, the profitable use of S-limonite in water treatment was examined. The divalent Fe in S-limonite was expected to produce OH radicals, as Fe 2+ ions and limonite thermally treated with H 2 do. Methylene blue was used for batch-wise monitoring of the decomposition performance. The decomposition rate was fast and the methylene blue solution color disappeared in only 10 s when a small amount of H 2 O 2 was added (1 mM in the sample solution) in the presence of S-limonite. The OH radicals were formed by a heterogeneous reaction on the S-limonite surface and Fenton reaction with dissolved Fe 2+ . The decomposition of pentachlorophenol was also examined; it was successfully decomposed in batch-wise tests. The surfaces of limonite before sulfurization, S-limonite, and S-limonite after use for water treatment were performed using scanning electron microscopy and X-ray photoelectron spectroscopy. The results show that S-limonite reverted to limonite after being used for water treatment

  8. Sulfurized limonite as material for fast decomposition of organic compounds by heterogeneous Fenton reaction

    Energy Technology Data Exchange (ETDEWEB)

    Toda, Kei, E-mail: todakei@sci.kumamoto-u.ac.jp [Department of Chemistry, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Tanaka, Toshinori; Tsuda, Yutaka; Ban, Masahiro; Koveke, Edwin P. [Department of Chemistry, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Koinuma, Michio [Department of Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Ohira, Shin-Ichi [Department of Chemistry, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan)

    2014-08-15

    Graphical abstract: - Highlights: • Used limonite degrades organic compounds by heterogeneous Fenton reaction. • Sulfurized limonite removes methylene blue color in seconds. • Recycled limonite can be used for biogas purification and wastewater treatment. - Abstract: Rapid decomposition of wastewater contaminants using sulfurized limonite (S-limonite) was investigated. Limonite is used for desulfurization of biogases, and S-limonite is obtained from desulfurization plants as solid waste. In this work, the profitable use of S-limonite in water treatment was examined. The divalent Fe in S-limonite was expected to produce OH radicals, as Fe{sup 2+} ions and limonite thermally treated with H{sub 2} do. Methylene blue was used for batch-wise monitoring of the decomposition performance. The decomposition rate was fast and the methylene blue solution color disappeared in only 10 s when a small amount of H{sub 2}O{sub 2} was added (1 mM in the sample solution) in the presence of S-limonite. The OH radicals were formed by a heterogeneous reaction on the S-limonite surface and Fenton reaction with dissolved Fe{sup 2+}. The decomposition of pentachlorophenol was also examined; it was successfully decomposed in batch-wise tests. The surfaces of limonite before sulfurization, S-limonite, and S-limonite after use for water treatment were performed using scanning electron microscopy and X-ray photoelectron spectroscopy. The results show that S-limonite reverted to limonite after being used for water treatment.

  9. Exact model reduction of combinatorial reaction networks

    Directory of Open Access Journals (Sweden)

    Fey Dirk

    2008-08-01

    Full Text Available Abstract Background Receptors and scaffold proteins usually possess a high number of distinct binding domains inducing the formation of large multiprotein signaling complexes. Due to combinatorial reasons the number of distinguishable species grows exponentially with the number of binding domains and can easily reach several millions. Even by including only a limited number of components and binding domains the resulting models are very large and hardly manageable. A novel model reduction technique allows the significant reduction and modularization of these models. Results We introduce methods that extend and complete the already introduced approach. For instance, we provide techniques to handle the formation of multi-scaffold complexes as well as receptor dimerization. Furthermore, we discuss a new modeling approach that allows the direct generation of exactly reduced model structures. The developed methods are used to reduce a model of EGF and insulin receptor crosstalk comprising 5,182 ordinary differential equations (ODEs to a model with 87 ODEs. Conclusion The methods, presented in this contribution, significantly enhance the available methods to exactly reduce models of combinatorial reaction networks.

  10. Evaluation of the extent of initial Maillard reaction during cooking some vegetables by direct measurement of the Amadori compounds.

    Science.gov (United States)

    Yu, Jiahao; Zhang, Shuqin; Zhang, Lianfu

    2018-01-01

    During vegetable cooking, one of the most notable and common chemical reactions is the Maillard reaction, which occurs as a result of thermal treatment and dehydration. Amadori compound determination provides a very sensitive indicator for early detection of quality changes caused by the Maillard reaction, as well as to retrospectively assess the heat treatment or storage conditions to which the product has been subjected. In this paper, a hydrophilic interaction liquid chromatographic-electrospray ionization-tandem mass spectrometric method was developed for the analysis of eight Amadori compounds, and the initial steps of the Maillard reaction during cooking (steaming, frying and baking) bell pepper, red pepper, yellow onion, purple onion, tomato and carrot were also assessed by quantitative determination of these Amadori compounds. These culinary treatments reduced moisture and increased the total content of Amadori compounds, which was not dependent on the type of vegetable or cooking method. Moreover, the effect of steaming on Amadori compound content and water loss was less than that by baking and frying vegetables. Further studies showed that the combination of high temperature and short time may lead to lower formation of Amadori compounds when baking vegetables. Culinary methods differently affected the extent of initial Maillard reaction when vegetables were made into home-cooked products. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  11. Unravelling the Maillard reaction network by multiresponse kinetic modelling

    NARCIS (Netherlands)

    Martins, S.I.F.S.

    2003-01-01

    The Maillard reaction is an important reaction in food industry. It is responsible for the formation of colour and aroma, as well as toxic compounds as the recent discovered acrylamide. The knowledge of kinetic parameters, such as rate constants and activation energy, is necessary to predict its

  12. Reactions of recoil tritium generated by the 3He(n,p)3H reaction with aromatic compounds -intramolecular tritium distribution and radiochemical yield

    International Nuclear Information System (INIS)

    Nogawa, N.; Morikawa, Naotake; Oohashi, Kunio; Matuoka, H.; Moki, T.; Moriya, T.

    1986-01-01

    Reactions of recoil tritium with benzoic acid, acetanilide and β-phenethyl alcohol were studied using the 3 He(=n,p) 3 H reaction. The tritium distribution in the aromatic ring is approximately uniform in all the irradiated compounds and the tritium activity per C-H bond in the methyl and ethylene groups is 7 to 8 relative to that of the corresponding ring as standard. These findings are substantially the same as those obtained previously by the 6 Li(n,α) 3 H reactions, suggesting the same mechanism of tritiation for both recoil reactions. The tritiated parent compounds were obtained in high radiochemical yields: 45% for benzoic acid, 30% for acetanilide, 12% for β-phenethyl alcohol. (author)

  13. Modeling of iodine radiation chemistry in the presence of organic compounds

    International Nuclear Information System (INIS)

    Taghipour, Fariborz; Evans, Greg J.

    2002-01-01

    A kinetic-based model was developed that simulates the radiation chemistry of iodine in the presence of organic compounds. The model's mechanistic description of iodine chemistry and generic semi-mechanistic reactions for various classes of organics, provided a reasonable representation of experimental results. The majority of the model and experimental results of iodine volatilization rates were in agreement within an order of magnitude

  14. The use of statistical models in heavy-ion reactions studies

    International Nuclear Information System (INIS)

    Stokstad, R.G.

    1984-01-01

    This chapter reviews the use of statistical models to describe nuclear level densities and the decay of equilibrated nuclei. The statistical models of nuclear structure and nuclear reactions presented here have wide application in the analysis of heavy-ion reaction data. Applications are illustrated with examples of gamma-ray decay, the emission of light particles and heavier clusters of nucleons, and fission. In addition to the compound nucleus, the treatment of equilibrated fragments formed in binary reactions is discussed. The statistical model is shown to be an important tool for the identification of products from nonequilibrium decay

  15. Modeling stochasticity in biochemical reaction networks

    International Nuclear Information System (INIS)

    Constantino, P H; Vlysidis, M; Smadbeck, P; Kaznessis, Y N

    2016-01-01

    Small biomolecular systems are inherently stochastic. Indeed, fluctuations of molecular species are substantial in living organisms and may result in significant variation in cellular phenotypes. The chemical master equation (CME) is the most detailed mathematical model that can describe stochastic behaviors. However, because of its complexity the CME has been solved for only few, very small reaction networks. As a result, the contribution of CME-based approaches to biology has been very limited. In this review we discuss the approach of solving CME by a set of differential equations of probability moments, called moment equations. We present different approaches to produce and to solve these equations, emphasizing the use of factorial moments and the zero information entropy closure scheme. We also provide information on the stability analysis of stochastic systems. Finally, we speculate on the utility of CME-based modeling formalisms, especially in the context of synthetic biology efforts. (topical review)

  16. 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...

  17. Testing the compounding structure of the CP-INARCH model

    OpenAIRE

    Weiß, Christian H.; Gonçalves, Esmeralda; Lopes, Nazaré Mendes

    2017-01-01

    A statistical test to distinguish between a Poisson INARCH model and a Compound Poisson INARCH model is proposed, based on the form of the probability generating function of the compounding distribution of the conditional law of the model. For first-order autoregression, the normality of the test statistics’ asymptotic distribution is established, either in the case where the model parameters are specified, or when such parameters are consistently estimated. As the test statistics’ law involv...

  18. Mathematical modeling of atmospheric fine particle-associated primary organic compound concentrations

    Science.gov (United States)

    Rogge, Wolfgang F.; Hildemann, Lynn M.; Mazurek, Monica A.; Cass, Glen R.; Simoneit, Bernd R. T.

    1996-08-01

    An atmospheric transport model has been used to explore the relationship between source emissions and ambient air quality for individual particle phase organic compounds present in primary aerosol source emissions. An inventory of fine particulate organic compound emissions was assembled for the Los Angeles area in the year 1982. Sources characterized included noncatalyst- and catalyst-equipped autos, diesel trucks, paved road dust, tire wear, brake lining dust, meat cooking operations, industrial oil-fired boilers, roofing tar pots, natural gas combustion in residential homes, cigarette smoke, fireplaces burning oak and pine wood, and plant leaf abrasion products. These primary fine particle source emissions were supplied to a computer-based model that simulates atmospheric transport, dispersion, and dry deposition based on the time series of hourly wind observations and mixing depths. Monthly average fine particle organic compound concentrations that would prevail if the primary organic aerosol were transported without chemical reaction were computed for more than 100 organic compounds within an 80 km × 80 km modeling area centered over Los Angeles. The monthly average compound concentrations predicted by the transport model were compared to atmospheric measurements made at monitoring sites within the study area during 1982. The predicted seasonal variation and absolute values of the concentrations of the more stable compounds are found to be in reasonable agreement with the ambient observations. While model predictions for the higher molecular weight polycyclic aromatic hydrocarbons (PAH) are in agreement with ambient observations, lower molecular weight PAH show much higher predicted than measured atmospheric concentrations in the particle phase, indicating atmospheric decay by chemical reactions or evaporation from the particle phase. The atmospheric concentrations of dicarboxylic acids and aromatic polycarboxylic acids greatly exceed the contributions that

  19. Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

    Energy Technology Data Exchange (ETDEWEB)

    Rosen, R.K.

    1989-12-01

    The trivalent uranium compound, (MeC{sub 5}H{sub 4}){sub 3}U(thf), serves as a one- or two-electron reducing agent towards azides, RN{sub 3}. These reactions produce either the uranium(IV) azide, (MeC{sub 5}H{sub 4}){sub 3}UN{sub 3}, or uranium(V) imides, (MeC{sub 5}H{sub 4}){sub 3}UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me{sub 3}XN{sub 3}, the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph{sub 3}XN{sub 3}, the azide is produced when X = C or Sn. For Ph{sub 3-x}CH{sub 3}N{sub 3}, the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC{sub 6}H{sub 4}N{sub 3}, only the imides are produced. The magnetic properties of uranium diimides, ((MeC{sub 5}H{sub 4}){sub 3}U){sub 2}({mu}-NRN), were investigated. Several uranium(III) amines, (MeC{sub 5}H{sub 4}){sub 3}U(NH{sub 2}R), were produced from (MeC{sub 5}H{sub 4}){sub 3}U(thf) and RNH{sub 2}, and NH{sub 3} was found to be a better ligand towards (MeC{sub 5}H{sub 4}){sub 3}U than is PMe{sub 3}.

  20. Modeling of Reaction Processes Controlled by Diffusion

    International Nuclear Information System (INIS)

    Revelli, Jorge

    2003-01-01

    Stochastic modeling is quite powerful in science and technology.The technics derived from this process have been used with great success in laser theory, biological systems and chemical reactions.Besides, they provide a theoretical framework for the analysis of experimental results on the field of particle's diffusion in ordered and disordered materials.In this work we analyze transport processes in one-dimensional fluctuating media, which are media that change their state in time.This fact induces changes in the movements of the particles giving rise to different phenomena and dynamics that will be described and analyzed in this work.We present some random walk models to describe these fluctuating media.These models include state transitions governed by different dynamical processes.We also analyze the trapping problem in a lattice by means of a simple model which predicts a resonance-like phenomenon.Also we study effective diffusion processes over surfaces due to random walks in the bulk.We consider different boundary conditions and transitions movements.We derive expressions that describe diffusion behaviors constrained to bulk restrictions and the dynamic of the particles.Finally it is important to mention that the theoretical results obtained from the models proposed in this work are compared with Monte Carlo simulations.We find, in general, excellent agreements between the theory and the simulations

  1. Chapter 8: Pyrolysis Mechanisms of Lignin Model Compounds Using a Heated Micro-Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Robichaud, David J.; Nimlos, Mark R.; Ellison, G. Barney

    2015-10-03

    Lignin is an important component of biomass, and the decomposition of its thermal deconstruction products is important in pyrolysis and gasification. In this chapter, we investigate the unimolecular pyrolysis chemistry through the use of singly and doubly substituted benzene molecules that are model compounds representative of lignin and its primary pyrolysis products. These model compounds are decomposed in a heated micro-reactor, and the products, including radicals and unstable intermediates, are measured using photoionization mass spectrometry and matrix isolation infrared spectroscopy. We show that the unimolecular chemistry can yield insight into the initial decomposition of these species. At pyrolysis and gasification severities, singly substituted benzenes typically undergo bond scission and elimination reactions to form radicals. Some require radical-driven chain reactions. For doubly substituted benzenes, proximity effects of the substituents can change the reaction pathways.

  2. Magnetic Field Effects on Photoelectrochemical Reactions of Porphyrin-Viologen Linked Compounds in an Ionic Liquid

    Science.gov (United States)

    Tahara, Hironobu; Yonemura, Hiroaki; Harada, Satoko; Yamada, Sunao

    2011-08-01

    Magnetic field effects (MFEs) on photoelectrochemical reactions of three porphyrin-viologen linked compounds with various methylene groups [ZnP(n)V (n=4,6,8)] were examined in 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]) as an ionic liquid using a two-electrode cell. Stable anodic photocurrents are produced by irradiating ZnP(n)V (n=4,6,8) in [BMIM][BF4] with visible light, and the MFEs on photocurrents were clearly observed in ZnP(n)V (n=4,6,8). The MFEs on photocurrents increase with magnetic field for lower magnetic fields (B ≤200 mT) and are constant for higher magnetic fields (B > 200 mT). The magnitude of the MFEs in ZnP(n)V (n=6,8) are larger than that in ZnP(4)V. The MFEs can be explained by radical pair mechanism. The magnitude of the MFEs is larger than those in electrodes modified with ZnP(n)V (n=4,6,8) as Langmuir-Blodgett films. The results are most likely attributable to the properties of [BMIM][BF4] and the mechanism of photoelectrochemical reaction.

  3. Prediction model of biocrude yield and nitrogen heterocyclic compounds analysis by hydrothermal liquefaction of microalgae with model compounds.

    Science.gov (United States)

    Sheng, Lili; Wang, Xin; Yang, Xiaoyi

    2018-01-01

    The model of biocrude yield and the nitrogen heterocyclic compounds in biocrude of microalgae hydrothermal liquefaction are two of the most concerned issues in this field at present. This study explored a hydrothermal liquefaction biocrude yield model involved in the interaction among biochemical compounds in microalgae and analysed nitrogen heterocyclic compounds in biocrude. The model compound (castor oil, soya protein and glucose) and Nanochloropsis were liquefied at 280°C for 1h. The products were analyzed by GC-MS, element analysis and FTIR. The results suggested that interactions among different components in microalgae enhanced biocrude yield. The biocrude yield prediction model involved cross-interactions performed more accurate than previous models.When the ratio of protein and carbohydrate around 3, the cross-interaction and nitrogen heterocyclic compounds in biocrude would both reach the highest extent. Copyright © 2017. Published by Elsevier Ltd.

  4. Prompt HO2 formation following the reaction of OH with aromatic compounds under atmospheric conditions.

    Science.gov (United States)

    Nehr, Sascha; Bohn, Birger; Wahner, Andreas

    2012-06-21

    The secondary formation of HO(2) radicals following OH + aromatic hydrocarbon reactions in synthetic air under normal pressure and temperature was investigated in the absence of NO after pulsed production of OH radicals. OH and HO(x) (=OH + HO(2)) decay curves were recorded using laser-induced fluorescence after gas-expansion. The prompt HO(2) yields (HO(2) formed without preceding NO reactions) were determined by comparison to results obtained with CO as a reference compound. This approach was recently introduced and applied to the OH + benzene reaction and was extended here for a number of monocyclic aromatic hydrocarbons. The measured HO(2) formation yields are as follows: toluene, 0.42 ± 0.11; ethylbenzene, 0.53 ± 0.10; o-xylene, 0.41 ± 0.08; m-xylene, 0.27 ± 0.06; p-xylene, 0.40 ± 0.09; 1,2,3-trimethylbenzene, 0.31 ± 0.06; 1,2,4-trimethylbenzene, 0.37 ± 0.09; 1,3,5-trimethylbenzene, 0.29 ± 0.08; hexamethylbenzene, 0.32 ± 0.08; phenol, 0.89 ± 0.29; o-cresol, 0.87 ± 0.29; 2,5-dimethylphenol, 0.72 ± 0.12; 2,4,6-trimethylphenol, 0.45 ± 0.13. For the alkylbenzenes HO(2) is the proposed coproduct of phenols, epoxides, and possibly oxepins formed in secondary reactions with O(2). In most product studies the only quantified coproducts were phenols whereas only a few studies reported yields of epoxides. Oxepins have not been observed so far. Together with the yields of phenols from other studies, the HO(2) yields determined in this work set an upper limit to the combined yields of epoxides and oxepins that was found to be significant (≤0.3) for all investigated alkylbenzenes except m-xylene. For the hydroxybenzenes the currently proposed HO(2) coproducts are dihydroxybenzenes. For phenol and o-cresol the determined HO(2) yields are matching the previously reported dihydroxybenzene yields, indicating that these are the only HO(2) forming reaction channels. For 2,5-dimethylphenol and 2,4,6-trimethylphenol no complementary product studies are available.

  5. Chemical predictive modelling to improve compound quality.

    Science.gov (United States)

    Cumming, John G; Davis, Andrew M; Muresan, Sorel; Haeberlein, Markus; Chen, Hongming

    2013-12-01

    The 'quality' of small-molecule drug candidates, encompassing aspects including their potency, selectivity and ADMET (absorption, distribution, metabolism, excretion and toxicity) characteristics, is a key factor influencing the chances of success in clinical trials. Importantly, such characteristics are under the control of chemists during the identification and optimization of lead compounds. Here, we discuss the application of computational methods, particularly quantitative structure-activity relationships (QSARs), in guiding the selection of higher-quality drug candidates, as well as cultural factors that may have affected their use and impact.

  6. Model Experiment of Thermal Runaway Reactions Using the Aluminum-Hydrochloric Acid Reaction

    Science.gov (United States)

    Kitabayashi, Suguru; Nakano, Masayoshi; Nishikawa, Kazuyuki; Koga, Nobuyoshi

    2016-01-01

    A laboratory exercise for the education of students about thermal runaway reactions based on the reaction between aluminum and hydrochloric acid as a model reaction is proposed. In the introductory part of the exercise, the induction period and subsequent thermal runaway behavior are evaluated via a simple observation of hydrogen gas evolution and…

  7. Computer modeling the boron compound factor in normal brain tissue

    International Nuclear Information System (INIS)

    Gavin, P.R.; Huiskamp, R.; Wheeler, F.J.; Griebenow, M.L.

    1993-01-01

    The macroscopic distribution of borocaptate sodium (Na 2 B 12 H 11 SH or BSH) in normal tissues has been determined and can be accurately predicted from the blood concentration. The compound para-borono-phenylalanine (p-BPA) has also been studied in dogs and normal tissue distribution has been determined. The total physical dose required to reach a biological isoeffect appears to increase directly as the proportion of boron capture dose increases. This effect, together with knowledge of the macrodistribution, led to estimates of the influence of the microdistribution of the BSH compound. This paper reports a computer model that was used to predict the compound factor for BSH and p-BPA and, hence, the equivalent radiation in normal tissues. The compound factor would need to be calculated for other compounds with different distributions. This information is needed to design appropriate normal tissue tolerance studies for different organ systems and/or different boron compounds

  8. Kinetic analysis of polyoxometalate (POM) oxidation of non-phenolic lignin model compound

    Science.gov (United States)

    Tomoya Yokoyama; Hou-min Chang; Ira A. Weinstock; Richard S. Reiner; John F. Kadla

    2003-01-01

    Kinetic and reaction mechanism of non-phenolic lignin model compounds under anaerobic polyoxometalate (POM), Na5(+1.9)[SiV1(-0.1)MoW10(+0.1) 40], bleaching conditions were examined. Analyses using a syringyl type model, 1-(3,4,5-trimethoxyphenyl)ethanol (1), a guaiacyl type, 1-(3,4- imethoxyphenyl)ethanol (2), and 1- (4-ethoxy-3,5-dimethoxyphenyl)ethanol (3) suggest...

  9. Geochemical controls on shale groundwaters: Results of reaction path modeling

    International Nuclear Information System (INIS)

    Von Damm, K.L.; VandenBrook, A.J.

    1989-03-01

    The EQ3NR/EQ6 geochemical modeling code was used to simulate the reaction of several shale mineralogies with different groundwater compositions in order to elucidate changes that may occur in both the groundwater compositions, and rock mineralogies and compositions under conditions which may be encountered in a high-level radioactive waste repository. Shales with primarily illitic or smectitic compositions were the focus of this study. The reactions were run at the ambient temperatures of the groundwaters and to temperatures as high as 250/degree/C, the approximate temperature maximum expected in a repository. All modeling assumed that equilibrium was achieved and treated the rock and water assemblage as a closed system. Graphite was used as a proxy mineral for organic matter in the shales. The results show that the presence of even a very small amount of reducing mineral has a large influence on the redox state of the groundwaters, and that either pyrite or graphite provides essentially the same results, with slight differences in dissolved C, Fe and S concentrations. The thermodynamic data base is inadequate at the present time to fully evaluate the speciation of dissolved carbon, due to the paucity of thermodynamic data for organic compounds. In the illitic cases the groundwaters resulting from interaction at elevated temperatures are acid, while the smectitic cases remain alkaline, although the final equilibrium mineral assemblages are quite similar. 10 refs., 8 figs., 15 tabs

  10. Synthesis, reactions and biological activity of some new bis-heterocyclic ring compounds containing sulphur atom

    Science.gov (United States)

    2013-01-01

    Background The derivatives of thieno[2,3-b]thiophene belong to a significant category of heterocyclic compounds, which have shown a wide spectrum of medical and industrial application. Results A new building block with two electrophilic center of thieno[2,3-b]thiophene derivatives 2 has been reported by one-pot reaction of diketone derivative 1 with Br2/AcOH in excellent yield. A variety of heteroaromatics having bis(1H-imidazo[1,2a] benzimidazole), bis(1H-imidazo[1,2-b][1,2,4]triazole)-3-methyl-4-phenylthieno[2,3-b]thiophene derivatives, dioxazolo-, dithiazolo-, and 1H-imidazolo-3-methyl-4-phenylthieno[2,3-b]thiophene derivatives as well pyrrolo, thiazolo -3-methyl-4-phenylthieno[2,3-b]thiophene derivatives have been designed, synthesized, characterized, and evaluated for their biological activity. Compounds 3–9 showed good bioassay result. These new derivatives were evaluated for anti-cancer activity against PC-3 cell lines, in vitro antioxidant potential and β-glucuronidase and α-glucosidase inhibitory activities. Compound 3 (IC50 = 56.26 ± 3.18 μM) showed a potent DPPH radical scavenging antioxidant activity and found to be more active than standard N-acetylcystein (IC50 = 105.9 ± 1.1 μM). Compounds 8a (IC50 = 13.2 ± 0.34 μM) and 8b (IC50 = 14.1 ± 0.28 μM) found as potent inhibitor of α-glucusidase several fold more active than the standard acarbose (IC50 = 841 ± 1.73 μM). Most promising results were obtained in β-glucuronidase enzyme inhibition assay. Compounds 5 (IC50 = 0.13 ± 0.019 μM), 6 (IC50 = 19.9 ± 0.285 μM), 8a (IC50 = 1.2 ± 0.0785 μM) and 9 (IC50 = 0.003 ± 0.09 μM) showed a potent inhibition of β-glucuronidase. Compound 9 was found to be several hundred fold more active than standard D-Saccharic acid 1,4-lactone (IC50 = 45.75 ± 2.16 μM). Conclusions Synthesis, characterization, and in vitro biological activity of a series of

  11. Thermodynamics of coproportionation reactions of homogeneous samarium (3) and yttrium (3) nitrates solvates with neutral organic phosphorus compounds

    International Nuclear Information System (INIS)

    Pyartman, A.K.

    1995-01-01

    Reaction heats of homogeneous samarium (3) and yttrium (3) nitrate solvates coproportionation with neutral organophosphoric compounds (tri-n.-butylphosphate, diisooctylmethylphosphonate, diisoamylmethylphosphonate) at T=298.15 K in hexane have been measured by thermochemical method. It has been ascertained that enthalpies of coproportionation reactions practically do not depend on the nature, concentration of rare earth metal (3) nitrate solvates in hexane, nature of neutral organophosphoric compound and constitute 1.1±-.2 kJ/mol. The Gibbs free energy of coproportionation reactions is -5.43 kJ/mol, while entropy of the reactions in 14.5±0.7 J/mol·K. 8 refs., 1 tab

  12. Influence of the vehicle on elicitation of contact allergic reactions to acrylic compounds in the guinea pig.

    Science.gov (United States)

    Björkner, B; Niklasson, B

    1984-11-01

    Many factors can influence the elicitation of hypersensitivity reactions in guinea pigs and humans. The effect which the vehicle might have on the test response in guinea pigs sensitized with various acrylic compounds, using the "guinea pig maximization test", has been investigated. A marked decrease in the number of positive animals was seen when acetone was used as test vehicle, compared to petrolatum. The same result was seen with alcohol as vehicle, when neopentyl glycol diacrylate (NPGDA) was used as an acrylic monomer model. The patch test locations on the guinea pig flank, also affected the test response. Half of the animals did not react when challenged near the abdomen, compared to a test site near the back. By means of HPLC-analysis, the possible adsorption of the acrylic monomer to the aluminium chamber or filter paper disc, was analysed. Our findings did not indicate that adsorption occurs. A decrease in the amount of acrylic monomer in the chamber with increasing time, was noted. There was a marked difference in the monomer residue between solutions with (darkness) and without (daylight) inhibitor. The monomer decrease was also more affected by an aluminium surface than a glass or filter paper surface. Aluminium oxide probably enhances the polymerization process. The discrepancy between the test results in this study, when petrolatum and acetone were used as test vehicles, is due to a polymerization process of the acrylic compounds. Thus, the petrolatum vehicle probably prevents polymerization of the acrylic monomer.

  13. ELECTRICAL RESISTIVITY AND SEEBECK COEFFICIENT IN Ca(LaMnO COMPOUNDS PREPARED BY SOLID STATE REACTION METHOD

    Directory of Open Access Journals (Sweden)

    Jorge I. Villa

    2017-01-01

    Full Text Available By using the solid state reaction method samples of  Ca1-xLaxMnO3 (0 ≤ x ≥ 0.15 were prepared. Their transport properties were studied by electrical resistivity rho(T and Seebeck coefficient S(T measurements as a function of temperature and lanthanum content, in the temperature range between 100 and 290K. The structural and morphological properties were studied by X-ray diffraction analysis (XRD and scanning electron microscopy (SEM, respectively. The Seebeck coefficient is negative throughout the studied temperature range indicating a conduction given by negative charge carriers, its magnitude decreases with the lanthanum content from |-261| mV/K to |-120| mV/K. The electrical resistivity shows a semiconducting behavior, it was interpreted in terms of small polaron hopping model. Thermoelectric properties of the obtained compounds were studied by the thermoelectric power factor PF, which reaches maximum values around 2mW/K2cm, these values become this kind of ceramics promising thermoelectric compound, to be used in technological applications.

  14. Kinetic modelling of the Maillard reaction between proteins and sugars

    NARCIS (Netherlands)

    Brands, C.M.J.

    2002-01-01

    Keywords: Maillard reaction, sugar isomerisation, kinetics, multiresponse modelling, brown colour formation, lysine damage, mutagenicity, casein, monosaccharides, disaccharides, aldoses, ketoses

    The aim of this thesis was to determine the kinetics of the Maillard reaction between

  15. Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

    Directory of Open Access Journals (Sweden)

    Burkhard Koenig

    2011-01-01

    Full Text Available N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald–Hartwig-type reactions, copper-mediated Ullmann-type and Chan–Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan–Lam reactions. Chan–Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald–Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C–N bond formation in the course of a total synthesis or drug synthesis.

  16. Ionic compounds lamination reaction and characteristics of photosensitive copper indium sulfide on titania nanotube arrays

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Horng-Yi, E-mail: hychang@mail.ntou.edu.tw [Department of Marine Engineering, National Taiwan Ocean University, Keelung 20224, Taiwan (China); Tzeng, Wei-Jei [Department of Marine Engineering, National Taiwan Ocean University, Keelung 20224, Taiwan (China); Lin, Chia-Hsin; Cheng, Syh-Yuh [Ceramic Microengineering Laboratory, Material and Chemical Research Laboratories, Industrial Technology Research Institute, Chutung 31060, Taiwan (China)

    2011-09-01

    Graphical abstract: Highlights: > Only good photocurrent density under UV irradiation for TiO{sub 2} (or TiCl{sub 4}) modified titania nanotubes (T-TNAs) demonstrates the response to visible light actually due to the CuInS{sub 2} photosensitivity on T-TNAs. > The suitable CuInS{sub 2} (CIS) film thickness can be completed to achieve the well crystallinity, coverage and high photosensitivity of CIS by combining the precursor concentration with deposition cycles. > An n-type CIS with a lower band gap (<1.5 eV) extending the absorption of the large solar spectrum into the infra-red range demonstrates the inorganic CIS potentially instead of organic dye to use in photosensitive solar cells by simple ionic compounds lamination reaction (ICLR) process. - Abstract: This study investigates using an inorganic photosensitive CuInS{sub 2} (CIS) coating instead of an organic dye on TiO{sub 2} nanotube arrays (TNAs). The stoichiometric characteristics by use of various deposition parameters such as precursor concentrations (0.1 M, 0.05 M, and 0.01 M) and deposition cycles (1-60 cycles) are then analyzed in relation to the crystallinity and photosensitivity. TNAs are synthesized by anodic oxidation of Ti metal, modified by the TiO{sub 2} film, and are subsequently annealed at 450 deg. C for 30 min, producing what are named T-TNAs. They show high photocatalytic efficiency and photosensitivity under UV-illumination. The photosensitive CIS coatings on the T-TNAs are processed by an ionic compounds lamination reaction (ICLR) method. The more immersion cycles and the higher the precursor concentration of copper sulfide, the more CIS peeled off as precipitates formed, which result in less indium sulfide deposition being required for reacting with the copper sulfide to reach stoichiometry. Near stoichiometric CIS can be obtained by controlling the precursor concentration and deposition cycles of the ICLR process. Good crystallinity and n-type characteristics are achieved by controlling

  17. Feshbach-Kerman-Koonin analysis of 93Nb reactions: P→Q transitions and reduced importance of multistep compound emission

    International Nuclear Information System (INIS)

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

    1993-01-01

    We have implemented multistep compound (MSC) and multistep direct (MSD) preequilibrium theories of Feshbach, Kerman, and Koonin (FKK) for the calculation of nucleon-induced reactions. Unlike most previous analyses, which have concentrated on just one of these multistep mechanisms, we consider both mechanisms as well as subsequent Hauser-Feshbach equilibrium emission, and describe the complete nucleon emission spectra and angular distributions quantum mechanically. We compare theoretical calculations of (n,n') and (n,p) reactions on 93 Nb at energies of 14, 20, and 25.7 MeV with experimental data. Our analysis suggests that the FKK theory should be modified to allow transitions from the MSD to MSC preequilibrium chains, and shows MSC processes to be less important than previously thought. We find that the MSD mechanism dominates preequilibrium emission even for incident neutron energies as low as 14 MeV. A model to account for preequilibrium flux cascading from the MSD to MSC chain is presented, and we check its validity with a least-squares fit to data which establishes the experimentally observed partitioning between MSD and MSC

  18. Effects of iron type in Fenton reaction on mineralization and biodegradability enhancement of hazardous organic compounds.

    Science.gov (United States)

    Khan, Eakalak; Wirojanagud, Wanpen; Sermsai, Nawarat

    2009-01-30

    The mineralization and biodegradability increase and their combination of two traditional and two relatively new organic contaminants by Fenton reagents with three different types of iron, Fe(2+), Fe(3+), and Fe(0) were investigated. The traditional contaminants examined were trichloroethene (TCE) and 2,4-dichlorophenol (2,4-DCP) while 1,4-dioxane (1,4-D) and 1,2,3-trichloropropane (TCP) were studied for the relatively new contaminants. The mineralization and biodegradability were represented by dissolved organic carbon (DOC) reduction and the ratio of biodegradable dissolved organic carbon and DOC, respectively. For all four contaminants, Fenton reagent using Fe(2+) was more effective in the DOC reduction than Fenton reagents using Fe(3+) and Fe(0) in most cases. The types of Fe that provided maximum biodegradability increase were not the same for all four compounds, Fe(3+) for TCE, Fe(0) for 2,4-DCP, Fe(2+) for 1,4-D, and Fe(3+) for TCP. When the combination of DOC elimination and biodegradability increase (least refractory fraction) was considered, Fe(2+) was the best choice except for 2,4-DCP which was susceptible to Fe(0) catalyzed Fenton reagent the most. The least refractory fractions remaining after 120 min of reaction were 20-25% for TCE, 2,4-DCP, and TCP and 30-40% for 1,4-D. The iron type in Fenton reaction also affected the type of mineralization kinetics of TCE, 2,4-DCP, and TCP as well as the types of degradation by-products of these contaminants. Some of the by-products found, such as isopropanol and propionic aldehyde, which were produced from Fe(0) catalyzed Fenton degradation of TCP, have not been previously reported.

  19. A kinetic reaction model for biomass pyrolysis processes in Aspen Plus

    International Nuclear Information System (INIS)

    Peters, Jens F.; Banks, Scott W.; Bridgwater, Anthony V.; Dufour, Javier

    2017-01-01

    Highlights: • Predictive kinetic reaction model applicable to any lignocellulosic feedstock. • Calculates pyrolysis yields and product composition as function of reactor conditions. • Detailed modelling of product composition (33 model compounds for the bio-oil). • Good agreement with literature regarding yield curves and product composition. • Successful validation with pyrolysis experiments in bench scale fast pyrolysis rig. - Abstract: This paper presents a novel kinetic reaction model for biomass pyrolysis processes. The model is based on the three main building blocks of lignocellulosic biomass, cellulose, hemicellulose and lignin and can be readily implemented in Aspen Plus and easily adapted to other process simulation software packages. It uses a set of 149 individual reactions that represent the volatilization, decomposition and recomposition processes of biomass pyrolysis. A linear regression algorithm accounts for the secondary pyrolysis reactions, thus allowing the calculation of slow and intermediate pyrolysis reactions. The bio-oil is modelled with a high level of detail, using up to 33 model compounds, which allows for a comprehensive estimation of the properties of the bio-oil and the prediction of further upgrading reactions. After showing good agreement with existing literature data, our own pyrolysis experiments are reported for validating the reaction model. A beech wood feedstock is subjected to pyrolysis under well-defined conditions at different temperatures and the product yields and compositions are determined. Reproducing the experimental pyrolysis runs with the simulation model, a high coincidence is found for the obtained fraction yields (bio-oil, char and gas), for the water content and for the elemental composition of the pyrolysis products. The kinetic reaction model is found to be suited for predicting pyrolysis yields and product composition for any lignocellulosic biomass feedstock under typical pyrolysis conditions

  20. The GRAPE code system for the calculation of precompound and compound nuclear reactions

    International Nuclear Information System (INIS)

    Gruppelaar, H.; Akkermans, J.M.

    1985-02-01

    The statistical exciton model following the master-equation approach has been improved and extended for application as an evaluation tool of double-differential reaction cross sections at incident nucleon energies of 5 to 50 MeV. For this purpose the code system GRAPE has been developed. An important characteristic of the proposed model is that consistency with equilibrium models has been demanded for the summed exciton-state densities as well as for the particle and γ-ray emission cross sections. Consistency with the adopted state densities has also been imposed upon the internal transition rates. A survey of the theory is given and the structure of the GRYPHON code is described. This report also contains a users' manual for GRYPHON

  1. Intramolecular Diels–Alder reaction as a key step in tandem or sequential processes: a versatile tool for the synthesis of fused and bridged bicyclic or polycyclic compounds.

    Digital Repository Service at National Institute of Oceanography (India)

    Parvatkar, P.T.; Kadam, H.K.; Tilve, S.G.

    This review summarizes the recent examples of tandem or sequential reactions used for the last 10 years for the synthesis of fused and bridged bicyclic or polycyclic compounds with IMDA cycloaddition as the key means to access these compounds...

  2. Radiolytic oxidation of propane: Computer modeling of the reaction scheme

    Science.gov (United States)

    Gupta, Avinash K.; Hanrahan, Robert J.

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25°C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. Minor products include i-butyl alcohol, t-amyl alcohol, n-butyl alcohol, n-amyl alcohol, and i-amyl alcohol. Small yields of i-hexyl alcohol and n-hexyl alcohol were also observed. There was no apparent difference in the G-values at pressures of 50, 100 and 150 torr. When the oxygen concentration was decreased below 5%, the yields of acetone, i-propyl alcohol, and n-propyl alcohol increased, the propionaldehyde yield decreased, and the yields of other products remained constant. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases.

  3. Kinetics of isotope exchange reactions involving intra- and intermolecular reactions: 1. Rate law for a system with two chemical compounds and three exchangeable atoms

    International Nuclear Information System (INIS)

    Xuelei Chu; Ohmoto, Hiroshi

    1991-01-01

    For an isotopic exchange reaction between two compounds (X and AB) in a homogeneous system, such as a gaseous or aqueous system, where one (AB) of them possesses two exchangeable atoms in non-equivalent positions and where one intramolecular isotope exchange (A ↔ B) and two intermolecular isotope exchange reactions (X ↔ A and X ↔ B) may occur, its rate law no longer obeys a pseudo-first order rate equation described for simple two-component systems by many previous investigators. The change with time of the δ value of each of the three components (X, A, and B) in a closed and homogeneous system is a complicated function of the initial δ values of the three components, the chemical concentrations of the two compounds, and the overall rate constants of the forward and reverse reactions involving the two intermolecular and one intramolecular reactions of isotope exchanges. Also, for some one of the three components, the change of its δ value with time may not be monotonic, and the relationship of 1n (1 - F) with time may be non-linear in a plot of 1n (1 - F) vs. t. In addition, the rate law of the isotope exchange reaction in this system also provides a quantitative method to estimate the overall rate constants for the one-intra-and two intermolecular isotope exchanges and the equilibrium isotopic fractionation factors among the three components

  4. Diazo compounds and N-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions.

    Science.gov (United States)

    Xiao, Qing; Zhang, Yan; Wang, Jianbo

    2013-02-19

    Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, with essentially no overlap or integration. Thus, an intriguing question has emerged: can cross-coupling and metal carbene transformations be merged into a single reaction cycle? Such a combination could facilitate the development of novel carbon-carbon bond-forming methodologies. Although this concept was first explored about 10 years ago, rapid developments inthis area have been achieved recently. Palladium catalysts can be used to couple diazo compounds with a wide variety of organic halides. Under oxidative coupling conditions, diazo compounds can also react with arylboronic acids and terminal alkynes. Both of these coupling reactions form carbon-carbon double bonds. As the key step in these catalytic processes, Pd carbene migratory insertion plays a vital role in merging the elementary steps of Pd intermediates, leading to novel carbon-carbon bond formations. Because the diazo substrates can be generated in situ from N-tosylhydrazones in the presence of base, the N-tosylhydrazones can be used as reaction partners, making this type of cross-coupling reaction practical in organic synthesis. N-Tosylhydrazones are easily derived from the corresponding aldehydes or ketones. The Pd-catalyzed cross-coupling of N-tosylhydrazones is considered a complementary reaction to the classic Shapiro reaction for converting carbonyl functionalities into carbon-carbon double bonds. It can also serve as an alternative approach for the Pd-catalyzed cross-coupling of carbonyl compounds, which is usually achieved via triflates. The combination of carbene formation and cross-coupling in a single catalytic cycle is not limited to Pd-catalyzed reactions. Recent studies of Cu-, Rh-, Ni-, and Co-catalyzed cross-coupling reactions with diazo

  5. Reactions of homolytic addition of polyhalogenoalkanes to unsafurated tin-organic compounds and their application in organic synthesis

    International Nuclear Information System (INIS)

    Rakhlin, V.I.; Mirskov, R.G.; Voronkov, M.G.

    1996-01-01

    Reactions of homolytic addition of polyhalogenoalkanes; including iodine compounds, to tin trialkylalkenyl derivatives are considered. They may be used as convenient method for synthesis of various polyhalogenoalkylsubstituted alicycles and heterocycles: cyclopropane, 1.3-dioxocycloalkanes, thiacycloalkanes, various nitrogen-containing heterocycles. 27 refs

  6. Proton transfer reaction-mass spectrometry volatile organic compound fingerprinting for monovarietal extra virgin olive oil identification

    NARCIS (Netherlands)

    Ruiz-Samblas, C.; Tres, A.; Koot, A.H.; Ruth, van S.M.; Gonzalez-Casado, A.; Cuadros-Rodriguez, L.

    2012-01-01

    Proton transfer reaction-mass spectrometry (PTR-MS) is a relatively new technique that allows the fast and accurate qualification of the volatile organic compound (VOC) fingerprint. This paper describes the analysis of thirty samples of extra virgin olive oil, of five different varieties of olive

  7. Bond cleavage reactions of the bridge structure in coal in the presence of hydrogen donating compounds; Suiso kyoyosei kagobutsu sonzaika deno sekitanchu no kakyo kozo no kairetsu hanno

    Energy Technology Data Exchange (ETDEWEB)

    Bando, N.; Kidena, K.; Murata, S.; Nomura, M. [Osaka University, Osaka (Japan). Faculty of Engineering

    1996-10-28

    In this paper, bond cleavage reactions are discussed in relation to the softening and solubilization of coal. Were used 9,10-dihydroanthracene (DHA) and 9,10-dihydrophenanthrene (DHP) as models of hydrogen donating compounds in coal, and bibenzyl, 1,2-diethane, benzylphenylether, and 1,5-dibenzylnaphthalene were used as models of bridge structure compounds. They were compared mutually, as to reactivity of coal against DHA and DHP. For the homolytic cleavage of bridges, DHA with excellent radical supplement performance provided excellent hydrogen donating performance. While, for the ipso-position cleavage of bridges, it was found that DHP can act as an effective hydrogen donor. For the reaction between coal and hydrogenated aromatic compounds, cleavage of relatively weak bonds, such as ether linkage and dimethylene linkage, occurred at about 380{degree}C, and hydrogen from DHA or DHP was consumed. On the other hand, the results suggested that the cleavage reaction at ipso-position affected by hydrogen donating solvent is also important at temperature range around 420{degree}C. 2 refs., 3 figs., 1 tab.

  8. The catalytic ozonization of model lignin compounds in the presence of Fe(III) ions

    Science.gov (United States)

    Ben'ko, E. M.; Mukovnya, A. V.; Lunin, V. V.

    2007-05-01

    The ozonization of several model lignin compounds (guaiacol, 2,6-dimethoxyphenol, phenol, and vanillin) was studied in acid media in the presence of iron(III) ions. It was found that Fe3+ did not influence the initial rate of the reactions between model phenols and ozone but accelerated the oxidation of intermediate ozonolysis products. The metal concentration dependences of the total ozone consumption and effective rate constants of catalytic reaction stages were determined. Data on reactions in the presence of oxalic acid as a competing chelate ligand showed that complex formation with Fe3+ was the principal factor that accelerated the ozonolysis of model phenols at the stage of the oxidation of carboxylic dibasic acids and C2 aldehydes formed as intermediate products.

  9. The formation of light absorbing insoluble organic compounds from the reaction of biomass burning precursors and Fe(III)

    Science.gov (United States)

    Lavi, Avi; Lin, Peng; Bhaduri, Bhaskar; Laskin, Alexander; Rudich, Yinon

    2017-04-01

    Dust particles and volatile organic compounds from fuel or biomass burning are two major components that affect air quality in urban polluted areas. We characterized the products from the reaction of soluble Fe(III), a reactive transition metal originating from dust particles dissolution processes, with phenolic compounds , namely, guaiacol, syringol, catechol, o- and p- cresol that are known products of incomplete fuel and biomass combustion but also from other natural sources such as humic compounds degradation. We found that under acidic conditions comparable to those expected on a dust particle surface, phenolic compounds readily react with dissolved Fe(III), leading to the formation of insoluble polymeric compounds. We characterized the insoluble products by x-ray photoelectron microscopy, UV-Vis spectroscopy, mass spectrometry, elemental analysis and thermo-gravimetric analysis. We found that the major chromophores formed are oligomers (from dimers to pentamers) of the reaction precursors that efficiently absorb light between 300nm and 500nm. High variability of the mass absorption coefficient of the reaction products was observed with catechol and guaiacol showing high absorption at the 300-500nm range that is comparable to that of brown carbon (BrC) from biomass burning studies. The studied reaction is a potential source for the in-situ production of secondary BrC material under dark conditions. Our results suggest a reaction path for the formation of bio-available iron in coastal polluted areas where dust particles mix with biomass burning pollution plumes. Such mixing can occur, for instance in the coast of West Africa or North Africa during dust and biomass burning seasons

  10. Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

    Science.gov (United States)

    Mu, Wei; Ben, Haoxi; Du, Xiaotang; Zhang, Xiaodan; Hu, Fan; Liu, Wei; Ragauskas, Arthur J; Deng, Yulin

    2014-12-01

    Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Semi classical model of the neutron resonance compound nucleus

    International Nuclear Information System (INIS)

    Ohkubo, Makio

    1995-01-01

    A Semi-classical model of compound nucleus is developed, where time evolution and recurrence for many degrees of freedom (oscillators) excited simultaneously are explicitly considered. The effective number of oscillators plays the role in the compound nucleus, and the nuclear temperatures are derived, which are in good agreement with the traditional values. Time structures of the compound nucleus at resonance are considered, from which equidistant level series with an envelope of strength function of giant resonance nature is obtained. S-matrix formulation for fine structure resonance is derived. (author)

  12. Statistical molecular design of balanced compound libraries for QSAR modeling.

    Science.gov (United States)

    Linusson, A; Elofsson, M; Andersson, I E; Dahlgren, M K

    2010-01-01

    A fundamental step in preclinical drug development is the computation of quantitative structure-activity relationship (QSAR) models, i.e. models that link chemical features of compounds with activities towards a target macromolecule associated with the initiation or progression of a disease. QSAR models are computed by combining information on the physicochemical and structural features of a library of congeneric compounds, typically assembled from two or more building blocks, and biological data from one or more in vitro assays. Since the models provide information on features affecting the compounds' biological activity they can be used as guides for further optimization. However, in order for a QSAR model to be relevant to the targeted disease, and drug development in general, the compound library used must contain molecules with balanced variation of the features spanning the chemical space believed to be important for interaction with the biological target. In addition, the assays used must be robust and deliver high quality data that are directly related to the function of the biological target and the associated disease state. In this review, we discuss and exemplify the concept of statistical molecular design (SMD) in the selection of building blocks and final synthetic targets (i.e. compounds to synthesize) to generate information-rich, balanced libraries for biological testing and computation of QSAR models.

  13. Modelling Chemical Reasoning to Predict and Invent Reactions.

    Science.gov (United States)

    Segler, Marwin H S; Waller, Mark P

    2017-05-02

    The ability to reason beyond established knowledge allows organic chemists to solve synthetic problems and invent novel transformations. Herein, we propose a model that mimics chemical reasoning, and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180 000 randomly selected binary reactions. The data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-)discovering novel transformations (even including transition metal-catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph and because each single reaction prediction is typically achieved in a sub-second time frame, the model can be used as a high-throughput generator of reaction hypotheses for reaction discovery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Including lateral interactions into microkinetic models of catalytic reactions

    DEFF Research Database (Denmark)

    Hellman, Anders; Honkala, Johanna Karoliina

    2007-01-01

    In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

  15. Behavior of asphaltene model compounds at w/o interfaces.

    Science.gov (United States)

    Nordgård, Erland L; Sørland, Geir; Sjöblom, Johan

    2010-02-16

    Asphaltenes, present in significant amounts in heavy crude oil, contains subfractions capable of stabilizing water-in-oil emulsions. Still, the composition of these subfractions is not known in detail, and the actual mechanism behind emulsion stability is dependent on perceived interfacial concentrations and compositions. This study aims at utilizing polyaromatic surfactants which contains an acidic moiety as model compounds for the surface-active subfraction of asphaltenes. A modified pulse-field gradient (PFG) NMR method has been used to study droplet sizes and stability of emulsions prepared with asphaltene model compounds. The method has been compared to the standard microscopy droplet counting method. Arithmetic and volumetric mean droplet sizes as a function of surfactant concentration and water content clearly showed that the interfacial area was dependent on the available surfactant at the emulsion interface. Adsorption of the model compounds onto hydrophilic silica has been investigated by UV depletion, and minor differences in the chemical structure of the model compounds caused significant differences in the affinity toward this highly polar surface. The cross-sectional areas obtained have been compared to areas from the surface-to-volume ratio found by NMR and gave similar results for one of the two model compounds. The mean molecular area for this compound suggested a tilted geometry of the aromatic core with respect to the interface, which has also been proposed for real asphaltenic samples. The film behavior was further investigated using a liquid-liquid Langmuir trough supporting the ability to form stable interfacial films. This study supports that acidic, or strong hydrogen-bonding fractions, can promote stable water-in-oil emulsion. The use of model compounds opens up for studying emulsion behavior and demulsifier efficiency based on true interfacial concentrations rather than perceived interfaces.

  16. Fruit tree model for uptake of organic compounds from soil

    DEFF Research Database (Denmark)

    Trapp, Stefan; Rasmussen, D.; Samsoe-Petersen, L.

    2003-01-01

    -state, and an example calculation is given. The Fruit Tree Model is compared to the empirical equation of Travis and Arms (T&A), and to results from fruits, collected in contaminated areas. For polar compounds, both T&A and the Fruit Tree Model predict bioconcentration factors fruit to soil (BCF, wet weight based......) of > 1. No empirical data are available to support this prediction. For very lipophilic compounds (log K-OW > 5), T&A overestimates the uptake. The conclusion from the Fruit Tree Model is that the transfer of lipophilic compounds into fruits is not relevant. This was also found by an empirical study...... with PCDD/F. According to the Fruit Tree Model, polar chemicals are transferred efficiently into fruits, but empirical data to verify these predictions are lacking....

  17. Reaction network modelling for kinetic parameters of pyrolytic reactions of CHON extractants in nuclear fuel processing waste management. Contributed Paper IT-07

    International Nuclear Information System (INIS)

    Gaikar, Vilas G.; Thaore, Vaishali

    2014-01-01

    The recovery and purification of plutonium (Pu) from uranium (U) and of U from Thorium (Th) in spent nuclear fuel reprocessing is accomplished by processes that employ organophosphorous compounds as extractants.The main objective of the present work was to develop a suitable kinetic model and to determine the kinetic parameters of the set of reactions involved in the pyrolysis of amides by fitting the experimental data in the reaction network model. The experimental data and analysis are expected to be useful in the steam pyrolysis of amide waste in fuel reprocessing in the nuclear industry. The basic approach was to understand the reaction mechanism of the steam pyrolysis of amides and then to estimate the reaction rate constants for the generation and consumption of different species by solving the model equations, allowing for the determination of important species in the reaction network

  18. Study of the angular momentum distribution of compound nuclei obtained from fusion reactions close to the Coulomb barrier

    International Nuclear Information System (INIS)

    Romain, P.

    1990-03-01

    The effect of the mass asymmetry of the input channel on the compound nuclei spin distribution. The 16 O + 144 Nd and 80 Se + 80 Se reactions produce the same 160 Er compound nucleus in the 38 to 68 MeV energy range. In certain cases, the incident energies required to form the compound nucleus, at the same excitation energies, are very close to the Coulomb barrier. In the experimental device, the 'Chateau de Cristal' multidetector and additional sensors are used. The angular momentum distribution of the different evaporation products are measured by gamma spectrometry techniques. The fusion cross sections are measured by the time-of-flight technique. Theoretical predictions and experimental results concerning the distribution of the compound nucleus angular momentum are compared [fr

  19. Irradiation effects on polymer-model compounds

    International Nuclear Information System (INIS)

    Seguchi, Tadao; Hayakawa, Naohiro; Tamura, Naoyuki; Katsumura, Yosuke; Hayashi, Nariyuki; Tabata, Yoneho

    1991-01-01

    Irradiation effects on n-paraffins and squalane, used as models of polymers, were investigated by product analysis. Four n-paraffins, C 20 H 42 , C 21 H 44 , C 23 H 48 and C 24 H 50 , and squalane (C 30 H 62 ) were γ-irradiated under vacuum in liquid, crystalline and glassy states. The evolved gases were analyzed by gas chromatography and changes in molecular weight were analyzed by liquid chromatography and mass spectroscopy. G-values for crosslinking of n-paraffins were 1.2 for crystalline states (at 25 0 C) and 1.7 for liquid states (at 55 0 C), and showed no difference between odd and even carbon numbers. The G-value of liquid squalane was 1.7; it was 1.3 for the glassy state at low temperature (-77 0 C). Double bonds were common in the crosslinked products, especially after liquid-phase irradiation. The probability of chain scission was estimated as being negligible, though a small number of chain-scission products (which were products of scission at chain-ends or side chains) were observed by gas analysis. (author)

  20. Mathematical modeling of the mixing zone for getting bimetallic compound

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Stanislav L. [Institute of Applied Mechanics, Ural Branch, Izhevsk (Russian Federation)

    2011-07-01

    A mathematical model of the formation of atomic bonds in metals and alloys, based on the electrostatic interaction between the outer electron shells of atoms of chemical elements. Key words: mathematical model, the interatomic bonds, the electron shell of atoms, the potential, the electron density, bimetallic compound.

  1. Effects of reaction-kinetic parameters on modeling reaction pathways in GaN MOVPE growth

    Science.gov (United States)

    Zhang, Hong; Zuo, Ran; Zhang, Guoyi

    2017-11-01

    In the modeling of the reaction-transport process in GaN MOVPE growth, the selections of kinetic parameters (activation energy Ea and pre-exponential factor A) for gas reactions are quite uncertain, which cause uncertainties in both gas reaction path and growth rate. In this study, numerical modeling of the reaction-transport process for GaN MOVPE growth in a vertical rotating disk reactor is conducted with varying kinetic parameters for main reaction paths. By comparisons of the molar concentrations of major Ga-containing species and the growth rates, the effects of kinetic parameters on gas reaction paths are determined. The results show that, depending on the values of the kinetic parameters, the gas reaction path may be dominated either by adduct/amide formation path, or by TMG pyrolysis path, or by both. Although the reaction path varies with different kinetic parameters, the predicted growth rates change only slightly because the total transport rate of Ga-containing species to the substrate changes slightly with reaction paths. This explains why previous authors using different chemical models predicted growth rates close to the experiment values. By varying the pre-exponential factor for the amide trimerization, it is found that the more trimers are formed, the lower the growth rates are than the experimental value, which indicates that trimers are poor growth precursors, because of thermal diffusion effect caused by high temperature gradient. The effective order for the contribution of major species to growth rate is found as: pyrolysis species > amides > trimers. The study also shows that radical reactions have little effect on gas reaction path because of the generation and depletion of H radicals in the chain reactions when NH2 is considered as the end species.

  2. Photosynthetic pigments and model compounds studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Jensen, N.-H.

    1980-05-01

    The photosynthetic pigments chlorophyll a and alltrans-β-carotene as well as the quinone model compound duroquinone have been studied in solution by pulse radiolysis combined with time-resolved absorption and resonance Raman spectroscopy. In benzene solution the excited triplet states of the subtrates were produced either directly in the case of duroquinone or by triplet energy transfer from triplet naphthalene in the case of chlorophyll a and β-carotene. All relevant rate constants involved in the reactions of the excited states in benzene were determined, including i) the rate constants for energy transfer from triplet naphthalene to chlorophyll a with k = (3.6+-0.6).10 9 M -1 s -1 and β-carotene with k = (10.7+-1.2).10 9 M -1 s -1 ii) the rate constants of triplet annihilation of chlorophyll a: (1.4+-0.3).10 9 M -1 s -1 , β-carotene: (3.6+-0.4).10 9 M -1 s -1 , duroquinone: (3.0+-0.6).10 9 M -1 s -1 . For β-carotene it is suggested that triplet-triplet annihilation produces the optically forbidden excited 1 Asub(g) state. The first-order components of the triplet decays were strongly dependent upon irradiation dose in the case of naphthalene and duroquinone but apparently only slightly dependent on or independent or irradiation dose in the case of chlorophyll a and β-carotene. Apparent bimolecular rate constants for triplet quenching by radiolytically produced free radicals are determined. The triplet state of duroquinone is quenched by ground state duroquinone with a rate constant of (1.2+-0.3).10 6 M -1 s -1 . The excited triplet state of all-trans-β-carotene has been investigated by time-resolved resonance Raman spectroscopy. Six transient Raman bands at 965 cm -1 , 1009 cm -1 , 1125 cm -1 , 1188 cm -1 , 1236 cm -1 and 1496 cm -1 were observed. The spectra suggest that the C = C band order is decreased and that the molecule may be substantially twisted, presumably at the 15,15 1 band, in the triplet state. The radical anion of chlorophyll a with

  3. Theoretical intercomparison of multi-step direct reaction models and computational intercomparison of multi-step direct reaction models

    International Nuclear Information System (INIS)

    Koning, A.J.

    1992-08-01

    In recent years several statistical theories have been developed concerning multistep direct (MSD) nuclear reactions. In addition, dominant in applications is a whole class of semiclassical models that may be subsumed under the heading of 'generalized exciton models'. These are basically MSD-type extensions on top of compound-like concepts. In this report the relationship between their underlying statistical MSD-postulates is highlighted. A command framework is outlined that enables to generate the various MSD theories through assigning statistical properties to different parts of the nuclear Hamiltonian. Then it is shown that distinct forms of nuclear randomness are embodied in the mentioned theories. All these theories appear to be very similar at a qualitative level. In order to explain the high energy-tails and forward-peaked angular distribution typical for particles emitted in MSD reactions, it is imagined that the incident continuum particle stepwise looses its energy and direction in a sequence of collisions, thereby creating new particle-hole pairs in the target system. At each step emission may take place. The statistical aspect comes in because many continuum states are involved in the process. These are supposed to display chaotic behavior, the associated randomness assumption giving rise to important simplifications in the expression for MSD emission cross sections. This picture suggests that mentioned MSD models can be interpreted as a variant of essentially one and the same theory. However, this appears not to be the case. To show this usual MSD distinction within the composite reacting nucleus between the fast continuum particle and the residual interactions, the nucleons of the residual core are to be distinguished from those of the leading particle with the residual system. This distinction will turn out to be crucial to present analysis. 27 refs.; 5 figs.; 1 tab

  4. Modelling human behaviours and reactions under dangerous environment

    OpenAIRE

    Kang, J; Wright, D K; Qin, S F; Zhao, Y

    2005-01-01

    This paper describes the framework of a real-time simulation system to model human behavior and reactions in dangerous environments. The system utilizes the latest 3D computer animation techniques, combined with artificial intelligence, robotics and psychology, to model human behavior, reactions and decision making under expected/unexpected dangers in real-time in virtual environments. The development of the system includes: classification on the conscious/subconscious behaviors and reactions...

  5. Nuclear structure effects in fusion-fission of compound systems 20,21,22Ne formed in 10,11B+10,11B reactions

    International Nuclear Information System (INIS)

    Singh, BirBikram; Kaur, Manpreet; Kaur, Varinderjit; Gupta, Raj K.

    2014-01-01

    The dynamical cluster-decay model (DCM) of Gupta and collaborators has been successfully applied to the decay of number of hot and rotating compound nuclei in different mass regions, formed in low-energy heavy ion reactions. Recently, its application to the binary symmetric decay (BSD) of very light mass compound systems 20,21,22 Ne formed in 10,11 B+ 10,11 B reactions at E lab =48 MeV is extended, as the experimental data for σ BSD Expt . is available, namely, for 20 Ne (∼ 270 mb), 21 Ne ( 22 Ne ( BSD DCM for the BSD of the three Ne systems is calculated, comprising fusion-fission σ ff and deep inelastic scattering/orbiting σorb contributions (evaluated empirically here) from compound nucleus CN and non-compound nucleus nCN processes, respectively. The significant observation from this study is that, of the total σ BSD DCM , σ ff contribution is very strong for the decay of 20 Ne (=195.270 mb; >70%), followed by 21 Ne (=65.723 mb; ∼50%) and 22 Ne (=8.677 mb; almost 10%). This means that the process of collective clusterization within the DCM is playing very strong role for the decay of 20 Ne

  6. Reaction of bromine and chlorine with phenolic compounds and natural organic matter extracts--Electrophilic aromatic substitution and oxidation.

    Science.gov (United States)

    Criquet, Justine; Rodriguez, Eva M; Allard, Sebastien; Wellauer, Sven; Salhi, Elisabeth; Joll, Cynthia A; von Gunten, Urs

    2015-11-15

    Phenolic compounds are known structural moieties of natural organic matter (NOM), and their reactivity is a key parameter for understanding the reactivity of NOM and the disinfection by-product formation during oxidative water treatment. In this study, species-specific and/or apparent second order rate constants and mechanisms for the reactions of bromine and chlorine have been determined for various phenolic compounds (phenol, resorcinol, catechol, hydroquinone, phloroglucinol, bisphenol A, p-hydroxybenzoic acid, gallic acid, hesperetin and tannic acid) and flavone. The reactivity of bromine with phenolic compounds is very high, with apparent second order rate constants at pH 7 in the range of 10(4) to 10(7) M(-1) s(-1). The highest value was recorded for the reaction between HOBr and the fully deprotonated resorcinol (k = 2.1 × 10(9) M(-1) s(-1)). The reactivity of phenolic compounds is enhanced by the activating character of the phenolic substituents, e.g. further hydroxyl groups. With the data set from this study, the ratio between the species-specific rate constants for the reactions of chlorine versus bromine with phenolic compounds was confirmed to be about 3000. Phenolic compounds react with bromine or chlorine either by oxidation (electron transfer, ET) or electrophilic aromatic substitution (EAS) processes. The dominant process mainly depends on the relative position of the hydroxyl substituents and the possibility of quinone formation. While phenol, p-hydroxybenzoic acid and bisphenol A undergo EAS, hydroquinone, catechol, gallic acid and tannic acid, with hydroxyl substituents in ortho or para positions, react with bromine by ET leading to quantitative formation of the corresponding quinones. Some compounds (e.g. phloroglucinol) show both partial oxidation and partial electrophilic aromatic substitution and the ratio observed for the pathways depends on the pH. For the reaction of six NOM extracts with bromine, electrophilic aromatic substitution

  7. Heavy ion fusion reactions: comparison among different models

    Energy Technology Data Exchange (ETDEWEB)

    Canto, L F; Carlson, B V; Hussein, M S

    1988-03-01

    A comparison among different ion fusion models is presented. In particular, the multistep aspects of the recently proposed Dinucleus Doorway Model are made explicit and the model is confronted with other compound nucleus limitation models. It is suggested that the latter models provide effective one-step descriptions of heavy ion fusion.

  8. Reaction-diffusion models of decontamination

    DEFF Research Database (Denmark)

    Hjorth, Poul G.

    A contaminant, which also contains a polymer is in the form of droplets on a solid surface. It is to be removed by the action of a decontaminant, which is applied in aqueous solution. The contaminant is only sparingly soluble in water, so the reaction mechanism is that it slowly dissolves...

  9. Multi-criteria comparative evaluation of spallation reaction models

    Science.gov (United States)

    Andrianov, Andrey; Andrianova, Olga; Konobeev, Alexandr; Korovin, Yury; Kuptsov, Ilya

    2017-09-01

    This paper presents an approach to a comparative evaluation of the predictive ability of spallation reaction models based on widely used, well-proven multiple-criteria decision analysis methods (MAVT/MAUT, AHP, TOPSIS, PROMETHEE) and the results of such a comparison for 17 spallation reaction models in the presence of the interaction of high-energy protons with natPb.

  10. Contribution of Histidine and Lysine to the Generation of Volatile Compounds in Jinhua Ham Exposed to Ripening Conditions Via Maillard Reaction.

    Science.gov (United States)

    Zhu, Chao-Zhi; Zhao, Jing-Li; Tian, Wei; Liu, Yan-Xia; Li, Miao-Yun; Zhao, Gai-Ming

    2018-01-01

    To evaluate the role of Maillard reactions in the generation of flavor compounds in Jinhua ham, the reactions of glucose and ethanal with histidine and lysine, respectively, were studied by simulating the ripening conditions of Jinhua ham. The volatile products produced were analyzed using solid phase microextraction-gas chromatography/mass spectrometry. The results showed that 8 volatile compounds were generated by the reaction of glucose and histidine and 10 volatile compounds were generated by the reaction of glucose and lysine. Reactions of ethanal with lysine and with histidine both generated 31 volatile compounds that contributed to the flavor of Jinhua ham. This indicates that histidine and lysine related to Maillard reactions possibly play important roles in the generation of the unique flavor compounds in Jinhua ham. This research demonstrates that free amino acids participate in the generation of volatile compounds from Jinhua ham via the Maillard reaction and provides a basic mechanism to explain flavor formation in Jinhua ham. Jinhua ham is a well-known traditional Chinese dry-cured meat product. However, the formation of the compounds comprising its special flavor is not well understood. Our results indicate that Maillard reactions occur in Jinhua ham under ripening conditions. This work illustrates the contribution of Maillard reactions to the flavor of Jinhua ham. © 2017 Institute of Food Technologists®.

  11. Use of shell model calculations in R-matrix studies of neutron-induced reactions

    International Nuclear Information System (INIS)

    Knox, H.D.

    1986-01-01

    R-matrix analyses of neutron-induced reactions for many of the lightest p-shell nuclei are difficult due to a lack of distinct resonance structure in the reaction cross sections. Initial values for the required R-matrix parameters, E,sub(lambda) and γsub(lambdac) for states in the compound system, can be obtained from shell model calculations. In the present work, the results of recent shell model calculations for the lithium isotopes have been used in R-matrix analyses of 6 Li+n and 7 Li+n reactions for E sub(n) 7 Li and 8 Li on the 6 Li+n and 7 Li+n reaction mechanisms and cross sections are discussed. (author)

  12. DSMC Modeling of Flows with Recombination Reactions

    Science.gov (United States)

    2017-06-23

    its exact analytic integration to provide equally simple temperature dependent reaction rate constant. This is mostly due to the discrete internal... discrete rotational mode may be replaced by its continuous analog, the vibrational mode cannot be simplified this way due to large energy spacing...Rogasinsky, “Analysis of the numerical techniques of the direct simulation Monte Carlo method in the rarefied gas dynamics,” Russ. J. Numer. Anal. Math

  13. Model photo reaction centers via genetic engineering

    Energy Technology Data Exchange (ETDEWEB)

    Zhiyu Wang; DiMagno, T.J.; Popov, M.; Norris, J.R. [Argonne National Lab., IL (United States)]|[Chicago Univ., IL (United States). Dept. of Chemistry; Chikin Chan; Fleming, G. [Chicago Univ., IL (United States). Dept. of Chemistry; Jau Tang; Hanson, D.; Schiffer, M. [Argonne National Lab., IL (United States)

    1992-12-31

    A series of reaction centers of Rhodococcus capsulatus isolated from a set of mutated organisms modified by site-directed mutagenesis at residues M208 and L181 are described. Changes in the amino acid at these sites affect both the energetics of the systems as well as the chemical kinetics for the initial ET event. Two empirical relations among the different mutants for the reduction potential and the ET rate are presented.

  14. Model photo reaction centers via genetic engineering

    Energy Technology Data Exchange (ETDEWEB)

    Zhiyu Wang; DiMagno, T.J.; Popov, M.; Norris, J.R. (Argonne National Lab., IL (United States) Chicago Univ., IL (United States). Dept. of Chemistry); Chikin Chan; Fleming, G. (Chicago Univ., IL (United States). Dept. of Chemistry); Jau Tang; Hanson, D.; Schiffer, M. (Argonne National Lab., IL (United States))

    1992-01-01

    A series of reaction centers of Rhodococcus capsulatus isolated from a set of mutated organisms modified by site-directed mutagenesis at residues M208 and L181 are described. Changes in the amino acid at these sites affect both the energetics of the systems as well as the chemical kinetics for the initial ET event. Two empirical relations among the different mutants for the reduction potential and the ET rate are presented.

  15. Nuclear reactions

    International Nuclear Information System (INIS)

    Lane, A.M.

    1980-01-01

    In reviewing work at Harwell over the past 25 years on nuclear reactions it is stated that a balance has to be struck in both experiment and theory between work on cross-sections of direct practical relevance to reactors and on those relevant to an overall understanding of reaction processes. The compound nucleus and direct process reactions are described. Having listed the contributions from AERE, Harwell to developments in nuclear reaction research in the period, work on the optical model, neutron capture theory, reactions at doorway states with fine structure, and sum-rules for spectroscopic factors are considered in more detail. (UK)

  16. Fate modelling of chemical compounds with incomplete data sets

    DEFF Research Database (Denmark)

    Birkved, Morten; Heijungs, Reinout

    2011-01-01

    Impact assessment of chemical compounds in Life Cycle Impact Assessment (LCIA) and Environmental Risk Assessment (ERA) requires a vast amount of data on the properties of the chemical compounds being assessed. These data are used in multi-media fate and exposure models, to calculate risk levels...... in an approximate way. The idea is that not all data needed in a multi-media fate and exposure model are completely independent and equally important, but that there are physical-chemical and biological relationships between sets of chemical properties. A statistical model is constructed to underpin this assumption...... and other indicators. ERA typically addresses one specific chemical, but in an LCIA, the number of chemicals encountered may be quite high, up to hundreds or thousands. This study explores the development of meta-models, which are supposed to reflect the “true”multi-media fate and exposure model...

  17. Dynamical hindrance to compound-nucleus formation in heavy-ion reactions

    International Nuclear Information System (INIS)

    Blocki, J.P.; Swiatecki, W.J.; Feldmeier, H.

    1986-05-01

    The model of a sharp-surfaced drop with one-body dissipation is used to map out the extra-extra push energy Esub(xx)(A 1 ,A 2 ) (i.e. the excess bombarding energy above the Coulomb barrier required to form a compound nucleus) in its dependence on the mass numbers A 1 , A 2 of the colliding nuclei. The calculated two-dimensional function Esub(xx)(A 1 ,A 2 ) may be scaled approximately to a one-dimensional dependence on a mean fissility parameter xsub(m) = (2/3)x + (1/3)xsub(e), where x is the total system's fissility and xsub(e) is the entrance channel 'effective' fissility. Apart from indications of possible nuclear structure effects, the theoretical predictions seem consistent with experimental data on evaporation residue measurements for system with A 1 =A 2 . For asymmetric systems the relation to experiment is unclear. A by-product is the calculation of nucleus-nucleus sticking times, which are generally found to be in the range around a few times 10 -21 s, but could be longer in special cases. (orig.)

  18. Laccase-mediator catalyzed conversion of model lignin compounds

    Science.gov (United States)

    Laccases play an important role in the biological breakdown of lignin and have great potential in the deconstruction of lignocellulosic feedstocks. We examined a variety of laccases, both commercially prepared and crude extracts, for their ability to oxidize three model lignol compounds (p-coumaryl...

  19. Modelling of chemical reactions in metallurgical processes

    OpenAIRE

    Kinaci, M. Efe; Lichtenegger, Thomas; Schneiderbauer, Simon

    2017-01-01

    Iron-ore reduction has attracted much interest in the last three decades since it can be considered as a core process in steel industry. The iron-ore is reduced to iron with the use of blast furnace and fluidized bed technologies. To investigate the harsh conditions inside fluidized bed reactors, computational tools can be utilized. One such tool is the CFD-DEM method, in which the gas phase reactions and governing equations are calculated in the Eulerian (CFD) side, whereas the particle reac...

  20. QSAR modeling and chemical space analysis of antimalarial compounds

    Science.gov (United States)

    Sidorov, Pavel; Viira, Birgit; Davioud-Charvet, Elisabeth; Maran, Uko; Marcou, Gilles; Horvath, Dragos; Varnek, Alexandre

    2017-05-01

    Generative topographic mapping (GTM) has been used to visualize and analyze the chemical space of antimalarial compounds as well as to build predictive models linking structure of molecules with their antimalarial activity. For this, a database, including 3000 molecules tested in one or several of 17 anti- Plasmodium activity assessment protocols, has been compiled by assembling experimental data from in-house and ChEMBL databases. GTM classification models built on subsets corresponding to individual bioassays perform similarly to the earlier reported SVM models. Zones preferentially populated by active and inactive molecules, respectively, clearly emerge in the class landscapes supported by the GTM model. Their analysis resulted in identification of privileged structural motifs of potential antimalarial compounds. Projection of marketed antimalarial drugs on this map allowed us to delineate several areas in the chemical space corresponding to different mechanisms of antimalarial activity. This helped us to make a suggestion about the mode of action of the molecules populating these zones.

  1. Ion-molecular reactions initiated by β-decay of tritium in tritiated compounds

    International Nuclear Information System (INIS)

    Akulov, G.P.

    1976-01-01

    Ion-molecular reactions initiated by β-decay of tritium and tritiated hydrocarbons have been systematized. The review describes the theoretical and experimental foundation of the radiochemical method of this important type of chemical interactions investigation. The reactions of the molecular ions of HeT + with methane, ethane, propane, butane and also with cycloalkanes from C 3 to C 6 are discussed. The reactions under consideration have been united into two groups: reactions involving HeT + ions and those involving carbonic ions. From the experimental results available, the conclusions have been drawn about the reactivity of these intermediate formations, about the mechanism of their interaction with organic substances, and also about the perspectives of using the radiochemical method in studies of ion-molecular reactions. The experimental results published before May 1974 are examined. The bibliography includes 162 references

  2. Pyrrole PMOs, incorporating new N-heterocyclic compounds on an ethene-PMO through Diels–Alder reactions

    Energy Technology Data Exchange (ETDEWEB)

    Esquivel, Dolores; De Canck, Els [Center for Ordered Materials, Organometallics and Catalysis, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium); Jiménez-Sanchidrián, César [Department of Organic Chemistry, Nanochemistry and Fine Chemistry Research Institute (IUIQFN), Faculty of Sciences, University of Córdoba, Campus de Rabanales, Marie Curie Building, Ctra. Nnal. IV, km 396, 14071 Córdoba (Spain); Romero-Salguero, Francisco J., E-mail: qo2rosaf@uco.es [Department of Organic Chemistry, Nanochemistry and Fine Chemistry Research Institute (IUIQFN), Faculty of Sciences, University of Córdoba, Campus de Rabanales, Marie Curie Building, Ctra. Nnal. IV, km 396, 14071 Córdoba (Spain); Van Der Voort, Pascal, E-mail: pascal.vandervoort@ugent.be [Center for Ordered Materials, Organometallics and Catalysis, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium)

    2014-11-14

    The ethenylene bridges on the walls of an ethenylene-bridged periodic mesoporous organosilica were successfully modified with a variety of pyrrole derivatives – pyrrole, methylpyrrole, dimethylpyrrole, trimethylpyrrole and 1-phenylpyrrole – through Diels–Alder reactions. X-ray diffraction measurements and N{sub 2} adsorption–desorption analysis confirmed the preservation of the ordering and mesoporosity of the parent material as well as the decoration of the pores with the surface Diels–Alder adducts. Moreover, other techniques such as DRIFT, {sup 13}C and {sup 29}Si nuclear magnetic resonances revealed the formation of the surface N-heterocyclic compounds at the parent ethenylene sites. - Highlights: • Chemical modification of the double bonds on an ethene-PMO through the Diels–Alder reaction. • A family of pyrrole derivatives act as dienes in the Diels–Alder reaction. • Well-ordering and mesoporosity are retained after the post-functionalization. • N-containing compounds on the surface of ethene-PMO are present after the Diels–Alder reaction.

  3. Pyrrole PMOs, incorporating new N-heterocyclic compounds on an ethene-PMO through Diels–Alder reactions

    International Nuclear Information System (INIS)

    Esquivel, Dolores; De Canck, Els; Jiménez-Sanchidrián, César; Romero-Salguero, Francisco J.; Van Der Voort, Pascal

    2014-01-01

    The ethenylene bridges on the walls of an ethenylene-bridged periodic mesoporous organosilica were successfully modified with a variety of pyrrole derivatives – pyrrole, methylpyrrole, dimethylpyrrole, trimethylpyrrole and 1-phenylpyrrole – through Diels–Alder reactions. X-ray diffraction measurements and N 2 adsorption–desorption analysis confirmed the preservation of the ordering and mesoporosity of the parent material as well as the decoration of the pores with the surface Diels–Alder adducts. Moreover, other techniques such as DRIFT, 13 C and 29 Si nuclear magnetic resonances revealed the formation of the surface N-heterocyclic compounds at the parent ethenylene sites. - Highlights: • Chemical modification of the double bonds on an ethene-PMO through the Diels–Alder reaction. • A family of pyrrole derivatives act as dienes in the Diels–Alder reaction. • Well-ordering and mesoporosity are retained after the post-functionalization. • N-containing compounds on the surface of ethene-PMO are present after the Diels–Alder reaction

  4. Radiation chemistry of salicylic and methyl substituted salicylic acids: Models for the radiation chemistry of pharmaceutical compounds

    International Nuclear Information System (INIS)

    Ayatollahi, Shakiba; Kalnina, Daina; Song, Weihua; Turks, Maris; Cooper, William J.

    2013-01-01

    Salicylic acid and its derivatives are components of many medications and moieties found in numerous pharmaceutical compounds. They have been used as models for various pharmaceutical compounds in pharmacological studies, for the treatment of pharmaceuticals and personal care products (PPCPs), and, reactions with natural organic matter (NOM). In this study, the radiation chemistry of benzoic acid, salicylic acid and four methyl substituted salicylic acids (MSA) is reported. The absolute bimolecular reaction rate constants for hydroxyl radical reaction with benzoic and salicylic acids as well as 3-methyl-, 4-methyl-, 5-methyl-, and 6-methyl-salicylic acid were determined (5.86±0.54)×10 9 , (1.07±0.07)×10 10 , (7.48±0.17)×10 9 , (7.31±0.29)×10 9 , (5.47±0.25)×10 9 , (6.94±0.10)×10 9 (M −1 s −1 ), respectively. The hydrated electron reaction rate constants were measured (3.02±0.10)×10 9 , (8.98±0.27)×10 9 , (5.39±0.21)×10 9 , (4.33±0.17)×10 9 , (4.72±0.15)×10 9 , (1.42±0.02)×10 9 (M −1 s −1 ), respectively. The transient absorption spectra for the six model compounds were examined and their role as model compounds for the radiation chemistry of pharmaceuticals investigated. - Highlights: • Free radical chemistry of salicylic and 4 methyl salicylic acids is investigated. • The transient absorptions spectra for model compounds are measured. • Absolute bimolecular reaction rate constants for hydroxyl radical are determined. • Solvated electron reaction rate constants are calculated. • The use of salicylic acids as models for pharmaceuticals is explored

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

    NARCIS (Netherlands)

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

    1968-01-01

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

  6. N-nitrosodimethylamine (NDMA) formation during ozonation of N,N-dimethylhydrazine compounds: Reaction kinetics, mechanisms, and implications for NDMA formation control.

    Science.gov (United States)

    Lim, Sungeun; Lee, Woongbae; Na, Soyoung; Shin, Jaedon; Lee, Yunho

    2016-11-15

    Compounds with N,N-dimethylhydrazine moieties ((CH 3 ) 2 N-N-) form N-nitrosodimethylamine (NDMA) during ozonation, but the relevant reaction chemistry is hitherto poorly understood. This study investigated the reaction kinetics and mechanisms of NDMA formation during ozonation of unsymmetrical dimethylhydrazine (UDMH) and daminozide (DMZ) as structural model N,N-dimethylhydrazine compounds. The reaction of ozone with these NDMA precursor compounds was fast, and k O3 at pH 7 was 2 × 10 6  M -1  s -1 for UDMH and 5 × 10 5  M -1  s -1 for DMZ. Molar NDMA yields (i.e., Δ[NDMA]/Δ[precursor] × 100) were 84% and 100% for UDMH and DMZ, respectively, determined at molar ozone dose ratio ([O 3 ] 0 /[precursor] 0 ) of ≥4 in the presence of tert-butanol as hydroxyl radical (OH) scavenger. The molar NDMA yields decreased significantly in the absence of tert-butanol, indicating OH formation and its subsequent reaction with the parent precursors forming negligible NDMA. The k OH at pH 7 was 4.9 × 10 9  M -1  s -1 and 3.4 × 10 9  M -1  s -1 for UDMH and DMZ, respectively. Reaction mechanisms are proposed in which an ozone adduct is formed at the nitrogen next to N,N-dimethylamine which decomposes via homolytic and heterolytic cleavages of the -N + -O-O-O - bond, forming NDMA as a final product. The heterolytic cleavage pathway explains the significant OH formation via radical intermediates. Overall, significant NDMA formation was found to be unavoidable during ozonation or even O 3 /H 2 O 2 treatment of waters containing N,N-dimethylhydrazine compounds due to their rapid reaction with ozone forming NDMA with high yield. Thus, source control or pre-treatment of N,N-dimethylhydrazine precursors and post-treatment of NDMA are proposed as the mitigation options. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Analytically solvable models of reaction-diffusion systems

    Energy Technology Data Exchange (ETDEWEB)

    Zemskov, E P; Kassner, K [Institut fuer Theoretische Physik, Otto-von-Guericke-Universitaet, Universitaetsplatz 2, 39106 Magdeburg (Germany)

    2004-05-01

    We consider a class of analytically solvable models of reaction-diffusion systems. An analytical treatment is possible because the nonlinear reaction term is approximated by a piecewise linear function. As particular examples we choose front and pulse solutions to illustrate the matching procedure in the one-dimensional case.

  8. Constituent rearrangement model and large transverse momentum reactions

    International Nuclear Information System (INIS)

    Igarashi, Yuji; Imachi, Masahiro; Matsuoka, Takeo; Otsuki, Shoichiro; Sawada, Shoji.

    1978-01-01

    In this chapter, two models based on the constituent rearrangement picture for large p sub( t) phenomena are summarized. One is the quark-junction model, and the other is the correlating quark rearrangement model. Counting rules of the models apply to both two-body reactions and hadron productions. (author)

  9. Alkoxyl- and carbon-centered radicals as primary agents for degrading non-phenolic lignin-substructure model compounds.

    Science.gov (United States)

    Ohashi, Yasunori; Uno, Yukiko; Amirta, Rudianto; Watanabe, Takahito; Honda, Yoichi; Watanabe, Takashi

    2011-04-07

    Lignin degradation by white-rot fungi proceeds via free radical reaction catalyzed by oxidative enzymes and metabolites. Basidiomycetes called selective white-rot fungi degrade both phenolic and non-phenolic lignin substructures without penetration of extracellular enzymes into the cell wall. Extracellular lipid peroxidation has been proposed as a possible ligninolytic mechanism, and radical species degrading the recalcitrant non-phenolic lignin substructures have been discussed. Reactions between the non-phenolic lignin model compounds and radicals produced from azo compounds in air have previously been analysed, and peroxyl radical (PR) is postulated to be responsible for lignin degradation (Kapich et al., FEBS Lett., 1999, 461, 115-119). However, because the thermolysis of azo compounds in air generates both a carbon-centred radical (CR) and a peroxyl radical (PR), we re-examined the reactivity of the three radicals alkoxyl radical (AR), CR and PR towards non-phenolic monomeric and dimeric lignin model compounds. The dimeric lignin model compound is degraded by CR produced by reaction of 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH), which under N(2) atmosphere cleaves the α-β bond in 1-(4-ethoxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)-1,3-propanediol to yield 4-ethoxy-3-methoxybenzaldehyde. However, it is not degraded by the PR produced by reaction of Ce(4+)/tert-BuOOH. In addition, it is degraded by AR produced by reaction of Ti(3+)/tert-BuOOH. PR and AR are generated in the presence and absence of veratryl alcohol, respectively. Rapid-flow ESR analysis of the radical species demonstrates that AR but not PR reacts with the lignin model compound. Thus, AR and CR are primary agents for the degradation of non-phenolic lignin substructures.

  10. Misfit Layer Compounds and Ferecrystals: Model Systems for Thermoelectric Nanocomposites

    Directory of Open Access Journals (Sweden)

    Devin R. Merrill

    2015-04-01

    Full Text Available A basic summary of thermoelectric principles is presented in a historical context, following the evolution of the field from initial discovery to modern day high-zT materials. A specific focus is placed on nanocomposite materials as a means to solve the challenges presented by the contradictory material requirements necessary for efficient thermal energy harvest. Misfit layer compounds are highlighted as an example of a highly ordered anisotropic nanocomposite system. Their layered structure provides the opportunity to use multiple constituents for improved thermoelectric performance, through both enhanced phonon scattering at interfaces and through electronic interactions between the constituents. Recently, a class of metastable, turbostratically-disordered misfit layer compounds has been synthesized using a kinetically controlled approach with low reaction temperatures. The kinetically stabilized structures can be prepared with a variety of constituent ratios and layering schemes, providing an avenue to systematically understand structure-function relationships not possible in the thermodynamic compounds. We summarize the work that has been done to date on these materials. The observed turbostratic disorder has been shown to result in extremely low cross plane thermal conductivity and in plane thermal conductivities that are also very small, suggesting the structural motif could be attractive as thermoelectric materials if the power factor could be improved. The first 10 compounds in the [(PbSe1+δ]m(TiSe2n family (m, n ≤ 3 are reported as a case study. As n increases, the magnitude of the Seebeck coefficient is significantly increased without a simultaneous decrease in the in-plane electrical conductivity, resulting in an improved thermoelectric power factor.

  11. Catalytic hydroprocessing of lignin β-O-4 ether bond model compound phenethyl phenyl ether over ruthenium catalysts

    NARCIS (Netherlands)

    Gomez-Monedero, B.; Faria, J.; Bimbela, F.; Ruiz, M.P.

    2017-01-01

    The catalytic hydroprocessing of phenethyl phenyl ether (PPE), a model compound of one of the most significant ether linkages within lignin structure, β-O-4, has been studied. Reactions were carried out using two ruthenium-based catalysts, supported on different materials: 3.8 wt.% Ru/C and 3.9 wt.%

  12. Gas Chromatographic-Ion Trap Mass Spectrometric Analysis of Volatile Organic Compounds by Ion-Molecule Reactions Using the Electron-Deficient Reagent Ion CCl{3/+}

    Science.gov (United States)

    Wang, Cheng-Zhong; Su, Yue; Wang, Hao-Yang; Guo, Yin-Long

    2011-10-01

    When using tetrachloromethane as the reagent gas in gas chromatography-ion trap mass spectrometry equipped with hybrid ionization source, the cation CCl{3/+} was generated in high abundance and further gas-phase experiments showed that such an electron-deficient reagent ion CCl{3/+} could undergo interesting ion-molecule reactions with various volatile organic compounds, which not only present some informative gas-phase reactions, but also facilitate qualitative analysis of diverse volatile compounds by providing unique mass spectral data that are characteristic of particular chemical structures. The ion-molecule reactions of the reagent ion CCl{3/+} with different types of compounds were studied, and results showed that such reactions could give rise to structurally diagnostic ions, such as [M + CCl3 - HCl]+ for aromatic hydrocarbons, [M - OH]+ for saturated cyclic ether, ketone, and alcoholic compounds, [M - H]+ ion for monoterpenes, M·+ for sesquiterpenes, [M - CH3CO]+ for esters, as well as the further fragment ions. The mechanisms of ion-molecule reactions of aromatic hydrocarbons, aliphatic ketones and alcoholic compounds with the reagent ion CCl{3/+} were investigated and proposed according to the information provided by MS/MS experiments and theoretical calculations. Then, this method was applied to study volatile organic compounds in Dendranthema indicum var. aromaticum and 20 compounds, including monoterpenes and their oxygen-containing derivatives, aromatic hydrocarbon and sesquiterpenes were identified using such ion-molecule reactions. This study offers a perspective and an alternative tool for the analysis and identification of various volatile compounds.

  13. Effect of solvation on reactions of aluminium, gallium, indium, zinc and cadmium with azo compounds

    International Nuclear Information System (INIS)

    Savvin, S.B.

    1985-01-01

    Colour reactions have been examined between Al, Ga, In, Zn, Cd and reagents of a group of chromotropic acid 2.7-bisazo derivatives (Picramin B, Picramin M, Methanyl B, sulphonitrophenol M, sulphonitrophenol B) in organo-aqueous solutions containing acetone, propanol, DMFA, DMSO and acetic acid. Sensitive colour reactions occur in all the cases in aceton- or propanol-containing solutions: more sensitive than in water for Al, Ga, In; new reactions for Zn and Cd which are specific for organo-aqueous media and not observed in aqueous solutions. Sensitive reactions are observed only for Al and Ga in DMSO or DMFA solutions. Zn, Cd and In do not give colour reactions in such solutions. Differences in colour reactions for the elements in DMFA- and DMSO-containing media are connected with different solvation effects of the solvents on certain cations. Preferable solvation of some cations has been confirmed by infrared studies and is in agreement with the data reported on selective solvation

  14. Electronic computer prediction of the type of the crystallization reaction of binary compounds on the base of electronic structure of components

    International Nuclear Information System (INIS)

    Kutolin, S.A.; Kotyukov, V.I.

    1979-01-01

    Presented are the criteria permitting to predict distectic and peritectic reactions of crystallization in narrow and wide regions of homogeneity of Asub(n)Bsub(m) binary compounds. Criteria are found as a result of identification of the crystallization reaction type for one hundred of known binary compounds. Predicting function arguments are Chebishev coefficients whose polynomials describe energy distribution of s-, p-, d-atoms of bands of corresponding compound components in condensed state and also Fermi energy atate in compound components and a content. Prediction relative error of distectic (peritectic) crystallization reaction is 6%, for wide homogeneity region - not more than 12 rel.% (for narrow - up to 1 at%). Presented are the prediction results for the most part of A 3 B and AB 3 binary compounds as well as the rare earth compounds of various composition

  15. Modeling Reaction Control System Effects on Mars Odyssey

    National Research Council Canada - National Science Library

    Hanna, Jill

    2002-01-01

    ...) simulations to determine rotational motion of the spacecraft. The main objective of this study was to assess the reaction control system models and their effects on the atmospheric flight of Odyssey...

  16. Stability Analysis of a Reaction-Diffusion System Modeling Atherogenesis

    KAUST Repository

    Ibragimov, Akif; Ritter, Laura; Walton, Jay R.

    2010-01-01

    This paper presents a linear, asymptotic stability analysis for a reaction-diffusionconvection system modeling atherogenesis, the initiation of atherosclerosis, as an inflammatory instability. Motivated by the disease paradigm articulated by Ross

  17. VR-SCOSMO: A smooth conductor-like screening model with charge-dependent radii for modeling chemical reactions.

    Science.gov (United States)

    Kuechler, Erich R; Giese, Timothy J; York, Darrin M

    2016-04-28

    To better represent the solvation effects observed along reaction pathways, and of ionic species in general, a charge-dependent variable-radii smooth conductor-like screening model (VR-SCOSMO) is developed. This model is implemented and parameterized with a third order density-functional tight binding quantum model, DFTB3/3OB-OPhyd, a quantum method which was developed for organic and biological compounds, utilizing a specific parameterization for phosphate hydrolysis reactions. Unlike most other applications with the DFTB3/3OB model, an auxiliary set of atomic multipoles is constructed from the underlying DFTB3 density matrix which is used to interact the solute with the solvent response surface. The resulting method is variational, produces smooth energies, and has analytic gradients. As a baseline, a conventional SCOSMO model with fixed radii is also parameterized. The SCOSMO and VR-SCOSMO models shown have comparable accuracy in reproducing neutral-molecule absolute solvation free energies; however, the VR-SCOSMO model is shown to reduce the mean unsigned errors (MUEs) of ionic compounds by half (about 2-3 kcal/mol). The VR-SCOSMO model presents similar accuracy as a charge-dependent Poisson-Boltzmann model introduced by Hou et al. [J. Chem. Theory Comput. 6, 2303 (2010)]. VR-SCOSMO is then used to examine the hydrolysis of trimethylphosphate and seven other phosphoryl transesterification reactions with different leaving groups. Two-dimensional energy landscapes are constructed for these reactions and calculated barriers are compared to those obtained from ab initio polarizable continuum calculations and experiment. Results of the VR-SCOSMO model are in good agreement in both cases, capturing the rate-limiting reaction barrier and the nature of the transition state.

  18. Formal modeling of a system of chemical reactions under uncertainty.

    Science.gov (United States)

    Ghosh, Krishnendu; Schlipf, John

    2014-10-01

    We describe a novel formalism representing a system of chemical reactions, with imprecise rates of reactions and concentrations of chemicals, and describe a model reduction method, pruning, based on the chemical properties. We present two algorithms, midpoint approximation and interval approximation, for construction of efficient model abstractions with uncertainty in data. We evaluate computational feasibility by posing queries in computation tree logic (CTL) on a prototype of extracellular-signal-regulated kinase (ERK) pathway.

  19. GC-MS quantitation of fragrance compounds suspected to cause skin reactions. 1.

    Science.gov (United States)

    Chaintreau, Alain; Joulain, Daniel; Marin, Christophe; Schmidt, Claus-Oliver; Vey, Matthias

    2003-10-22

    Recent changes in European legislation require monitoring of 24 volatile compounds in perfumes as they might elicit skin sensitization. This paper reports a GC-MS quantitation procedure for their determination in fragrance concentrates. GC and MS conditions were optimized for a routine use: analysis within 30 min, solvent and internal standard selection, and stock solution stability. Calibration curves were linear in the range of 2-100 mg/L with coefficients of determination in excess of 0.99. The method was tested using real perfumes spiked with known amounts of reference compounds.

  20. Electrochemical reactions at sacrificial electrodes : Part VI. Synthesis of cadmium alkoxides and their coordination compounds

    International Nuclear Information System (INIS)

    Banait, J.S.; Singh, Baljit

    1991-01-01

    Cadmium alkoxides [Cd(OR) 2 ; R=methyl, ethyl, n-propyl, n-butyl and n-amyl], have been synthesised by the electrolysis of alcohols at a cadmium anode. These alkoxides do not form coordination compounds when refluxed with the ligands like 2,2'-bipyridine, 1,10-phenanthroline, dimethylsulphoxide and acetone. However, coordination compounds with the general formula, Cd(OR) 2 .L, have been prepared when the solutions of these ligands in alcohols are electrolysed at a cadmium anode. The products have been characterised by elemental analyses and IR data. Current efficiencies of all these systems are quite high. (author). 21 refs., 2 tabs

  1. Synthesis and Regioselective Reaction of Some Unsymmetrical Heterocyclic Chalcone Derivatives and Spiro Heterocyclic Compounds as Antibacterial Agents.

    Science.gov (United States)

    El-Hashash, Maher A; Rizk, Sameh A; Atta-Allah, Saad R

    2015-12-10

    A number of novel heterocyclic chalcone derivatives can be synthesized by thermal and microwave tools. Treatment of 4-(4-Acetylamino- and/or 4-bromo-phenyl)-4-oxobut-2-enoic acids with hydrogen peroxide in alkaline medium were afforded oxirane derivatives 2. Reaction of the epoxide 2 with 2-amino-5-aryl-1,3,4-thiadiazole derivatives yielded chalcone of imidazo[2,1-b]thiadiazole derivative 4 via two thermal routes. In one pot reaction of 4-bromoacetophenone, diethyloxalate, and 2-amino-5-aryl-1,3,4-thiadiazole derivatives in MW irradiation (W 250 and T 150 °C) under eco-friendly conditions afforded an unsuitable yield of the desired chalcone 4d. The chalcone derivatives 4 were used as a key starting material to synthesize some new spiroheterocyclic compounds via Michael and aza-Michael adducts. The chalcone 4f was similar to the aryl-oxo-vinylamide derivatives for the inhibition of tyrosine kinase and cancer cell growth. The electron-withdrawing substituents, such as halogens, and 2-amino-1,3,4-thiadiazole moeity decreasing the electron density, thereby decreasing the energy of HOMO, and the presence of imidazothiadiazole moiety should improve the antibacterial activity. Thus, the newly synthesized compounds were evaluated for their anti-bacterial activity against (ATCC 25923), (ATCC 10987), (ATCC 274,) and (SM514). The structure of the newly synthesized compounds was confirmed by elemental analysis and spectroscopic data.

  2. Precompound decay models for medium energy nuclear reactions

    International Nuclear Information System (INIS)

    Blann, M.

    1989-11-01

    The formulations used for precompound decay models are presented and explained in terms of the physics of the intranuclear cascade model. Several features of spectra of medium energy (10--1000 MeV) reactions are summarized. Results of precompound plus evaporation calculations from the code ALICE are compared with a wide body of proton, alpha, and heavy ion induced reaction data to illustrate both the power and deficiencies of predicting yield of these reactions in the medium energy regime. 23 refs., 13 figs

  3. Study of the emission oxidative reactions of ruthenium (II) complex by cationic compounds in anionic micelles

    International Nuclear Information System (INIS)

    Bonilha, J.B.S.

    1985-01-01

    The oxidative quenching of the emission of the tetraanionic complex tris (4,4' dicarboxylate - 2,2' - bipyridine ruthenium (II) in aqueous solution, by both organic and inorganic compounds in presence of anionic detergents, above and below the critical micelle concentration is studied. The organic cations, the inorganic ion and detergents used are shown. (M.J.C.) [pt

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

    International Nuclear Information System (INIS)

    Carlson, B.V.

    2003-01-01

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

  5. The asymmetric hetero-Diels-Alder reaction in the syntheses of biologically relevant compounds.

    Science.gov (United States)

    Eschenbrenner-Lux, Vincent; Kumar, Kamal; Waldmann, Herbert

    2014-10-13

    The hetero-Diels-Alder reaction is one of the most powerful transformations in the chemistry toolbox for the synthesis of aza- and oxa-heterocycles embodying multiple stereogenic centers. However, as compared to other cycloadditions, in particular the dipolar cycloadditions and the Diels-Alder reaction, the hetero-Diels-Alder reaction has been much less explored and exploited in organic synthesis. Nevertheless, this powerful transformation has opened up efficient and creative routes to biologically relevant small molecules and different natural products which contain six-membered oxygen or nitrogen ring systems. Recent developments in this field, in particular in the establishment of enantioselectively catalyzed hetero-Diels-Alder cycloadditions steered by a plethora of different catalysts and the application of the resulting small molecules in chemical biology and medicinal chemistry research, are highlighted in this Minireview. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Multiresponse kinetic modelling of Maillard reaction and caramelisation in a heated glucose/wheat flour system.

    Science.gov (United States)

    Kocadağlı, Tolgahan; Gökmen, Vural

    2016-11-15

    The study describes the kinetics of the formation and degradation of α-dicarbonyl compounds in glucose/wheat flour system heated under low moisture conditions. Changes in the concentrations of glucose, fructose, individual free amino acids, lysine and arginine residues, glucosone, 1-deoxyglucosone, 3-deoxyglucosone, 3,4-dideoxyglucosone, 5-hydroxymethyl-2-furfural, glyoxal, methylglyoxal and diacetyl concentrations were determined to form a multiresponse kinetic model for isomerisation and degradation reactions of glucose. Degradation of Amadori product mainly produced 1-deoxyglucosone. Formation of 3-deoxyglucosone proceeded directly from glucose and also Amadori product degradation. Glyoxal formation was predominant from glucosone while methylglyoxal and diacetyl originated from 1-deoxyglucosone. Formation of 5-hydroxymethyl-2-furfural from fructose was found to be a key step. Multi-response kinetic modelling of Maillard reaction and caramelisation simultaneously indicated quantitatively predominant parallel and consecutive pathways and rate limiting steps by estimating the reaction rate constants. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Modeling and Simulation of Claus Unit Reaction Furnace

    Directory of Open Access Journals (Sweden)

    Maryam Pahlavan

    2016-01-01

    Full Text Available Reaction furnace is the most important part of the Claus sulfur recovery unit and its performance has a significant impact on the process efficiency. Too many reactions happen in the furnace and their kinetics and mechanisms are not completely understood; therefore, modeling reaction furnace is difficult and several works have been carried out on in this regard so far. Equilibrium models are commonly used to simulate the furnace, but the related literature states that the outlet of furnace is not in equilibrium and the furnace reactions are controlled by kinetic laws; therefore, in this study, the reaction furnace is simulated by a kinetic model. The predicted outlet temperature and concentrations by this model are compared with experimental data published in the literature and the data obtained by PROMAX V2.0 simulator. The results show that the accuracy of the proposed kinetic model and PROMAX simulator is almost similar, but the kinetic model used in this paper has two importance abilities. Firstly, it is a distributed model and can be used to obtain the temperature and concentration profiles along the furnace. Secondly, it is a dynamic model and can be used for analyzing the transient behavior and designing the control system.

  8. Cellular automaton model of coupled mass transport and chemical reactions

    International Nuclear Information System (INIS)

    Karapiperis, T.

    1994-01-01

    Mass transport, coupled with chemical reactions, is modelled as a cellular automaton in which solute molecules perform a random walk on a lattice and react according to a local probabilistic rule. Assuming molecular chaos and a smooth density function, we obtain the standard reaction-transport equations in the continuum limit. The model is applied to the reactions a + b ↔c and a + b →c, where we observe interesting macroscopic effects resulting from microscopic fluctuations and spatial correlations between molecules. We also simulate autocatalytic reaction schemes displaying spontaneous formation of spatial concentration patterns. Finally, we propose and discuss the limitations of a simple model for mineral-solute interaction. (author) 5 figs., 20 refs

  9. Synthesis of Pyrroloquinones via a CAN Mediated Oxidative Free Radical Reaction of 1,3-Dicarbonyl Compounds with Aminoquinones

    Directory of Open Access Journals (Sweden)

    Thao Nguyen

    2013-01-01

    Full Text Available Pyrroloquinone ring systems are important structural units present in many biologically active molecules including a number of marine alkaloids. For example, they are found in a series of marine metabolites, such as tsitsikammamines, zyzzyanones, wakayin, and terreusinone. Several of these alkaloids have exhibited antimicrobial, antimalarial, antifungal, antitumor, and photoprotecting activities. Synthesis of pyrroloquinone unit is the key step in the synthesis of many of these important organic molecules. Here, we present a ceric (IV ammonium nitrate (CAN mediated oxidative free radical cyclization reaction of 1,3-dicarbonyl compounds with aminoquinones as a facile methodology for making various substituted pyrroloquinones. 1,3-dicarbonyl compounds used in this study are ethyl acetoacetate, acetylacetone, benzoyl acetone, and N,N-dimethyl acetoacetamide. The aminoquinones used in this study are 2-(benzylaminonaphthalene-1,4-dione and 6-(benzylamino-1-tosyl-1H-indole-4,7-dione. The yields of the synthesized pyrroloquinones ranged from 23–91%.

  10. Reaction of low-molecular-mass organoselenium compounds (and their sulphur analogues) with inflammation-associated oxidants

    DEFF Research Database (Denmark)

    Carroll, L.; Davies, Michael J.; Pattison, D. I.

    2015-01-01

    Selenium is an essential trace element in mammals, with the majority specifically encoded as seleno-L-cysteine into a range of selenoproteins. Many of these proteins play a key role in modulating oxidative stress, via either direct detoxification of biological oxidants, or repair of oxidised...... the chemistry of low-molecular-mass organoselenium compounds (e.g. selenoethers, diselenides and selenols) with inflammatory oxidants, with a particular focus on the reaction kinetics and product studies, with the differences in reactivity between selenium and sulphur analogues described in the selected...... examples. These data provide insight into the therapeutic potential of low-molecular-mass selenium-containing compounds to modulate the activity of both radical and molecular oxidants and provide protection against inflammation-induced damage. Progress in their therapeutic development (including modulation...

  11. THREE DIMENSIONAL CFD MODELLING OF FLOW STRUCTURE IN COMPOUND CHANNELS

    Directory of Open Access Journals (Sweden)

    Usman Ghani

    2010-10-01

    Full Text Available The computational modeling of three dimensional flows in a meandering compound channel has been performed in this research work. The flow calculations are performed by solving 3D steady state continuity and Reynolds averaged Navier-Stokes equations. The turbulence closure is approximated with standard - turbulence model. The model equations are solved numerically with a general purpose software package. A comprehensive validation of the simulated results against the experimental data and a demonstration that the software used in this study has matured enough for investigating practical engineering problems are the major contributions of this paper. The model was initially validated. This was achieved by computing streamwise point velocities at different depths of various sections and depth averaged velocities at three cross sections along the main channel and comparing these results with experimental data. After the validation of the model, predictions were made for different flow parameters including velocity contours at the surface, pressure distribution, turbulence intensity etc. The results gave an overall understanding of these flow variables in meandering channels. The simulation also established the good prediction capability of the standard - turbulence model for flows in compound channels.

  12. Enhanced emission of non-compound light particles in the reaction plane

    International Nuclear Information System (INIS)

    Tsang, M.B.

    1984-01-01

    In an experiment performed at the K500 cyclotron at Michigan State University, light particles in coincidence with two fission fragments for 14 N induced reactions on 197 Au at 420 MeV incident energy have been measured. The fission fragments were detected with two large area position sensitive parallel plate avalanche detectors. Light particle telescopes consisting of silicon-ΔE and Nal-E detectors were placed both in and out of the plane defined by the centers of the two fission detectors and the beam axis. The momentum transferred to the composite system was determined by measuring the folding angle between the two outgoing fission fragments. Unlike observations with more fissile targets, however, transfer and inelastic reactions characterized by small linear momentum transfers contribute negligibly to the fission cross section for reactions on the 197 Au target. For events which lead to fission, the most probable linear momentum transfer corresponded to about 85% of the beam momentum. This is similar to the most probable momentum transfer observed for fusion-like reactions on 238 U at the same beam energy. Much of the missing momentum is carried away by non-equilibrium light particle emission

  13. Classical kinematic model for direct reactions of oriented reagents

    International Nuclear Information System (INIS)

    Schechter, I.; Prisant, M.G.; Levine, R.D.

    1987-01-01

    A simple kinematic model based on the concept of an orientation-dependent critical configuration for reaction is introduced and applied. The model serves two complementary purposes. In the predictive mode the model provides an easily implemented procedure for computing the reactivity of oriented reagents (including those actually amenable to measure) from a given potential energy surface. The predictions of the model are compared against classical trajectory results for the H + D 2 reaction. By use of realistic potential energy surfaces the model is applied to the Li + HF and O + HCl reactions where the HX molecules are pumped by a polarized laser. A given classical trajectory is deemed reactive or not according to whether it can surmount the barrier at that particular orientation. The essential difference with the model of Levine and Bernstein is that the averaging over initial conditions is performed by using a Monte Carlo integration. One can therefore use the correct orientation-dependent shape (and not only height) of the barrier to reaction and, furthermore, use oriented or aligned reagents. Since the only numerical step is a Monte Carlo sampling of initial conditions, very many trajectories can be run. This suffices to determine the reaction cross section for different initial conditions. To probe the products, they have employed the kinematic approach of Elsum and Gordon. The result is a model where, under varying initial conditions, examining final-state distributions or screening different potential energy surfaces can be efficiently carried out

  14. Identification of reaction compounds in micrometric layers from gothic paintings using combined SR-XRD and SR-FTIR.

    Science.gov (United States)

    Salvadó, Nati; Butí, Salvador; Nicholson, James; Emerich, Hermann; Labrador, Ana; Pradell, Trinitat

    2009-07-15

    Synchrotron radiation X-ray diffraction (micro-SR-XRD) and Fourier transform infrared spectroscopy (micro-SR-FTIR) are used in the non-destructive identification of reaction and aging compounds from micrometric ancient painting layers. The combination of the micrometer size and non-destructive nature of the techniques together with the high resolution and brilliance of the synchrotron radiation has proved to be a procedure most advantageous for the study of reaction, aging and degradation processes. Copper, lead and calcium carboxylates and oxalates are determined in the chromatic, preparation and alteration layers from 15th century egg tempera and oil paintings. Their nature and crystallinity have been assessed. Some hypothesis about the mechanisms of development of both carboxylates and oxalates are presented.

  15. P-matrix in the quark compound bag model

    International Nuclear Information System (INIS)

    Kalashnikova, Yu.S.; Narodetskij, I.M.; Veselov, A.I.

    1983-01-01

    Meaning of the P-matrix analysis is discussed within the quark compound bag (QCB) model. The most general version of this model is considered including the arbitrary coupling between quark and hadronic channels and the arbitrary smearipg of the surface interection region. The behaviour of P-matrix poles as functions of matching radius r,L0 is discussed for r 0 > + . In conclusion are presented the parameters of an illustrative set of NN potentials that has been obtained from the P-matrix fit to experimental data

  16. Quest for consistent modelling of statistical decay of the compound nucleus

    Science.gov (United States)

    Banerjee, Tathagata; Nath, S.; Pal, Santanu

    2018-01-01

    A statistical model description of heavy ion induced fusion-fission reactions is presented where shell effects, collective enhancement of level density, tilting away effect of compound nuclear spin and dissipation are included. It is shown that the inclusion of all these effects provides a consistent picture of fission where fission hindrance is required to explain the experimental values of both pre-scission neutron multiplicities and evaporation residue cross-sections in contrast to some of the earlier works where a fission hindrance is required for pre-scission neutrons but a fission enhancement for evaporation residue cross-sections.

  17. Iodometric microdetermination of phosphorus in organic compounds by use of An amplification reaction

    OpenAIRE

    Al Kubaisi, A. H. [عبد الله حسين الكبيسي; Farag, A. B.; Amin, R. R.

    1994-01-01

    A high chemical amplification method is described for the iodometric microdetermination of phosphorus in organic compounds. This method depends on combustion by the oxygen flask, absorption of the combustion products in distilled water and conversion to orthophosphoric acid with bromine water. The phosphoric acid produced is then allowed to react with sodium molybdate in acid medium to form phosphomolybdic acid which is extracted into a mixture of diethyl ether and pentanol (5:1, V/V), and ba...

  18. Kinetic mechanism for modeling of electrochemical reactions.

    Science.gov (United States)

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

    2012-04-01

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

  19. Models of direct reactions and quantum pre-equilibrium for nucleon scattering on spherical nuclei

    International Nuclear Information System (INIS)

    Dupuis, M.

    2006-01-01

    When a nucleon collides with a target nucleus, several reactions may occur: elastic and inelastic scatterings, charge exchange... In order to describe these reactions, different models are involved: the direct reactions, pre-equilibrium and compound nucleus models. Our goal is to study, within a quantum framework and without any adjustable parameter, the direct and pre-equilibrium reactions for nucleons scatterings off double closed-shell nuclei. We first consider direct reactions: we are studying nucleon scattering with the Melbourne G-matrix, which represents the interaction between the projectile and one target nucleon, and with random phase approximation (RPA) wave functions which describe all target states. This is a fully microscopic approach since no adjustable parameters are involved. A second part is dedicated to the study of nucleon inelastic scattering for large energy transfer which necessarily involves the pre-equilibrium mechanism. Several models have been developed in the past to deal with pre-equilibrium. They start from the Born expansion of the transition amplitude which is associated to the inelastic process and they use several approximations which have not yet been tested. We have achieved some comparisons between second order cross sections which have been calculated with and without these approximations. Our results allow us to criticize some of these approximations and give several directions to improve the quantum pre-equilibrium models. (author)

  20. Electron and ligand transfer reactions between cyclometallated platinum(II) compounds and thallium(III) carboxylates

    NARCIS (Netherlands)

    Koten, G. van; Ploeg, A.F.M.J. van der; Vrieze, K.

    1982-01-01

    Reaction of trans-[(2-Me{2}NCH{2}C{6}H{4}{2}Pt}I{}I{] with Tl}I{}I{}I{(O{2}CR){3} (R = Me, i-Pr) gave direct elimination of Tl}I{(O{2}CR) and formation of the oxidative addition product [(2-Me{2}NCH{2}C{6}H{4}){2}Pt}I{}V{ (O{2}CR){2}], in two isomeric forms. A structure with the carbon ligands in

  1. Some Reactions of Dinitrogen Complexes of Aryldicyclopentadienyl Titanium(III) Compounds

    NARCIS (Netherlands)

    Weij, F.W. van der; Teuben, J.H.

    1976-01-01

    The reduction of dinitrogen to NH3 and N2H4 upon thermolysis of (Cp2TiR)2N2 (R = C6H5, m-, p-CH3C6H4, CH2C6H5) is reported. The amounts of NH3 obtained from the reactions of (Cp2TiR)2N2 with sodium naphthalene, n-BuLi and i-PrMgCl are discussed.

  2. Lindley frailty model for a class of compound Poisson processes

    Science.gov (United States)

    Kadilar, Gamze Özel; Ata, Nihal

    2013-10-01

    The Lindley distribution gain importance in survival analysis for the similarity of exponential distribution and allowance for the different shapes of hazard function. Frailty models provide an alternative to proportional hazards model where misspecified or omitted covariates are described by an unobservable random variable. Despite of the distribution of the frailty is generally assumed to be continuous, it is appropriate to consider discrete frailty distributions In some circumstances. In this paper, frailty models with discrete compound Poisson process for the Lindley distributed failure time are introduced. Survival functions are derived and maximum likelihood estimation procedures for the parameters are studied. Then, the fit of the models to the earthquake data set of Turkey are examined.

  3. Effect of Selected Mercapto Flavor Compounds on Acrylamide Elimination in a Model System

    Directory of Open Access Journals (Sweden)

    Zhiyong Xiong

    2017-05-01

    Full Text Available The effect of four mercapto flavor compounds (1,2-ethanedithiol, 1-butanethiol, 2-methyl-3-furanthiol, and 2-furanmethanethiol on acrylamide elimination were investigated in model systems. The obtained results showed that mercaptans assayed were effective in elimination arylamide in a model system. Their reactivities for decreasing acrylamide content depended on mercaptan’s molecular structure and acrylamide disappearance decreased in the following order: 1,2-ethanedithiol > 2-methyl-3-furanthiol > 1-butanethiol > 2-furanmethanethiol. Mercaptans were added to acrylamide to produce the corresponding 3-(alkylthio propionamides. This reaction was irreversible and only trace amounts of acrylamide were formed by thermal heating of 3-(alkylthio propanamide. Although a large amount disappeared, only part of the acrylamide conversed into 3-(alkylthio propionamides. All of these results constitute a fundamental proof of the complexity of the reactions involved in the removal of free acrylamide in foods. This implies mercapto flavor/aroma may directly or indirectly reduce the level of acrylamide in food processing. This study could be regarded as a pioneer contribution on acrylamide elimination in a model system by the addition of mercapto flavor compounds.

  4. On the description of the (HI, xn) reaction excitation functions for the case of weakly fissioning compound nuclei

    International Nuclear Information System (INIS)

    Kamanin, V.V.; Karamyan, S.A.

    1980-01-01

    A possibility to obtain parameters of nuclear temperature and critical angular momentum for the compound nucleus production on the base of the (HI, xn) reaction excitation function description are considered for the case of weakly fissioning nuclei. Experimental data on 152 Sm( 12 C, 2n) 162 Er, 148 Nd( 16 O, 3n) 161 Er, sup(150)Nd(sup(16)O, 3-5n)sup(163-161)Er, sup(148)Nd(sup(18)O, 4-5n)sup(162,161)Er, sup(118)Sn(sup(40)Ar, 5-6n)sup(153,152)Er and sup(74)Ge(sup(84)Kr, 5-6n)sup(153,152)Er reactions are discussed. The formulae, taking into accout the distribution of compound nuclei in angular momentum and competition between channels of the neutron and γ-ray emission, are given. The formulae are applied for the description of the excitation functions, characterized by a good accuracy of the particle energy measuring. A satisfactory accordance between the calculation and experiment is achieved. The conclusion on sensitivity of the nuclear temperature values to exact evaluation of competition between the neutron and γ-ray emission channels is drawn

  5. Reaction of intermetallic compounds of the ScT composition (T=Ag, Cu, Zn, Ni) with hydrogen

    International Nuclear Information System (INIS)

    Shilkin, S.P.; Volkova, L.S.; Tarasov, B.P.

    1995-01-01

    Reaction of intermetallic compounds of ScT composition (T=Ag, Cu, Zn, Ni), crystallized in CsCl structural type, with hydrogen at 0.2-10 MPa pressure and 293-673 K temperature is studied by chemical, x-ray phase and complex thermogravimetry analysis methods. It is shown that under such conditions hydrogen absorption by ScAg and ScCu is accompanied by the decay of their source matrices into scandium dihydride and metal silver and copper respectively. For ScZn a fine-dispersion mixture of scandium dihydride with zinc and hydride phase of a new zinc-containing intermetallic compound appears to be the finite reaction product. In case of ScNi a hydride phase of ScNiH 2.6 composition is produced, which is crystallized in a rhombic syngony with the lattice periods: a=0.5281±0.0007, b=0.7393±0.0009 and c=0.3327±0.0004 nm. 9 refs.; 2 tabs

  6. Investigation on chemistry of model compounds of technetium radiopharmaceuticals

    International Nuclear Information System (INIS)

    Muenze, R.; Hartmann, E.

    1983-01-01

    The report summarized experimental and theoretical results concerning the chemical structures and the biodistribution of hydrophilic technetium chelates with hydroxycarboxylic and aminopolycarboxylic acids, thiol compounds and aliphatic and aromatic nitrogen compounds as ligands. Methods which are suitable for synthesizing and characterizing defined chelates of Tc(V), Tc(IV) and Tc(III) have been developed for crystlline substances and species in solution, respectively. For certain types of technetium chelates three dimensional structure models were calculated from atomic parameters. The electron energies and electron distribution of Tc(V) thiol compounds were calculated by quantum chemical methods in order to interprete physical properties of these substances. Biodistribution studies revealed relationships between the osteotropic behaviour and the structure of phosphorous and non-phosphorous technetium chelates and between the kidney uptake and ligand exchange ability of Tc(V) hydroxycarboxylates. Important parameters for the production of technetium-99m kits have been elaborated and used for the optimization of radiopharmaceuticals (bone-, kidney and hepatobiliaer agents). (author)

  7. Activated by Combined Magnrtic Field Gravitropic Reaction Reply on Nanodose of Biologicaly Active Compounds

    Science.gov (United States)

    Sheykina, Nadezhda; Bogatina, Nina

    The new science direction nanotechnologies initiated a big jump in the pharmacology and medicine. This leads to the big development of homeopathy. The most interest appeared while investigating of the reaction of biological object on the nano dose of iologically substances. The changing of concentration (in nmol/l) of biologically active material is also possible during weak energy action. For instance, weak combined magnetic field may change a little the concentration of ions that are oriented parallel to the external magnetic field and, by the analogy with said above, lead to the similar effects. Simple estimations give the value for the threshold to the magnetic field by two orders smaller than the geomagnetic field. By this investigation we wanted to understand whether the analogy in the action of nano dose of biologically active substances and weak combined magnetic field presents and whether the action of one of these factors may be replaced by other one. The effect of one of biologically active substances NPA (Naphtyl-Phtalame Acid) solution with the concentration 0.01 mol/l on the gravitropic reaction of cress roots was investigated. It was shown that its effect was the inhibition of cress roots gravitropic reaction. The same inhibition was achieved by the combined magnetic field action on the cress roots, germinated in water. The alternative component of the combined magnetic field coincided formally with the cyclotron frequency of NPA ions. So the analogy in the action of nano dose of biologically active substances and weak combined magnetic field was shown. The combined magnetic field using allows to decrease sufficiently the dose of biologically active substances. This fact can be of great importance in pharmacy and medicine.

  8. Cellular automaton model of mass transport with chemical reactions

    International Nuclear Information System (INIS)

    Karapiperis, T.; Blankleider, B.

    1993-10-01

    The transport and chemical reactions of solutes are modelled as a cellular automaton in which molecules of different species perform a random walk on a regular lattice and react according to a local probabilistic rule. The model describes advection and diffusion in a simple way, and as no restriction is placed on the number of particles at a lattice site, it is also able to describe a wide variety of chemical reactions. Assuming molecular chaos and a smooth density function, we obtain the standard reaction-transport equations in the continuum limit. Simulations on one-and two-dimensional lattices show that the discrete model can be used to approximate the solutions of the continuum equations. We discuss discrepancies which arise from correlations between molecules and how these discrepancies disappear as the continuum limit is approached. Of particular interest are simulations displaying long-time behaviour which depends on long-wavelength statistical fluctuations not accounted for by the standard equations. The model is applied to the reactions a + b ↔ c and a + b → c with homogeneous and inhomogeneous initial conditions as well as to systems subject to autocatalytic reactions and displaying spontaneous formation of spatial concentration patterns. (author) 9 figs., 34 refs

  9. Hydrodeoxygenation of O-containing polycyclic model compounds using a novel organometallic catalyst-precursor

    Energy Technology Data Exchange (ETDEWEB)

    Kirby, S.R.; Song, C.S.; Schobert, H.H. [Pennsylvania State University, University Park, PA (United States). Dept. of Materials Science and Engineering

    1996-09-05

    Compounds containing oxygen functional groups, especially phenols, are undesirable components of coal-derived liquids. Removal of these compounds from the products of coal liquefaction is required. A beneficial alternative would be the removal of these compounds, or the prevention of their formation, during the liquefaction reaction itself, rather than as a separate processing step. A novel organometallic catalyst precursor containing Co and Mo has been studied as a potential hydrogenation catalyst for coal liquefaction. To ascertain the hydrodeoxygenation activity of this catalyst under liquefaction conditions, model compounds were investigated. Anthrone, 2,6-di-r-btuyl-4-methyl-phenol, dinaphthyl ether and xanthene were reacted in the presence of the Co-Mo catalyst precursor and a precursor containing only Mo over a range of temperatures, providing a comparison of conversions to deoxygenated products. These conversions give an indication of the hydrodeoxygenating abilities of organometallic catalyst precursors within a coal liquefaction system. For example, at 400{degree}C dinaphthyl ether was converted 100% (4.5% O-containing products) in the presence of the Co-Mo organometallic precursor, compared to 76.5% conversion (7.4% O-products) in the presence of the Mo catalyst.

  10. Modeling Electric Double-Layers Including Chemical Reaction Effects

    DEFF Research Database (Denmark)

    Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.

    2014-01-01

    A physicochemical and numerical model for the transient formation of an electric double-layer between an electrolyte and a chemically-active flat surface is presented, based on a finite elements integration of the nonlinear Nernst-Planck-Poisson model including chemical reactions. The model works...... for symmetric and asymmetric multi-species electrolytes and is not limited to a range of surface potentials. Numerical simulations are presented, for the case of a CaCO3 electrolyte solution in contact with a surface with rate-controlled protonation/deprotonation reactions. The surface charge and potential...... are determined by the surface reactions, and therefore they depends on the bulk solution composition and concentration...

  11. A Compound Model for the Origin of Earth's Water

    Science.gov (United States)

    Izidoro, A.; de Souza Torres, K.; Winter, O. C.; Haghighipour, N.

    2013-04-01

    One of the most important subjects of debate in the formation of the solar system is the origin of Earth's water. Comets have long been considered as the most likely source of the delivery of water to Earth. However, elemental and isotopic arguments suggest a very small contribution from these objects. Other sources have also been proposed, among which local adsorption of water vapor onto dust grains in the primordial nebula and delivery through planetesimals and planetary embryos have become more prominent. However, no sole source of water provides a satisfactory explanation for Earth's water as a whole. In view of that, using numerical simulations, we have developed a compound model incorporating both the principal endogenous and exogenous theories, and investigating their implications for terrestrial planet formation and water delivery. Comets are also considered in the final analysis, as it is likely that at least some of Earth's water has cometary origin. We analyze our results comparing two different water distribution models, and complement our study using the D/H ratio, finding possible relative contributions from each source and focusing on planets formed in the habitable zone. We find that the compound model plays an important role by showing greater advantage in the amount and time of water delivery in Earth-like planets.

  12. A COMPOUND MODEL FOR THE ORIGIN OF EARTH'S WATER

    International Nuclear Information System (INIS)

    Izidoro, A.; Winter, O. C.; De Souza Torres, K.; Haghighipour, N.

    2013-01-01

    One of the most important subjects of debate in the formation of the solar system is the origin of Earth's water. Comets have long been considered as the most likely source of the delivery of water to Earth. However, elemental and isotopic arguments suggest a very small contribution from these objects. Other sources have also been proposed, among which local adsorption of water vapor onto dust grains in the primordial nebula and delivery through planetesimals and planetary embryos have become more prominent. However, no sole source of water provides a satisfactory explanation for Earth's water as a whole. In view of that, using numerical simulations, we have developed a compound model incorporating both the principal endogenous and exogenous theories, and investigating their implications for terrestrial planet formation and water delivery. Comets are also considered in the final analysis, as it is likely that at least some of Earth's water has cometary origin. We analyze our results comparing two different water distribution models, and complement our study using the D/H ratio, finding possible relative contributions from each source and focusing on planets formed in the habitable zone. We find that the compound model plays an important role by showing greater advantage in the amount and time of water delivery in Earth-like planets.

  13. Neurotoxicity in Preclinical Models of Occupational Exposure to Organophosphorus Compounds

    Science.gov (United States)

    Voorhees, Jaymie R.; Rohlman, Diane S.; Lein, Pamela J.; Pieper, Andrew A.

    2017-01-01

    Organophosphorus (OPs) compounds are widely used as insecticides, plasticizers, and fuel additives. These compounds potently inhibit acetylcholinesterase (AChE), the enzyme that inactivates acetylcholine at neuronal synapses, and acute exposure to high OP levels can cause cholinergic crisis in humans and animals. Evidence further suggests that repeated exposure to lower OP levels insufficient to cause cholinergic crisis, frequently encountered in the occupational setting, also pose serious risks to people. For example, multiple epidemiological studies have identified associations between occupational OP exposure and neurodegenerative disease, psychiatric illness, and sensorimotor deficits. Rigorous scientific investigation of the basic science mechanisms underlying these epidemiological findings requires valid preclinical models in which tightly-regulated exposure paradigms can be correlated with neurotoxicity. Here, we review the experimental models of occupational OP exposure currently used in the field. We found that animal studies simulating occupational OP exposures do indeed show evidence of neurotoxicity, and that utilization of these models is helping illuminate the mechanisms underlying OP-induced neurological sequelae. Still, further work is necessary to evaluate exposure levels, protection methods, and treatment strategies, which taken together could serve to modify guidelines for improving workplace conditions globally. PMID:28149268

  14. Deep brain stimulation: custom-made silicone-coated pulse-generator implantation after allergic reaction to generator compounds.

    Science.gov (United States)

    Anthofer, Judith; Herbst, Andreas; Janzen, Annettte; Lange, Max; Brawanski, Alexander; Schlaier, Juergen

    2018-02-01

    Deep brain stimulation for Parkinson's disease has become an established treatment option in recent years. The method and its application in clinical practice has proved to be safe and effective. Nevertheless, procedure-related and hardware-related complications occur. We present a rare case of a patient with an allergic reaction to the impulse generator. The patient suffered from delayed wound-healing deficits with several wound revisions and generator repositionings. After diagnosis of an allergic reaction to components of the generator, a custom-made silicon-coated model was implanted. Hereafter, no wound healing-deficit occurred throughout long-term follow-up. Allergic reaction to hardware components may lead to wound-healing deficits. In such cases, custom-made silicon-coated models may be an effective treatment option.

  15. Stereoselective synthesis of organosulfur compounds incorporating N-aromatic heterocyclic motifs and quaternary carbon centers via a sulfa-Michael triggered tandem reaction.

    Science.gov (United States)

    Qin, Tianyou; Cheng, Lu; Zhang, Sean Xiao-An; Liao, Weiwei

    2015-06-14

    A novel sulfa-Michael addition (SMA)-triggered tandem reaction was developed by combining a SMA reaction with a simultaneous rearomatization process utilizing a less reactive carbonyl group as an intramolecular electrophile partner, which provided a unique synthetic route to access various organosulfur compounds incorporating an N-aromatic heterocyclic motif and quaternary carbon centers.

  16. Implementation of a vibrationally linked chemical reaction model for DSMC

    Science.gov (United States)

    Carlson, A. B.; Bird, Graeme A.

    1994-01-01

    A new procedure closely linking dissociation and exchange reactions in air to the vibrational levels of the diatomic molecules has been implemented in both one- and two-dimensional versions of Direct Simulation Monte Carlo (DSMC) programs. The previous modeling of chemical reactions with DSMC was based on the continuum reaction rates for the various possible reactions. The new method is more closely related to the actual physics of dissociation and is more appropriate to the particle nature of DSMC. Two cases are presented: the relaxation to equilibrium of undissociated air initially at 10,000 K, and the axisymmetric calculation of shuttle forebody heating during reentry at 92.35 km and 7500 m/s. Although reaction rates are not used in determining the dissociations or exchange reactions, the new method produces rates which agree astonishingly well with the published rates derived from experiment. The results for gas properties and surface properties also agree well with the results produced by earlier DSMC models, equilibrium air calculations, and experiment.

  17. Reactions of H-radicals with aromatic halogeno compounds in aqueous solutions

    International Nuclear Information System (INIS)

    Lichtscheidl, J.; Getoff, N.

    1979-01-01

    The spectroscopic and kinetic data of the short lived intermediates obtained by the attack of H-radicals on fluoro-, chloro-, bromobenzene, benzylchloride and phenethylchloride in aqueous solutions were studied by pulse radiolysis technique. The first three yield cyclohexadienylradicals (k equals 1-1.5 x 10 9 dm 3 mol -1 s -1 ) with chatacteristic absorption maxima in the region 220-330 nm. In the case of benzylchloride a quantitative abstraction of chlorine by the H-atoms is observed (k = 9.5 x 10 8 dm 3 mol -1 s -1 ) leading to the formation of the benzylradical (Λsub(max)=257, 303, 317.5 nm). The attack of H-atoms on phenethylchloride can occur on the aromatic ring forming also a cyclohexadienylradical (k = 2.0 x 10 9 dm 3 mol -1 s -1 , lambdasub(max)=317, 323 nm) as well as on the side chain (k = 1.5 x 10 8 dm 3 mol -1 s -1 ) yielding H 2 . The intermediates decay according to a second order reaction with k = 2 to 4.6 x 10 9 dm 3 mol -1 s -1 . To elucidate reaction mechanisms, steady state radiolysis experiments on the same systems were performed. (auth.)

  18. Mechanistic interpretation of glass reaction: Input to kinetic model development

    International Nuclear Information System (INIS)

    Bates, J.K.; Ebert, W.L.; Bradley, J.P.; Bourcier, W.L.

    1991-05-01

    Actinide-doped SRL 165 type glass was reacted in J-13 groundwater at 90 degree C for times up to 278 days. The reaction was characterized by both solution and solid analyses. The glass was seen to react nonstoichiometrically with preferred leaching of alkali metals and boron. High resolution electron microscopy revealed the formation of a complex layer structure which became separated from the underlying glass as the reaction progressed. The formation of the layer and its effect on continued glass reaction are discussed with respect to the current model for glass reaction used in the EQ3/6 computer simulation. It is concluded that the layer formed after 278 days is not protective and may eventually become fractured and generate particulates that may be transported by liquid water. 5 refs., 5 figs. , 3 tabs

  19. Anaphylactic reaction to probiotics. Cow's milk and hen's egg allergens in probiotic compounds.

    Science.gov (United States)

    Martín-Muñoz, María Flora; Fortuni, Monserrat; Caminoa, Magdalena; Belver, Teresa; Quirce, Santiago; Caballero, Teresa

    2012-12-01

    Probiotics are used in the treatment of allergic diseases. We investigated the safety of probiotics for subjects with food allergy. Labels of probiotics commercially available in Spain were examined to assess their content of cow's milk or hen's egg. Skin prick tests with these compounds (20 mg/ml) were performed in five children allergic to cow's milk, five children allergic to hen's white egg, and five control subjects non-allergic to food. Three serum pools: I (positive-specific IgE to cow's milk and hen's egg white proteins), II (positive-specific IgE to cow's milk and negative to hen's egg white proteins), and III (negative-specific IgE to cow's milk and positive to hen's egg white proteins) were used to detect cow's milk and hen's egg white allergens in probiotics. ImmunoCAP(®) (Phadia), in-house ELISA, SDS-PAGE immunoblotting, and inhibition studies of these assays were performed. Proteins were quantified by enzyme-immunoassay. Eleven probiotics were studied. No label advertised about egg content, eight labels warned about lactose, lactic acid or cow's milk, one label claimed to be milk-free, and two gave no information. Cow's milk proteins were detected, by at least one lab technique, in 10/11 probiotics, three over 2.5 mg/kg (21, 52, 112 mg/kg). Hen's egg white proteins were detected in 3/11 probiotics, only one had more than 2.5 mg/kg (47 mg/kg). Probiotic compounds may contain hidden allergens of food and may not be safe for subjects with allergy to cow's milk or hen's egg. © 2012 John Wiley & Sons A/S.

  20. Characteristic antioxidant activity and comprehensive flavor compound profile of scallop (Chlamys farreri) mantle hydrolysates-ribose Maillard reaction products.

    Science.gov (United States)

    Han, Jia-Run; Yan, Jia-Nan; Sun, Shi-Guang; Tang, Yue; Shang, Wen-Hui; Li, Ao-Ting; Guo, Xiao-Kun; Du, Yi-Nan; Wu, Hai-Tao; Zhu, Bei-Wei; Xiong, Youling L

    2018-09-30

    The objective of the present study was to improve the utilization of scallop (Chlamys farreri) byproducts by using Maillard reaction. Scallop mantle hydrolysates (SMHs) were prepared using neutrase then reacted with ribose. Thirty-four peptides were identified from SMHs by UPLC-Q-TOF-MS, and the abundance of Asp and Lys suggested the strong Maillard reactivity. The formation of Schiff's base as well as modification of amide I, II and III bands in Maillard reaction products (MRPs) was confirmed by ultraviolet-visible, fluorescence, and Fourier transform infrared spectroscopy. Thirty volatile compounds were produced by the reaction of SMHs with ribose. Moreover, MRPs with enhanced radical scavenging and anti-linoleic acid peroxidation activities over SMHs promoted the survival and reduced the DNA damage of HepG2 cells treated with hydrogen peroxide. These results suggest that SMHs-ribose MRPs can be potentially used as food antioxidant for suppressing of lipid oxidation or protecting of cell from oxidative damage. Copyright © 2018 Elsevier Ltd. All rights reserved.

  1. Regression analysis of a chemical reaction fouling model

    International Nuclear Information System (INIS)

    Vasak, F.; Epstein, N.

    1996-01-01

    A previously reported mathematical model for the initial chemical reaction fouling of a heated tube is critically examined in the light of the experimental data for which it was developed. A regression analysis of the model with respect to that data shows that the reference point upon which the two adjustable parameters of the model were originally based was well chosen, albeit fortuitously. (author). 3 refs., 2 tabs., 2 figs

  2. Aquatic pathways model to predict the fate of phenolic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Aaberg, R.L.; Peloquin, R.A.; Strenge, D.L.; Mellinger, P.J.

    1983-04-01

    Organic materials released from energy-related activities could affect human health and the environment. To better assess possible impacts, we developed a model to predict the fate of spills or discharges of pollutants into flowing or static bodies of fresh water. A computer code, Aquatic Pathways Model (APM), was written to implement the model. The computer programs use compartmental analysis to simulate aquatic ecosystems. The APM estimates the concentrations of chemicals in fish tissue, water and sediment, and is therefore useful for assessing exposure to humans through aquatic pathways. The APM will consider any aquatic pathway for which the user has transport data. Additionally, APM will estimate transport rates from physical and chemical properties of chemicals between several key compartments. The major pathways considered are biodegradation, fish and sediment uptake, photolysis, and evaporation. The model has been implemented with parameters for distribution of phenols, an important class of compounds found in the water-soluble fractions of coal liquids. Current modeling efforts show that, in comparison with many pesticides and polyaromatic hydrocarbons (PAH), the lighter phenolics (the cresols) are not persistent in the environment. The properties of heavier molecular weight phenolics (indanols, naphthols) are not well enough understood at this time to make similar judgements. For the twelve phenolics studied, biodegradation appears to be the major pathway for elimination from aquatic environments. A pond system simulation (using APM) of a spill of solvent refined coal (SRC-II) materials indicates that phenol, cresols, and other single cyclic phenolics are degraded to 16 to 25 percent of their original concentrations within 30 hours. Adsorption of these compounds into sediments and accumulation by fish was minor.

  3. Modeling human behaviors and reactions under dangerous environment.

    Science.gov (United States)

    Kang, J; Wright, D K; Qin, S F; Zhao, Y

    2005-01-01

    This paper describes the framework of a real-time simulation system to model human behavior and reactions in dangerous environments. The system utilizes the latest 3D computer animation techniques, combined with artificial intelligence, robotics and psychology, to model human behavior, reactions and decision making under expected/unexpected dangers in real-time in virtual environments. The development of the system includes: classification on the conscious/subconscious behaviors and reactions of different people; capturing different motion postures by the Eagle Digital System; establishing 3D character animation models; establishing 3D models for the scene; planning the scenario and the contents; and programming within Virtools Dev. Programming within Virtools Dev is subdivided into modeling dangerous events, modeling character's perceptions, modeling character's decision making, modeling character's movements, modeling character's interaction with environment and setting up the virtual cameras. The real-time simulation of human reactions in hazardous environments is invaluable in military defense, fire escape, rescue operation planning, traffic safety studies, and safety planning in chemical factories, the design of buildings, airplanes, ships and trains. Currently, human motion modeling can be realized through established technology, whereas to integrate perception and intelligence into virtual human's motion is still a huge undertaking. The challenges here are the synchronization of motion and intelligence, the accurate modeling of human's vision, smell, touch and hearing, the diversity and effects of emotion and personality in decision making. There are three types of software platforms which could be employed to realize the motion and intelligence within one system, and their advantages and disadvantages are discussed.

  4. Synthesis of α-amino-1,3-dicarbonyl compounds via Ugi flow chemistry reaction: access to functionalized 1,2,3-triazoles.

    Science.gov (United States)

    Vasconcelos, Stanley N S; Fornari, Evelin; Caracelli, Ignez; Stefani, Hélio A

    2017-11-01

    The Ugi multicomponent reaction has been used as an important synthetic route to obtain compounds with potential biological activity. We present the rapid and efficient synthesis of [Formula: see text]-amino-1,3-dicarbonyl compounds in moderate to good yields via Ugi flow chemistry reactions performed with a continuous flow reactor. Such [Formula: see text]-amino-1,3-dicarbonyl compounds can act as precursors for the production of [Formula: see text]-amino acids via hydrolysis of the ethyl ester group as well as building blocks for the synthesis of novel compounds with the 1,2,3-triazole ring. The [Formula: see text]-amino acid derivatives of the Ugi flow chemistry reaction products were then used for dipeptide synthesis.

  5. A model for reaction rates in turbulent reacting flows

    Science.gov (United States)

    Chinitz, W.; Evans, J. S.

    1984-01-01

    To account for the turbulent temperature and species-concentration fluctuations, a model is presented on the effects of chemical reaction rates in computer analyses of turbulent reacting flows. The model results in two parameters which multiply the terms in the reaction-rate equations. For these two parameters, graphs are presented as functions of the mean values and intensity of the turbulent fluctuations of the temperature and species concentrations. These graphs will facilitate incorporation of the model into existing computer programs which describe turbulent reacting flows. When the model was used in a two-dimensional parabolic-flow computer code to predict the behavior of an experimental, supersonic hydrogen jet burning in air, some improvement in agreement with the experimental data was obtained in the far field in the region near the jet centerline. Recommendations are included for further improvement of the model and for additional comparisons with experimental data.

  6. Advanced modeling of reaction cross sections for light nuclei

    International Nuclear Information System (INIS)

    Resler, D.A.

    1991-01-01

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

  7. Photometric investigation of tungsten (6) reaction with monoazo compound based on pyrogallol

    International Nuclear Information System (INIS)

    Gambarov, D.G.; Gusejnov, A.G.

    1980-01-01

    The possibility has been studied to use a new monoazo compound 2,3,4-trihydroxy-4'-sulfoazobenzene (TSAB) for the photometric determination of tungsten in steels. The maximum yield of W(6) complex is observed in the interval from 0.3 NHCl to pH2. The maximum absorption of the complex is observed at 460 nm and that of reagent - at 380 nm. The complex coloring immediately develops and in stable for more than one day. Molar coefficient of complex extinctior equals 43000+-300. Tungsten concentration interval being determined in 0.3 N HCl is 10-140 μg/25 ml. Tungsten determination technique in chromium-nickel-tungsten and chromium-silicon-nickel steels is given. If steel samples contain Mo > 0.1 mg, Y > 0.2 mg, Zr > 1.0 mg, Fe > 0.03 mg and Si > 0.3 mg then it is necessary to separate Mo, Y and Zr beforehand. Fe and Si are respectively well camouflaged by ascorbic acid and EDTA

  8. Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration – Literature Review

    Energy Technology Data Exchange (ETDEWEB)

    Krupka, Kenneth M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cantrell, Kirk J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McGrail, B. Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2010-09-01

    Permanent storage of anthropogenic CO2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO2 sequestration. A review of thermodynamic data for CO2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO2 and CH4 gases, carbonate aqueous species, and carbonate minerals. Values of ΔfG298° and/or log Kr,298° are available for essentially all of these compounds. However, log Kr,T° or heat capacity values at temperatures above 298 K exist for less than

  9. Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration - Literature Review

    International Nuclear Information System (INIS)

    Krupka, Kenneth M.; Cantrell, Kirk J.; McGrail, B. Peter

    2010-01-01

    Permanent storage of anthropogenic CO 2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO 2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO 2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO 2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO 2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO 2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO 2 sequestration. A review of thermodynamic data for CO 2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO 2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO 2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO 2 and CH 4 gases, carbonate aqueous species, and carbonate minerals. Values of Δ f G 298 o and/or log K r,298 o are available for essentially all of these compounds. However, log K r,T o or heat capacity values at temperatures above 298 K exist

  10. Oxidative treatment of bromide-containing waters: formation of bromine and its reactions with inorganic and organic compounds--a critical review.

    Science.gov (United States)

    Heeb, Michèle B; Criquet, Justine; Zimmermann-Steffens, Saskia G; von Gunten, Urs

    2014-01-01

    Bromide (Br(-)) is present in all water sources at concentrations ranging from ≈ 10 to >1000 μg L(-1) in fresh waters and about 67 mg L(-1) in seawater. During oxidative water treatment bromide is oxidized to hypobromous acid/hypobromite (HOBr/OBr(-)) and other bromine species. A systematic and critical literature review has been conducted on the reactivity of HOBr/OBr(-) and other bromine species with inorganic and organic compounds, including micropollutants. The speciation of bromine in the absence and presence of chloride and chlorine has been calculated and it could be shown that HOBr/OBr(-) are the dominant species in fresh waters. In ocean waters, other bromine species such as Br2, BrCl, and Br2O gain importance and may have to be considered under certain conditions. HOBr reacts fast with many inorganic compounds such as ammonia, iodide, sulfite, nitrite, cyanide and thiocyanide with apparent second-order rate constants in the order of 10(4)-10(9)M(-1)s(-1) at pH 7. No rate constants for the reactions with Fe(II) and As(III) are available. Mn(II) oxidation by bromine is controlled by a Mn(III,IV) oxide-catalyzed process involving Br2O and BrCl. Bromine shows a very high reactivity toward phenolic groups (apparent second-order rate constants kapp ≈ 10(3)-10(5)M(-1)s(-1) at pH 7), amines and sulfamides (kapp ≈ 10(5)-10(6)M(-1)s(-1) at pH 7) and S-containing compounds (kapp ≈ 10(5)-10(7)M(-1)s(-1) at pH 7). For phenolic moieties, it is possible to derive second-order rate constants with a Hammett-σ-based QSAR approach with [Formula in text]. A negative slope is typical for electrophilic substitution reactions. In general, kapp of bromine reactions at pH 7 are up to three orders of magnitude greater than for chlorine. In the case of amines, these rate constants are even higher than for ozone. Model calculations show that depending on the bromide concentration and the pH, the high reactivity of bromine may outweigh the reactions of chlorine during

  11. Studies on ligand exchange reaction of functionalized mercaptothiadiazole compounds onto citrate capped gold nanoparticles

    International Nuclear Information System (INIS)

    Kalimuthu, Palraj; John, S. Abraham

    2010-01-01

    Mercaptothiadiazole ligands functionalized with thiol (2,5-dimercapto-1,3,4-thiadiazole (DMT)) and methyl (5-methyl-2-mercapto-1,3,4-thiadiazole (MMT)) groups capped onto citrate capped gold nanoparticles (C-AuNPs) by ligand exchange reaction was investigated by UV-vis spectroscopy, FT-IR spectroscopy and transmission electron microscopy (TEM) techniques. The surface plasmon resonance band at 522 nm for C-AuNPs was shifted to 530 nm after capping with DMT whereas an additional band was observed at 630 nm due to aggregation in addition to a shift in the band at 522 nm after capping of MMT onto C-AuNPs. Thus, capping of DMT onto C-AuNPs leads to the formation of stable AuNPs while capping of MMT leads to the formation of unstable AuNPs. FT-IR studies show that the citrate ions were completely replaced by both DMT and MMT ligands from the AuNPs. TEM images indicate that the size and shape of the AuNPs remain same after capping of these ligands.

  12. Kinetics of reaction of peroxynitrite with selenium- and sulfur-containing compounds

    DEFF Research Database (Denmark)

    Storkey, Corin; Pattison, David I.; Ignasiak, Marta T.

    2015-01-01

    with peroxynitrite with high rate constants. Low molecular mass selenols react particularly rapidly with peroxynitrite, with second order rate constants k2 in the range 5.1×105-1.9×106 M-1 s-1, and 250-830 fold faster than the corresponding thiols (RSH) and many other endogenous biological targets. Reactions......Peroxynitrite (the physiological mixture of ONOOH and its anion, ONOO-) is a powerful biologically-relevant oxidant capable of oxidizing and damaging a range of important targets including sulfides, thiols, lipids, proteins, carbohydrates and nucleic acids. Excessive production of peroxynitrite...... of peroxynitrite with selenides, including selenosugars are approximately 15-fold faster than their sulfur homologs with k2 approximately 2.5×103 M-1 s-1. The rate constants for diselenides and sulfides were slower with k2 0.72-1.3×103 M-1 s-1 and approximately 2.1×102 M-1 s-1 respectively. These studies...

  13. The influence of vegetable bioactive compounds on systemic immune reactions to ionizing radiation action

    International Nuclear Information System (INIS)

    Coretchi, Liuba; Plavan, Irina; Bahnarel, Ion; Rosca, Andrei

    2015-01-01

    The paper presents the summary of the scientific results analysis of the published in the last 10 years studies of the influence of secondary metabolites essential oils and essential-oil plants extracts, on the resistance/sensitivity of the animal and human body to the action of ionizing radiation. An essential problem is the development of new nanotechnologies for mitigation the onset of side effects caused by the use of ionizing radiation therapy of patients with different types of cancer. Widespread application of phyto therapy empiric reveals the beneficial effect of essential oils and essential-oil plants extracts on the immune system. The considered substances have natural antioxidant properties and contribute to the elimination of free radicals which are formed in the body under the action of stress, including ionizing radiation. This reveals about their use in mitigation of ionizing radiation action effects, as a radio protector agent. Unlike other preparations, used to activate the immune system, essential oils at low concentrations show a long-lasting system immune stimulation action. More of that, during their administration the onset of adverse reactions have not been demonstrated. (authors)

  14. Modeling the Thiophene HDS reaction on a molecular level

    NARCIS (Netherlands)

    Diemann, E.; Weber, T.; Müller, A.

    1994-01-01

    The structure of MoS2/Al2O3 catalyst and the initial step of the hydrodesulfurization (HDS) reaction using an experimental model have been studied by in situ Raman-, infrared emission (IRE)-, inelastic electron tunneling (IET)-spectroscopy and thermal desorption measurements accompanied by molecular

  15. An Analysis of Descriptors of Volatile Organic Compounds and Their Impact on Rate Constant for Reaction with Hydroxyl Radicals

    Science.gov (United States)

    2018-05-01

    5e. TASK NUMBER 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) Excet, Inc.; 2108 Emmorton Park Road , Suite 201...SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) Defense Threat Reduction Agency, 8725 John J. Kingman Road , MSC 6201, Fort Belvoir, VA 22060...bond descriptors may be useful for the construction of predictive modeling. 15. SUBJECT TERMS Volatile organic compound (VOC) Chemical descriptors

  16. Modelling and experimental evaluation of reaction kinetics in reactive extraction for chiral separation of amines, amino acids and amino-alcohols

    NARCIS (Netherlands)

    Steensma, M.; Kuipers, N.J.M.; de Haan, A.B.; Kwant, Gerard

    2007-01-01

    This paper reports on determination of the intrinsic reaction kinetics in reactive extraction of chiral compounds. It is important to know the mass transfer rates and reaction kinetics separately for a reliable scale-up. A kinetic model is developed to interpret the experimental data from the

  17. An approach to accidents modeling based on compounds road environments.

    Science.gov (United States)

    Fernandes, Ana; Neves, Jose

    2013-04-01

    The most common approach to study the influence of certain road features on accidents has been the consideration of uniform road segments characterized by a unique feature. However, when an accident is related to the road infrastructure, its cause is usually not a single characteristic but rather a complex combination of several characteristics. The main objective of this paper is to describe a methodology developed in order to consider the road as a complete environment by using compound road environments, overcoming the limitations inherented in considering only uniform road segments. The methodology consists of: dividing a sample of roads into segments; grouping them into quite homogeneous road environments using cluster analysis; and identifying the influence of skid resistance and texture depth on road accidents in each environment by using generalized linear models. The application of this methodology is demonstrated for eight roads. Based on real data from accidents and road characteristics, three compound road environments were established where the pavement surface properties significantly influence the occurrence of accidents. Results have showed clearly that road environments where braking maneuvers are more common or those with small radii of curvature and high speeds require higher skid resistance and texture depth as an important contribution to the accident prevention. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. KINETICS OF A SILICATE COMPOSITION GELATION IN PRESENCE OF REACTION RATE REGULATING COMPOUNDS

    Directory of Open Access Journals (Sweden)

    Olga Titova

    2013-12-01

    Full Text Available The influence of organic and inorganic additions on the formation rate of the silicate gels standard systems – sodium silicate solution in model fresh water was studied. As a result of the experiments were selected optimum concentrations of additives - gelation time regulators

  19. Electrophilic properties of patulin. Adduct structures and reaction pathways with 4-bromothiophenol and other model nucleophiles.

    Science.gov (United States)

    Fliege, R; Metzler, M

    2000-05-01

    The mycotoxin patulin (PAT) is believed to exert its cytotoxic and chromosome-damaging effects by forming covalent adducts with essential cellular thiols. Since the chemical structures of such adducts are unknown to date, we have studied the reaction of PAT and its O-acetylated derivative with the monofunctional thiol model compound 4-bromothiophenol (BTP), which was chosen due to analytical advantages. By means of analytical and preparative high-performance liquid chromatography, 16 adducts of PAT and 3 adducts of acetyl-PAT were isolated and their chemical structures elucidated by (1)H and (13)C NMR, IR, and UV spectroscopy. Time course studies and analysis of daughter product formation from isolated intermediate adducts led to a detailed scheme for the reaction of PAT with BTP. The structures of adducts of PAT formed with other model nucleophiles, e. g., the aliphatic thiol 2-mercaptoethanol and the aromatic amine 4-bromoaniline, were also elucidated and found to corroborate the reaction scheme. In addition, one further reaction pathway was observed with 2-mercaptoethanol, which appears to be independent from those found for BTP. Our study with model nucleophiles provides insights into the electrophilic reactivity of PAT and proved to be useful for the structure elucidation of PAT adducts with biological nucleophiles of toxicological relevance, as will be reported by Fliege and Metzler [(2000) Chem. Res. Toxicol. 13, 373-381].

  20. Reaction

    African Journals Online (AJOL)

    abp

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

  1. Interaction of arsenic compounds with model phospholipid membranes

    International Nuclear Information System (INIS)

    Jemiola-Rzeminska, Malgorzata; Rivera, Cecilia; Suwalsky, Mario; Strzalka, Kazimierz

    2007-01-01

    This study is part of a project aimed at examining the influence of arsenic on biological membranes. By the use of differential scanning calorimetry (DSC) we have followed the thermotropic behavior of multilamellar vesicles prepared from dimyristoylphosphatidylcholine (DMPC) and dimyristoylphosphatidylethanolamine (DMPE) upon incorporation of sodium arsenite (AsI), disodium arsenate (AsII), cacodylic acid (AsIII) and disodium methyl arsenate (AsIV). The effectiveness of perturbations exerted by various arsenic compounds on thermotropic phase transition was further analysed in terms of thermodynamic parameters: transition temperature, enthalpy and molar heat capacity, determined for lipid/As systems on the basis of heating and cooling scans. It is found that while it only has a slight influence on the thermotropic properties of DMPC, arsenic is able to significantly modify DMPE model membranes

  2. Modifying conjoint methods to model managers' reactions to business environmental trends : an application to modeling retailer reactions to sales trends

    NARCIS (Netherlands)

    Oppewal, H.; Louviere, J.J.; Timmermans, H.J.P.

    2000-01-01

    This article proposes and demonstrates how conjoint methods can be adapted to allow the modeling of managerial reactions to various changes in economic and competitive environments and their effects on observed sales levels. Because in general micro-level data on strategic decision making over time

  3. KINETIC MODELS STUDY OF HYDRODESULPHURIZATION VACUUM DISTILLATE REACTION

    Directory of Open Access Journals (Sweden)

    AbdulMunem A. Karim

    2013-05-01

    Full Text Available    This study deals with  kinetics of hydrodesulphurization (HDS reaction of vacuum gas oil (611-833 K which was distillated from Kirkuk crude oil and which was obtained by blending the fractions, light vacuum gas oil (611 - 650 K, medium vacuum gas oil (650-690 K, heavy vacuum gas oil (690-727 K and very heavy vacuum gas oil (727-833 K.   The vacuum gas oil was hydrotreated on a commercial cobalt-molybdenum alumina catalyst presulfied at specified conditions in a laboratory trickle bed reactor. The reaction temperature range (583-643 K,liquid hourly space velocity range (1.5-3.75 h-1 and hydrogen pressure was kept constant at 3.5 MPa with hydrogen to oil ratio about 250 lt/lt.           The conversion results for desulphurization reaction appeared to obey the second order reaction. According to this model, the rate constants for desulphurization reaction were determined. Finally, the apparent activation energy (Ea, enthalpy of activation ( H* and entropy ( S* were calculated based on the values of rate constant (k2 and were equal 80.3792 KJ/mole, 75.2974 KJ/mole and 197.493 J/mole, respectively.

  4. Transformation of technogenic compounds of Ni, Cu, Zn and Pb in different soil types in model experiment

    International Nuclear Information System (INIS)

    Ladonin, D.V.; Smirnova, M.S.; Karpukhin, M.M.; Plyaskina, O.V.

    2008-01-01

    In model experiment fractional distribution of Ni, Cu, Zn and Pb in soils artificially polluted with readily and sparingly soluble compounds (nitrates and oxides respectively) of these heavy metals was investigated. It is shown that heavy metals fractional distribution may strongly vary depending on the form in which the metal deposits in the soil. Transformation of heavy metals oxides is controlled by two main factors: solubility of an oxide and characteristics of reactions between dissolution products and the soil components

  5. Modelling biochemical reaction systems by stochastic differential equations with reflection.

    Science.gov (United States)

    Niu, Yuanling; Burrage, Kevin; Chen, Luonan

    2016-05-07

    In this paper, we gave a new framework for modelling and simulating biochemical reaction systems by stochastic differential equations with reflection not in a heuristic way but in a mathematical way. The model is computationally efficient compared with the discrete-state Markov chain approach, and it ensures that both analytic and numerical solutions remain in a biologically plausible region. Specifically, our model mathematically ensures that species numbers lie in the domain D, which is a physical constraint for biochemical reactions, in contrast to the previous models. The domain D is actually obtained according to the structure of the corresponding chemical Langevin equations, i.e., the boundary is inherent in the biochemical reaction system. A variant of projection method was employed to solve the reflected stochastic differential equation model, and it includes three simple steps, i.e., Euler-Maruyama method was applied to the equations first, and then check whether or not the point lies within the domain D, and if not perform an orthogonal projection. It is found that the projection onto the closure D¯ is the solution to a convex quadratic programming problem. Thus, existing methods for the convex quadratic programming problem can be employed for the orthogonal projection map. Numerical tests on several important problems in biological systems confirmed the efficiency and accuracy of this approach. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. Modelling of structural effects on chemical reactions in turbulent flows

    Energy Technology Data Exchange (ETDEWEB)

    Gammelsaeter, H.R.

    1997-12-31

    Turbulence-chemistry interactions are analysed using algebraic moment closure for the chemical reaction term. The coupling between turbulence and chemical length and time scales generate a complex interaction process. This interaction process is called structural effects in this work. The structural effects are shown to take place on all scales between the largest scale of turbulence and the scales of the molecular motions. The set of equations describing turbulent correlations involved in turbulent reacting flows are derived. Interactions are shown schematically using interaction charts. Algebraic equations for the turbulent correlations in the reaction rate are given using the interaction charts to include the most significant couplings. In the frame of fundamental combustion physics, the structural effects appearing on the small scales of turbulence are proposed modelled using a discrete spectrum of turbulent scales. The well-known problem of averaging the Arrhenius law, the specific reaction rate, is proposed solved using a presumed single variable probability density function and a sub scale model for the reaction volume. Although some uncertainties are expected, the principles are addressed. Fast chemistry modelling is shown to be consistent in the frame of algebraic moment closure when the turbulence-chemistry interaction is accounted for in the turbulent diffusion. The modelling proposed in this thesis is compared with experimental data for an laboratory methane flame and advanced probability density function modelling. The results show promising features. Finally it is shown a comparison with full scale measurements for an industrial burner. All features of the burner are captured with the model. 41 refs., 33 figs.

  7. Reactivity of Cork Extracts with (+)-Catechin and Malvidin-3-O-glucoside in Wine Model Solutions: Identification of a New Family of Ellagitannin-Derived Compounds (Corklins).

    Science.gov (United States)

    Azevedo, Joana; Fernandes, Ana; Oliveira, Joana; Brás, Natércia F; Reis, Sofia; Lopes, Paulo; Roseira, Isabel; Cabral, Miguel; Mateus, Nuno; de Freitas, Victor

    2017-10-04

    The aim of this study was to evaluate the reactivity of phenolic compounds extracted from cork stoppers to wine model solutions with two major wine components, namely, (+)-catechin and malvidin-3-O-glucoside. Besides the formation of some compounds already described in the literature, these reactions also yielded a new family of ellagitannin-derived compounds, named herein as corklins. This new family of compounds that were found to result from the interaction between ellagitannins in alcoholic solutions and (+)-catechin were structurally characterized by mass spectroscopy, nuclear magnetic resonance, and computational methods.

  8. Limitations of the Weissler reaction as a model reaction for measuring the efficiency of hydrodynamic cavitation.

    Science.gov (United States)

    Morison, K R; Hutchinson, C A

    2009-01-01

    The Weissler reaction in which iodide is oxidised to a tri-iodide complex (I(3)(-)) has been widely used for measurement of the intensity of ultrasonic and hydrodynamic cavitation. It was used in this work to compare ultrasonic cavitation at 24 kHz with hydrodynamic cavitation using two different devices, one a venturi and the other a sudden expansion, operated up to 8.7 bar. Hydrodynamic cavitation had a maximum efficiency of about 5 x 10(-11) moles of I(3)(-) per joule of energy compared with the maximum of almost 8 x 10(-11) mol J(-1) for ultrasonic cavitation. Hydrodynamic cavitation was found to be most effective at 10 degrees C compared with 20 degrees C and 30 degrees C and at higher upstream pressures. However, it was found that in hydrodynamic conditions, even without cavitation, I(3)(-) was consumed at a rapid rate leading to an equilibrium concentration. It was concluded that the Weissler reaction was not a good model reaction for the assessment of the effectiveness of hydrodynamic cavitation.

  9. Ionic liquid [OMIm][OAc] directly inducing oxidation cleavage of the β-O-4 bond of lignin model compounds.

    Science.gov (United States)

    Yang, Yingying; Fan, Honglei; Meng, Qinglei; Zhang, Zhaofu; Yang, Guanying; Han, Buxing

    2017-08-03

    We explored the oxidation reactions of lignin model compounds directly induced by ionic liquids under metal-free conditions. In this work, it was found that ionic liquid 1-octyl-3-methylimidazolium acetate as a solvent could promote the aerobic oxidation of lignin model compound 2-phenoxyacetophenone (1) and the yields of phenol and benzoic acid from 1 could be as high as 96% and 86%, respectively. A possible reaction pathway was proposed based on a series of control experiments. An acetate anion from the ionic liquid attacked the hydrogen from the β-carbon thereby inducing the cleavage of the C-O bond of the aromatic ether. Furthermore, it was found that 2-(2-methoxyphenoxy)-1-phenylethanone (4) with a methoxyl group could also be transformed into aromatic products in this simple reaction system and the yields of phenol and benzoic acid from 4 could be as high as 98% and 85%, respectively. This work provides a simple way for efficient transformation of lignin model compounds.

  10. Improvement on reaction model for sodium-water reaction jet code and application analysis

    International Nuclear Information System (INIS)

    Itooka, Satoshi; Saito, Yoshinori; Okabe, Ayao; Fujimata, Kazuhiro; Murata, Shuuichi

    2000-03-01

    In selecting the reasonable DBL on steam generator (SG), it is necessary to improve analytical method for estimating the sodium temperature on failure propagation due to overheating. Improvement on sodium-water reaction (SWR) jet code (LEAP-JET ver.1.30) and application analysis to the water injection tests for confirmation of code propriety were performed. On the improvement of the code, a gas-liquid interface area density model was introduced to develop a chemical reaction model with a little dependence on calculation mesh size. The test calculation using the improved code (LEAP-JET ver.1.40) were carried out with conditions of the SWAT-3·Run-19 test and an actual scale SG. It is confirmed that the SWR jet behavior on the results and the influence to analysis result of a model are reasonable. For the application analysis to the water injection tests, water injection behavior and SWR jet behavior analyses on the new SWAT-1 (SWAT-1R) and SWAT-3 (SWAT-3R) tests were performed using the LEAP-BLOW code and the LEAP-JET code. In the application analysis of the LEAP-BLOW code, parameter survey study was performed. As the results, the condition of the injection nozzle diameter needed to simulate the water leak rate was confirmed. In the application analysis of the LEAP-JET code, temperature behavior of the SWR jet was investigated. (author)

  11. The regio- and stereospecific synthesis of diarylpropenyllithium compounds from dimethylamino- and dimethylaminomethyl-substituted diarylacetylenes viatransmetallation reactions involving diarylpropenylmagnesium and tin compounds

    NARCIS (Netherlands)

    Koten, G. van; Hoedt, R.W.M. ten; Noltes, J.G.

    1979-01-01

    Dimethylamino- and dimethylaminomethyl-substituted diarylacetylenes were prepared by the Pd(PPh{3}){4}-catalyzed coupling reaction of dimethylamino- and dimethylaminomethyl-substituted aryl halides with arylacetylenes.Reaction of the asymmetric diarylacetylenes with methylmagnesium bromide in the

  12. On the (R,s,Q) Inventory Model when Demand is Modelled as a Compound Process

    NARCIS (Netherlands)

    Janssen, F.B.S.L.P.; Heuts, R.M.J.; de Kok, T.

    1996-01-01

    In this paper we present an approximation method to compute the reorder point s in a (R; s; Q) inventory model with a service level restriction, where demand is modelled as a compound Bernoulli process, that is, with a xed probability there is positive demand during a time unit, otherwise demand is

  13. Numerical Simulation of Hydrogen Combustion: Global Reaction Model and Validation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yun [School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an (China); Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, NY (United States); Liu, Yinhe, E-mail: yinheliu@mail.xjtu.edu.cn [School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an (China)

    2017-11-20

    Due to the complexity of modeling the combustion process in nuclear power plants, the global mechanisms are preferred for numerical simulation. To quickly perform the highly resolved simulations with limited processing resources of large-scale hydrogen combustion, a method based on thermal theory was developed to obtain kinetic parameters of global reaction mechanism of hydrogen–air combustion in a wide range. The calculated kinetic parameters at lower hydrogen concentration (C{sub hydrogen} < 20%) were validated against the results obtained from experimental measurements in a container and combustion test facility. In addition, the numerical data by the global mechanism (C{sub hydrogen} > 20%) were compared with the results by detailed mechanism. Good agreement between the model prediction and the experimental data was achieved, and the comparison between simulation results by the detailed mechanism and the global reaction mechanism show that the present calculated global mechanism has excellent predictable capabilities for a wide range of hydrogen–air mixtures.

  14. Numerical Simulation of Hydrogen Combustion: Global Reaction Model and Validation

    International Nuclear Information System (INIS)

    Zhang, Yun; Liu, Yinhe

    2017-01-01

    Due to the complexity of modeling the combustion process in nuclear power plants, the global mechanisms are preferred for numerical simulation. To quickly perform the highly resolved simulations with limited processing resources of large-scale hydrogen combustion, a method based on thermal theory was developed to obtain kinetic parameters of global reaction mechanism of hydrogen–air combustion in a wide range. The calculated kinetic parameters at lower hydrogen concentration (C hydrogen < 20%) were validated against the results obtained from experimental measurements in a container and combustion test facility. In addition, the numerical data by the global mechanism (C hydrogen > 20%) were compared with the results by detailed mechanism. Good agreement between the model prediction and the experimental data was achieved, and the comparison between simulation results by the detailed mechanism and the global reaction mechanism show that the present calculated global mechanism has excellent predictable capabilities for a wide range of hydrogen–air mixtures.

  15. A thermal conductivity model for U-­Si compounds

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yongfeng [Idaho National Lab. (INL), Idaho Falls, ID (United States); Andersson, Anders David Ragnar [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-02-02

    U3Si2 is a candidate for accident tolerant nuclear fuel being developed as an alternative to UO2 in commercial light water reactors (LWRs). One of its main benefits compared to UO2 is higher thermal conductivity that increases with temperature. This increase is contrary to UO2, for which the thermal conductivity decreases with temperature. The reason for the difference is the electronic origin of thermal conductivity in U3Si2, as compared to the phonon mechanism responsible for thermal transport in UO2. The phonon thermal conductivity in UO2 is unusually low for a fluorite oxide due to the strong interaction with the spins in the paramagnetic phase. The thermal conductivity of U3Si2 as well as other U-­Si compounds has been measured experimentally [1-­4]. However, for fuel performance simulations it is also critical to model the degradation of the thermal conductivity due to damage and microstructure evolution caused by the reactor environment (irradiation and high temperature). For UO2 this reduction is substantial and it has been the topic of extensive NEAMS research resulting in several publications [5, 6]. There are no data or models for the evolution of the U3Si2 thermal conductivity under irradiation. We know that the intrinsic thermal conductivities of UO2 (semi-conductor) and U3Si2 (metal) are very different, and we do not necessarily expect the dependence on damage to be the same either, which could present another advantage for the silicide fuel. In this report we summarize the first step in developing a model for the thermal conductivity of U-­Si compounds with the goal of capturing the effect of damage in U3Si2. Next year, we will focus on lattice damage. We will also attempt to assess the impact of fission gas bubbles.

  16. Semi empirical model for astrophysical nuclear fusion reactions of 1≤Z≤15

    International Nuclear Information System (INIS)

    Manjunatha, H.C.; Seenappa, L.; Sridhar, K.N.

    2017-01-01

    The fusion reaction is one of the most important reactions in the stellar evolution. Due to the complicated reaction mechanism of fusion, there is great uncertainty in the reaction rate which limits our understanding of various stellar objects. Low z elements are formed through many fusion reactions such as "4He+"1"2C→"1"6O, "1"2C+"1"2C→"2"0Ne+"4He, "1"2C+"1"2C→"2"3Na, "1"2C+"1"2C→"2"3Mg, "1"6O+"1"6O→"2"8Si+"4He, "1"2C+"1H→"1"3N and "1"3C+"4He→"1"6O. A detail study is required on Coulomb and nuclear interaction in formation of low Z elements in stars through fusion reactions. For astrophysics, the important energy range extends from 1 MeV to 3 MeV in the center of mass frame, which is only partially covered by experiments. In the present work, we have studied the basic fusion parameters such as barrier heights (V_B), positions (R_B), curvature of the inverted parabola (ħω_1) for fusion barrier, cross section and compound nucleus formation probability (P_C_N) and fusion process in the low Z element (1≤Z≤15) formation process. For each isotope, we have studied all possible projectile-target combinations. We have also studied the astrophysical S(E) factor for these reactions. Based on this study, we have formulated the semi empirical relations for barrier heights (V_B), positions (R_B), curvature of the inverted parabola and hence for the fusion cross section and astrophysical S(E) factor. The values produced by the present model compared with the experiments and data available in the literature. (author)

  17. Diabatic models with transferrable parameters for generalized chemical reactions

    International Nuclear Information System (INIS)

    Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

    2017-01-01

    Diabatic models applied to adiabatic electron-transfer theory yield many equations involving just a few parameters that connect ground-state geometries and vibration frequencies to excited-state transition energies and vibration frequencies to the rate constants for electron-transfer reactions, utilizing properties of the conical-intersection seam linking the ground and excited states through the Pseudo Jahn-Teller effect. We review how such simplicity in basic understanding can also be obtained for general chemical reactions. The key feature that must be recognized is that electron-transfer (or hole transfer) processes typically involve one electron (hole) moving between two orbitals, whereas general reactions typically involve two electrons or even four electrons for processes in aromatic molecules. Each additional moving electron leads to new high-energy but interrelated conical-intersection seams that distort the shape of the critical lowest-energy seam. Recognizing this feature shows how conical-intersection descriptors can be transferred between systems, and how general chemical reactions can be compared using the same set of simple parameters. Mathematical relationships are presented depicting how different conical-intersection seams relate to each other, showing that complex problems can be reduced into an effective interaction between the ground-state and a critical excited state to provide the first semi-quantitative implementation of Shaik’s “twin state” concept. Applications are made (i) demonstrating why the chemistry of the first-row elements is qualitatively so different to that of the second and later rows, (ii) deducing the bond-length alternation in hypothetical cyclohexatriene from the observed UV spectroscopy of benzene, (iii) demonstrating that commonly used procedures for modelling surface hopping based on inclusion of only the first-derivative correction to the Born-Oppenheimer approximation are valid in no region of the chemical

  18. Studies in coal liquefaction with application to the SRC and related processes. Quarterly report, August 1981-October 1981. [Using model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Tarrer, A. R.; Guin, J. A.; Curtis, C. W.

    1981-01-01

    Model compound reactions were studied to evaluate the effects of mass transfer, solvent type, solvent blending, hydrogen partial pressure, temperature, reactant concentration, additive loading and its preparation, etc. Naphthalene hydrogenation and benzothiophene hydrodesulfurization were investigated under the conditions comparable to commercial coal liquefaction and related processes. Both of these reaction systems were observed to be surface reaction controlled under the reaction conditions used in this work. Certain aromatic compounds were observed to cause a reduction in the reaction rates of naphthalene and benzothiophene. Single stage coal dissolution was investigated using tetralin as a hydrogen donor solvent and a commercial cobalt-molybdate catalyst. A spinning basket system was developed to allow injection of the catalyst at a desired time in the reaction cycle. This catalyst injection technique proved to be reliable for the exploratory work done here. The degree of catalyst deactivation was rated by comparing the activities of the spent catalyst for model compound (naphthalene and cumene) reactivities relative to those of the fresh catalyst. No substantial reduction in deactivation was observed to result with delayed contacting of the catalyst with the coal-tetralin reaction mixture. The effect of reaction temperature on the initial rate of catalyst deactivation was also studied.

  19. Diffusion-controlled reactions modeling in Geant4-DNA

    Energy Technology Data Exchange (ETDEWEB)

    Karamitros, M., E-mail: matkara@gmail.com [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, INCIA, UMR 5287, F-33400 Talence (France); Luan, S. [University of New Mexico, Department of Computer Science, Albuquerque, NM (United States); Bernal, M.A. [Instituto de Física Gleb Wataghin, Universidade Estadual de Campinas, SP (Brazil); Allison, J. [Geant4 Associates International Ltd (United Kingdom); Baldacchino, G. [CEA Saclay, IRAMIS, LIDYL, Radiation Physical Chemistry Group, F-91191 Gif sur Yvette Cedex (France); CNRS, UMR3299, SIS2M, F-91191 Gif sur Yvette Cedex (France); Davidkova, M. [Nuclear Physics Institute of the ASCR, Prague (Czech Republic); Francis, Z. [Saint Joseph University, Faculty of Sciences, Department of Physics, Mkalles, Beirut (Lebanon); Friedland, W. [Helmholtz Zentrum München, German Research Center for Environmental Health, Institute of Radiation Protection, Ingolstädter Landstr. 1, 85764 Neuherberg (Germany); Ivantchenko, V. [Ecoanalytica, 119899 Moscow (Russian Federation); Geant4 Associates International Ltd (United Kingdom); Ivantchenko, A. [Geant4 Associates International Ltd (United Kingdom); Mantero, A. [SwHaRD s.r.l., via Buccari 9, 16153 Genova (Italy); Nieminem, P.; Santin, G. [ESA-ESTEC, 2200 AG Noordwijk (Netherlands); Tran, H.N. [Division of Nuclear Physics and Faculty of Applied Sciences, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam); Stepan, V. [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); Nuclear Physics Institute of the ASCR, Prague (Czech Republic); Incerti, S., E-mail: incerti@cenbg.in2p3.fr [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France)

    2014-10-01

    Context Under irradiation, a biological system undergoes a cascade of chemical reactions that can lead to an alteration of its normal operation. There are different types of radiation and many competing reactions. As a result the kinetics of chemical species is extremely complex. The simulation becomes then a powerful tool which, by describing the basic principles of chemical reactions, can reveal the dynamics of the macroscopic system. To understand the dynamics of biological systems under radiation, since the 80s there have been on-going efforts carried out by several research groups to establish a mechanistic model that consists in describing all the physical, chemical and biological phenomena following the irradiation of single cells. This approach is generally divided into a succession of stages that follow each other in time: (1) the physical stage, where the ionizing particles interact directly with the biological material; (2) the physico-chemical stage, where the targeted molecules release their energy by dissociating, creating new chemical species; (3) the chemical stage, where the new chemical species interact with each other or with the biomolecules; (4) the biological stage, where the repairing mechanisms of the cell come into play. This article focuses on the modeling of the chemical stage. Method This article presents a general method of speeding-up chemical reaction simulations in fluids based on the Smoluchowski equation and Monte-Carlo methods, where all molecules are explicitly simulated and the solvent is treated as a continuum. The model describes diffusion-controlled reactions. This method has been implemented in Geant4-DNA. The keys to the new algorithm include: (1) the combination of a method to compute time steps dynamically with a Brownian bridge process to account for chemical reactions, which avoids costly fixed time step simulations; (2) a k–d tree data structure for quickly locating, for a given molecule, its closest reactants. The

  20. Visible-light-induced, Ir-catalyzed reactions of N-methyl-N-((trimethylsilylmethylaniline with cyclic α,β-unsaturated carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Dominik Lenhart

    2014-04-01

    Full Text Available N-Methyl-N-((trimethylsilylmethylaniline was employed as reagent in visible-light-induced, iridium-catalyzed addition reactions to cyclic α,β-unsaturated carbonyl compounds. Typical reaction conditions included the use of one equivalent of the reaction substrate, 1.5 equivalents of the aniline and 2.5 mol % (in MeOH or 1.0 mol % (in CH2Cl2 [Ir(ppy2(dtbbpy]BF4 as the catalyst. Two major reaction products were obtained in combined yields of 30–67%. One product resulted from aminomethyl radical addition, the other product was a tricyclic compound, which is likely formed by attack of the intermediately formed α-carbonyl radical at the phenyl ring. For five-membered α,β-unsaturated lactone and lactam substrates, the latter products were the only products isolated. For the six-membered lactones and lactams and for cyclopentenone the simple addition products prevailed.

  1. Mathematical Model of Synthesis Catalyst with Local Reaction Centers

    Directory of Open Access Journals (Sweden)

    I. V. Derevich

    2017-01-01

    Full Text Available The article considers a catalyst granule with a porous ceramic passive substrate and point active centers on which an exothermic synthesis reaction occurs. A rate of the chemical reaction depends on the temperature according to the Arrhenius law. Heat is removed from the pellet surface in products of synthesis due to heat transfer. In our work we first proposed a model for calculating the steady-state temperature of a catalyst pellet with local reaction centers. Calculation of active centers temperature is based on the idea of self-consistent field (mean-field theory. At first, it is considered that powers of the reaction heat release at the centers are known. On the basis of the found analytical solution, which describes temperature distribution inside the granule, the average temperature of the reaction centers is calculated, which then is inserted in the formula for heat release. The resulting system of transcendental algebraic equations is transformed into a system of ordinary differential equations of relaxation type and solved numerically to achieve a steady-state value. As a practical application, the article considers a Fischer-Tropsch synthesis catalyst granule with active cobalt metallic micro-particles. Cobalt micro-particles are the centers of the exothermic reaction of hydrocarbons macromolecular synthesis. Synthesis occurs as a result of absorption of the components of the synthesis gas on metallic cobalt. The temperature distribution inside the granule for a single local center and reaction centers located on the same granule diameter is found. It was found that there is a critical temperature of reactor exceeding of which leads to significant local overheating of the centers - thermal explosion. The temperature distribution with the local reaction centers is qualitatively different from the granule temperature, calculated in the homogeneous approximation. It is shown that, in contrast to the homogeneous approximation, the

  2. Ozonation of hospital raw wastewaters for cytostatic compounds removal. Kinetic modelling and economic assessment of the process

    Energy Technology Data Exchange (ETDEWEB)

    Ferre-Aracil, J. [Universitat Politècnica de València – EPSA, Department of Chemical and Nuclear Engineering. Institute for Industrial, Radiophysical and Environmental Safety (ISIRYM), Pl. Ferrandiz i Carbonell, 03801 Alcoi, Alicante (Spain); Valcárcel, Y. [Environmental Health and Ecotoxicology Research Group, Universidad Rey Juan Carlos, Avd. Atenas s/n, Móstoles, 28922 Alcorcón (Spain); Negreira, N.; López de Alda, M. [Water and Soil Quality Research Group, Department of Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), C/ Jordi Girona 18-26, 08034 Barcelona (Spain); Barceló, D. [Water and Soil Quality Research Group, Department of Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), C/ Jordi Girona 18-26, 08034 Barcelona (Spain); Catalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park of the University of Girona, Emili Grahit 101, 17003 Girona (Spain); Cardona, S.C. [Universitat Politècnica de València – EPSA, Department of Chemical and Nuclear Engineering. Institute for Industrial, Radiophysical and Environmental Safety (ISIRYM), Pl. Ferrandiz i Carbonell, 03801 Alcoi, Alicante (Spain); Navarro-Laboulais, J., E-mail: jnavarla@iqn.upv.es [Universitat Politècnica de València – EPSA, Department of Chemical and Nuclear Engineering. Institute for Industrial, Radiophysical and Environmental Safety (ISIRYM), Pl. Ferrandiz i Carbonell, 03801 Alcoi, Alicante (Spain)

    2016-06-15

    The kinetics of the ozone consumption for the pretreatment of hospital wastewater has been analysed in order to determine the reaction rate coefficients between the ozone and the readily oxidisabled organic matter and cytostatic compounds. The wastewater from a medium size hospital was treated with ozone and peroxone methodologies, varying the ozone concentration, the reaction time and the hydrogen peroxide doses. The analysis shows that there are four cytostatic compounds, i.e. irinotecan, ifosfamide, cyclophosphamide and capecitabine, detected in the wastewaters and they are completely removed with reasonably short times after the ozone treatment. Considering the reactor geometry, the gas hydrodynamics, the mass transfer of ozone from gas to liquid and the reaction of all oxidisable compounds of the wastewater it is possible to determine the chemical ozone demand, COzD, of the sample as 256 mg O{sub 3} L{sup −1} and the kinetic rate coefficient with the dissolved organic matter as 8.4 M{sup −1} s{sup −1}. The kinetic rate coefficient between the ozone and the cyclophosphamide is in the order of 34.7 M{sup −1} s{sup −1} and higher for the other cytostatics. The direct economic cost of the treatment was evaluated considering this reaction kinetics and it is below 0.3 €/m{sup 3} under given circumstances. - Highlights: • 17 cytostatic compounds were analysed and 4 detected by SPE-LC/MS-MS. • The ozonation is 100% effective on the removal of the detected cytostatics. • The kinetics of cytostatic ozonation reaction is modeled by competitive kinetics. • The economic cost of the treatment of hospital wastewater was assessed.

  3. Ozonation of hospital raw wastewaters for cytostatic compounds removal. Kinetic modelling and economic assessment of the process

    International Nuclear Information System (INIS)

    Ferre-Aracil, J.; Valcárcel, Y.; Negreira, N.; López de Alda, M.; Barceló, D.; Cardona, S.C.; Navarro-Laboulais, J.

    2016-01-01

    The kinetics of the ozone consumption for the pretreatment of hospital wastewater has been analysed in order to determine the reaction rate coefficients between the ozone and the readily oxidisabled organic matter and cytostatic compounds. The wastewater from a medium size hospital was treated with ozone and peroxone methodologies, varying the ozone concentration, the reaction time and the hydrogen peroxide doses. The analysis shows that there are four cytostatic compounds, i.e. irinotecan, ifosfamide, cyclophosphamide and capecitabine, detected in the wastewaters and they are completely removed with reasonably short times after the ozone treatment. Considering the reactor geometry, the gas hydrodynamics, the mass transfer of ozone from gas to liquid and the reaction of all oxidisable compounds of the wastewater it is possible to determine the chemical ozone demand, COzD, of the sample as 256 mg O 3 L −1 and the kinetic rate coefficient with the dissolved organic matter as 8.4 M −1 s −1 . The kinetic rate coefficient between the ozone and the cyclophosphamide is in the order of 34.7 M −1 s −1 and higher for the other cytostatics. The direct economic cost of the treatment was evaluated considering this reaction kinetics and it is below 0.3 €/m 3 under given circumstances. - Highlights: • 17 cytostatic compounds were analysed and 4 detected by SPE-LC/MS-MS. • The ozonation is 100% effective on the removal of the detected cytostatics. • The kinetics of cytostatic ozonation reaction is modeled by competitive kinetics. • The economic cost of the treatment of hospital wastewater was assessed.

  4. Measurements of Volatile Organic Compounds Using Proton Transfer Reaction – Mass Spectrometry during the MILAGRO 2006 Campaign

    Directory of Open Access Journals (Sweden)

    E. C. Fortner

    2009-01-01

    Full Text Available Volatile organic compounds (VOCs were measured by proton transfer reaction – mass spectrometry (PTR-MS on a rooftop in the urban mixed residential and industrial area North Northeast of downtown Mexico City as part of the Megacity Initiative – Local and Global Research Observations (MILAGRO 2006 field campaign. Thirty eight individual masses were monitored during the campaign and many species were quantified including methanol, acetaldehyde, toluene, the sum of C2 benzenes, the sum of C3 benzenes, acetone, isoprene, benzene, and ethyl acetate. The VOC measurements were analyzed to gain a better understanding of the type of VOCs present in the MCMA, their diurnal patterns, and their origins. Diurnal profiles of weekday and weekend/holiday aromatic VOC concentrations showed the influence of vehicular traffic during the morning rush hours and during the afternoon hours. Plumes including elevated toluene as high as 216 parts per billion (ppb and ethyl acetate as high as 183 ppb were frequently observed during the late night and early morning hours, indicating the possibility of significant industrial sources of the two compounds in the region. Wind fields during those peak episodes revealed no specific direction for the majority of the toluene plumes but the ethyl acetate plumes arrived at the site when winds were from the Southwest or West. The PTR-MS measurements combined with other VOC measuring techniques at the field site as well as VOC measurements conducted in other areas of the Mexico City Metropolitan Area (MCMA will help to develop a better understanding of the spatial pattern of VOCs and its variability in the MCMA.

  5. Developed Hybrid Model for Propylene Polymerisation at Optimum Reaction Conditions

    Directory of Open Access Journals (Sweden)

    Mohammad Jakir Hossain Khan

    2016-02-01

    Full Text Available A statistical model combined with CFD (computational fluid dynamic method was used to explain the detailed phenomena of the process parameters, and a series of experiments were carried out for propylene polymerisation by varying the feed gas composition, reaction initiation temperature, and system pressure, in a fluidised bed catalytic reactor. The propylene polymerisation rate per pass was considered the response to the analysis. Response surface methodology (RSM, with a full factorial central composite experimental design, was applied to develop the model. In this study, analysis of variance (ANOVA indicated an acceptable value for the coefficient of determination and a suitable estimation of a second-order regression model. For better justification, results were also described through a three-dimensional (3D response surface and a related two-dimensional (2D contour plot. These 3D and 2D response analyses provided significant and easy to understand findings on the effect of all the considered process variables on expected findings. To diagnose the model adequacy, the mathematical relationship between the process variables and the extent of polymer conversion was established through the combination of CFD with statistical tools. All the tests showed that the model is an excellent fit with the experimental validation. The maximum extent of polymer conversion per pass was 5.98% at the set time period and with consistent catalyst and co-catalyst feed rates. The optimum conditions for maximum polymerisation was found at reaction temperature (RT 75 °C, system pressure (SP 25 bar, and 75% monomer concentration (MC. The hydrogen percentage was kept fixed at all times. The coefficient of correlation for reaction temperature, system pressure, and monomer concentration ratio, was found to be 0.932. Thus, the experimental results and model predicted values were a reliable fit at optimum process conditions. Detailed and adaptable CFD results were capable

  6. Construction and Optimization of a Heterologous Pathway for Protocatechuate Catabolism in Escherichia coli Enables Bioconversion of Model Aromatic Compounds.

    Science.gov (United States)

    Clarkson, Sonya M; Giannone, Richard J; Kridelbaugh, Donna M; Elkins, James G; Guss, Adam M; Michener, Joshua K

    2017-09-15

    The production of biofuels from lignocellulose yields a substantial lignin by-product stream that currently has few applications. Biological conversion of lignin-derived compounds into chemicals and fuels has the potential to improve the economics of lignocellulose-derived biofuels, but few microbes are able both to catabolize lignin-derived aromatic compounds and to generate valuable products. While Escherichia coli has been engineered to produce a variety of fuels and chemicals, it is incapable of catabolizing most aromatic compounds. Therefore, we engineered E. coli to catabolize protocatechuate, a common intermediate in lignin degradation, as the sole source of carbon and energy via heterologous expression of a nine-gene pathway from Pseudomonas putida KT2440. We next used experimental evolution to select for mutations that increased growth with protocatechuate more than 2-fold. Increasing the strength of a single ribosome binding site in the heterologous pathway was sufficient to recapitulate the increased growth. After optimization of the core pathway, we extended the pathway to enable catabolism of a second model compound, 4-hydroxybenzoate. These engineered strains will be useful platforms to discover, characterize, and optimize pathways for conversions of lignin-derived aromatics. IMPORTANCE Lignin is a challenging substrate for microbial catabolism due to its polymeric and heterogeneous chemical structure. Therefore, engineering microbes for improved catabolism of lignin-derived aromatic compounds will require the assembly of an entire network of catabolic reactions, including pathways from genetically intractable strains. Constructing defined pathways for aromatic compound degradation in a model host would allow rapid identification, characterization, and optimization of novel pathways. We constructed and optimized one such pathway in E. coli to enable catabolism of a model aromatic compound, protocatechuate, and then extended the pathway to a related

  7. Forced thermal cycling of catalytic reactions: experiments and modelling

    DEFF Research Database (Denmark)

    Jensen, Søren; Olsen, Jakob Lind; Thorsteinsson, Sune

    2007-01-01

    Recent studies of catalytic reactions subjected to fast forced temperature oscillations have revealed a rate enhancement increasing with temperature oscillation frequency. We present detailed studies of the rate enhancement up to frequencies of 2.5 Hz. A maximum in the rate enhancement is observed...... at about 1 Hz. A model for the rate enhancement that includes the surface kinetics and the dynamic partial pressure variations in the reactor is introduced. The model predicts a levelling off of the rate enhancement with frequency at about 1 Hz. The experimentally observed decrease above 1 Hz is explained...

  8. On microscopic simulations of systems with model chemical reactions

    International Nuclear Information System (INIS)

    Gorecki, J.; Gorecka, J.N.

    1998-01-01

    Large scale computer simulations of model chemical systems play the role of idealized experiments in which theories may be tested. In this paper we present two applications of microscopic simulations based on the reactive hard sphere model. We investigate the influence of internal fluctuations on an oscillating chemical system and observe how they modify the phase portrait of it. Another application, we consider, is concerned with the propagation of a chemical wave front associated with a thermally activated reaction. It is shown that the nonequilibrium effects increase the front velocity if compared with the velocity of the front generated by a nonactivated process characterized by the same rate constant. (author)

  9. Model compounds for heavy crude oil components and tetrameric acids: Characterization and interfacial behaviour

    Energy Technology Data Exchange (ETDEWEB)

    Nordgaard, Erland Loeken

    2009-07-01

    analogue. The model compounds display the same high interfacial activity and film behaviour. One of the model compounds, BP10, forms a cross-linked network with Ca2+, crucial for naphthenate deposit formation. On the other hand, no glass transition was found for BP10. Reactions with Ca2+ under emulsified conditions demonstrated the extreme influence of the available interfacial area. Finally, the acid-base properties of several tetra acids were investigated by potentiometric titrations. A high apparent pKa with hysteresis depending on the titration direction was observed for BP10, and could be explained and modelled based on the tetra acid being present as a micellar solution. (Author)

  10. Advanced Model Compounds for Understanding Acid-Catalyzed Lignin Depolymerization: Identification of Renewable Aromatics and a Lignin-Derived Solvent.

    Science.gov (United States)

    Lahive, Ciaran W; Deuss, Peter J; Lancefield, Christopher S; Sun, Zhuohua; Cordes, David B; Young, Claire M; Tran, Fanny; Slawin, Alexandra M Z; de Vries, Johannes G; Kamer, Paul C J; Westwood, Nicholas J; Barta, Katalin

    2016-07-20

    The development of fundamentally new approaches for lignin depolymerization is challenged by the complexity of this aromatic biopolymer. While overly simplified model compounds often lack relevance to the chemistry of lignin, the direct use of lignin streams poses significant analytical challenges to methodology development. Ideally, new methods should be tested on model compounds that are complex enough to mirror the structural diversity in lignin but still of sufficiently low molecular weight to enable facile analysis. In this contribution, we present a new class of advanced (β-O-4)-(β-5) dilinkage models that are highly realistic representations of a lignin fragment. Together with selected β-O-4, β-5, and β-β structures, these compounds provide a detailed understanding of the reactivity of various types of lignin linkages in acid catalysis in conjunction with stabilization of reactive intermediates using ethylene glycol. The use of these new models has allowed for identification of novel reaction pathways and intermediates and led to the characterization of new dimeric products in subsequent lignin depolymerization studies. The excellent correlation between model and lignin experiments highlights the relevance of this new class of model compounds for broader use in catalysis studies. Only by understanding the reactivity of the linkages in lignin at this level of detail can fully optimized lignin depolymerization strategies be developed.

  11. Synthesis of model compounds derived from natural clerodane insect antifeedants

    NARCIS (Netherlands)

    Klein Gebbinck, E.A.

    1999-01-01

    Insect antifeedants are compounds with the ability to reduce or inhibit insect feeding without directly killing the insect. Such compounds offer a number of properties that are highly desirable in environmentally friendly crop protection agents. Although the principle of insect control

  12. Bayesian inference of chemical kinetic models from proposed reactions

    KAUST Repository

    Galagali, Nikhil

    2015-02-01

    © 2014 Elsevier Ltd. Bayesian inference provides a natural framework for combining experimental data with prior knowledge to develop chemical kinetic models and quantify the associated uncertainties, not only in parameter values but also in model structure. Most existing applications of Bayesian model selection methods to chemical kinetics have been limited to comparisons among a small set of models, however. The significant computational cost of evaluating posterior model probabilities renders traditional Bayesian methods infeasible when the model space becomes large. We present a new framework for tractable Bayesian model inference and uncertainty quantification using a large number of systematically generated model hypotheses. The approach involves imposing point-mass mixture priors over rate constants and exploring the resulting posterior distribution using an adaptive Markov chain Monte Carlo method. The posterior samples are used to identify plausible models, to quantify rate constant uncertainties, and to extract key diagnostic information about model structure-such as the reactions and operating pathways most strongly supported by the data. We provide numerical demonstrations of the proposed framework by inferring kinetic models for catalytic steam and dry reforming of methane using available experimental data.

  13. Multienzyme Immobilized Polymeric Membrane Reactor for the Transformation of a Lignin Model Compound

    Directory of Open Access Journals (Sweden)

    Rupam Sarma

    2018-04-01

    Full Text Available We have developed an integrated, multienzyme functionalized membrane reactor for bioconversion of a lignin model compound involving enzymatic catalysis. The membrane bioreactors were fabricated through the layer-by-layer assembly approach to immobilize three different enzymes (glucose oxidase, peroxidase and laccase into pH-responsive membranes. This novel membrane reactor couples the in situ generation of hydrogen peroxide (by glucose oxidase to oxidative conversion of a lignin model compound, guaiacylglycerol-β-guaiacyl ether (GGE. Preliminary investigation of the efficacy of these functional membranes towards GGE degradation is demonstrated under convective flow mode. Over 90% of the initial feed could be degraded with the multienzyme immobilized membranes at a residence time of approximately 22 s. GGE conversion product analysis revealed the formation of oligomeric oxidation products upon reaction with peroxidase, which may be a potential hazard to membrane bioreactors. These oxidation products could further be degraded by laccase enzymes in the multienzymatic membranes, explaining the potential of multi enzyme membrane reactors. The multienzyme incorporated membrane reactors were active for more than 30 days of storage time at 4 °C. During this time span, repetitive use of the membrane reactor was demonstrated involving 5–6 h of operation time for each cycle. The membrane reactor displayed encouraging performance, losing only 12% of its initial activity after multiple cycles of operation.

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

    Science.gov (United States)

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

    2011-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Louis D Weise

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

  16. Position-specific isotope modeling of organic micropollutants transformation through different reaction pathways

    International Nuclear Information System (INIS)

    Jin, Biao; Rolle, Massimo

    2016-01-01

    The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. To demonstrate specific features of the modeling approach, we simulated the degradation of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model accurately reproduces the multi-element isotope data observed in previous experimental studies. Furthermore, it precisely captures the dual element isotope trends characteristic of different reaction pathways as well as their range of variation consistent with observed bulk isotope fractionation. It was also possible to directly validate the model capability to predict the evolution of position-specific isotope ratios with available experimental data. Therefore, the approach is useful both for a mechanism-based evaluation of experimental results and as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. - Highlights: • Mechanism-based, position-specific isotope modeling of micropollutants degradation. • Simultaneous description of concentration and primary and secondary isotope effects. • Key features of the model are demonstrated with three illustrative examples. • Model as a tool to explore reaction mechanisms and to design experiments. - We propose a modeling approach incorporating mechanistic information and

  17. On quark model relations for hypercharge-exchange reactions

    International Nuclear Information System (INIS)

    Kluyver, J.C.; Blokzijl, R.; Massaro, G.G.G.; Wolters, G.F.; Grossmann, P.; Lamb, P.R.; Wells, J.

    1978-01-01

    Peripheral two-body reactions of the type K - p → M 0 + Λ, Σ 0 or Σ 0 (1385) are considered. Predictions based on the additive quark model and SU(6) baryon wave functions are tested against data on cross sections and polarisations for given momentum transfer. Data obtained in a high statistics experiment at 4.2 GeV/c K - momentum, as well as data from a large variety of other experiments are used. Highly significant violations of these predictions are observed in the data. These violations are shown to occur in a systematic fashion, according to which SU(6) must be relaxed, but the amplitude structure implied by additivity would remain valid. As an application an amplitude analysis for natural parity exchange reactions with M 0 = π, phi and rho respectively is performed, which determines a relative phase, which cannot be obtained in model-independent analysis. Also reactions with M 0 = delta or B are considered, and some implications for coupling constants are discussed. (Auth.)

  18. Reaction-diffusion modeling of hydrogen in beryllium

    Energy Technology Data Exchange (ETDEWEB)

    Wensing, Mirko; Matveev, Dmitry; Linsmeier, Christian [Forschungszentrum Juelich GmbH, Institut fuer Energie- und Klimaforschung - Plasmaphysik (Germany)

    2016-07-01

    Beryllium will be used as first-wall material for the future fusion reactor ITER as well as in the breeding blanket of DEMO. In both cases it is important to understand the mechanisms of hydrogen retention in beryllium. In earlier experiments with beryllium low-energy binding states of hydrogen were observed by thermal desorption spectroscopy (TDS) which are not yet well understood. Two candidates for these states are considered: beryllium-hydride phases within the bulk and surface effects. The retention of deuterium in beryllium is studied by a reaction rate approach using a coupled reaction diffusion system (CRDS)-model relying on ab initio data from density functional theory calculations (DFT). In this contribution we try to assess the influence of surface recombination.

  19. Quantum Chemical Modeling of Enzymatic Reactions: The Case of Decarboxylation.

    Science.gov (United States)

    Liao, Rong-Zhen; Yu, Jian-Guo; Himo, Fahmi

    2011-05-10

    We present a systematic study of the decarboxylation step of the enzyme aspartate decarboxylase with the purpose of assessing the quantum chemical cluster approach for modeling this important class of decarboxylase enzymes. Active site models ranging in size from 27 to 220 atoms are designed, and the barrier and reaction energy of this step are evaluated. To model the enzyme surrounding, homogeneous polarizable medium techniques are used with several dielectric constants. The main conclusion is that when the active site model reaches a certain size, the solvation effects from the surroundings saturate. Similar results have previously been obtained from systematic studies of other classes of enzymes, suggesting that they are of a quite general nature.

  20. Maruhn-Greiner Maximum for Confirmation of Low Energy Nuclear Reactions (LENR) via a Compound Nucleus with Double Magic Numbers

    Science.gov (United States)

    Hora, Heinrich; Miley, George

    2007-03-01

    One of the most convincing facts about LENR due to deuterons (ds) or protons of very high concentration in host metals of palladium is the measurement of the large scale minimum in the reaction probability with product elements centered around the nucleon number A = 153. The local maximum was measured in this region is similar to fission of uranium at A = 119 where the local maximum follows the Maruhn-Greiner mechanism^1. We suggest this phenomenon can be explained by the strong screening of the Maxwellian ds on the degenerate rigid electron background within the swimming electrons at the metal surface or thin filem interfaces. The deuterons behave like neutrals at distances of above 2 picometers (pm) and form clusters due to soft attraction in the range of thermal energy; 10 pm diameter clusters can react over long time scales (10^6 s) with Pd leading to double magic number compound nuclei 306x126 decaying via fission to an A=153 element distribution. J. Maruhn et al, Phys. Rev. Letters 32, 548 (1974) H. Hora, G.H. Miley, CzechJ. Phys. 48, 1111 (1998)

  1. Students' Visualisation of Chemical Reactions--Insights into the Particle Model and the Atomic Model

    Science.gov (United States)

    Cheng, Maurice M. W.

    2018-01-01

    This paper reports on an interview study of 18 Grade 10-12 students' model-based reasoning of a chemical reaction: the reaction of magnesium and oxygen at the submicro level. It has been proposed that chemical reactions can be conceptualised using two models: (i) the "particle model," in which a reaction is regarded as the simple…

  2. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    International Nuclear Information System (INIS)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C; Pace, Molly; Kim, Young Jin; Jardine, Philip M.; Watson, David B.

    2007-01-01

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M. partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M. species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions

  3. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

    Science.gov (United States)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

    2007-06-16

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  4. Compound and Geometry-Dependent Pre-Compound Models to Calculate the Nuclear Data for Fusion Reactors

    International Nuclear Information System (INIS)

    Jahn, Helmut

    2005-01-01

    Compound and geometry-dependent pre-compound nuclear reactions are very useful concepts of nuclear theory to calculate cross sections of neutrons of around 14 MeV and below scattered by nuclei of material of installations producing energy of nuclear fusion. If these concepts are used to discuss and improve the experimental data they have to be completed by DWBA-type contributions to the small-step region of the incident neutron which can account for the angular distribution of the scattered neutron because there is the difficulty to separate experimentally the incoming from the scattered beam. The angle integrated cross-section in this region can be shown to be accounted for the surface dependent components of Blanns geometry-dependent precompound mechanism of the statistical state density and level density contributions of the compound and precompound components beeing calculated according to the recent developments of Anzaldo using the analytic number theory. The experimental data have been taken from the results of Hermsdorf, Meister, Sassonov, Seeliger, Seidel, Shahin and of A.Takahashi

  5. Interpretation of some (p,n), (n,p), and (3He, p) reactions by means of the statistical multistep compound emission theory

    International Nuclear Information System (INIS)

    Bonetti, R.; Milazzo, L.C.; Melanotte, M.

    1983-01-01

    A number of (p,n), (n,p), and ( 3 He, p) reactions have been interpreted on the basis of the statistical multistep compound emission mechanism. Good agreement with experiment is found both in spectrum shape and in the value of the coherence widths

  6. Product ion distributions for the reactions of NO+ with some N-containing and O-containing heterocyclic compounds obtained using SRI-TOF-MS

    Czech Academy of Sciences Publication Activity Database

    Mochalski, P.; Unterkofler, K.; Španěl, Patrik; Smith, D.; Amann, A.

    2015-01-01

    Roč. 386, JUL 2015 (2015), s. 42-46 ISSN 1387-3806 Institutional support: RVO:61388955 Keywords : heterocyclic compounds * SRI-TOF-MS * NO+ reactions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.183, year: 2015

  7. Modeling the reactions catalyzed by coenzyme B12-dependent enzymes.

    Science.gov (United States)

    Sandala, Gregory M; Smith, David M; Radom, Leo

    2010-05-18

    catalysis depends on a delicate energy balance. Radical-based enzyme reactions are often difficult to probe experimentally, so theoretical investigations have a particularly valuable role to play in their study. Our research demonstrates that a small-model approach can provide important and revealing insights into the mechanism of action of AdoCbl-dependent enzymes.

  8. Investigation of a Monte Carlo model for chemical reactions

    International Nuclear Information System (INIS)

    Hamm, R.N.; Turner, J.E.; Stabin, M.G.

    1998-01-01

    Monte Carlo computer simulations are in use at a number of laboratories for calculating time-dependent yields, which can be compared with experiments in the radiolysis of water. We report here on calculations to investigate the validity and consistency of the procedures used for simulating chemical reactions in our code, RADLYS. Model calculations were performed of the rate constants themselves. The rates thus determined showed an expected rapid decline over the first few hundred ps and a very gradual decline thereafter out to the termination of the calculations at 4.5 ns. Results are reported for different initial concentrations and numbers of reactive species. Generally, the calculated rate constants are smallest when the initial concentrations of the reactants are largest. It is found that inhomogeneities that quickly develop in the initial random spatial distribution of reactants persist in time as a result of subsequent chemical reactions, and thus conditions may poorly approximate those assumed from diffusion theory. We also investigated the reaction of a single species of one type placed among a large number of randomly distributed species of another type with which it could react. The distribution of survival times of the single species was calculated by using three different combinations of the diffusion constants for the two species, as is sometimes discussed in diffusion theory. The three methods gave virtually identical results. (orig.)

  9. Reaction times to weak test lights. [psychophysics biological model

    Science.gov (United States)

    Wandell, B. A.; Ahumada, P.; Welsh, D.

    1984-01-01

    Maloney and Wandell (1984) describe a model of the response of a single visual channel to weak test lights. The initial channel response is a linearly filtered version of the stimulus. The filter output is randomly sampled over time. Each time a sample occurs there is some probability increasing with the magnitude of the sampled response - that a discrete detection event is generated. Maloney and Wandell derive the statistics of the detection events. In this paper a test is conducted of the hypothesis that the reaction time responses to the presence of a weak test light are initiated at the first detection event. This makes it possible to extend the application of the model to lights that are slightly above threshold, but still within the linear operating range of the visual system. A parameter-free prediction of the model proposed by Maloney and Wandell for lights detected by this statistic is tested. The data are in agreement with the prediction.

  10. Precompound Reactions: Basic Concepts

    International Nuclear Information System (INIS)

    Weidenmueller, H. A.

    2008-01-01

    Because of the non-zero nuclear equilibration time, the compound-nucleus scattering model fails when the incident energy exceeds 10 or 20 MeV, and precompound reactions become important. Basic ideas used in the quantum-statistical approaches to these reactions are described

  11. 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.

  12. Non-universal spreading exponents in a catalytic reaction model

    International Nuclear Information System (INIS)

    De Andrade, Marcelo F; Figueiredo, W

    2011-01-01

    We investigated the dependence of the spreading critical exponents and the ultimate survival probability exponent on the initial configuration of a nonequilibrium catalytic reaction model. The model considers the competitive reactions between two different monomers, A and B, where we take into account the energy couplings between nearest neighbor monomers, and the adsorption energies, as well as the temperature T of the catalyst. For each value of T the model shows distinct absorbing states, with different concentrations of the two monomers. Employing an epidemic analysis, we established the behavior of the spreading exponents as we started the Monte Carlo simulations with different concentrations of the monomers. The exponents were determined as a function of the initial concentration ρ A, ini of A monomers. We have also considered initial configurations with correlations for a fixed concentration of A monomers. From the determination of three spreading exponents, and the ultimate survival probability exponent, we checked the validity of the generalized hyperscaling relation for a continuous set of initial states, random and correlated, which are dependent on the temperature of the catalyst

  13. Use of nuclear reaction models in cross section calculations

    International Nuclear Information System (INIS)

    Grimes, S.M.

    1975-03-01

    The design of fusion reactors will require information about a large number of neutron cross sections in the MeV region. Because of the obvious experimental difficulties, it is probable that not all of the cross sections of interest will be measured. Current direct and pre-equilibrium models can be used to calculate non-statistical contributions to neutron cross sections from information available from charged particle reaction studies; these are added to the calculated statistical contribution. Estimates of the reliability of such calculations can be derived from comparisons with the available data. (3 tables, 12 figures) (U.S.)

  14. Alpha-transfer reactions and the pairing-vibration model

    International Nuclear Information System (INIS)

    Betts, R.R.

    1977-01-01

    The pairing-vibration model with isospin is extended to include α-transfer reactions. Selection rules and expressions for transition strengths are derived and compared with experimental results for A = 40--66 nuclei. The selection rules are found to be followed quite well in the examples studied. The systematics of ground-state transition strengths are qualitatively quite well reproduced although the quantitative agreement is poor. When the changing nature of the pairing quanta is incorporated using two-particle transfer data the agreement becomes quantitatively good. Evidence is presented for clustering other than that due to pairing in 40 Ca and 44 Ti

  15. Kinetic modelling of Amadori N-(1-deoxy-D-fructos-1-yl)-glycine degradation pathways. Part I - Reaction mechanism

    NARCIS (Netherlands)

    Martins, S.I.F.S.; Marcelis, A.T.M.; Boekel, van M.A.J.S.

    2003-01-01

    The fate of the Amadori compound N-(1-deoxy--fructos-1-yl)-glycine (DFG) was studied in aqueous model systems as a function of pH and temperature. The samples were heated at 100 and 120 °C with initial reaction pH of 5.5 and 6.8. Special attention was paid to the formation of the free amino acid,

  16. Test of level density models from reactions of Li6 on Fe58 and Li7 on Fe57

    Science.gov (United States)

    Oginni, B. M.; Grimes, S. M.; Voinov, A. V.; Adekola, A. S.; Brune, C. R.; Carter, D. E.; Heinen, Z.; Jacobs, D.; Massey, T. N.; O'Donnell, J. E.; Schiller, A.

    2009-09-01

    The reactions of Li6 on Fe58 and Li7 on Fe57 have been studied at 15 MeV beam energy. These two reactions produce the same compound nucleus, Cu64. The charged particle spectra were measured at backward angles. The data obtained have been compared with Hauser-Feshbach model calculations. The level density parameters of Ni63 and Co60 have been obtained from the particle evaporation spectra. We also find contributions from the break up of the lithium projectiles to the low energy region of the α spectra.

  17. Yields of hydrogen peroxide from the reaction of hydroxyl radical with organic compounds in solution and ice

    Directory of Open Access Journals (Sweden)

    T. Hullar

    2011-07-01

    Full Text Available Hydrogen peroxide (HOOH is a significant oxidant in atmospheric condensed phases (e.g., cloud and fog drops, aqueous particles, and snow that also photolyzes to form hydroxyl radical (OH. OH can react with organics in aqueous phases to form organic peroxyl radicals and ultimately reform HOOH, but the efficiency of this process in atmospheric aqueous phases, as well as snow and ice, is not well understood. We investigate HOOH formation from OH attack on 10 environmentally relevant organic compounds: formaldehyde, formate, glycine, phenylalanine, benzoic acid, octanol, octanal, octanoic acid, octanedioic acid, and 2-butoxyethanol. Liquid and ice samples with and without nitrate (as an OH source were illuminated using simulated solar light, and HOOH formation rates were measured as a function of pH and temperature. For most compounds, the formation rate of HOOH without nitrate was the same as the background formation rate in blank water (i.e., illumination of the organic species does not produce HOOH directly, while formation rates with nitrate were greater than the water control (i.e., reaction of OH with the organic species forms HOOH. Yields of HOOH, defined as the rate of HOOH production divided by the rate of OH production, ranged from essentially zero (glycine to 0.24 (octanal, with an average of 0.12 ± 0.05 (95 % CI. HOOH production rates and yields were higher at lower pH values. There was no temperature dependence of the HOOH yield for formaldehyde or octanedioic acid between −5 to 20 °C and ice samples had approximately the same HOOH yield as the aqueous solutions. In contrast, HOOH yields in formate solutions were higher at 5 and 10 °C compared to −5 and 20 °C. Yields of HOOH in ice for solutions containing nitrate and either phenylalanine, benzoate, octanal, or octanoic acid were indistinguishable from zero. Our HOOH yields were approximately

  18. Modeling transport and reaction in an electric DC field

    Energy Technology Data Exchange (ETDEWEB)

    Arnerdal, K.; Neretnieks, I. [Dept. of Chemical Engineering and Technology, Royal Inst. of Tech. (Sweden)

    2001-07-01

    Remediation of contaminated soils from heavy metals can be accomplished by subjecting the soil to an electric DC field. In an electric field dissolved metals will move to either the cathode or the anode depending on their charges. During the course of remediation, precipitated and sorbed species will dissolve as the solute is depleted. Our previous remediation experiments on kaolinite soil and sandy loam show high remediation efficiency. In new experiments we studied the reaction and transport of copper in sand and sand/bentonite mixtures with a constant applied potential. For clays with high pH buffer capacity and cation exchange capacity the results were not satisfying, because of insufficient desorption of the metals from the clay. The parameters measured at different time intervals were potential gradient, current density, pH and metal concentration. We present a mathematical and numerical model that is used for interpretation of the results from the remediation experiments. The model uses electromigration and diffusion to describe the transport of heavy metals and other ions. The remediation experiments are supplemented by batch experiments used to assess the acid neutralisation capacity and sorption distribution coefficients at different pH's for the heavy metal ions. These are essential data needed for the modelling and can be used to assess if a remediation could be accomplished within reasonable time. The results show that the reaction data used to explain acid neutralisation capacity estimated in batch experiments can be used to model the main trends of the development of the current density and the potential profile. However the pH profile and the free copper concentration can not be modelled with this equilibrium description. (orig.)

  19. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction

    Directory of Open Access Journals (Sweden)

    Cobbs Gary

    2012-08-01

    Full Text Available Abstract Background Numerous models for use in interpreting quantitative PCR (qPCR data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Results Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the

  20. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction.

    Science.gov (United States)

    Cobbs, Gary

    2012-08-16

    Numerous models for use in interpreting quantitative PCR (qPCR) data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the literature. They also give better estimates of

  1. Modeling of Syngas Reactions and Hydrogen Generation Over Sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Kamil Klier; Jeffery A. Spirko; Michael L. Neiman

    2002-09-17

    The objective of the research is to analyze pathways of reactions of hydrogen with oxides of carbon over sulfides, and to predict which characteristics of the sulfide catalyst (nature of metal, defect structure) give rise to the lowest barriers toward oxygenated hydrocarbon product. Reversal of these pathways entails the generation of hydrogen, which is also proposed for study. In this first year of study, adsorption reactions of H atoms and H{sub 2} molecules with MoS{sub 2}, both in molecular and solid form, have been modeled using high-level density functional theory. The geometries and strengths of the adsorption sites are described and the methods used in the study are described. An exposed MO{sup IV} species modeled as a bent MoS{sub 2} molecule is capable of homopolar dissociative chemisorption of H{sub 2} into a dihydride S{sub 2}MoH{sub 2}. Among the periodic edge structures of hexagonal MoS{sub 2}, the (1{bar 2}11) edge is most stable but still capable of dissociating H{sub 2}, while the basal plane (0001) is not. A challenging task of theoretically accounting for weak bonding of MoS{sub 2} sheets across the Van der Waals gap has been addressed, resulting in a weak attraction of 0.028 eV/MoS{sub 2} unit, compared to the experimental value of 0.013 eV/MoS{sub 2} unit.

  2. Mass transfer model for two-layer TBP oxidation reactions

    International Nuclear Information System (INIS)

    Laurinat, J.E.

    1994-01-01

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments. Three cases were investigated: (1) transfer of water into the TBP layer with sparging of both the aqueous and TBP layers, (2) transfer of water into the TBP layer with sparging of just the TBP layer, and (3) transfer of butanol into the aqueous layer with sparging of both layers. The TBP layer was comprised of 99% pure TBP (spiked with butanol for the butanol transfer experiments), and the aqueous layer was comprised of either water or an aluminum nitrate solution. The liquid layers were air sparged to simulate the mixing due to the evolution of gases generated by oxidation reactions. A plastic tube and a glass frit sparger were used to provide different size bubbles. Rates of mass transfer were measured using infrared spectrophotometers provided by SRTC/Analytical Development

  3. Nicotiana tabacum as model for ozone - plant surface reactions

    Science.gov (United States)

    Jud, Werner; Fischer, Lukas; Wohlfahrt, Georg; Tissier, Alain; Canaval, Eva; Hansel, Armin

    2015-04-01

    Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. The ensuing injuries have been related to the uptake of ozone through the stomatal pores and oxidative effects damaging the internal leaf tissue. A striking question of current research is the environment and plant specific partitioning of ozone loss between gas phase, stomatal or plant surface sink terms. Here we show results from ozone fumigation experiments using various Nicotiana Tabacum varieties, whose surfaces are covered with different amounts of unsaturated diterpenoids exuded by their glandular trichomes. Exposure to elevated ozone levels (50 to 150 ppbv) for 5 to 15 hours in an exceptionally clean cuvette system did neither result in a reduction of photosynthesis nor caused any visible leaf damage. Both these ozone induced stress effects have been observed previously in ozone fumigation experiments with the ozone sensitive tobacco line Bel-W3. In our case ozone fumigation was accompanied by a continuous release of oxygenated volatile organic compounds, which could be clearly associated to their condensed phase precursors for the first time. Gas phase reactions of ozone were avoided by choosing a high enough gas exchange rate of the plant cuvette system. In the case of the Ambalema variety, that is known to exude only the diterpenoid cis-abienol, ozone fumigation experiments yield the volatiles formaldehyde and methyl vinyl ketone (MVK). The latter could be unequivocally separated from isomeric methacrolein (MACR) by the aid of a Selective Reagent Ion Time-of-Flight Mass Spectrometer (SRI-ToF-MS), which was switched every six minutes from H3O+ to NO+ primary ion mode and vice versa. Consistent with the picture of an ozone protection mechanism caused by reactive diterpenoids at the leaf surface are the results from dark-light experiments. The ozone loss obtained from the

  4. Coupling between solute transport and chemical reactions models

    International Nuclear Information System (INIS)

    Samper, J.; Ajora, C.

    1993-01-01

    During subsurface transport, reactive solutes are subject to a variety of hydrodynamic and chemical processes. The major hydrodynamic processes include advection and convection, dispersion and diffusion. The key chemical processes are complexation including hydrolysis and acid-base reactions, dissolution-precipitation, reduction-oxidation, adsorption and ion exchange. The combined effects of all these processes on solute transport must satisfy the principle of conservation of mass. The statement of conservation of mass for N mobile species leads to N partial differential equations. Traditional solute transport models often incorporate the effects of hydrodynamic processes rigorously but oversimplify chemical interactions among aqueous species. Sophisticated chemical equilibrium models, on the other hand, incorporate a variety of chemical processes but generally assume no-flow systems. In the past decade, coupled models accounting for complex hydrological and chemical processes, with varying degrees of sophistication, have been developed. The existing models of reactive transport employ two basic sets of equations. The transport of solutes is described by a set of partial differential equations, and the chemical processes, under the assumption of equilibrium, are described by a set of nonlinear algebraic equations. An important consideration in any approach is the choice of primary dependent variables. Most existing models cannot account for the complete set of chemical processes, cannot be easily extended to include mixed chemical equilibria and kinetics, and cannot handle practical two and three dimensional problems. The difficulties arise mainly from improper selection of the primary variables in the transport equations. (Author) 38 refs

  5. Testing antidepressant compounds in a neuropsychological model of drug action

    NARCIS (Netherlands)

    Cerit, Hilal

    2015-01-01

    Although much research effort has been put into the development of new antidepressant drugs, the process of developing a drug often fails at the stage of large randomized controlled trials (RCTs) in which an initially promising compound appears to lack efficacy after all. Several experimental

  6. Evidence for dynamic behavior of O2 in oxy-heme model compounds

    International Nuclear Information System (INIS)

    Montiel-Montoya, R.; Bill, E.; Trautwein, A.X.; Winkler, H.

    1986-01-01

    The authors have performed Moessbauer studies on several oxy-heme model compounds, and for two of them they have also derived the three dimensional structure from X-ray studies. The X-ray structure analysis of these model compounds provides the information that O 2 occupies three different sites in one and only two sites in the other. (Auth.)

  7. Polyfunctional beta-Dicarbonyl Compounds by Michael Addition Reactions of Ester Enolates to alpha-Benzylidene and alpha-Alkylidene-beta-dicarbonyl Compounds

    Czech Academy of Sciences Publication Activity Database

    Holan, Martin; Pohl, Radek; Císařová, I.; Jahn, Ullrich

    -, č. 18 (2012), s. 3459-3475 ISSN 1434-193X R&D Projects: GA ČR GA203/09/1936 Institutional research plan: CEZ:AV0Z40550506 Keywords : Michael addition * diastereoselectivity * regioselectivity * enols * dicarbonyl compounds Subject RIV: CC - Organic Chemistry Impact factor: 3.344, year: 2012

  8. Evolution of the Maillard Reaction in Glutamine or Arginine-Dextrinomaltose Model Systems

    Directory of Open Access Journals (Sweden)

    Silvia Pastoriza

    2016-12-01

    Full Text Available Enteral formulas are foods designed for medical uses to feed patients who are unable to eat normally. They are prepared by mixing proteins, amino acids, carbohydrates and fats and submitted to sterilization. During thermal treatment, the Maillard reaction takes place through the reaction of animo acids with reducing sugars. Thus, although glutamine and arginine are usually added to improve the nutritional value of enteral formulas, their final concentration may vary. Thus, in the present paper the early, intermediate, and advanced states of the Maillard reaction were studied in model systems by measuring loss of free amino acids through the decrease of fluorescence intensity with o-phtaldialdehyde (OPA, 5-Hydroximethylfurfural (HMF, furfural, glucosylisomaltol, fluorescence, and absorbance at 420 nm. The systems were prepared by mixing glutamine or arginine with dextrinomaltose (similar ingredients to those used in special enteral formula, and heated at 100 °C, 120 °C and 140 °C for 0 to 30 min. The recorded changes in the concentration of furanic compounds was only useful for longer heating times of high temperatures, while absorbance and fluorescence measurements were useful in all the assayed conditions. In addition, easiness and sensitivity of absorbance and fluorescence make them useful techniques that could be implemented as indicators for monitoring the manufacture of special enteral formulas. Glucosylisomaltol is a useful indicator to monitor the manufacture of glutamine-enriched enteral formulas.

  9. Evolution of the Maillard Reaction in Glutamine or Arginine-Dextrinomaltose Model Systems.

    Science.gov (United States)

    Pastoriza, Silvia; Rufián-Henares, José Ángel; García-Villanova, Belén; Guerra-Hernández, Eduardo

    2016-12-07

    Enteral formulas are foods designed for medical uses to feed patients who are unable to eat normally. They are prepared by mixing proteins, amino acids, carbohydrates and fats and submitted to sterilization. During thermal treatment, the Maillard reaction takes place through the reaction of animo acids with reducing sugars. Thus, although glutamine and arginine are usually added to improve the nutritional value of enteral formulas, their final concentration may vary. Thus, in the present paper the early, intermediate, and advanced states of the Maillard reaction were studied in model systems by measuring loss of free amino acids through the decrease of fluorescence intensity with o -phtaldialdehyde (OPA), 5-Hydroximethylfurfural (HMF), furfural, glucosylisomaltol, fluorescence, and absorbance at 420 nm. The systems were prepared by mixing glutamine or arginine with dextrinomaltose (similar ingredients to those used in special enteral formula), and heated at 100 °C, 120 °C and 140 °C for 0 to 30 min. The recorded changes in the concentration of furanic compounds was only useful for longer heating times of high temperatures, while absorbance and fluorescence measurements were useful in all the assayed conditions. In addition, easiness and sensitivity of absorbance and fluorescence make them useful techniques that could be implemented as indicators for monitoring the manufacture of special enteral formulas. Glucosylisomaltol is a useful indicator to monitor the manufacture of glutamine-enriched enteral formulas.

  10. Chemical Reductive Transformations of Synthetic Organic Compounds. Probe Compound Studies and Mechanistic Modeling

    National Research Council Canada - National Science Library

    Peyton, Gary

    2001-01-01

    .... A kinetic model that was previously developed to describe the results of batch AOP treatment by H2O2/UV did not give satisfactory predictive results obtained when extended to describe flow experiments...

  11. Enantioselective Synthesis of α-Mercapto-β-amino Esters via Rh(II)/Chiral Phosphoric Acid-Cocatalyzed Three-Component Reaction of Diazo Compounds, Thiols, and Imines.

    Science.gov (United States)

    Xiao, Guolan; Ma, Chaoqun; Xing, Dong; Hu, Wenhao

    2016-12-02

    An enantioselective method for the synthesis of α-mercapto-β-amino esters has been developed via a rhodium(II)/chiral phosphoric acid-cocatalyzed three-component reaction of diazo compounds, thiols, and imines. This transformation is proposed to proceed through enantioselective trapping of the sulfonium ylide intermediate generated in situ from the diazo compound and thiol by the phosphoric acid-activated imine. With this method, a series of α-mercapto-β-amino esters were obtained in good yields with moderate to good stereoselectivities.

  12. An efficient synthesis of β-amino ketone compounds through one-pot three-component Mannich-type reactions using bismuth nitrate as catalyst

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2015-07-01

    Full Text Available Three components one-pot Mannich reaction of aromatic ketone, aromatic aldehyde and aromatic amines has been efficiently catalyzed by recyclable bismuth nitrate (Bi(NO33, BN at ambient temperature to give various β-amino carbonyl compounds in high yields. This method has advantages of mild condition, no environmental pollution, and simple work-up procedures. Most importantly, β-amino carbonyl compounds with ortho-substituted aromatic amines are obtained in acceptable to moderate yields by this methodology.

  13. A multi-pathway model for photosynthetic reaction center

    International Nuclear Information System (INIS)

    Qin, M.; Shen, H. Z.; Yi, X. X.

    2016-01-01

    Charge separation occurs in a pair of tightly coupled chlorophylls at the heart of photosynthetic reaction centers of both plants and bacteria. Recently it has been shown that quantum coherence can, in principle, enhance the efficiency of a solar cell, working like a quantum heat engine. Here, we propose a biological quantum heat engine (BQHE) motivated by Photosystem II reaction center (PSII RC) to describe the charge separation. Our model mainly considers two charge-separation pathways which is more than that typically considered in the published literature. We explore how these cross-couplings increase the current and power of the charge separation and discuss the effects of multiple pathways in terms of current and power. The robustness of the BQHE against the charge recombination in natural PSII RC and dephasing induced by environments is also explored, and extension from two pathways to multiple pathways is made. These results suggest that noise-induced quantum coherence helps to suppress the influence of acceptor-to-donor charge recombination, and besides, nature-mimicking architectures with engineered multiple pathways for charge separations might be better for artificial solar energy devices considering the influence of environments.

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

    International Nuclear Information System (INIS)

    Garrison, W.M.

    1983-11-01

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

  15. Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Cong [Argonne National Lab. (ANL), Argonne, IL (United States); Evans, Tabitha J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Cheng, Lei [Argonne National Lab. (ANL), Argonne, IL (United States); Nimlos, Mark R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Mukarakate, Calvin [National Renewable Energy Lab. (NREL), Golden, CO (United States); Robichaud, David J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Assary, Rajeev S. [Argonne National Lab. (ANL), Argonne, IL (United States); Curtiss, Larry A. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2015-10-02

    These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Major products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.

  16. An Equilibrium-Based Model of Gas Reaction and Detonation

    International Nuclear Information System (INIS)

    Trowbridge, L.D.

    2000-01-01

    During gaseous diffusion plant operations, conditions leading to the formation of flammable gas mixtures may occasionally arise. Currently, these could consist of the evaporative coolant CFC-114 and fluorinating agents such as F2 and ClF3. Replacement of CFC-114 with a non-ozone-depleting substitute is planned. Consequently, in the future, the substitute coolant must also be considered as a potential fuel in flammable gas mixtures. Two questions of practical interest arise: (1) can a particular mixture sustain and propagate a flame if ignited, and (2) what is the maximum pressure that can be generated by the burning (and possibly exploding) gas mixture, should it ignite? Experimental data on these systems, particularly for the newer coolant candidates, are limited. To assist in answering these questions, a mathematical model was developed to serve as a tool for predicting the potential detonation pressures and for estimating the composition limits of flammability for these systems based on empirical correlations between gas mixture thermodynamics and flammability for known systems. The present model uses the thermodynamic equilibrium to determine the reaction endpoint of a reactive gas mixture and uses detonation theory to estimate an upper bound to the pressure that could be generated upon ignition. The model described and documented in this report is an extended version of related models developed in 1992 and 1999

  17. Energetics of hydrogen bonding in proteins: a model compound study.

    OpenAIRE

    Habermann, S. M.; Murphy, K. P.

    1996-01-01

    Differences in the energetics of amide-amide and amide-hydroxyl hydrogen bonds in proteins have been explored from the effect of hydroxyl groups on the structure and dissolution energetics of a series of crystalline cyclic dipeptides. The calorimetrically determined energetics are interpreted in light of the crystal structures of the studied compounds. Our results indicate that the amide-amide and amide-hydroxyl hydrogen bonds both provide considerable enthalpic stability, but that the amide-...

  18. Effects of electric current upon catalytic steam reforming of biomass gasification tar model compounds to syngas

    International Nuclear Information System (INIS)

    Tao, Jun; Lu, Qiang; Dong, Changqing; Du, Xiaoze; Dahlquist, Erik

    2015-01-01

    Highlights: • ECR technique was proposed to convert biomass gasification tar model compounds. • Electric current enhanced the reforming efficiency remarkably. • The highest toluene conversion reached 99.9%. • Ni–CeO 2 /γ-Al 2 O 3 exhibited good stability during the ECR performance. - Abstract: Electrochemical catalytic reforming (ECR) technique, known as electric current enhanced catalytic reforming technique, was proposed to convert the biomass gasification tar into syngas. In this study, Ni–CeO 2 /γ-Al 2 O 3 catalyst was prepared, and toluene was employed as the major feedstock for ECR experiments using a fixed-bed lab-scale setup where thermal electrons could be generated and provided to the catalyst. Several factors, including the electric current intensity, reaction temperature and steam/carbon (S/C) ratio, were investigated to reveal their effects on the conversion of toluene as well as the composition of the gas products. Moreover, toluene, two other tar model compounds (benzene and 1-methylnaphthalene) and real tar (tar-containing wastewater) were subjected to the long period catalytic stability tests. All the used catalysts were analyzed to determine their carbon contents. The results indicated that the presence of electric current enhanced the catalytic performance remarkably. The toluene conversion reached 99.9% under the electric current of 4 A, catalytic temperature of 800 °C and S/C ratio of 3. Stable conversion performances of benzene, 1-methylnaphthalene and tar-containing wastewater were also observed in the ECR process. H 2 and CO were the major gas products, while CO 2 and CH 4 were the minor ones. Due to the promising capability, the ECR technique deserves further investigation and application for efficient tar conversion

  19. Steam reforming of different biomass tar model compounds over Ni/Al_2O_3 catalysts

    International Nuclear Information System (INIS)

    Artetxe, Maite; Alvarez, Jon; Nahil, Mohamad A.; Olazar, Martin; Williams, Paul T.

    2017-01-01

    Highlights: • Order of reactivity: anisole > furfural > indene > phenol > toluene > methyl naphthalene. • Higher coke deposition for oxygenates (1.5–2.8%) than for aromatics (0.5–0.8%). • Amorphous coke is deposited for oxygenates and filamentous carbon for aromatics. • Ni content of 20 wt.% shows the higher conversion (90%) and H_2 potential (63%). - Abstract: This work focuses on the removal of the tar derived from biomass gasification by catalytic steam reforming on Ni/Al_2O_3 catalysts. Different tar model compounds (phenol, toluene, methyl naphthalene, indene, anisole and furfural) were individually steam reformed (after dissolving each one in methanol), as well as a mixture of all of them, at 700 °C under a steam/carbon (S/C) ratio of 3 and 60 min on stream. The highest conversions and H_2 potential were attained for anisole and furfural, while methyl naphthalene presented the lowest reactivity. Nevertheless, the higher reactivity of oxygenates compared to aromatic hydrocarbons promoted carbon deposition on the catalyst (in the 1.5–2.8 wt.% range). When the concentration of methanol is decreased in the feedstock and that of toluene or anisole is increased, the selectivity to CO is favoured in the gaseous products, thus increasing coke deposition on the catalyst and decreasing catalyst activity for the steam reforming reaction. Moreover, an increase in Ni loading in the catalyst from 5 to 20% enhances carbon conversion and H_2 formation in the steam reforming of a mixture of all the model compounds studied, but these values decrease for a Ni content of 40%. Coke formation also increased by increasing Ni loading, attaining its maximum value for 40% Ni (6.5 wt.%).

  20. Virtual disjunct eddy covariance measurements of organic compound fluxes from a subalpine forest using proton transfer reaction mass spectrometry

    Directory of Open Access Journals (Sweden)

    T. G. Karl

    2002-01-01

    Full Text Available A `virtual' disjunct eddy covariance (vDEC device was tested with field measurements of biogenic VOC fluxes at a subalpine forest site in the Rocky Mountains of the USA. A PTR-MS instrument was used as the VOC sensor. Daily peak emission fluxes of 2-methyl-3-buten-2-ol (MBO, methanol, acetone and acetaldehyde were around 1.5, 1, 0.8 and 0.4 mg m-2 h-1, respectively. High pass filtering due to long sampling lines was investigated in laboratory experiments, and suggested that VOC losses in PTFA lines are generally governed by diffusion laws. Memory effects and surface reactions did not seem to play a dominant role. Model estimates of MBO fluxes compared well with measured fluxes. The results also suggest that latent heat and sensible heat fluxes are reasonably well correlated with VOC fluxes and could be used to predict variations in VOC emissions. The release of MBO, methanol, acetone and acetaldehyde resulted in significant change of tropospheric oxidant levels and a 10--40% increase in ozone levels, as inferred from a photochemical box model. We conclude that vDEC with a PTR-MS instrument is a versatile tool for simultaneous field analysis of multiple VOC fluxes.

  1. Mixing-assisted oxidative desulfurization of model sulfur compounds using polyoxometalate/H2O2 catalytic system

    OpenAIRE

    Angelo Earvin Sy Choi; Susan Roces; Nathaniel Dugos; Meng-Wei Wan

    2016-01-01

    Desulfurization of fossil fuel derived oil is needed in order to comply with environmental regulations. Dibenzothiophene and benzothiophene are among the predominant sulfur compound present in raw diesel oil. In this study, mixing-assisted oxidative desulfurization of dibenzothiophene and benzothiophene were carried out using polyoxometalate/H2O2 systems and a phase transfer agent. The effects of reaction time (2–30 min) and temperature (30–70 °C) were examined in the oxidation of model sulfu...

  2. Filtration and Hydrogen Reaction Modeling in a Depleted Uranium Bed

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Kwang Jin; Kim, Yean Jin; Ahn, Do Hee; Chung, Hong Suk [UST, Daejeon (Korea, Republic of); Kang, Hee Seok [KAERI, Daejeon (Korea, Republic of); Yun, Sei Hun [NFRI, Daejeon (Korea, Republic of)

    2016-05-15

    The storage and delivery system (SDS) stores the hydrogen isotopes and delivers them to the fuel injection system. Depleted uranium (DU) was chosen as a hydrogen isotope storage material. The hydrogen isotopes stored in the SDS are in the form of DU hydride confined in the primary and secondary containment within a glove box with an argon atmosphere. In this study, we performed a modeling study of the SDS. A modeling study is practically important because an experimental study requires comparatively more money and time. We estimated the hydrogen atomic ratio in DU hydride by two empirical equations we formulated. Two empirical equations are used to determine Pressure-Composition-Temperature (PCT) curves and the hydrogen atomic ratio in DU hydride. In addition, we present the effect of pressure and temperature in the hydriding and dehydriding. A modeling study of the SDS was performed in this study. It is practically important to save more money and time. The hydrogen atomic ratio in the DU hydride was estimated using two empirical equations. The two empirical equations are modified and reformulated to determine PCT curves and the hydrogen atomic ratio in DU hydride. All parameters that are required to solve two empirical equations are obtained from the experimental data. The derived parameters are utilized for the numerical simulations. In the numerical simulations, the effects of pressure and temperature on both the hydriding and dehydriding reaction rates are confirmed.

  3. The influence of model resolution on ozone in industrial volatile organic compound plumes.

    Science.gov (United States)

    Henderson, Barron H; Jeffries, Harvey E; Kim, Byeong-Uk; Vizuete, William G

    2010-09-01

    Regions with concentrated petrochemical industrial activity (e.g., Houston or Baton Rouge) frequently experience large, localized releases of volatile organic compounds (VOCs). Aircraft measurements suggest these released VOCs create plumes with ozone (O3) production rates 2-5 times higher than typical urban conditions. Modeling studies found that simulating high O3 productions requires superfine (1-km) horizontal grid cell size. Compared with fine modeling (4-kmin), the superfine resolution increases the peak O3 concentration by as much as 46%. To understand this drastic O3 change, this study quantifies model processes for O3 and "odd oxygen" (Ox) in both resolutions. For the entire plume, the superfine resolution increases the maximum O3 concentration 3% but only decreases the maximum Ox concentration 0.2%. The two grid sizes produce approximately equal Ox mass but by different reaction pathways. Derived sensitivity to oxides of nitrogen (NOx) and VOC emissions suggests resolution-specific sensitivity to NOx and VOC emissions. Different sensitivity to emissions will result in different O3 responses to subsequently encountered emissions (within the city or downwind). Sensitivity of O3 to emission changes also results in different simulated O3 responses to the same control strategies. Sensitivity of O3 to NOx and VOC emission changes is attributed to finer resolved Eulerian grid and finer resolved NOx emissions. Urban NOx concentration gradients are often caused by roadway mobile sources that would not typically be addressed with Plume-in-Grid models. This study shows that grid cell size (an artifact of modeling) influences simulated control strategies and could bias regulatory decisions. Understanding the dynamics of VOC plume dependence on grid size is the first step toward providing more detailed guidance for resolution. These results underscore VOC and NOx resolution interdependencies best addressed by finer resolution. On the basis of these results, the

  4. Investigating actinide compounds within a hybrid MCSCF-DFT model

    International Nuclear Information System (INIS)

    Fromager, E.; Jensen, H.J.A.; Wahlin, P.; Real, F.; Wahlgren, U.

    2007-01-01

    Complete text of publication follows: Investigations of actinide chemistry with quantum chemical methods still remain a complicated task since it requires an accurate and efficient treatment of the environment (crystal or solvent) as well as relativistic and electron correlation effects. Concerning the latter, the current correlated methods, based on either Density-Functional Theory (DFT) or Wave-Function Theory (WFT), have their advantages and drawbacks. On the one hand, Kohn-Sham DFT (KS-DFT) calculates the dynamic correlation quite accurately and at a fairly low computational cost. However, it does not treat adequately the static correlation, which is significant in some actinide compounds because of the near-degeneracy of the 5f orbitals: a first example is the bent geometry obtained in KS-DFT(B3LYP) for the neptunyl ion NpO 2 3+ , which is found to be linear within a Multi-Configurational Self-Consistent Field (MCSCF) model [1]. A second one is the stable and bent geometry obtained in KS-DFT(B3LYP) for the plutonyl ion PuO 2 4+ , which disintegrates at the MCSCF level [1]. On the other hand, WFT can describe the static correlation, using for example a MCSCF model, but then an important part of the dynamic correlation has to be neglected. This can be recovered with perturbation-theory based methods like for example CASPT2 or NEVPT2, but their computational complexity prevents large scale calculations. It is therefore of great interest to develop a hybrid MCSCF-DFT model which combines the best of both WFT and DFT approaches. The merge of WFT and DFT can be achieved by splitting the two-electron interaction into long-range and short-range parts [2]. The long-range part is then treated by WFT and the short-range part by DFT. We use the so-called 'erf' long-range interaction erf(μr 12 )/r 12 , which is based on the standard error function, and where μ is a free parameter which controls the long/short-range decomposition. The newly proposed recipe for the

  5. α-Bromodiazoacetamides – a new class of diazo compounds for catalyst-free, ambient temperature intramolecular C–H insertion reactions

    Directory of Open Access Journals (Sweden)

    Åsmund Kaupang

    2013-07-01

    Full Text Available In this work, we introduce a new class of halodiazocarbonyl compounds, α-halodiazoacetamides, which through a metal-free, ambient-temperature thermolysis perform intramolecular C–H insertions to produce α-halo-β-lactams. When carried out with α-bromodiazoacetamides bearing cyclic side chains, the thermolysis reaction affords bicyclic α-halo-β-lactams, in some cases in excellent yields, depending on the ring size and substitution pattern of the cyclic amide side chains.

  6. Inflammatory bowel disease and patterns of volatile organic compounds in the exhaled breath of children: A case-control study using Ion Molecule Reaction-Mass Spectrometry.

    Science.gov (United States)

    Monasta, Lorenzo; Pierobon, Chiara; Princivalle, Andrea; Martelossi, Stefano; Marcuzzi, Annalisa; Pasini, Francesco; Perbellini, Luigi

    2017-01-01

    Inflammatory bowel diseases (IBD) profoundly affect quality of life and have been gradually increasing in incidence, prevalence and severity in many areas of the world, and in children in particular. Patients with suspected IBD require careful history and clinical examination, while definitive diagnosis relies on endoscopic and histological findings. The aim of the present study was to investigate whether the alveolar air of pediatric patients with IBD presents a specific volatile organic compounds' (VOCs) pattern when compared to controls. Patients 10-17 years of age, were divided into four groups: Crohn's disease (CD), ulcerative colitis (UC), controls with gastrointestinal symptomatology, and surgical controls with no evidence of gastrointestinal problems. Alveolar breath was analyzed by ion molecule reaction mass spectrometry. Four models were built starting from 81 molecules plus the age of subjects as independent variables, adopting a penalizing LASSO logistic regression approach: 1) IBDs vs. controls, finally based on 18 VOCs plus age (sensitivity = 95%, specificity = 69%, AUC = 0.925); 2) CD vs. UC, finally based on 13 VOCs plus age (sensitivity = 94%, specificity = 76%, AUC = 0.934); 3) IBDs vs. gastroenterological controls, finally based on 15 VOCs plus age (sensitivity = 94%, specificity = 65%, AUC = 0.918); 4) IBDs vs. controls, built starting from the 21 directly or indirectly calibrated molecules only, and finally based on 12 VOCs plus age (sensitivity = 94%, specificity = 71%, AUC = 0.888). The molecules identified by the models were carefully studied in relation to the concerned outcomes. This study, with the creation of models based on VOCs profiles, precise instrumentation and advanced statistical methods, can contribute to the development of new non-invasive, fast and relatively inexpensive diagnostic tools, with high sensitivity and specificity. It also represents a crucial step towards gaining further insights on the etiology of IBD through the

  7. A Data-Driven Sparse-Learning Approach to Model Reduction in Chemical Reaction Networks

    OpenAIRE

    Harirchi, Farshad; Khalil, Omar A.; Liu, Sijia; Elvati, Paolo; Violi, Angela; Hero, Alfred O.

    2017-01-01

    In this paper, we propose an optimization-based sparse learning approach to identify the set of most influential reactions in a chemical reaction network. This reduced set of reactions is then employed to construct a reduced chemical reaction mechanism, which is relevant to chemical interaction network modeling. The problem of identifying influential reactions is first formulated as a mixed-integer quadratic program, and then a relaxation method is leveraged to reduce the computational comple...

  8. Formation of high-molecular-weight compounds via the heterogeneous reactions of gaseous C8-C10 n-aldehydes in the presence of atmospheric aerosol components

    Science.gov (United States)

    Han, Yuemei; Kawamura, Kimitaka; Chen, Qingcai; Mochida, Michihiro

    2016-02-01

    A laboratory study on the heterogeneous reactions of straight-chain aldehydes was performed by exposing n-octanal, nonanal, and decanal vapors to ambient aerosol particles. The aerosol and blank filters were extracted using methanol. The extracts were nebulized and the resulting compositions were examined using a high-resolution time-of-flight aerosol mass spectrometer. The mass spectral analysis showed that the exposures of the aldehydes to aerosol samples increased the peak intensities in the high mass range. The peaks in the mass spectra of the aerosol samples after exposure to different aldehydes were characterized by a homologous series of peak shifts due to the addition of multiple CH2 units. This result is explained by the formation of high-molecular-weight (HMW) compounds that contain single or multiple aldehyde moieties. The HMW fragment peaks for the blank filters exposed to n-aldehydes were relatively weak, indicating an important contribution from the ambient aerosol components to the formation of the HMW compounds. Among the factors affecting the overall interaction of aldehydes with atmospheric aerosol components, gas phase diffusion possibly limited the reactions under the studied conditions; therefore, their occurrence to a similar degree in the atmosphere is not ruled out, at least for the reactions involving n-nonanal and decanal. The major formation pathways for the observed HMW products may be the self-reactions of n-aldehydes mediated by atmospheric aerosol components and the reactions of n-aldehydes with organic aerosol components. The observed formation of HMW compounds encourages further investigations into their effects on the aerosol properties as well as the organic aerosol mass in the atmosphere.

  9. Chemical Reaction and Flow Modeling in Fullerene and Nanotube Production

    Science.gov (United States)

    Scott, Carl D.; Farhat, Samir; Greendyke, Robert B.

    2004-01-01

    The development of processes to produce fullerenes and carbon nanotubes has largely been empirical. Fullerenes were first discovered in the soot produced by laser ablation of graphite [1]and then in the soot of electric arc evaporated carbon. Techniques and conditions for producing larger and larger quantities of fullerenes depended mainly on trial and error empirical variations of these processes, with attempts to scale them up by using larger electrodes and targets and higher power. Various concepts of how fullerenes and carbon nanotubes were formed were put forth, but very little was done based on chemical kinetics of the reactions. This was mainly due to the complex mixture of species and complex nature of conditions in the reactors. Temperatures in the reactors varied from several thousand degrees Kelvin down to near room temperature. There are hundreds of species possible, ranging from atomic carbon to large clusters of carbonaceous soot, and metallic catalyst atoms to metal clusters, to complexes of metals and carbon. Most of the chemical kinetics of the reactions and the thermodynamic properties of clusters and complexes have only been approximated. In addition, flow conditions in the reactors are transient or unsteady, and three dimensional, with steep spatial gradients of temperature and species concentrations. All these factors make computational simulations of reactors very complex and challenging. This article addresses the development of the chemical reaction involved in fullerene production and extends this to production of carbon nanotubes by the laser ablation/oven process and by the electric arc evaporation process. In addition, the high-pressure carbon monoxide (HiPco) process is discussed. The article is in several parts. The first one addresses the thermochemical aspects of modeling; and considers the development of chemical rate equations, estimates of reaction rates, and thermodynamic properties where they are available. The second part

  10. Sonochemical synthesis, characterization, and effects of temperature, power ultrasound and reaction time on the morphological properties of two new nanostructured mercury(II) coordination supramolecule compounds.

    Science.gov (United States)

    Hayati, Payam; Rezvani, Ali Reza; Morsali, Ali; Molina, Daniel Ruiz; Geravand, Samira; Suarez-Garcia, Salvio; Villaecija, Miguel Angel Moreno; García-Granda, S; Mendoza-Meroño, Rafael; Retailleau, Pascal

    2017-07-01

    Two new mercury(II) coordination supramolecular compounds (CSCs) (1D and 0D), [Hg(L)(I) 2 ] n (1) and [Hg 2 (L') 2 (SCN) 2 ]·2H 2 O (2) (L=2-amino-4-methylpyridine and L'=2,6-pyridinedicarboxlic acid), have been synthesized under different experimental conditions. Micrometric crystals (bulk) or nano-sized materials have been obtained depending on using the branch tube method or sonochemical irradiation. All materials have been characterized by field emission scanning electron microscope (FESEM), scanning electron microscopy (SEM), powder X-ray diffraction (PXRD) and FT-IR spectroscopy. Single crystal X-ray analyses on compounds 1 and 2 show that Hg 2+ ions are 4-coordinated and 5-coordinated, respectively. Topological analysis shows that the compound 1 and 2 have 2C1, sql net. The thermal stability of compounds 1 and 2 in bulk and nano-size has been studied by thermal gravimetric (TG), differential thermal analyses (DTA) for 1 and differential scanning calorimetry (DSC) for 2, respectively. Also, by changing counter ions were obtained various structures 1 and 2 (1D and 0D, respectively). The role of different parameters like power of ultrasound irradiation, reaction time and temperature on the growth and morphology of the nano-structures are studied. Results suggest that increasing power ultrasound irradiation and temperature together with reducing reaction time and concentration of initial reagents leads to a decrease in particle size. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. A Versatile Route to Unstable Diazo Compounds via Oxadiazolines and their Use in Aryl–Alkyl Cross‐Coupling Reactions

    Science.gov (United States)

    Greb, Andreas; Poh, Jian‐Siang; Greed, Stephanie; Battilocchio, Claudio; Pasau, Patrick; Blakemore, David C.

    2017-01-01

    Abstract Coupling of readily available boronic acids and diazo compounds has emerged recently as a powerful metal‐free carbon–carbon bond forming method. However, the difficulty in forming the unstable diazo compound partner in a mild fashion has hitherto limited their general use and the scope of the transformation. Here, we report the application of oxadiazolines as precursors for the generation of an unstable family of diazo compounds using flow UV photolysis and their first use in divergent protodeboronative and oxidative C(sp2)−C(sp3) cross‐coupling processes, with excellent functional‐group tolerance. PMID:29088512

  12. Adsorption and degradation of model volatile organic compounds by a combined titania-montmorillonite-silica photocatalyst

    International Nuclear Information System (INIS)

    Chen Jiangyao; Li Guiying; He Zhigui; An Taicheng

    2011-01-01

    Highlights: → Adsorptive combined titania-montmorillonite-silica photocatalysts synthesized. → All catalysts had relatively high adsorption capacities of multinary VOCs. → All catalysts preferred to adsorb the VOCs with higher polarity. → CTMS80 can effectively photocatalytically remove VOCs of various components. - Abstract: A series of adsorptive photocatalysts, combined titania-montmorillonite-silica were synthesized. The resultant photocatalysts consisted of more and more spherically agglomerated TiO 2 particles with increasing of TiO 2 content, and anatase was the only crystalline phase with nano-scale TiO 2 particles. With increasing of the cation exchange capacity to TiO 2 molar ratio, specific surface area and pore volume increased very slightly. In a fluidized bed photocatalytic reactor by choosing toluene, ethyl acetate and ethanethiol as model pollutants, all catalysts had relatively high adsorption capacities and preferred to adsorb higher polarity pollutants. Langmuir isotherm model better described equilibrium data compared to Freundlich model. Competitive adsorptions were observed for the mixed pollutants on the catalysts, leading to decrease adsorption capacity for each pollutant. The combined titania-montmorillonite-silica photocatalyst exhibited excellent photocatalytic removal ability to model pollutants of various components. Almost 100% of degradation efficiency was achieved within 120 min for each pollutant with about 500 ppb initial concentration, though the efficiencies of multi-component compounds slightly decreased. All photocatalytic reactions followed the Langmuir-Hinshelwood model. Degradation rate constants of multi-component systems were lower than those for single systems, following the order of toluene < ethyl acetate < ethanethiol, and increased with the increase of adsorption capacities for different pollutants of various components.

  13. Towards a lumped reaction model for future designer fuels

    Energy Technology Data Exchange (ETDEWEB)

    Vandersickel, A.; Wright, Y.M.; Boulouchos, K. [ETH Zurich, Aerothermochemistry and Combustion Systems Laboratory, Zurich (Switzerland). Inst. of Energy Technology

    2009-07-01

    The homogeneous charge compression ignition (HCCI) is one of the most promising engine processes to simultaneously reduce nitrogen oxide and soot emissions. However, its applicability is hindered by its relatively limited operating range. Designer fuels offer unique possibilities for tailoring evaporation and auto-ignition properties, offering a means to control and expand the HCCI operation range. The identification of HCCI relevant fuel properties as well as the definition of a new fuel index able to describe a fuels suitability for HCCI was required in order to develop such designer fuels. This paper discussed a numerical and experimental investigation of a large set of technical fuels covering a wide range of properties. The paper discussed mechanism development approaches, optimization of the lumped mechanism, and and results. Zheng's 7-step reaction mechanism was successfully coupled with a genetic optimization algorithm and fitted to n-heptane ignition delay data. It was concluded that the presented coupled approach could improve the predictive quality of the model and demonstrate that the Zheng model was sufficiently elaborate to emulate the influence of temperature, pressure, exhaust gas recirculation and lambda on ignition. 8 refs., 1 tab., 3 figs.

  14. Towards a lumped reaction model for future designer fuels

    International Nuclear Information System (INIS)

    Vandersickel, A.; Wright, Y.M.; Boulouchos, K.

    2009-01-01

    The homogeneous charge compression ignition (HCCI) is one of the most promising engine processes to simultaneously reduce nitrogen oxide and soot emissions. However, its applicability is hindered by its relatively limited operating range. Designer fuels offer unique possibilities for tailoring evaporation and auto-ignition properties, offering a means to control and expand the HCCI operation range. The identification of HCCI relevant fuel properties as well as the definition of a new fuel index able to describe a fuels suitability for HCCI was required in order to develop such designer fuels. This paper discussed a numerical and experimental investigation of a large set of technical fuels covering a wide range of properties. The paper discussed mechanism development approaches, optimization of the lumped mechanism, and and results. Zheng's 7-step reaction mechanism was successfully coupled with a genetic optimization algorithm and fitted to n-heptane ignition delay data. It was concluded that the presented coupled approach could improve the predictive quality of the model and demonstrate that the Zheng model was sufficiently elaborate to emulate the influence of temperature, pressure, exhaust gas recirculation and lambda on ignition. 8 refs., 1 tab., 3 figs.

  15. Learned Helplessness: A Model to Understand and Overcome a Child's Extreme Reaction to Failure.

    Science.gov (United States)

    Balk, David

    1983-01-01

    The author reviews literature on childrens' reactions to perceived failure and offers "learned helplessness" as a model to explain why a child who makes a mistake gives up. Suggestions for preventing these reactions are given. (Author/JMK)

  16. Simulation and Statistical Inference of Stochastic Reaction Networks with Applications to Epidemic Models

    KAUST Repository

    Moraes, Alvaro

    2015-01-01

    Networks (SRNs), that are intended to describe the time evolution of interacting particle systems where one particle interacts with the others through a finite set of reaction channels. SRNs have been mainly developed to model biochemical reactions

  17. Selecting a Response in Task Switching: Testing a Model of Compound Cue Retrieval

    Science.gov (United States)

    Schneider, Darryl W.; Logan, Gordon D.

    2009-01-01

    How can a task-appropriate response be selected for an ambiguous target stimulus in task-switching situations? One answer is to use compound cue retrieval, whereby stimuli serve as joint retrieval cues to select a response from long-term memory. In the present study, the authors tested how well a model of compound cue retrieval could account for a…

  18. Development of corresponding states model for estimation of the surface tension of chemical compounds

    DEFF Research Database (Denmark)

    Gharagheizi, Farhad; Eslamimanesh, Ali; Sattari, Mehdi

    2013-01-01

    include critical temperature or temperature/critical volume/acentric factor/critical pressure/reduced temperature/reduced normal boiling point temperature/molecular weight of the compounds. Around 1,300 surface tension data of 118 random compounds are used for developing the first model (a four...

  19. A kinetic study of the redox reactions of complex cyanides of iron, molybdenum and tungsten with compounds of the group VI A elements

    International Nuclear Information System (INIS)

    Dennis, C.R.

    1981-01-01

    The kinetic study arises out of the fact that few is known about redox kinetics of complex cyanides of molybdenum and tungsten. The redox kinetics of the complex cyanides of iron with organic and inorganic compounds are well known in organic chemistry. This comparitive study is done to obtain more information on redox reactions of complex cyanides of molybdenum and tungsten considering its greater applicability in organic and inorganic chemistry because of the propitious reduction potential of this complex cyanide in acidic and alkaline mediums. Various redox systems are kinetically investigated regarding the influence of the oxidising agent, reducing agent hydrogen ions and alkaline-metal ions on the reaction rate. A reaction mechanism is proposed for every system

  20. Modeling and analysis of liquid deuterium-water reactions

    International Nuclear Information System (INIS)

    Taleyarkhan, R.P.

    1995-01-01

    This Presentation highlights the following: Overview of LD 2 -water reactions their connections to research reactors with cold sources; some key features and ingredients of vapor explosions in general; Examination of results of 1970 experiment at Grenoble Nuclear Research Center; Thermodynamic evaluations of energetics of explosive LD 2 -D 2 O reactions. This presentation concentrates only on the technical aspects of LD 2 /LH 2 - water reactions; it is not intended to draw/imply safety-related conclusions for research reactors

  1. A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reaction flows

    Science.gov (United States)

    Magnotti, F.; Diskin, G.; Matulaitis, J.; Chinitz, W.

    1984-01-01

    The use of silane (SiH4) as an effective ignitor and flame stabilizing pilot fuel is well documented. A reliable chemical kinetic mechanism for prediction of its behavior at the conditions encountered in the combustor of a SCRAMJET engine was calculated. The effects of hydrogen addition on hydrocarbon ignition and flame stabilization as a means for reduction of lengthy ignition delays and reaction times were studied. The ranges of applicability of chemical kinetic models of hydrogen-air combustors were also investigated. The CHARNAL computer code was applied to the turbulent reaction rate modeling.

  2. Modeling non-adiabatic photoexcited reaction dynamics in condensed phases

    International Nuclear Information System (INIS)

    Coker, D.F.

    2003-01-01

    Reactions of photoexcited molecules, ions, and radicals in condensed phase environments involve non-adiabatic dynamics over coupled electronic surfaces. We focus on how local environmental symmetries can effect non-adiabatic coupling between excited electronic states and thus influence, in a possibly controllable way, the outcome of photo-excited reactions. Semi-classical and mixed quantum-classical non-adiabatic molecular dynamics methods, together with semi-empirical excited state potentials are used to probe the dynamical mixing of electronic states in different environments from molecular clusters, to simple liquids and solids, and photo-excited reactions in complex reaction environments such as zeolites

  3. A semi-classical model for the description of angular distribution of light particles emitted in nuclear reactions

    International Nuclear Information System (INIS)

    Zhang Jingshang

    1990-04-01

    A semi-classical model of multi-step direct and compound nuclear reactions has been proposed to describe the angular distributions of light particles emitted in reaction processes induced by nucleons with energies of several tens of MeV. The exact closed solution for the time-dependent master equation of the exciton model is applied. Based on the Fermi gas model, the scattering kernel for two-nucleon collisions includes the influence of the Fermi motion and the Pauli exclusion principle, which give a significant improvement in the description of the rise of the backward distributions. The angle-energy correlation for the first few steps of the collision process (multi-step direct process) yields further improvements in the description of the angular distribution. The pick-up mechanism is employed to describe the composite particle emission. This reasonable physical picture reproduces the experimental data of the energy spectra of composite particles satisfactorily. The angular distribution of the emitted composite particles is determined by an angular factor in terms of the momentum conservation of the nucleons forming the composite cluster. The generalized master equation is employed for the multi-step compound process. Thus a classical approach has been established to calculate the double differential cross sections for all kinds of particles emitted in multi-step nuclear reaction processes. (author). 19 refs, 6 figs, 1 tab

  4. Quark compound bag (QCB) model and nucleon-nucleon interaction

    International Nuclear Information System (INIS)

    Simonov, Yu.A.

    1983-01-01

    Quark degrees of freedom are treated in the NN system in the framework of the QCB model. The resulting QCB potential is in agreement with experimental data. P-matrix analysis inherent to the QCB model is discussed in detail. Applications of the QCB model are given including the weak NN interaction

  5. Construction and Optimization of a Heterologous Pathway for Protocatechuate Catabolism in Escherichia coli Enables Bioconversion of Model Aromatic Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Clarkson, Sonya M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biosciences Division; Giannone, Richard J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Kridelbaugh, Donna M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biosciences Division; Elkins, James G. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biosciences Division; Guss, Adam M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biosciences Division; Michener, Joshua K. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biosciences Division, BioEnergy Science Center; Vieille, Claire [Michigan State Univ., East Lansing, MI (United States)

    2017-07-21

    The production of biofuels from lignocellulose yields a substantial lignin by-product stream that currently has few applications. Biological conversion of lignin-derived compounds into chemicals and fuels has the potential to improve the economics of lignocellulose-derived biofuels, but few microbes are able both to catabolize lignin-derived aromatic compounds and to generate valuable products. WhileEscherichia colihas been engineered to produce a variety of fuels and chemicals, it is incapable of catabolizing most aromatic compounds. Therefore, we engineeredE. colito catabolize protocatechuate, a common intermediate in lignin degradation, as the sole source of carbon and energy via heterologous expression of a nine-gene pathway fromPseudomonas putidaKT2440. Then, we used experimental evolution to select for mutations that increased growth with protocatechuate more than 2-fold. Increasing the strength of a single ribosome binding site in the heterologous pathway was sufficient to recapitulate the increased growth. After optimization of the core pathway, we extended the pathway to enable catabolism of a second model compound, 4-hydroxybenzoate. These engineered strains will be useful platforms to discover, characterize, and optimize pathways for conversions of lignin-derived aromatics.

    IMPORTANCELignin is a challenging substrate for microbial catabolism due to its polymeric and heterogeneous chemical structure. Therefore, engineering microbes for improved catabolism of lignin-derived aromatic compounds will require the assembly of an entire network of catabolic reactions, including pathways from genetically intractable strains. By constructing defined pathways for aromatic compound degradation in a model host would allow rapid

  6. Kinetic modelling of reactions in heated disaccharide-casein systems

    NARCIS (Netherlands)

    Brands, C.M.J.; Boekel, van M.A.J.S.

    2003-01-01

    The reactions occurring in disaccharide-casein reaction mixtures during heating at 120 degreesC and pH 6.8 were studied. The existence of two main degradation routes were established: (1) Isomerisation of the aldose sugars lactose and maltose in their ketose isomers lactulose and maltulose,

  7. Nonlinear variational models for reaction and diffusion systems

    International Nuclear Information System (INIS)

    Tanyi, G.E.

    1983-08-01

    There exists a natural metric w.r.t. which the density dependent diffusion operator is harmonic in the sense of Eells and Sampson. A physical corollary of this statement is the property that any two regular points on the orbit of a reaction or diffusion operator can be connected by a path along which the reaction rate is constant. (author)

  8. Modeling of a dissolution system for transuranic compounds

    International Nuclear Information System (INIS)

    Chiba, Z.; Dease, C.

    1991-02-01

    A system is currently being developed at Lawrence Livermore Laboratory to treat transuranic wastes by means of a mediated electrochemical oxidation process. The process involves generating Ag( ++ ) from a solution of silver nitrate and nitric acid in an electrochemical cell. Ag( ++ ) is highly reactive and is capable of attacking many organic and inorganic substances. In particular, if a mixture of particles containing transuranic and other scrap metal oxides is allowed to react with Ag( ++ ) in a nitric acid solution, the transuranic oxides will dissolve and can be removed with the solution leaving the other insoluble oxides behind. The dissolution of the transuranic oxides by reactions with Ag( ++ ) occurs due to further oxidation to higher valence states and the formation of soluble ions such as MO 2 + and MO 2 ++ . 7 refs., 5 figs., 1 tab

  9. Formation of radical anions of radiosensitizers and related model compounds via electrospray ionization

    DEFF Research Database (Denmark)

    Feketeová, Linda; Albright, Abigail L; Sørensen, Brita Singers

    2014-01-01

    Radiosensitizers are used in radiotherapy to enhance tumour control of radioresistant hypoxic tumours. While the detailed mechanism of radiosensitization is still unknown, the formation of radical anions is believed to be a key step. Thus understanding the ionization reactions of radiosensitizers......, misonidazole and related compounds using a hybrid linear ion trap – Fourier Transform Ion Cyclotron Resonance mass spectrometer (Finnigan-LTQ-FT). A key finding is that negative electrospray ionization of these radiosensitizers leads to the formation of radical anions, allowing their fragmentation reactions...

  10. Stability Analysis of a Reaction-Diffusion System Modeling Atherogenesis

    KAUST Repository

    Ibragimov, Akif

    2010-01-01

    This paper presents a linear, asymptotic stability analysis for a reaction-diffusionconvection system modeling atherogenesis, the initiation of atherosclerosis, as an inflammatory instability. Motivated by the disease paradigm articulated by Ross, atherogenesis is viewed as an inflammatory spiral with a positive feedback loop involving key cellular and chemical species interacting and reacting within the intimal layer of muscular arteries. The inflammatory spiral is initiated as an instability from a healthy state which is defined to be an equilibrium state devoid of certain key inflammatory markers. Disease initiation is studied through a linear, asymptotic stability analysis of a healthy equilibrium state. Various theorems are proved, giving conditions on system parameters guaranteeing stability of the health state, and a general framework is developed for constructing perturbations from a healthy state that exhibit blow-up, which are interpreted as corresponding to disease initiation. The analysis reveals key features that arterial geometry, antioxidant levels, and the source of inflammatory components (through coupled third-kind boundary conditions or through body sources) play in disease initiation. © 2010 Society for Industrial and Applied Mathematics.

  11. A Signal Detection Model of Compound Decision Tasks

    Science.gov (United States)

    2006-12-01

    strict isolation (for many examples of such models see Egan, 1975; Macmillan & Creelman , 1991). The result has been twofold: A rich corpus of decision...Macmillan & Creelman , 1991). It is important to point out that SDT models are primarily decision models. They specify the rules and procedures for how...Broadbent, 1958; Macmillan & Creelman , 1991; Nolte & Jaarsma, 1967; Swensson & Judy, 1981; Tanner & Norman, 1954). To better understand how these two

  12. Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

    Directory of Open Access Journals (Sweden)

    C. Mouchel-Vallon

    2013-01-01

    Full Text Available The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation to 70% (octane oxidation of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively. Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

  13. A Temperature-Dependent Hysteresis Model for Relaxor Ferroelectric Compounds

    National Research Council Canada - National Science Library

    Raye, Julie K; Smith, Ralph C

    2004-01-01

    This paper summarizes the development of a homogenized free energy model which characterizes the temperature-dependent hysteresis and constitutive nonlinearities inherent to relaxor ferroelectric materials...

  14. Identifying developmental vascular disruptor compounds using a predictive signature and alternative toxicity models

    Science.gov (United States)

    Identifying Developmental Vascular Disruptor Compounds Using a Predictive Signature and Alternative Toxicity Models Presenting Author: Tamara Tal Affiliation: U.S. EPA/ORD/ISTD, RTP, NC, USA Chemically induced vascular toxicity during embryonic development can result in a wide...

  15. Reversible bulk-phase change of anthroyl compounds for photopatterning based on photodimerization in the molten state and thermal back reaction.

    Science.gov (United States)

    Kihara, Hideyuki; Yoshida, Masaru

    2013-04-10

    As new organic materials for rewritable photopatterning, 2-anthroyl and 9-anthroyl ester compounds were synthesized. Their bulk-phase changes (we use "bulk-phase change" as complete phase change in a mass of a material neither in a surface nor in a small quantity in this study) triggered by photodimerization under melting conditions (melt-photodimerization) and subsequent thermal back reactions were investigated. All the anthroyl compounds exhibited melting points lower than ca. 160 °C, and they were nearly quantitatively converted to the corresponding photodimers by UV irradiation at temperatures of ∼5 °C higher than their respective melting points. We found that there were two kinds of bulk-phase change behaviors through the photoreaction. Two of the anthroyl compounds remained isotropic and lost fluidity during the melt-photodimerization. The obtained photodimers exhibited robust solid-state amorphous phases at room temperature. In contrast, the other three anthroyl compounds showed crystallization during the melt-photodimerization. The resulting photodimers changed from isotropic to crystalline phases, even at high temperature. Various experiments revealed that the bulk phase of the photodimers was affected not by the existence of regioisomers but by their fluidity at the photoirradiation temperature. The latter three photodimers retained enough fluidity, reflecting their high molecular mobilities at the photoirradiation temperature at which the isothermal crystallization occurred. The other two products were not able to crystallize due to low fluidity, resulting in amorphous phases. We also found that all the photodimers reverted to the corresponding monomers by thermal back reaction and recovered their initial photochemical and thermal properties. Using these reversible bulk-phase changes of the anthroyl compounds, we successfully demonstrated rewritable photopatterning in not only negative images but also positive ones, based on the optical contrast

  16. Carbon-14 studies on the role of oxygen-containing compounds in the reaction mechanism of the Fischer-Tropsch synthesis

    International Nuclear Information System (INIS)

    Aksoy, H.A.

    1975-01-01

    In this work the behaviour of organic oxygen compounds has been studied in the reaction mechanism of Fischer-Tropsch synthesis using the tracer method. As an oxygen carrying tracer materials i-propanole (2- 14 C), acetone (2- 14 C) and ethanole (1- 14 C) have been added to the synthesis gas. The synthesis experiments are performed under standard conditions: The synthesis products are separated in suitable fractions and then studied by gas- and radio-gaschromatography. As a result the C-number distributions of the synthesis products are obtained as a function of concentration (weight %, mol %) and radioactivity (activity %). On this basis the relative molar activities have been calculated for certain compounds and fractions. Adding i-propanole- 14 C a great part of the tracer compound is transformed to acetone- 14 C, however adding acetone- 14 C to the synthesis gas a large amount of i-propanole- 14 C is produced. The main hydrocarbon reaction product from i-propanol and acetone is propane. Besides propane also propene is produced with equal molar radioactivity. This indicates that the formation of adsorbed oxygen compounds, as they may also be produced by chemisorption from alcohols or carbonyle compounds, is the first step in the formation of hydrocarbons by hydrogenolytic separation of oxygen. Comparing the results obtained with ethanole- 14 C and i-propanole- 14 C as a tacer material, for ethane an essentially lower molar activity is obtained when adding ethanole- 14 C compared with propane when adding i-propanole- 14 C. This corresponds with a particularly low desorption probability at the C 2 -hydrocarbon level. (orig./HK) [de

  17. Mixing-assisted oxidative desulfurization of model sulfur compounds using polyoxometalate/H2O2 catalytic system

    Directory of Open Access Journals (Sweden)

    Angelo Earvin Sy Choi

    2016-07-01

    Full Text Available Desulfurization of fossil fuel derived oil is needed in order to comply with environmental regulations. Dibenzothiophene and benzothiophene are among the predominant sulfur compound present in raw diesel oil. In this study, mixing-assisted oxidative desulfurization of dibenzothiophene and benzothiophene were carried out using polyoxometalate/H2O2 systems and a phase transfer agent. The effects of reaction time (2–30 min and temperature (30–70 °C were examined in the oxidation of model sulfur compounds mixed in toluene. A pseudo first-order reaction kinetic model and the Arrhenius equation were utilized in order to evaluate the kinetic rate constant and activation energy of each catalyst tested in the desulfurization process. Results showed the order of catalytic activity and activation energy of the different polyoxometalate catalysts to be H3PW12O40 > H3PM12O40 > H4SiW12O40 for both dibenzothiophene and benzothiophene.

  18. Splitting and non splitting are pollution models photochemical reactions in the urban areas of greater Tehran area

    International Nuclear Information System (INIS)

    Heidarinasab, A.; Dabir, B.; Sahimi, M.; Badii, Kh.

    2003-01-01

    During the past years, one of the most important problems has been air pollution in urban areas. In this regards, ozone, as one of the major products of photochemical reactions, has great importance. The term 'photochemical' is applied to a number of secondary pollutants that appear as a result of sun-related reactions, ozone being the most important one. So far various models have been suggested to predict these pollutants. In this paper, we developed the model that has been introduced by Dabir, et al. [4]. In this model more than 48 chemical species and 114 chemical reactions are involved. The result of this development, showed good to excellent agreement across the region for compounds such as O 3 , NO, NO 2 , CO, and SO 2 with regard to VOC and NMHC. The results of the simulation were compared with previous work [4] and the effects of increasing the number of components and reactions were evaluated. The results of the operator splitting method were compared with non splitting solving method. The result showed that splitting method with one-tenth time step collapsed with non splitting method (Crank-Nicolson, under-relaxation iteration method without splitting of the equation terms). Then we developed one dimensional model to 3-D and were compared with experimental data

  19. In silico strain optimization by adding reactions to metabolic models

    Directory of Open Access Journals (Sweden)

    Correia Sara

    2012-12-01

    Full Text Available Nowadays, the concerns about the environment and the needs to increase the productivity at low costs, demand for the search of new ways to produce compounds with industrial interest. Based on the increasing knowledge of biological processes, through genome sequencing projects, and high-throughput experimental techniques as well as the available computational tools, the use of microorganisms has been considered as an approach to produce desirable compounds. However, this usually requires to manipulate these organisms by genetic engineering and/ or changing the enviromental conditions to make the production of these compounds possible. In many cases, it is necessary to enrich the genetic material of those microbes with hereologous pathways from other species and consequently adding the potential to produce novel compounds.

  20. Position-specific isotope modeling of organic micropollutants transformations through different reaction pathways

    Science.gov (United States)

    Jin, Biao; Rolle, Massimo

    2016-04-01

    Organic compounds are produced in vast quantities for industrial and agricultural use, as well as for human and animal healthcare [1]. These chemicals and their metabolites are frequently detected at trace levels in fresh water environments where they undergo degradation via different reaction pathways. Compound specific stable isotope analysis (CSIA) is a valuable tool to identify such degradation pathways in different environmental systems. Recent advances in analytical techniques have promoted the fast development and implementation of multi-element CSIA. However, quantitative frameworks to evaluate multi-element stable isotope data and incorporating mechanistic information on the degradation processes [2,3] are still lacking. In this study we propose a mechanism-based modeling approach to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. We validate the proposed approach with the concentration and multi-element isotope data of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model precisely captures the dual element isotope trends characteristic of different reaction pathways and their range of variation consistent with observed multi-element (C, N) bulk isotope fractionation. The proposed approach can also be used as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. [1] Schwarzenbach, R.P., Egli, T., Hofstetter, T.B., von Gunten, U., Wehrli, B., 2010. Global Water Pollution and Human Health. Annu. Rev. Environ. Resour. doi:10.1146/annurev-environ-100809-125342. [2] Jin, B., Haderlein, S.B., Rolle, M

  1. Consideration of the Verleur model of far-infrared spectroscopy of ternary compounds

    International Nuclear Information System (INIS)

    Robouch, B. V.; Kisiel, A.; Sheregii, E. M.

    2001-01-01

    The clustering model proposed by Verleur and Barker [Phys. Rev. 149, 715 (1966)] to interpret far infrared data for face-centered-cubic ternary compounds is critically analyzed. It is shown that their approach, satisfactory for fitting some ternary compound spectral curves, is too restricted by its one-parameter β model to be able to describe preferences (with respect to a random distribution case) for the five tetrahedron configurations

  2. A Versatile Route to Unstable Diazo Compounds via Oxadiazolines and their Use in Aryl-Alkyl Cross-Coupling Reactions.

    Science.gov (United States)

    Greb, Andreas; Poh, Jian-Siang; Greed, Stephanie; Battilocchio, Claudio; Pasau, Patrick; Blakemore, David C; Ley, Steven V

    2017-12-22

    Coupling of readily available boronic acids and diazo compounds has emerged recently as a powerful metal-free carbon-carbon bond forming method. However, the difficulty in forming the unstable diazo compound partner in a mild fashion has hitherto limited their general use and the scope of the transformation. Here, we report the application of oxadiazolines as precursors for the generation of an unstable family of diazo compounds using flow UV photolysis and their first use in divergent protodeboronative and oxidative C(sp 2 )-C(sp 3 ) cross-coupling processes, with excellent functional-group tolerance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. N-nitrosodimethylamine (NDMA) formation from the ozonation of model compounds.

    Science.gov (United States)

    Marti, Erica J; Pisarenko, Aleksey N; Peller, Julie R; Dickenson, Eric R V

    2015-04-01

    Nitrosamines are a class of toxic disinfection byproducts commonly associated with chloramination, of which several were included on the most recent U.S. EPA Contaminant Candidate List. Nitrosamine formation may be a significant barrier to ozonation in water reuse applications, particularly for direct or indirect potable reuse, since recent studies show direct formation during ozonation of natural water and treated wastewaters. Only a few studies have identified precursors which react with ozone to form N-nitrosodimethylamine (NDMA). In this study, several precursor compound solutions, prepared in ultrapure water and treated wastewater, were subjected to a 10 M excess of ozone. In parallel experiments, the precursor solutions in ultrapure water were exposed to gamma radiation to determine NDMA formation as a byproduct of reactions of precursor compounds with hydroxyl radicals. The results show six new NDMA precursor compounds that have not been previously reported in the literature, including compounds with hydrazone and carbamate moieties. Molar yields in deionized water were 61-78% for 3 precursors, 12-23% for 5 precursors and NDMA formation for the other precursors. NDMA formation due to chloramination was minimal compared to formation due to ozonation, suggesting distinct groups of precursor compounds for these two oxidants. Hydroxyl radical reactions with the precursors will produce NDMA, but formation is much greater in the presence of molecular ozone. Also, hydroxyl radical scavenging during ozonation leads to increased NDMA formation. Molar conversion yields were higher for several precursors in wastewater as compared to deionized water, which could be due to catalyzed reactions with constituents found in wastewater or hydroxyl radical scavenging. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Transport Properties of a Kinetic Model for Chemical Reactions without Barriers

    International Nuclear Information System (INIS)

    Alves, Giselle M.; Kremer, Gilberto M.; Soares, Ana Jacinta

    2011-01-01

    A kinetic model of the Boltzmann equation for chemical reactions without energy barrier is considered here with the aim of evaluating the reaction rate and characterizing the transport coefficient of shear viscosity for the reactive system. The Chapman-Enskog solution of the Boltzmann equation is used to compute the chemical reaction effects, in a flow regime for which the reaction process is close to the final equilibrium state. Some numerical results are provided illustrating that the considered chemical reaction without energy barrier can induce an appreciable influence on the reaction rate and on the transport coefficient of shear viscosity.

  5. Model reduction of detailed-balanced reaction networks by clustering linkage classes

    NARCIS (Netherlands)

    Rao, Shodhan; Jayawardhana, Bayu; van der Schaft, Abraham; Findeisen, Rolf; Bullinger, Eric; Balsa-Canto, Eva; Bernaerts, Kristel

    2016-01-01

    We propose a model reduction method that involves sequential application of clustering of linkage classes and Kron reduction. This approach is specifically useful for chemical reaction networks with each linkage class having less number of reactions. In case of detailed balanced chemical reaction

  6. Characterisation of model compounds and a synthetic coal by TG/MS/FTIR to represent the pyrolysis behaviour of coal

    Energy Technology Data Exchange (ETDEWEB)

    Arenillas, A.; Pevida, C.; Rubiera, F.; Garcia, R.; Pis, J.J. [Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo (Spain)

    2004-06-01

    Coal pyrolysis is the initial, accompanying reaction of a number of coal conversion processes such as hydrogenation, combustion and gasification. However, because of the inherent complexity of coal composition, it is difficult to describe coal pyrolysis clearly. Single model compounds have been used before in order to provide additional insight into the complex processes that occur in the pyrolysis of coal. Yet the picture obtained is a simplified one and certain important aspects such as coal structure, interactions between different surface groups and cross-links are omitted. The approach used in this work involves the preparation of a synthetic coal, SC, with a known structure by curing a mixture of single, well-defined model compounds. By means of chemical characterisation, the SC was shown to contain the macroscopic features of a high volatile coal (proximate and ultimate analyses). FTIR characterisation revealed the presence of functional groups similar to those of coal in the structure of the SC. Temperature-programmed pyrolysis tests were performed in a thermobalance linked to a mass spectrometer and a Fourier transform infrared analyser (TG/MS/FTIR). The thermal behaviour of the synthetic coal (i.e., rate of mass loss and the evolution profiles of gaseous compounds during pyrolysis tests) is very similar to that of the high volatile bituminous coal which was used as a reference material. The great advantage of using SC lies in the fact that its composition and structure can be accurately determined and employed in subsequent applications in basic and mechanistic studies.

  7. A modeling approach for compounds affecting body composition.

    Science.gov (United States)

    Gennemark, Peter; Jansson-Löfmark, Rasmus; Hyberg, Gina; Wigstrand, Maria; Kakol-Palm, Dorota; Håkansson, Pernilla; Hovdal, Daniel; Brodin, Peter; Fritsch-Fredin, Maria; Antonsson, Madeleine; Ploj, Karolina; Gabrielsson, Johan

    2013-12-01

    Body composition and body mass are pivotal clinical endpoints in studies of welfare diseases. We present a combined effort of established and new mathematical models based on rigorous monitoring of energy intake (EI) and body mass in mice. Specifically, we parameterize a mechanistic turnover model based on the law of energy conservation coupled to a drug mechanism model. Key model variables are fat-free mass (FFM) and fat mass (FM), governed by EI and energy expenditure (EE). An empirical Forbes curve relating FFM to FM was derived experimentally for female C57BL/6 mice. The Forbes curve differs from a previously reported curve for male C57BL/6 mice, and we thoroughly analyse how the choice of Forbes curve impacts model predictions. The drug mechanism function acts on EI or EE, or both. Drug mechanism parameters (two to three parameters) and system parameters (up to six free parameters) could be estimated with good precision (coefficients of variation typically mass and FM changes at different drug provocations using a similar model for man. Surprisingly, model simulations indicate that an increase in EI (e.g. 10 %) was more efficient than an equal lowering of EI. Also, the relative change in body mass and FM is greater in man than in mouse at the same relative change in either EI or EE. We acknowledge that this assumes the same drug mechanism impact across the two species. A set of recommendations regarding the Forbes curve, vehicle control groups, dual action on EI and loss, and translational aspects are discussed. This quantitative approach significantly improves data interpretation, disease system understanding, safety assessment and translation across species.

  8. Reaction Wheel Disturbance Model Extraction Software, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Reaction wheel disturbances are some of the largest sources of noise on sensitive telescopes. Such wheel-induced mechanical noises are not well characterized....

  9. Reaction Wheel Disturbance Model Extraction Software, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — Reaction wheel mechanical noise is one of the largest sources of disturbance forcing on space-based observatories. Such noise arises from mass imbalance, bearing...

  10. Dynamic Modelling and Identification of Precipitation Reactions in Full-Scale WWTP

    DEFF Research Database (Denmark)

    Mbamba, Christian Kazadi; Tait, Stephan; Flores-Alsina, Xavier

    , this paper evaluates plant-wide modelling of precipitation reactions using a generic approach integrated within activated sludge and anaerobic models. Preliminary results of anaerobic digester sludge in batch system suggest that the model is able to simulate the dynamics of precipitation reactions. Kinetic...

  11. Multivariate characterisation and quantitative structure-property relationship modelling of nitroaromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Joensson, S. [Man-Technology-Environment Research Centre, Department of Natural Sciences, Orebro University, 701 82 Orebro (Sweden)], E-mail: sofie.jonsson@nat.oru.se; Eriksson, L.A. [Department of Natural Sciences and Orebro Life Science Center, Orebro University, 701 82 Orebro (Sweden); Bavel, B. van [Man-Technology-Environment Research Centre, Department of Natural Sciences, Orebro University, 701 82 Orebro (Sweden)

    2008-07-28

    A multivariate model to characterise nitroaromatics and related compounds based on molecular descriptors was calculated. Descriptors were collected from literature and through empirical, semi-empirical and density functional theory-based calculations. Principal components were used to describe the distribution of the compounds in a multidimensional space. Four components described 76% of the variation in the dataset. PC1 separated the compounds due to molecular weight, PC2 separated the different isomers, PC3 arranged the compounds according to different functional groups such as nitrobenzoic acids, nitrobenzenes, nitrotoluenes and nitroesters and PC4 differentiated the compounds containing chlorine from other compounds. Quantitative structure-property relationship models were calculated using partial least squares (PLS) projection to latent structures to predict gas chromatographic (GC) retention times and the distribution between the water phase and air using solid-phase microextraction (SPME). GC retention time was found to be dependent on the presence of polar amine groups, electronic descriptors including highest occupied molecular orbital, dipole moments and the melting point. The model of GC retention time was good, but the precision was not precise enough for practical use. An important environmental parameter was measured using SPME, the distribution between headspace (air) and the water phase. This parameter was mainly dependent on Henry's law constant, vapour pressure, log P, content of hydroxyl groups and atmospheric OH rate constant. The predictive capacity of the model substantially improved when recalculating a model using these five descriptors only.

  12. Estimation of rate constants of PCB dechlorination reactions using an anaerobic dehalogenation model.

    Science.gov (United States)

    Karakas, Filiz; Imamoglu, Ipek

    2017-02-15

    This study aims to estimate anaerobic dechlorination rate constants (k m ) of reactions of individual PCB congeners using data from four laboratory microcosms set up using sediment from Baltimore Harbor. Pathway k m values are estimated by modifying a previously developed model as Anaerobic Dehalogenation Model (ADM) which can be applied to any halogenated hydrophobic organic (HOC). Improvements such as handling multiple dechlorination activities (DAs) and co-elution of congeners, incorporating constraints, using new goodness of fit evaluation led to an increase in accuracy, speed and flexibility of ADM. DAs published in the literature in terms of chlorine substitutions as well as specific microorganisms and their combinations are used for identification of pathways. The best fit explaining the congener pattern changes was found for pathways of Phylotype DEH10, which has the ability to remove doubly flanked chlorines in meta and para positions, para flanked chlorines in meta position. The range of estimated k m values is between 0.0001-0.133d -1 , the median of which is found to be comparable to the few available published biologically confirmed rate constants. Compound specific modelling studies such as that performed by ADM can enable monitoring and prediction of concentration changes as well as toxicity during bioremediation. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Chemical modeling of irreversible reactions in nuclear waste-water-rock systems

    International Nuclear Information System (INIS)

    Wolery, T.J.

    1981-02-01

    Chemical models of aqueous geochemical systems are usually built on the concept of thermodynamic equilibrium. Though many elementary reactions in a geochemical system may be close to equilibrium, others may not be. Chemical models of aqueous fluids should take into account that many aqueous redox reactions are among the latter. The behavior of redox reactions may critically affect migration of certain radionuclides, especially the actinides. In addition, the progress of reaction in geochemical systems requires thermodynamic driving forces associated with elementary reactions not at equilibrium, which are termed irreversible reactions. Both static chemical models of fluids and dynamic models of reacting systems have been applied to a wide spectrum of problems in water-rock interactions. Potential applications in nuclear waste disposal range from problems in geochemical aspects of site evaluation to those of waste-water-rock interactions. However, much further work in the laboratory and the field will be required to develop and verify such applications of chemical modeling

  14. Evaluation of Chemical Kinetic for Mathematics Model Reduction of Cadmium Reaction Rate, Constant and Reaction Orde in to Electrochemical Process

    International Nuclear Information System (INIS)

    Prayitno

    2007-01-01

    The experiment was reduction of cadmium rate with electrochemical influenced by time process, concentration, current strength and type of electrode plate. The aim of the experiment was to know the influence, mathematic model reduction of cadmium the reaction rate, reaction rate constant and reaction orde influenced by time process, concentration, current strength and type of electrode plate. Result of research indicate the time processing if using plate of copper electrode is during 30 minutes and using plate of aluminium electrode is during 20 minutes. Condition of strong current that used in process of electrochemical is only 0.8 ampere and concentration effective is 5.23 mg/l. The most effective type Al of electrode plate for reduction from waste and the efficiency of reduction is 98 %. (author)

  15. Synthesis and preliminary biological evaluation of a small library of hybrid compounds based on Ugi isocyanide multicomponent reactions with a marine natural product scaffold.

    Science.gov (United States)

    Avilés, Edward; Prudhomme, Jacques; Le Roch, Karine G; Franzblau, Scott G; Chandrasena, Kevin; Mayer, Alejandro M S; Rodríguez, Abimael D

    2015-11-15

    A mixture-based combinatorial library of five Ugi adducts (4-8) incorporating known antitubercular and antimalarial pharmacophores was successfully synthesized, starting from the naturally occurring diisocyanide 3, via parallel Ugi four-center three-component reactions (U-4C-3CR). The novel α-acylamino amides obtained were evaluated for their antiinfective potential against laboratory strains of Mycobacterium tuberculosis H37Rv and chloroquine-susceptible 3D7 Plasmodium falciparum. Interestingly, compounds 4-8 displayed potent in vitro antiparasitic activity with higher cytotoxicity in comparison to their diisocyanide precursor 3, with the best compound exhibiting an IC50 value of 3.6 nM. Additionally, these natural product inspired hybrids potently inhibited in vitro thromboxane B2 (TXB2) and superoxide anion (O2(-)) generation from Escherichia coli lipopolysaccharide (LPS)-activated rat neonatal microglia, with concomitant low short-term toxicity. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. New evidence on the formation of oxidizing species in corona discharge in contact with liquid and their reactions with organic compounds.

    Science.gov (United States)

    Magureanu, M; Dobrin, D; Bradu, C; Gherendi, F; Mandache, N B; Parvulescu, V I

    2016-12-01

    The objective of these investigations is to understand in more detail how organic compounds in water are degraded during plasma treatment. The formation of oxidizing species (ozone (O 3 ), hydrogen peroxide (H 2 O 2 ) and hydroxyl radicals (OH)) in a pulsed corona discharge in contact with liquid is investigated. The degradation of a target organic compound (methylparaben) in aqueous solution was increased when combining plasma treatment with ozonation, using the O 3 generated in the discharge. Enhanced mass transfer of O 3 obtained in this plasma+O 3 configuration leads to a six fold increase of MeP oxidation rate. The evolution of oxidants concentration during treatment of MeP solutions provides information on their consumption in reactions with MeP and its oxidation products. The correlation of MeP degradation results (MeP removal and mineralization) with O 3 consumption and the identified reaction products confirms that although O 3 plays an important role in the degradation, for the mineralization OH radicals have an essential contribution. The concentration of OH radicals is diminished in the solutions containing MeP as compared to plasma-treated water, indicating OH consumption in reactions with the target compound and its degradation products. The concentration of H 2 O 2 in the liquid can be either increased or reduced in the presence of MeP, depending on its initial concentration. On the one hand, decomposition of H 2 O 2 by OH or O 3 is suppressed in the presence of MeP, but on the other hand less OH radicals are available for its formation. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. A variable reaction rate model for chlorine decay in drinking water due to the reaction with dissolved organic matter.

    Science.gov (United States)

    Hua, Pei; Vasyukova, Ekaterina; Uhl, Wolfgang

    2015-05-15

    A second order kinetic model for simulating chlorine decay in bulk water due to the reaction with dissolved organic matter (DOM) was developed. It takes into account the decreasing reactivity of dissolved organic matter using a variable reaction rate coefficient (VRRC) which decreases with an increasing conversion. The concentration of reducing species is surrogated by the maximum chlorine demand. Temperature dependency, respectively, is described by the Arrhenius-relationship. The accuracy and adequacy of the proposed model to describe chlorine decay in bulk water were evaluated and shown for very different waters and different conditions such as water mixing or rechlorination by applying statistical tests. It is thus very well suited for application in water quality modeling for distribution systems. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Reactions of 4-nitro-1,2,3-triazole with alkylating agents and compounds with activated multiple bonds

    Energy Technology Data Exchange (ETDEWEB)

    Vereshchagin, L.I.; Kuznetsova, N.I.; Kirillova, L.P.; Shcherbakov, V.V.; Sukhanov, G.T.; Gareev, G.A.

    1987-01-01

    When 4-nitro-1,2,3-triazole is alkylated, a mixture of N1- and N2-isomers is formed, with the latter usually predominating. The same behavior is also observed in addition reactions of 4-nitrotriazole to activated multiple bonds.

  19. Reactions of uranium (III) and (IV) compounds with ketones, nitriles and acid chlorides. Towards a use of uranium complexes in organic synthesis

    International Nuclear Information System (INIS)

    Adam, Raymond

    1993-01-01

    In this research thesis, the author shows that various organic molecules can be interestingly transformed into uranium complexes with degrees of oxidation of +3 or +4. In a first part, the author describes reactions of carbonyl compounds with the UCl 4 -Na(Hg) reducing system. Then, he addresses reductions of ketones, nitriles and acid chlorides by a uranium (III) complex: Cp 3 U(THF). The third part reports a detailed study of the reduction of ketones by U(BH 4 ) 4 [fr

  20. Batch and Flow Photochemical Benzannulations Based on the Reaction of Ynamides and Diazo Ketones. Application to the Synthesis of Polycyclic Aromatic and Heteroaromatic Compounds

    Science.gov (United States)

    Willumstad, Thomas P.; Haze, Olesya; Mak, Xiao Yin; Lam, Tin Yiu; Wang, Yu-Pu; Danheiser*, Rick L.

    2013-01-01

    Highly substituted polycyclic aromatic and heteroaromatic compounds are produced via a two-stage tandem benzannulation/cyclization strategy. The initial benzannulation step proceeds via a pericyclic cascade mechanism triggered by thermal or photochemical Wolff rearrangement of a diazo ketone. The photochemical process can be performed using a continuous flow reactor which facilitates carrying out reactions on a large scale and minimizes the time required for photolysis. Carbomethoxy ynamides as well as more ketenophilic bissilyl ynamines and N-sulfonyl and N-phosphoryl ynamides serve as the reaction partner in the benzannulation step. In the second stage of the strategy, RCM generates benzofused nitrogen heterocycles, and various heterocyclization processes furnish highly substituted and polycyclic indoles of types that were not available by using the previous cyclobutenone-based version of the tandem strategy. PMID:24116731

  1. Global emissions and models of photochemically active compounds

    International Nuclear Information System (INIS)

    Penner, J.E.; Atherton, C.S.; Graedel, T.E.

    1993-01-01

    Anthropogenic emissions from industrial activity, fossil fuel combustion, and biomass burning are now known to be large enough (relative to natural sources) to perturb the chemistry of vast regions of the troposphere. A goal of the IGAC Global Emissions Inventory Activity (GEIA) is to provide authoritative and reliable emissions inventories on a 1 degree x 1 degree grid. When combined with atmospheric photochemical models, these high quality emissions inventories may be used to predict the concentrations of major photochemical products. Comparison of model results with measurements of pertinent species allows us to understand whether there are major shortcomings in our understanding of tropospheric photochemistry, the budgets and transport of trace species, and their effects in the atmosphere. Through this activity, we are building the capability to make confident predictions of the future consequences of anthropogenic emissions. This paper compares IGAC recommended emissions inventories for reactive nitrogen and sulfur dioxide to those that have been in use previously. We also present results from the three-dimensional LLNL atmospheric chemistry model that show how emissions of anthropogenic nitrogen oxides might potentially affect tropospheric ozone and OH concentrations and how emissions of anthropogenic sulfur increase sulfate aerosol loadings

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

    Science.gov (United States)

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

    2017-10-01

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

  3. Flow chemistry as a discovery tool to access sp2-sp3 cross-coupling reactions via diazo compounds.

    Science.gov (United States)

    Tran, Duc N; Battilocchio, Claudio; Lou, Shing-Bong; Hawkins, Joel M; Ley, Steven V

    2015-02-01

    The work takes advantage of an important feature of flow chemistry, whereby the generation of a transient species (or reactive intermediate) can be followed by a transfer step into another chemical environment, before the intermediate is reacted with a coupling partner. This concept is successfully applied to achieve a room temperature sp 2 -sp 3 cross coupling of boronic acids with diazo compounds, these latter species being generated from hydrazones under flow conditions using MnO 2 as the oxidant.

  4. Fluxes of biogenic volatile organic compounds measured and modelled above a Norway spruce forest

    Science.gov (United States)

    Juráň, Stanislav; Fares, Silvano; Pallozzi, Emanuele; Guidolotti, Gabriele; Savi, Flavia; Alivernini, Alessandro; Calfapietra, Carlo; Večeřová, Kristýna; Křůmal, Kamil; Večeřa, Zbyněk; Cudlín, Pavel; Urban, Otmar

    2016-04-01

    Fluxes of biogenic volatile organic compounds (BVOCs) were investigated at Norway spruce forest at Bílý Kříž in Beskydy Mountains of the Czech Republic during the summer 2014. A proton-transfer-reaction-time-of-flight mass spectrometer (PTR-TOF-MS, Ionicon Analytik, Austria) has been coupled with eddy-covariance system. Additionally, Inverse Lagrangian Transport Model has been used to derive fluxes from concentration gradient of various monoterpenes previously absorbed into n-heptane by wet effluent diffusion denuder with consequent quantification by gas chromatography with mass spectrometry detection. Modelled data cover each one day of three years with different climatic conditions and previous precipitation patterns. Model MEGAN was run to cover all dataset with monoterpene fluxes and measured basal emission factor. Highest fluxes measured by eddy-covariance were recorded during the noon hours, represented particularly by monoterpenes and isoprene. Inverse Lagrangian Transport Model suggests most abundant monoterpene fluxes being α- and β-pinene. Principal component analysis revealed dependencies of individual monoterpene fluxes on air temperature and particularly global radiation; however, these dependencies were monoterpene specific. Relationships of monoterpene fluxes with CO2 flux and relative air humidity were found to be negative. MEGAN model correlated to eddy-covariance PTR-TOF-MS measurement evince particular differences, which will be shown and discussed. Bi-directional fluxes of oxygenated short-chain volatiles (methanol, formaldehyde, acetone, acetaldehyde, formic acid, acetic acid, methyl vinyl ketone, methacrolein, and methyl ethyl ketone) were recorded by PTR-TOF-MS. Volatiles of anthropogenic origin as benzene and toluene were likely transported from the most benzene polluted region in Europe - Ostrava city and adjacent part of Poland around Katowice, where metallurgical and coal mining industries are located. Those were accumulated during

  5. Some information needs for air quality modeling. [Environmental effects of sulfur compounds

    Energy Technology Data Exchange (ETDEWEB)

    Hill, F B

    1975-09-01

    The following topics were considered at the workshop: perturbation of the natural sulfur cycle by human activity; ecosystem responses to a given environmental dose of sulfur compounds; movement of sulfur compounds within the atmosphere; air quality models; contribution of biogenic sulfur compounds to atmospheric burden of sulfur; production of acid rain from sulfur dioxide; meteorological processes; and rates of oxidation of SO/sub 2/ via direct photo-oxidation, oxidation resulting from photo-induced free radical chemistry, and catalytic oxidation in cloud droplets and on dry particles. (HLW)

  6. Study of the fusion process in 28Si + 28Si and 28Si + 12C reactions: search for deformation effects in the 56Ni and 40Ca compound nuclei

    International Nuclear Information System (INIS)

    Rousseau, M.

    2000-12-01

    The initial purpose of this work was to find likely deformed configurations in light nuclei with alpha sub-structure, through the study of light particle emission during the decay of 56 Ni and 40 Ca nuclei produced in the 28 Si + 28 Si and 28 Si + 12 C reactions respectively. The first chapter is an introduction and this work is presented as a contribution to the study of fusion-fission processes that have been recently discovered in light heavy ion reactions. The second chapter is dedicated to experimental methods and particularly to the ICARE multi-detector that operates on a Vivitron Tandem accelerator. In the third chapter we present and discuss experimental observables, we show that most experimental data can be interpreted as the consequence of the formation of a completely balanced (in all its freedom degrees) system (the compound nucleus) that de-excites through the statistical emission of light particles. In the chapter 4 we interpret the energy spectra and angular correlation for both reactions in the framework of the statistical model through the use of codes based on the Hauser-Feshbach method. We show that it is necessary to introduce a dependence in terms of angular moment for the moment of inertia to fit well experimental data. Important disagreements concerning the 28 Si + 12 C reactions back the idea of a significant emission of 8 Be cluster in the exit channel 32 S + 8 Be. We show that this emission is due to an alpha transfer. (A.C.)

  7. Quasielastic reactions

    International Nuclear Information System (INIS)

    Hansen, O.

    1983-01-01

    A brief review is presented of the experimental and theoretical situation regarding transfer reactions and inelastic scattering. In the first category there is little (very little) precision data for heavy projectiles and consequently almost no experience with quantitative theoretical analysis. For the inelastic scattering the rather extensive data strongly supports the coupled channels models with collective formfactors. At the most back angles, at intensities about 10 -5 of Rutherford scattering, a second, compound-like mechanism becomes dominant. The description of the interplay of these two opposite mechanisms provides a new challenge for our understanding

  8. Study of n-Butyl Acrylate Self-Initiation Reaction Experimentally and via Macroscopic Mechanistic Modeling

    Directory of Open Access Journals (Sweden)

    Ahmad Arabi Shamsabadi

    2016-04-01

    Full Text Available This paper presents an experimental study of the self-initiation reaction of n-butyl acrylate (n-BA in free-radical polymerization. For the first time, the frequency factor and activation energy of the monomer self-initiation reaction are estimated from measurements of n-BA conversion in free-radical homo-polymerization initiated only by the monomer. The estimation was carried out using a macroscopic mechanistic mathematical model of the reactor. In addition to already-known reactions that contribute to the polymerization, the model considers a n-BA self-initiation reaction mechanism that is based on our previous electronic-level first-principles theoretical study of the self-initiation reaction. Reaction rate equations are derived using the method of moments. The reaction-rate parameter estimates obtained from conversion measurements agree well with estimates obtained via our purely-theoretical quantum chemical calculations.

  9. Modelling uptake into roots and subsequent translocation of neutral and ionisable organic compounds

    DEFF Research Database (Denmark)

    Trapp, Stefan

    2000-01-01

    A study on uptake of neutral and dissociating organic compounds from soil solution into roots, and their subsequent translocation, was undertaken using model simulations. The model approach combines the processes of lipophilic sorption, electrochemical interactions, ion trap, advection in xylem...... and dilution by growth. It needs as input data, apart fromplant properties, log KOW, pKa and the valency number of the compound, and pH and chemical concentration in the soil solution. Equilibrium and dynamic (steady-state) models were tested against measured data from several authors, including non...

  10. The reaction of slag in cement, theory and computer modelling

    NARCIS (Netherlands)

    Chen, Wei; Brouwers, H.J.H.; Fischer, H.B

    2006-01-01

    For a better understanding of the performance of slag in concrete, evaluating the feasibility of using one certain type of slag and possible improvement of its use in practice, fundamental knowledge about its reaction and interaction with other constituents is important. While the researches on

  11. Modeling Human Exposure Levels to Airborne Volatile Organic Compounds by the Hebei Spirit Oil Spill

    OpenAIRE

    Kim, Jong Ho; Kwak, Byoung Kyu; Ha, Mina; Cheong, Hae-Kwan; Yi, Jongheop

    2012-01-01

    Objectives The goal was to model and quantify the atmospheric concentrations of volatile organic compounds (VOCs) as the result of the Hebei Spirit oil spill, and to predict whether the exposure levels were abnormally high or not. Methods We developed a model for calculating the airborne concentration of VOCs that are produced in an oil spill accident. The model was applied to a practical situation, namely the Hebei Spirit oil spill. The accuracy of the model was verified by comparing the res...

  12. Atypical McMurry Cross-Coupling Reactions Leading to a New Series of Potent Antiproliferative Compounds Bearing the Key [Ferrocenyl-Ene-Phenol] Motif

    Directory of Open Access Journals (Sweden)

    Pascal Pigeon

    2014-07-01

    Full Text Available In the course of the preparation of a series of ferrocenyl derivatives of diethylstilbestrol (DES, in which one of the 4-hydroxyphenyl moieties was replaced by a ferrocenyl group, the McMurry reaction of chloropropionylferrocene with a number of mono-aryl ketones unexpectedly yielded the hydroxylated ferrocenyl DES derivatives, 5a–c, in poor yields (10%–16%. These compounds showed high activity on the hormone-independent breast cancer cell line MDA-MB-231 with IC50 values ranging from 0.14 to 0.36 µM. Surprisingly, non-hydroxylated ferrocenyl DES, 4, showed only an IC50 value of 1.14 µM, illustrating the importance of the hydroxyethyl function in this promising new series. For comparison, McMurry reactions of the shorter chain analogue chloroacetylferrocene were carried out to see the difference in behaviour with mono-aryl ketones versus a diaryl ketone. The effect of changing the length of the alkyl chain adjacent to the phenolic substituent of the hydroxylated ferrocenyl DES was studied, a mechanistic rationale to account for the unexpected products is proposed, and the antiproliferative activities of all of these compounds on MDA-MB-231 cells lines were measured and compared. X-ray crystal structures of cross-coupled products and of pinacol-pinacolone rearrangements are reported.

  13. DJ-1-dependent protective activity of DJ-1-binding compound no. 23 against neuronal cell death in MPTP-treated mouse model of Parkinson's disease

    Directory of Open Access Journals (Sweden)

    Kazuko Takahashi-Niki

    2015-03-01

    Full Text Available Parkinson's disease (PD is caused by dopaminergic cell death in the substantia nigra, leading to a reduced level of dopamine in the striatum. Oxidative stress is one of the causes of PD. Since symptomatic PD therapies are used, identification of compounds or proteins that inhibit oxidative stress-induced neuronal cell death is necessary. DJ-1 is a causative gene product of familial PD and plays a role in anti-oxidative stress reaction. We have identified various DJ-1-binding compounds, including compound-23, that restored neuronal cell death and locomotion defects observed in neurotoxin-induced PD models. In this study, wild-type and DJ-1-knockout mice were injected intraperitoneally with 1 mg/kg of compound-23 and then with 30 mg/kg of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP at 1 h after injection. Five days after administration, the effects of compound-23 on MPTP-induced locomotion deficits, on dopaminergic cell death and on brain dopamine levels were analyzed by rotor rod tests, by staining cells with an anti-TH antibody and by an HPLC, respectively. The results showed that compound-23 inhibited MPTP-induced reduction of retention time on the rotor rod bar, neuronal cell death in the substantia nigra and striatum and dopamine content in wild-type mice but not in DJ-1-knockout mice, indicating a DJ-1-dependent effect of compound-23.

  14. Contribution of DIAMANT and EUROGAM detectors association to the study of heavy ion-induced fusion-evaporation reactions. Application to the de-excitation study of 90Ru compound nucleus formed in the 32S + 58Ni reaction at 120 MeV

    International Nuclear Information System (INIS)

    Bourgine, Frederic

    1996-01-01

    For the first time, the sensitivity of statistical evaporation model has been established in detail from 1 H and 4 He energy distributions analysis for different exit channels. The association of the light charged particle multidetector DIAMANT and the γ-spectrometer EUROGAM II shows that precise study of the compound nucleus high spin states deexcitation can be done for small particle channels. These channels are fed by the biggest angular momentum values of the compound nucleus. The analysis of pα channel in 32 S + 58 Ni at 120 MeV reaction exhibits that a particles have an energy distribution which leads to an entry region of the residual nucleus 85 Nb parallel to the yrast line. (author) [fr

  15. The Dangling model in the construction of compound sentences with regard to verb tenses

    Directory of Open Access Journals (Sweden)

    Mahmoud Mehravaran

    2016-02-01

    the mistakes of some of the grammars. This research project has for the first time introduced constructive models of compound sentences in a comprehensive research taking in to account the tense of the verbs. The primary question in this research project is which kind of sentences can be considered as compound and what is the constructive of such a sentence? When defining a compound sentences, grammarians either shave the same beliefs or differ in their ideas. But all grammarians agree to the fact that a compound sentences has more than one verb. Different definitions are due to different criteria adapted in constructing a compound sentences. To construct a noun, and adjective, a verb and a sentence we should take similar and precise criteria to our consideration. In the grammatical units of noun, adjectives, and verbs construction means connecting two or more parts that can convey one similar meaning and its parts are dependent upon one another.  In the construction of compound sentences there must be the same criteria so that its applications can be truly recognized and identified just like the previously mentioned grammatical units. The first step to arrive at a criterion in defining and identifying compound sentences, is to separate this discussion from connective sentences that are relate to each other with connectives are called connective sentences. But sentences which are constructed with dependent making connectives and their parts are dependent upon one another are called compound sentences. Therefore the signs of compound sentences with regard to constructions and the meaning of criterion are as follows: 1 They have more than one verb. 2 The consistence of two or more dependent phrases. 3 Phrases construct a complete sentences all together and convey one similar message. 4 One of the phrases is the main clause and the other one is the subordinate one. 5 The phrases or subordinate clauses can be related to one of the major parts and they can take a

  16. The Dangling model in the construction of compound sentences with regard to verb tenses

    Directory of Open Access Journals (Sweden)

    Mahmoud Mehravaran

    2016-01-01

    the mistakes of some of the grammars. This research project has for the first time introduced constructive models of compound sentences in a comprehensive research taking in to account the tense of the verbs. The primary question in this research project is which kind of sentences can be considered as compound and what is the constructive of such a sentence? When defining a compound sentences, grammarians either shave the same beliefs or differ in their ideas. But all grammarians agree to the fact that a compound sentences has more than one verb. Different definitions are due to different criteria adapted in constructing a compound sentences. To construct a noun, and adjective, a verb and a sentence we should take similar and precise criteria to our consideration. In the grammatical units of noun, adjectives, and verbs construction means connecting two or more parts that can convey one similar meaning and its parts are dependent upon one another.  In the construction of compound sentences there must be the same criteria so that its applications can be truly recognized and identified just like the previously mentioned grammatical units. The first step to arrive at a criterion in defining and identifying compound sentences, is to separate this discussion from connective sentences that are relate to each other with connectives are called connective sentences. But sentences which are constructed with dependent making connectives and their parts are dependent upon one another are called compound sentences. Therefore the signs of compound sentences with regard to constructions and the meaning of criterion are as follows: 1 They have more than one verb. 2 The consistence of two or more dependent phrases. 3 Phrases construct a complete sentences all together and convey one similar message. 4 One of the phrases is the main clause and the other one is the subordinate one. 5 The phrases or subordinate clauses can be related to one of the major parts and they can take a

  17. Studies on allergic reactions after exposure to platinum compounds; Untersuchungen ueber allergische Reaktionen bei Exposition gegen Platinverbindungen (VPT 07A)

    Energy Technology Data Exchange (ETDEWEB)

    Merget, R; Schultze-Werninghaus, G [Berufsgenossenschaftliche Kliniken, Bergmannsheil - Universitaetsklinik, Medizinische Klinik und Poliklinik, Abt. fuer Pneumologie, Allergologie und Schlafmedizin, Bochum (Germany)

    1998-12-31

    The aim of the present study was to assess the allergic hazard potential of Pt-containing substances emitted from automotive catalytic converters for the population. This was done by determining exposure-effect relationships in subjects occupationally exposed to platinum compounds in a catalytic converter manufacturing company. The company had been deemed suitable because it could be assumed that the extensive technical industrial safety measures implemented there would make for a considerably reduced exposure to platinum compounds compared to, for example, a platinum separating plant. Exposure-effect relationships were determined on the basis of platinum measurements in a catalytic-converter-manufacturing plant and of a record of new sickness cases. [Deutsch] Ziel der Untersuchung war eine Risikoabschaetzung des Allergie-Gefaehrdungspotentials Pt-haltiger Automobilkatalysatoremittate fuer die Bevoelkerung durch Ermittlung der Expositions-Wirkungsbeziehung bei beruflich gegenueber Platinverbindungen Exponierten in einem Katalysatorfertigungsbertrieb. Der gewaehlte Katalysatorbetrieb war deshalb als geeignet betrachtet worden, weil durch weitgehende technische Arbeitsschutzmassnahmen eine wesentlich geringere Exposition gegenueber Platinverbindungen anzunehmen war als zum Beispiel in Platinscheidereien. Die Expositions-Wirkungsbeziehung sollte durch Platinmessungen in einem Katalysator-Betrieb und Erfassung der Haeufigkeit von Neuerkrankungen im Laengsschnitt definiert werden. (orig.)

  18. Kinetics and mechanism of superoxide radical reactions with some biologically important compounds in aqueous solutions. Pulse radiolysis

    Science.gov (United States)

    Revina, A. A.; Amiragova, M. I.; Volod'ko, V. V.; Vannikov, A. V.

    Microsecond pulse radiolysis of oxygenated aqueous solutions containing 0.02 mol dm -3 sodium formate and 2 mmol dm -3 phosphate buffer at pH 7 was used to generate superoxide anion radicals. The influence of some biologically important compounds upon the rate of O ⨪2 decay was monitored spectrophotometrically in the range of 245-300 nm. Hematoporphyrin (HP), hemin C (HC), catalase (Cat), cobalt sulfophthalocyanine (CoTSPc) were studied. Among the investigated compounds only Cat was found to show a high catalytic efficiency towards the self-decay of O ⨪2. A red shift of O ⨪2 absorption band and slowing down of its decay were observed to take place by adding HP or CoTSPc to the solutions containing formate ions in excess. This effect is associated with the formation of a transient superoxo-complex. An appearance of an intermediate species with absorption maxima at 350 nm and half-life of about 2s was observed to accompany the superoxo-complex of CoTSPc decay. In the aerated solution of HP the intensity of absorbance at 260 nm was found to be independent of the presence of formate ions.

  19. Kinetics and mechanism of superoxide radical reactions with some biologically important compounds in aqueous solutions. Pulse radiolysis

    International Nuclear Information System (INIS)

    Revina, A.A.; Volod'ko, V.V.; Vannikov, A.V.

    1989-01-01

    Microsecond pulse radiolysis of oxygenated aqueous solutions containing 0.02 mol dm -3 sodium formate and 2 mmol dm -3 phosphate buffer at pH 7 was used to generate superoxide anion radicals. The influence of some biologically important compounds upon the rate of O 2 .-bar decay as monitored spectrophotometrically in the range of 245-300 nm. Hematoporphyrin (HP), hemin C (HC), catalase (Cat), cobalt sulfophthalocyanine (CoTSPc) were studied. Among the investigated compounds only Cat was found to show a high catalytic efficiency towards the self-decay of O 2 .-bar . A red shift of 0 2 .-bar absorption band and slowing down of its decay were observed to take place by adding HP or CoTSPc to the solutions containing formate ions in excess. This effect is associated with the formation of a transient superoxo-complex. An appearance of an intermediate species with absorption maxima at 350 nm and half-life of about 2 s was observed to accompany the superoxo-complex of CoTSPc decay. In the aerated solution of HP the intensity of absorbance at 260 nm was found to be independent of the presence of formate ions. (author)

  20. Studies on allergic reactions after exposure to platinum compounds; Untersuchungen ueber allergische Reaktionen bei Exposition gegen Platinverbindungen (VPT 07A)

    Energy Technology Data Exchange (ETDEWEB)

    Merget, R.; Schultze-Werninghaus, G. [Berufsgenossenschaftliche Kliniken, Bergmannsheil - Universitaetsklinik, Medizinische Klinik und Poliklinik, Abt. fuer Pneumologie, Allergologie und Schlafmedizin, Bochum (Germany)

    1997-12-31

    The aim of the present study was to assess the allergic hazard potential of Pt-containing substances emitted from automotive catalytic converters for the population. This was done by determining exposure-effect relationships in subjects occupationally exposed to platinum compounds in a catalytic converter manufacturing company. The company had been deemed suitable because it could be assumed that the extensive technical industrial safety measures implemented there would make for a considerably reduced exposure to platinum compounds compared to, for example, a platinum separating plant. Exposure-effect relationships were determined on the basis of platinum measurements in a catalytic-converter-manufacturing plant and of a record of new sickness cases. [Deutsch] Ziel der Untersuchung war eine Risikoabschaetzung des Allergie-Gefaehrdungspotentials Pt-haltiger Automobilkatalysatoremittate fuer die Bevoelkerung durch Ermittlung der Expositions-Wirkungsbeziehung bei beruflich gegenueber Platinverbindungen Exponierten in einem Katalysatorfertigungsbertrieb. Der gewaehlte Katalysatorbetrieb war deshalb als geeignet betrachtet worden, weil durch weitgehende technische Arbeitsschutzmassnahmen eine wesentlich geringere Exposition gegenueber Platinverbindungen anzunehmen war als zum Beispiel in Platinscheidereien. Die Expositions-Wirkungsbeziehung sollte durch Platinmessungen in einem Katalysator-Betrieb und Erfassung der Haeufigkeit von Neuerkrankungen im Laengsschnitt definiert werden. (orig.)