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Sample records for mcmurry reaction conditions

  1. Remarkable Features of the McMurry Reaction Conditions in Dimerization of Formyl- and 2-Formylvinylpurpurinimides. Electrochemistry of Monomeric Ni(II) Purpurinimide and the Corresponding Dyads

    PubMed Central

    Goswami, Lalit N.; Ethirajan, Manivannan; Dobhal, Mahabeer P.; Zhang, Min; Missert, Joseph R.; Shibata, Masayuki; Kadish, Karl M.; Pandey, Ravindra K.

    2009-01-01

    To investigate the electrochemical properties of purpurinimide dyads and electron transfer sites for their reduction and oxidation, a series of dimers with variable C-C linkages were synthesized. For the preparation of these novel structures, the formyl and 2-formylvinyl substituents were regioselectively introduced at positions-3 and 20 of Ni(II) purpurinimides by the Vilsmeier reaction. The Ni(II) complexes were then subjected to the McMurry reaction under two different conditions with unexpected results being obtained. For example, the reaction of formyl purpurinimides with TiCl3(DME)1.5 failed to produce the desired C-C dimers and the starting compounds were recovered almost quantitatively. Under similar reaction conditions, the 20-(2-formylvinyl)purpurinimide also did not dimerize but gave instead unexpected benzoisobacteriochlorins via an intramolecular cyclization. However, treatment of the 3-formyl- and 20-formyl-purpurinimides with TiCl4/Zn gave the corresponding dimers linked with one double bond (trans-) in modest yields. Under similar conditions, Ni(II) purpurinimides containing a 2-formylvinyl substituent either at position-3 or position-20 afforded the respective C-C dimers, where the purpurinimide moieties were joined with a trans-trans-trans- hexatriene linker. Molecular modeling data suggest that the nature of the conformational energy difference found in all trans- vs. trans-cis-trans- conformers of the dimers connected by a hexatriene linker at the meso- or β-position of the macrocycle is not due to the intrinsic conformational energy difference of the linker region, which is identical for both dimers. PMID:19072690

  2. Crossed McMurry Coupling Reactions for Porphycenic Macrocycles: Non-Statistical Selectivity and Rationalisation.

    PubMed

    Cowie, Thomas Y; Kennedy, Lorna; Żurek, Justyna M; Paterson, Martin J; Bebbington, Magnus W P

    2015-06-01

    Crossed McMurry reactions of bifuran- or bithiophenedicarbaldehydes with bipyrroledicarbaldehydes have been studied for the first time. Only those porphycenic macrocycles derived from homocoupled McMurry products were formed. The results are explained by using both density functional theory and electron propagator computations to model the electron affinity of the dialdehyde starting materials. It was predicted that bifuran\\bithiophene cross-coupling would indeed occur, and this was demonstrated by the first synthesis of a novel dioxa,dithio hetero-porphycenoid annulene. This approach will allow the prior identification of viable substrates for related crossed McMurry reactions.

  3. Crossed McMurry Coupling Reactions for Porphycenic Macrocycles: Non-Statistical Selectivity and Rationalisation

    PubMed Central

    Cowie, Thomas Y; Kennedy, Lorna; Żurek, Justyna M; Paterson, Martin J; Bebbington, Magnus W P

    2015-01-01

    Crossed McMurry reactions of bifuran- or bithiophenedicarbaldehydes with bipyrroledicarbaldehydes have been studied for the first time. Only those porphycenic macrocycles derived from homocoupled McMurry products were formed. The results are explained by using both density functional theory and electron propagator computations to model the electron affinity of the dialdehyde starting materials. It was predicted that bifuran\\bithiophene cross-coupling would indeed occur, and this was demonstrated by the first synthesis of a novel dioxa,dithio hetero-porphycenoid annulene. This approach will allow the prior identification of viable substrates for related crossed McMurry reactions. PMID:26213484

  4. Synthesis of sterically hindered ortho-substituted tetraphenylethenes. Electronic effects in the McMurry olefination reaction.

    PubMed

    Chung, Mee-Kyung; Qi, Guizhong; Stryker, Jeffrey M

    2006-03-30

    [reaction: see text] Contrary to literature consensus, the McMurry olefination reaction can be extended to the direct synthesis of sterically encumbered tetrakis(2-substituted) tetraphenylethenes from the corresponding 2,2'-disubstituted benzophenones. The reaction exploits previously unrecognized substrate-based electronic effects that dominate over otherwise controlling steric considerations and provides highly efficient access to derivatives of tetrakis(2-hydroxyphenyl)ethene, a novel preorganized ligand system for polymetallic coordination chemistry and catalysis.

  5. 2-Carbaborane-3-phenyl-1H-indoles--synthesis via McMurry reaction and cyclooxygenase (COX) inhibition activity.

    PubMed

    Laube, Markus; Neumann, Wilma; Scholz, Matthias; Lönnecke, Peter; Crews, Brenda; Marnett, Lawrence J; Pietzsch, Jens; Kniess, Torsten; Hey-Hawkins, Evamarie

    2013-02-01

    Cyclooxygenase-2 (COX-2) inhibitors have been the focus of medicinal chemistry efforts for years, and many compounds that exhibit high selectivity and affinity have been developed. As carbaboranes represent interesting pharmacophores as phenyl mimetics in drug development, this paper presents the synthesis of carbaboranyl derivatives of COX-2-selective 2,3-disubstituted indoles. Despite the lability of carbaboranes under reducing conditions, 2-carbaborane-3-phenyl-1H-indoles could be synthesized by McMurry cyclization of the corresponding amides. Whereas the meta-carbaboranyl-substituted derivatives lacked COX inhibitory activity, an ortho-carbaboranyl analogue was active, but showed a selectivity shift toward COX-1.

  6. 2-Carbaborane-3-phenyl-1H-indoles – Synthesis via McMurry Reaction and COX Inhibition Activity

    PubMed Central

    Neumann, Wilma; Scholz, Matthias; Lönnecke, Peter; Crews, Brenda; Marnett, Lawrence J.; Pietzsch, Jens; Kniess, Torsten

    2013-01-01

    Cyclooxygenase-2 (COX-2) inhibitors have been in the focus of medicinal chemistry for years and many compounds exhibiting high selectivity and affinity were developed. As carbaboranes represent interesting pharmacophores as phenyl mimetics in drug development, this paper presents the synthesis of carbaboranyl derivatives of COX-2-selective 2,3-disubstituted indoles. Despite the lability of carbaboranes under reducing conditions, 2-carbaborane-3-phenyl-1H-indoles could be synthesized by McMurry cyclization of the corresponding amides. While the meta-carbaboranyl-substituted derivatives (3a-c) lacked COX inhibition activity, the ortho-carbaboranyl analog (3d) was active but showed a selectivity shift towards COX-1. PMID:23303738

  7. Atypical McMurry cross-coupling reactions leading to a new series of potent antiproliferative compounds bearing the key [ferrocenyl-ene-phenol] motif.

    PubMed

    Pigeon, Pascal; Görmen, Meral; Kowalski, Konrad; Müller-Bunz, Helge; McGlinchey, Michael J; Top, Siden; Jaouen, Gérard

    2014-07-17

    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.

  8. New para-para stilbenophanes: synthesis by McMurry coupling, conformational analysis and inhibition of tubulin polymerisation.

    PubMed

    Álvarez, Raquel; López, Vilmarí; Mateo, Carmen; Medarde, Manuel; Peláez, Rafael

    2011-03-14

    The synthesis of a new family of methoxy-substituted [2.7]- and [2.8]paracyclophanes linked by 3-oxapentamethylene-1,5-dioxy and hexamethylene-1,6-dioxy bridges has been carried out by using the McMurry methodology. Related indole compounds were also synthesised. Olefin-to-diol ratios depended on the bridge length, the structure of the aromatic ring and the reaction conditions. Macrocyclisation, the methoxy substituents and the presence of a rigid indole moiety restricted the conformational equilibria, as observed by NMR spectroscopy and according to theoretical calculations. The synthesised compounds display micromolar tubulin polymerisation inhibitory activity. The conformational implications on the tubulin polymerisation inhibitory activity derived from the macrocyclisation when compared with combretastatins, closely related stilbenes, are also discussed.

  9. 'GREENER' CHEMICAL SYNTHESES USING ALTERNATE REACTION CONDITIONS

    EPA Science Inventory

    Microwave (MW) irradiation in conjunction with water as reaction media has proven to be a greener chemical approach for expeditious N-alkylation reactions of amines and hydrazines wherein the reactions under mildly basic conditions afford tertiary amines and double N-alkylation t...

  10. Expert system for predicting reaction conditions: the Michael reaction case.

    PubMed

    Marcou, G; Aires de Sousa, J; Latino, D A R S; de Luca, A; Horvath, D; Rietsch, V; Varnek, A

    2015-02-23

    A generic chemical transformation may often be achieved under various synthetic conditions. However, for any specific reagents, only one or a few among the reported synthetic protocols may be successful. For example, Michael β-addition reactions may proceed under different choices of solvent (e.g., hydrophobic, aprotic polar, protic) and catalyst (e.g., Brønsted acid, Lewis acid, Lewis base, etc.). Chemoinformatics methods could be efficiently used to establish a relationship between the reagent structures and the required reaction conditions, which would allow synthetic chemists to waste less time and resources in trying out various protocols in search for the appropriate one. In order to address this problem, a number of 2-classes classification models have been built on a set of 198 Michael reactions retrieved from literature. Trained models discriminate between processes that are compatible and respectively processes not feasible under a specific reaction condition option (feasible or not with a Lewis acid catalyst, feasible or not in hydrophobic solvent, etc.). Eight distinct models were built to decide the compatibility of a Michael addition process with each considered reaction condition option, while a ninth model was aimed to predict whether the assumed Michael addition is feasible at all. Different machine-learning methods (Support Vector Machine, Naive Bayes, and Random Forest) in combination with different types of descriptors (ISIDA fragments issued from Condensed Graphs of Reactions, MOLMAP, Electronic Effect Descriptors, and Chemistry Development Kit computed descriptors) have been used. Models have good predictive performance in 3-fold cross-validation done three times: balanced accuracy varies from 0.7 to 1. Developed models are available for the users at http://infochim.u-strasbg.fr/webserv/VSEngine.html . Eventually, these were challenged to predict feasibility conditions for ∼50 novel Michael reactions from the eNovalys database (originally

  11. Biogeochemical Reactions Under Simulated Europa Ocean Conditions

    NASA Astrophysics Data System (ADS)

    Amashukeli, X.; Connon, S. A.; Gleeson, D. F.; Kowalczyk, R. S.; Pappalardo, R. T.

    2007-12-01

    Galileo data have demonstrated the probable presence of a liquid water ocean on Europa, and existence of salts and carbon dioxide in the satellite's surface ice (e.g., Carr et al., 1998; McCord et al., 1999, Pappalardo et al., 1999; Kivelson et al., 2000). Subsequently, the discovery of chemical signatures of extinct or extant life in Europa's ocean and on its surface became a distinct possibility. Moreover, understanding of Europa's potential habitability is now one of the major goals of the Europa Orbiter Flagship mission. It is likely, that in the early stages of Europa's ocean formation, moderately alkaline oceanic sulfate-carbonate species and a magnetite-silicate mantel could have participated in low-temperature biogeochemical sulfur, iron and carbon cycles facilitated by primitive organisms (Zolotov and Shock, 2004). If periodic supplies of fresh rock and sulfate-carbonate ions are available in Europa's ocean, then an exciting prospect exists that life may be present in Europa's ocean today. In our laboratory, we began the study of the plausible biogeochemical reactions under conditions appropriate to Europa's ocean using barophilic psychrophilic organisms that thrive under anaerobic conditions. In the near absence of abiotic synthetic pathways due to low Europa's temperatures, the biotic synthesis may present a viable opportunity for the formation of the organic and inorganic compounds under these extreme conditions. This work is independent of assumptions regarding hydrothermal vents at Europa's ocean floor or surface-derived oxidant sources. For our studies, we have fabricated a high-pressure (5,000 psi) reaction vessel that simulates aqueous conditions on Europa. We were also successful at reviving barophilic psychrophilic strains of Shewanella bacterium, which serve as test organisms in this investigation. Currently, facultative barophilic psychrophilic stains of Shewanella are grown in the presence of ferric food source; the strains exhibiting iron

  12. Action of bimetallic nanocatalysts under reaction conditions and during catalysis: evolution of chemistry from high vacuum conditions to reaction conditions.

    PubMed

    Tao, Franklin Feng; Zhang, Shiran; Nguyen, Luan; Zhang, Xueqiang

    2012-12-21

    Bimetallic catalysts are one of the main categories of metal catalysts due to the tunability of electronic and geometric structures through alloying a second metal. The integration of a second metal creates a vast number of possibilities for varying the surface structure and composition of metal catalysts toward designing new catalysts. It is well acknowledged that the surface composition, atomic arrangement, and electronic state of bimetallic catalysts could be different from those before a chemical reaction or catalysis based on ex situ studies. Thanks to advances in electron-based surface analytical techniques, the surface chemistry and structure of bimetallic nanoparticles can be characterized under reaction conditions and during catalysis using ambient pressure analytical techniques including ambient pressure XPS, ambient pressure STM, X-ray absorption spectroscopy and others. These ambient pressure studies revealed various restructurings in the composition and arrangement of atoms in the surface region of catalysts under reaction conditions or during catalysis compared to that before reaction. These restructurings are driven by thermodynamic and kinetic factors. The surface energy of the constituent metals and adsorption energy of reactant molecules or dissociated species on a metal component are two main factors from the point of view of thermodynamics. Correlations between the authentic surface structure and chemistry of catalysts during catalysis and simultaneous catalytic performance were built for understanding catalytic mechanisms of bimetallic catalysts toward designing new catalysts with high activity, selectivity, and durability.

  13. Latent inhibition of conditioned disgust reactions in rats.

    PubMed

    López, Matías; Gasalla, Patricia; Vega, Mercedes; Limebeer, Cheryl L; Rock, Erin M; Tuerke, Katharine J; Bedard, Holly; Parker, Linda A

    2010-05-01

    The present experiments, using the latent inhibition (LI) paradigm, evaluated the effect of nonreinforced exposure to saccharin on the acquisition of an LiCl-induced saccharin aversion as measured by conditioned disgust reactions in the taste reactivity test and conditioned taste avoidance in a consumption test. When rats were preexposed to saccharin by bottle exposure (Experiments 1 and 3), LI was evidenced only by conditioned taste avoidance (bottle testing), but not by conditioned disgust reactions (intraoral [IO] testing). On the other hand, when rats were preexposed to saccharin by IO infusion (Experiments 2 and 3), LI was evidenced only by conditioned disgust reactions, but not by conditioned taste avoidance. Experiment 4 showed that LI of conditioned disgust reactions does not appear to be affected by a context shift from preexposure to testing phases. These results show that the expression of LI of both conditioned taste avoidance and conditioned disgust reactions depends critically on a common method of flavor exposure during preexposure and testing.

  14. Optimization of ligation reaction conditions in gene synthesis.

    PubMed

    Theriault, N Y; Carter, J B; Pulaski, S P

    1988-05-01

    Several phosphorylation, annealing and ligation reaction conditions have been investigated for the enzymatic assembly of genes of interest. The use of longer oligodeoxyribonucleotides (40-60 bases long) also improved the enzymatic reaction. Furthermore, the use of longer oligonucleotides and the elimination of long stretches of G's or C's lowered the mutation rate.

  15. GREEN CHEMICAL SYNTHESIS THROUGH CATALYSIS AND ALTERNATE REACTION CONDITIONS

    EPA Science Inventory

    Green chemical synthesis through catalysis and alternate reaction conditions

    Encompassing green chemistry techniques and methodologies, we have initiated several projects at the National Risk Management Research laboratory that focus on the design and development of chemic...

  16. High explosive violent reaction (HEVR) from slow heating conditions

    SciTech Connect

    Vigil, A.S.

    1999-03-01

    The high explosives (HEs) developed and used at the Los Alamos National Laboratory are designed to be insensitive to impact and thermal insults under all but the most extreme conditions. Nevertheless, violent reactions do occasionally occur when HE is involved in an accident. The HE response is closely dependent on the type of external stimulus that initiates the reaction. For example, fast heating of conventional HE will probably result in fairly benign burning, while long-term, slow heating of conventional HE is more likely to produce an HEVR that will do much more damage to the immediate surroundings. An HEVR (High Explosive Violent Reaction) can be defined as the rapid release of energy from an explosive that ranges from slightly faster than a deflagration (very rapid burning) to a reaction that approaches a detonation. A number of thermal analyses have been done to determine slow heat/cook-off conditions that produce HE self-heating that can build up to a catastrophic runaway reaction. The author specifies the conditions that control reaction violence, describes experiments that produced an HEVR, describes analyses done to determine a heating rate threshold for HEVR, and lists possible HEVR situations.

  17. Chemical reactions in viscous liquids under space conditions

    NASA Astrophysics Data System (ADS)

    Kondyurin, A.; Lauke, B.; Richter, E.

    A long-term human flight needs a large-size space ships with artificial self-regulating ecological life-support system. The best way for creation of large-size space ship is a synthesis of light construction on Earth orbit, that does not need a high energy transportation carriers from Earth surface. The construction can be created by the way of chemical polymerisation reaction under space environment. But the space conditions are very specific for chemical reactions. A high vacuum, high energy particles, X-rays, UV- and VUV-irradiations, atomic oxygen, microgravity have a significant influence on chemical reactions. Polymerisation reactions in liquid active mixture were studied in simulated space environment. The epoxy resins based on Bisphenol A and amine curing agents were investigated under vacuum, microwave plasma discharge and ion beam. An acceleration of polymerisation reaction with free radicals formation was observed. The polymerisation reaction can be carried out under space environment. The study was supported by Alexander von Humboldt Foundation (A. Kondyurin) and European Space Agency, ESTEC (contract 17083/03/NL/Sfe "Space Environmental Effects on the Polymerisation of Composite Structures").

  18. Homogeneous-Heterogeneous Reactions in Peristaltic Flow with Convective Conditions

    PubMed Central

    Hayat, Tasawar; Tanveer, Anum; Yasmin, Humaira; Alsaedi, Ahmed

    2014-01-01

    This article addresses the effects of homogeneous-heterogeneous reactions in peristaltic transport of Carreau fluid in a channel with wall properties. Mathematical modelling and analysis have been carried out in the presence of Hall current. The channel walls satisfy the more realistic convective conditions. The governing partial differential equations along with long wavelength and low Reynolds number considerations are solved. The results of temperature and heat transfer coefficient are analyzed for various parameters of interest. PMID:25460608

  19. Kinetics of homoallylic/homobenzylic rearrangement reactions under combustion conditions.

    PubMed

    Wang, Zhaohui; Zhang, Lidong; Zhang, Feng

    2014-08-28

    Homoallylic/homobenzylic radicals refer to typical radicals with the radical site located at the β position from the vinyl/phenyl group. These radicals are largely involved in combustion systems, such as the pyrolysis or oxidation of alkenes, cycloalkanes, and aromatics. The 1,2-vinyl/phenyl migration via two steps (cyclization/fission) is a peculiar reaction type for the homoallylic/homobenzylic radicals, entitled homoallylic/homobenzylic rearrangement, which has been studied by theoretical calculations including the Hirshfeld atomic charge analysis in the present work. With the help of rate constant calculations, the competition between this reaction channel and other possible pathways under combustion temperatures (500-2000 K) were evaluated. Analogous 1,3- and 1,4-vinyl/phenyl migration reactions for similar radicals with the radical sites located at the γ and δ positions from the vinyl/phenyl group were also computed. The results indicate that the 1,2-vinyl/phenyl migration is particularly important for the kinetics of unimolecular reactions of homoallylic radicals under 1500 K; nevertheless, it still has noticeable contribution at higher temperature. For those radicals with the radical site at the γ or δ positions, the respective 1,3- or 1,4-vinyl/phenyl migration channel plays an insignificant role under combustion conditions.

  20. Effects of Meteorological Conditions on Reactions to Noise Exposure

    NASA Technical Reports Server (NTRS)

    Shepherd, Kevin P. (Technical Monitor); Fields, James M.

    2004-01-01

    More than 80,000 residents' responses to transportation noise at different times of year provide the best, but imprecise, statistical estimates of the effects of season and meteorological conditions on community response to noise. Annoyance with noise is found to be slightly statistically significantly higher in the summer than in the winter in a seven-year study in the Netherlands. Analyses of 41 other surveys drawn from diverse countries, climates, and times of year find noise annoyance is increased by temperature, and may be increased by more sunshine, less precipitation, and reduced wind speeds. Meteorological conditions on the day of the interview or the immediately preceding days do not appear to have any more effect on reactions than do the conditions over the immediately preceding weeks or months.

  1. Reactions of aminomalononitrile with electrophiles. [simulating prebiotic conditions

    NASA Technical Reports Server (NTRS)

    Thanassi, J. W.

    1975-01-01

    Aminomalononitrile (HCN trimer) reacts with electrophiles such as aldehydes and acrylonitrile under very mild conditions of temperature and pH to produce intermediates which, after acid hydrolysis, yield amino acids. The following amino acids have been identified and quantitated: glycine, D,L-erythro- and D,L-threo-beta-hydroxyaspartic acids, D,L glutamic acid, and D,L-threonine and allo-threonine. The mechanism of their formation and the possible significance of these reactions in prebiotic syntheses are discussed.

  2. MICROWAVE-ACCELERATED MULTICOMPONENT REACTIONS UNDER SOLVENT-FREE CONDITIONS

    EPA Science Inventory

    The application of microwave-accelerated solventless synthetic protocols in multicomponent (MCC) reactions will be exemplified by several condensation and cyclization reactions including the rapid one-pot assembly of valuable heterocyclic compounds from in situ generated intermed...

  3. Impact of reaction conditions on grafting acrylamide onto starch

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have explored the radical initiated graft polymerization reaction of acrylamide onto starch where the solvent, concentration, temperature and reaction times were varied. We have found that the morphology of the resulting grafted polymer is dramatically different and is dependent on the reaction c...

  4. Presidential Green Chemistry Challenge: 2008 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2008 award winner, Nalco Company, developed 3D TRASAR technology to monitor the condition of cooling water continuously and add chemicals only when needed, saving water and energy.

  5. Regimes of chemical reaction waves initiated by nonuniform initial conditions for detailed chemical reaction models.

    PubMed

    Liberman, M A; Kiverin, A D; Ivanov, M F

    2012-05-01

    Regimes of chemical reaction wave propagation initiated by initial temperature nonuniformity in gaseous mixtures, whose chemistry is governed by chain-branching kinetics, are studied using a multispecies transport model and a detailed chemical model. Possible regimes of reaction wave propagation are identified for stoichiometric hydrogen-oxygen and hydrogen-air mixtures in a wide range of initial pressures and temperature levels, depending on the initial non-uniformity steepness. The limits of the regimes of reaction wave propagation depend upon the values of the spontaneous wave speed and the characteristic velocities of the problem. It is shown that one-step kinetics cannot reproduce either quantitative neither qualitative features of the ignition process in real gaseous mixtures because the difference between the induction time and the time when the exothermic reaction begins significantly affects the ignition, evolution, and coupling of the spontaneous reaction wave and the pressure wave, especially at lower temperatures. We show that all the regimes initiated by the temperature gradient occur for much shallower temperature gradients than predicted by a one-step model. The difference is very large for lower initial pressures and for slowly reacting mixtures. In this way the paper provides an answer to questions, important in practice, about the ignition energy, its distribution, and the scale of the initial nonuniformity required for ignition in one or another regime of combustion wave propagation.

  6. Regimes of chemical reaction waves initiated by nonuniform initial conditions for detailed chemical reaction models

    NASA Astrophysics Data System (ADS)

    Liberman, M. A.; Kiverin, A. D.; Ivanov, M. F.

    2012-05-01

    Regimes of chemical reaction wave propagation initiated by initial temperature nonuniformity in gaseous mixtures, whose chemistry is governed by chain-branching kinetics, are studied using a multispecies transport model and a detailed chemical model. Possible regimes of reaction wave propagation are identified for stoichiometric hydrogen-oxygen and hydrogen-air mixtures in a wide range of initial pressures and temperature levels, depending on the initial non-uniformity steepness. The limits of the regimes of reaction wave propagation depend upon the values of the spontaneous wave speed and the characteristic velocities of the problem. It is shown that one-step kinetics cannot reproduce either quantitative neither qualitative features of the ignition process in real gaseous mixtures because the difference between the induction time and the time when the exothermic reaction begins significantly affects the ignition, evolution, and coupling of the spontaneous reaction wave and the pressure wave, especially at lower temperatures. We show that all the regimes initiated by the temperature gradient occur for much shallower temperature gradients than predicted by a one-step model. The difference is very large for lower initial pressures and for slowly reacting mixtures. In this way the paper provides an answer to questions, important in practice, about the ignition energy, its distribution, and the scale of the initial nonuniformity required for ignition in one or another regime of combustion wave propagation.

  7. Uranium plasma emission at gas-core reaction conditions

    NASA Technical Reports Server (NTRS)

    Williams, M. D.; Jalufka, N. W.; Hohl, F.; Lee, J. H.

    1976-01-01

    The results of uranium plasma emission produced by two methods are reported. For the first method a ruby laser was focused on the surface of a pure U-238 sample to create a plasma plume with a peak plasma density of about 10 to the 20th power/cu cm and a temperature of about 38,600 K. The absolute intensity of the emitted radiation, covering the range from 300 to 7000 A was measured. For the second method, the uranium plasma was produced in a 20 kilovolt, 25 kilojoule plasma-focus device. The 2.5 MeV neutrons from the D-D reaction in the plasma focus are moderated by polyethylene and induce fissions in the U-235. Spectra of both uranium plasmas were obtained over the range from 30 to 9000 A. Because of the low fission yield the energy input due to fissions is very small compared to the total energy in the plasma.

  8. Platelet reactions to modified surfaces under dynamic conditions.

    PubMed

    Rhodes, N P; Shortland, A P; Rattray, A; Williams, D F

    1998-12-01

    The influence of surfaces on the reactions of platelets in whole blood under laminar flow was investigated in a cone and plate viscometer. Citrated whole blood was exposed to steel, PMMA and PMMA modified with PEO at low (500 s(-1)) and high (4000 s(-1)) wall shear rates at room temperature for a period of 100 s. Treated blood samples were fixed with paraformaldehyde, stained with a monoclonal antibody for CD41 (platelet GPIIb/IIIa) conjugated with phycoerythrin and analyzed by flow cytometry. The reactions of platelets (microparticle generation and formation of platelet-platelet, platelet-red blood cell and red blood cell-microparticle aggregates) to these environments were quantified. Additionally, the size of platelet-platelet aggregates was assessed. The percentage platelet aggregation and numbers of microparticles generated were independent of surface type at any shear rate. The composition of the aggregates formed was influenced by the surface: at low and high shear rates PMMA caused the generation of platelet-platelet aggregates of the greatest size. The numbers of red blood cell-platelet and red blood cell-microparticle aggregates also varied depending on the surface. Fewer red blood cell-platelet aggregates were formed at higher shear rates, whereas the reverse was true for red blood cell-microparticle aggregates. It is concluded that these variations may help to explain the differential effects of surfaces to the induction of distant thrombotic events: microparticles may be protected from loss from the blood stream by their association with red blood cells at high shear rates.

  9. Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

    ERIC Educational Resources Information Center

    Tellinghuisen, Joel

    2006-01-01

    Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

  10. Reactions to Ostracism in Adolescents with Autism Spectrum Conditions

    ERIC Educational Resources Information Center

    Sebastian, Catherine; Blakemore, Sarah-Jayne; Charman, Tony

    2009-01-01

    Little is known about how adolescents with autism spectrum conditions (ASC) experience the initial impact of ostracism. This study investigated whether a mild, short-term episode of experimentally induced ostracism (Cyberball) would affect self-reported anxiety, mood, and the extent to which four social needs (self-esteem, belonging, control and…

  11. Characteristics of uranium carbonitride microparticles synthesized using different reaction conditions

    SciTech Connect

    Silva, Chinthaka M; Lindemer, Terrence; Voit, Stewart L; Hunt, Rodney Dale; Besmann, Theodore M; Terrani, Kurt A; Snead, Lance Lewis

    2014-11-01

    Three sets of different experimental conditions by changing the cover gases during the sample preparation were tested to synthesize uranium carbonitride (UC1-xNx) microparticles. In the first two sets of experiments using (N2 to N2-4%H2 to Ar) and (Ar to N2 to Ar) environments, single phase UC1-xNx was synthesized. When reducing environments (Ar-4%H2 to N2-4%H2 to Ar-4%H2) were utilized, theoretical densities up to 97% of single phase UC1-xNx kernels were obtained. Physical and chemical characteristics such as density, phase purity, and chemical compositions of the synthesized UC1-xNx materials for the diferent experimental conditions used are provided. In-depth analysis of the microstrutures of UC1-xNx has been carried out and is discussed with the objective of large batch fabrication of high density UC1-xNx kernels.

  12. Reactions to ostracism in adolescents with autism spectrum conditions.

    PubMed

    Sebastian, Catherine; Blakemore, Sarah-Jayne; Charman, Tony

    2009-08-01

    Little is known about how adolescents with autism spectrum conditions (ASC) experience the initial impact of ostracism. This study investigated whether a mild, short-term episode of experimentally induced ostracism (Cyberball) would affect self-reported anxiety, mood, and the extent to which four social needs (self-esteem, belonging, control and meaningful existence) were threatened in adolescents with ASC and matched controls. Anxiety and the four needs were negatively affected by ostracism in both groups. However, ostracism did not modulate mood in the ASC group, and a number of possible interpretations of this group difference are discussed. In general, the results of this study suggest that normative models of ostracism are applicable to ASC.

  13. Characteristics of uranium carbonitride microparticles synthesized using different reaction conditions

    NASA Astrophysics Data System (ADS)

    Silva, Chinthaka M.; Lindemer, Terrence B.; Voit, Stewart R.; Hunt, Rodney D.; Besmann, Theodore M.; Terrani, Kurt A.; Snead, Lance L.

    2014-11-01

    Three sets of experimental conditions were tested to synthesize uranium carbonitride (UC1-xNx) kernels from gel-derived urania-carbon microspheres. Primarily, three sequences of gases were used, N2 to N2-4%H2 to Ar, Ar to N2 to Ar, and Ar-4%H2 to N2-4%H2 to Ar-4%H2. Physical and chemical characteristics such as geometrical density, phase purity, and chemical compositions of the synthesized UC1-xNx were measured. Single-phase kernels were commonly obtained with densities generally ranging from 85% to 93% TD and values of x as high as 0.99. In-depth analysis of the microstrutures of UC1-xNx has been carried out and is discussed with the objective of large batch fabrication of high density UC1-xNx kernels.

  14. Kinetics of OH + CO reaction under atmospheric conditions

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

    A pulsed laser photolysis-pulsed laser-induced fluorescence technique is used to directly measure the temperature, pressure, and H2O concentration dependence on k1 in air. K1 is found to increase linearly with increasing pressure at pressures of not greater than 1 atm, and the pressure dependence of k1 at 299 K is the same in N2 buffer gas as in O2 buffer gas. The rate constant in the low-pressure limit and the slope of the k1 versus pressure dependence are shown to be the same at 262 K as at 299 K. The present results significantly reduce the current atmospheric model uncertainties in the temperature dependence under atmospheric conditions, in the third body efficiency of O2, and in the effect of water vapor on k1.

  15. Reaction Behaviors of Glycine under Super- and Subcritical Water Conditions

    NASA Astrophysics Data System (ADS)

    Alargov, Dimitar K.; Deguchi, Shigeru; Tsujii, Kaoru; Horikoshi, Koki

    2002-02-01

    The influence of temperature and pressure on the dimerization and decomposition of glycine under simulated hydrothermal system conditions was studied by injecting a glycine solution into water in the sub- and supercritical state. The experiments at five different temperatures of supplied water - 250, 300, 350, 374, and 400 °C - were performed at 22.2 and 40.0 MPa. At 350 °C, experiments under 15.0-40.0 MPa were conducted. Diglycine, triglycine (trace), diketopiperazine, and an unidentified product with a high molecular mass (433 Da) were the main products of oligomerization. The results show that temperature and pressure influence the extent of dimerization and decomposition of glycine. The maximum of dimers formation was observed at 350 and 375 °C at 22.2 and 40.0 MPa, respectively, and coincided with a high rate of glycine decomposition. Glycine, alanine, aspartic acid, as well as other amino acids, were obtained by injecting a mixture of formaldehyde and ammonia. The results support the oligomerization and synthesis of amino acids in a submarine hydrothermal system.

  16. Impact of reaction conditions on architecture and rheological properties of starch graft polyacrylamide polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We carried out experiments examining the impact that solvent selection and reaction conditions have on the radical initiated graft polymerization reaction of acrylamide onto starch. We have also evaluated the rheological properties the starch graftpolyacrylamide product when a gel is formed in water...

  17. Deoxyribonucleic Acid Polymerase of Rous Sarcoma Virus: Reaction Conditions and Analysis of the Reaction Product Nucleic Acids

    PubMed Central

    Bishop, D. H. L.; Ruprecht, Ruth; Simpson, R. W.; Spiegelman, S.

    1971-01-01

    Reaction conditions for Rous sarcoma virus ribonucleic acid (RNA)-instructed deoxyribonucleic acid (DNA) polymerase activity are described whereby the viral RNA is relatively protected from endogenous or added nuclease activity. Three analyses of reaction product nucleic acids (3H-RNA, 32P-DNA) were compared, namely, gel electrophoresis, Cs2SO4 gradient centrifugation, and hydroxyapatite column chromatography. It was found that hydroxyapatite analysis could be misleading unless the state of the template RNA was monitored concomitantly with the DNA analysis. Gel electrophoresis and Cs2SO4 gradient centrifugation gave comparable results. It was concluded that analyses of the product of reverse transcriptase reactions should not only refer to the template RNA and product DNA species, but also be performed with virus or viral RNA which do not have or obtain nicks in the 60S RNA. Otherwise, interpretation of the results would have the ambiguity of potential artifacts caused by those degraded RNA molecules. PMID:4332143

  18. The oxidation of carbon monoxide on polycrystalline rhodium under knudsen conditions. II. Reaction with nitrogen monoxide

    NASA Astrophysics Data System (ADS)

    Lintz, Hans-Günther; Weisker, Tilman

    1985-09-01

    The reaction between carbon monoxide and nitrogen monoxide on a polycrystalline rhodium ribbon under stationary conditions is followed by mass spectrometry. In the temperature range 300 to 1100 K the ratio of the partial pressures of the reactants varies between 0.1 < pNO/ pCO < 100 at values of the total pressure in the reactor from 10 -4 to 10 -5 Torr. The results can be interpreted qualitatively by a simple elementary reaction sequence. Simulation using literature values of the kinetic constants leads to semi-quantitative agreement with experimental results. No isothermal oscillations of the reaction rate could be observed under the stated conditions.

  19. Kinetics and corrosion products of aqueous nitrate reduction by iron powder without reaction conditions control.

    PubMed

    Fan, Xiaomeng; Guan, Xiaohong; Ma, Jun; Ai, Hengyu

    2009-01-01

    Although considerable research has been conducted on nitrate reduction by zero-valent iron powder (Fe0), these studies were mostly operated under anaerobic conditions with invariable pH that was unsuitable for practical application. Without reaction conditions (dissolved oxygen or reaction pH) control, this work aimed at subjecting the kinetics of denitrification by microscale Fe0 (160-200 mesh) to analysis the factors affecting the denitrification of nitrate and the composition of iron reductive products coating upon the iron surface. Results of the kinetics study have indicated that a higher initial concentration of nitrate would yield a greater reaction rate constant. The reduction rate of nitrate increased with increasing Fe0 dosage. The reaction can be described as a pseudo-first order reaction with respect to nitrate concentration or Fe0 dosage. Experimental results also suggested that nitrate reduction by microscale Fe0 without reaction condition control primarily was an acid-driven surface-mediated process, and the reaction order was 0.65 with respect to hydrogen ion concentration. The analyses of X-ray diffractometry and X-ray photoelectron spectroscopy indicated that a black coating, consisted of Fe2O3, Fe3O4 and FeO(OH), was formed on the surface of iron grains as an iron corrosion product when the system initial pH was lower than 5. The proportion of FeO(OH) increased as reaction time went on, whereas the proportion of Fe3O4 decreased.

  20. Optimized Reaction Conditions for Amide Bond Formation in DNA-Encoded Combinatorial Libraries.

    PubMed

    Li, Yizhou; Gabriele, Elena; Samain, Florent; Favalli, Nicholas; Sladojevich, Filippo; Scheuermann, Jörg; Neri, Dario

    2016-08-08

    DNA-encoded combinatorial libraries are increasingly being used as tools for the discovery of small organic binding molecules to proteins of biological or pharmaceutical interest. In the majority of cases, synthetic procedures for the formation of DNA-encoded combinatorial libraries incorporate at least one step of amide bond formation between amino-modified DNA and a carboxylic acid. We investigated reaction conditions and established a methodology by using 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide, 1-hydroxy-7-azabenzotriazole and N,N'-diisopropylethylamine (EDC/HOAt/DIPEA) in combination, which provided conversions greater than 75% for 423/543 (78%) of the carboxylic acids tested. These reaction conditions were efficient with a variety of primary and secondary amines, as well as with various types of amino-modified oligonucleotides. The reaction conditions, which also worked efficiently over a broad range of DNA concentrations and reaction scales, should facilitate the synthesis of novel DNA-encoded combinatorial libraries.

  1. Three-phase slug flow in microchips can provide beneficial reaction conditions for enzyme liquid-liquid reactions.

    PubMed

    Cech, Jiří; Přibyl, Michal; Snita, Dalimil

    2013-01-01

    Here, we introduce a solution to low stability of a two-phase slug flow with a chemical reaction occurring at the phase interface in a microfluidic reactor where substantial merging of individual reacting slugs results in the loss of uniformity of the flow. We create a three-phase slug flow by introducing a third fluid phase into the originally two-phase liquid-liquid slug flow, which generates small two-phase liquid slugs separated by gas phase. Introduction of the third phase into our system efficiently prevents merging of slugs and provides beneficial reaction conditions, such as uniform flow pattern along the whole reaction capillary, interfacial area with good reproducibility, and intensive water-oil interface renewal. We tested the three-phase flow on an enzyme hydrolysis of soybean oil and compared the reaction conversion with those from unstable two-phase slug flows. We experimentally confirmed that the three-phase slug flow arrangement provides conversions and pressure drops comparable or even better with two-phase liquid-liquid arrangements.

  2. Optimized Conditions for Passerini-Smiles Reactions and Applications to Benzoxazinone Syntheses.

    PubMed

    Martinand-Lurin, Elodie; Dos Santos, Aurélie; Robineau, Emmanuelle; Retailleau, Pascal; Dauban, Philippe; Grimaud, Laurence; El Kaïm, Laurent

    2016-09-21

    Initial conditions disclosed for the Passerini-Smiles reaction are associated with a lack of efficiency that has prevented chemists from using it since its discovery. We wish to report herein our thorough study in the development of new experimental conditions for this coupling between electron-poor phenols, isocyanides, and carbonyl derivatives. These new conditions have been applied to several synthetic strategies towards benzoxazinones.

  3. Role of (α ,n ) reactions under r -process conditions in neutrino-driven winds reexamined

    NASA Astrophysics Data System (ADS)

    Mohr, Peter

    2016-09-01

    Background: The astrophysical r -process occurs in an explosive astrophysical event under extremely neutron-rich conditions, leading to (n ,γ )-(γ ,n ) equilibrium along isotopic chains which peaks around neutron separation energies of a few MeV. Nuclei with larger Z are usually produced by β- decay, but under certain conditions also α -induced reactions may become relevant for the production of nuclei with Z +2 . Purpose: The uncertainties of the reaction rates of these α -induced reactions are discussed within the statistical model. As an example, α -induced (α ,n ) and (α ,x n ) reaction cross sections for the neutron-rich 86Se nucleus are studied in detail. Method: In a first step, the relevance of (α ,n ) and (α ,x n ) reactions is analyzed. Next the uncertainties are determined from a variation of the α -nucleus potential which is the all-dominant parameter for the astrophysical Z →Z +2 reaction rate. Results: It is found that the r -process flow towards nuclei with larger Z is essentially influenced only by the α -nucleus potential whereas the other ingredients of the statistical model play a very minor role. This finding is based on the fact that the flow towards larger Z depends on the sum over all (α ,x n ) cross sections, which is practically identical to the total α -induced reaction cross section. Conclusions: α -nucleus potentials play an important role under certain r -process conditions because the flow towards larger Z depends sensitively on the total α -induced reaction cross section. The uncertainty of the reaction rate is about a factor of two to three at higher temperatures and exceeds one order of magnitude at very low temperatures.

  4. Unexpected ring-opening reactions of aziridines with aldehydes catalyzed by nucleophilic carbenes under aerobic conditions.

    PubMed

    Liu, Yan-Kai; Li, Rui; Yue, Lei; Li, Bang-Jing; Chen, Ying-Chun; Wu, Yong; Ding, Li-Sheng

    2006-04-13

    [reaction: see text] The chemoselective ring opening of N-tosyl aziridines with aldehydes catalyzed by an N-heterocyclic carbene was investigated under aerobic conditions. Unexpected carboxylates of 1,2-amino alcohols from the corresponding aldehydes, rather than the acyl anion ring-opened beta-amino ketones, were exclusively obtained. A plausible mechanism for this unprecedented carbene-mediated reaction was also proposed.

  5. Characterization of reaction conditions providing rapid and specific cysteine alkylation for peptide-based mass spectrometry.

    PubMed

    Paulech, Jana; Solis, Nestor; Cordwell, Stuart J

    2013-01-01

    Alkylation converts Cys thiols to thioethers and prevents unwanted side reactions, thus facilitating mass spectrometric identification of Cys-containing peptides. Alkylation occurs preferentially at Cys due to its high nucleophilicity, however reactions at other such sites are possible. N-ethylmaleimide (NEM) shows rapid reaction kinetics with Cys and careful definition of reaction conditions results in little reactivity at other sites. Analysis of a protein standard alkylated under differing reaction conditions (pH, NEM concentrations and reaction times) was performed using liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) and selected reaction monitoring (SRM) of NEM-modified and unmodified peptide pairs. Mis-alkylation sites at primary and secondary amines were identified and limited to one equivalent of NEM. No evidence for hydroxyl or thioether alkylation was observed. Improved specificity was achieved by restricting the pH below neutral, NEM concentration below 10mM and/or reaction time to below 5min. Maximal removal of Cys activity was observed in tissue homogenates at 40mM NEM within 1min, dependent upon efficient protein denaturation. SRM assays identified peptide-specific levels of mis-alkylation, indicating that NEM-modified to unmodified ratios did not exceed 10%, with the exception of Cys alkylation that proceeded to 100%, and some Lys residues that resulted in tryptic missed cleavages. High reactivity was observed for His residues considering their relatively low abundance. These data indicate that rapid and specific Cys alkylation is possible with NEM under relatively mild conditions, with more abrasive conditions leading to increased non-specific alkylation without appreciable benefit for MS-based proteomics.

  6. Tribological reactions of perfluoroalkyl polyether oils with stainless steel under ultrahigh vacuum conditions at room temperature

    NASA Technical Reports Server (NTRS)

    Mori, Shigeyuki; Morales, Wilfredo

    1989-01-01

    The reaction between three types of commercial perfluoroalkyl polyether (PFPE) oils and stainless steel 440C was investigated experimentally during sliding under ultrahigh vacuum conditions at room temperature. It is found that the tribological reaction of PFPE is mainly affected by the activity of the mechanically formed fresh surfaces of metals rather than the heat generated at the sliding contacts. The fluorides formed on the wear track act as a boundary layer, reducing the friction coefficient.

  7. A stronger necessary condition for the multistationarity of chemical reaction networks.

    PubMed

    Soliman, Sylvain

    2013-11-01

    Biochemical reaction networks grow bigger and bigger, fed by the high-throughput data provided by biologists and bred in open repositories of models allowing merging and evolution. Nevertheless, since the available data is still very far from permitting the identification of the increasing number of kinetic parameters of such models, the necessity of structural analyses for describing the dynamics of chemical networks appears stronger every day. Using the structural information, notably from the stoichiometric matrix, of a biochemical reaction system, we state a more strict version of the famous Thomas' necessary condition for multistationarity. In particular, the obvious cases where Thomas' condition was trivially satisfied, mutual inhibition due to a multimolecular reaction and mutual activation due to a reversible reaction, can now easily be ruled out. This more strict condition shall not be seen as some version of Thomas' circuit functionality for the continuous case but rather as related and complementary to the whole domain of the structural analysis of (bio)chemical reaction systems, as pioneered by the chemical reaction network theory.

  8. Onset conditions for gas phase reaction and nucleation in the CVD of transition metal oxides

    NASA Technical Reports Server (NTRS)

    Collins, J.; Rosner, D. E.; Castillo, J.

    1992-01-01

    A combined experimental/theoretical study is presented of the onset conditions for gas phase reaction and particle nucleation in hot substrate/cold gas CVD of transition metal oxides. Homogeneous reaction onset conditions are predicted using a simple high activation energy reacting gas film theory. Experimental tests of the basic theory are underway using an axisymmetric impinging jet CVD reactor. No vapor phase ignition has yet been observed in the TiCl4/O2 system under accessible operating conditions (below substrate temperature Tw = 1700 K). The goal of this research is to provide CVD reactor design and operation guidelines for achieving acceptable deposit microstructures at the maximum deposition rate while simultaneously avoiding homogeneous reaction/nucleation and diffusional limitations.

  9. Critical ignition conditions in exothermically reacting systems for arbitrary reaction kinetics

    NASA Astrophysics Data System (ADS)

    Filimonov, Valeriy Yu.; Koshelev, Konstantin B.

    2016-08-01

    In this work, a universal method for determination of the critical ignition conditions taking into account the reactant consumption is proposed. Based on the analysis of the phase trajectories equation, the equation for maximal temperatures of exothermic reactions was obtained. In this case, the asymptotic criterion of ignition is determined by the impossibility of slow reaction mode realization with low value of maximum temperature. The method allows demarcating the regions of low- and high-temperature modes of exothermic reactions and to establish the criteria of transition to the region of high-temperature modes. The corresponding parametric diagrams can be characterized as the bifurcation ones (bistability). It was found that the region of thermal explosion (TE) existence is bounded by the classical TE conditions from below and by the degeneration conditions from above. The comparison of analytical calculation results with the results of numerical calculation gives a satisfactory agreement.

  10. Probing fast ribozyme reactions under biological conditions with rapid quench-flow kinetics.

    PubMed

    Bingaman, Jamie L; Messina, Kyle J; Bevilacqua, Philip C

    2017-03-14

    Reaction kinetics on the millisecond timescale pervade the protein and RNA fields. To study such reactions, investigators often perturb the system with abiological solution conditions or substrates in order to slow the rate to timescales accessible by hand mixing; however, such perturbations can change the rate-limiting step and obscure key folding and chemical steps that are found under biological conditions. Mechanical methods for collecting data on the millisecond timescale, which allow these perturbations to be avoided, have been developed over the last few decades. These methods are relatively simple and can be conducted on affordable and commercially available instruments. Here, we focus on using the rapid quench-flow technique to study the fast reaction kinetics of RNA enzymes, or ribozymes, which often react on the millisecond timescale under biological conditions. Rapid quench of ribozymes is completely parallel to the familiar hand-mixing approach, including the use of radiolabeled RNAs and fractionation of reactions on polyacrylamide gels. We provide tips on addressing and preventing common problems that can arise with the rapid-quench technique. Guidance is also offered on ensuring the ribozyme is properly folded and fast-reacting. We hope that this article will facilitate the broader use of rapid-quench instrumentation to study fast-reacting ribozymes under biological reaction conditions.

  11. Pybox monolithic miniflow reactors for continuous asymmetric cyclopropanation reaction under conventional and supercritical conditions.

    PubMed

    Burguete, M I; Cornejo, A; García-Verdugo, E; Gil, María J; Luis, S V; Mayoral, J A; Martínez-Merino, V; Sokolova, M

    2007-06-08

    Supported catalysts having pybox chiral moieties were prepared as macroporous monolithic miniflow systems. These catalysts are based on styrene-divinylbenzene polymeric backbones having different compositions and pybox chiral moieties. Their corresponding ruthenium complexes were tested for the continuous flow cyclopropanation reaction between styrene and ethyldiazoacetate (EDA) under conventional conditions and in supercritical carbon dioxide (scCO2). Ru-Pybox monolithic miniflow reactors not only provided a highly efficient and robust heterogeneous chiral catalyst but also allowed us to develop more environmental reaction conditions without sacrificing the global efficiency of the process.

  12. Experimental Studies of Hydrogenation and Other Reactions on Surfaces Under Astrophysically Relevant Conditions

    NASA Technical Reports Server (NTRS)

    Vidali, Gianfranco

    1998-01-01

    The goal of our project is to study hydrogen recombination reactions on solid surfaces under conditions that are relevant in astrophysics. Laboratory experiments were conducted using low-flux, cold atomic H and D beams impinging on a sample kept under ultra high vacuum conditions. Realistic analogues of interstellar dust grains were used. Our results show that current models for hydrogen recombination reactions have to be modified to take into account the role of activated diffusion of H on surfaces even at low temperature.

  13. Michael addition reactions for the modification of gold nanoparticles facilitated by hyperbaric conditions.

    PubMed

    Hartlen, Kurtis D; Ismaili, Hossein; Zhu, Jun; Workentin, Mark S

    2012-01-10

    The chemical interfacial modification of organic solvent soluble 2.4 ± 0.5 nm maleimide-modified monolayer protected gold nanoparticles (2-C(12)AuNPs) with primary or secondary amines via Michael addition reactions is demonstrated. Michael addition reactions between 2-C(12)AuNPs and primary or secondary amines at ambient temperature and pressure and under the conditions where the AuNP is soluble and stable are possible albeit sluggish, often taking days to weeks to go to completion. The rates and efficacies of the these same reactions are drastically increased at hyperbaric pressure conditions (11 000 atm) with no observed adverse effect to the gold nanoparticle stability. The resulting Michael addition adducts (3-C(12)AuNPs) formed from 2-C(12)AuNPs and the corresponding amines were characterized by TEM and by comparison of the (1)H NMR spectra of the 3-C(12)AuNPs with those of model reactions of the same amines with N-dodecylmaleimide, 2. The Michael addition reactions occur more readily with 2 rather than 2-C(12)AuNPs, consistent with the local environment of the latter imposing additional steric or other barriers to the reaction. The use of hyperbaric conditions makes the reaction of the organic solvent soluble 2-C(12)AuNP via Michael addition a viable interfacial modification process that is otherwise impractical. The results also suggest that it is a useful protocol for facilitating Michael addition reactions generally in solution at low temperatures.

  14. Carboxymethylation of Cassava Starch in Different Solvents and Solvent-Water Mixtures: Optimization of Reaction Conditions

    NASA Astrophysics Data System (ADS)

    Nwokocha, Louis M.; Ogunmola, Gabiel B.

    The influence of reaction medium on carboxymethylation process was investigated by treating cassava starch with sodium monochloroacetate in different solvents and solvent-water mixtures under alkaline conditions. The amount of carboxyl groups introduced into the starch moiety was determined titrimetrically and used to calculate the Degree of Substitution (DS) and Reaction Efficiency (RE). The results showed that carboxymethylation is significantly affected by the nature of reaction medium at p<0.05. Carboxymethylation in different solvent-water mixtures showed that aqueous 80% n-propanol offered the best medium for carboxymethylation. Optimization of reaction conditions in aqueous 80% n-propanol showed that the best condition for carboxymethylation was at starch-liquor ratio of 1:3, NaOH/reagent molar ratio of 4.0 and reagent-starch molar ratio of 0.35. An increase in temperature was required to effect the reaction at shorter time. At 55°C the highest values of DS and RE achieved in 0.5 h would require three hours to achieve the same values of DS and RE at 45°C.

  15. Review and analysis of high temperature chemical reactions and the effect of non-equilibrium conditions

    NASA Technical Reports Server (NTRS)

    Johnson, R. E.

    1986-01-01

    Chemical reactions at high temperatures have been considered extensively because of their importance to the heating effects on re-entry of space vehicles. Data on these reactions however, are not abundant and even when found there are discrepancies in data collected by various investigators. In particular, data for recombination reactions are calculated from the dissociation reactions or vice versa through the equilibrium constant. This involves the use of the principle of detailed balancing. This principle is discussed in reference to conditions where it is valid as well as to those where it is not valid. Related topics that merit further study or for which applicable information was available are briefly mentioned in an appendix to this report.

  16. Using Group-Inquiry to Study Differing Reaction Conditions in the E2 Elimination of Cyclohexyl Halides

    ERIC Educational Resources Information Center

    Long, Robert D.

    2012-01-01

    In this experiment, students individually conduct one of several variations of an E2 dehydrohalogenation reaction on a cyclohexyl halide substrate for 30 min, which is sufficient only for a partial reaction to occur. The variations examine reaction conditions including different leaving groups, decreased reaction temperature, or reduced base…

  17. Environmental Transmission Electron Microscopy Study of Diesel Carbon Soot Combustion under Simulated Catalytic-Reaction Conditions.

    PubMed

    Mori, Kohsuke; Watanabe, Keitaro; Sato, Takeshi; Yamashita, Hiromi

    2015-05-18

    Environmental transmission electron microscopy (ETEM) is used to monitor the catalytic combustion of diesel carbon soot upon exposure to molecular oxygen at elevated temperatures by using a gas-injection specimen heating holder. The reaction conditions simulated in the ETEM experiments reconstruct real conditions effectively. This study demonstrated for the first time that soot combustion occurs at the soot-catalyst interface for both Ag/CeO2 and Cu/BaO/La2 O3 catalysts.

  18. Sharper Graph-Theoretical Conditions for the Stabilization of Complex Reaction Networks

    PubMed Central

    Knight, Daniel; Shinar, Guy; Feinberg, Martin

    2015-01-01

    Across the landscape of all possible chemical reaction networks there is a surprising degree of stable behavior, despite what might be substantial complexity and nonlinearity in the governing differential equations. At the same time there are reaction networks, in particular those that arise in biology, for which richer behavior is exhibited. Thus, it is of interest to understand network-structural features whose presence enforces dull, stable behavior and whose absence permits the dynamical richness that might be necessary for life. We present conditions on a network’s Species-Reaction Graph that ensure a high degree of stable behavior, so long as the kinetic rate functions satisfy certain weak and natural constraints. These graph-theoretical conditions are considerably more incisive than those reported earlier. PMID:25600138

  19. [The effect of noradrenaline on the neuronal reactions of the motor cortex evoked by conditional stimulation].

    PubMed

    Storozhuk, V M; Stezhka, V V; Ivanova, S F

    1990-01-01

    In chronic experiments on cats the influence of iontophoretic application of adrenomimetic ephedrin and beta-adrenoblocker obsidan (propranolol) on motor cortex neuron reactions following conditional stimuli was investigated under instrumental placing reaction. It was shown for a majority of neurons that the background impulse activity and reactions following conditional stimulation were suppressed by the influence of ephedrin and on the contrary were increased by obsidan application. It is concluded that there exists a consistent tonic suppressing influence of the noradrenergic system on background and evoked cortical neurons impulse activity in the natural state. It is supposed that noradrenergic influence temporal increase may serve as an important link in mechanisms of external inhibition during stress situations, aversive effects, and distractive external excitations.

  20. Radiolytic reactions of nitro blue tetrazolium under oxidative and reductive conditions: a pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Kovacs, A.; Wojnarovits, L.; Baranyai, M.; Moussa, A.; Othman, I.; McLaughlin, W. L.

    1999-08-01

    The radiolytic reactions of the ditetrazolium salt nitro blue tetrazolium chloride (NBTCl 2) were studied by pulse radiolysis technique in aqueous solution under reducing and oxidising conditions with the aim of potential dosimetry application. Under reducing conditions the fast formation of the tetrazolinyl radical is observed that is followed by the appearance of monoformazan (MF +), i.e. one of the tetrazolium rings is reduced to formazan. The formation of the water-insoluble diformazan, i.e. the result of the second reduction step was not observed in pulse radiolysis. Formazan formation was not found under oxidative conditions.

  1. Analysis of initial reactions of MALDI based on chemical properties of matrixes and excitation condition.

    PubMed

    Lai, Yin-Hung; Wang, Chia-Chen; Chen, Chiu Wen; Liu, Bo-Hong; Lin, Sheng Hsien; Lee, Yuan Tseh; Wang, Yi-Sheng

    2012-08-16

    This investigation concerns the initial chemical reactions that affect the ionization of matrixes in matrix-assisted laser desorption/ionization (MALDI). The study focuses on the relaxations of photon energy that occur on a comparable time scale to that of ionization, in which the available laser energy is shared and the ionization condition is changed. The relaxations include fluorescence, fragmentation, and nonradiative relaxation from the excited state to the ground state. With high absorption cross section and long excited-state lifetime, photoionization of matrix plays an important role if sufficient laser energy is used. Under other conditions, thermal ionization of the molecule in the ground state is predicted to be one of the important reactions. Evidence of change in the branching ratio of initial reactions with the matrix and the excitation wavelength was obtained with α-cyano-4-hydroxycinnamic acid, sinapinic acid, 2,5-dihydroxybenzoic acid, and 2,4,6-trihydroxyacetophenone. These matrixes are studied by obtaining their mixed crystal absorption spectra, fluorescence properties, laser-induced infrared emission, and product ions. The exact ionization pathway depends on the chemical properties of matrixes and the excitation conditions. This concept may explain the diversity of experimental results observed in MALDI experiments, which provides an insight into the ensemble of chemical reactions that govern the generation of ions.

  2. Reversible Reshaping of Supported Metal Nanoislands Under Reaction Conditions in a Minimalistic Lattice Model

    NASA Astrophysics Data System (ADS)

    Korobov, A.

    2016-05-01

    The shape of (nano)islands is among significant factors of the catalytic activity of supported catalysts. A lattice model of the reshaping under reaction conditions is suggested and studied by means of kinetic Monte Carlo simulations. It is rooted in experimental findings and is simplified as far as possible to still demonstrate reversible compact—ramified shape transitions. This simple model with complex behavior demonstrates several reshaping regimes and is considered as a possible sub-network of more realistic networks of heterogeneous catalytic reactions.

  3. Method and apparatus for measuring coupled flow, transport, and reaction processes under liquid unsaturated flow conditions

    DOEpatents

    McGrail, Bernard P.; Martin, Paul F.; Lindenmeier, Clark W.

    1999-01-01

    The present invention is a method and apparatus for measuring coupled flow, transport and reaction processes under liquid unsaturated flow conditions. The method and apparatus of the present invention permit distinguishing individual precipitation events and their effect on dissolution behavior isolated to the specific event. The present invention is especially useful for dynamically measuring hydraulic parameters when a chemical reaction occurs between a particulate material and either liquid or gas (e.g. air) or both, causing precipitation that changes the pore structure of the test material.

  4. A proposed abiotic reaction scheme for hydroxylamine and monochloramine under chloramination relevant drinking water conditions.

    PubMed

    Wahman, David G; Speitel, Gerald E; Machavaram, Madhav V

    2014-09-01

    Drinking water monochloramine (NH2Cl) use may promote ammonia-oxidizing bacteria (AOB). AOB use (i) ammonia monooxygenase for biological ammonia (NH3) oxidation to hydroxylamine (NH2OH) and (ii) hydroxylamine oxidoreductase for NH2OH oxidation to nitrite. NH2Cl and NH2OH may react, providing AOB potential benefits and detriments. The NH2Cl/NH2OH reaction would benefit AOB by removing the disinfectant (NH2Cl) and releasing their growth substrate (NH3), but the NH2Cl/NH2OH reaction would also provide a possible additional inactivation mechanism besides direct NH2Cl reaction with cells. Because biological NH2OH oxidation supplies the electrons required for biological NH3 oxidation, the NH2Cl/NH2OH reaction provides a direct mechanism for NH2Cl to inhibit NH3 oxidation, starving the cell of reductant by preventing biological NH2OH oxidation. To investigate possible NH2Cl/NH2OH reaction implications on AOB, an understanding of the underlying abiotic reaction is first required. The present study conducted a detailed literature review and proposed an abiotic NH2Cl/NH2OH reaction scheme (RS) for chloramination relevant drinking water conditions (μM concentrations, air saturation, and pH 7-9). Next, RS literature based kinetics and end-products were evaluated experimentally between pHs 7.7 and 8.3, representing (i) the pH range for future experiments with AOB and (ii) mid-range pHs typically found in chloraminated drinking water. In addition, a (15)N stable isotope experiment was conducted to verify nitrous oxide and nitrogen gas production and their nitrogen source. Finally, the RS was slightly refined using the experimental data and an AQUASIM implemented kinetic model. A chloraminated drinking water relevant RS is proposed and provides the abiotic reaction foundation for future AOB biotic experiments.

  5. Correlation changes in EEG, conditioned and behavioral reactions with various degrees of oxygen insufficiency

    NASA Technical Reports Server (NTRS)

    Agadzhanyan, N. A.; Zakharova, I. N.; Kalyuzhnyy, L. V.; Dvorzhak, I. I.; Moravek, M.; Tsmiral, Y. I.

    1974-01-01

    The dynamics of change in bioelectric activity of the brain during acute hypoxia are studied for the time that working capacity and active consciousness are preserved, and to establish the correlation between EEG changes and behavioral reactions under oxygen starvation. Changes in body functions and behavioral disturbances are related to the degree of oxygen saturation in the blood, to bioelectric activity of the brain, and to an increase in conditioned reflexes. The capacity for adequate reaction to external signals and for coordinated psychomotor activity after loss of consciousness returns to man after 30 seconds. Repeated effects of hypoxia produce changes in the physiological reactions of the body directed toward better adaptation to changing gaseous environments.

  6. Maturation conditions and boar affect timing of cortical reaction in porcine oocytes.

    PubMed

    Romar, R; Coy, P; Rath, D

    2012-09-15

    The cortical reaction induces changes at the egg's Zona pellucida (ZP), perivitelline space and/or oolemma level, blocking polyspermic fertilization. We studied the timing of sperm penetration and cortical reaction in pig oocytes matured under different conditions and inseminated with different boars. Immature (germinal vesicle stage) and in vitro matured (IVM) (metaphase II stage) oocytes were inseminated and results assessed at different hours post insemination. Penetrability and polyspermy rates increased with gamete coincubation time and were higher in IVM oocytes. A strong boar effect was observed in IVF results. Cortical reaction (assessed as area occupied by cortical granules) and galactose-β(1-3)-Nacetylgalactosamine residues on ZP (area labeled by peanut agglutinin lectin, PNA) were assessed in IVM and in vivo matured (IVV) oocytes at different hours post insemination. After maturation, IVM and IVV oocytes displayed similar area occupied by cortical granules and it decreased in fertilized oocytes compared to unfertilized ones. Cortical reaction was influenced by boar and was faster in polyspermic than in monospermic oocytes, and in IVM than in IVV oocytes. The outer ZP of inseminated oocytes appeared stained by PNA and the labeled area increased along with gamete coculture time. This labeling was also observed after insemination of isolated ZP, indicating that this modification in ZP carbohydrates is not induced by cortical reaction. The steady and maintained cortical reaction observed at 4 to 5 h post insemination in IVV monospermic oocytes might reflect the physiological time course of this important event in pigs. Both maturation conditions and boar affect cortical granules release.

  7. Reservoir-Condition Pore-Scale Imaging of Reaction in Carbonates using Synchrotron Fast Tomography

    NASA Astrophysics Data System (ADS)

    Menke, H. P.; Andrew, M. G.; Bijeljic, B.; Blunt, M. J.

    2015-12-01

    Carbon capture and storage in carbonate reservoirs is essential for mitigating climate change. Supercritical CO2 mixed with host brine is acidic and can dissolve the surrounding pore structure and change flow dynamics. However, the type, speed, and magnitude of the dissolution are dependent on both the reactive transport properties of the pore-fluid and the intrinsic properties of the rock. Understanding how changes in the pore structure, chemistry, and flow properties affect dissolution is vital for successful predictive modelling both on the pore-scale and for up-scaled reservoir simulations. Reaction in carbonates has been studied at the pore-scale but has never been imaged dynamically in situ. We present an experimental method whereby both lab-based benchtop instruments and 'Pink Beam' synchrotron radiation are used in X-ray microtomography to investigate pore structure changes during supercritical CO2 injection at reservoir conditions. Three types of pure limestone rock with broadly varying rock topology were imaged under the same reservoir conditions. Flow-rate and brine acidity was varied in successive experiments by half an order of magnitude to gain insight into the impact of flow, transport, and physical heterogeneity. The images were binarized and the magnitude of dissolution was identified on a voxel-by-voxel basis to extract pore-by-pore dissolution data. The impact of dissolution on flow characteristics was studied by computing the evolution of the pore-scale velocity fields with a flow solver. We found that increasing rock heterogeneity increased channelized flow [Figure 1] through preferential pathways and that higher flow rate increased total dissolution. Additionally, decreasing reaction rate lowered overall reaction rate and made axial flow less uniform. Experimentally measured reaction rates in real rocks are at least an order of magnitude lower when compared to batch experiments. We provide evidence that this can be due to transport limitations

  8. Experimental study of the reaction of methane with petroleum hydrocarbons in geological conditions

    NASA Astrophysics Data System (ADS)

    Gold, Thomas; Gordon, Benjamin E.; Streett, William; Bilson, Elizabeth; Patnaik, Pradyot

    1986-11-01

    In order to assess the possible role of methane in petroleum formation, we studied the reaction of methane with liquid hydrocarbons representing the three main classes of compounds dominant in crude oil. The experimental reaction conditions simulated those of a geological setting for petroleum formations, at 1000 atm and 150-250°C in the presence of montmorillonite, a natural clay catalyst. Since we expected very slow reaction rates and thus low yields, we used 14C labeled methane to trace the reaction products. We report here the detection of ethylbenzene and ethyltoluene formed by the interaction of methane with benzene and toluene, respectively. Instead of methylation of benzene, predominantly C 2 addition occurred, although very small amounts of products corresponding to C 1 addition were also detected. We propose that catalytic dissociation of methane occurred, forming ethylene which participated in a Friedel-Crafts type alkylation process of the aromatic ring on the catalyst surface. In addition to ring alkylation, side reactions such as polymerization of unsaturates (ethylene, acetylene) appeared to have occurred on the catalyst surface. The nature of these polymers is yet to be determined.

  9. Experimental study of the reaction of methane with petroleum hydrocarbons in geological conditions

    SciTech Connect

    Gold, T.; Gordon, B.E.; Streett, W.; Bilson, E.; Patnaik, P.

    1986-11-01

    In order to assess the possible role of methane in petroleum formation, they studied the reaction of methane with liquid hydrocarbons representing the three main classes of compounds dominant in crude oil. The experimental reaction conditions simulated those of a geological setting for petroleum formations, at 1000 atm and 150-250/sup 0/C in the presence of montmorillonite, a natural clay catalyst. Since they expected very slow reaction rates and thus low yields, we used /sup 14/C labeled methane to trace the reaction products. They report here the detection of ethylbenzene and ethyltoluene formed by the interaction of methane with benzene and toluene, respectively. Instead of methylation of benzene, predominantly C/sub 2/ addition occurred, although very small amounts of products corresponding to C/sub 1/ addition were also detected. They propose that catalytic dissociation of methane occurred, forming ethylene which participated in a Friedel-Crafts type alkylation process of the aromatic ring on the catalyst surface. In addition to ring alkylation, side reactions such as polymerization of unsaturates (ethylene, acetylene) appeared to have occurred on the catalyst surface. The nature of these polymers is yet to be determined.

  10. Optimization of reaction conditions for improving nutritional properties in heat moisture treated maize starch.

    PubMed

    Ye, Xiaoting; Lu, Fei; Yao, Tianming; Gan, Renyou; Sui, Zhongquan

    2016-12-01

    Impact of heat-moisture treatment (HMT) on nutritional properties of normal maize starch (NMS) under various reaction conditions was investigated. NMS was adjusted to moisture levels of 20%, 25%, 30% and 35% and heated at 80, 100, 120 and 140°C for 4, 8, 12 and 16h. Response surface methodology (RSM) based on Box-Behnken design (BBD) was employed to obtain the optimal combination of moisture level (X1: 20-30%), length of heating (X2: 4-12h), and temperature (X3: 100-140°C). The optimum reaction condition decreased rapidly digestible starch (RDS) from 87.10% to 82.21%, when NMS was subjected to HMT at 23.6% moisture content and heated at 114.8°C for 9.04h. The ANOVA measurement and confirmation experiments were performed to verify the predictive value and the RSM model, indicating that temperature was the main factor to determine the digestion rate of HMT NMS. The results suggested that RDS was not correlated to heating length but positively correlated to temperature and moisture content. Reaction condition had no correlations with slowly digestible starch (SDS) and resistant starch (RS). This study could provide more information for producing low-glycemic index products.

  11. Search for reaction conditions and catalyst for selective prebiotic formation of Aldopentoses from Glycolaldehyde and Formaldehyde

    NASA Astrophysics Data System (ADS)

    Delidovich, Irina; Taran, Oxana; Parmon, Valentin; Gromov, Nikolay

    2012-07-01

    Formation of organic compounds from simple precursors appears to have been one of the first steps from geochemistry towards modern biochemistry. The Earth lagoons, hydrothermal springs, cosmic dust, meteorites, protoplanetary disk, etc. has been considered as the possible ``reactors'' in which the prebiotic synthesis could have taken place. The finding of reactions and reaction conditions which allow to produce the high yields of the biologically relevant substances from simple compounds could help us to verify different hypothesis of plausible prebotic conditions. In this work we have studied the formation of vitally important sugars, namely aldopentoses (ribose, xylose, lyxose and arabinose), from glycolaldehyde and formaldehyde over catalysts. Aldopentoses nowadays play the important roles as the components of polysaccharides, glycosides, nucleic acids and ATP. Glycolaldehyde is the simplest monosaccharide, which was found in the interstellar space [1], where it could be generated as a result of several processes, for instance, condensation of formaldehyde under UV-radiation [2]. In this work the peculiarities of interaction between glycolaldehyde and formaldehyde in the presence of soluble (phosphate and borate buffers) and solid (minerals apatite and montmorillonites) catalysts were studied. The dependences of composition of the reaction products on the catalyst nature, molar ratio of substrates, pH value of reaction mixture were revealed. The yields of aldopentoses amount to ca. 60-65% in the presence of borate catalyst under optimized reaction conditions. Borate acts not only as a catalyst, but also as the stabilizer of active intermediates and aldopentoses from side reactions [3]. Borates are present in some mineral and clays (serpentine, montmorillonite etc.) and in water of Cityhot springs (Geyser valley, placeKamchatka) in rather high concentrations. Therefore catalysis by borates could be considered as plausible prebotic condition. Acknowledgements. We

  12. Preparation of cationized pine sawdust for nitrate removal: Optimization of reaction conditions.

    PubMed

    Keränen, Anni; Leiviskä, Tiina; Hormi, Osmo; Tanskanen, Juha

    2015-09-01

    Anion exchange materials were prepared from pine sawdust (Pinus sylvestris, PSD) through cationizing treatment with N-(3-chloro-2-hydroxypropyl) trimethyl ammonium chloride (CHMAC) in the presence of NaOH. Response surface methodology (RSM) was used to find the optimal reaction conditions. Three factors were chosen: reaction temperature (26-94 °C), reaction time (0.32-3.7 h) and NaOH/CHMAC molar ratio (0.19-2.2). Product yield (%) was used as a response. A quadratic model was fitted to the experimental data. The optimal conditions were: a reaction temperature of 57 °C, a reaction time of 1.8 h and a NaOH/CHMAC molar ratio of 1.32. A maximum nitrogen content of 2.6% was obtained at 60 °C, 3.7 h and a molar ratio of 1.2. The molar ratio had the greatest impact on the response. Regression analysis revealed that over 95% of the variance can be explained by the model. A maximum nitrate sorption capacity of 15.3 ± 1.4 mg N/g was achieved. The effect of CHMAC dose was also studied (a NaOH/CHMAC molar ratio of 1.2): 0.064 mol/g PSD was found to be near the optimum. Nitrate-contaminated groundwater (27.5 mg/l NO3) was treated with CPSD. Doses of 3-6 g/l resulted in 59-71% nitrate reduction.

  13. Hydraulic Fracturing Fluid Reaction with Shale in Experiments at Unconventional Gas Reservoir Conditions

    NASA Astrophysics Data System (ADS)

    Paukert, A. N.; Hakala, A.; Jarvis, K. B.

    2015-12-01

    Despite the marked increase in hydraulic fracturing for unconventional natural gas production over the past decade, reactions between hydraulic fracturing fluids (HFF) and shale reservoirs remain poorly reported in the scientific literature. Shale-HFF interaction could cause mineral dissolution, releasing matter from the shale, or mineral precipitation that degrades reservoir permeability. Furthermore, data are limited on whether scale inhibitors are effective at preventing mineral precipitation and whether these inhibitors adversely affect reservoir fluid chemistry and permeability. To investigate HFF-rock interaction within shale reservoirs, we conducted flow-through experiments exposing Marcellus Shale to synthetic HFF at reservoir conditions (66oC, 20MPa). Outcrop shale samples were cored, artificially fractured, and propped open with quartz sand. Synthetic HFFs were mixed with chemical additives similar to those used for Marcellus Shale gas wells in Ohio and Southwestern Pennsylvania (FracFocus.org). We evaluated differences between shale reactions with HFF made from natural freshwater and reactions with HFF made from synthetic produced water (designed to simulate produced water that is diluted and re-used for subsequent hydraulic fracturing). We also compared reactions with HFFs including hydrochloric acid (HCl) to represent the initial acid stage, and HFFs excluding HCl. Reactions were determined through changes in fluid chemistry and X-ray CT and SEM imaging of the shale before and after experiments. Results from experiments with HFF containing HCl showed dissolution of primary calcite, as expected. Experiments using HFF made from synthetic produced water had significant mineral precipitation, particularly of barium and calcium sulfates. X-ray CT images from these experiments indicate precipitation of minerals occurred either along the main fracture or within smaller splay fractures, depending on fluid composition. These experiments suggest that HFF

  14. Consistency between kinetics and thermodynamics: general scaling conditions for reaction rates of nonlinear chemical systems without constraints far from equilibrium.

    PubMed

    Vlad, Marcel O; Popa, Vlad T; Ross, John

    2011-02-03

    We examine the problem of consistency between the kinetic and thermodynamic descriptions of reaction networks. We focus on reaction networks with linearly dependent (but generally kinetically independent) reactions for which only some of the stoichiometric vectors attached to the different reactions are linearly independent. We show that for elementary reactions without constraints preventing the system from approaching equilibrium there are general scaling relations for nonequilibrium rates, one for each linearly dependent reaction. These scaling relations express the ratios of the forward and backward rates of the linearly dependent reactions in terms of products of the ratios of the forward and backward rates of the linearly independent reactions raised to different scaling powers; the scaling powers are elements of the transformation matrix, which relates the linearly dependent stoichiometric vectors to the linearly independent stoichiometric vectors. These relations are valid for any network of elementary reactions without constraints, linear or nonlinear kinetics, far from equilibrium or close to equilibrium. We show that similar scaling relations for the reaction routes exist for networks of nonelementary reactions described by the Horiuti-Temkin theory of reaction routes where the linear dependence of the mechanistic (elementary) reactions is transferred to the overall (route) reactions. However, in this case, the scaling conditions are valid only at the steady state. General relationships between reaction rates of the two levels of description are presented. These relationships are illustrated for a specific complex reaction: radical chlorination of ethylene.

  15. Influence of reaction condition on viscosity of polyurethane modified epoxy based on glycerol monooleate

    NASA Astrophysics Data System (ADS)

    Triwulandari, Evi; Ramadhan, Mohammad Kemilau; Ghozali, Muhammad

    2017-01-01

    Polyurethane modified epoxy based on glycerol monooleate (PME-GMO) was synthesized. GMO as polyol for synthesis of PME-GMO was synthesized via Fisher Esterification between oleic acid from palm oil and glycerol by using sulfuric acid as catalyst with time variation i.e. 3, 4, 5 and 6 hours at 160°C. Characterizations of GMO were carried out by analysis of acid number, hydroxyl value and FTIR. The data show that the conversion of oleic acid to ester compound is directly proportional with the increasing of reaction time but the enhancement is not significant after 3 hours. Furthermore, GMO product was used as polyol for modification of epoxy with polyurethane. Modification of epoxy with polyurethane was performed by reacted epoxy, tolonate and GMO simultaneously in one step. In this research, the reaction condition was varied i.e. time reaction (0.5; 1; 1.5; 2; 2.5 hours), composition of polyurethane used (10%, 20% toward epoxy) and rasio of tolonate and GMO (NCO/OH ratio) as component of polyurethane (1.5 and 2.5). Characterization of polyurethane modified epoxy based on glycerol (PME-GMO) was conducted by viscosity and FTIR analysis. The viscosity of PME-GMO increased with increasing of reaction time, polyurethane composition and NCO/OH ratio.

  16. Runaway reactions, their courses and the methods to establish safe process conditions

    NASA Astrophysics Data System (ADS)

    Gustin, J. L.

    1991-08-01

    Much of the literature on runaway reactions deals with the consequences such as mechanical damage toxic and flammable release. The DIERS literature provides effective methods for vent sizing where experimental information is requested. Thermal stability measurements provide information on the onset temperature and kinetic data for chemical reactions. There is less information on the way the runaway reactions occur whereas the runaway reactions may have different causes. The purpose of this paper is to describe the various process deviations which can cause a runaway reaction to occur and to discuss the experimental information necessary for risk assessment, the choice of a safe process and the mitigation of the consequences of the runaway reaction. Each possible hazardous process deviation is illustrated by examples from the process industry and/or relevant experimental information obtained from laboratory experiments. The typical hazardous situations to be considered are the following: 1) The homogeneous thermal runaway due to too high a temperature. 2) The homogeneous runaway reaction by unintended introduction of additional reactants or catalyst. 3) The heterogeneous runaway reaction due to too high a local temperature. 4) The heterogeneous runaway reaction caused by slow heat conduction to the outside. 5) The runaway reaction caused by excess residence time at the process temperature (autocatalytic reactions). 6) The runaway reaction caused by reactant accumulation. The controling reactant feed rate is higher than the consumption rate perhaps because the temperature is too low, or the catalyst is absent. 7) The runaway reaction due to the pressurization of the enclosure by gaseous oxidizing intermediates (typical of nitric oxidations). 8) The runaway reaction due to phase separation of unstable species (liquids, solids) by loss of mixing or on cooling. 9) The runaway reaction on mixing of fast reacting chemicals in separate phases. 10)The runaway reaction due

  17. Formation of flavor components by the reaction of amino acid and carbonyl compounds in mild conditions.

    PubMed

    Pripis-Nicolau, L; de Revel, G; Bertrand, A; Maujean, A

    2000-09-01

    This work describe products of reactions between four alpha-dicarbonyl compounds (diacetyl, pentan-2,3-dione, glyoxal, and methylglyoxal) or two alpha-hydroxy ketones, (acetoine and acetol) and amino acids present in wines. The results shows the formation of odorous products or strong-smelling additives resulting from the Maillard and Strecker reaction in a primarily aqueous medium, at low temperature and low pH ( approximately pH 3.5) of the wine. GC/FID, GC/FPD, GC/NPD and GC/MS techniques were used. The olfactive characteristics of the products are described. In the presence of sulfur amino acids and in particular cysteine, many products were formed with a heterocycle production such as pyrazines and methylpyrazines, methylthiazoles, acetylthiazoles, acetylthiazolines, acetylthiazolidines, trimethyloxazole, and dimethylethyloxazoles. These various compounds present odors of sulfur, cornlike, pungent, nut, popcorn, roasted hazelnut, toasted, roasted, and ripe fruits. The chemical conditions of the model reactions are specified. The influence of temperature and pH on the reactions in the presence of cysteine were also studied.

  18. Organocatalytic acetylation of starch: effect of reaction conditions on DS and characterisation of esterified granules.

    PubMed

    Tupa, Maribel Victoria; Ávila Ramírez, Jhon Alejandro; Vázquez, Analía; Foresti, María Laura

    2015-03-01

    Starch acetates with varying degree of substitution (DS) were prepared by a novel solvent-free organocatalytic methodology. The acetylation protocol involved a non-toxic biobased α-hydroxycarboxylic acid as catalyst, and proceeded with high efficiency in absence of solvents. The effect of reaction conditions including reaction temperature (90-140 °C), catalyst load (0-2.3 g/g starch), acetic anhydride/starch weight ratio (6.5-13.5 g/g), and starch moisture content (0.6-14.8%) on the DS of the esters was evaluated. The analysis performed showed that the increase of temperature and catalyst concentration resulted in higher DS values, and evidenced a beneficial contribution of native starch moisture content on the substitution level achieved. Variation of reaction conditions allowed starch esters to be obtained with DS in the 0.03-2.93 range. Starch esters were characterised in terms of morphology, chemical structure, thermal properties, and distribution in polar/non polar liquid systems.

  19. Behavior of Supported Palladium Oxide Nanoparticles under Reaction Conditions, Studied with near Ambient Pressure XPS.

    PubMed

    Jürgensen, Astrid; Heutz, Niels; Raschke, Hannes; Merz, Klaus; Hergenröder, Roland

    2015-08-04

    Near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) is a promising method to close the "pressure gap", and thus, study the surface composition during heterogeneous reactions in situ. The specialized spectrometers necessary for this analytical technique have recently been adapted to operate with a conventional X-ray source, making it available for routine quantitative analysis in the laboratory. This is shown in the present in situ study of the partial oxidation of 2-propanol catalyzed with PdO nanoparticles supported on TiO2, which was investigated under reaction conditions as a function of gas composition (alcohol-to-oxygen ratio) and temperature. Exposure of the nanoparticles to 2-propanol at 30 °C leads to immediate partial reduction of the PdO, followed by a continuous reduction of the remaining PdO during heating. However, gaseous oxygen inhibits the reduction of PdO below 90 °C, and the oxidation of 2-propanol to carboxylates only occurs in the presence of oxygen above 90 °C. These results support the theory that metallic palladium is the active catalyst material, and they show that environmental conditions affect the nanoparticles and the reaction process significantly. The study also revealed challenges and limitations of this analytical method. Specifically, the intensity and fixed photon energy of a conventional X-ray source limit the spectral resolution and surface sensitivity of lab-based NAP-XPS, which affect precision and accuracy of the quantitative analysis.

  20. Lipase-catalyzed synthesis of ascorbyl oleate in acetone: optimization of reaction conditions and lipase reusability.

    PubMed

    Stojanović, Marija; Velićković, Dušan; Dimitrijević, Aleksandra; Milosavić, Nenad; Knežević-Jugović, Zorica; Bezbradica, Dejan

    2013-01-01

    Lipase-catalyzed ascorbyl oleate synthesis is eco-friendly and selective way of production of liposoluble biocompatible antioxidants, but still not present on an industrial level due to the high biocatalyst costs. In this study, response surface methodology was applied in order to estimate influence of individual experimental factors, identify interactions among them, and to determine optimum conditions for enzymatic synthesis of ascorbyl oleate in acetone, in terms of limiting substrate conversion, product yield, and yield per mass of consumed enzyme. As a biocatalyst, commercial immobilized preparation of lipase B from Candida antarctica, Novozym 435, was used. In order to develop cost-effective process, at reaction conditions at which maximum amount of product per mass of biocatalyst was produced (60°C, 0.018 % (v/v) of water, 0.135 M of vitamin C, substrates molar ratio 1:8, and 0.2 % (w/v) of lipase), possibilities for further increase of ester yield were investigated. Addition of molecular sieves at 4(th) hour of reaction enabled increase of yield from 16.7 mmol g⁻¹ to 19.3 mmol g⁻¹. Operational stability study revealed that after ten reaction cycles enzyme retained 48 % of its initial activity. Optimized synthesis with well-timed molecular sieves addition and repeated use of lipase provided production of 153 mmol per gram of enzyme. Further improvement of productivity was achieved using procedure for the enzyme reactivation.

  1. Effect of hydrothermal reaction time and alkaline conditions on the electrochemical properties of reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Vermisoglou, E. C.; Giannakopoulou, T.; Romanos, G.; Giannouri, M.; Boukos, N.; Lei, C.; Lekakou, C.; Trapalis, C.

    2015-12-01

    Reduced graphene oxide sheets (rGO) were prepared by hydrothermal treatment of aqueous dispersions of graphite oxide (GtO) applied for short (4 h) and prolonged reaction times (19-24 h). The effect of process duration as well as the alkaline conditions (pH ∼10) by addition of K2CO3 on the quality characteristics of the produced rGO materials was investigated. Both reduction and exfoliation occurred during this process as it was evidenced by FTIR and XRD data. SEM, TEM and HRTEM microscopy displayed highly exfoliated rGO materials. XPS verified that the re-establishment of the conjugated graphene network is more extensive for prolonged times of hydrothermal processing in accordance to Raman spectroscopy measurements. The sample produced under alkaline conditions bore fewer defects and almost 5 times higher BET surface area (∼181 m2/g) than the sample with no pH adjustment (∼34 m2/g) for the same hydrothermal reaction time (19 h), attributed to the developed microporosity. The specific capacitance of this material estimated by electrochemical impedance using three-electrode cell and KCl aqueous solution as an electrolyte was ∼400-500 F/g. When EDLC capacitors were fabricated from rGO materials the electrochemical testing in organic electrolyte i.e. TEABF4 in PC, revealed that the shortest hydrothermal reaction time (4 h) was more efficient resulting in capacitance around 60 F/g.

  2. Specificity of psychomotor reactions in the conditions of support deprivation including effects of countermeasures

    NASA Astrophysics Data System (ADS)

    Nichiporuk, Igor; Ivanov, Oleg

    Activity of the cosmonaut demands high level of psychomotor reactions (PMR) which can vary during space flight under the influences of psychophysiological state’s variability and unusual inhabitancy that causes the necessity of PMR estimation’s inclusion into quality monitoring of capacity for work (CW). A main objective of research was a study of features of visual-motor reactions (VMR) and elements of CW of the person within simulation of microgravity effects via 7-day dry immersion (DI) in healthy male-volunteers 20-35 years old. The experimental data were received which testified to peculiarities of VMR and recognition of simple figures of main colors of a visible spectrum (red, green, blue, the RGB-standard) in the conditions of the DI characterized by support deprivation and decreased proprioceptive afferentation - in a control series and in a series with use of mioelectrostimulation as a countermeasure.

  3. Study of effects of some reaction conditions on ethanolysis of rapeseed oil with dispergation.

    PubMed

    Cernoch, Michal; Hájek, Martin; Skopal, Frantisek

    2010-02-01

    The alkaline-catalyzed (KOH) ethanolysis of rapeseed oil with the help of a mechanical disperser was researched in this study. The effects of chosen reaction conditions (independent variables: the reaction temperature and time, the amount of catalyst, the molar ratio ethanol to oil and the rotation frequency of the disperser) on the ethanolysis process and ways for the improvement of the transesterification and separation process were studied. The transesterification of oil, the separation of the ester phase from the glycerol phase and qualitative properties of the ester phase were monitored by many dependent variables (e.g. the yield of the ester phase, the weight concentration of glycerides, the content of potassium ions, etc.). The measured data was analyzed by multi-linear regression with the help of many statistical tests (significance of parameters, exclusion of outliers, etc.). The created mathematical models describing the relations between the independent and dependent variables were verified by several independent experiments.

  4. Long-term behavior of reaction-diffusion equations with nonlocal boundary conditions on rough domains

    NASA Astrophysics Data System (ADS)

    Gal, Ciprian G.; Warma, Mahamadi

    2016-08-01

    We investigate the long term behavior in terms of finite dimensional global and exponential attractors, as time goes to infinity, of solutions to a semilinear reaction-diffusion equation on non-smooth domains subject to nonlocal Robin boundary conditions, characterized by the presence of fractional diffusion on the boundary. Our results are of general character and apply to a large class of irregular domains, including domains whose boundary is Hölder continuous and domains which have fractal-like geometry. In addition to recovering most of the existing results on existence, regularity, uniqueness, stability, attractor existence, and dimension, for the well-known reaction-diffusion equation in smooth domains, the framework we develop also makes possible a number of new results for all diffusion models in other non-smooth settings.

  5. Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions

    PubMed Central

    Kalz, Kai F.; Kraehnert, Ralph; Dvoyashkin, Muslim; Dittmeyer, Roland; Gläser, Roger; Krewer, Ulrike; Reuter, Karsten

    2016-01-01

    Abstract In the future, (electro‐)chemical catalysts will have to be more tolerant towards a varying supply of energy and raw materials. This is mainly due to the fluctuating nature of renewable energies. For example, power‐to‐chemical processes require a shift from steady‐state operation towards operation under dynamic reaction conditions. This brings along a number of demands for the design of both catalysts and reactors, because it is well‐known that the structure of catalysts is very dynamic. However, in‐depth studies of catalysts and catalytic reactors under such transient conditions have only started recently. This requires studies and advances in the fields of 1) operando spectroscopy including time‐resolved methods, 2) theory with predictive quality, 3) kinetic modelling, 4) design of catalysts by appropriate preparation concepts, and 5) novel/modular reactor designs. An intensive exchange between these scientific disciplines will enable a substantial gain of fundamental knowledge which is urgently required. This concept article highlights recent developments, challenges, and future directions for understanding catalysts under dynamic reaction conditions. PMID:28239429

  6. Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions.

    PubMed

    Kalz, Kai F; Kraehnert, Ralph; Dvoyashkin, Muslim; Dittmeyer, Roland; Gläser, Roger; Krewer, Ulrike; Reuter, Karsten; Grunwaldt, Jan-Dierk

    2017-01-09

    In the future, (electro-)chemical catalysts will have to be more tolerant towards a varying supply of energy and raw materials. This is mainly due to the fluctuating nature of renewable energies. For example, power-to-chemical processes require a shift from steady-state operation towards operation under dynamic reaction conditions. This brings along a number of demands for the design of both catalysts and reactors, because it is well-known that the structure of catalysts is very dynamic. However, in-depth studies of catalysts and catalytic reactors under such transient conditions have only started recently. This requires studies and advances in the fields of 1) operando spectroscopy including time-resolved methods, 2) theory with predictive quality, 3) kinetic modelling, 4) design of catalysts by appropriate preparation concepts, and 5) novel/modular reactor designs. An intensive exchange between these scientific disciplines will enable a substantial gain of fundamental knowledge which is urgently required. This concept article highlights recent developments, challenges, and future directions for understanding catalysts under dynamic reaction conditions.

  7. Method of experimental determination of the kinetic constants in fast polymerization reactions in nonisothermal diffusion conditions

    SciTech Connect

    Prochukhan, Yu.A.; Berlin, A.A.; Enikolopyan, N.S.

    1986-09-01

    A new method for the experimental determination of the kinetic constants k/sub p/ and k/sub t/ in fast polymerization reactions on the example of cationic (under the effect of AlCl/sub 3/, BF/sub 3/, and other catalysts) liquid phase polymerization of isobutylene in a flow was suggested. The study of the macrokinetic features of low-temperature polymerization of isobutylene revealed the specific conditions of the occurrence of the process (quasi-ideal displacement) which are characterized by the relative constancy and uniformity of the distribution of the concentrations of the reacting substances along the flow section.

  8. A Molecular Dynamics Study of Chemical Reactions of Solid Pentaerythritol Tetranitrate at Extreme Conditions

    SciTech Connect

    Wu, C J; Manaa, M R; Fried, L E

    2006-05-30

    We have carried out density functional based tight binding (DFTB) molecular dynamics (MD) simulation to study energetic reactions of solid Pentaerythritol Tetranitrate (PETN) at conditions approximating the Chapman-Jouguet (CJ) detonation state. We found that the initial decomposition of PETN molecular solid is characterized by uni-molecular dissociation of the NO{sub 2}groups. Interestingly, energy release from this powerful high explosive was found to proceed in several stages. The large portion of early stage energy release was found to be associated with the formation of H{sub 2}O molecules within a few picoseconds of reaction. It took nearly four times as long for majority of CO{sub 2} products to form, accompanied by a slow oscillatory conversion between CO and CO{sub 2}. The production of N{sub 2} starts after NO{sub 2} loses its oxygen atoms to hydrogen or carbon atoms to form H{sub 2}O or CO. We identified many intermediate species that emerge and contribute to reaction kinetics, and compared our simulation with a thermo-chemical equilibrium calculation. In addition, a detailed chemical kinetics of formation of H{sub 2}O, CO, and CO{sub 2} were developed. Rate constants of formations of H{sub 2}O, CO{sub 2} and N{sub 2} were reported.

  9. Effect of moisture conditions and transfers on alkali silica reaction damaged structures

    SciTech Connect

    Multon, Stephane; Toutlemonde, Francois

    2010-06-15

    The aim of this paper is to point out the water driving effect on the alkali silica reaction (ASR) expansion and particularly when modifications of moisture conditions occur. After being submitted to a unidirectional moisture gradient during 14 months, the upper faces of ASR reactive beams were covered by water for 9 months. This late water supply on the upper face rapidly produced large expansions, which mainly occurred along the transverse and the vertical directions resulting in large longitudinal cracks. Companion nonreactive specimens were kept in the same environmental conditions in order to quantify the basic characteristics of moisture-dependent expansive behaviour of the material. The paper focuses on the effects of late water supply or late drying on already ASR-damaged concrete, which is a significant concern for real-life structures. Both structural effects of late water supply on ASR progress in already damaged structures and interpretation of such phenomena are described.

  10. Atomic-Scale Observations of Catalyst Structures under Reaction Conditions and during Catalysis.

    PubMed

    Tao, Franklin Feng; Crozier, Peter A

    2016-03-23

    Heterogeneous catalysis is a chemical process performed at a solid-gas or solid-liquid interface. Direct participation of catalyst atoms in this chemical process determines the significance of the surface structure of a catalyst in a fundamental understanding of such a chemical process at a molecular level. High-pressure scanning tunneling microscopy (HP-STM) and environmental transmission electron microscopy (ETEM) have been used to observe catalyst structure in the last few decades. In this review, instrumentation for the two in situ/operando techniques and scientific findings on catalyst structures under reaction conditions and during catalysis are discussed with the following objectives: (1) to present the fundamental aspects of in situ/operando studies of catalysts; (2) to interpret the observed restructurings of catalyst and evolution of catalyst structures; (3) to explore how HP-STM and ETEM can be synergistically used to reveal structural details under reaction conditions and during catalysis; and (4) to discuss the future challenges and prospects of atomic-scale observation of catalysts in understanding of heterogeneous catalysis. This Review focuses on the development of HP-STM and ETEM, the in situ/operando characterizations of catalyst structures with them, and the integration of the two structural analytical techniques for fundamentally understanding catalysis.

  11. Reaction of perfluoroalkylpolyethers (PFPE) with 440C steel in vacuum under sliding conditions at room temperature

    NASA Technical Reports Server (NTRS)

    Mori, Shigeyuki; Morales, Wilfredo

    1989-01-01

    Reactions of perfluoroalkylpolyethers (PFPE: Fomblin, Demnum and Krytox) were studied during the sliding contact of stainless steel specimens under ultrahigh vacuum conditions. All three fluids reacted with the steel specimens during sliding. Fomblin, which has acetal linkages, decomposed under the sliding conditions generating gaseous products, (COF2 and fluorinated carbons) which were detected by a quadrupole mass spectrometer. Gaseous products were not detected for the Demnum and Krytox fluids. The amount of gaseous products from Fomblin increased with increasing sliding speed. At the end of the sliding experiments, the wear scar and deposits on the specimens were examined by small spot size XPS. The oxide layer on the specimen surface was removed during sliding, and metal fluorides were formed on the worn surface. The surface of the wear scar and deposits were covered with adsorbed PFPE. Based on these results, it was concluded that the decomposition reaction on Fomblin was initiated by contacting the fluid with a fresh metal surface which was formed during sliding.

  12. Rapid and effective oxidative pretreatment of woody biomass at mild reaction conditions and low oxidant loadings

    PubMed Central

    2013-01-01

    Background One route for producing cellulosic biofuels is by the fermentation of lignocellulose-derived sugars generated from a pretreatment that can be effectively coupled with an enzymatic hydrolysis of the plant cell wall. While woody biomass exhibits a number of positive agronomic and logistical attributes, these feedstocks are significantly more recalcitrant to chemical pretreatments than herbaceous feedstocks, requiring higher chemical and energy inputs to achieve high sugar yields from enzymatic hydrolysis. We previously discovered that alkaline hydrogen peroxide (AHP) pretreatment catalyzed by copper(II) 2,2΄-bipyridine complexes significantly improves subsequent enzymatic glucose and xylose release from hybrid poplar heartwood and sapwood relative to uncatalyzed AHP pretreatment at modest reaction conditions (room temperature and atmospheric pressure). In the present work, the reaction conditions for this catalyzed AHP pretreatment were investigated in more detail with the aim of better characterizing the relationship between pretreatment conditions and subsequent enzymatic sugar release. Results We found that for a wide range of pretreatment conditions, the catalyzed pretreatment resulted in significantly higher glucose and xylose enzymatic hydrolysis yields (as high as 80% for both glucose and xylose) relative to uncatalyzed pretreatment (up to 40% for glucose and 50% for xylose). We identified that the extent of improvement in glucan and xylan yield using this catalyzed pretreatment approach was a function of pretreatment conditions that included H2O2 loading on biomass, catalyst concentration, solids concentration, and pretreatment duration. Based on these results, several important improvements in pretreatment and hydrolysis conditions were identified that may have a positive economic impact for a process employing a catalyzed oxidative pretreatment. These improvements include identifying that: (1) substantially lower H2O2 loadings can be used that

  13. Iodine-catalyzed disproportionation of aryl-substituted ethers under solvent-free reaction conditions.

    PubMed

    Jereb, Marjan; Vražič, Dejan

    2013-03-28

    Iodine was demonstrated to be an efficient catalyst for disproportionation of aryl-substituted ethers under solvent-free reaction conditions. Variously substituted 1,1,1',1'-tetraaryldimethyl ethers were transformed into the corresponding diarylketone and diarylmethane derivatives. I2-catalyzed transformation of 4-methoxyphenyl substituted ethers yielded mono- and dialkylated Friedel-Crafts products as well. Treatment of trityl alkyl and trityl benzyl ethers with a catalytic amount of iodine produced triphenylmethane and the corresponding aldehydes and ketones. The electron-donating substituents facilitated the reaction, while the electron-withdrawing groups retarded it; the difference in reactivity is not very high. Such an observation may be in favour of hydride transfer, predominantly from the less electron rich side of the ether with more stable carbocation formation. With the isotopic studies it was established that a substantial portion of the C-H bond scission took place in the rate-determining step, while the carbonyl oxygen atom originated from the starting ether, and not from the air. The transformation took place under air and under argon, and HI was not a functioning catalyst.

  14. Application of click chemistry conditions for 5-bromo-2'-deoxyuridine determination through Fenton and related reactions.

    PubMed

    Cappella, Paolo; Pulici, Maurizio; Gasparri, Fabio

    2015-01-05

    Mixtures of ascorbate and copper used in certain click chemistry experimental conditions act as oxidizing agents, catalyzing the formation of reactive oxygen species through Fenton and related reactions. Hydroxyl radicals act as chemical nucleases, introducing DNA strand breaks that can be exploited for BrdU immunostaining in place of acid denaturation. This procedure is readily applicable to high content analysis and flow cytometry assays, and provides results comparable to click chemistry EdU cycloaddition and classical BrdU immunodetection. Importantly, this approach allows preservation of labile epitopes such as phosphoproteins. This unit describes an optimized method that successfully employs Fenton chemistry for simultaneous detection of phosphoproteins and BrdU in intact cells.

  15. Influence of home cooking conditions on Maillard reaction products in beef.

    PubMed

    Trevisan, Aurea Juliana Bombo; de Almeida Lima, Daniele; Sampaio, Geni Rodrigues; Soares, Rosana Aparecida Manólio; Markowicz Bastos, Deborah Helena

    2016-04-01

    The influence of home cooking methods on the generation of Maillard reaction products (MRP) in beef was investigated. Grilling and frying hamburgers to an internal temperature below 90 °C mainly generated furosine. When the temperature reached 90 °C and 100 °C, furosine content decreased by 36% and fluorescent compounds increased by up to 98%. Baking meat at 300 °C, the most severe heat treatment studied, resulted in the formation of carboxymethyllysine. Boiling in water caused very low MRP formation. Acrylamide concentrations in grilled, fried or baked meat were extremely low. Home cooking conditions leading to low MRP generation and pleasant colours were obtained and could be used to guide diabetic and chronic renal patients on how to reduce their carboxymethyllysine intake.

  16. Radiative flow of a tangent hyperbolic fluid with convective conditions and chemical reaction

    NASA Astrophysics Data System (ADS)

    Hayat, Tasawar; Qayyum, Sajid; Ahmad, Bashir; Waqas, Muhammad

    2016-12-01

    The objective of present paper is to examine the thermal radiation effects in the two-dimensional mixed convection flow of a tangent hyperbolic fluid near a stagnation point. The analysis is performed in the presence of heat generation/absorption and chemical reaction. Convective boundary conditions for heat and mass transfer are employed. The resulting partial differential equations are reduced into nonlinear ordinary differential equations using appropriate transformations. Series solutions of momentum, energy and concentration equations are computed. The characteristics of various physical parameters on the distributions of velocity, temperature and concentration are analyzed graphically. Numerical values of skin friction coefficient, local Nusselt and Sherwood numbers are computed and examined. It is observed that larger values of thermal and concentration Biot numbers enhance the temperature and concentration distributions.

  17. Effects of reaction conditions on cellulose structures synthesized in vitro by bacterial cellulose synthases.

    PubMed

    Penttilä, Paavo A; Sugiyama, Junji; Imai, Tomoya

    2016-01-20

    Cellulose was synthesized by cellulose synthases extracted from the Komagataeibacter xylinus (formerly known as Gluconacetobacter xylinus). The effects of temperature and centrifugation of the reaction solution on the synthesis products were investigated. Cellulose with number-average degree of polymerization (DPn) roughly in the range 60-80 and cellulose II crystal structure was produced under all conditions. The amount of cellulose varied with temperature and centrifugation, and the centrifugation at 2000 × g also slightly reduced the DPn. Cellulose production was maximal around the temperature 35 °C and without centrifugation. At higher temperatures and during centrifugation at 2000 × g the proteins started to denature, causing differences also in the morphology of the cellulosic aggregates, as seen with electron microscopy. These observations serve as a basis for discussions about the factors affecting the structure formation and chain length of in vitro synthesized cellulose.

  18. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis.

    PubMed

    Nguyen, Luan; Tao, Franklin Feng

    2016-06-01

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  19. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

    NASA Astrophysics Data System (ADS)

    Nguyen, Luan; Tao, Franklin Feng

    2016-06-01

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  20. Neutrality condition and response law for nonlinear reaction-diffusion equations, with application to population genetics

    NASA Astrophysics Data System (ADS)

    Vlad, Marcel Ovidiu; Moran, Federico; Tsuchiya, Masa; Cavalli-Sforza, L. Luca; Oefner, Peter J.; Ross, John

    2002-06-01

    We study a general class of nonlinear macroscopic evolution equations with ``transport'' and ``reaction'' terms which describe the dynamics of a species of moving individuals (atoms, molecules, quasiparticles, organisms, etc.). We consider that two types of individuals exist, ``not marked'' and ``marked,'' respectively. We assume that the concentrations of both types of individuals are measurable and that they obey a neutrality condition, that is, the kinetic and transport properties of the ``not marked'' and ``marked'' individuals are identical. We suggest a response experiment, which consists in varying the fraction of ``marked'' individuals with the preservation of total fluxes, and show that the response of the system can be represented by a linear superposition law even though the underlying dynamics of the system is in general highly nonlinear. The linear response law is valid even for large perturbations and is not the result of a linearization procedure but rather a necessary consequence of the neutrality condition. First, we apply the response theorem to chemical kinetics, where the ``marked species'' is a molecule labeled with a radioactive isotope and there is no kinetic isotope effect. The susceptibility function of the response law can be related to the reaction mechanism of the process. Secondly we study the geographical distribution of the nonrecurrent, nonreversible neutral mutations of the nonrecombining portion of the Y chromosome from human populations and show that the fraction of mutants at a given point in space and time obeys a linear response law of the type introduced in this paper. The theory may be used for evaluating the geographic position and the moment in time where and when a mutation originated.

  1. Chemical and Physical Reactions of Wellbore Cement under CO2 Storage Conditions: Effects of Cement Additives

    NASA Astrophysics Data System (ADS)

    Kutchko, B. G.; Strazisar, B. R.; Huerta, N.; Lowry, G. V.; Dzombak, D. A.; Thaulow, N.

    2008-12-01

    Sequestration of CO2 into geologic formations requires long-term storage and low leakage rates to be effective. Active and abandoned wells in candidate storage formations must be evaluated as potential leakage points. Wellbore integrity is an important part of an overall integrated assessment program being developed at NETL to assess potential risks at CO2 storage sites. Such a program is needed for ongoing policy and regulatory decisions for geologic carbon sequestration. The permeability and integrity of the cement in the well is a primary factor affecting its ability to prevent leakage. Cement must be able to maintain low permeability over lengthy exposure to reservoir conditions in a CO2 injection and storage scenario. Although it is known that cement may be altered by exposure to CO2, the results of ongoing research indicate that cement curing conditions, fluid properties, and cement additives play a significant role in the rate of alteration and reaction. The objective of this study is to improve understanding of the factors affecting wellbore cement integrity for large-scale geologic carbon sequestration projects. Due to the high frequency use of additives (pozzolan) in wellbore cement, it is also essential to understand the reaction of these cement-pozzolan systems upon exposure to CO2 under sequestration conditions (15.5 MPa and 50°C). Laboratory experiments were performed to determine the physical and chemical changes, as well as the rate of alteration of commonly used pozzolan-cement systems under simulated sequestration reservoir conditions, including both supercritical CO2 and CO2-saturated brine. The rate of alteration of the cement-pozzolan systems is considerably faster than with neat cement. However, the alteration of physical properties is much less significant with the pozzolanic blends. Permeability of a carbonated pozzolanic cement paste remains sufficiently small to block significant vertical migration of CO2 in a wellbore. All of the

  2. Highly diastereoselective and regioselective copper-catalyzed nitrosoformate dearomatization reaction under aerobic-oxidation conditions.

    PubMed

    Yang, Weibo; Huang, Long; Yu, Yang; Pflästerer, Daniel; Rominger, Frank; Hashmi, A Stephen K

    2014-04-01

    An unprecedented copper-catalyzed acylnitroso dearomatization reaction, which expands the traditional acylnitroso ene reaction and acylnitroso Diels-Alder reaction to a new type of transformation, has been developed under aerobic oxidation. Intermolecular and intra-/intermolecular reaction modes demonstrate an entirely different N- or O-acylnitroso selectivity. Hence, we can utilize this reaction as a highly diastereoselective access to a series of new pyrroloindoline derivatives, which are important structural motifs for natural-product synthesis.

  3. A more robust model of the biodiesel reaction, allowing identification of process conditions for significantly enhanced rate and water tolerance.

    PubMed

    Eze, Valentine C; Phan, Anh N; Harvey, Adam P

    2014-03-01

    A more robust kinetic model of base-catalysed transesterification than the conventional reaction scheme has been developed. All the relevant reactions in the base-catalysed transesterification of rapeseed oil (RSO) to fatty acid methyl ester (FAME) were investigated experimentally, and validated numerically in a model implemented using MATLAB. It was found that including the saponification of RSO and FAME side reactions and hydroxide-methoxide equilibrium data explained various effects that are not captured by simpler conventional models. Both the experiment and modelling showed that the "biodiesel reaction" can reach the desired level of conversion (>95%) in less than 2min. Given the right set of conditions, the transesterification can reach over 95% conversion, before the saponification losses become significant. This means that the reaction must be performed in a reactor exhibiting good mixing and good control of residence time, and the reaction mixture must be quenched rapidly as it leaves the reactor.

  4. Simplified models of transport and reactions in conditions of CO2 storage in saline aquifers

    NASA Astrophysics Data System (ADS)

    Suchodolska, Katarzyna; Labus, Krzysztof

    2016-04-01

    Simple hydrogeochemical models may serve as tools of preliminary assessment of CO2 injection and sequestraton impact on the aquifer and cap-rocks. In order to create models of reaction and transport in conditions of CO2 injection and storage, the TOUGHREACT simulator, and the Geochemist's Workbench software were applied. The chemical composition of waters for kinetic transport models based on the water - rock equilibrium calculations. Analyses of reaction and transport of substances during CO2 injection and storage period were carried out in three scenarios: one-dimensional radial model, and two-dimensional model of CO2 injection and sequestration, and one-dimensional model of aquifer - cap-rock interface. Modeling was performed in two stages. The first one simulated the immediate changes in the aquifer and insulating rocks impacted by CO2 injection (100 days in case of reaction model and 30 years in transport and reaction model), the second - enabled assessment of long-term effects of sequestration (20000 years). Reactions' quality and progress were monitored and their effects on formation porosity and sequestration capacity in form of mineral, residual and free phase of CO2 were calculated. Calibration of numerical models (including precipitation of secondary minerals, and correction of kinetics parameters) describing the initial stage of injection, was based on the experimental results. Modeling allowed to evaluate the pore space saturation with gas, changes in the composition and pH of pore waters, relationships between porosity and permeability changes and crystallization or dissolution minerals. We assessed the temporal and spatial extent of crystallization processes, and the amount of carbonates trapping. CO2 in mineral form. The calculated sequestration capacity of analyzed formations reached n·100 kg/m3 for the: dissolved phase - CO(aq), gas phase - CO2(g) and mineral phase, but as much as 101 kg/m3 for the supercritical phase - SCCO2. Processes of gas

  5. A Knoevenagel Initiated Annulation Reaction Using Room Temperature or Microwave Conditions

    ERIC Educational Resources Information Center

    Cook, A. Gilbert

    2007-01-01

    An experiment is presented that has the student execute a Knoevenagel initiated annulation reaction. The reaction can be carried out either through use of a microwave reactor or by allowing the mixture to stand at room temperature for two days. The student is then challenged to identify the reaction product through a guided prelab exercise of the…

  6. Influence of reaction conditions on the properties of solution-processed Cu2ZnSnS4 nanocrystals

    NASA Astrophysics Data System (ADS)

    Qu, Yongtao; Zoppi, Guillaume; Miles, Robert W.; Beattie, Neil S.

    2014-12-01

    Cu2ZnSnS4 nanocrystals were fabricated by hot injection of sulphur into a solution of metallic precursors. By careful control of the reaction conditions it was possible to control the elemental composition of the nanocrystals such that they are suitable for earth abundant photovoltaic absorbers. When the reaction temperature increased from 195 °C to 240 °C the energy band gap of the nanocrystals decreased from 1.65 eV to 1.39 eV. This variation is explained by the identification of a mixed wurtzite-kesterite phase at lower reaction temperatures and secondary phase Cu2SnS3 at higher temperatures. Moreover, the existence of wurtzite structure depends critically on the reaction cooling rate. The reaction time was also found to have a strong effect on the nanocrystals which became increasingly copper poor and zinc rich as the reaction evolved. As the reaction time increase from 15 min to 60 min, the energy band gap increased from 1.42 eV to 1.84 eV. This variation is discussed in terms of the sample doping. The results demonstrate the importance of optimizing the reaction conditions to produce high quality Cu2ZnSnS4 nanocrystals.

  7. Experimental studies of gas-aerosol reactions

    NASA Astrophysics Data System (ADS)

    Gupta, Anand

    1991-05-01

    The aqueous phase oxidation of SO2 by H2O2 is believed to the principle mechanism for atmospheric sulfate formation in cloud droplets. However, no studies in noncloud aerosol systems have been reported. The objective is to quantify the importance of the noncloud liquid phase reactions of SO2 by H2O2 in the atmosphere. Growth rates of submicron droplets exposed to SO2 and H2O2 were measured using the tandem differential mobility analyzer (TDMA) technique (Rader and McMurry, 1986). The technique uses differential mobility analyzers (DMA's) to generate monodisperse particles and to measure particle size after the reaction. To facilitate submicron monodisperse droplet production with the DMA, a low-ion-concentration charter capable of generating singly charged particles up to 1.0 microns was developed and experimentally evaluated. The experiments were performed using dry and deliquesced (NH4)2SO4 particles with SO2 and H2O2 concentrations from 0-860 ppb and 0-150 ppb, respectively. No growth was observed for dry particles. For droplets greater than or equal to 0.3 microns, the fractional diameter growth was independent of particle size and for droplets less than or equal to 0.2 microns, it decreased as particle size decreased. The observed decrease is due to NH3 evaporation. As ammonia evaporates, droplet pH decreases causing the oxidation rate to decrease, leading to a lower growth rate. To predict the size-dependent growth rates, a theoretical model was developed using solution thermodynamics, gas/particle equilibrium, and chemical kinetics. The experimental and theoretical results are in reasonable agreement. For dry (NH4)2SO4 particles exposed to SO2, H2O2, NH3, and H2O vapor, surface reaction-controlled growth was observed. Particle growth was very sensitive to particle composition. No growth was observed for Polystyrene latex particles, whereas (NH4)2SO4 particles doped with catalysts (Fe(2+), Fe(3+), Mn(2+) and Cu(2+)) in a molar ratio of 1:500 grew slower than

  8. Experimental Studies of Gas-Aerosol Reactions

    NASA Astrophysics Data System (ADS)

    Gupta, Anand

    1991-02-01

    The aqueous phase oxidation of SO_2 by H_2O_2 is believed to be the principle mechanism for atmospheric sulfate formation in cloud droplets. However, no studies in noncloud aerosol systems have been reported. The objective of this thesis is to quantify the importance of the noncloud liquid phase reactions of SO_2 by H_2O_2 in the atmosphere. In this thesis growth rates of submicron droplets exposed to SO_2 and H_2 O_2 were measured using the tandem differential mobility analyzer (TDMA) technique (Rader and McMurry, 1986). The technique uses differential mobility analyzers (DMAs) to generate monodisperse particles and to measure particle size after the reaction. To facilitate submicron monodisperse droplet production with the DMA, a low-ion-concentration charger capable of generating singly charged particles up to 1.0 μm was developed and experimentally evaluated. The experiments were performed using dry and deliquesced (NH_4)_2SO _4 particles with SO_2 and H_2O_2 concentrations from 0-860 ppb and 0-150 ppb, respectively. No growth was observed for dry particles. For droplets >=0.3 mum, the fractional diameter growth was independent of particle size and for droplets <=0.2 mum, it decreased as particle size decreased. The observed decrease is due to NH_3 evaporation. As ammonia evaporates, droplet pH decreases causing the oxidation rate to decrease, leading to a lower growth rate. To predict the size-dependent growth rates, a theoretical model was developed using solution thermodynamics, gas/particle equilibrium and chemical kinetics. The experimental and theoretical results are in reasonable agreement. For dry (NH_4) _2SO_4 particles exposed to SO_2, H_2O _2, NH_3 and H_2O vapor, surface reaction-controlled growth was observed. Particle growth was very sensitive to particle composition. No growth was observed for Polystyrene latex particles, whereas (NH_4) _2SO_4 particles doped with catalysts (Fe^{2+} , Fe^{3+}, Mn ^{2+}, Cu^{2+ }) in a molar ratio of 1:500 grew

  9. 1,4-Addition of TMSCCl₃ to nitroalkenes: efficient reaction conditions and mechanistic understanding.

    PubMed

    Wu, Na; Wahl, Benoit; Woodward, Simon; Lewis, William

    2014-06-16

    Improved synthetic conditions allow preparation of TMSCCl3 in good yield (70%) and excellent purity. Compounds of the type NBu4X [X=Ph3SiF2 (TBAT), F (tetrabutylammonium fluoride, TBAF), OAc, Cl and Br] act as catalytic promoters for 1,4-additions to a range of cyclic and acyclic nitroalkenes, in THF at 0-25 °C, typically in moderate to excellent yields (37-95%). TBAT is the most effective promoter and bromide the least effective. Multinuclear NMR studies ((1)H, (19)F, (13)C and (29)Si) under anaerobic conditions indicate that addition of TMSCCl3 to TBAT (both 0.13 M) at -20 °C, in the absence of nitroalkene, leads immediately to mixtures of Me3SiF, Ph3SiF and NBu4CCl3. The latter is stable to at least 0 °C and does not add nitroalkene from -20 to 0 °C, even after extended periods. Nitroalkene, in the presence of TMSCCl3 (both 0.13 M at -20 °C), when treated with TBAT, leads to immediate formation of the 1,4-addition product, suggesting the reaction proceeds via a transient [Me3Si(alkene)CCl3] species, in which (alkene) indicates an Si⋅⋅⋅O coordinated nitroalkene. The anaerobic catalytic chain is propagated through the kinetic nitronate anion resulting from 1,4 CCl3(-) addition to the nitroalkene. This is demonstrated by the fact that isolated NBu4[CH2=NO2] is an efficient promoter. Use of H2C=CH(CH2)2CH=CHNO2 in air affords radical-derived bicyclic products arising from aerobic oxidation.

  10. 1,4-Addition of TMSCCl3 to Nitroalkenes: Efficient Reaction Conditions and Mechanistic Understanding

    PubMed Central

    Wu, Na; Wahl, Benoit; Woodward, Simon; Lewis, William

    2014-01-01

    Improved synthetic conditions allow preparation of TMSCCl3 in good yield (70 %) and excellent purity. Compounds of the type NBu4X [X=Ph3SiF2 (TBAT), F (tetrabutylammonium fluoride, TBAF), OAc, Cl and Br] act as catalytic promoters for 1,4-additions to a range of cyclic and acyclic nitroalkenes, in THF at 0–25 °C, typically in moderate to excellent yields (37–95 %). TBAT is the most effective promoter and bromide the least effective. Multinuclear NMR studies (1H, 19F, 13C and 29Si) under anaerobic conditions indicate that addition of TMSCCl3 to TBAT (both 0.13 M) at −20 °C, in the absence of nitroalkene, leads immediately to mixtures of Me3SiF, Ph3SiF and NBu4CCl3. The latter is stable to at least 0 °C and does not add nitroalkene from −20 to 0 °C, even after extended periods. Nitroalkene, in the presence of TMSCCl3 (both 0.13 M at −20 °C), when treated with TBAT, leads to immediate formation of the 1,4-addition product, suggesting the reaction proceeds via a transient [Me3Si(alkene)CCl3] species, in which (alkene) indicates an Si⋅⋅⋅O coordinated nitroalkene. The anaerobic catalytic chain is propagated through the kinetic nitronate anion resulting from 1,4 CCl3− addition to the nitroalkene. This is demonstrated by the fact that isolated NBu4[CH2−NO2] is an efficient promoter. Use of H2C−CH(CH2)2CH−CHNO2 in air affords radical-derived bicyclic products arising from aerobic oxidation. PMID:24849249

  11. Optimization of reaction conditions by RSM and structure characterization of sulfated locust bean gum.

    PubMed

    Wang, Junlong; Yang, Ting; Tian, Jia; Liu, Wenxi; Jing, Fan; Yao, Jian; Zhang, Ji; Lei, Ziqiang

    2014-12-19

    Sulfated derivatives of galactomannan from locust bean gum (LBG) with the degree of substitution (DS) of 0.34-1.07 were synthesized using chlorosulfonic acid/pyridine (CSA/Py) method. Box-Behnken design (BBD) of response surface methodology (RSM) was employed to optimize the reaction conditions. Results of FT-IR and X-ray photoelectron spectroscopy (XPS) indicated that SO3H groups were widely present in sulfated LBG (SLBG). (13)C NMR result revealed that sulfation had occurred and C-6 substitution was predominant in SLBG. All sulfated samples showed a decrease in Mw and more broad molar mass distribution in size exclusion chromatography combined with laser light scattering (SEC-LLS) analysis. Results of MW - [Formula: see text] showed a decrease in fractal dimension (df) value. Laser light scattering results also showed a conformation transition from a compact chain conformation of branched clusters to a random coil conformation of SLBG. Compared to LBG and SLBG with low DS and molecular weight, SLBG2 exhibited an internal structure of random coil with a DS of 1.07. DS and molecular weight had great influence on its conformation in aqueous solution. Our results confirmed that the degradation of polysaccharide and SO3H groups improved significantly the stiffness of the chains due to the electrostatic effect.

  12. Subduction-related rodingites from East Othris, Greece: Mineral reactions and physicochemical conditions of formation

    NASA Astrophysics Data System (ADS)

    Koutsovitis, Petros; Magganas, Andreas; Pomonis, Panagiotis; Ntaflos, Theodoros

    2013-07-01

    The partly to pervasively metasomatized doleritic and gabbroic dykes or small to medium sized bodies found in East Othris, within Mid to Late Jurassic serpentinized peridotites of ophiolitic units and ophiolitic mélange formations are classified as rodingites and can be divided into two types. Type 1 rodingites are mainly characterized by the frequent occurrence of prehnite, while Type 2 rodingites include mostly garnets and vesuvianite. Isocon analysis showed that rodingitization essentially occurred with mass and volume preservation. Desilification, depletion of alkalies, as well as Ca enrichment was more intense for the Type 2 rodingites. Al, Fe and Mg remained rather immobile, while Ti, Y, Zr and REE were variably depleted. Rodingitization took place in an intraoceanic subduction system. It occurred in three successive stages during the exhumation of the mafic-ultramafic mantle wedge rocks in a fore-arc setting within a serpentinitic subduction channel, which developed close to the slab. The incorporation of the mafic rocks to the subduction channel probably resulted after entraining a directed mantle flow towards the slab. The first stage of rodingitization formed mainly grossular, hydrogrossular, Ti- and Cr-bearing hydrogarnets and calcite under relatively acidic and mildly oxidizing physicochemical conditions, with increased CO2/H2O ratio. During the second and more extensive rodingitization stage, alkaline and reducing conditions prevailed and CO2/H2O ratio was decreased. The modeling of the mineral reactions of this stage, using the software winTWQ v. 2.34 in the CFMASH system, reveals that in Type 1 rocks prehnite replaced most of the initial garnet, while Type 2 rocks continued to be rodingitized, mostly forming grossular and/or hydrogrossular and chlorite. Hydrogrossular, instead of grossular, was crystallized from hydrous fluids under high silica activity. Type 2 rodingites underwent further rodingitization during the third stage, due to infiltration

  13. A comparison between taste avoidance and conditioned disgust reactions induced by ethanol and lithium chloride in preweanling rats

    PubMed Central

    Arias, Carlos; Pautassi, Ricardo Marcos; Molina, Juan Carlos; Spear, Norman E.

    2011-01-01

    Adult rats display taste avoidance and disgust reactions when stimulated with gustatory stimuli previously paired with aversive agents such as lithium chloride (LiCl). By the second postnatal week of life, preweanling rats also display specific behaviors in response to a tastant conditioned stimulus (CS) that predicts LiCl-induced malaise. The present study compared conditioned disgust reactions induced by LiCl or ethanol (EtOH) in preweanling rats. In Experiment 1 we determined doses of ethanol and LiCl that exert similar levels of conditioned taste avoidance. After having equated drug dosage in terms of conditioned taste avoidance, 13-Day old rats were given a single pairing of a novel taste (saccharin) and either LiCl or ethanol (2.5 g/kg; Experiment 2). Saccharin intake and emission of disgust reactions were assessed 24 and 48 hours after training. Pups given paired presentations of saccharin and the aversive agents (ethanol or LiCl) consumed less saccharin during the first testing Day than controls. These pups also showed more aversive behavioral reactions to the gustatory CS than controls. Specifically, increased amounts of grooming, general activity, head shaking and wall climbing as well as reduced mouthing were observed in response to the CS. Conditioned aversive reactions but not taste avoidance were still evident on the second testing Day. In conclusion, a taste CS paired with post-absorptive effects of EtOH and LiCl elicited a similar pattern of conditioned rejection reactions in preweanling rats. These results suggest that similar mechanisms may be underlying CTAs induced by LiCl and a relatively high EtOH dose. PMID:20806327

  14. The Aldol Addition and Condensation: The Effect of Conditions on Reaction Pathway

    ERIC Educational Resources Information Center

    Crouch, R. David; Richardson, Amie; Howard, Jessica L.; Harker, Rebecca L.; Barker, Kathryn H.

    2007-01-01

    The reaction of a ketone and an aldehyde in aqueous Na[subscript 2]CO[subscript 2] is described. This experiment is performed in the absence of strong bases or organic solvents and offers the opportunity for students to observe the critical role that reaction temperature and base strength have in determining the product of the base-mediated…

  15. Conditions for diffusion-limited and reaction-limited recombination in nanostructured solar cells

    SciTech Connect

    Ansari-Rad, Mehdi; Anta, Juan A.; Arzi, Ezatollah

    2014-04-07

    The performance of Dye-sensitized solar cells (DSC) and related devices made of nanostructured semiconductors relies on a good charge separation, which in turn is achieved by favoring charge transport against recombination. Although both processes occur at very different time scales, hence ensuring good charge separation, in certain cases the kinetics of transport and recombination can be connected, either in a direct or an indirect way. In this work, the connection between electron transport and recombination in nanostructured solar cells is studied both theoretically and by Monte Carlo simulation. Calculations using the Multiple-Trapping model and a realistic trap distribution for nanostructured TiO{sub 2} show that for attempt-to-jump frequencies higher than 10{sup 11}–10{sup 13} Hz, the system adopts a reaction limited (RL) regime, with a lifetime which is effectively independent from the speed of the electrons in the transport level. For frequencies lower than those, and depending on the concentration of recombination centers in the material, the system enters a diffusion-limited regime (DL), where the lifetime increases if the speed of free electrons decreases. In general, the conditions for RL or DL recombination depend critically on the time scale difference between recombination kinetics and free-electron transport. Hence, if the former is too rapid with respect to the latter, the system is in the DL regime and total thermalization of carriers is not possible. In the opposite situation, a RL regime arises. Numerical data available in the literature, and the behavior of the lifetime with respect to (1) density of recombination centers and (2) probability of recombination at a given center, suggest that a typical DSC in operation stays in the RL regime with complete thermalization, although a transition to the DL regime may occur for electrolytes or hole conductors where recombination is especially rapid or where there is a larger dispersion of energies of

  16. Conditions for diffusion-limited and reaction-limited recombination in nanostructured solar cells

    NASA Astrophysics Data System (ADS)

    Ansari-Rad, Mehdi; Anta, Juan A.; Arzi, Ezatollah

    2014-04-01

    The performance of Dye-sensitized solar cells (DSC) and related devices made of nanostructured semiconductors relies on a good charge separation, which in turn is achieved by favoring charge transport against recombination. Although both processes occur at very different time scales, hence ensuring good charge separation, in certain cases the kinetics of transport and recombination can be connected, either in a direct or an indirect way. In this work, the connection between electron transport and recombination in nanostructured solar cells is studied both theoretically and by Monte Carlo simulation. Calculations using the Multiple-Trapping model and a realistic trap distribution for nanostructured TiO2 show that for attempt-to-jump frequencies higher than 1011-1013 Hz, the system adopts a reaction limited (RL) regime, with a lifetime which is effectively independent from the speed of the electrons in the transport level. For frequencies lower than those, and depending on the concentration of recombination centers in the material, the system enters a diffusion-limited regime (DL), where the lifetime increases if the speed of free electrons decreases. In general, the conditions for RL or DL recombination depend critically on the time scale difference between recombination kinetics and free-electron transport. Hence, if the former is too rapid with respect to the latter, the system is in the DL regime and total thermalization of carriers is not possible. In the opposite situation, a RL regime arises. Numerical data available in the literature, and the behavior of the lifetime with respect to (1) density of recombination centers and (2) probability of recombination at a given center, suggest that a typical DSC in operation stays in the RL regime with complete thermalization, although a transition to the DL regime may occur for electrolytes or hole conductors where recombination is especially rapid or where there is a larger dispersion of energies of electron acceptors.

  17. Design and demonstration of a dynamometric horseshoe for measuring ground reaction loads of horses during racing conditions.

    PubMed

    Roland, Elizabeth S; Hull, Maury L; Stover, Susan M

    2005-10-01

    Because musculoskeletal injuries to racehorses are common, instrumentation for the study of factors (e.g. track surface), which affect the ground reaction loads in horses during racing conditions, would be useful. The objectives of the work reported by this paper were to (1) design and construct a novel dynamometric horseshoe that is capable of measuring the complete ground reaction loading during racing conditions, (2) characterize static and dynamic measurement errors, and (3) demonstrate the usefulness of the instrument by collecting example data during the walk, trot, canter, and gallop for a single subject. Using electrical resistance strain gages, a dynamometric horseshoe was designed and constructed to measure the complete ground reaction force and moment vectors and the center of pressure. To mimic the load transfer surface of the hoof, the shape of the surface contacting the ground was similar to that of the solar surface of the hoof. Following static calibration, the measurement accuracy was determined. The root mean squared errors (RMSE) were 3% of full scale for the force component normal to the hoof and 9% for force components in the plane of the hoof. The dynamic calibration determined that the natural frequency with the full weight of a typical horse was 1744 Hz. Example data were collected during walking on a ground surface and during trotting, cantering, and galloping on a treadmill. The instrument successfully measured the complete ground reaction load during all four gaits. Consequently the dynamometric horseshoe is useful for studying factors, which affect ground reaction loads during racing conditions.

  18. Methods for quantifying the influences of pressure and temperature variation on metal hydride reaction rates measured under isochoric conditions.

    PubMed

    Voskuilen, Tyler G; Pourpoint, Timothée L

    2013-11-01

    Analysis techniques for determining gas-solid reaction rates from gas sorption measurements obtained under non-constant pressure and temperature conditions often neglect temporal variations in these quantities. Depending on the materials in question, this can lead to significant variations in the measured reaction rates. In this work, we present two new analysis techniques for comparison between various kinetic models and isochoric gas measurement data obtained under varying temperature and pressure conditions in a high pressure Sievert system. We introduce the integral pressure dependence method and the temperature dependence factor as means of correcting for experimental variations, improving model-measurement fidelity, and quantifying the effect that such variations can have on measured reaction rates. We use measurements of hydrogen absorption in LaNi5 and TiCrMn to demonstrate the effect of each of these methods and show that their use can provide quantitative improvements in interpretation of kinetics measurements.

  19. Dynamics of morphological manifestations of reactions of the organism under conditions of hypergravitation

    NASA Technical Reports Server (NTRS)

    Knyazeva, G. D.; Podymov, V. K.; Savina, Y. A.

    1975-01-01

    The dynamics of the reaction of the hypothalamus-hypophysis-adrenal system to g-forces of 4 G's magnitude reveal a phasal nature of the adaptational system, dependent both on duration of force and position of the body.

  20. Refined transition-state models for proline-catalyzed asymmetric Michael reactions under basic and base-free conditions.

    PubMed

    Sharma, Akhilesh K; Sunoj, Raghavan B

    2012-12-07

    The stereocontrolling transition state (TS) models for C-C bond formation relying on hydrogen bonding have generally been successful in proline-catalyzed aldol, Mannich, α-amination, and α-aminoxylation reactions. However, the suitability of the hydrogen-bonding model in protic and aprotic conditions as well as under basic and base-free conditions has not been well established for Michael reactions. Through a comprehensive density functional theory investigation, we herein analyze different TS models for the stereocontrolling C-C bond formation, both in the presence and absence of a base in an aprotic solvent (THF). A refined stereocontrolling TS for the Michael reaction between cyclohexanone and nitrostyrene is proposed. The new TS devoid of hydrogen bonding between the nitro group of nitrostyrene and carboxylic acid of proline, under base-free conditions, is found to be more preferred over the conventional hydrogen-bonding model besides being able to reproduce the experimentally observed stereochemical outcome. A DBU-bound TS is identified as more suitable for rationalizing the origin of asymmetric induction under basic reaction conditions. In both cases, the most preferred approach of nitrostyrene is identified as occurring from the face anti to the carboxylic acid of proline-enamine. The predicted enantio- and diastereoselectivities are in very good agreement with the experimental observations.

  1. A General and Highly Selective Cobalt-Catalyzed Hydrogenation of N-Heteroarenes under Mild Reaction Conditions.

    PubMed

    Adam, Rosa; Cabrero-Antonino, Jose R; Spannenberg, Anke; Junge, Kathrin; Jackstell, Ralf; Beller, Matthias

    2017-02-14

    Herein, a general and efficient method for the homogeneous cobalt-catalyzed hydrogenation of N-heterocycles, under mild reaction conditions, is reported. Key to success is the use of the tetradentate ligand tris(2-(diphenylphosphino)phenyl)phosphine). This non-noble metal catalyst system allows the selective hydrogenation of heteroarenes in the presence of a broad range of other sensitive reducible groups.

  2. Reaction conditions affecting the relationship between thiobarbituric acid reactivity and lipid peroxides in human plasma.

    PubMed

    Lapenna, D; Ciofani, G; Pierdomenico, S D; Giamberardino, M A; Cuccurullo, F

    2001-08-01

    The thiobarbituric acid (TBA) reactivity of human plasma was studied to evaluate its adequacy in quantifying lipid peroxidation as an index of systemic oxidative stress. Two spectrophotometric TBA tests based on the use of either phosphoric acid (pH 2.0, method A) or trichloroacetic plus hydrochloric acid (pH 0.9, method B) were employed with and without sodium sulfate (SS) to inhibit sialic acid (SA) reactivity with TBA. To correct for background absorption, the absorbance values at 572 nm were subtracted from those at 532 nm, which represent the absorption maximum of the TBA:MDA adduct. Method B gave values of TBA-reactive substances (TBARS) 2-fold higher than those detected with method A. SS lowered TBARS by about 50% with both methods, indicating a significant involvement of SA in plasma TBA reactivity. Standard SA, at a physiologically relevant concentration of 1.5 mM, reacted with TBA, creating interference problems, which were substantially eliminated by SS plus correction for background absorbance. When method B was carried out in the lipid and protein fraction of plasma, SS inhibited by 65% TBARS formation only in the latter. Protein TBARS may be largely ascribed to SA-containing glycoproteins and, to a minor extent, protein-bound MDA. Indeed, EDTA did not affect protein TBARS assessed in the presence of SS. TBA reactivity of whole plasma and of its lipid fraction was instead inhibited by EDTA, suggesting that lipoperoxides (and possibly monofunctional lipoperoxidation aldehydes) are involved as MDA precursors in the TBA test. Pretreatment of plasma with KI, a specific reductant of hydroperoxides, decreased TBARS by about 27%. Moreover, aspirin administration to humans to inhibit prostaglandin endoperoxide generation reduced plasma TBARS by 40%. In conclusion, reaction conditions affect the relationship between TBA reactivity and lipid peroxidation in human plasma. After correction for the interfering effects of SA in the TBA test, 40% of plasma TBARS

  3. Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions

    PubMed Central

    Oberholzer, Miriam; Frech, Christian M.

    2014-01-01

    Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family of easy accessible, very cheap, and air stable, but highly active and universally applicable C-C cross-coupling catalysts with an excellent functional group tolerance. Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1), the least stable complex within this series towards protons; e.g. in the form of water, allows an eased nanoparticle formation and hence, proved to be the most active Heck catalyst within this series at 100 °C and is a very rare example of an effective and versatile catalyst system that efficiently operates under mild reaction conditions. Rapid and complete catalyst degradation under work-up conditions into phosphonates, piperidinium salts and other, palladium-containing decomposition products assure an easy separation of the coupling products from catalyst and ligands. The facile, cheap, and rapid synthesis of 1,1',1"-(phosphinetriyl)tripiperidine and 1 respectively, the simple and convenient use as well as its excellent catalytic performance in the Heck reaction at 100 °C make 1 to one of the most attractive and greenest Heck catalysts available. We provide here the visualized protocols for the ligand and catalyst syntheses as well as the reaction protocol for Heck reactions performed at 10 mmol scale at 100 °C and show that this catalyst is suitable for its use in organic syntheses. PMID:24686532

  4. Reaction condition optimization and kinetic investigation of roasting zinc oxide ore using (NH4)2SO4

    NASA Astrophysics Data System (ADS)

    Shao, Hong-mei; Shen, Xiao-yi; Sun, Yi; Liu, Yan; Zhai, Yu-chun

    2016-10-01

    An orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore using (NH4)2SO4. The optimized reaction conditions are defined as an (NH4)2SO4/zinc molar ratio of 1.4:1, a roasting temperature of 440°C, and a thermostatic time of 60 min. The molar ratio of (NH4)2SO4/zinc is the most predominant factor and the roasting temperature is the second significant factor that governs the zinc extraction. Thermogravimetric-differential thermal analysis was used for (NH4)2SO4 and zinc mixed in a molar ratio of 1.4:1 at the heating rates of 5, 10, 15, and 20 K·min-1. Two strong endothermic peaks indicate that the complex chemical reactions occur at approximately 290°C and 400°C. XRD analysis was employed to examine the transformations of mineral phases during roasting process. Kinetic parameters, including reaction apparent activation energy, reaction order, and frequency factor, were calculated by the Doyle-Ozawa and Kissinger methods. Corresponding to the two endothermic peaks, the kinetic equations were obtained.

  5. Supervisors' attitudes and skills for active listening with regard to working conditions and psychological stress reactions among subordinate workers.

    PubMed

    Mineyama, Sachiko; Tsutsumi, Akizumi; Takao, Soshi; Nishiuchi, Kyoko; Kawakami, Norito

    2007-03-01

    We investigated whether supervisors' listening attitudes and skills were related to working conditions and psychological stress reactions among their subordinates. The subjects included 41 male supervisors and their immediate subordinates (n=203). The supervisors completed a short version of the Active Listening Attitude Scale (ALAS) consisting of two subscales: Listening Attitude and Listening Skill for Active Listening. The subordinates rated working conditions and their psychological stress reactions using selected scales of the Job Content Questionnaire and the Brief Job Stress Questionnaire. Those subordinates who worked under supervisors with a higher score of Listening Attitude and Listening Skill reported a more favorable psychological stress reaction than those who worked under supervisors with a lower score of Listening Attitude and Listening Skill. Those subordinates who worked under supervisors with a higher score of Listening Skill reported higher worksite support than those who worked under supervisors with a lower score of Listening Skill. Those subordinates who worked under supervisors with a higher score of Listening Attitude reported higher job control than those who worked under supervisors with a lower score of Listening Attitude. A supervisor's listening attitude and skill appeared to affect psychological stress reactions predominantly among male subordinates than among female subordinates. Psychological stress reactions were lower among younger subordinates who worked under supervisors with high listening skill, while no statistically difference was observed among older subordinates. These findings suggest that a supervisor's listening attitude and skill have an effect on working conditions and psychological stress reactions among subordinates and that the effects vary according to the subordinates' sex and age.

  6. Study of condition-dependent decomposition reactions; Part I. The thermal behaviour and decomposition of 2-nitrobenzoyl chloride.

    PubMed

    Lever, Sarah D; Papadaki, Maria

    2004-11-11

    The risks associated with batch processing in the manufacture of chemicals and pharmaceuticals via highly exothermic reactions are of special interest due to the possibility of runaway reactions. o-Nitrated benzoyl chlorides are intermediates in the production of agrochemicals and are produced via the reaction of o-nitrated carboxylic acids with thionyl chloride in a solvent mixture. ortho-Nitrated acyl chlorides have exploded violently on attempted distillation on numerous occasions. An inadequate investigation of the process prior to large-scale operation is the most likely cause. Here we present preliminary results of studies on the decomposition of 2-nitrobenzoyl chloride. This study has revealed that the decomposition reaction is strongly condition dependent. The heating rate of the sample plays a preponderant role in the course of the decomposition reaction. That renders the interpretation of differential scanning calorimetry (DSC) or adiabatic calorimetry measurements, which are routinely used to assess the thermochemistry and safety of the large-scale reactions, problematic. Following this on-going study, we report here key features of the system that have been identified.

  7. Acrylamide formation from asparagine under low-moisture Maillard reaction conditions. 1. Physical and chemical aspects in crystalline model systems.

    PubMed

    Robert, Fabien; Vuataz, Gilles; Pollien, Philippe; Saucy, Françoise; Alonso, Maria-Isabelle; Bauwens, Isabelle; Blank, Imre

    2004-11-03

    The formation of acrylamide in crystalline model systems based on asparagine and reducing sugars was investigated under low-moisture reaction conditions. The acrylamide amounts were correlated with physical changes occurring during the reaction. Molecular mobility of the precursors turned out to be a critical parameter in solid systems, which is linked to the melting behavior and the release of crystallization water of the reaction sample. Heating binary mixtures of asparagine monohydrate and anhydrous reducing sugars led to higher acrylamide amounts in the presence of fructose compared to glucose. Differential scanning calorimetry measurements performed in open systems indicated melting of fructose at 126 degrees C, whereas glucose and galactose fused at 157 and 172 degrees C, respectively. However, glucose was the most reactive and fructose the least efficient sugar in anhydrous liquid systems, indicating that at given molecular mobility the chemical reactivity of the sugar was the major driver in acrylamide formation. Furthermore, reaction time and temperature were found to be covariant parameters: acrylamide was preferably formed by reacting glucose and asparagine at 120 degrees C for 60 min, whereas 160 degrees C was required at shorter reaction time (5 min). These results suggest that, in addition to the chemical reactivity of ingredients, their physical state as well as reaction temperature and time would influence the formation of acrylamide during food processing.

  8. In situ characterization of catalysts and membranes in a microchannel under high-temperature water gas shift reaction conditions

    NASA Astrophysics Data System (ADS)

    Cavusoglu, G.; Dallmann, F.; Lichtenberg, H.; Goldbach, A.; Dittmeyer, R.; Grunwaldt, J.-D.

    2016-05-01

    Microreactor technology with high heat transfer in combination with stable catalysts is a very attractive approach for reactions involving major heat effects such as methane steam reforming and to some extent, also the high temperature water gas shift (WGS) reaction. For this study Rh/ceria catalysts and an ultrathin hydrogen selective membrane were characterized in situ in a microreactor specially designed for x-ray absorption spectroscopic measurements under WGS conditions. The results of these experiments can serve as a basis for further development of the catalysts and membranes.

  9. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

    PubMed Central

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A.; Wäckerlin, Aneliia; Meyer, Ernst

    2017-01-01

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect – oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level. PMID:28327642

  10. Textured catalysts, methods of making textured catalysts, and methods of catalyzing reactions conducted in hydrothermal conditions

    DOEpatents

    Werpy, Todd [West Richland, WA; Wang, Yong [Richland, WA

    2003-12-30

    A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

  11. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons.

    PubMed

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A; Wäckerlin, Aneliia; Meyer, Ernst

    2017-03-22

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

  12. Dynamic three-dimensional pore-scale imaging of reaction in a carbonate at reservoir conditions.

    PubMed

    Menke, Hannah P; Bijeljic, Branko; Andrew, Matthew G; Blunt, Martin J

    2015-04-07

    Quantifying CO2 transport and average effective reaction rates in the subsurface is essential to assess the risks associated with underground carbon capture and storage. We use X-ray microtomography to investigate dynamic pore structure evolution in situ at temperatures and pressures representative of underground reservoirs and aquifers. A 4 mm diameter Ketton carbonate core is injected with CO2-saturated brine at 50 °C and 10 MPa while tomographic images are taken at 15 min intervals with a 3.8 μm spatial resolution over a period of 2(1/2) h. An approximate doubling of porosity with only a 3.6% increase in surface area to volume ratio is measured from the images. Pore-scale direct simulation and network modeling on the images quantify an order of magnitude increase in permeability and an appreciable alteration of the velocity field. We study the uniform reaction regime, with dissolution throughout the core. However, at the pore scale, we see variations in the degree of dissolution with an overall reaction rate which is approximately 14 times lower than estimated from batch measurements. This work implies that in heterogeneous rocks, pore-scale transport of reactants limits dissolution and can reduce the average effective reaction rate by an order of magnitude.

  13. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

    NASA Astrophysics Data System (ADS)

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A.; Wäckerlin, Aneliia; Meyer, Ernst

    2017-03-01

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect – oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

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

    NASA Technical Reports Server (NTRS)

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

    1997-01-01

    The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic

  15. Population dynamics, information transfer, and spatial organization in a chemical reaction network under spatial confinement and crowding conditions.

    PubMed

    Bellesia, Giovanni; Bales, Benjamin B

    2016-10-01

    We investigate, via Brownian dynamics simulations, the reaction dynamics of a generic, nonlinear chemical network under spatial confinement and crowding conditions. In detail, the Willamowski-Rossler chemical reaction system has been "extended" and considered as a prototype reaction-diffusion system. Our results are potentially relevant to a number of open problems in biophysics and biochemistry, such as the synthesis of primitive cellular units (protocells) and the definition of their role in the chemical origin of life and the characterization of vesicle-mediated drug delivery processes. More generally, the computational approach presented in this work makes the case for the use of spatial stochastic simulation methods for the study of biochemical networks in vivo where the "well-mixed" approximation is invalid and both thermal and intrinsic fluctuations linked to the possible presence of molecular species in low number copies cannot be averaged out.

  16. Population dynamics, information transfer, and spatial organization in a chemical reaction network under spatial confinement and crowding conditions

    NASA Astrophysics Data System (ADS)

    Bellesia, Giovanni; Bales, Benjamin B.

    2016-10-01

    We investigate, via Brownian dynamics simulations, the reaction dynamics of a generic, nonlinear chemical network under spatial confinement and crowding conditions. In detail, the Willamowski-Rossler chemical reaction system has been "extended" and considered as a prototype reaction-diffusion system. Our results are potentially relevant to a number of open problems in biophysics and biochemistry, such as the synthesis of primitive cellular units (protocells) and the definition of their role in the chemical origin of life and the characterization of vesicle-mediated drug delivery processes. More generally, the computational approach presented in this work makes the case for the use of spatial stochastic simulation methods for the study of biochemical networks in vivo where the "well-mixed" approximation is invalid and both thermal and intrinsic fluctuations linked to the possible presence of molecular species in low number copies cannot be averaged out.

  17. Kinetic and products study of the gas-phase reaction of Lewisite with ozone under atmospheric conditions.

    PubMed

    Wang, Haitao; Zhang, Yuanpeng; Guo, Xiaodi; Shao, Yusheng; Gao, Runli; Liang, Dejian; Sun, Hao

    2016-02-01

    The rate constant for the gas-phase reaction of O3 and Lewisite was studied in air using the smog chamber technique. The experiments were carried out under pseudo-first-order reaction conditions with [O3]≪[Lewisite]. The observed rate constant of O3 with Lewisite was (7.83 ± 0.38) × 10(-19)cm(3)/(molecule·sec) at 298 ± 2K. Lewisite was discussed in terms of reactivity with O3 and its relationship with the ionization potential. Our results show that the rate constant for the gas-phase reaction of O3 with Lewisite is in line with the trend of the rate constants of O3 with haloalkenes.

  18. Reaction time and movement velocity abnormalities in Parkinson's disease under different task conditions.

    PubMed

    Montgomery, E B; Nuessen, J; Gorman, D S

    1991-09-01

    We examined reaction times, movement velocities, and the associated agonist and antagonist muscle behaviors in nine Parkinson's disease (PD) patients and eight normal subjects before and after medications, using a wrist extension task to changing locations of a visual target. Targets changing 500 msec before an auditory "go" signal act as a preparatory cue, while targets changing at the time of the go signal provide a combined auditory and visual stimulus. Late target changes allowed examination of (1) reaction times during an ongoing movement, and (2) movement in the presence and absence of visual targets. PD prolonged the time from the onset agonist electromyographic activity and reduction of antagonist activity to movement onset. Both were shortened by preparatory cues and combined visual and auditory go signals. PD slowed movement only in a subset of trials in which there was movement to a displayed target.

  19. Effect of method of heterogenization of ephedrine and reaction conditions on the enantioselectivity of Michael additions

    SciTech Connect

    Krotov, V.V.; Staroverov, S.M.; Nesterenko, P.N.; Lisichkin. G.V.

    1987-11-10

    A series of heterogeneous catalysts for asymmetric Michael additions was synthesized based on ephedrine chemically bound to the surface of silica. The length of the hydrocarbon chain binding the active center to the support surface affects the sign of rotation of the reaction product from the asymmetric addition of thiophenol to benzylideneacetophenone. Grafting ephedrine to the silica surface via a short hydrocarbon chain results in a change in the configuration of the reaction product. Silanol groups on the silica surface are involved in the transition state, as evidenced by data obtained using silica which has been exhaustively treated with trimethylchlorosilane. The absolute specific rotation of 1,3-diphenyl-3-thiophenylpropan-1-one has been established.

  20. General reaction conditions for the palladium-catalyzed vinylation of aryl chlorides with potassium alkenyltrifluoroborates.

    PubMed

    Alacid, Emilio; Nájera, Carmen

    2009-11-06

    Activated and deactivated aryl and heteroaryl chlorides are efficiently cross-coupled with potassium vinyl- and alkenyltrifluoroborates using 4-hydroxyacetophenone oxime derived palladacycle as precatalyst in 1 to 3 mol % Pd loading, Binap as ligand, and Cs(2)CO(3) as base in DMF at 120 degrees C. The reactions can also be performed using Pd(OAc)(2) as Pd(0) source, although with lower efficiency. Bidentate ligands such as Binap and dppp can be used, the former being the best choice. Only in the case of deactivated aryl chlorides should the reaction temperature be increased to 160 degrees C to achieve good yields. The corresponding cross-coupled compounds, such as styrenes, stilbenes, and alkenylarenes, are obtained in good yields and with high regio- and diastereoselectivity.

  1. Controlling thermo-reversibility of gelatin gels through a peroxidase-catalyzed reaction under mild conditions for mammalian cells.

    PubMed

    Sakai, Shinji; Moriyama, Kousuke; Kawakami, Koei

    2011-01-01

    A variety of cross-linking methods is used for obtaining gelatin gels having a tolerance to thermo-reversible gel-sol transition at physiological temperature. In this paper, we investigated the applicability of horseradish peroxidase-catalyzed cross-linking of tyrosine residues originally contained in native gelatin molecules for preparing such gelatin gels. The gelatin gels obtained through exposure to the enzymatic reaction showed a higher resistance to thermo-reversibility at 37°C than gels obtained through a thermally-induced gelation alone. In addition, the resistance property to thermo-reversible gel-sol transition was tunable by controlling enzymatic reaction conditions: higher peroxidase concentration and thermally-induced pre-gelation accomplished by cooling the gelatin solution prior to the enzymatic reaction produced gels with higher resistance to thermo-reversibility. Fibroblast cells enclosed in the gelatin gels obtained through the enzymatic reaction with thermally-induced pre-gelation showed 93% viability. These results demonstrate the feasibility of peroxidase-catalyzed reaction for obtaining gelatin gels having a tolerance to thermo-reversible gel-to-sol transition at physiological temperature toward applications in biomedical and biopharmaceutical fields.

  2. Conditions for the critical phenomena in a dynamic model of an electrocatalytic reaction

    NASA Astrophysics Data System (ADS)

    Firstova, Natalia; Shchepakina, Elena

    2017-02-01

    In the paper, a detailed study of the critical phenomena mechanism in a model of an electrocatalytic reaction is carried out. The use of the geometric theory of integral manifolds allows us to show the relationship between the critical regime and the stability loss delay of the slow integral manifold of the corresponding differential system. The asymptotic formula for the critical value of the control parameter is obtained.

  3. A study of different indicators of Maillard reaction with whey proteins and different carbohydrates under adverse storage conditions.

    PubMed

    Leiva, Graciela E; Naranjo, Gabriela B; Malec, Laura S

    2017-01-15

    This study examined different indicators of each stage of Maillard reaction under adverse storage conditions in a system with whey proteins and lactose or glucose. The analysis of lysine loss by the o-phthaldialdehyde method can be considered a good indicator of the early stage, showing considerable differences in reactivity when systems with mono and disaccharides were analyzed. Capillary electrophoresis proved to be a sensitive method for evaluating the extent of glycosylation of the native proteins, providing valuable information when the loss of lysine was not significant. The estimation of the Amadori compound from the determination of total 5-hydroxymethyl-2-furfuraldehyde would have correlate well with reactive lysine content if the advanced stages of the reaction had not been reached. For assessing the occurrence of the intermediate and final stages, the measurement of free 5-hydroxymethyl-2-furfuraldehyde and color, proved not to be suitable for storage conditions.

  4. Reaction norm model to describe environmental sensitivity across first lactation in dairy cattle under tropical conditions.

    PubMed

    Bignardi, Annaiza Braga; El Faro, Lenira; Pereira, Rodrigo Junqueira; Ayres, Denise Rocha; Machado, Paulo Fernando; de Albuquerque, Lucia Galvão; Santana, Mário Luiz

    2015-10-01

    Reaction norm models have been widely used to study genotype by environment interaction (G × E) in animal breeding. The objective of this study was to describe environmental sensitivity across first lactation in Brazilian Holstein cows using a reaction norm approach. A total of 50,168 individual monthly test day (TD) milk yields (10 test days) from 7476 complete first lactations of Holstein cattle were analyzed. The statistical models for all traits (10 TDs and for 305-day milk yield) included the fixed effects of contemporary group, age of cow (linear and quadratic effects), and days in milk (linear effect), except for 305-day milk yield. A hierarchical reaction norm model (HRNM) based on the unknown covariate was used. The present study showed the presence of G × E in milk yield across first lactation of Holstein cows. The variation in the heritability estimates implies differences in the response to selection depending on the environment where the animals of this population are evaluated. In the average environment, the heritabilities for all traits were rather similar, in range from 0.02 to 0.63. The scaling effect of G × E predominated throughout most of lactation. Particularly during the first 2 months of lactation, G × E caused reranking of breeding values. It is therefore important to include the environmental sensitivity of animals according to the phase of lactation in the genetic evaluations of Holstein cattle in tropical environments.

  5. Reaction pathways towards the formation of dolomite-analogues at ambient conditions

    NASA Astrophysics Data System (ADS)

    Pimentel, Carlos; Pina, Carlos M.

    2016-04-01

    In this paper we present results of a study of the crystallisation behaviour of the dolomite-analogues norsethite and PbMg(CO3)2 at room temperature and atmospheric pressure. Whereas precipitation of norsethite was previously obtained by mixing solutions (Hood et al., 1974; Pimentel and Pina, 2014a,b), we report, for the first time, the synthesis of PbMg(CO3)2 by using the same method. The formation of both phases was promoted by ageing slurries for periods of time ranging from a few days (norsethite) up to 6 months (PbMg(CO3)2). The crystallisation of both norsethite and PbMg(CO3)2 occurs by sequences of dissolution-precipitation reactions involving several amorphous and crystalline precursor phases, which were identified and characterised by X-ray diffraction and scanning electron microscopy. Depending on the initial composition and Ba:Mg and Pb:Mg ratios in the slurries, different precursors and reaction kinetics were observed. This demonstrates the existence of different reaction pathways towards the formation of the investigated dolomite-analogues. Our experimental results provide new insights into the possible mechanisms of formation of dolomite and other double carbonates in nature.

  6. An effective rate equation approach to reaction kinetics in small volumes: theory and application to biochemical reactions in nonequilibrium steady-state conditions.

    PubMed

    Grima, R

    2010-07-21

    Chemical master equations provide a mathematical description of stochastic reaction kinetics in well-mixed conditions. They are a valid description over length scales that are larger than the reactive mean free path and thus describe kinetics in compartments of mesoscopic and macroscopic dimensions. The trajectories of the stochastic chemical processes described by the master equation can be ensemble-averaged to obtain the average number density of chemical species, i.e., the true concentration, at any spatial scale of interest. For macroscopic volumes, the true concentration is very well approximated by the solution of the corresponding deterministic and macroscopic rate equations, i.e., the macroscopic concentration. However, this equivalence breaks down for mesoscopic volumes. These deviations are particularly significant for open systems and cannot be calculated via the Fokker-Planck or linear-noise approximations of the master equation. We utilize the system-size expansion including terms of the order of Omega(-1/2) to derive a set of differential equations whose solution approximates the true concentration as given by the master equation. These equations are valid in any open or closed chemical reaction network and at both the mesoscopic and macroscopic scales. In the limit of large volumes, the effective mesoscopic rate equations become precisely equal to the conventional macroscopic rate equations. We compare the three formalisms of effective mesoscopic rate equations, conventional rate equations, and chemical master equations by applying them to several biochemical reaction systems (homodimeric and heterodimeric protein-protein interactions, series of sequential enzyme reactions, and positive feedback loops) in nonequilibrium steady-state conditions. In all cases, we find that the effective mesoscopic rate equations can predict very well the true concentration of a chemical species. This provides a useful method by which one can quickly determine the

  7. Influences of acidic reaction and hydrolytic conditions on monosaccharide composition analysis of acidic, neutral and basic polysaccharides.

    PubMed

    Wang, Qing-Chi; Zhao, Xia; Pu, Jiang-Hua; Luan, Xiao-Hong

    2016-06-05

    Monosaccharide composition analysis is important for structural characterization of polysaccharides. To investigate the influences of acidic reaction and hydrolytic conditions on monosaccharide composition analysis of polysaccharides, we chose alginate, starch, chitosan and chondroitin sulfate as representative of acidic, neutral, basic and complex polysaccharides to compare the release degree of monosaccharides under different hydrolytic conditions. The hydrolysis stability of 10 monosaccharide standards was also explored. Results showed that the basic sugars were hard to release but stable, the acidic sugars (uronic acids) were easy to release but unstable, and the release and stability of neutral sugars were in between acidic and basic sugars. In addition, the hydrolysis process was applied to monosaccharide composition analysis of Hippocampus trimaculatus polysaccharide and the appropriate hydrolytic condition was accorded with that of the above four polysaccharides. Thus, different hydrolytic conditions should be used for the monosaccharide composition analysis of polysaccharides based on their structural characteristics.

  8. Evolution of fracture permeability of ultramafic rocks at hydrothermal conditions: An experimental study on serpentinization reactions

    NASA Astrophysics Data System (ADS)

    Farough, A.; Moore, D. E.; Lockner, D. A.; Lowell, R. P.

    2014-12-01

    Serpentinization of ultramafic rocks, during which olivine and pyroxene minerals are replaced by serpentine, magnetite, brucite and talc, is associated with hydrothermal activity at slow and ultraslow mid-ocean ridges. Serpentinization reactions affect hydrothermal fluid circulation by changing permeability of the oceanic crust. To advance our understanding of the evolution of permeability accompanying serpentinization reactions, we performed a series of flow-through experiments at a temperature of 260˚C, a confining pressure of 50 MPa, and a pore pressure of 20±2 MPa on cylindrical cores of ultramafic rocks (18 mm in diameter and 23 mm length) containing a single through-going tensile fracture. Pore fluid flow was in one direction and was collected routinely for chemical analysis. A 7.5 mm thick layer of the same rock, crushed and sieved (0.18-1.0 mm) was placed on the inlet end of the sample to produce a reactive heated reservoir for the pore fluid before entering the fracture. Multiple peridotite samples were tested, to investigate the effect of mineral assemblage on fluid-rock interaction and permeability. The initial effective permeability of the samples varied between 10-(15-18)m2, and it decreased by about 2 orders of magnitude in 7-10 days, showing that serpentinization reactions result in an initially rapid decrease in permeability. The best fit equation for the observed rate of change in permeability (k) is in the form of dk/dt=Ae-0.01t, where A is a constant and t is time. This result suggests that the rate of serpentine formation is largely controlled by the initial permeability rather than the properties of the reacting rock. Assuming flow between parallel plates, we find the effective crack width decreases by approximately 2 orders of magnitude during the experiments. The fluid chemistry and mineralogy data support the occurrence of serpentinization reactions. The early peak and monotonic decrease in the concentration of Mg, and Si in pore fluid

  9. Investigation of reaction conditions on morphology and optical properties of Zinc Oxide Nanorods

    NASA Astrophysics Data System (ADS)

    Almodarresiyeh, H. A.; Abakshonok, A. V.; Agabekov, V. E.; Eryomin, A. N.; Shahab, S. N.

    2014-08-01

    Zinc oxide nanoparticles (ZnO NPs) were synthesized by precipitation method in the presence of various polymers. Rod shaped ZnO NPs (length ~ 1 micron) were obtained at 70 °C in a reaction medium containing 10-20 mM of zinc nitrate hexahydrate (Zn(NO3)2·6H2O), 0.05-0.1 mg/ml of polyethylenimine (PEI) and 20 mM of hexamethylenetetramine (HMT). Properties of ZnO NPs were characterized by fluorescence, UV-visible spectroscopy, atomic force and transmission electron microscopy.

  10. Solubility and Reaction Rates of Aluminum Solid Phases Under Geothermal Conditions

    SciTech Connect

    Benezeth, P.; Palmer, D.A.; Wesolowski, D.J.; Anovitz, L.M.

    2000-05-28

    Experimental studies involving equilibrium solubility and dissolution/precipitation rates were initiated on aluminum hydroxide phases prevalent under geothermal reservoir conditions. A large capacity, hydrogen-electrode concentration cell (HECC) was constructed specifically for this purpose.

  11. Housing conditions influence cortical and behavioural reactions of sheep in response to videos showing social interactions of different valence.

    PubMed

    Vögeli, Sabine; Wolf, Martin; Wechsler, Beat; Gygax, Lorenz

    2015-05-01

    Mood, as a long-term affective state, is thought to modulate short-term emotional reactions in animals, but the details of this interplay have hardly been investigated experimentally. Apart from a basic interest in this affective system, mood is likely to have an important impact on animal welfare, as bad mood may taint all emotional experience. In the present study about mood - emotion interaction, 29 sheep were kept under predictable, stimulus-rich or unpredictable, stimulus-poor housing conditions, to induce different mood states. In an experiment, the animals were confronted with video sequences of social interactions of conspecifics showing agonistic interactions, ruminating or tolerantly co-feeding as stimuli of different valences. Emotional reactions were assessed by measuring frontal brain activity using functional near-infrared spectroscopy and by recording behavioral reactions. Attentiveness of the sheep decreased from videos showing agonistic interactions to ruminating sheep to those displaying co-feeding sheep. Seeing agonistic interactions was also associated with a deactivation of the frontal cortex, specifically in animals living under predictable, stimulus-rich housing conditions. These sheep generally showed less attentiveness and locomotor activity and they had their ears in a forward position less often and in a backward position more often than the sheep from the unpredictable, stimulus-poor conditions. Housing conditions influenced how the sheep behaved, which can either be thought to be mediated by mood or by the animals' previous experience with stimulus-richness in their housing conditions. Frontal cortical activity may not depend on valence only, but also on the perceptual channel through which the stimuli were perceived.

  12. Palladium-Catalyzed α-Arylation of Zinc Enolates of Esters: Reaction Conditions and Substrate Scope

    PubMed Central

    Hama, Takuo; Ge, Shaozhong; Hartwig, John F.

    2013-01-01

    The intermolecular α-arylation of esters by palladium-catalyzed coupling of aryl bromides with zinc enolates of esters is reported. Reactions of three different types of zinc enolates have been developed. α-Arylation of esters occurs in high yields with isolated Reformatsky reagents, with Reformatsky reagents generated from α-bromo esters and activated zinc, and with zinc enolates generated by quenching lithium enolates of esters with zinc chloride. The use of zinc enolates, instead of alkali metal enolates, greatly expands the scope of the arylation of esters. The reactions occur at room temperature or at 70 °C with bromoarenes containing cyano, nitro, ester, keto, fluoro, enolizable hydrogen, hydroxyl or amino functionality and with bromopyridines. The scope of esters encompasses acyclic acetates, propionates, and isobutyrates, α-alkoxyesters, and lactones. The arylation of zinc enolates of esters was conducted with catalysts bearing the hindered pentaphenylferrocenyl di-tert-butylphosphine (Q-phos) or the highly reactive dimeric Pd(I) complex {[P(t-Bu)3]PdBr}2. PMID:23931445

  13. Sticking probability of CO on an oxygen covered Pd(110) surface under reaction conditions

    NASA Astrophysics Data System (ADS)

    Goschnick, J.; Grunze, M.; Loboda-Cackovic, J.; Block, J. H.

    1987-10-01

    The adsorption of carbon monoxide into an oxygen overlayer on a Pd(110) surface and its conversion to CO 2 was studied by quantitative mass spectrometric methods and video recorded LEED. For temperatures with negligible desorption of CO ( T≤420 K) the sticking probability of CO into the oxygen adsorbate is reduced by approximately 1/2 compared to a CO adsorbate on a clean Pd(110) surface of the same coverage. The evaluation reveals that each oxygen adatom effectively blocks more than ten sites for CO adsorption, which is explained by the influence of adsorbed oxygen on the transition probability of the CO precursor to the chemisorbed state. Initially due to a locally higher sticking probability CO is adsorbed at defects of the c(2×4) oxygen overlayer. After consumption of less ordered oxygen regions further reaction is restricted to the domain boundaries of the reactands and propagates preferably in an unidirectional fashion along the surface troughs with a constant turnover number until whole domains of oxygen have been consumed by the reaction.

  14. Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions

    DOE PAGES

    Zheng, Haiyan; Li, Kuo; Cody, George D.; ...

    2016-08-25

    Acetonitrile (CH3CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. In this study, it is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH···N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp2 and sp3more » bonded carbon. Lastly, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst.« less

  15. Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

    PubMed

    Zheng, Haiyan; Li, Kuo; Cody, George D; Tulk, Christopher A; Dong, Xiao; Gao, Guoying; Molaison, Jamie J; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-Kwang

    2016-09-19

    Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst.

  16. [Behavioral reactions of animals subjected in the prenatal development period to space flight conditions].

    PubMed

    Apanasenko, Z I; Kuznetsova, M A; Korotkova, V Iu

    1986-01-01

    The Wistar female rats were flown on the biosatellite Cosmos-1514 during their pregnancy days 13-18. Offspring (at the age 1 to 3 months) of four of these rats were used to investigate their behavioral reactions in the open field and mazes of different design, food attraction being applied. Control rats of matched pregnancy term were kept either in a vivarium or in a biosatellite mockup where all flight factors, except for weightlessness, were simulated. It was found that exposure to weightlessness in the above intrauterine developmental period caused no serious changes in the behavioral reactions of rats during their postnatal development. The number of refusals and errors and the latency period were similar in the rats from the flight and control groups. Changes were seen only in fine behavioral regulation. The flown animals displayed a lower research activity in the open field, a longer time of search in the maze, a far longer time or grooming and a greater number of inadequate movements, and a stronger response to external inhibiting stimuli. These changes seem to be caused by a slight attenuation of the basic nervous processes (primarily, inhibitory) and a decrease of their balance and lability. These effects may be associated with an inhibitory influence of space flight factors on the maturation of cortical structures.

  17. Hot-Fire Testing of 100 LB(sub F) LOX/LCH4 Reaction Control Engine at Altitude Conditions

    NASA Technical Reports Server (NTRS)

    Marshall, William M.; Kleinhenz, Julie E.

    2010-01-01

    Liquid oxygen/liquid methane (LO2/LCH4 ) has recently been viewed as a potential green propulsion system for both the Altair ascent main engine (AME) and reaction control system (RCS). The Propulsion and Cryogenic Advanced Development Project (PCAD) has been tasked by NASA to develop these green propellant systems to enable safe and cost effective exploration missions. However, experience with LO2/LCH4 as a propellant combination is limited, so testing of these systems is critical to demonstrating reliable ignition and performance. A test program of a 100 lb f reaction control engine (RCE) is underway at the Altitude Combustion Stand (ACS) of the NASA Glenn Research Center, with a focus on conducting tests at altitude conditions. These tests include a unique propellant conditioning feed system (PCFS) which allows for the inlet conditions of the propellant to be varied to test warm to subcooled liquid propellant temperatures. Engine performance, including thrust, c* and vacuum specific impulse (I(sub sp,vac)) will be presented as a function of propellant temperature conditions. In general, the engine performed as expected, with higher performance at warmer propellant temperatures but better efficiency at lower propellant temperatures. Mixture ratio effects were inconclusive within the uncertainty bands of data, but qualitatively showed higher performance at lower ratios.

  18. The necessary and sufficient conditions of therapeutic personality change: Reactions to Rogers' 1957 article.

    PubMed

    Samstag, Lisa Wallner

    2007-09-01

    Carl Rogers' article (see record 2007-14639-002) on the necessary and sufficient conditions for personality change has had a significant impact on the field of psychotherapy and psychotherapy research. He emphasized the client as arbiter of his or her own subjective experience and tested his hypothesized therapist-offered conditions of change using recorded sessions. This aided in demystifying the therapeutic process and led to a radical shift in the listening stance of the therapist. I briefly outline my views regarding the influence of the ideas presented in this work, describe the intellectual and cultural context of the times, and discuss a number of ways in which the therapist-offered conditions for psychological transformation are neither necessary nor sufficient. (PsycINFO Database Record (c) 2010 APA, all rights reserved).

  19. Kinetics of elementary steps in the reactions of atomic bromine with isoprene and 1,3-butadiene under atmospheric conditions.

    PubMed

    Laine, Patrick L; Sohn, Yoon S; Nicovich, J Michael; McKee, Michael L; Wine, Paul H

    2012-06-21

    Laser flash photolysis of CF(2)Br(2) has been coupled with time-resolved detection of atomic bromine by resonance fluorescence spectroscopy to investigate the gas-phase kinetics of early elementary steps in the Br-initiated oxidations of isoprene (2-methyl-1,3-butadiene, Iso) and 1,3-butadiene (Bu) under atmospheric conditions. At T ≥ 526 K, measured rate coefficients for Br + isoprene are independent of pressure, suggesting that hydrogen transfer (1a) is the dominant reaction pathway. The following Arrhenius expression adequately describes all kinetic data at 526 K ≤ T ≤ 673 K: k(1a)(T) = (1.22 ± 0.57) × 10(-11) exp[(-2100 ± 280)/T] cm(3) molecule(-1) s(-1) (uncertainties are 2σ and represent precision of the Arrhenius parameters). At 271 K ≤ T ≤ 357 K, kinetic evidence for the reversible addition reactions Br + Iso ↔ Br-Iso (k(1b), k(-1b)) and Br + Bu ↔ Br-Bu (k(3b), k(-3b)) is observed. Analysis of the approach to equilibrium data allows the temperature- and pressure-dependent rate coefficients k(1b), k(-1b), k(3b), and k(-3b) to be evaluated. At atmospheric pressure, addition of Br to each conjugated diene occurs with a near-gas-kinetic rate coefficient. Equilibrium constants for the addition/dissociation reactions are obtained from k(1b)/k(-1b) and k(3b)/k(-3b), respectively. Combining the experimental equilibrium data with electronic structure calculations allows both second- and third-law analyses of thermochemistry to be carried out. The following thermochemical parameters for the addition reactions 1b and 3b at 0 and 298 K are obtained (units are kJ mol(-1) for Δ(r)H and J mol(-1) K(-1) for Δ(r)S; uncertainties are accuracy estimates at the 95% confidence level): Δ(r)H(0)(1b) = -66.6 ± 7.1, Δ(r)H(298)(1b) = -67.5 ± 6.6, and Δ(r)S(298)(3b) = -93 ± 16; Δ(r)H(0)(3b) = -62.4 ± 9.0, Δ(r)H(298)(3b) = -64.5 ± 8.5, and Δ(r)S(298)(3b) = -94 ± 20. Examination of the effect of added O(2) on Br kinetics under conditions where reversible

  20. Reaction Norms in Natural Conditions: How Does Metabolic Performance Respond to Weather Variations in a Small Endotherm Facing Cold Environments?

    PubMed Central

    Petit, Magali; Vézina, François

    2014-01-01

    Reaction norms reflect an organisms' capacity to adjust its phenotype to the environment and allows for identifying trait values associated with physiological limits. However, reaction norms of physiological parameters are mostly unknown for endotherms living in natural conditions. Black-capped chickadees (Poecile atricapillus) increase their metabolic performance during winter acclimatization and are thus good model to measure reaction norms in the wild. We repeatedly measured basal (BMR) and summit (Msum) metabolism in chickadees to characterize, for the first time in a free-living endotherm, reaction norms of these parameters across the natural range of weather variation. BMR varied between individuals and was weakly and negatively related to minimal temperature. Msum varied with minimal temperature following a Z-shape curve, increasing linearly between 24°C and −10°C, and changed with absolute humidity following a U-shape relationship. These results suggest that thermal exchanges with the environment have minimal effects on maintenance costs, which may be individual-dependent, while thermogenic capacity is responding to body heat loss. Our results suggest also that BMR and Msum respond to different and likely independent constraints. PMID:25426860

  1. Reaction norms in natural conditions: how does metabolic performance respond to weather variations in a small endotherm facing cold environments?

    PubMed

    Petit, Magali; Vézina, François

    2014-01-01

    Reaction norms reflect an organisms' capacity to adjust its phenotype to the environment and allows for identifying trait values associated with physiological limits. However, reaction norms of physiological parameters are mostly unknown for endotherms living in natural conditions. Black-capped chickadees (Poecile atricapillus) increase their metabolic performance during winter acclimatization and are thus good model to measure reaction norms in the wild. We repeatedly measured basal (BMR) and summit (Msum) metabolism in chickadees to characterize, for the first time in a free-living endotherm, reaction norms of these parameters across the natural range of weather variation. BMR varied between individuals and was weakly and negatively related to minimal temperature. Msum varied with minimal temperature following a Z-shape curve, increasing linearly between 24°C and -10°C, and changed with absolute humidity following a U-shape relationship. These results suggest that thermal exchanges with the environment have minimal effects on maintenance costs, which may be individual-dependent, while thermogenic capacity is responding to body heat loss. Our results suggest also that BMR and Msum respond to different and likely independent constraints.

  2. The effect of reaction conditions on formation of wet precipitated calcium phosphates

    NASA Astrophysics Data System (ADS)

    Huang, Chen; Cao, Peng

    2015-03-01

    The precipitation process discussed in the present study involves the addition of alkaline solutions to an acidic calcium phosphate suspension. Several parameters (pH, pH buffer reagent, ageing and stirring) were investigated. The synthesized powders were calcined at 1000°C for 1 h in air, in order to study the thermal stability and crystalline phase compositions. X-ray diffraction (XRD) and ESEM analysis were used for sample characterization. It is found that all these processing parameters affect the crystalline phases evolved and resultant microstructures. Phase evolution occurred at an elevated pH level. The pH buffer reagent would affect both the phase composition and microstructure. Ageing was essential for the phase maturation. Stirring accelerated the reaction process by providing a homogeneous medium for precipitation.

  3. A new synthesis of TATB using inexpensive starting materials and mild reaction conditions

    SciTech Connect

    Mitchell, A.R.; Pagoria, P.F.; Schmidt, R.D.

    1996-04-01

    TATB is currently manufactured in US by nitration of the expensive TCB to give 2,4,6-trichloro-1,3,5-trinitrobenzene which is then aminated to yield TATB. Elevated temperatures (150 C) are required for both reactions. There is a need for a more economical synthesis of TATB that also addresses current environmental issues. We have recently found that 1,1,1-trimethylhydrazinium iodide (TMHI) allows the amination of nitroarenes at ambient temperature via Vicarious Nucleophilic Substitution of hydrogen. TMHI reacts with picramide in presence of strong base (NaOMe or t-BuOK) to give TATB in over 95% yield. TMHI and picramide can be obtained from either inexpensive starting materials or surplus energetic materials from demilitarization activities, such as the 30,000 metric tons of UDMH (surplus rocket propellant) from the former Soviet Union.

  4. Reaction Weakening of Dunite in Friction Experiments at Hydrothermal Conditions and Its Relevance to Subduction Zones

    NASA Astrophysics Data System (ADS)

    Moore, D. E.; Lockner, D. A.

    2014-12-01

    To improve our understanding of processes occurring in the mantle wedge near the downdip limit of seismicity in subduction zones, we conducted triaxial friction tests on dunite gouge at temperatures in the range 200-350°C, 50 MPa fluid pressure and 100 MPa effective normal stress. Dunite, quartzite, and granite forcing blocks were used respectively to approximate changing rock/fluid chemistry with decreasing distance above the subduction thrust. All experiments were characterized by an initial increase in frictional strength to a peak value, followed by a decrease associated with shearing-enhanced alteration of the dunite gouge. Reaction products and the extent of weakening varied with the chemical environment. In the dunite-block experiments, strength gradually declined from the peak value to a coefficient of friction, µ ~ 0.5-0.6, consistent with the frictional strength of serpentine that formed on the shear surfaces from alteration of the gouge. Interaction of dunite gouge with quartzite and granite driving blocks resulted in significantly greater weakening, to μ ~ 0.3, at temperatures of 250°C and higher. Talc and serpentine partly replaced dunite gouge sheared between quartzite blocks, and metastable saponitic smectite clays crystallized in dunite sheared between granite blocks, as a result of fluid-assisted chemical exchange with the minerals in the wall rocks. These results suggest that rapid and substantial weakening can occur in the mantle wedge immediately overlying the subducting slab. Whichever the chemical environment, attainment of peak strength typically was accompanied by oscillatory slip with small stress drops that gradually was replaced by stable slip with increasing displacement. This oscillatory behavior in some ways resembles the tremor events that have been reported near the forearc mantle corner in subduction zones, and it may indicate the possible involvement of mineral reactions in some instances of tremor.

  5. Spectroscopy of unbound states under quasifree scattering conditions: One-neutron knockout reaction of {sup 14}Be

    SciTech Connect

    Crespo, R.; Deltuva, A.; Rodriguez-Gallardo, M.; Cravo, E.; Fonseca, A. C.

    2009-01-15

    Full Faddeev-type calculations are performed for one-neutron knockout reaction of {sup 14}Be on proton target at 69 MeV/nucleon incident energy. Inclusive transverse momentum distributions for the outgoing ({sup 12}Be+n) system and semi-inclusive cross sections are presented. A significant proton-core single scattering contribution emerges where the valence neutron has nonzero angular momentum relative to the core. This indicates that distorted-wave impulse approximation is inadequate and the complete multiple scattering series must be taken into account for the considered reaction. The magnitude of the semi-inclusive cross section at quasifree scattering conditions is a clear signature of the angular momentum of the valence nucleon.

  6. Acetylation of bacterial cellulose catalyzed by citric acid: Use of reaction conditions for tailoring the esterification extent.

    PubMed

    Ávila Ramírez, Jhon Alejandro; Gómez Hoyos, Catalina; Arroyo, Silvana; Cerrutti, Patricia; Foresti, María Laura

    2016-11-20

    Bacterial cellulose (BC) nanoribbons were partially acetylated by a simple direct solvent-free route catalyzed by citric acid. The assay of reaction conditions within chosen intervals (i.e. esterification time (0.5-7h), catalyst content (0.08-1.01mmol/mmol AGU), and temperature (90-140°C)), illustrated the flexibility of the methodology proposed, with reaction variables which can be conveniently manipulated to acetylate BC to the required degree of substitution (DS) within the 0.20-0.73 interval. Within this DS interval, characterization results indicated a surface-only process in which acetylated bacterial cellulose with tunable DS, preserved fibrous structure and increased hydrophobicity could be easily obtained. The feasibility of reusing the catalyst/excess acylant in view of potential scale-up was also illustrated.

  7. Active sites in Cu-SSZ-13 deNOx catalyst under reaction conditions: a XAS/XES perspective

    NASA Astrophysics Data System (ADS)

    Lomachenko, Kirill A.; Borfecchia, Elisa; Bordiga, Silvia; Soldatov, Alexander V.; Beato, Pablo; Lamberti, Carlo

    2016-05-01

    Cu-SSZ-13 is a highly active catalyst for the NH3-assisted selective catalytic reduction (SCR) of the harmful nitrogen oxides (NOx, x=1, 2). Since the catalytically active sites for this reaction are mainly represented by isolated Cu ions incorporated into the zeolitic framework, element-selective studies of Cu local environment are crucial to fully understand the enhanced catalytic properties of this material. Herein, we highlight the recent advances in the characterization of the most abundant Cu-sites in Cu-SSZ-13 upon different reaction-relevant conditions made employing XAS and XES spectroscopies, complemented by computational analysis. A concise review of the most relevant literature is also presented.

  8. Barrier crossing with concentration boundary conditions in biological channels and chemical reactions

    NASA Astrophysics Data System (ADS)

    Barcilon, Victor; Chen, Duanpin; Eisenberg, Robert S.; Ratner, Mark A.

    1993-01-01

    Ions move into biological cells through pores in proteins called ionic channels, driven by gradients of potential and concentration imposed across the channel, impeded by potential barriers and friction within the pore. It is tempting to apply to channels the chemical theory of barrier crossing, but important issues must first be solved: Concentration boundary conditions must be used and flux must be predicted for applied potentials of all sizes and for barriers of all shapes, in particular, for low barriers. We use a macroscopic analysis to describe the flux as a convolution integral of a mathematically defined adjoint function, a Green's function. It so happens that the adjoint function also describes the first-passage time of a single particle moving between boundary conditions independent of concentration. The (experimentally observable) flux is computed from analytical formulas, from simulations of discrete random walks, and from simulations of the Langevin or reduced Langevin equations, with indistinguishable results. If the potential barrier has a single, large, parabolic peak, away from either boundary, an approximate expression reminiscent of Kramers' formula can be used to determine the flux. The fluxes predicted can be compared with measurements of current through single channels under a wide range of experimental conditions.

  9. Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions

    NASA Technical Reports Server (NTRS)

    McCollom, T. M.; Ritter, G.; Simoneit, B. R.

    1999-01-01

    Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

  10. Pentavalent uranium oxide via reduction of [UO2]2+ under hydrothermal reaction conditions.

    PubMed

    Belai, Nebebech; Frisch, Mark; Ilton, Eugene S; Ravel, Bruce; Cahill, Christopher L

    2008-11-03

    The synthesis, crystal structure, and spectroscopic characterization of [U(V)(H2O)2(U(VI)O2)2O4(OH)](H2O)4 (1), a mixed-valent U(V)/U(VI) oxide material, are reported. The hydrothermal reaction of UO2(2+) with Zn and hydrazine at 120 degrees C for three days yields 1 in the form of a dark red crystalline solid. Compound 1 has been characterized by a combination of single-crystal and powder X-ray diffraction (XRD), elemental analysis, thermogravimetric analysis, X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The structure consists of an extended sheet of edge and corner shared U(VI) pentagonal bipyramids that are further connected by edge sharing to square bipyramidal U(V) units. The overall topology is similar to the mineral ianthinite. The uranium L(III)-edge XAS revealed features consistent with those observed by single-crystal X-ray diffraction. High resolution XPS data analysis of the U4f region confirmed the oxidation states of U as originally assigned from XRD analysis and bond valence summations.

  11. Pentavalent Uranium Oxide via Reduction of [UO2]2+ Under Hydrothermal Reaction Conditions

    SciTech Connect

    Balai, N.; Frisch, M; Ilton, E; Ravel, B; Cahill, C

    2008-01-01

    The synthesis, crystal structure, and spectroscopic characterization of [UV(H2O)2(UVIO2)2O4(OH)](H2O)4 (1), a mixed-valent UV/UVI oxide material, are reported. The hydrothermal reaction of UO22+ with Zn and hydrazine at 120 degrees C for three days yields 1 in the form of a dark red crystalline solid. Compound 1 has been characterized by a combination of single-crystal and powder X-ray diffraction (XRD), elemental analysis, thermogravimetric analysis, X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The structure consists of an extended sheet of edge and corner shared UVI pentagonal bipyramids that are further connected by edge sharing to square bipyramidal UV units. The overall topology is similar to the mineral ianthinite. The uranium L|||-edge XAS revealed features consistent with those observed by single-crystal X-ray diffraction. High resolution XPS data analysis of the U4f region confirmed the oxidation states of U as originally assigned from XRD analysis and bond valence summations.

  12. Pentavalent Uranium Oxide via Reduction of [UO2]2+ Under Hydrothermal Reaction Conditions

    SciTech Connect

    Belai, Nebebech; Frisch, Mark; Ilton, Eugene S.; Ravel, Bruce; Cahill, Christopher L.

    2008-11-03

    The synthesis, crystal structure and spectroscopic characterization of [UV(H2O)2(UVIO2)2O4(OH)](H2O)4 (1), a mixed-valent UV/UVI oxide material, are reported. The hydrothermal reaction of UO22+ with Zn and hydrazine at 120 °C for three days yields 1 in the form of a dark red crystalline solid. Compound 1 has been characterized by a combination of single-crystal and powder X-ray diffraction (XRD), elemental analysis, thermogravimetric analysis, X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The structure consists of an extended sheet of edge and point shared UVI pentagonal bipyramids that are further connected by edge sharing to square bipyramidal UV units. The overall topology is similar to the mineral ianthinite. The uranium L|||-edge XAS revealed features consistent with those observed by single-crystal X-ray diffraction. High resolution XPS data analysis of the U4f region confirmed the oxidation states of U as originally assigned from XRD analysis and bond valence summations.

  13. Optimisation of the reaction conditions for the production of cross-linked starch with high resistant starch content.

    PubMed

    Kahraman, Kevser; Koksel, Hamit; Ng, Perry K W

    2015-05-01

    The optimum reaction conditions (temperature and pH) for the preparation of cross-linked (CL) corn and wheat starches with maximum resistant starch (RS) content were investigated by using response surface methodology (RSM). According to the preliminary results, five levels were selected for reaction temperature (38-70 °C) and pH (10-12) in the main study. RS contents of the CL corn and wheat starch samples increased with increasing temperature and pH, and pH had a greater influence on RS content than had temperature. The maximum RS content (with a maximum p value of 0.4%) was obtained in wheat starch cross-linked at 38 °C and pH 12. In the case of CL corn starch, the optimum condition was 70 °C and pH 12. CL corn and wheat starch samples were also produced separately under the optimum conditions and their RS contents were 80.4% and 83.9%, respectively. These results were also in agreement with the values predicted by RSM.

  14. A Novel Endo-β-N-Acetylglucosaminidase Releases Specific N-Glycans Depending on Different Reaction Conditions

    PubMed Central

    De Moura Bell, Juliana Maria Leite Nobrega; Frese, Steven A.; Liu, Yan; Mills, David A.; Block, David E.; Barile, Daniela

    2015-01-01

    Milk glycoproteins are involved in different functions and contribute to different cellular processes, including adhesion and signaling, and shape the development of the infant micro-biome. Methods have been developed to study the complexities of milk protein glycosylation and understand the role of N-glycans in protein functionality. Endo-β-N-acetylglucosaminidase (EndoBI-1) isolated from Bifidobacterium longum subsp. infantis ATCC 15697 is a recently isolated heat-stable enzyme that cleaves the N-N′-diacetyl chitobiose moiety found in the N-glycan core. The effects of different processing conditions (pH, temperature, reaction time, and enzyme/protein ratio) were evaluated for their ability to change EndoBI-1 activity on bovine colostrum whey glycoproteins using advanced mass spectrometry. This study shows that EndoBI-1 is able to cleave a high diversity of N-glycan structures. Nano-LC-Chip–Q-TOF MS data also revealed that different reaction conditions resulted in different N-glycan compositions released, thus modifying the relative abundance of N-glycan types. In general, more sialylated N-glycans were released at lower temperatures and pH values. These results demonstrated that EndoBI-1 is able to release a wide variety of N-glycans, whose compositions can be selectively manipulated using different processing conditions. PMID:26101185

  15. Chemical reaction conditions in a Danish 80 MW{sub th} CFB-boiler co-firing straw and coal

    SciTech Connect

    Hansen, P.F.B.

    1997-12-31

    Future boilers to be constructed in Denmark including boilers intended for energy conversion of biomass (straw and wood chips) will be designed for Ultra Super Critical steam data. The high steam temperatures and subsequently metal temperatures in the superheaters will increase the corrosion hazard significantly. Severe superheater corrosion observed in the convective path and on test tubes inserted into the loop seal of a Danish 80 MW{sub th} Ahlstroem Pyroflow CFB boiler co-firing coal and straw initiated this study on the conditions under which the chemical reactions occur and deposits form. Load changes--caused by variations in public demand for district heating shifts the reaction conditions in the loop seal between predominantly reducing and predominantly oxidizing conditions. Furthermore the external particle circulation rate and the local temperatures are strongly affected. Deposits collected in the loop seal on temperature controlled probes reveals Cl concentrations more than Twenty Thousand times higher than found in the surrounding bed material. The results are discussed and suggestions on how to reduce high temperature corrosion and superheater fouling are presented.

  16. A VUV photoionization study of the multichannel reaction of phenyl radicals with 1,3-butadiene under combustion relevant conditions.

    PubMed

    Golan, Amir; Ahmed, Musahid; Mebel, Alexander M; Kaiser, Ralf I

    2013-01-07

    We studied the reaction of phenyl radicals (C(6)H(5)) with 1,3-butadiene (H(2)CCHCHCH(2)) exploiting a high temperature chemical reactor under combustion-like conditions (300 Torr, 873 K). The reaction products were probed in a supersonic beam by utilizing VUV radiation from the Advanced Light Source and by recording the experimental PIE curves at mass-to-charge ratios of m/z = 130 (C(10)H(10)(+)), 116 (C(9)H(8)(+)), and 104 (C(8)H(8)(+)). Our data suggest that the atomic hydrogen (H), methyl (CH(3)), and vinyl (C(2)H(3)) losses are open with estimated branching ratios of about 86 ± 4%, 8 ± 2%, and 6 ± 2%, respectively. The isomer distributions were probed further by fitting the experimentally recorded PIE curves with a linear combination of the PIE curves of individual C(10)H(10), C(9)H(8), and C(8)H(8) isomers. These fits indicate the formation of three C(10)H(10) isomers (trans-1,3-butadienylbenzene, 1,4-dihydronaphthalene, 1-methylindene), three C(9)H(8) isomers (indene, phenylallene, 1-phenyl-1-methylacetylene), and a C(8)H(8) isomer (styrene). A comparison with results from recent crossed molecular beam studies of the 1,3-butadiene-phenyl radical reaction and electronic structure calculations suggests that trans-1,3-butadienylbenzene (130 amu), 1,4-dihydronaphthalene (130 amu), and styrene (104 amu) are reaction products formed as a consequence of a bimolecular reaction between the phenyl radical and 1,3-butadiene. 1-Methylindene (130 amu), indene (116 amu), phenylallene (116 amu), and 1-phenyl-1-methylacetylene (116 amu) are synthesized upon reaction of the phenyl radical with three C(4)H(6) isomers: 1,2-butadiene (H(2)CCCH(CH(3))), 1-butyne (HCCC(2)H(5)), and 2-butyne (CH(3)CCCH(3)); these C(4)H(6) isomers can be formed from 1,3-butadiene via hydrogen atom assisted isomerization reactions or via thermal rearrangements of 1,3-butadiene involving hydrogen shifts in the high temperature chemical reactor.

  17. Silicon-based Lewis acid assisted cinchona alkaloid catalysis: highly enantioselective aza-Michael reaction under solvent-free conditions.

    PubMed

    Yang, Hua-Meng; Li, Li; Li, Fei; Jiang, Ke-Zhi; Shang, Jun-Yan; Lai, Guo-Qiao; Xu, Li-Wen

    2011-12-16

    The study showed that a combination of an achiral silicon-based Lewis acid and chiral Lewis base, such as iodotrimethylsilane (TMSI) and cinchonine, generated a highly enantioselective catalyst system under solvent-free conditions which gave aromatic β-amino ketones with up to >99% ee. Mechanistic studies demonstrate the enhanced asymmetric induction may be due to the combined and competitive activation of a carbonyl moiety of chalcone with cinchonine and the silicon-based Lewis acid in the aza-Michael reaction.

  18. The effect of preparation conditions on the structure and mechanical properties of reaction-sintered silicon nitride

    NASA Technical Reports Server (NTRS)

    Heinrich, J.

    1980-01-01

    The microstructure of reaction sintered silicon nitride (RSSN) was changed over a wide range by varying the grain density, grain size of the silicon starting powder, nitriding conditions, and by introducing artificial pores. The influence of single microstructural parameters on mechanical properties like room temperature strength, creep behavior, and resistance to thermal shock was investigated. The essential factors influencing these properties were found to be total porosity, pore size distribution, and the fractions of alpha and beta Si3N4. In view of high temperature engineering applications of RSSN, potentials for optimizing the material's properties by controlled processing are discussed.

  19. Calcium phosphate scaffold from biogenic calcium carbonate by fast ambient condition reactions

    NASA Astrophysics Data System (ADS)

    Dutta, Abhishek; Fermani, Simona; Arjun Tekalur, Srinivasan; Vanderberg, Abigail; Falini, Giuseppe

    2011-12-01

    Calcium phosphate biogenic materials are biocompatible and promote bioactivity and osteoconductivity, which implies their natural affinity and tendency to bond directly to bones subsequently replacing the host bone after implantation owing to its biodegradability. Calcium hydrogen phosphate dihydrate, CaHPO 4·2H 2O, is known to be a nucleation precursor, in aqueous solutions, for apatitic calcium phosphates and, hence, a potential starting material for bone substitutes. Numerous approaches, via hydrothermal and ambient synthetic routes, have been used to produce calcium phosphate from biogenic calcium carbonate, taking advantage of the peculiar architecture and composition of the latter. In this article, the lamellar region of the cuttlefish bone ( Sepia officinalis) was used as a framework for the organized deposition of calcium phosphate crystals, at ambient conditions via a fast procedure involving an amorphous calcium carbonate intermediate, and ending with a conversion to calcium phosphate and a fixation procedure, thereby resulting in direct conversion of biogenic calcium carbonate into calcium phosphates at ambient conditions from the scale of months to hours.

  20. Dynamic Pore-scale Reservoir-condition Imaging of Reaction in Carbonates Using Synchrotron Fast Tomography.

    PubMed

    Menke, Hannah P; Andrew, Matthew G; Vila-Comamala, Joan; Rau, Christoph; Blunt, Martin J; Bijeljic, Branko

    2017-02-21

    Underground storage permanence is a major concern for carbon capture and storage. Pumping CO2 into carbonate reservoirs has the potential to dissolve geologic seals and allow CO2 to escape. However, the dissolution processes at reservoir conditions are poorly understood. Thus, time-resolved experiments are needed to observe and predict the nature and rate of dissolution at the pore scale. Synchrotron fast tomography is a method of taking high-resolution time-resolved images of complex pore structures much more quickly than traditional µ-CT. The Diamond Lightsource Pink Beam was used to dynamically image dissolution of limestone in the presence of CO2-saturated brine at reservoir conditions. 100 scans were taken at a 6.1 µm resolution over a period of 2 hours. The images were segmented and the porosity and permeability were measured using image analysis and network extraction. Porosity increased uniformly along the length of the sample; however, the rate of increase of both porosity and permeability slowed at later times.

  1. Cortisol reaction in success and failure condition in endogenous depressed patients and controls.

    PubMed

    Croes, S; Merz, P; Netter, P

    1993-01-01

    The authors studied differences in cortisol response to controllable and uncontrollable stress and its relationship to Seligman's theory of learned helplessness in hospitalized unipolar depressed patients (11 nontreated, acutely depressed; 11 treated patients) and 11 age and sex matched controls hospitalized for traumatic surgery. Control and lack of control were achieved by induction of success and failure in a simple number addition test and applied in balanced order on 2 consecutive days. Saliva cortisol samples were collected before and after the test. No group differences in baseline cortisol levels were observed. Cortisol increased after uncontrollable and decreased after controllable stress in control patients, whereas cortisol decreased after both conditions in the acutely depressed group and less so in the treated group, although they were as emotionally upset after failure as controls. Thus, the normally observed ability of the neuroendocrine system to discriminate between controllable and uncontrollable stress deteriorates with increasing severity of depression.

  2. Synthesis of branched cores by poly-O-alkylation reaction under phase transfer conditions. A systematic study

    NASA Astrophysics Data System (ADS)

    Landeros, José M.; Silvestre, Hugo A.; Guadarrama, Patricia

    2013-04-01

    In the present paper is described a systematic study of poly-O-alkylation reactions of pentaerythritol (PE) and 1,1,1-tris(hydroxymethyl)ethane (TME) by 1,4 Michael addition, under phase transfer catalysis (PTC), considering the effect of: (1) the organophilicity of PTC (three different catalysts were tested), (2) PTC concentration (from catalytic to equimolar conditions), and (3) the regime of addition of reactants coexisting in the aqueous phase of the heterogeneous reaction system. The less organophilic transfer agent showed the best performance on these reactions. In our case, benzyltriethylammonium chloride (TEBAC) gathers the best features. The presence of NaOH as base, promotes the interfacial mechanism and not the bulk one. Out of the optimal range of concentration of NaOH (35-40%), competition between nucleophiles can occur, due to the saturation of the medium. Regarding the regime of addition of reactants, the scenario where NaOH and TEBAC are less time in contact, favors the formation of the desired products. Finally, the deprotection of tert-butyl groups of the poly-O-alkylated compounds is described, to get branched cores with terminal carboxylic acid groups in good yields (90-94%). Spectroscopic properties, such as IR, 1H and 13C NMR, of the synthesized compounds are also described.

  3. Gas-phase reaction of methyl isothiocyanate and methyl isocyanate with hydroxyl radicals under static relative rate conditions.

    PubMed

    Lu, Zhou; Hebert, Vincent R; Miller, Glenn C

    2014-02-26

    Gaseous methyl isothiocyanate (MITC), the principal breakdown product of the soil fumigant metam sodium (sodium N-methyldithiocarbamate), is an inhalation exposure concern to persons living near treated areas. Inhalation exposure also involves gaseous methyl isocyanate (MIC), a highly reactive and toxic transformation product of MITC. In this work, gas-phase hydroxyl (OH) radical reaction rate constants of MITC and MIC have been determined using a static relative rate technique under controlled laboratory conditions. The rate constants obtained are 15.36 × 10(-12) cm(3) molecule(-1) s(-1) for MITC and 3.62 × 10(-12) cm(3) molecule(-1) s(-1) for MIC. The average half-lives of MITC and MIC in the atmosphere are estimated to be 15.7 and 66.5 h, respectively. The molar conversion of MITC to MIC for OH radical reactions is 67% ± 8%, which indicates that MIC is the primary product of the MITC-OH reaction in the gas phase.

  4. Biodiesel production from various oils under supercritical fluid conditions by Candida antartica lipase B using a stepwise reaction method.

    PubMed

    Lee, Jong Ho; Kwon, Cheong Hoon; Kang, Jeong Won; Park, Chulhwan; Tae, Bumseok; Kim, Seung Wook

    2009-05-01

    In this study, we evaluate the effects of various reaction factors, including pressure, temperature, agitation speed, enzyme concentration, and water content to increase biodiesel production. In addition, biodiesel was produced from various oils to establish the optimal enzymatic process of biodiesel production. Optimal conditions were determined to be as follows: pressure 130 bar, temperature 45 degrees C, agitation speed 200 rpm, enzyme concentration 20%, and water contents 10%. Among the various oils used for production, olive oil showed the highest yield (65.18%) upon transesterification. However, when biodiesel was produced using a batch system, biodiesel conversion yield was not increased over 65%; therefore, a stepwise reaction was conducted to increase biodiesel production. When a reaction medium with an initial concentration of methanol of 60 mmol was used and adjusted to maintain this concentration of methanol every 1.5 h during biodiesel production, the conversion yield of biodiesel was 98.92% at 6 h. Finally, reusability was evaluated using immobilized lipase to determine if this method was applicable for industrial biodiesel production. When biodiesel was produced repeatedly, the conversion rate was maintained at over 85% after eight reuses.

  5. Role of choline and glycine betaine in the formation of N,N-dimethylpiperidinium (mepiquat) under Maillard reaction conditions.

    PubMed

    Bessaire, Thomas; Tarres, Adrienne; Stadler, Richard H; Delatour, Thierry

    2014-01-01

    This study is the first to examine the role of choline and glycine betaine, naturally present in some foods, in particular in cereal grains, to generate N,N-dimethylpiperidinium (mepiquat) under Maillard conditions via transmethylation reactions involving the nucleophile piperidine. The formation of mepiquat and its intermediates piperidine - formed by cyclisation of free lysine in the presence of reducing sugars - and N-methylpiperidine were monitored over time (240°C, up to 180 min) using high-resolution mass spectrometry in a model system comprised of a ternary mixture of lysine/fructose/alkylating agent (choline or betaine). The reaction yield was compared with data recently determined for trigonelline, a known methylation agent present naturally in coffee beans. The role of choline and glycine betaine in nucleophilic displacement reactions was further supported by experiments carried out with stable isotope-labelled precursors (¹³C- and deuterium-labelled). The results unequivocally demonstrated that the piperidine ring of mepiquat originates from the carbon chain of lysine, and that either choline or glycine betaine furnishes the N-methyl groups. The kinetics of formation of the corresponding demethylated products of both choline and glycine betaine, N,N-demethyl-2-aminoethanol and N,N-dimethylglycine, respectively, were also determined using high-resolution mass spectrometry.

  6. QuadraPure-Supported Palladium Nanocatalysts for Microwave-Promoted Suzuki Cross-Coupling Reaction under Aerobic Condition

    PubMed Central

    Loh, Poh Lee; Juan, Joon Ching; Yarmo, Mohd Ambar; Yusop, Rahimi M.

    2014-01-01

    Cross-linked resin-captured palladium (XL-QPPd) was readily prepared by simple physical adsorption onto the high loading QuadraPure macroporous resin and a subsequent reduction process. To enhance the mechanical stability, entrapped palladium nanocatalysts were cross-linked with succinyl chloride. Both transmission electron microscopy images and X-ray diffraction analysis revealed that the palladium nanoparticles were well dispersed with diameters ranging in 4–10 nm. The catalyst performed good catalytic activity in microwave-promoted Suzuki cross-coupling reactions in water under aerobic condition with mild condition by using various aryl halides and phenylboronic acid. In addition, the catalyst showed an excellent recyclability without significant loss of catalytic activity. PMID:25054185

  7. Correlation of Impact Conditions, Interface Reactions, Microstructural Evolution, and Mechanical Properties in Kinetic Spraying of Metals: A Review

    NASA Astrophysics Data System (ADS)

    Kim, Jaeick; Lee, Changhee

    2016-12-01

    In the past, most studies into kinetic spraying technology focused on basic research, but a large portion of current research is devoted to industrial applications of the technology. To advance, however, studies about industrial applications of kinetic spraying require profound understanding of the scientific foundations of the kinetic spray process. Nevertheless, no one has yet provided a well-organized summary of the correlations among impact conditions, interface reactions, microstructural evolution, and mechanical properties across the whole field of kinetic spraying technology. This paper provides such an overview of these correlations for kinetic spraying of metals. For each correlation, the interactions between the given conditions and the material properties of the metal feedstock powder are the most influential. These interactions are so complicated that it is difficult to systematically classify all cases into certain types. Nonetheless, we try to explain and summarize the critical factors and their roles in each relationship.

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

    PubMed

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

    2017-03-31

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

  9. QuadraPure-supported palladium nanocatalysts for microwave-promoted Suzuki cross-coupling reaction under aerobic condition.

    PubMed

    Liew, Kin Hong; Loh, Poh Lee; Juan, Joon Ching; Yarmo, Mohd Ambar; Yusop, Rahimi M

    2014-01-01

    Cross-linked resin-captured palladium (XL-QPPd) was readily prepared by simple physical adsorption onto the high loading QuadraPure macroporous resin and a subsequent reduction process. To enhance the mechanical stability, entrapped palladium nanocatalysts were cross-linked with succinyl chloride. Both transmission electron microscopy images and X-ray diffraction analysis revealed that the palladium nanoparticles were well dispersed with diameters ranging in 4-10 nm. The catalyst performed good catalytic activity in microwave-promoted Suzuki cross-coupling reactions in water under aerobic condition with mild condition by using various aryl halides and phenylboronic acid. In addition, the catalyst showed an excellent recyclability without significant loss of catalytic activity.

  10. Malonic acid concentration as a control parameter in the kinetic analysis of the Belousov-Zhabotinsky reaction under batch conditions.

    PubMed

    Blagojević, Slavica M; Anić, Slobodan R; Cupić, Zeljko D; Pejić, Natasa D; Kolar-Anić, Ljiljana Z

    2008-11-28

    The influence of the initial malonic acid concentration [MA]0 (8.00 x 10(-3) < or = [MA]0 < or = 4.30 x 10(-2) mol dm(-3)) in the presence of bromate (6.20 x 10(-2) mol dm(-3)), bromide (1.50 x 10(-5) mol dm(-3)), sulfuric acid (1.00 mol dm(-3)) and cerium sulfate (2.50 x 10(-3) mol dm(-3)) on the dynamics and the kinetics of the Belousov-Zhabotinsky (BZ) reactions was examined under batch conditions at 30.0 degrees C. The kinetics of the BZ reaction was analyzed by the earlier proposed method convenient for the examinations of the oscillatory reactions. In the defined region of parameters where oscillograms with only large-amplitude relaxation oscillations appeared, the pseudo-first order of the overall malonic acid decomposition with a corresponding rate constant of 2.14 x 10(-2) min(-1) was established. The numerical results on the dynamics and kinetics of the BZ reaction, carried out by the known skeleton model including the Br2O species, were in good agreement with the experimental ones. The already found saddle node infinite period (SNIPER) bifurcation point in transition from a stable quasi-steady state to periodic orbits and vice versa is confirmed by both experimental and numerical investigations of the system under consideration. Namely, the large-amplitude relaxation oscillations with increasing periods between oscillations in approaching the bifurcation points at the beginning and the end of the oscillatory domain, together with excitability of the stable quasi-steady states in their vicinity are obtained.

  11. Adsorption and reaction of methanol on supported palladium catalysts: microscopic-level studies from ultrahigh vacuum to ambient pressure conditions.

    PubMed

    Bäumer, Marcus; Libuda, Jörg; Neyman, Konstantin M; Rösch, Notker; Rupprechter, Günther; Freund, Hans-Joachim

    2007-07-21

    We investigated the decomposition and (partial) oxidation of methanol on Pd based catalysts in an integrated attempt, simultaneously bridging both the pressure and the materials gap. Combined studies were performed on well-defined Pd model catalysts based on ordered Al(2)O(3) and Fe(3)O(4) thin films, on well-defined particles supported on powders and on Pd single crystals. The interaction of Pd nanoparticles and Pd(111) with CH(3)OH and CH(3)OH/O(2) mixtures was examined from ultrahigh vacuum conditions up to ambient pressures, utilizing a broad range of surface specific vibrational spectroscopies which included IRAS, TR-IRAS, PM-IRAS, SFG, and DRIFTS. Detailed kinetic studies in the low pressure region were performed by molecular beam methods, providing comprehensive insights into the microkinetics of the reaction system. The underlying microscopic processes were studied theoretically on the basis of specially designed 3-D nanocluster models containing approximately 10(2) metal atoms. The efficiency of this novel modelling approach was demonstrated by rationalizing and complementing pertinent experimental results. In order to connect these results to the behavior under ambient conditions, kinetic and spectroscopic investigations were performed in reaction cells and lab reactors. Specifically, we focused on (1) particle size and structure dependent effects in methanol oxidation and decomposition, (2) support effects and their relation to activity and selectivity, (3) the influence of poisons such as carbon, and (4) the role of oxide and surface oxide formation on Pd nanoparticles.

  12. Synthesis of Pd(0) nanocatalyst using lignin in water for the Mizoroki-Heck reaction under solvent-free conditions.

    PubMed

    Marulasiddeshwara, M B; Kumar, P Raghavendra

    2016-02-01

    Palladium(0) nanospheres with an average size of 1-5 nm were synthesized and stabilized by lignin in water without any reducing agent. The lignin supported palladium(0) nanoparticles (lignin@Pd-NPs) were characterized by UV-vis., FT-IR, SEM, TEM, HRICP-AES, EDX and PXRD. Absence of the peak at 430 nm in UV-vis., spectrum confirmed the reduction of Pd(II) to Pd(0). The five characteristic peaks at (111), (200), (220), (311) and (222) corresponding to the 2θ values 40°, 46.7°, 67.9°, 81.9° and 86.9°, respectively, appeared in PXRD spectrum indicated the crystallographic planes of Pd(0) with fcc structure. The Pd(0) loaded on lignin was 0.0467 mmol/g determined by HRICP-AES and 0.89% (w/w) by EDX. The performance of lignin@Pd-NPs catalyst have been investigated for the Mizoroki-Heck CC bond formation reactions between n-butyl propene-2-enoate and halobenzenes and substituted halobenzenes in polar to highly polar solvents as well as under solvent-free conditions in the presence of organic or inorganic bases. The lignin@Pd-NPs was found to be a highly efficient catalyst to yield the desired products of up to 94% under solvent-free conditions in short reaction times. The catalyst was heterogeneous and hence recovered by filtration and reused several times in the subsequent batches of the same reaction.

  13. Evolution of fracture permeability through fluid rock reaction under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Yasuhara, Hideaki; Polak, Amir; Mitani, Yasuhiro; Grader, Abraham S.; Halleck, Phillip M.; Elsworth, Derek

    2006-04-01

    We report flow-through experiments on a natural fracture in novaculite under moderate effective stresses (˜ 1.4 MPa) and temperatures (20-120 °C) to examine the effect on flow and transport characteristics. The efflux of fluid and dissolved minerals were measured throughout the 3150-h experiment. After the experiment the fracture was imaged by X-ray CT, impregnated with Wood's metal, and a cast recovered of the Wood's metal-filled fracture. These measurements constrain the evolution of fracture structure, and the change in permeability that resulted from stress- and temperature-dependent dissolution at both propping asperities and fracture void surfaces. During the first 1500 h, the aperture of one fracture decreased from 18.5 to 7.5 μm, when it was loaded with constant effective stress of 1.4 MPa, at room temperature, and a flow rate decreasing with time from 1 to 0.0625 mL/min. This reduction is attributed to the removal of mineral mass from bridging asperities. After 1500 h the fracture aperture increased, ultimately reaching 13 μm. Apparently the dominant dissolution process switched from prop removal to etching of the void surfaces. We used X-ray CT images, digital radiographs, and fracture casts as independent methods to constrain the resulting architecture of the evolved fracture porosity, and developed a simple process-based model to examine the relative roles of asperity removal and free-face dissolution. The comparison of the model with the measurements identifies the relative importance of mass removal at fracture faces and at propping asperities. The experiments underscore the importance of dissolution in determining the sense, the rates and the magnitude of permeability-enhancement within rock fractures stimulated by chemical permeants in geothermal and petroleum reservoirs, and to a lesser degree under natural conditions pushed far-from-equilibrium.

  14. Investigation of influence of hypomagnetic conditions closely similar to interplanetary magnetic filed on behavioral and vegetative reactions of higher mammals

    NASA Astrophysics Data System (ADS)

    Krivova, Natalie; Trukhanov, Kiril; Zamotshina, Tatyana; Zaeva, Olga; Khodanovich, Marina; Misina, Tatyana; Tukhvatulin, Ravil; Suhko, Valery

    To study the influence of long being under reduced magnetic field on behavioral and vegetative reactions of higher mammals the white rat males were put into the 700-1000 times reduced geomagnetic field (50-70 nT) for 25 days. Such field was obtained by using automatic compensation of the horizontal and vertical components of the GMF at a frequencies up to 10 Hz by means of solenoids of the experimental magnetic system. Control animals were located in the same room under usual laboratory GMF conditions (52 uT). Two days before the experiment the behavioral reactions were studied in the "open field" by means of a set of tests, characterizing the level of emotionality, moving and orientational-investigative activities of the animals under conditions of unimpeded behavior. 60 white underbred rat males with the initial body mass of 200 g were divided into three clusters. Animals with average indices were selected for the experiment. We have judged behavioral reaction disturbances of the rats under hypomagnetic conditions using videotape recordings carried out in the entire course of the chronic experiment. According to the obtained results during the period of maximum activity (from 230 to 330 a.m.) the number of interrelations between the individuals increased appreciably for experimental rats including interrelations with aggressive character. This was real during all 25 days of observation. We observed a certain dynamics of this index differed from that of the control group. We have also analyzed the final period of observation from the 21th to the 25th days. In this period we studied the 24 hours' dynamics of interrelations which were noted during 5 minutes in every hour around the clock. In the control group the number of interrelation was at a constantly low level. For experimental animals the number of interrelations was higher in the night hours than in the day ones. Moreover it exceeded the similar indexes observed from the 1st to the 20th day. For example from

  15. Effect of the reaction conditions on the performance of Au-Pd/TiO(2) catalyst for the direct synthesis of hydrogen peroxide.

    PubMed

    Piccinini, Marco; Ntainjua, Edwin; Edwards, Jennifer K; Carley, Albert F; Moulijn, Jacob A; Hutchings, Graham J

    2010-03-14

    The direct synthesis of hydrogen peroxide from H(2) and O(2) has been studied using a high activity AuPd/TiO(2) catalyst. In particular, the effect of variation in the reaction conditions on the productivity of hydrogen peroxide formation is investigated in detail. The effect of H(2)/O(2) molar ratio, temperature, total pressure and solvent composition has been studied and optimised conditions identified. In addition, the effect of carrying out the synthesis reaction in the presence of hydrogen peroxide is investigated and the competing reactions of hydrogen peroxide formation, decomposition and hydrogenation are discussed and optimal operating conditions are identified.

  16. Synthesis and Characterization of AlCl3 Impregnated Molybdenum Oxide as Heterogeneous Nano-Catalyst for the Friedel-Crafts Acylation Reaction in Ambient Condition.

    PubMed

    Jadhav, Arvind H; Chinnappan, Amutha; Hiremath, Vishwanath; Seo, Jeong Gil

    2015-10-01

    Aluminum trichloride (AlCl3) impregnated molybdenum oxide heterogeneous nano-catalyst was prepared by using simple impregnation method. The prepared heterogeneous catalyst was characterized by powder X-ray diffraction, FT-IR spectroscopy, solid-state NMR spectroscopy, SEM imaging, and EDX mapping. The catalytic activity of this protocol was evaluated as heterogeneous catalyst for the Friedel-Crafts acylation reaction at room temperature. The impregnated MoO4(AlCl2)2 catalyst showed tremendous catalytic activity in Friedel-Crafts acylation reaction under solvent-free and mild reaction condition. As a result, 84.0% yield of acyl product with 100% consumption of reactants in 18 h reaction time at room temperature was achieved. The effects of different solvents system with MoO4(AlCl2)2 catalyst in acylation reaction was also investigated. By using optimized reaction condition various acylated derivatives were prepared. In addition, the catalyst was separated by simple filtration process after the reaction and reused several times. Therefore, heterogeneous MoO4(AlCl2)2 catalyst was found environmentally benign catalyst, very convenient, high yielding, and clean method for the Friedel-Crafts acylation reaction under solvent-free and ambient reaction condition.

  17. Attentional focus influences postural control and reaction time performances only during challenging dual-task conditions in healthy young adults.

    PubMed

    Remaud, Anthony; Boyas, Sébastien; Lajoie, Yves; Bilodeau, Martin

    2013-11-01

    The dual-task paradigm has previously been used to investigate the attentional demands associated with postural control. Previous studies have identified both the focus of attention and the difficulty of a postural task as potential factors influencing dual-task performance. The aim of this study was to examine how the instructed focus of attention influences dual-task performance during quiet standing tasks of various levels of difficulty. Thirteen young adults participated in two testing sessions consisting of standing as still as possible on a force platform in different postural conditions, while simultaneously performing a simple reaction time (RT) task. Postural task difficulty was manipulated by various combinations of three bases of support (feet together, tandem and single leg) and two visual conditions (eyes opened and closed). Participants were instructed to focus on either their balance or their RT performance, depending on the testing session. When comparing postural control with respect to session focus, anterior-posterior sway velocity decreased with the addition of the simple RT task when the focus was on balance, but only during the more difficult dual-task conditions. In contrast, sway area and medial-lateral sway velocity did not change between the two instructed focus sessions. Participants responded faster in all dual-task conditions when focusing on RT performance than on balance. The modified attention allocation index indicated that participants' ability to modulate their allocation of attentional resources to respond positively to instruction was more pronounced in the most challenging postural condition. The present findings could have important implications for the interpretation of dual-task performance in both clinical and research settings.

  18. Real-Time Optical Monitoring of Flow Kinetics and Gas Phase Reactions Under High-Pressure OMCVD Conditions

    NASA Technical Reports Server (NTRS)

    Dietz, N.; McCall, S.; Bachmann, K. J.

    2001-01-01

    This contribution addresses the real-time optical characterization of gas flow and gas phase reactions as they play a crucial role for chemical vapor phase depositions utilizing elevated and high pressure chemical vapor deposition (HPCVD) conditions. The objectives of these experiments are to validate on the basis of results on real-time optical diagnostics process models simulation codes, and provide input parameter sets needed for analysis and control of chemical vapor deposition at elevated pressures. Access to microgravity is required to retain high pressure conditions of laminar flow, which is essential for successful acquisition and interpretation of the optical data. In this contribution, we describe the design and construction of the HPCVD system, which include access ports for various optical methods of real-time process monitoring and to analyze the initial stages of heteroepitaxy and steady-state growth in the different pressure ranges. To analyze the onset of turbulence, provisions are made for implementation of experimental methods for in-situ characterization of the nature of flow. This knowledge will be the basis for the design definition of experiments under microgravity, where gas flow conditions, gas phase and surface chemistry, might be analyzed by remote controlled real-time diagnostics tools, developed in this research project.

  19. Stress response in Pectobacterium atrosepticum SCRI1043 under starvation conditions: adaptive reactions at a low population density.

    PubMed

    Petrova, Olga; Gorshkov, Vladimir; Daminova, Amina; Ageeva, Marina; Moleleki, Lucy N; Gogolev, Yuri

    2014-01-01

    The adaptive reactions of plant pathogenic bacterium Pectobacterium atrosepticum SCRI1043 under starvation conditions were studied. The main emphasis was given to the peculiarities of stress responses depending on the bacterial population densities. When bacteria were subjected to starvation at high population densities (10(7)-10(9) CFU ml(-1)), their adaptive reactions conformed to the conventional conception of bacterial adaptation related to autolysis of part of the population, specific modification of cell ultrastructure, activation of expression of stress responsive genes and acquiring cross protection against other stress factors. In contrast, at low initial population densities (10(3)-10(5) CFU ml(-1)), as described in our recent work, the cell density increased due to multiple cell division despite the absence of exogenous growth substrate. Here we present data that demonstrate that such unconventional behavior is part of a stress response, which provides increased stress tolerance while retaining virulence. Cell morphology and gene expression in high- and low-cell-density starving Pba cultures were compared. Our investigation demonstrates the existence of alternative adaptive strategies enabling pathogenic bacteria to cope with a variety of stress factors, including starvation, especially necessary when residing outside of their host.

  20. ACCURATE TIME-DEPENDENT WAVE PACKET STUDY OF THE H{sup +}+LiH REACTION AT EARLY UNIVERSE CONDITIONS

    SciTech Connect

    Aslan, E.; Bulut, N.; Castillo, J. F.; Banares, L.; Aoiz, F. J.; Roncero, O.

    2012-11-01

    The dynamics and kinetics of the H{sup +} + LiH reaction have been studied using a quantum reactive time-dependent wave packet (TDWP) coupled-channel quantum mechanical method on an ab initio potential energy surface at conditions of the early universe. The total reaction probabilities for the H{sup +} + LiH(v = 0, j = 0) {yields} H{sup +} {sub 2} + Li process have been calculated from 5 Multiplication-Sign 10{sup -3} eV up to 1 eV for total angular momenta J from 0 to 110. Using a Langevin model, integral cross sections have been calculated in that range of collision energies and extrapolated for energies below 5 Multiplication-Sign 10{sup -3} eV. The calculated rate constants are found to be nearly independent of temperature in the 10-1000 K interval with a value of Almost-Equal-To 10{sup -9} cm{sup 3} s{sup -1}, which is in good agreement with estimates used in evolutionary models of the early universe lithium chemistry.

  1. Synthesis of cellulose triacetate from cotton cellulose by using NIS as a catalyst under mild reaction conditions.

    PubMed

    El Nemr, Ahmed; Ragab, Safaa; El Sikaily, Amany; Khaled, Azza

    2015-10-05

    This research discusses the acetylation of cotton cellulose with acetic anhydride without solvents. The acetylation was done in the presence of different amounts of N-Iodosuccinimide (NIS) as a catalyst; this took place under mild reaction conditions. The extent of acetylation was measured by the weight percent gain (WPG) that varied from 24.71 to 71.83%. Cotton cellulose acetates, with the degree of substitution (DS) that ranged from 0.89 to 2.84, were prepared in one step. The cellulose triacetate, with a degree of substitution (DS) 2.84, was obtained. The WPG and DS were easily controlled by changing the reaction duration (1-5h), and the concentration of the catalyst (0.05 g, 0.075 g and 0.10 g for 1g of cellulose) in 25 ml of acetic anhydride. NIS was recognized as a novel and more successful catalyst for the acetylation of hydroxyl groups in cotton cellulose. Formation of the acetates and the calculation of the degree of substitution were performed by FT-IR, Raman, and (1)H NMR.

  2. Dextran-based self-healing hydrogels formed by reversible diels-alder reaction under physiological conditions.

    PubMed

    Wei, Zhao; Yang, Jian Hai; Du, Xiao Jing; Xu, Feng; Zrinyi, Miklos; Osada, Yoshihito; Li, Fei; Chen, Yong Mei

    2013-09-01

    A dextran-based self-healing hydrogel is prepared by reversible Diels-Alder reaction under physiological conditions. Cytocompatible fulvene-modified dextran as main polymer chains and dichloromaleic-acid-modified poly(ethylene glycol) as cross-linkers are used. Both macro- and microscopic observation as well as the rheological recovery test confirm the self-healing property of the dextran-l-poly(ethylene glycol) hydrogels ("l" means "linked-by"). In addition, scanning electrochemical microscopy is used to qualitatively and quantitatively in situ track the self-healing process of the hydrogel for the first time. It is found that the longitudinal depth of scratch on hydrogel surface almost completely healed at 37 °C after 7 h. This work represents a facile approach for fabrication of polysaccharide self-healing hydrogel, which can be potentially used in several biomedical fields.

  3. Stationary Conditions of the Electron Density Along the Reaction Path: Connection with Conceptual DFT and Information Theory.

    PubMed

    Gonzalez, Carlos A; Squitieri, Emilio; Franco, Hector J; Rincon, Luis C

    2017-01-26

    The Kohn-Sham density functional theory (DFT) formalism has been used to investigate the influence of the stationary behavior of the electron density (ρ(r⃗;s)) along a minimum energy path on the corresponding stationary conditions observed in the total potential energy of the reactive system, information theory measures (Shannon information entropy and Onicescu information energy), and chemical reactivity indexes (the chemical hardness). The theoretical treatment presented in this work, combined with DFT calculations on 3 different test reactions: Ḣ' + H2, Ḣ' + CH4 and H(-) + CH4, suggest that for any reactive system, properties that can be cast as a functional of the electron density, must exhibit stationary points along the IRC path modulated by the corresponding stationary behavior of the electron density.

  4. Microscale imaging and identification of Fe speciation and distribution during fluid-mineral reactions under highly reducing conditions.

    PubMed

    Mayhew, L E; Webb, S M; Templeton, A S

    2011-05-15

    The oxidation state, speciation, and distribution of Fe are critical determinants of Fe reactivity in natural and engineered environments. However, it is challenging to follow dynamic changes in Fe speciation in environmental systems during progressive fluid-mineral interactions. Two common geological and aquifer materials-basalt and Fe(III) oxides-were incubated with saline fluids at 55 °C under highly reducing conditions maintained by the presence of Fe(0). We tracked changes in Fe speciation after 48 h (incipient water-rock reaction) and 10 months (extensive water-rock interaction) using synchrotron-radiation μXRF maps collected at multiple energies (ME) within the Fe K-edge. Immediate PCA analysis of the ME maps was used to optimize μXANES analyses; in turn, refitting the ME maps with end-member XANES spectra enabled us to detect and spatially resolve the entire variety of Fe-phases present in the system. After 48 h, we successfully identified and mapped the major Fe-bearing components of our samples (Fe(III) oxides, basalt, and rare olivine), as well as small quantities of incipient brucite associated with olivine. After 10 months, the Fe(III)-oxides remained stable in the presence of Fe(0), whereas significant alteration of basalt to minnesotaite and chlinochlore had occurred, providing new insights into heterogeneous Fe speciation in complex geological media under highly reducing conditions.

  5. The influence of mass-transport conditions on the ethanol oxidation reaction (EOR) mechanism of Pt/C electrocatalysts.

    PubMed

    Bach Delpeuch, Antoine; Jacquot, Marjorie; Chatenet, Marian; Cremers, Carsten

    2016-09-14

    This study aims to provide further understanding of the influence of different parameters that control mass-transport (the revolution rate of the rotating disk electrode and the potential scan rate) on the ethanol oxidation reaction (EOR). The experiments were conducted on a home-made carbon-supported 20 wt% Pt/C electrocatalyst, synthesized using a modified polyol method, and characterized in terms of physicochemical properties by thermogravimetric analysis (TGA), powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The EOR at the thin active layer of this electrocatalyst was characterized using both differential electrochemical mass spectrometry (DEMS) in a flow cell configuration and the rotating disc electrode (RDE). The results demonstrate that operating under stationary conditions (low scan rate and high RDE speed) hinders complete ethanol electrooxidation into CO2 and favors the poisoning of the electrocatalyst surface by hydroxide and strong ethanol adsorbates. As such, the EOR appears to be more efficient and faster under dynamic conditions than in near steady-state.

  6. Charge distribution analysis of catalysts under simulated reaction conditions. Final report, October 1, 1993--June 30, 1995

    SciTech Connect

    Freund, F.

    1996-02-01

    A new technique has been developed to measure mobile charge carriers in dielectric materials, insulators and catalysts. The technique, Charge Distribution Analysis, is based on the measurement of the dielectric polarization in an electric field gradient, contact-free, at 0 Hertz under minimum perturbation conditions. The measured parameter is the force F{sup +-} experienced by the sample in a gradient of reversible polarity. CDA allows to determine the sign of the majority charge carriers and the density of surface charges which may be correlated to the chemical or catalytic activity. Throughout this work a microbalance has been used as a force-sensing device. CDA can be applied to any dielectric material, compact or porous, in inert or reactive and corrosive gas environments. To conduct CDA experiments under simulated reaction conditions that are relevant to coal liquefaction research, e.g. in reactive and in part chemically corrosive atmospheres, several modifications were introduced to the current design. In particular, the stainless steel sample chamber and furnace/electrode assembly were built, and the gas flow system was redesigned. The CDA instrument was equipped with new data acquisition capabilities. Tests were performed in inert gases and in reactive and corrosive atmosphere between ambient temperature and 500{degrees}C on iron oxide and partially sulfidized iron oxide catalysts as well as on pyrite (FeS{sub 2}) single crystals.

  7. Clinical profiles of adverse drug reactions spontaneously reported at a single Korean hospital dedicated to children with complex chronic conditions

    PubMed Central

    Kim, Bomi; Kim, Sunwha Zara; Lee, Jin; Jung, Ae Hee; Jung, Sun-Hoi; Hahn, Hyeon-Joo; Kang, Hye Ryun

    2017-01-01

    Children with complex chronic conditions (CCC) are presumed to be vulnerable to adverse drug reactions (ADRs). The clinical profiles of ADRs in CCC are not well known. Herein, we aim to describe the ADR profiles in CCC with regard to typical presentations and vulnerable groups. We accessed the ADR yearly reports at a tertiary children's hospital whose practice is mainly dedicated to CCC and descriptively analyzed their clinical profiles according to the presence of a complex chronic condition, ADR severity, and age groups. A total of 1841 cases were analyzed, among which 1258 (68.3%) were mild, 493 (26.8%) moderate, and 90 (4.9%) cases were severe. A total of 1581 (85.9%) cases of complex chronic condition were reported. The proportion of CCC in each severity group increased as the ADR becomes more severe. In CCC, ADRs were most frequently reported by nurses in the adolescent group and in cases where the symptoms involved the gastrointestinal system. The class of antineoplastic and immunomodulating drugs was the most commonly suspected of causing an ADR, followed by one of the antibiotics. When we focus on the trend across the age groups, the ratio of severe-to-total ADRs decreased with older age. Among severe cases, the ratio of off-label prescription-related cases was the highest in the infant/toddler group and decreased as the groups aged. In conclusion, ADRs of CCCs admitted to a tertiary children’s hospital have a unique profile. These groups are vulnerable to ADRs and thus they should be monitored closely, especially when they are infants or toddlers, so that severe ADRs can be identified and treated immediately. PMID:28199420

  8. Selection of reference genes for quantitative reverse-transcription polymerase chain reaction normalization in Brassica napus under various stress conditions.

    PubMed

    Wang, Zheng; Chen, Yu; Fang, Hedi; Shi, Haifeng; Chen, Keping; Zhang, Zhiyan; Tan, Xiaoli

    2014-10-01

    Data normalization is essential for reliable output of quantitative real-time reverse-transcription polymerase chain reaction (qRT-PCR) assays, as the unsuitable choice of reference gene(s), whose expression might be influenced by exogenous treatments in plant tissues, could cause misinterpretation of results. To date, no systematic studies on reference genes have been performed in stressed Brassica napus. In this study, we investigated the expression variations of nine candidate reference genes in 40 samples of B. napus leaves subjected to various exogenous treatments. Parallel analyses by geNorm and NormFinder revealed that optimal reference genes differed across the different sets of samples. The best-ranked reference genes were PP2A and TIP41 for salt stress, TIP41 and ACT7 for heavy metal (Cr(6+)) stress, PP2A and UBC21 for drought stress, F-box and SAND for cold stress, F-box and ZNF for salicylic acid stress, TIP41, ACT7, and PP2A for methyl jasmonate stress, TIP41 and ACT7 for abscisic acid stress, and TIP41, UBC21, and PP2A for Sclerotinia sclerotiorum stress. Two newly employed reference genes, TIP41 and PP2A, showed better performances, suggesting their suitability in multiple conditions. To further validate the suitability of the reference genes, the expression patterns of BnWRKY40 and BnMKS1 were studied in parallel. This study is the first systematic analysis of reference gene selection for qRT-PCR normalization in B. napus, an agriculturally important crop, under different stress conditions. The results will contribute toward more accurate and widespread use of qRT-PCR in gene analysis of the genus Brassica.

  9. Highly Regio- and Stereoselective Diels-Alder Cycloadditions via Two-Step and Multicomponent Reactions Promoted by Infrared Irradiation under Solvent-Free Conditions

    PubMed Central

    Flores-Conde, Maria Ines; Reyes, Leonor; Herrera, Rafael; Rios, Hulme; Vazquez, Miguel A.; Miranda, Rene; Tamariz, Joaquin; Delgado, Francisco

    2012-01-01

    Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17), under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO) calculations. PMID:22489113

  10. Activity of Co-N multi walled carbon nanotubes electrocatalysts for oxygen reduction reaction in acid conditions

    NASA Astrophysics Data System (ADS)

    Osmieri, Luigi; Monteverde Videla, Alessandro H. A.; Specchia, Stefania

    2015-03-01

    Two catalysts are synthesized by wet impregnation of multi walled carbon nanotubes (MWCNT) with a complex formed between Co(II) ions and the nitrogen-containing molecule 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ), followed by one or two identical heat treatments in N2 atmosphere at 800 °C for 3 h. Catalysts are fully characterized by FESEM, EDX, BET, XRD, FTIR, TGA, XPS analyses, and electrochemical techniques. The electrocatalytic activity towards oxygen reduction reaction (ORR) of the catalysts in acid conditions is assessed by means of a rotating disk electrode (RDE) apparatus and a specific type of cell equipped with a gas diffusion working electrode (GDE). In both testing approaches, the catalyst heat-treated twice (Co-N/MWCNT-2) exhibits higher electroactivity than the catalyst heat-treated once (Co-N/MWCNT-1). Chronoamperometries both in RDE and GDE cell are also performed, showing less electroactivity decay and better current performance for the catalyst heat-treated twice.

  11. CO2 reaction with hydrated class H well cement under geologic sequestration conditions: effects of flyash admixtures.

    PubMed

    Kutchko, Barbara G; Strazisar, Brian R; Huerta, Nicolas; Lowry, Gregory V; Dzombak, David A; Thaulow, Niels

    2009-05-15

    The rate and mechanism of reaction of pozzolan-amended Class H cement exposed to both supercritical CO2 and CO2-saturated brine were determined under geologic sequestration conditions to assess the potential impact of cement degradation in existing, wells on CO2 storage integrity. The pozzolan additive chosen, Type F flyash, is the most common additive used in cements for well sealing in oil-gas field operations. The 35:65 and 65:35 (v/v) pozzolan-cement blends were exposed to supercritical CO2 and CO2-saturated brine and underwent cement carbonation. Extrapolation of the carbonation rate for the 35:65 case suggests a penetration depth of 170-180 mm for both the CO2-saturated brine and supercritical CO2 after 30 years. Despite alteration in both pozzolan systems, the reacted cement remained relatively impermeable to fluid flow after exposure to brine solution saturated with CO2, with values well below the American Petroleum Institute recommended maximum well cement permeability of 200 microD. Analyses of 50: 50 pozzolan-cement cores from a production well in a sandstone reservoir exhibited carbonation and low permeability to brine solution saturated with CO2, which are consistent with our laboratory findings.

  12. Clean bio-oil production from fast pyrolysis of sewage sludge: effects of reaction conditions and metal oxide catalysts.

    PubMed

    Park, Hyun Ju; Heo, Hyeon Su; Park, Young-Kwon; Yim, Jin-Heong; Jeon, Jong-Ki; Park, Junhong; Ryu, Changkook; Kim, Seung-Soo

    2010-01-01

    Fast pyrolysis of sewage sludge was carried out under different reaction conditions, and its effects on bio-oil characteristics were studied. The effect of metal oxide catalysts on the removal of chlorine in the bio-oil was also investigated for four types of catalysts. The optimal pyrolysis temperature for bio-oil production was found to be 450 degrees C, while much smaller and larger feed sizes adversely influenced production. Higher flow and feeding rates were more effective but did not greatly affect bio-oil yields. The use of the product gas as the fluidizing medium gave an increased bio-oil yield. Metal oxide catalysts (CaO and La2O3) contributed to a slight decrease in bio-oil yield and an increase in water content but were significantly effective in removal of chlorine from the bio-oil. The fixed catalyst bed system exhibited a higher removal rate than when metal oxide-supported alumina was used as the fluidized bed material.

  13. Reference genes for quantitative real-time polymerase chain reaction studies in soybean plants under hypoxic conditions.

    PubMed

    Nakayama, T J; Rodrigues, F A; Neumaier, N; Marcelino-Guimarães, F C; Farias, J R B; de Oliveira, M C N; Borém, A; de Oliveira, A C B; Emygdio, B M; Nepomuceno, A L

    2014-02-13

    Quantitative real-time polymerase chain reaction (RT-qPCR) is a powerful tool used to measure gene expression. However, because of its high sensitivity, the method is strongly influenced by the quality and concentration of the template cDNA and by the amplification efficiency. Relative quantification is an effective strategy for correcting random and systematic errors by using the expression level of reference gene(s) to normalize the expression level of the genes of interest. To identify soybean reference genes for use in studies of flooding stress, we compared 5 candidate reference genes (CRGs) with the NormFinder and GeNorm programs to select the best internal control. The expression stability of the CRGs was evaluated in root tissues from soybean plants subjected to hypoxic conditions. Elongation factor 1-beta and actin-11 were identified as the most appropriate genes for RT-qPCR normalization by both the NormFinder and GeNorm analyses. The expression profiles of the genes for alcohol dehydrogenase 1, sucrose synthase 4, and ascorbate peroxidase 2 were analyzed by comparing different normalizing combinations (including no normalization) of the selected reference genes. Here, we have identified potential genes for use as references for RT-qPCR normalization in experiments with soybean roots growing in O2-depleted environments, such as flooding-stressed plants.

  14. CO{sub 2} reaction with hydrated class H well cement under geologic sequestration conditions: effects of flyash admixtures

    SciTech Connect

    Barbara G. Kutchko; Brian R. Strazisar; Nicolas Huerta; Gregory V. Lowry; David A. Dzombak; Niels Thaulow

    2009-05-15

    The rate and mechanism of reaction of pozzolan-amended Class H cement exposed to both supercritical CO{sub 2} and CO{sub 2}-saturated brine were determined under geologic sequestration conditions to assess the potential impact of cement degradation in existing wells on CO{sub 2} storage integrity. The pozzolan additive chosen, Type F flyash, a by-product of coal combustion, is the most common additive used in cements for well sealing in oil-gas field operations. The 35:65 and 65:35 (v/v) pozzolan-cement blends were exposed to supercritical CO{sub 2} and CO{sub 2}-saturated brine and underwent cement carbonation. Extrapolation of the carbonation rate for the 35:65 case suggests a penetration depth of 170-180 mm for both the CO{sub 2}-saturated brine and supercritical CO{sub 2} after 30 years. Despite alteration in both pozzolan systems, the reacted cement remained relatively impermeable to fluid flow after exposure to brine solution saturated with CO{sub 2}, with values well below the American Petroleum Institute recommended maximum well cement permeability of 200 {mu}D. Analyses of 50:50 pozzolan-cement cores from a production well in a sandstone reservoir exhibited carbonation and low permeability to brine solution saturated with CO{sub 2}, which are consistent with our laboratory findings. 16 refs., 4 figs., 1 tab.

  15. Synthesis of different-sized silver nanoparticles by simply varying reaction conditions with leaf extracts of Bauhinia variegata L.

    PubMed

    Kumar, V; Yadav, S K

    2012-03-01

    Green synthesis of nanoparticles is one of the crucial requirements in today's climate change scenario all over the world. In view of this, leaf extract (LE) of Bauhinia variegata L. possessing strong antidiabetic and antibacterial properties has been used to synthesise silver nanoparticles (SNP) in a controlled manner. Various-sized SNP (20-120 nm) were synthesised by varying incubation temperature, silver nitrate and LE concentrations. The rate of SNP synthesis and their size increased with increase in AgNO(3) concentration up to 4 mM. With increase in LE concentration, size and aggregation of SNP was increased. The size and aggregation of SNP were also increased at temperatures above and below 40°C. This has suggested that size and dispersion of SNP can be controlled by varying reaction components and conditions. Polarity-based fractionation of B. variegata LE has suggested that only water-soluble fraction is responsible for SNP synthesis. Fourier transform infrared spectroscopy analysis revealed the attachment of polyphenolic and carbohydrate moieties to SNP. The synthesised SNPs were found stable in double distilled water, BSA and phosphate buffer (pH 7.4). On the contrary, incubation of SNP with NaCl induced aggregation. This suggests the safe use of SNP for various in vivo applications.

  16. Ethanol Conversion to Hydrocarbons on HZSM-5: Effect of Reaction Conditions and Si/Al Ratio on the Product Distributions

    SciTech Connect

    Ramasamy, Karthikeyan K.; Wang, Yong

    2014-11-17

    The Conversion of ethanol to hydrocarbon over HZSM-5 zeolite with different Si/Al ratios was investigated under various reaction conditions. The catalyst with a higher Si/Al ratio (low acid density) deactivated faster and generated more unsaturated compounds at a similar time-on-stream. Temperature affects the catalytic activity with respect to liquid hydrocarbon generation and the hydrocarbon product composition. At lower temperatures (~300°C), the catalyst deactivated faster with respect to the liquid hydrocarbon formation. Higher temperatures (~400°C) reduced the formation of liquid range hydrocarbons and formed more gaseous fractions. Weight hourly space velocity was also found to affect product selectivity with higher weight hourly space velocity leading to a higher extent of ethylene formation. The experimental results were analyzed in terms of the product composition and the coke content with respect to catalyst time-on-stream and compared with the catalyst lifetime with respect to the variables tested on the conversion of ethanol to hydrocarbon.

  17. The Influence of Sorbent Properties and Reaction Conditions on Attrition of Limestone by Impact Loading in Fluidized Beds

    NASA Astrophysics Data System (ADS)

    Scala, Fabrizio; Salatino, Piero

    The extent of attrition associated with impact loading was studied for five different limestones pre-processed in fluidized bed under different reaction conditions. The experimental procedure was based on the measurement of the amount and the particle size distribution of the debris generated upon impact of sorbent samples against a target at velocities between 10 and 45 m/s. The effect of calcination, sulfation and calcination/re-carbonation on impact damage was assessed. Fragmentation by impact loading of the limestones was significant and increased with the impact velocity. Lime samples displayed the largest propensity to undergo impact damage, followed by sulfated, re-carbonated and raw limestones. Fragmentation of the sulfated samples followed a partem typical of the failure of brittle materials. On the other hand, the behavior of lime samples better conformed to a disintegration failure mode, with extensive generation of very fine fragments. Raw limestone and re-carbonated lime samples followed either of the two patterns depending on the sorbent nature. The extent of particle fragmentation increased after multiple impacts, but the incremental amount of fragments generated upon one impact decreased with the number of successive impacts.

  18. In-Cylinder Reaction Chemistry and Kinetics During Negative Valve Overlap Fuel Injection Under Low-Oxygen Conditions

    SciTech Connect

    Kalaskar, Vickey B; Szybist, James P; Splitter, Derek A; Pihl, Josh A; Gao, Zhiming; Daw, C Stuart

    2013-01-01

    Fuel injection into the negative valve overlap (NVO) period is a common method for controlling combustion phasing in homogeneous charge compression ignition (HCCI) as well as other forms of advanced combustion. During this event, at least a portion of the fuel hydrocarbons can be converted to products containing significant levels of H2 and CO, as well as other short chain hydrocarbons by means of thermal cracking, water-gas shift, and partial oxidation reactions, depending on the availability of oxygen and the time-temperature-pressure history. The resulting products alter the autoignition properties of the combined fuel mixture for HCCI. Fuel-rich chemistry in a partial oxidation environment is also relevant to other high efficiency engine concepts (e.g., the dedicated EGR (D-EGR) concept from SWRI). In this study, we used a unique 6-stroke engine cycle to experimentally investigate the chemistry of a range of fuels injected during NVO under low oxygen conditions. Fuels investigated included iso-octane, iso-butanol, ethanol, and methanol. Products from NVO chemistry were highly dependent on fuel type and injection timing, with iso-octane producing less than 1.5% hydrogen and methanol producing more than 8%. We compare the experimental trends with CHEMKIN (single zone, 0-D model) predictions using multiple kinetic mechanisms available in the current literature. Our primary conclusion is that the kinetic mechanisms investigated are unable to accurately predict the magnitude and trends of major species we observed.

  19. Reactions of transplanted neurocentral synchondroses to different conditions of mechanical stress. A methodological study on the rat.

    PubMed Central

    Rönning, O; Kylämarkula, S

    1979-01-01

    In order to elucidate the reactions of neurocentral synchondroses to different forces, the first cervical vertebra of 10 or 25 days old rats was transplanted into sex-matched litter mates. Some vertebrae were transplanted as a whole, in some only the ventral part with its synchondroses was transplanted and, in others the lumen was furnished with an expanding sponge or a spring. The transplantation was done subcutaneously and, in the case of the fragments, intracerebrally as well. The synchondroses of the vertebrae transplanted at 10 days did not differ very much from those of the host 5, 10 or 15 days after the operation, whereas in the vertebrae transplanted at 25 days the synchondroses underwent synostosis earlier than in situ. The synchondroses of the transplanted fragments, and especially of those placed intracerebrally, remained open longer than those in the whole vertebral transplants; the sponge and and the spring also delayed closure. In the synchondroses transplanted at 25 days there was a strong reduction in alcian blue staining, whereas in the spring loaded synchondroses the stainability persisted longer, maybe as an adaptation to the tensile force. It seems that the inherent potential of the neurocentral synchondroses to obliterate at a certain time can be altered by changing the biomechanical conditions. Images Fig. 2 Fig. 3 Fig. 4 Fig. 5 PMID:489467

  20. Optimization of reaction conditions to fabricate nano-silver using Couroupita guianensis Aubl. (leaf & fruit) and its enhanced larvicidal effect

    NASA Astrophysics Data System (ADS)

    Vimala, R. T. V.; Sathishkumar, Gnanasekar; Sivaramakrishnan, Sivaperumal

    2015-01-01

    Currently bioactive principles of plants and their nanoproducts have been extensively studied in agriculture and medicine. In this study Couroupita guianensis Aubl. leaf and fruit extracts were selected for rapid and cost-effective synthesis of silver nanoparticles (leaf-LAgNPs and fruit-FAgNPs). Various physiological conditions such as temperature, pH, concentration of metal ions, stoichiometric proportion of reaction mixture and reaction time showed influence on the size, dispersity and synthesis rate of AgNPs. Generation of AgNPs was initially confirmed with the surface plasmon vibrations at 420 nm in UV-visible spectrophotometer. The results recorded from X-ray diffractometer (XRD) and Transmission electron microscope (TEM) supports the biosynthesis of cubic crystalline LAgNPs & FAgNPs with the size ranges between 10-45 nm and 5-15 nm respectively. Surface chemistry of synthesized AgNPs was studied with Fourier transform infrared spectroscopy (FTIR), it reveals that water soluble phenolic compounds present in the extracts act as reducing and stabilizing agent. Leaf, fruit extracts and synthesized AgNPs were evaluated against IV instar larvae of Aedes aegypti (Diptera; Culicidae). Furthermore, different extracts and synthesized AgNPs showed dose dependent larvicidal effect against A. aegypti after 24 h of treatment. Compare to all extracts such as ethyl acetate (leaf; LC50 - 44.55 ppm and LC90 - 318.39 ppm & fruit; LC50 - 49.96 ppm and LC90 - 568.84 ppm respectively) and Methanol (leaf; LC50 - 85.75 ppm and LC90 - 598.63 ppm & fruit; LC50 - 67.78 ppm and LC90 - 714.45 ppm respectively) synthesized AgNPs showed extensive mortality rate (LAgNPs; LC50 - 2.1 ppm and LC90 - 5.59 ppm & FAgNPs; LC50 - 2.09 ppm and LC90 - 5.7 ppm). Hence, this study proves that C. guianensis is a potential bioresource for stable, reproducible nanoparticle synthesis (AgNPs) and also can be used as an efficient mosquito control agent.

  1. Optimization of reaction conditions to fabricate nano-silver using Couroupita guianensis Aubl. (leaf & fruit) and its enhanced larvicidal effect.

    PubMed

    Vimala, R T V; Sathishkumar, Gnanasekar; Sivaramakrishnan, Sivaperumal

    2015-01-25

    Currently bioactive principles of plants and their nanoproducts have been extensively studied in agriculture and medicine. In this study Couroupita guianensis Aubl. leaf and fruit extracts were selected for rapid and cost-effective synthesis of silver nanoparticles (leaf-LAgNPs and fruit-FAgNPs). Various physiological conditions such as temperature, pH, concentration of metal ions, stoichiometric proportion of reaction mixture and reaction time showed influence on the size, dispersity and synthesis rate of AgNPs. Generation of AgNPs was initially confirmed with the surface plasmon vibrations at 420 nm in UV-visible spectrophotometer. The results recorded from X-ray diffractometer (XRD) and Transmission electron microscope (TEM) supports the biosynthesis of cubic crystalline LAgNPs & FAgNPs with the size ranges between 10-45 nm and 5-15 nm respectively. Surface chemistry of synthesized AgNPs was studied with Fourier transform infrared spectroscopy (FTIR), it reveals that water soluble phenolic compounds present in the extracts act as reducing and stabilizing agent. Leaf, fruit extracts and synthesized AgNPs were evaluated against IV instar larvae of Aedes aegypti (Diptera; Culicidae). Furthermore, different extracts and synthesized AgNPs showed dose dependent larvicidal effect against A. aegypti after 24h of treatment. Compare to all extracts such as ethyl acetate (leaf; LC50 - 44.55 ppm and LC90 - 318.39 ppm & fruit; LC50 - 49.96 ppm and LC90 - 568.84 ppm respectively) and Methanol (leaf; LC50 - 85.75 ppm and LC90 - 598.63 ppm & fruit; LC50 - 67.78 ppm and LC90 - 714.45 ppm respectively) synthesized AgNPs showed extensive mortality rate (LAgNPs; LC50 - 2.1 ppm and LC90 - 5.59 ppm & FAgNPs; LC50 - 2.09 ppm and LC90 - 5.7 ppm). Hence, this study proves that C. guianensis is a potential bioresource for stable, reproducible nanoparticle synthesis (AgNPs) and also can be used as an efficient mosquito control agent.

  2. Combined temperature-programmed reaction and in-situ x-ray scattering studies of size-selected silver clusters under realistic reaction conditions in the epoxidation of propene.

    SciTech Connect

    Vajda, S.; Lee, S.; Sell, K.; Barke, I.; Kleibert, A.; von Oeynhausen, V.; Meiwes-Broer, K. H.; Rodriguez, A. F.; Elam, J. W.; Pellin, M. M.; Lee, B.; Seifert, S.; Winans, R. W.; Yale Univ.; Univ. Rostock; Swiss Light Source

    2009-09-28

    The catalytic activity and dynamical shape changes in size-selected nanoclusters at work are studied under realistic reaction conditions by using a combination of simultaneous temperature-programmed reaction with in situ grazing-incidence small angle x-ray scattering. This approach allows drawing a direct correlation between nanocatalyst size, composition, shape, and its function under realistic reaction conditions for the first time. The approach is illustrated in a chemical industry highly relevant selective partial oxidation of propene on a monodisperse silver nanocatalyst. The shape of the catalyst undergoes rapid change already at room temperature upon the exposure to the reactants, followed by a complex evolution of shape with increasing temperature. Acrolein formation is observed around 50 C while the formation of the propylene oxide exhibits a sharp onset at 80 C and is leveling off at 150 C. At lower temperatures acrolein is produced preferentially to propylene oxide; at temperatures above 100 C propylene oxide is favored.

  3. Acetamide hydrolyzing activity of Bacillus megaterium F-8 with bioremediation potential: optimization of production and reaction conditions.

    PubMed

    Sogani, Monika; Bakre, Prakash P; Mathur, Nupur; Sharma, Pratibha; Bhatnagar, Pradeep

    2014-01-01

    Bacillus megaterium F-8 exhibited an intracellular acetamide hydrolyzing activity (AHA) when cultivated in modified nutrient broth with 3% tryptone, 1.5% yeast extract, and 0.5% sodium chloride, at pH 7.2, 45 °C for 24 h. Maximum AHA was recorded in the culture containing 0.1 M of sodium phosphate buffer, (pH 7.5) at 45 °C for 20 min with 0.2 % of acetonitrile and resting cells of B. megaterium F-8 equivalent to 0.2 ml culture broth. This activity was stable up to 55 °C and was completely inactivated at or above 60 °C. Maximum acyl transferase activity (ATA) was recorded in the reaction medium containing 0.1 M of potassium phosphate buffer, (pH 8.0) at 55 °C for 5 min with 0.85 mM of acetamide as acyl donor and hydroxylamine hydrochloride as acyl acceptor and resting cells of B. megaterium F-8 equivalent to 0.94 mg cells (dry weight basis). This activity was stable up to 60 °C and a rapid decline in enzyme activity was recorded above it. Under the optimized conditions, this organism hydrolyzed various nitriles and amides such as propionitrile, propionamide, caprolactam, acetamide, and acrylamide to corresponding acids. Acyl group transfer capability of this organism was used for the production of acetohydroxamic acid. ATA of B. megaterium F-8 showed broad substrate specificity such as for acetamide followed by propionamide, acrylamide, and lactamide. This amide hydrolyzing and amidotransferase activity of B. megaterium F-8 has potential applications in enzymatic synthesis of hydroxamic acids and bioremediation of nitriles and amides contaminated soil and water system.

  4. Non-Precious Metals Catalyze Formal [4 + 2] Cycloaddition Reactions of 1,2-Diazines and Siloxyalkynes under Ambient Conditions

    PubMed Central

    2015-01-01

    Copper(I) and nickel(0) complexes catalyze the formal [4 + 2] cycloaddition reactions of 1,2-diazines and siloxyalkynes, a reaction hitherto best catalyzed by silver salts. These catalysts based on earth abundant metals are not only competent, but the copper catalyst, in particular, promotes cycloadditions of pyrido[2,3-d]pyridazine and pyrido[3,4-d]pyridazine, enabling a new synthesis of quinoline and isoquinoline derivatives, as well as the formal [2 + 2] cycloaddition reaction of cyclohexenone with a siloxyalkyne. PMID:24911346

  5. Determination of the in vivo NAD:NADH ratio in Saccharomyces cerevisiae under anaerobic conditions, using alcohol dehydrogenase as sensor reaction.

    PubMed

    Bekers, K M; Heijnen, J J; van Gulik, W M

    2015-08-01

    With the current quantitative metabolomics techniques, only whole-cell concentrations of NAD and NADH can be quantified. These measurements cannot provide information on the in vivo redox state of the cells, which is determined by the ratio of the free forms only. In this work we quantified free NAD:NADH ratios in yeast under anaerobic conditions, using alcohol dehydrogenase (ADH) and the lumped reaction of glyceraldehyde-3-phosphate dehydrogenase and 3-phosphoglycerate kinase as sensor reactions. We showed that, with an alternative accurate acetaldehyde determination method, based on rapid sampling, instantaneous derivatization with 2,4 diaminophenol hydrazine (DNPH) and quantification with HPLC, the ADH-catalysed oxidation of ethanol to acetaldehyde can be applied as a relatively fast and simple sensor reaction to quantify the free NAD:NADH ratio under anaerobic conditions. We evaluated the applicability of ADH as a sensor reaction in the yeast Saccharomyces cerevisiae, grown in anaerobic glucose-limited chemostats under steady-state and dynamic conditions. The results found in this study showed that the cytosolic redox status (NAD:NADH ratio) of yeast is at least one order of magnitude lower, and is thus much more reduced, under anaerobic conditions compared to aerobic glucose-limited steady-state conditions. The more reduced state of the cytosol under anaerobic conditions has major implications for (central) metabolism. Accurate determination of the free NAD:NADH ratio is therefore of importance for the unravelling of in vivo enzyme kinetics and to judge accurately the thermodynamic reversibility of each redox reaction.

  6. The catalytic effect of water, water dimers and water trimers on H2S + (3)O2 formation by the HO2 + HS reaction under tropospheric conditions.

    PubMed

    Zhang, Tianlei; Yang, Chen; Feng, Xukai; Kang, Jiaxin; Song, Liang; Lu, Yousong; Wang, Zhiyin; Xu, Qiong; Wang, Wenliang; Wang, Zhuqing

    2016-06-29

    In this article, the reaction mechanisms of H2S + (3)O2 formation by the HO2 + HS reaction without and with catalyst X (X = H2O, (H2O)2 and (H2O)3) have been investigated theoretically at the CCSD(T)/6-311++G(3df,2pd)//B3LYP/6-311+G(2df,2p) level of theory, coupled with rate constant calculations by using conventional transition state theory. Our results show that in the presence of catalyst X (X = H2O, (H2O)2 and (H2O)3) into the channel of H2S + (3)O2 formation, the reactions between the SH radical and HO2(H2O)n (n = 1-3) complexes are more favorable than the corresponding reactions of the HO2 radical with HS(H2O)n (n = 1-3) complexes due to the lower barrier of the former reactions and the higher concentrations of HO2(H2O)n (n = 1-3) complexes. Meanwhile, the catalytic effect of water, water dimers and water trimers is mainly taken from the contribution of a single water vapor molecule, since the total effective rate constant of HO2H2O + HS and H2OHO2 + HS reactions was, respectively, larger by 7-9 and 9-12 orders of magnitude than that of SH + HO2(H2O)2 and SH + HO2(H2O)3 reactions. Besides, the enhancement factor of water vapor is only 0.37% at 240 K, while at high temperatures, such as 425 K, the positive water vapor effect is enhanced up to 38.00%, indicating that at high temperatures the positive water effect is obvious under atmospheric conditions. Overall, these results show how water and water clusters catalyze the gas phase reactions under atmospheric conditions.

  7. Mechanistic Studies Lead to Dramatically Improved Reaction Conditions for the Cu-Catalyzed Asymmetric Hydroamination of Olefins

    PubMed Central

    2015-01-01

    Enantioselective copper(I) hydride (CuH)-catalyzed hydroamination has undergone significant development over the past several years. To gain a general understanding of the factors governing these reactions, kinetic and spectroscopic studies were performed on the CuH-catalyzed hydroamination of styrene. Reaction profile analysis, rate order assessment, and Hammett studies indicate that the turnover-limiting step is regeneration of the CuH catalyst by reaction with a silane, with a phosphine-ligated copper(I) benzoate as the catalyst resting state. Spectroscopic, electrospray ionization mass spectrometry, and nonlinear effect studies are consistent with a monomeric active catalyst. With this insight, targeted reagent optimization led to the development of an optimized protocol with an operationally simple setup (ligated copper(II) precatalyst, open to air) and short reaction times (<30 min). This improved protocol is amenable to a diverse range of alkene and alkyne substrate classes. PMID:26522837

  8. Efficient batch and continuous flow Suzuki cross-coupling reactions under mild conditions, catalysed by polyurea-encapsulated palladium (II) acetate and tetra-n-butylammonium salts.

    PubMed

    Lee, Connie K Y; Holmes, Andrew B; Ley, Steven V; McConvey, Ian F; Al-Duri, Bushra; Leeke, Gary A; Santos, Regina C D; Seville, Jonathan P K

    2005-04-28

    Suzuki cross-coupling reactions are effected in both conventional organic solvents, under continuous flow conditions at 70 degree C, and in batch mode in supercritical carbon dioxide (scCO2), at temperatures as low as 40 degrees C in the presence of palladium(II) acetate microencapsulated in polyurea [PdEnCat] and tetra-n-butylammonium salts.

  9. CATALYST-FREE REACTIONS UNDER SOLVENT-FEE CONDITIONS: MICROWAVE-ASSISTED SYNTHESIS OF HETEROCYCLIC HYDRAZONES BELOW THE MELTING POINT OF NEAT REACTANTS: JOURNAL ARTICLE

    EPA Science Inventory

    NRMRL-CIN-1437 Jeselnik, M., Varma*, R.S., Polanc, S., and Kocevar, M. Catalyst-free Reactions under Solvent-fee Conditions: Microwave-assisted Synthesis of Heterocyclic Hydrazones below the Melting Point of Neat Reactants. Published in: Chemical Communications 18:1716-1717 (200...

  10. A π-electronic covalent organic framework catalyst: π-walls as catalytic beds for Diels-Alder reactions under ambient conditions.

    PubMed

    Wu, Yang; Xu, Hong; Chen, Xiong; Gao, Jia; Jiang, Donglin

    2015-06-25

    We report a strategy for developing π-electronic covalent organic frameworks as heterogeneous catalysts that enable the use of columnar π-walls as catalytic beds to facilitate organic transformations in their one-dimensional open channels. The π-frameworks exhibit outstanding catalytic activity, promote Diels-Alder reactions under ambient conditions and are robust for cycle use.

  11. Metabolic and cardiorespiratory reactions in tennis-players in laboratory testing and under sport-specific conditions.

    PubMed

    Smekal, G; Baron, R; Pokan, R; Dirninger, K; Bachl, N

    1995-01-01

    Metabolic and cardiorespiratory reactions were investigated during a sport-specific incremental field test (FT) for tennis and compared with a treadmill step test (TT) in a group of 13 trained male tennis players. In both the FT and the TT lactate acid (La), heart rate and oxygen uptake (VO2) were measured. VO2 was determined using a portable telemetric system (K2, Cosmed, Italy). Aerobic- (AT) and anaerobic threshold (ANT) at a blood lactate concentration of 2 mmol/l and at 4 mmol/l respectively was indicated to characterize the endurance capacity of the athletes. In both FT and TT, minimum value of lactate equivalent (LE(min)), measured in every exercise test, was also registered. At AT and ANT values for HR (AT: p < 0.001; ANT: p < 0.001) and VO2 (AT: p < 0.001; ANT: p < 0.001) were significantly higher in FT than in TT at submaximal loads. At LE(min) only higher values for HR (p < 0.05) were registered in FT. In contrast to maximum range significantly higher values for VO2 (p < 0.001) could be seen in TT (there were no significant differences for HR). Comparing maximum lactate (La(max)) subjects reached a higher lactate (p < 0.05) in TT. A particular aim of our investigation was to characterize the individual cardiopulmonal and metabolic adaptation of tennis players, considering sport-specific criteria. As a result, differences in cardiorespiratory and metabolic adaptations could be determined between laboratory TT and FT. This finding seems to point to the fact that, using field testing in addition to laboratory exercise testing, makes a better judgement of aerobic and anaerobic endurance under sport-specific conditions possible. Furthermore, it was important for us to put data, determined in the field test into practice, using the given pattern of the field test as an element of training. This kind of training has the advantage of combining an individually intensity-controlled specific endurance training for tennis with a training of technical skills.

  12. Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

    2015-04-01

    Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

  13. Reaction to frustration in high and low feather pecking lines of laying hens from commercial or semi-natural rearing conditions.

    PubMed

    Rodenburg, T B; Koene, P; Spruijt, B M

    2004-02-27

    The effect of rearing conditions on feather pecking and reaction to frustration was studied in two lines of laying hens. From commercial rearing conditions (large group, no mother hen), seven birds from a high feather pecking line (HC birds) and eight birds from a low feather pecking line (LC birds) were used. From semi-natural rearing conditions (small group, mother hen present) seven birds from the high feather pecking line (HN birds) were used. Feather pecking behaviour of HC, LC, and HN groups was recorded for 30 min. After that, each bird was food deprived and trained to peck a key for a food reward in a Skinnerbox. After training, each bird was subjected to a frustration session in a Skinnerbox, where the feeder was covered with Perspex. Three HC birds showed severe feather pecking, compared with one HN bird and zero LC birds. Differences in reaction to frustration were found between birds from different lines, but not in birds from different rearing conditions. LC birds tended to put their head in the feeder more frequently than HC birds over all sessions. Although limited, this study indicates that rearing conditions influence feather pecking, but not reaction to frustration.

  14. A two-step reaction scheme leading to singlet carbene species that can be detected under matrix conditions for the reaction of Zr(3F) with either CH3F or CH3CN.

    PubMed

    Torres, Ana E; Castro, Guadalupe; Pablo-Pedro, Ricardo; Colmenares, Fernando

    2014-04-30

    The results obtained from CASSCF-MRMP2 calculations are used to rationalize the singlet complexes detected under matrix-isolation conditions for the reactions of laser-ablated Zr((3)F) atoms with the CH3F and CH3CN molecules, without invoking intersystem crossings between electronic states with different multiplicities. The reaction Zr((3)F) + CH3 F evolves to the radical products ZrF· + ·CH3. This radical asymptote is degenerate to that emerging from the singlet channel of the reactants Zr((1)D) + CH3 F because they both exhibit the same electronic configuration in the metal fragment. Hence, the caged radicals obtained under cryogenic-matrix conditions can recombine through triplet and singlet paths. The recombination of the radical species along the low-multiplicity channel produces the inserted structures H3C-Zr-F and H2C=ZrHF experimentally detected. For the Zr((3)F) + CH3 CN reaction, a similar two-step reaction scheme involving the radical fragments ZrNC· + ·CH3 explains the presence of the singlet complexes H C-Zr-NC and H2 C=Zr(H)NC revealed in the IR-matrix spectra upon UV irradiation.

  15. Universal reaction mechanism of boronic acids with diols in aqueous solution: kinetics and the basic concept of a conditional formation constant.

    PubMed

    Furikado, Yuki; Nagahata, Tomomi; Okamoto, Takuya; Sugaya, Tomoaki; Iwatsuki, Satoshi; Inamo, Masahiko; Takagi, Hideo D; Odani, Akira; Ishihara, Koji

    2014-10-06

    To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants (Ka(BL)) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red S, and phenylboronic acid and alizarin red S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a) the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b) the determined pKa values of HBLs. The use of the conditional formation constant, K', based on the main reaction: RB(OH)2 + H2L (K1)⇌ RB(L)(OH)(-) + H3O(+) instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B') with uncomplexed diol species (L') to form boronic acid diol complex species (esters, BL') in aqueous solution at pH 5-11: B' + L' (K')⇌ BL'. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution.

  16. In situ monitoring of the acetylene decomposition and gas temperature at reaction conditions for the deposition of carbon nanotubes using linear Raman scattering.

    PubMed

    Reinhold-López, Karla; Braeuer, Andreas; Popovska, Nadejda; Leipertz, Alfred

    2010-08-16

    To understand the reaction mechanisms taking place by growing carbon nanotubes via the catalytic chemical vapor deposition process, a strategy to monitor in situ the gas phase at reaction conditions was developed applying linear Raman spectroscopy. The simultaneous determination of the gas temperature and composition was possible by a new strategy of the evaluation of the Raman spectra. In agreement to the well-known exothermic decomposition of acetylene, a gas temperature increase was quantified when acetylene was added to the incident flow. Information about exhaust gas recirculation and location of the maximal acetylene conversion was derived from the composition measurements.

  17. A reaction cell with sample laser heating for in situ soft X-ray absorption spectroscopy studies under environmental conditions.

    PubMed

    Escudero, Carlos; Jiang, Peng; Pach, Elzbieta; Borondics, Ferenc; West, Mark W; Tuxen, Anders; Chintapalli, Mahati; Carenco, Sophie; Guo, Jinghua; Salmeron, Miquel

    2013-05-01

    A miniature (1 ml volume) reaction cell with transparent X-ray windows and laser heating of the sample has been designed to conduct X-ray absorption spectroscopy studies of materials in the presence of gases at atmospheric pressures. Heating by laser solves the problems associated with the presence of reactive gases interacting with hot filaments used in resistive heating methods. It also facilitates collection of a small total electron yield signal by eliminating interference with heating current leakage and ground loops. The excellent operation of the cell is demonstrated with examples of CO and H2 Fischer-Tropsch reactions on Co nanoparticles.

  18. Liquid-Assisted Grinding Accelerating: Suzuki-Miyaura Reaction of Aryl Chlorides under High-Speed Ball-Milling Conditions.

    PubMed

    Jiang, Zhi-Jiang; Li, Zhen-Hua; Yu, Jing-Bo; Su, Wei-Ke

    2016-10-21

    The effect of liquid-assisted grinding has been studied using mechanical Suzuki-Miyaura reaction of aryl chlorides as the model reaction. Catalytic systems of Davephos and PCy3 are tested respectively showing strong influences from different liquids. Unexpected improvement of yield over 55% is observed using alcohols as additives, which is explained by in situ formed alkoxides and their participation in oxidative addition. Further expansion of substrates using Pd(OAc)2/PCy3/MeOH system gives desired products in good to high yields.

  19. How Pragmatic Interpretations Arise from Conditionals: Profiling the Affirmation of the Consequent Argument with Reaction Time and EEG Measures

    ERIC Educational Resources Information Center

    Bonnefond, Mathilde; Van der Henst, Jean-Baptiste; Gougain, Marion; Robic, Suzanne; Olsen, Matthew D.; Weiss, Oshri; Noveck, Ira

    2012-01-01

    Conditional reasoning consists in combining a conditional premise with a categorical premise and inferring a conclusion from them. Two well-known conditional arguments are Modus Ponens (MP: "If P then Q; P//"therefore Q), which is logically valid and Affirmation of the Consequent (AC: "If P then Q; Q//"therefore "P"), which is not. The latter is…

  20. Relevance of the Channel Leading to Formaldehyde + Triplet Ethylidene in the O((3)P) + Propene Reaction under Combustion Conditions.

    PubMed

    Cavallotti, Carlo; Leonori, Francesca; Balucani, Nadia; Nevrly, Vaclav; Bergeat, Astrid; Falcinelli, Stefano; Vanuzzo, Gianmarco; Casavecchia, Piergiorgio

    2014-12-04

    Comprehension of the detailed mechanism of O((3)P) + unsaturated hydrocarbon reactions is complicated by the existence of many possible channels and intersystem crossing (ISC) between triplet and singlet potential energy surfaces (PESs). We report synergic experimental/theoretical studies of the O((3)P) + propene reaction by combining crossed molecular beams experiments using mass spectrometric detection at 9.3 kcal/mol collision energy (Ec) with high-level ab initio electronic structure calculations of the triplet PES and RRKM/master equation computations of branching ratios (BRs) including ISC. At high Ec's and temperatures higher than 1000 K, main products are found to be formaldehyde (H2CO) and triplet ethylidene ((3)CH3CH) formed in a reaction channel that has never been identified or considered significant in previous kinetics studies at 300 K and that, as such, is not included in combustion kinetics models. Global and channel-specific rate constants were computed and are reported as a function of temperature and pressure. This study shows that BRs of multichannel reactions useful for combustion modeling cannot be extrapolated from room-temperature kinetics studies.

  1. Exploring the Gas Phase Synthesis of the Elusive Class of Boronyls and the Mechanism of Boronyl Radical Reactions under Single Collision Conditions.

    PubMed

    Kaiser, Ralf I; Balucani, Nadia

    2016-12-19

    Until recently, the chemistry of boronyl (BO), a diatomic radical isolectronic with the cyano (CN) species, has remained unknown. The boronyl group is characterized by a boron-oxygen multiple bond, and because of the inherent electron deficiency of the boron atom, boronyls (RBO) are highly reactive and typically only exist in their cyclotrimeric form (RBO)3. Due to their invaluable role as reactants, the isolation of the monomers in gas phase experiments has been extensively sought after by the organic synthesis and physical organic chemistry communities but never achieved. Besides the interests from a physical organic and synthetic point of view, boronyls also play a role as reaction intermediates in boron-assisted rocket propulsion systems. In this Account, we review recent experimental work in which gas phase organo boronyl monomers (RBO) are formed via bimolecular reactions of the boronyl radical (BO) with C2-C6 unsaturated hydrocarbons. The investigated hydrocarbons are widely exploited as fuels, and their reactions with boronyl radicals under single collision conditions lead to the formation of organo boronyls. Our studies also elucidate the mechanisms of their formation reactions thus furnishing a comprehension at the molecular level of this reaction class. The variety of the employed hydrocarbon substrates has allowed us to systematically classify the chemical behavior of the boronyl radicals. With the exception of the case of the dimethylacetylene reaction, the boron monoxide radical versus atomic hydrogen exchange mechanisms were always open leading to the formation of highly unsaturated organo boronyl monomers (RBO), which could be easily identified because they cannot trimerize under single collision conditions. Besides the hydrogen displacement pathway, methylacetylene, dimethylacetylene, and propylene, carrying one or two methyl groups, were also found to eliminate a methyl group. In all systems, the reactions were barrierless, indirect, and initiated

  2. Production of High Galacto-oligosaccharides by Pectinex Ultra SP-L: Optimization of Reaction Conditions and Immobilization on Glyoxyl-Functionalized Silica.

    PubMed

    González-Delgado, Isabel; Segura, Yolanda; Morales, Gabriel; López-Muñoz, María-José

    2017-03-01

    A rational optimization for the synthesis of galacto-oligosaccharides (GOS) from lactose catalyzed by β-galactosidase from Aspergillus aculeatus, included in the commercial product Pectinex Ultra SP-L, has been performed by using experimental design and surface response methodology. This accurate tool optimized empirical production of the most desired high-GOS (tri-GOS and tetra-GOS) up to 16.4% under the following reaction conditions: 59 °C, 4 U/mL free enzyme concentration, pH 6.5, 250 g/L initial lactose concentration, and 20 h of reaction. The statistical analysis revealed temperature and initial lactose concentration as critical parameters. The successful immobilization of the enzyme on a glyoxyl-functionalized porous silica support slightly increased the yield toward high-GOS (17.6%), especially tri-GOS yield (15.3%), under the optimized reaction conditions as compared to the free enzyme. Furthermore, the promotion of the transgalactosylation reaction toward tri-GOS production increased 1.5-fold the productivity of high-GOS as compared to the free enzyme.

  3. Microwave-Assisted Condensation Reactions of Acetophenone Derivatives and Activated Methylene Compounds with Aldehydes Catalyzed by Boric Acid under Solvent-Free Conditions.

    PubMed

    Brun, Elodie; Safer, Abdelmounaim; Carreaux, François; Bourahla, Khadidja; L'helgoua'ch, Jean-Martial; Bazureau, Jean-Pierre; Villalgordo, Jose Manuel

    2015-06-23

    We here disclosed a new protocol for the condensation of acetophenone derivatives and active methylene compounds with aldehydes in the presence of boric acid under microwave conditions. Implementation of the reaction is simple, healthy and environmentally friendly owing to the use of a non-toxic catalyst coupled to a solvent-free procedure. A large variety of known or novel compounds have thus been prepared, including with substrates bearing acid or base-sensitive functional groups.

  4. [Change of character of directed motor reactions of female crickets Gryllus argentinus Sauss. to intraspecies signals under conditions of sensory pathology at different stages of adult ontogenesis].

    PubMed

    Zhemchuzhnikov, M K; Kniazev, A N

    2011-01-01

    The character of motor activity of female crickets Gryllus argentinus Sauss. was studied in norm and under conditions of inactivation of cercal organ at realization of reproductive and protective behavior at various steps of adult ontogenesis (at the 2nd, 7th, and 12th day). There are described and analyzed various forms of female motor reactions on a movable track-ball at presentation f models of male intraspecies call and aggressive signals. The reversible inactivation or cereal receptors was shown to lead to disturbance of mechanisms of realization of normal reproductive behavior in the end of prereproductive and in the beginning of reproductive periods of adult ontogenesis. This is manifested as a significant decrease of reactions of positive phonotaxis in response to presentation of model of the male call signal in individuals with experimental sensory pathology as compared with the control cricket group (norm). No significant differences in portions of typical directed motor reactions were established in norm and under conditions of sensory pathology at presentation of aggressive signal. Thus, we have managed to show that preservation of tympanal organ is the necessary, but not sufficient condition of realization of adequate acoustic reproductive behavior. Only by working together, the distant mechanoreceptor systems (the cereal and the tympanal ones) are able to provide adequate behavior. This confirmed to earlier put forward hypothesis about interaction of distant mechanoreceptor systems and about the existence of the single sensory complex necessary for realization of insect adequate behavior.

  5. C/H{sub 2}O reaction under supercritical conditions and their repercussions in the preparation of activated carbon

    SciTech Connect

    Salvador, F.; Senchez-Montero, M.J.; Izquierdo, C.

    2007-09-15

    Two chars prepared by carbonization of oak wood and anthracite were used to perform a comparative study of the gasification with supercritical water (SCW) and with steam. This work reports the effects of the type of char, the activating agent, temperature, flow rate, and particle size employed on the kinetics, mechanism of reaction, and the characteristics of the activated carbons obtained. The results show that the reactivity of the two chars is much higher with SCW than with steam. Although this increase can be explained in terms of the greater penetration of SCW and diffusional effects in the pore structure of the chars, some aspects suggest a possible change in the mechanism of reaction favored by the formation of clusters in SCW. The evolution of porosity was also found to differ when the char was gasified with SCW and with steam, being governed strongly by the starting material. When the oak char was activated with SCW, the smallest microporosity was broadened from the very first moments due to its very open pore structure, providing carbons with larger micropores and some mesoporosity. In contrast, in the case of the anthracite char, with a narrower pore structure, the evolution of the porosity was slower and less uniform, favoring external gasification of the particle. Accordingly, the carbons had a broader distribution of micropores, and mesoporosity was scarce.

  6. Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions

    SciTech Connect

    Zheng, Haiyan; Li, Kuo; Cody, George D.; Tulk, Christopher A.; Dong, Xiao; Gao, Guoying; Molaison, Jamie J.; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N.; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-kwang

    2016-08-25

    Acetonitrile (CH3CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. In this study, it is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH···N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp2 and sp3 bonded carbon. Lastly, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst.

  7. [Effects of several exorphins and endorphins on the escape reaction of the cockroach Periplaneta americana under elevated temperature conditions].

    PubMed

    Gritsaĭ, O B; Dubynin, V A; Bespalova, Zh D; Pilipenko, V E

    2009-01-01

    The ability of several alimentary opioid peptides (exorphin C, rubiscolin-5, cytochrophi-4) and endorphins (met-enkephalin, dynotphin A(1-10), beta-neoendorphin) to change the escape reaction of the cockroaches Periplaneta americana at their placement into a hot chamber was studied. The ED50 values increasing twice the insect stay time in the hot chamber as well as duration and dynamics of the effects were determined. It has been shown that ED5 decreases statistically significantly with increase of the length of the peptide molecule and its affinity of duration of the effects and to an increase of their affinity to delta-receptors - to prolongation of the reaction (more than150 min). In the group of alimentary peptides (exorphins) the most active was a fragment of D-ribulose-1,5-biphosphate carboxylase/oxigenase rubiscolin-5 (ED5 = 386 nM per individual). This might indicate a specific ability of some plant proteins to regulate (decrease) the insect protective behavior.

  8. Exploration of surface chemistry and structure of catalysts under reaction condition and during catalysis with surface-sensitive in-situ techniques

    NASA Astrophysics Data System (ADS)

    Tao, Franklin (Feng)

    2014-03-01

    In heterogeneous catalysis, each catalytic event occurs on a catalytic site. The catalytic site typically consists of a couple of or a few atoms of a catalyst which pack into a structure to offer specific electronic state to turn on a catalytic reaction. Surface structure and chemistry are the key for understanding a catalytic mechanism. From thermodynamic point of view, the surface structure of a catalyst depends on the environment of reactant gases or liquid around the catalyst. Thus, the surface chemistry and structure of a catalyst under a reaction condition or during catalysis (in an environment of reactant(s) with certainly pressure) could be different from those from ex-situ studies. In-situ surface science characterization techniques have been developed for disclosing the hidden surface chemistry and structure of catalysts under reaction conditions or during catalysis. In-situ ambient pressure XPS (AP-XPS) and ambient pressure STM (AP-STM) are two of these surface-sensitive techniques appropriate for exploring surface chemistry and structure, respectively. In this talk, I will present the origin of pressure dependent surface chemistry and structure from thermodynamic point of view. AP-XPS and AP-STM techniques will be introduced briefly. I will focus on (1) the evolution of surface composition and oxidation state of a reducible oxide and how the evolution is correlated to the corresponding catalytic performances, (2) the distribution of surface elements on surface of a bimetallic catalyst under a reaction condition and how a restructuring is used to generate a new surface with different catalytic performance, and (3) geometric restructuring of a metal catalyst surface at atomic scale and how it is related to its catalytic performances. This work is supported by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy under the grant DE-FG02-12ER1635.

  9. Encouraging conceptual change: the use of bridging analogies in the teaching of action reaction forces and the `at rest' condition in physics

    NASA Astrophysics Data System (ADS)

    Bryce, Tom; MacMillan, Kenneth

    2005-06-01

    The qualitative study described in this paper examined the effectiveness of bridging analogies intended to bring about conceptual change as part of a constructivist approach to teaching about action reaction forces in the ‘at rest’ condition in physics. Twenty-one 15-year-old students were involved in the investigation with subgroups previously exposed to different information regarding forces, weight and the accepted cause of the reaction force, in simple physical arrangements, including objects on tables. In-depth ‘think aloud’ interviews were used to track each student’s conceptual status as they worked with bridging analogies and transcript coding was carried out using open and axial coding (as in a grounded theory methodology). The findings showed that the bridging analogies were effective in engaging students with the idea of action reaction forces; students were adept in mapping each of the analogies to the target concept and using them to generate and refine their causal theories for the reaction force. There was evidence to suggest that, for some students, bridging analogies were more effective in bringing about conceptual change than didactic teaching. Their use extends beyond illustrative purposes and supports the development of meta-cognitive skills.

  10. Dynamic transformation of small Ni particles during methanation of CO2 under fluctuating reaction conditions monitored by operando X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Mutz, B.; Carvalho, H. W. P.; Kleist, W.; Grunwaldt, J.-D.

    2016-05-01

    A 10 wt.-% Ni/Al2O3 catalyst with Ni particles of about 4 nm was prepared and applied in the methanation of CO2 under dynamic reaction conditions. Fast phase transformations between metallic Ni, NiO and NiCO3 were observed under changing reaction atmospheres using operando X-ray absorption spectroscopy (XAS). Removing H2 from the feed gas and, thus, simulating a H2 dropout during the methanation reaction led to oxidation of the active sites. The initial reduced state of the Ni particles could not be recovered under methanation atmosphere (H2/CO2 = 4); this was only possible with an effective reactivation step applying H2 at increased temperatures. Furthermore, the cycling of the gas atmospheres resulted in a steady deactivation of the catalyst. Operando XAS is a powerful tool to monitor these changes and the behavior of the catalyst under working conditions to improve the understanding of the catalytic processes and deactivation phenomena.

  11. Externally controlled pressure and temperature microreactor for in situ x-ray diffraction, visual and spectroscopic reaction investigations under supercritical and subcritial conditions

    SciTech Connect

    Diefenbacher, J.; McKelvy, M.; Chizemeshya, A.V.; Wolf, G.H.

    2010-07-13

    A microreactor has been developed for in situ, spectroscopic investigations of materials and reaction processes with full external pressure and temperature control from ambient conditions to 400 C and 310 bar. The sample chamber is in direct contact with an external manifold, whereby gases, liquids or fluids can be injected and their activities controlled prior to and under investigation conditions. The microreactor employs high strength, single crystal moissanite windows which allow direct probe beam interaction with a sample to investigate in situ reaction processes and other materials properties. The relatively large volume of the cell, along with full optical accessibility and external temperature and pressure control, make this reaction cell well suited for experimental investigations involving any combination of gas, fluid, and solid interactions. The microreactor's capabilities are demonstrated through an in situ x-ray diffraction study of the conversion of a meta-serpentine sample to magnesite under high pressure and temperature. Serpentine is one of the mineral candidates for the implementation of mineral carbonation, an intriguing carbon sequestration candidate technology.

  12. Externally controlled pressure and temperature microreactor for in situ x-ray diffraction, visual and spectroscopic reaction investigations under supercritical and subcritical conditions

    SciTech Connect

    Diefenbacher, Jason; McKelvy, Michael; Chizmeshya, Andrew V.G.; Wolf, George H.

    2005-01-01

    A microreactor has been developed for in situ, spectroscopic investigations of materials and reaction processes with full external pressure and temperature control from ambient conditions to 400 deg. C and 310 bar. The sample chamber is in direct contact with an external manifold, whereby gases, liquids or fluids can be injected and their activities controlled prior to and under investigation conditions. The microreactor employs high strength, single crystal moissanite windows which allow direct probe beam interaction with a sample to investigate in situ reaction processes and other materials properties. The relatively large volume of the cell, along with full optical accessibility and external temperature and pressure control, make this reaction cell well suited for experimental investigations involving any combination of gas, fluid, and solid interactions. The microreactor's capabilities are demonstrated through an in situ x-ray diffraction study of the conversion of a meta-serpentine sample to magnesite under high pressure and temperature. Serpentine is one of the mineral candidates for the implementation of mineral carbonation, an intriguing carbon sequestration candidate technology.

  13. Impact of Flight Enthalpy, Fuel Simulant, and Chemical Reactions on the Mixing Characteristics of Several Injectors at Hypervelocity Flow Conditions

    NASA Technical Reports Server (NTRS)

    Drozda, Tomasz G.; Baurle, Robert A.; Drummond, J. Philip

    2016-01-01

    The high total temperatures or total enthalpies required to duplicate the high-speed flight conditions in ground experiments often place stringent requirements on the material selection and cooling needs for the test articles and intrusive flow diagnostic equipment. Furthermore, for internal flows, these conditions often complicate the use of nonintrusive diagnostics that need optical access to the test section and interior portions of the flowpath. Because of the technical challenges and increased costs associated with experimentation at high values of total enthalpy, an attempt is often made to reduce it. This is the case for the Enhanced Injection and Mixing Project (EIMP) currently underway in the Arc-Heated Scramjet Test Facility at the NASA Langley Research Center. The EIMP aims to investigate supersonic combustion ramjet (scramjet) fuel injection and mixing physics, improve the understanding of underlying physical processes, and develop enhancement strategies and functional relationships between mixing performance and losses relevant to flight Mach numbers greater than 8. The experiments will consider a "direct-connect" approach and utilize a Mach 6 nozzle to simulate the combustor entrance flow of a scramjet engine. However, while the value of the Mach number is matched to that expected at the combustor entrance in flight, the maximum value of the total enthalpy for these experiments is limited by the thermal-structural limits of the uncooled experimental hardware. Furthermore, the fuel simulant is helium, not hydrogen. The use of "cold" flows and non-reacting mixtures of fuel simulants for mixing experiments is not new and has been extensively utilized as a screening technique for scramjet fuel injectors. In this study, Reynolds-averaged simulations are utilized (RAS) to systematically verify the implicit assumptions used by the EIMP. This is accomplished by first performing RAS of mixing for two injector configurations at planned nominal experimental

  14. Anaphylaxis-Like Reactions

    MedlinePlus

    ... Home Conditions Anaphylaxis Anaphylaxis-Like Reactions Anaphylaxis-Like Reactions Make an Appointment Refer a Patient Ask a ... exposed to a foreign substance, some people suffer reactions identical to anaphylaxis, but no allergy (IgE antibody) ...

  15. A multi-scale model of the oxygen reduction reaction on highly active graphene nanosheets in alkaline conditions

    NASA Astrophysics Data System (ADS)

    Vazquez-Arenas, Jorge; Ramos-Sanchez, Guadalupe; Franco, Alejandro A.

    2016-10-01

    A multi-scale model based on a mean field approach, is proposed to describe the ORR mechanism on N-GN catalysts in alkaline media. The model implements activation energies calculated with Density Functional Theory (DFT) at the atomistic level, and scales up them into a continuum framework describing the cathode/electrolyte interface at the mesoscale level. The model also considers mass and momentum transports arising in the region next to the rotating electrode for all ionic species and O2; correction of potential drop and electrochemical double-layer capacitance. Most fitted parameters describing the kinetics of ORR elementary reactions are sensitive in the multi-scale model, which results from the incorporation of activation energies using the mean field method, unlike single-scale modelling Errors in the deviations from activation energies are found to be moderate, except for the elementary step (2) related to the formation of O2ads, which can be assigned to the inherent DFT limitations. The consumption of O2ads to form OOHads is determined as the rate-determining step as a result of its highest energy barrier (163.10 kJ mol-1) in the system, the largest error obtained for the deviation from activation energy (28.15%), and high sensitivity. This finding is confirmed with the calculated surface concentration and coverage of electroactive species.

  16. Reaction and transport in debonded wellbore casing-cement interfaces under CO2 storage conditions: From batch reaction tests to flow-through experiments on the 2m length scale

    NASA Astrophysics Data System (ADS)

    Wolterbeek, Tim; Peach, Colin; Spiers, Chris

    2014-05-01

    Debonding at interfaces between wellbore casing and cement is widely recognized as providing potential pathways for leakage from CO2 storage systems. This study addresses how the transport properties of such debonding-defects are affected by chemical reaction between cement, steel and CO2-bearing fluids. Our first set of experiments investigates near-static conditions, representative for stages prior to the formation of a fully connected defect network. Debonded cement-steel interfaces were simulated by constructing composite samples containing a spacer-imposed gap. Each sample was reacted with CO2 and an aqueous fluid, at 80°C and 14 MPa applied CO2 pressure, in seven sequential batch reaction runs (cumulative duration: 72 days). Permeability was measured after each run and microstructural analyses were performed after completion of the experiment. Reaction-induced permeability changes were limited, being less than one order of magnitude for all samples. Corrosion scale (Fe-carbonate, minor Fe-hydroxide) formed within the gap, on the surfaces of both the steel and cement. Here, the observed lack of Ca-carbonates suggests this corrosion scale produced a significant reduction in cement carbonation, similar to the decrease in corrosion rate observed when corrosion scale forms a protective film on steel. In contrast, Ca-carbonate did precipitate on the cement at locations beneath the spacers used to create the gap between the cement and steel plates, where corrosion scale did not form. Overall, the thin corrosion scale films on the cement surfaces seem to inhibit release of Ca from the cement into the gap and impede the precipitation of Ca- carbonates, which in other studies was found to promote sealing in fractured cement. Our batch reaction results imply that in local debonding-defects where corrosion scale development is insufficient to produce sealing, the scale's retarding effect on further reaction has the potential to maintain an open interfacial pathway

  17. The ReactorSTM: Atomically resolved scanning tunneling microscopy under high-pressure, high-temperature catalytic reaction conditions

    SciTech Connect

    Herbschleb, C. T.; Tuijn, P. C. van der; Roobol, S. B.; Navarro, V.; Bakker, J. W.; Liu, Q.; Stoltz, D.; Cañas-Ventura, M. E.; Verdoes, G.; Spronsen, M. A. van; Bergman, M.; Crama, L.; Taminiau, I.; Frenken, J. W. M.; Ofitserov, A.; Baarle, G. J. C. van

    2014-08-15

    To enable atomic-scale observations of model catalysts under conditions approaching those used by the chemical industry, we have developed a second generation, high-pressure, high-temperature scanning tunneling microscope (STM): the ReactorSTM. It consists of a compact STM scanner, of which the tip extends into a 0.5 ml reactor flow-cell, that is housed in a ultra-high vacuum (UHV) system. The STM can be operated from UHV to 6 bars and from room temperature up to 600 K. A gas mixing and analysis system optimized for fast response times allows us to directly correlate the surface structure observed by STM with reactivity measurements from a mass spectrometer. The in situ STM experiments can be combined with ex situ UHV sample preparation and analysis techniques, including ion bombardment, thin film deposition, low-energy electron diffraction and x-ray photoelectron spectroscopy. The performance of the instrument is demonstrated by atomically resolved images of Au(111) and atom-row resolution on Pt(110), both under high-pressure and high-temperature conditions.

  18. Model predictions of realgar precipitation by reaction of As(III) with synthetic mackinawite under anoxic conditions

    USGS Publications Warehouse

    Gallegos, T.J.; Han, Y.-S.; Hayes, K.F.

    2008-01-01

    This study investigates the removal of As(III) from solution using mackinawite, a nanoparticulate reduced iron sulfide. Mackinawite suspensions (0.1-40 g/L) effectively lower initial concentrations of 1.3 ?? 10 -5 M As(III) from pH 5-10, with maximum removal occurring under acidic conditions. Based on Eh measurements, it was found that the redox state of the system depended on the mackinawite solids concentration and pH. Higher initial mackinawite concentrations and alkaline pH resulted in a more reducing redox condition. Given this, the pH edge data were modeled thermodynamically using pe (-log[e-]) as a fitting parameter and linear pe-pH relationships within the range of measured Eh values as a function of pH and mackinawite concentration. The model predicts removal of As(III) from solution by precipitation of realgar with the formation of secondary oxidation products, greigite or a mixed-valence iron oxide phase, depending on pH. This study demonstrates that mackinawite is an effective sequestration agent for As(III) and highlights the importance of incorporating redox into models describing the As-Fe-S-H2O system. ?? 2008 American Chemical Society.

  19. The Impact of Non-Enzymatic Reactions and Enzyme Promiscuity on Cellular Metabolism during (Oxidative) Stress Conditions

    PubMed Central

    Piedrafita, Gabriel; Keller, Markus A; Ralser, Markus

    2015-01-01

    Cellular metabolism assembles in a structurally highly conserved, but functionally dynamic system, known as the metabolic network. This network involves highly active, enzyme-catalyzed metabolic pathways that provide the building blocks for cell growth. In parallel, however, chemical reactivity of metabolites and unspecific enzyme function give rise to a number of side products that are not part of canonical metabolic pathways. It is increasingly acknowledged that these molecules are important for the evolution of metabolism, affect metabolic efficiency, and that they play a potential role in human disease—age-related disorders and cancer in particular. In this review we discuss the impact of oxidative and other cellular stressors on the formation of metabolic side products, which originate as a consequence of: (i) chemical reactivity or modification of regular metabolites; (ii) through modifications in substrate specificity of damaged enzymes; and (iii) through altered metabolic flux that protects cells in stress conditions. In particular, oxidative and heat stress conditions are causative of metabolite and enzymatic damage and thus promote the non-canonical metabolic activity of the cells through an increased repertoire of side products. On the basis of selected examples, we discuss the consequences of non-canonical metabolic reactivity on evolution, function and repair of the metabolic network. PMID:26378592

  20. The Impact of Non-Enzymatic Reactions and Enzyme Promiscuity on Cellular Metabolism during (Oxidative) Stress Conditions.

    PubMed

    Piedrafita, Gabriel; Keller, Markus A; Ralser, Markus

    2015-09-10

    Cellular metabolism assembles in a structurally highly conserved, but functionally dynamic system, known as the metabolic network. This network involves highly active, enzyme-catalyzed metabolic pathways that provide the building blocks for cell growth. In parallel, however, chemical reactivity of metabolites and unspecific enzyme function give rise to a number of side products that are not part of canonical metabolic pathways. It is increasingly acknowledged that these molecules are important for the evolution of metabolism, affect metabolic efficiency, and that they play a potential role in human disease-age-related disorders and cancer in particular. In this review we discuss the impact of oxidative and other cellular stressors on the formation of metabolic side products, which originate as a consequence of: (i) chemical reactivity or modification of regular metabolites; (ii) through modifications in substrate specificity of damaged enzymes; and (iii) through altered metabolic flux that protects cells in stress conditions. In particular, oxidative and heat stress conditions are causative of metabolite and enzymatic damage and thus promote the non-canonical metabolic activity of the cells through an increased repertoire of side products. On the basis of selected examples, we discuss the consequences of non-canonical metabolic reactivity on evolution, function and repair of the metabolic network.

  1. Novel microchip for in situ TEM imaging of living organisms and bio-reactions in aqueous conditions.

    PubMed

    Liu, Kuo-Liang; Wu, Chien-Chen; Huang, Ying-Jung; Peng, Hwei-Ling; Chang, Hwan-You; Chang, Pin; Hsu, Long; Yew, Tri-Rung

    2008-11-01

    A novel and disposable microchip (K-kit) with SiO(2) nano-membranes was developed and used as a specimen kit for in situ imaging of living organisms in an aqueous condition using transmission electron microscopy (TEM) without equipment modification. This K-kit enabled the successful TEM observation of living Escherichia coli cells and the tellurite reduction process in Klebsiella pneumoniae. The K. pneumoniae and Saccharomyces cerevisiae can stay alive in K-kit after continuous TEM imaging for up to 14 s and 42 s, respectively. Besides, different tellurite reduction profiles in cells grown in aerobic and anaerobic environments can be clearly revealed. These results demonstrate that the K-kit developed in this paper can be useful for observing living organisms and monitoring biological processes in situ.

  2. Experimental Investigation of Augmented Spark Ignition of a LO2/LCH4 Reaction Control Engine at Altitude Conditions

    NASA Technical Reports Server (NTRS)

    Kleinhenz, Julie; Sarmiento, Charles; Marshall, William

    2012-01-01

    The use of nontoxic propellants in future exploration vehicles would enable safer, more cost-effective mission scenarios. One promising green alternative to existing hypergols is liquid methane (LCH4) with liquid oxygen (LO2). A 100 lbf LO2/LCH4 engine was developed under the NASA Propulsion and Cryogenic Advanced Development project and tested at the NASA Glenn Research Center Altitude Combustion Stand in a low pressure environment. High ignition energy is a perceived drawback of this propellant combination; so this ignition margin test program examined ignition performance versus delivered spark energy. Sensitivity of ignition to spark timing and repetition rate was also explored. Three different exciter units were used with the engine s augmented (torch) igniter. Captured waveforms indicated spark behavior in hot fire conditions was inconsistent compared to the well-behaved dry sparks. This suggests that rising pressure and flow rate increase spark impedance and may at some point compromise an exciter s ability to complete each spark. The reduced spark energies of such quenched deliveries resulted in more erratic ignitions, decreasing ignition probability. The timing of the sparks relative to the pressure/flow conditions also impacted the probability of ignition. Sparks occurring early in the flow could trigger ignition with energies as low as 1 to 6 mJ, though multiple, similarly timed sparks of 55 to 75 mJ were required for reliable ignition. Delayed spark application and reduced spark repetition rate both correlated with late and occasional failed ignitions. An optimum time interval for spark application and ignition therefore coincides with propellant introduction to the igniter.

  3. A carborane-derivative "click" reaction under heterogeneous conditions for the synthesis of a promising lipophilic MRI/GdBNCT agent.

    PubMed

    Toppino, Antonio; Bova, Maria Elena; Geninatti Crich, Simonetta; Alberti, Diego; Diana, Eliano; Barge, Alessandro; Aime, Silvio; Venturello, Paolo; Deagostino, Annamaria

    2013-01-07

    In this study, the Huisgen reaction has been used to functionalise a carborane cage with a lipophilic moiety and a 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) ligand to obtain a new Gd boron neutron-capture therapy (BNCT)/magnetic resonance imaging (MRI) agent. The introduction of the triazole units has been accomplished under both heterogeneous conditions, by the use of a Cu-supported ionic-liquid catalyst, and homogeneous conditions. The ability of the Gd complex of the synthesised ligand to form stable adducts with low-density lipoproteins (LDLs) has been evaluated and then MRI has been performed on tumour melanoma cells incubated in the presence of a Gd-complex/LDL imaging probe. It has been concluded that the high amount of intracellular boron necessary to perform BNCT can be reached even in the presence of a relatively low-boron-containing LDL concentration.

  4. A laboratory test setup for in situ measurements of the dielectric properties of catalyst powder samples under reaction conditions by microwave cavity perturbation: set up and initial tests.

    PubMed

    Dietrich, Markus; Rauch, Dieter; Porch, Adrian; Moos, Ralf

    2014-09-10

    The catalytic behavior of zeolite catalysts for the ammonia-based selective catalytic reduction (SCR) of nitrogen oxides (NOX) depends strongly on the type of zeolite material. An essential precondition for SCR is a previous ammonia gas adsorption that occurs on acidic sites of the zeolite. In order to understand and develop SCR active materials, it is crucial to know the amount of sorbed ammonia under reaction conditions. To support classical temperature-programmed desorption (TPD) experiments, a correlation of the dielectric properties with the catalytic properties and the ammonia sorption under reaction conditions appears promising. In this work, a laboratory test setup, which enables direct measurements of the dielectric properties of catalytic powder samples under a defined gas atmosphere and temperature by microwave cavity perturbation, has been developed. Based on previous investigations and computational simulations, a resonator cavity and a heating system were designed, installed and characterized. The resonator cavity is designed to operate in its TM010 mode at 1.2 GHz. The first measurement of the ammonia loading of an H-ZSM-5 zeolite confirmed the operating performance of the test setup at constant temperatures of up to 300 °C. It showed how both real and imaginary parts of the relative complex permittivity are strongly correlated with the mass of stored ammonia.

  5. A Laboratory Test Setup for in Situ Measurements of the Dielectric Properties of Catalyst Powder Samples under Reaction Conditions by Microwave Cavity Perturbation: Set up and Initial Tests

    PubMed Central

    Dietrich, Markus; Rauch, Dieter; Porch, Adrian; Moos, Ralf

    2014-01-01

    The catalytic behavior of zeolite catalysts for the ammonia-based selective catalytic reduction (SCR) of nitrogen oxides (NOX) depends strongly on the type of zeolite material. An essential precondition for SCR is a previous ammonia gas adsorption that occurs on acidic sites of the zeolite. In order to understand and develop SCR active materials, it is crucial to know the amount of sorbed ammonia under reaction conditions. To support classical temperature-programmed desorption (TPD) experiments, a correlation of the dielectric properties with the catalytic properties and the ammonia sorption under reaction conditions appears promising. In this work, a laboratory test setup, which enables direct measurements of the dielectric properties of catalytic powder samples under a defined gas atmosphere and temperature by microwave cavity perturbation, has been developed. Based on previous investigations and computational simulations, a resonator cavity and a heating system were designed, installed and characterized. The resonator cavity is designed to operate in its TM010 mode at 1.2 GHz. The first measurement of the ammonia loading of an H-ZSM-5 zeolite confirmed the operating performance of the test setup at constant temperatures of up to 300 °C. It showed how both real and imaginary parts of the relative complex permittivity are strongly correlated with the mass of stored ammonia. PMID:25211199

  6. Insight into chemoselectivity of nitroarene hydrogenation: A DFT-D3 study of nitroarene adsorption on metal surfaces under the realistic reaction conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Lidong; Cao, Xiao-Ming; Hu, P.

    2017-01-01

    The adsorption of nitrobenzene and 4-nitrostyrene on the Pt(111) and the Au(111) surfaces under the general reaction condition of nitroarene catalytic hydrogenation is investigated utilizing periodic density functional theory calculations with the Grimme's empirical three-body dispersion correction to understand the influence of adsorption configurations on chemoselectivity of nitroarene compound hydrogenation. It is found that at the low coverage both nitrobenzene and 4-nitrostyrene tend to adsorb paralleling to the Pt(111) and the Au(111) surfaces. Based on the crystal orbital Hamilton population analysis, it is found that the chemical bonding between nitro group and Pt(111) surface is weak. The adsorption configurations of nitrobenzene and 4-nitrostyrene are determined by the chemisorption strength of phenyl group and vinyl group. Under the reaction condition, the 1/9 ML nitrobenzene and 4/9 ML hydrogen atom can be coadsorbed while the 1/6 ML 4-nitrostyrene and 1/3 ML hydrogen atom can be coadsorbed on Pt(111). With the increase of the coverage, nitrobenzene still remains its paralleled adsorption configuration while the adsorption configuration of 4-nitrostyrene is switched to the tilted adsorption configuration through vinyl group without the chemisorption of phenyl and nitro group on Pt(111). In addition, the competitive adsorption with hydrogen will not change the adsorption configuration of nitrobenzene and 4-nitrostyrene under the reaction condition. On Au(111), the physical adsorption strength determines the adsorption configuration. The paralleled adsorption with the shortest average distance between the adsorbate and Au(111) surface is preferred. At the paralleled adsorption configuration, the chemoselectivities of the hydrogenation on these functional groups are similar if only in terms of geometric configuration. However, the hydrogenation on nitro group encounters the problem of steric hindrance at the tilted adsorption configuration through vinyl

  7. PAH formation under single collision conditions: reaction of phenyl radical and 1,3-butadiene to form 1,4-dihydronaphthalene.

    PubMed

    Kaiser, R I; Parker, D S N; Zhang, F; Landera, A; Kislov, V V; Mebel, A M

    2012-05-03

    The crossed beam reactions of the phenyl radical (C(6)H(5), X(2)A(1)) with 1,3-butadiene (C(4)H(6), X(1)A(g)) and D6-1,3-butadiene (C(4)D(6), X(1)A(g)) as well as of the D5-phenyl radical (C(6)D(5), X(2)A(1)) with 2,3-D2-1,3-butadiene and 1,1,4,4-D4-1,3-butadiene were carried out under single collision conditions at collision energies of about 55 kJ mol(-1). Experimentally, the bicyclic 1,4-dihydronaphthalene molecule was identified as a major product of this reaction (58 ± 15%) with the 1-phenyl-1,3-butadiene contributing 34 ± 10%. The reaction is initiated by a barrierless addition of the phenyl radical to the terminal carbon atom of the 1,3-butadiene (C1/C4) to form a bound intermediate; the latter underwent hydrogen elimination from the terminal CH(2) group of the 1,3-butadiene molecule leading to 1-phenyl-trans-1,3-butadiene through a submerged barrier. The dominant product, 1,4-dihydronaphthalene, is formed via an isomerization of the adduct by ring closure and emission of the hydrogen atom from the phenyl moiety at the bridging carbon atom through a tight exit transition state located about 31 kJ mol(-1) above the separated products. The hydrogen atom was found to leave the decomposing complex almost parallel to the total angular momentum vector and perpendicularly to the rotation plane of the decomposing intermediate. The defacto barrierless formation of the 1,4-dihydronaphthalene molecule involving a single collision between a phenyl radical and 1,3-butadiene represents an important step in the formation of polycyclic aromatic hydrocarbons (PAHs) and their partially hydrogenated counterparts in combustion and interstellar chemistry.

  8. Phosphorylation and dephosphorylation of spectrin from human erythrocyte ghosts under physiological conditions: autocatalysis rather than reaction with separate kinase and phosphatase.

    PubMed Central

    Imhof, B A; Acha-Orbea, H J; Libermann, T A; Reber, B F; Lanz, J H; Winterhalter, K H; Birchmeier, W

    1980-01-01

    The mechanism of phosphosylation and dephosphorylation of spectrin from human erythrocyte membranes has been examined under closely physiological conditions. The results support the hypothesis that spectrin is an autophosphorylating and dephosphorylating system. (i) Extraction from ghosts of up to 85% of the kinase (casein kinase) suggested to catalyze the reaction [see Fairbanks, G., Avruch, J., Dino, E. J. & Patel, V. P. (1978) J. Supramol. Struct. 9, 97--112] only slightly reduced spectrin component 2 phosphorylation and did not affect ATP-induced changes in the ghosts' shapes. (ii) A spectrin--actin complex isolated from endocytotic inside-out vesicles under hyperteonic conditions contained virtually no casein kinase activity and still exhibited a largely intact phosphorylation machinery. (iii) Photoaffinity labeling experiments indicated that spectrin component 2 fulfills the necessary prerequisite of the hypothesis--i.e., it contains its own ATP-binding site. (iv) Under various conditions, spectrin phosphorylation and dephospohrylation seem to be tightly coupled. The implications of these findings for the understanding of spectrin function and the maintenance of erythrocyte shape are discussed. Images PMID:6932020

  9. Phosphorylation and dephosphorylation of spectrin from human erythrocyte ghosts under physiological conditions: autocatalysis rather than reaction with separate kinase and phosphatase.

    PubMed

    Imhof, B A; Acha-Orbea, H J; Libermann, T A; Reber, B F; Lanz, J H; Winterhalter, K H; Birchmeier, W

    1980-06-01

    The mechanism of phosphosylation and dephosphorylation of spectrin from human erythrocyte membranes has been examined under closely physiological conditions. The results support the hypothesis that spectrin is an autophosphorylating and dephosphorylating system. (i) Extraction from ghosts of up to 85% of the kinase (casein kinase) suggested to catalyze the reaction [see Fairbanks, G., Avruch, J., Dino, E. J. & Patel, V. P. (1978) J. Supramol. Struct. 9, 97--112] only slightly reduced spectrin component 2 phosphorylation and did not affect ATP-induced changes in the ghosts' shapes. (ii) A spectrin--actin complex isolated from endocytotic inside-out vesicles under hyperteonic conditions contained virtually no casein kinase activity and still exhibited a largely intact phosphorylation machinery. (iii) Photoaffinity labeling experiments indicated that spectrin component 2 fulfills the necessary prerequisite of the hypothesis--i.e., it contains its own ATP-binding site. (iv) Under various conditions, spectrin phosphorylation and dephospohrylation seem to be tightly coupled. The implications of these findings for the understanding of spectrin function and the maintenance of erythrocyte shape are discussed.

  10. Catalytic reduction of NO by CO over rhodium catalysts. 2. Effect of oxygen on the nature, population, and reactivity of surface species formed under reaction conditions

    SciTech Connect

    Kondarides, D.I.; Chafik, T.; Verykios, X.E.

    2000-04-01

    The effect of oxygen on the nature, population, and reactivity of surface species formed during reduction of NO by CO over Rh/TiO{sub 2} catalysts has been examined employing FTIR and transient MS techniques. It has been found that the activity of Rh is hindered by accumulation of surface oxygen originating from NO decomposition and gas-phase oxygen in the feed. Adsorbed CO and reduced TiO{sub 2{minus}x} species in the vicinity of Rh particles act as oxygen atom scavengers and, under fuel-rich conditions, remove atomic oxygen from the surface and restore the catalytic properties. Results of the present study provide additional evidence that production of N{sub 2} is related to dissociation of adsorbed Rh-NO{sup {minus}} while production of N{sub 2}O is related to the presence of Rh(NO){sub 2}. The presence of reduced RH{sup 0} sites is necessary for the formation of both reduction products. In the absence of oxygen in the feed, surface isocyanate species are also observed under reaction conditions. Their formation requires the presence of adjacent Rh{sup 0}-CO and reduced Rh{sup 0} sites. Although these species are favored under conditions in which NO conversion to reduction products is observed, there is no evidence that they are catalytically active species.

  11. A series of phenyl sulfonate metal coordination polymers as catalysts for one-pot Biginelli reactions under solvent-free conditions.

    PubMed

    Wang, Jin-Hua; Tang, Gui-Mei; Wang, Yong-Tao; Cui, Yue-Zhi; Wang, Jun-Jie; Ng, Seik Weng

    2015-10-28

    Three new metal coordination polymers, namely, [Co(DPP)2(H2O)2]·(BS)2·2H2O (1), [Co(DPP)2(H2O)2]·(ABS)2·2H2O (2) and [Co(DPP)2(MBS)2] (3) [DPP = 1,3-di(pyridin-4-yl)propane, BS = phenyl sulfonic acid, ABS = p-aminobenzene sulfonic acid, MBS = p-methylbenzene sulfonic acid] were obtained under hydrothermal conditions. Complexes 1-3 were structurally characterized using X-ray single-crystal diffraction, XRD and IR spectroscopy. Both complexes 1 and 2 display a 1D tape structure. Meanwhile, complex 3 exhibits a 2D layer and further stacks via C-Hπ interactions to generate a three-dimensional supramolecular architecture. These three metal coordination polymers have been applied as catalysts for the green synthesis of a variety of 3,4-dihydropyrimidin-2(1H)-ones under solvent-free conditions through the Biginelli reaction. Interestingly, the catalysis products have been obtained in high yields under eco-friendly synthesis conditions.

  12. Dynamics of intracellular dopamine contents in the rat brain during the formation of conditioned contextual fear and extinction of an acoustic startle reaction.

    PubMed

    Storozheva, Z I; Afanas'ev, I I; Proshin, A T; Kudrin, V S

    2003-05-01

    Extracellular dopamine contents in the caudate nucleus, nucleus accumbens, and prefrontal cortex of the rat brain were measured during two sessions of extinction of an acoustic startle reaction--each consisting of ten sound stimuli, the two sessions separated by 24 h--with simultaneous recording of freezing behavior. The results demonstrated a decrease in extracellular dopamine levels in the caudate nucleus and an increase in the nucleus accumbens during both sessions of extinction, with return to initial immediately after sessions ended. During the second session, the amplitude of startle responses and the magnitude of changes in dopamine levels in both structures were significantly smaller than during the first session. Between the sessions, dopamine levels in the caudate nucleus remained constant, while those in the nucleus accumbens decreased. The prefrontal cortex showed increases in dopamine levels during both sessions of extinction, as well as between the two sessions. The amplitude of the startle reaction was found to correlate with dopamine levels in the prefrontal cortex after the end of the corresponding extinction session and with the dopamine level before the start of the second session. The freezing time before the start of sound stimulation in the second session, this being a measure of conditioned fear, correlated with the dopamine level in the caudate nucleus on the training day and with the dopamine level in the nucleus accumbens before the start of the second session. The role of the dopaminergic system in the mechanisms forming and realizing the various components of defensive behavior are discussed.

  13. Design of an in-house ambient pressure AP-XPS using a bench-top X-ray source and the surface chemistry of ceria under reaction conditions.

    PubMed

    Tao, Franklin Feng

    2012-04-21

    A new in-house ambient pressure XPS (AP-XPS) was designed for the study of surfaces of materials under reaction conditions and during catalysis. Unique features of this in-house AP-XPS are the use of monochromated Al Kα and integration of a minimized reaction cell, and working conditions of up to 500 °C in gases of tens of Torr. Generation of oxygen vacancies on ceria and filling them with oxygen atoms were characterized in operando.

  14. Role of the Support and Reaction Conditions on the Vapor-Phase Deoxygenation of m-Cresol over Pt/C and Pt/TiO2 Catalysts

    SciTech Connect

    Griffin, Michael B.; Ferguson, Glen A.; Ruddy, Daniel A.; Biddy, Mary J.; Beckham, Gregg T.; Schaidle, Joshua A.

    2016-04-01

    The catalytic deoxygenation of biomass fast pyrolysis vapors offers a promising route for the sustainable production of liquid transportation fuels. However, a clear understanding of the mechanistic details involved in this process has yet to be achieved, and questions remain regarding the role of the catalyst support and the influence of reaction conditions. In order to gain insight into these questions, the deoxygenation of m-cresol was investigated over Pt/C and Pt/TiO2 catalysts using experimental and computational techniques. The performance of each catalyst was evaluated in a packed-bed reactor under two conditions (523 K, 2.0 MPa and 623 K, 0.5 MPa), and the energetics of the ring hydrogenation, direct deoxygenation, and tautomerization mechanisms were calculated over hydrogen-covered Pt(111) and oxygen vacancies on the surface of TiO2(101). Over Pt(111), ring hydrogenation to 3-methylcyclohexanone and 3-methylcyclohexanol was found to be the most energetically favorable pathway. Over TiO2(101), tautomerization and direct deoxygenation to toluene were identified as additional energetically favorable routes. These calculations are consistent with the experimental data, in which Pt/TiO2 was more active on a metal site basis and exhibited higher selectivity to toluene at 623 K relative to Pt/C. On the basis of these results, it is likely that the reactivity of Pt/TiO2 and Pt/C is driven by the metallic phase at 523 K, while contributions from the TiO2 support enhance deoxygenation at 623 K. These results highlight the synergistic effects between hydrogenation catalysts and reducible metal oxide supports and provide insight into the reaction pathways responsible for their enhanced deoxygenation performance.

  15. Role of the Support and Reaction Conditions on the Vapor-Phase Deoxygenation of m-Cresol over Pt/C and Pt/TiO2 Catalysts

    DOE PAGES

    Griffin, Michael B.; Ferguson, Glen A.; Ruddy, Daniel A.; ...

    2016-03-23

    The catalytic deoxygenation of biomass fast pyrolysis vapors offers a promising route for the sustainable production of liquid transportation fuels. However, a clear understanding of the mechanistic details involved in this process has yet to be achieved, and questions remain regarding the role of the catalyst support and the influence of reaction conditions. In order to gain insight into these questions, the deoxygenation of m-cresol was investigated over Pt/C and Pt/TiO2 catalysts using experimental and computational techniques. The performance of each catalyst was evaluated in a packed-bed reactor under two conditions (523 K, 2.0 MPa and 623 K, 0.5 MPa),more » and the energetics of the ring hydrogenation, direct deoxygenation, and tautomerization mechanisms were calculated over hydrogen-covered Pt(111) and oxygen vacancies on the surface of TiO2(101). Over Pt(111), ring hydrogenation to 3-methylcyclohexanone and 3-methylcyclohexanol was found to be the most energetically favorable pathway. Over TiO2(101), tautomerization and direct deoxygenation to toluene were identified as additional energetically favorable routes. These calculations are consistent with the experimental data, in which Pt/TiO2 was more active on a metal site basis and exhibited higher selectivity to toluene at 623 K relative to Pt/C. On the basis of these results, it is likely that the reactivity of Pt/TiO2 and Pt/C is driven by the metallic phase at 523 K, while contributions from the TiO2 support enhance deoxygenation at 623 K. These results highlight the synergistic effects between hydrogenation catalysts and reducible metal oxide supports and provide insight into the reaction pathways responsible for their enhanced deoxygenation performance.« less

  16. Simulation of blast-furnace raceway conditions in a wire-mesh reactor: interference by the reactions of molybdenum mesh and initial results

    SciTech Connect

    Long Wu; N. Paterson; D.R. Dugwell; R. Kandiyoti

    2006-12-15

    A novel trapped air injection system has been built for a wire-mesh reactor to enable tests with short exposure times to air that are intended to simulate typical residence times in blast-furnace raceways. Initial tests have shown that the molybdenum wire-mesh sample-holder reacts with O{sub 2} under conditions intended for this work. By varying the proportions of solid MoO{sub 2} (weight gain), vapor phase oxides (weight loss) may form, depending on reaction conditions. Oxide formation pathways thus become relevant to coal weight loss determinations during experiments. If, in addition to solid MoO{sub 2} formation, significant formation of vapor phase oxides occurs, then the weight change is more complicated to understand and the impact on the O{sub 2} concentration cannot be unravelled. Furthermore, it turns out that O{sub 2}-scavenging by the mesh affects the amount of O{sub 2} that is available to react with the coal sample. It was concluded that it is only possible to conduct reliable tests under conditions which the favor the formation of solid MoO{sub 2} only, as this leads to a quantifiable weight gain. Its impact can then be accounted for in the evaluation of the experimental weight change. In the case of MoO{sub 2} formation, the impact of the mesh oxidation on the amount of O{sub 2} available to react with the sample can also be estimated. It has been found that the wire-mesh reactor, equipped with the trapped air injection system, can be used to obtain valid data at up to 1600{sup o} C and 0.5 MPa. This pressure is similar to that of the blast-furnace raceway, but the temperature is several hundred degrees lower. However, preliminary tests have shown that useful kinetic data on the extents of reaction can be obtained with the equipment, provided it is operated under conditions that minimize the formation of vapor phase Mo oxides. 18 refs., 13 figs., 3 tabs.

  17. Si-rich layer formation on olivine surfaces during reaction with water and supercritical carbon dioxide under conditions relevant for geologic carbon storage

    NASA Astrophysics Data System (ADS)

    Johnson, N. C.; Jackson, A.; Maher, K.; Bird, D. K.; Brown, G. E.

    2013-12-01

    The reaction of Mg-silicate minerals (i.e. olivine) with carbon dioxide (CO2) is a promising method for secure, long-term, geologic carbon storage. Several technical challenges must be overcome before implementing mineral carbonation technology on a large scale, one of which is slow reaction kinetics. This study probes surface reaction limitations of olivine carbonation, specifically the formation of a passivating, Si-rich layer on olivine surfaces upon exposure to water and CO2 under sequestration conditions (elevated temperature and pressure). A series of batch reactions were performed at 60°C and 100 bar CO2 pressure in Dickson-style rocker bombs, varying the length of reaction and the amount of mixing (rocking). The initial aqueous phase was spiked with 29Si. Fluid samples were taken periodically and analyzed for cation content, alkalinity, and dissolved inorganic carbon. At the end of each experiment, the solid products were analyzed with a Sensitive High Resolution Ion Microprobe Reverse Geometry (SHRIMP-RG) in order to measure the amount of 29Si incorporated into the Si-rich layer on reacted olivine grains. We also cut cross sections of reacted grains from each experiment using a Focused Ion Beam (FIB) which were thinned to <100nm and imaged using Transmission Electron Microscopy (TEM). SHRIMP-RG results show incorporation of 29Si on olivine grain surfaces reacted for 19 days with no mixing, and TEM images of olivine grains from the same experiment show an amorphous, Si-rich layer that is 30nm thick. Similarly, SHRIMP-RG results for olivine grains reacted for 19 days with mixing indicate 29SiO2 precipitation and TEM images reveal a Si-rich layer 60nm thick. In both experiments, EDS (energy dispersive spectroscopy) data show a step change in composition from the bulk rock to the surface layer in addition to the sharp crystalline/amorphous interface visible in the TEM images. Olivine from the unmixed experiment also has a slow decrease in Mg relative to Si

  18. The impact of raw materials and baking conditions on Maillard reaction products, thiamine, folate, phytic acid and minerals in white bread.

    PubMed

    Helou, Cynthia; Gadonna-Widehem, Pascale; Robert, Nathalie; Branlard, Gérard; Thebault, Jacques; Librere, Sarah; Jacquot, Sylvain; Mardon, Julie; Piquet-Pissaloux, Agnès; Chapron, Sophie; Chatillon, Antoine; Niquet-Léridon, Céline; Tessier, Frédéric J

    2016-06-15

    The aim of this study was to develop a white bread with improved nutrient contents and reduced levels of potentially harmful Maillard reaction products such as N(ε)-carboxymethyllysine (CML) and 5-hydroxymethylfurfural (HMF). Assays were carried out through a full factorial experimental design allowing the simultaneous analysis of four factors at two levels: (1) wheat flour extraction rates (ash content: 0.60%-0.72%), (2) leavening agents (bakers' yeast - bakers' yeast and sourdough), (3) prebaking and (4) baking conditions (different sets of time and temperature). The baking conditions affected HMF and CML as well as certain mineral contents. A reduced baking temperature along with a prolonged heat treatment was found to be favourable for reducing both the CML (up to 20%) and HMF concentrations (up to 96%). The presence of sourdough decreased the formation of CML (up to 28%), and increased the apparent amounts of calcium (up to 8%) and manganese (up to 17.5%) probably through acidification of the dough. The extraction rate of flours as well as interactions between multiple factors also affected certain mineral content. However, compounds like folate, thiamine, copper, zinc, iron and phytic acid were not affected by any of the factors studied.

  19. Reaction mechanism for the aqueous-phase mineral carbonation of heat-activated serpentine at low temperatures and pressures in flue gas conditions.

    PubMed

    Pasquier, Louis-César; Mercier, Guy; Blais, Jean-François; Cecchi, Emmanuelle; Kentish, Sandra

    2014-05-06

    Mineral carbonation is known as one of the safest ways to sequester CO2. Nevertheless, the slow kinetics and low carbonation rates constitute a major barrier for any possible industrial application. To date, no studies have focused on reacting serpentinite with a relatively low partial pressure of CO2 (pCO2) close to flue gas conditions. In this work, finely ground and heat-treated serpentinite [Mg3Si2O5(OH)4] extracted from mining residues was reacted with a 18.2 vol % CO2 gas stream at moderate global pressures to investigate the effect on CO2 solubility and Mg leaching. Serpentinite dissolution rates were also measured to define the rate-limiting step. Successive batches of gas were contacted with the same serpentinite to identify surface-limiting factors using scanning electron microscopy (SEM) analysis. Investigation of the serpentinite carbonation reaction mechanisms under conditions close to a direct flue gas treatment showed that increased dissolution rates could be achieved relative to prior work, with an average Mg dissolution rate of 3.55 × 10(-11) mol cm(-2) s(-1). This study provides another perspective of the feasibility of applying a mineral carbonation process to reduce industrial greenhouse gas (GHG) emissions from large emission sources.

  20. Free energy distribution and hydrothermal mineral precipitation in Hadean submarine alkaline vent systems: Importance of iron redox reactions under anoxic conditions

    NASA Astrophysics Data System (ADS)

    Shibuya, Takazo; Russell, Michael J.; Takai, Ken

    2016-02-01

    Thermodynamic calculations of mixing between hypothetical seawater and hydrothermal fluid in the Hadean deep ocean were carried out to predict saturation states of mineral precipitates and redox reactions that could occur in Hadean submarine alkaline hydrothermal systems associated with the serpentinization of ultramafic rocks. In the calculations, the seawater was assumed to be weakly acidic (pH = 5.5) and to include carbon dioxide, ferrous iron and silica, with or without nitrate, while the Hadean hydrothermal fluid was assumed to be highly alkaline (pH = 11) and to contain abundant molecular hydrogen, methane and bisulfide, based on the Archean geologic record, the modern low-temperature alkaline hydrothermal vent fluid (Lost City field), and experimental and theoretical considerations. The modeling indicates that potential mineral precipitates in the mixing zone (hydrothermal chimney structures) could consist mainly of iron sulfides but also of ferrous serpentine and brucite, siderite, and ferric iron-bearing minerals such as goethite, hematite and/or magnetite as minor phases. The precipitation of ferric iron-bearing minerals suggests that chemical iron oxidation would be made possible by pH shift even under anoxic condition. In the mixing zone, comprising an inorganic barrier precipitated at the interface of the two contrasting solutions, various redox reactions release free energy with the potential to drive endergonic reactions, assuming the involvement of coupling inorganic protoenzymes. Hydrogenotrophic methanogenesis and acetogenesis - long considered the most ancient forms of biological energy metabolisms - are able to achieve higher maximum energy yield (>0.5 kJ/kg hydrothermal fluid) than those in the modern serpentinization-associated seafloor hydrothermal systems (e.g., Kairei field). Furthermore, the recently proposed methanotrophic acetogenesis pathway was also thermodynamically investigated. It is known that methanotrophic acetogenesis would

  1. Impact of reaction conditions on the simultaneous production of polysaccharides and bio-oil from heterotrophically grown Chlorella sorokiniana by a unique sequential hydrothermal liquefaction process.

    PubMed

    Miao, Chao; Chakraborty, Moumita; Chen, Shulin

    2012-04-01

    A two-step sequential hydrothermal liquefaction (SEQHTL) model for simultaneous extraction of polysaccharide at the first step followed by bio-oil in the second was established. The effects of reaction temperature, residence time, and biomass/water ratio on the product distribution of each SEQHTL step were evaluated. Maximum yield (32wt.%) of polysaccharides was obtained at 160°C, 20min and 1:9 biomass/water ratio. Considering the operation cost and bio-oil yield (>30%); 240°C, 20min and 1:9 biomass/water ratio was preferred as ideal SEQHTL condition for bio-oil extraction. SEQHTL always produced ∼5% more bio-oil and ∼50% less bio-char than direct hydrothermal liquefaction (DHTL). Free fatty acid content of the bio-oils exhibited a sharp decrease with increase in temperature. Comparative analysis of the energy input and net energy balance showed that SEQHTL requires ∼15% less MJ/kg bio-oil than DHTL. Energy recovery rate for SEQHTL is nearly 4% higher than the DHTL.

  2. Combination of heterogeneous Fenton-like reaction and photocatalysis using Co-TiO₂nanocatalyst for activation of KHSO₅ with visible light irradiation at ambient conditions.

    PubMed

    Chen, Qingkong; Ji, Fangying; Guo, Qian; Fan, Jianping; Xu, Xuan

    2014-12-01

    A novel coupled system using Co-TiO₂was successfully designed which combined two different heterogeneous advanced oxidation processes, sulfate radical based Fenton-like reaction (SR-Fenton) and visible light photocatalysis (Vis-Photo), for degradation of organic contaminants. The synergistic effect of SR-Fenton and Vis-Photo was observed through comparative tests of 50mg/L Rhodamine B (RhB) degradation and TOC removal. The Rhodamine B degradation rate and TOC removal were 100% and 68.1% using the SR-Fenton/Vis-Photo combined process under ambient conditions, respectively. Moreover, based on XRD, XPS and UV-DRS characterization, it can be deduced that tricobalt tetroxide located on the surface of the catalyst is the SR-Fenton active site, and cobalt ion implanted in the TiO₂lattice is the reason for the visible light photocatalytic activity of Co-TiO₂. Finally, the effects of the calcination temperature and cobalt concentration on the synergistic performance were also investigated and a possible mechanism for the synergistic system was proposed. This coupled system exhibited excellent catalytic stability and reusability, and almost no dissolution of Co²⁺ was found.

  3. Effects of heat-moisture treatment reaction conditions on the physicochemical and structural properties of maize starch: moisture and length of heating.

    PubMed

    Sui, Zhongquan; Yao, Tianming; Zhao, Yue; Ye, Xiaoting; Kong, Xiangli; Ai, Lianzhong

    2015-04-15

    Changes in the properties of normal maize starch (NMS) and waxy maize starch (WMS) after heat-moisture treatment (HMT) under various reaction conditions were investigated. NMS and WMS were adjusted to moisture levels of 20%, 25% and 30% and heated at 100 °C for 2, 4, 8 and 16 h. The results showed that moisture content was the most important factor in determining pasting properties for NMS, whereas the heating length was more important for WMS. Swelling power decreased in NMS but increased in WMS, and while the solubility index decreased for both samples, the changes were largely determined by moisture content. The gelatinisation temperatures of both samples increased with increasing moisture content but remained unchanged with increasing heating length. The Fourier transform infrared (FT-IR) absorbance ratio was affected to different extents by the moisture levels but remained constant with increasing the heating length. The X-ray intensities increased but relative crystallinity decreased to a greater extent with increasing moisture content. This study showed that the levels of moisture content and length of heating had significant impacts on the structural and physicochemical properties of normal and waxy maize starches but to different extents.

  4. ENERGETICS TRANSFER IN THE PHOTODYNAMIC REACTIONS. I. PHOTODYNAMIC SENSITIVITY OF THE RETINA. II. PHOTODYNAMIC ACTION AND CANCER. III. PHOTOCHEMICAL SYNTHESIS OF AMINO ACIDS IN ABIOGENIC CONDITIONS.

    DTIC Science & Technology

    PHOTOSENSITIVITY(BIOLOGICAL), *CANCER, * AMINO ACIDS , RETINA, PHOTOCHEMICAL REACTIONS, RETINA, PATHOLOGY, RESPIRATION, GLYCOLYSIS, FISHES, ELECTROPHYSIOLOGY, FORMALDEHYDE, CATALYSTS, LIGHT, STIMULATION(PHYSIOLOGY), CHEMORECEPTORS, OXYGEN, ULTRAVIOLET RADIATION, MICE, ITALY.

  5. Comparison of human serum and bovine serum albumins on oxidation dynamics induced by talaporfin sodium photosensitization reaction with albumin rich conditions: solution experiments

    NASA Astrophysics Data System (ADS)

    Kurotsu, Mariko; Nakamura, Tetsuya; Takahashi, Mei; Ogawa, Emiyu; Arai, Tsunenori

    2014-02-01

    In order to understand extracellular-photosensitization reaction (PR) using talaporfin sodium, we studied comparison of oxidation dynamics of albumin and talaporfin sodium in solution system by visible and ultraviolet absorption spectrum measurements. Almost all talaporfin sodium particles may be bound to albumin in interstitial fluid, and this binding would affect the oxidation dynamics during this PR. Bovine serum albumin (BSA) is commonly used in vitro study but its binding characteristics with talaporfin sodium are different from human serum albumin (HSA). PR was operated in a solution composed of 20 μg/ml talaporfin sodium and 1.3 mg/ml HSA or BSA to simulate myocardial extracellular PR condition. Laser radiation of 662 nm was irradiated to this solution with irradiance of 0.29 W/cm2. Absorption spectra of these solutions were measured during the PR. We estimated oxidized ratio by absorption difference around 240 nm before and after the PR. Talaporfin sodium was oxidized 100% with HSA and BSA by the PR of 100 J/cm2 in radiant exposure. On the other hand, HSA and BSA were oxidized 60% and 94%, respectively in this radiant exposure. Q-band absorption peak of talaporfin sodium with HSA was shifted to 1 nm longer wavelength increasing radiant exposure up to 100 J/cm2. This longer wavelength shift would mean binding ratio of non-oxidized talaporfin sodium to non-oxidized HSA was increased with increasing radiant exposure. Therefore it would be possible that PR with talaporfin sodium bound to HSA might present efficient PDT than PR bound to BSA.

  6. Preventing Alkyne-Alkyne (i.e., Glaser) Coupling Associated with the ATRP Synthesis of Alkyne-Functional Polymers/Macromonomers and for Alkynes under Click (i.e., CuAAC) Reaction Conditions.

    PubMed

    Leophairatana, Porakrit; Samanta, Sanjoy; De Silva, Chathuranga C; Koberstein, Jeffrey T

    2017-03-15

    Alkyne-functional polymers synthesized by ATRP exhibit bimodal molecular weight distributions indicating the occurrence of some undesirable side reaction. By modeling the molecular weight distributions obtained under various reaction conditions, we show that the side reaction is alkyne-alkyne (i.e., Glaser) coupling. Glaser coupling accounts for as much as 20% of the polymer produced, significantly compromising the polymer functionality and undermining the success of subsequent click reactions in which they are used. Glaser coupling does not occur during ATRP but during postpolymerization workup upon first exposure to air. Two strategies are reported that effectively eliminate these coupling reactions without the need for a protecting group for the alkyne-functional initiator: (1) maintaining low temperature post-ATRP upon exposure to air followed by immediate removal of copper catalyst; (2) adding excess reducing agents post-ATRP which prevent the oxidation of Cu(I) catalyst required by the Glaser coupling mechanism. Post-ATRP Glaser coupling was also influenced by the ATRP synthesis ligand used. The order of ligand activity for catalyzing Glaser coupling was: linear bidentate > tridentate > tetradentate. We find that Glaser coupling is not problematic in ARGET-ATRP of alkyne-terminated polymers because a reducing agent is present during polymerization, however the molecular weight distribution is broadened compared to ATRP due to the presence of oxygen. Glaser coupling can also occur for alkynes held under CuAAC reaction conditions but again can be eliminated by adding appropriate reducing agents.

  7. Piper-betle-shaped nano-S-catalyzed synthesis of 1-amidoalkyl-2-naphthols under solvent-free reaction condition: a greener "nanoparticle-catalyzed organic synthesis enhancement" approach.

    PubMed

    Das, Vijay K; Borah, Madhurjya; Thakur, Ashim J

    2013-04-05

    Nano-S prepared by an annealing process showed excellent catalytic activity for the synthesis of 1-amidoalkyl-2-naphthols under solvent-free reaction condition at 50 °C. The catalyst could be reused up to the fifth cycle without loss in its action. The green-ness of the present protocol was also measured using green metrics drawing its superiority.

  8. High catalytic activity of palladium(II)-exchanged mesoporous sodalite and NaA zeolite for bulky aryl coupling reactions: reusability under aerobic conditions.

    PubMed

    Choi, Minkee; Lee, Dong-Hwan; Na, Kyungsu; Yu, Byung-Woo; Ryoo, Ryong

    2009-01-01

    Exchange for the better: Mesoporous sodalite and NaA zeolite exchanged with Pd(2+) exhibit remarkably high activity and reusability in C-C coupling reactions under aerobic atmosphere. It is proposed that the catalytic reactions are mediated by a molecular Pd(0) species generated in situ within the pores (see picture), which is oxidized back to Pd(2+) by O(2), preventing the formation of catalytically inactive Pd(0) agglomerates.

  9. Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications

    NASA Astrophysics Data System (ADS)

    Wu, Q. Q.; Huang, L. B.; Liang, H.; Zhao, Y.; Huang, D.; Chen, Z. M.

    2015-06-01

    Hydrogen peroxide (H2O2) and organic peroxides play important roles in the cycle of oxidants and the formation of secondary aerosols in the atmosphere. Recent field observations have suggested that the budget of peroxyacetic acid (PAA, CH3C(O)OOH) is potentially related to the aerosol phase processes, especially to secondary aerosol formation. Here, we present the first laboratory measurements of the uptake coefficient of gaseous PAA and H2O2 onto ambient fine particulate matter (PM2.5) as a function of relative humidity (RH) at 298 K. The results show that the PM2.5, which was collected in an urban area, can take up PAA and H2O2 at the uptake coefficient (γ) of 10-4, and both γPAA and γH2O2 increase with increasing RH. The value of γPAA at 90 % RH is 5.4 ± 1.9 times that at 3 % RH, whereas γH2O2 at 90 % RH is 2.4 ± 0.5 times that at 3 % RH, which suggests that PAA is more sensitive to the RH variation than H2O2 is. Considering the larger Henry's law constant of H2O2 than that of PAA, the smaller RH sensitivity of the H2O2 uptake coefficient suggests that the enhanced uptake of peroxide compounds on PM2.5 under humid conditions is dominated by chemical processes rather than dissolution. Considering that mineral dust is one of the main components of PM2.5 in Beijing, we also determined the uptake coefficients of gaseous PAA and H2O2 on authentic Asian Dust storm (ADS) and Arizona Test Dust (ATD) particles. Compared to ambient PM2.5, ADS shows a similar γ value and RH dependence in its uptake coefficient for PAA and H2O2, while ATD gives a negative dependence on RH. The present study indicates that, in addition to the mineral dust in PM2.5, other components (e.g., soluble inorganic salts) are also important to the uptake of peroxide compounds. When the heterogeneous reaction of PAA on PM2.5 is considered, its atmospheric lifetime is estimated to be 3.0 h on haze days and 7.1 h on non-haze days, values that are in good agreement with the field observations.

  10. Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications

    NASA Astrophysics Data System (ADS)

    Wu, Q. Q.; Huang, L. B.; Liang, H.; Zhao, Y.; Huang, D.; Chen, Z. M.

    2015-02-01

    Hydrogen peroxide (H2O2) and organic peroxides play important roles in the cycle of oxidants and the formation of secondary aerosols in the atmosphere. Recent field observations suggest that peroxyacetic acid (PAA, CH3C(O)OOH) is one of the most important organic peroxides in the atmosphere, whose budget is potentially related to the aerosols. Here we present the first laboratory measurements of the uptake coefficient of gaseous PAA and H2O2 onto the ambient fine particulate matter (PM2.5) as a function of relative humidity (RH) at 298 K. The results show that the PM2.5, which was collected in an urban area, can take up PAA and H2O2 at the uptake coefficient (γ) of 10-4, and both γPAA and γH2O2 increase with increasing RH. However, γPAA is more sensitive to the RH variation than is γH2O2, which indicates that the enhanced uptake of peroxide compounds on PM2.5 under humid conditions is dominated by chemical processes rather than dissolution. Considering that mineral dust is one of the main components of PM2.5, we also determined the uptake coefficients of gaseous PAA and H2O2 on authentic Asian Dust Storm (ADS) and Arizona Test Dust (ATD) particles. Compared to ambient PM2.5, ADS shows a similar γ value and RH dependence in its uptake coefficient for PAA and H2O2, while ATD gives a negative dependence on RH. The present study indicates that in addition to the mineral dust in PM2.5, other components (e.g., inorganic soluble salts) are also important to the uptake of peroxide compounds. When the heterogeneous reaction of PAA on PM2.5 is considered, its atmospheric lifetime is estimated to be 3.3 h on haze days and 7.6 h on non-haze days, values which agree well with the field observed result.

  11. The effect of restricted hydration on the rate of reaction of glucose 6-phosphate dehydrogenase, phosphoglucose isomerase, hexokinase and fumarase. Relevance for metabolism in xeric (near-dry) conditions

    PubMed Central

    Stevens, Evelyn; Stevens, Lewis

    1979-01-01

    A method is described for the measurement of enzyme activity under xeric conditions. The reaction mixtures had water contents ranging between 0.1 and 0.6g/g of reaction mixture. For glucose 6-phosphate dehydrogenase, hexokinase and fumarase, enzyme activity became detectable (about 0.05% of the fully hydrated rate) when the water content was about 0.2g/g of reaction mixture, and for phosphoglucose isomerase, around 0.15g/g of reaction mixture. With the water content raised to 0.3g/g of reaction mixture the reaction rates were only increased to 0.1–3% of the fully hydrated rate. When the combined rates for phosphoglucose isomerase and glucose 6-phosphate dehydrogenase were measured, reasonable agreement was found between the experimental data and those calculated from the individual experimentally determined rates on the assumption that diffusion was not further limiting. A method was devised for measuring the diffusion coefficients of low-molecular-weight substances in solutions having low water contents. The diffusion coefficients of riboflavin in sorbitol solution decreased by about 100-fold when the water content of the latter was reduced from 3 to 0.25g/g of sorbitol. It is concluded that to detect enzyme activity a certain minimal amount of water is required and that above this minimum the rate is still restricted by diffusion limitation. The relevance of the results to the physical state of water in reaction mixtures and to metabolism in seeds and spores in xeric conditions is discussed. PMID:475753

  12. MOF catalysis of Fe(II)-to-Fe(III) reaction for an ultrafast and one-step generation of the Fe2O3@MOF composite and uranium(vi) reduction by iron(ii) under ambient conditions.

    PubMed

    Xiong, Yang Yang; Li, Jian Qiang; Yan, Chang Sheng; Gao, Heng Ya; Zhou, Jian Ping; Gong, Le Le; Luo, Ming Biao; Zhang, Le; Meng, Pan Pan; Luo, Feng

    2016-08-07

    Herein, we demonstrate that Zn-MOF-74 enables the ultrafast and one-step generation of the Fe2O3@MOF composite once Zn-MOF-74 contacts with FeSO4 solution. This unique reaction can be further applied in catalysis of U(vi) reduction by Fe(ii) under ambient conditions. The results provide a highly renovated strategy for U(vi) reduction by Fe(ii) just under ambient conditions, which completely subvert all established methods about U(vi) reduction by Fe(ii) in which O2- and CO2-free conditions are absolutely required.

  13. Design, development, and demonstration of a fully LabVIEW controlled in situ electrochemical Fourier transform infrared setup combined with a wall-jet electrode to investigate the electrochemical interface of nanoparticulate electrocatalysts under reaction conditions.

    PubMed

    Nesselberger, Markus; Ashton, Sean J; Wiberg, Gustav K H; Arenz, Matthias

    2013-07-01

    We present a detailed description of the construction of an in situ electrochemical ATR-FTIR setup combined with a wall-jet electrode to investigate the electrocatalytic properties of nanoparticulate catalysts in situ under controlled mass transport conditions. The presented setup allows the electrochemical interface to be probed in combination with the simultaneous determination of reaction rates. At the same time, the high level of automation allows it to be used as a standard tool in electrocatalysis research. The performance of the setup was demonstrated by probing the oxygen reduction reaction on a platinum black catalyst in sulfuric electrolyte.

  14. Synthesis of [Sb2W20Fe2II(H2O)6O70](10-) with iron powder under mild conditions and its applications in both catalytic Fenton reaction and electrochemical sensing of ascorbic acid.

    PubMed

    Sun, Minghui; Li, Fengyan; Yu, Longjiao; Wang, Ya; Xu, Lin

    2016-02-14

    The first Krebs-type tungstoantimonate containing ferrous ions Na2H4[C3H5N2]4[Sb2W20Fe2(II)(H2O)6O70]·12H2O (1) was prepared by a new route of synthesis under mild reaction conditions. The facile synthesis route represented a favourable tactic for the successful synthesis of Fe(II)-based polyoxometalate. Its applications in both catalytic Fenton reaction and electrochemical sensing of ascorbic acid were also investigated primarily.

  15. Green synthesis of Pd/CuO nanoparticles by Theobroma cacao L. seeds extract and their catalytic performance for the reduction of 4-nitrophenol and phosphine-free Heck coupling reaction under aerobic conditions.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Bagherzadeh, Mojtaba

    2015-06-15

    We report the green synthesis of palladium/CuO nanoparticles (Pd/CuO NPs) using Theobroma cacao L. seeds extract and their catalytic activity for the reduction of 4-nitrophenol and Heck coupling reaction under aerobic conditions. The catalyst was characterized using the powder XRD, TEM, EDS, UV-vis and FT-IR. This method has the advantages of high yields, elimination of surfactant, ligand and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity.

  16. Suitable conditions for advanced oxidation process by the amount of ozone reaction and the amount of dioxin degradation in landfill leachate

    NASA Astrophysics Data System (ADS)

    Yoshikawa, Katsuhiko; Kanjo, Yoshinori; Matsufuji, Yasushi; Fukunaga, Isao; Urabe, Shinro; Yagi, Yoshio

    One of the processes to degrade dioxin in landfill leachate is the AOP(advanced oxidation process) method that uses ultraviolet rays or hydrogen peroxide together with ozone. In this research, we used the experimental result of the AOP method and applied to various kinds of experimental systems to determine the relationship between the amount of ozone reaction and the amount of dioxin degradation. The main results were as follows: The TOC(Total Organic Carbon) in the raw leachate consumed the supplied ozone by approximately 3.1(mgO3/mgTOC). It could be expressed in a linear equation between the ozone reaction amount revised by the TOC and the amount of dioxin degradation, and the slope was about 11.5(pgDXN/mgO3). A function of AOP can be expressed by comparing the quantity of suitable ozone reaction to the dioxin degradation. From the degradation ratio of each homologs, the degradation is mainly caused by the hydroxyl radical. To follow the dioxin discharge standard value, it is sufficient to guarantee the revised ozone reaction amount is more than 200mg/l.

  17. Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe{sub 2}O{sub 4} complex oxide catalyst

    SciTech Connect

    Pardeshi, Satish K.; Pawar, Ravindra Y.

    2010-05-15

    The CaFe{sub 2}O{sub 4} spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 {sup o}C which was lower than that of ferrite prepared by other methods. CaFe{sub 2}O{sub 4} catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H{sub 2}O{sub 2} (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 {+-} 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 {+-} 2 mol% and minor product phenyl acetaldehyde up to 9 {+-} 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H{sub 2}O{sub 2} molar ratio and solvents on the conversion and product distribution were studied.

  18. CATALYST-FREE REACTIONS UNDER SOLVENT-FEE CONDITIONS: MICROWAVE-ASSISTED SYNTHESIS OF HETEROCYCLIC HYDRAZONES BELOW THE MELTING POINT OF NEAT REACTANTS

    EPA Science Inventory

    The reaction of neat 5- or 8-oxobenzopyran-2(1H)-ones with a variety of aromatic and heteroaromatic hydrazines are remarkable accelerated upon irradiation in a household microwave oven in the absence of any catalyst, solid support or solvent thus providing an environmentally frie...

  19. Connecting the dots: Semi-analytical and random walk numerical solutions of the diffusion–reaction equation with stochastic initial conditions

    SciTech Connect

    Paster, Amir; Bolster, Diogo; Benson, David A.

    2014-04-15

    We study a system with bimolecular irreversible kinetic reaction A+B→∅ where the underlying transport of reactants is governed by diffusion, and the local reaction term is given by the law of mass action. We consider the case where the initial concentrations are given in terms of an average and a white noise perturbation. Our goal is to solve the diffusion–reaction equation which governs the system, and we tackle it with both analytical and numerical approaches. To obtain an analytical solution, we develop the equations of moments and solve them approximately. To obtain a numerical solution, we develop a grid-less Monte Carlo particle tracking approach, where diffusion is modeled by a random walk of the particles, and reaction is modeled by annihilation of particles. The probability of annihilation is derived analytically from the particles' co-location probability. We rigorously derive the relationship between the initial number of particles in the system and the amplitude of white noise represented by that number. This enables us to compare the particle simulations and the approximate analytical solution and offer an explanation of the late time discrepancies. - Graphical abstract:.

  20. Aldehyde-alcohol reactions catalyzed under mild conditions by chromium(III) terephthalate metal organic framework (MIL-101) and phosphotungstic acid composites.

    PubMed

    Bromberg, Lev; Hatton, T Alan

    2011-12-01

    Porous materials based on chromium(III) terephthalate metal organic frameworks (MIL-101) and their composites with phosphotungstic acid (PTA) were studied as heterogeneous acid catalysts in aldehyde-alcohol reactions exemplified by acetaldehyde-phenol (A-P) condensation and dimethylacetal formation from benzaldehyde and methanol (B-M reaction). The MIL-101 was synthesized solvothermically in water, and the MIL101/PTA composite materials were obtained by either impregnation of the already prepared MIL-101 porous matrix with phosphotungstic acid solution or by solvothermic treatment of aqueous mixtures of Cr(NO(3))(3), and terephthalic and phosphotungstic acids. The MIL101/PTA materials appeared to be effective catalysts for both A-P and B-M reactions occurring at room temperature, with half-lives ranging from 0.5 h (A-P) to 1.5-2 h (B-M) and turnover numbers over 600 for A-P and over 2900 for the B-M reaction, respectively. A synergistic effect of the strong acidic moieties (PTA) addition to mildly acidic Brønsted and Lewis acid cites of the MIL-101 was observed with the MIL101/PTA composites. The ability of the PTA and MIL101/PTA materials to strongly absorb and condense acetaldehyde vapors was discovered, with the MIL101/PTA absorbing over 10-fold its dry weight of acetaldehyde condensate at room temperature. The acetaldehyde was converted rapidly to crotonaldehyde and higher-molecular-weight compounds while in contact with MIL-101 and MIL101/PTA materials. The stability of the MIL-101 and MIL101/PTA catalysts was assessed within four cycles of the 1-day alcohol-aldehyde reactions in terms of the overall catalyst recovery, PTA or Cr content, and reaction rate constants in each cycle. The loss of the catalyst over 4 cycles was approximately 10 wt % for all tested catalysts due to the incomplete recovery and minute dissolution of the components. The reaction rates in all cycles remained unchanged and the catalyst losses stopped after the third cycle. The developed

  1. Reaction mechanism and optimal conditions for preparation of high-quality vanadium oxide films by organic sol-gel for optoelectronic applications

    NASA Astrophysics Data System (ADS)

    Sun, Minghui; Wen, Yuejiang; Xu, Xiangdong; Wang, Meng; He, Qiong; Jiang, Yadong; Dai, Zelin; Gu, Yu; Chen, Zhegeng

    2016-03-01

    Although vanadium oxides (VO x ) are important functional materials for academic research and industrial applications, the reaction mechanism of VO x prepared by organic sol-gel remains unclear. In order to investigate this mechanism, VO x organic sols were reacted at different temperatures, by which various VO x thin films were prepared. The products were systematically characterized by infrared spectroscopy, Raman spectroscopy, UV-vis spectroscopy, thermogravimetric analysis, scanning electron microscopy, x-ray diffraction, and a high resistance meter. Results reveal that vanadium alkoxides are created through an alcoholysis reaction of V2O5 powder and isobutyl alcohol, and then a condensation reaction of the vanadium alkoxides leads to the formation of VO x networks. The as-prepared sols are strongly temperature-dependent, causing different chemical structures and physical properties for the resulting VO x films. Particularly, a moderate temperature of 110 °C prompts both alcoholysis and condensation reactions, and thus the VO x films that are produced by the sol reacted at 110 °C possess a low resistivity of 23 Ω cm, a high temperature coefficient resistance (TCR) of  -3.2% K-1, and a low average transmittance of 54% in 580-1100 nm, compared with those prepared by the sols reacted at lower or higher temperatures. Therefore, 110 °C is a desirable sol temperature for producing VO x films serving as high-quality bolometric materials for uncooled infrared detectors. This work discloses not only the reaction mechanism of VO x films prepared by organic sol-gel, but also the route to yield desirable VO x films for optoelectronic applications.

  2. Dimethyl sulfoxide participant iron-mediated cascade oxidation/α-formylation reaction of substituted 2,3-dihydropyrroles under air and protonic acid free condition.

    PubMed

    Zhang, Zhiguo; Tian, Qing; Qian, Jingjing; Liu, Qingfeng; Liu, Tongxin; Shi, Lei; Zhang, Guisheng

    2014-09-05

    An efficient and Brønsted acid free one-pot protocol to directly generate structurally sophisticated α-formylpyrrole derivatives in moderate to good yields has been demonstrated, involving an iron-mediated domino oxidation/formylation reaction of readily available 2,3-dihydro-1H-pyrroles in dimethyl sulfoxide and air atmosphere, in which dimethyl sulfoxide acts as the formyl donor. A possible mechanism is presented.

  3. Mn(2+)-mediated homogeneous Fenton-like reaction of Fe(III)-NTA complex for efficient degradation of organic contaminants under neutral conditions.

    PubMed

    Li, Yifan; Sun, Jianhui; Sun, Sheng-Peng

    2016-08-05

    In this work, we report a novel Mn(2+)-mediated Fenton-like process based on Fe(III)-NTA complex that is super-efficient at circumneutral pH range. Kinetics experiments showed that the presence of Mn(2+) significantly enhanced the effectiveness of Fe(III)-NTA complex catalyzed Fenton-like reaction. The degradation rate constant of crotamiton (CRMT), a model compound, by the Fe(III)- NTA_Mn(2+) Fenton-like process was at least 1.6 orders of magnitude larger than that in the absence of Mn(2+). Other metal ions such as Ca(2+), Mg(2+), Co(2+) and Cu(2+) had no impacts or little inhibitory effect on the Fe(III)-NTA complex catalyzed Fenton-like reaction. The generation of hydroxyl radical (HO) and superoxide radical anion (O2(-)) in the Fe(III)-NTA_Mn(2+) Fenton-like process were suggested by radicals scavenging experiments. The degradation efficiency of CRMT was inhibited significantly (approximately 92%) by the addition of HO scavenger 2-propanol, while the addition of O2(-) scavenger chloroform resulted in 68% inhibition. Moreover, the results showed that other chelating agents such as EDTA- and s,s-EDDS-Fe(III) catalyzed Fenton-like reactions were also enhanced significantly by the presence of Mn(2+). The mechanism involves an enhanced generation of O2(-) from the reactions of Mn(2+)-chelates with H2O2, indirectly promoting the generation of HO by accelerating the reduction rate of Fe(III)-chelates to Fe(II)- chelates.

  4. Measurement of mutation and repair in mammalian cells/action of specific mutagens and antimutagens/genome exposure reaction in cancer and other disease conditions. Final subcontract report, April 1, 1996- March 31, 1996

    SciTech Connect

    Puck, T.T.

    1996-09-01

    This is the final report for the project dealing with the the measurement of mutation and repair in mammalian cells, action of specific mutagens and antimutagens, and genome exposure reaction in cancer and other disease conditions. The overall objectives of this research are threefold: to develop and improve methodology for measurement of mutation and repair in mammalian cells and to apply it to measurement of the effectiveness of mutagens, antimutagens, and other molecules to as to achieve greater power in prevention of cancer and genetic disease; to analyze theoretically and experimentally the action of specific mutagens and antimutagens; and to investigate the role of genome exposure reaction in cancer and other disease conditions to secure improve preventive and treatment modalities.

  5. Studies in Reaction to Disability. XII: Structure of Attitudes toward the Physically Disabled; Disability Factor Scales--Amputation, Blindness, Cosmetic Conditions.

    ERIC Educational Resources Information Center

    Siller, Jerome; And Others

    To describe and to develop instruments to measure attitudes toward amputees, the blind, and those with cosmetic conditions, three groups of subjects responded to one of three large pools of items tapping attitudes toward the three disability conditions. Three new groups of about 500 subjects of diverse demographic characteristics were given one of…

  6. Initial inhomogeneity-induced crazy-clock behavior in the iodate-arsenous acid reaction in a buffered medium under stirred batch conditions.

    PubMed

    Valkai, László; Csekő, György; Horváth, Attila K

    2015-09-14

    It is unambiguously demonstrated that in the case of an autocatalytic reaction, initial inhomogeneities induced by the imperfectly mixed part of the overall volume may result in a serious irreproducibility of the individual kinetic runs. A statistically meaningful number of repetitions, however, gives rise to a reproducible cumulative probability distribution curve often referred to as a support of the stochastic feature. The iodate-arsenous acid reaction being autocatalytic with respect to both iodide and hydrogen ions displays clock behavior. However, the time lag necessary for the appearance of iodine, even in buffered solution, varies in an apparently random manner. Careful analysis of the variation of the different parameters like stirring rate, overall volume, geometry of the reactor and the way of mixing the reactants led us to conclude that the fate of the individual samples is determined at the initial stage when the reacting system is per se inhomogeneous. The place, the size of the so-called ignition volume, where the reacting system is imperfectly stirred, as well as the residence time spent there by the imperfectly mixed reactants all seem to depend on external factors.

  7. The reaction rates of O2 with closed-shell and open-shell Al(x)⁻ and Ga(x)⁻ clusters under single-collision conditions: experimental and theoretical investigations toward a generally valid model for the hindered reactions of O2 with metal atom clusters.

    PubMed

    Neumaier, Marco; Olzmann, Matthias; Kiran, Boggavarapu; Bowen, Kit H; Eichhorn, Bryan; Stokes, Sarah T; Buonaugurio, Angela; Burgert, Ralf; Schnöckel, Hansgeorg

    2014-03-05

    In order to characterize the oxidation of metallic surfaces, the reactions of O2 with a number of Al(x)(-) and, for the first time, Ga(x)(-) clusters as molecular models have been investigated, and the results are presented here for x = 9-14. The rate coefficients were determined with FT-ICR mass spectrometry under single-collision conditions at O2 pressures of ~10(-8) mbar. In this way, the qualitatively known differences in the reactivities of the even- and odd-numbered clusters toward O2 could be quantified experimentally. To obtain information about the elementary steps, we additionally performed density functional theory calculations. The results show that for both even- and odd-numbered clusters the formation of the most stable dioxide species, [M(x)O2](-), proceeds via the less stable peroxo species, [M(x)(+)···O2(2-)](-), which contains M-O-O-M moieties. We conclude that the formation of these peroxo intermediates may be a reason for the decreased reactivity of the metal clusters toward O2. This could be one of the main reasons why O2 reactions with metal surfaces proceed more slowly than Cl2 reactions with such surfaces, even though O2 reactions with both Al metal and Al clusters are more exothermic than are reactions of Cl2 with them. Furthermore, our results indicate that the spin-forbidden reactions of (3)O2 with closed-shell clusters and the spin-allowed reactions with open-shell clusters to give singlet [M(x)(+)···O2(2-)](-) are the root cause for the observed even/odd differences in reactivity.

  8. Operando QEXAFS studies of Ni₂P during thiophene hydrodesulfurization: direct observation of Ni-S bond formation under reaction conditions.

    PubMed

    Wada, Takahiro; Bando, Kyoko K; Miyamoto, Takeshi; Takakusagi, Satoru; Oyama, S Ted; Asakura, Kiyotaka

    2012-03-01

    Structural changes in Ni(2)P/MCM-41 were followed by quick extended X-ray absorption fine structure (QEXAFS) and were directly related to changes in X-ray absorption near-edge structure (XANES) which had been used earlier for the study of the active catalyst phase. An equation is proposed to correct the transient QEXAFS spectra up to second-order in time to remove spectral distortions induced by structural changes occurring during measurements. A good correlation between the corrected QEXAFS and the XANES spectral changes was found, giving support to the conclusions derived from the XANES in the previous work, namely that the formation of a Ni-S bond in a surface NiPS phase is involved in the active site for the hydrodesulfurization reaction.

  9. An alkaline one-pot reaction to synthesize luminescent Eu-BTC MOF nanorods, highly pure and water-insoluble, under room conditions

    NASA Astrophysics Data System (ADS)

    Medina-Velazquez, D. Y.; Alejandre-Zuniga, B. Y.; Loera-Serna, S.; Ortiz, E. M.; Morales-Ramirez, A. de J.; Garfias-Garcia, E.; Garcia-Murillo, A.; Falcony, C.

    2016-12-01

    The increasing demand for optoelectronic devices requires the development of luminescent materials with high luminescence efficiency and low energy demands, and the metalorganic frameworks (MOFs) with lanthanides ions offer great potential in this area. The metalorganic materials provide properties of flexibility, low density, low-cost methods of synthesis, and insolubility in water, which gives them an advantage over traditional phosphors. In this study, a benzenetricarboxylate ligand (BTC) with a Eu3+ MOF was synthesized, and its structural and luminescent properties were measured. The metalorganic compound was generated in a one-pot reaction from europium nitrate and trimesic acid precursors. Through characterization by X-ray diffraction powder, infrared spectroscopy, SEM structural characterization, and luminescent spectroscopy, the formation of Europium benzenetricarboxylate (Eu-BTC) MOF nanorods was tested and the calculated value was in the range of 30-60 nm. A red luminescent emission with high intensity was observed for all the procedures.

  10. Establishment of conditions for the detection of bovine herpesvirus-1 by polymerase chain reaction using primers in the thymidine kinase region.

    PubMed Central

    Yason, C V; Harris, L M; McKenna, P K; Wadowska, D; Kibenge, F S

    1995-01-01

    Polymerase chain reaction (PCR) for detection of bovine herpesvirus-1 (BHV-1) was developed and optimized using 22 bp sense and 20 bp antisense primers in the thymidine kinase (TK) coding region. The amplification product is 183 bp long. The PCR optimization was done using BHV-1 tissue culture supernate (BHV-1TCS), concentrated BHV-1 tissue culture supernate (cBHV-1TCS) and sucrose gradient purified BHV-1 (pBHV-1). The sensitivity of four methods of sample preparation which are standard DNA extraction, modified proteinase K (PK) digestion, GeneReleaserTM + 34 cycles or + 44 cycles, and boiling were compared with virus isolation (VI) using BHV-1TCS. The incorporation of 10% glycerol in the reaction mixture, the incubation in PK for 18 hours and predenaturation of samples and cooling in ice prior to PCR were essential for the amplification of BHV-1 DNA for samples prepared by standard DNA extraction and modified PK digestion. The preparation of samples by Gene-ReleaserTM, a proprietary nucleic acid releasing cocktail, showed 10 to 1,000-fold increase in sensitivity compared to standard DNA extraction and modified PK digestion. No amplification was observed in samples prepared by boiling. The sample preparation of BHV-1 LA strain by GeneReleaserTM showed sensitivity equivalent to virus isolation. The BHV-1 TK PCR using GeneReleaserTM has a detection limit of 1 picogram and 10 fentograms of purified BHV-1 DNA using ethidium bromide stained gel and Southern blot hybridization, respectively. It could detect viral DNA in 1,000 infected cells in a total suspension of 10,000 cells using either ethidium bromide stained gel or Southern blot hybridization. Images Fig. 1. Fig. 2. Fig. 3. PMID:7648533

  11. Polyionic polymers – heterogeneous media for metal nanoparticles as catalyst in Suzuki–Miyaura and Heck–Mizoroki reactions under flow conditions

    PubMed Central

    Mennecke, Klaas

    2009-01-01

    Summary The preparation of monolithic polyionic supports which serve as efficient heterogeneous supports for palladium(0) nanoparticles is described. These functionalized polymers were incorporated inside a flow reactor and employed in Suzuki–Miyaura and Heck cross couplings under continuous flow conditions. PMID:19590749

  12. A new cascade-less engine operated from subsonic to hypersonic conditions: designed by computational fluid dynamics of compressible turbulence with chemical reactions

    NASA Astrophysics Data System (ADS)

    Naitoh, Ken; Nakamura, Kazushi; Emoto, Takehiro

    2010-12-01

    By using our computational fluid dynamic models, a new type of single engine capable of operating over a wide range of Mach numbers from subsonic to hypersonic regimes is proposed for airplanes, whereas traditional piston engines, turbojet engines, and scram engines work only under a narrower range of operating conditions. The new engine has no compressors or turbines such as those used in conventional turbojet engines. An important point is its system of super multijets that collide to compress gas for the transonic regime. Computational fluid dynamics is applied to clarify the potential of this engine. The peak pressure at the combustion center is over 2.5 MPa, while that just before ignition is over 1.0 MPa. The maximum power of this engine will be sufficient for actual use. Under the conditions of higher Mach numbers, the main intake passage located in front of the super multijet nozzles, takes in air more. That results in a ram or scramjet engine for supersonic and hypersonic conditions.

  13. Role of anions and reaction conditions in the preparation of uranium(VI), neptunium(VI), and plutonium(VI) borates.

    PubMed

    Wang, Shuao; Villa, Eric M; Diwu, Juan; Alekseev, Evgeny V; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2011-03-21

    U(VI), Np(VI), and Pu(VI) borates with the formula AnO(2)[B(8)O(11)(OH)(4)] (An = U, Np, Pu) have been prepared via the reactions of U(VI) nitrate, Np(VI) perchlorate, or Pu(IV) or Pu(VI) nitrate with molten boric acid. These compounds are all isotypic and consist of a linear actinyl(VI) cation, AnO(2)(2+), surrounded by BO(3) triangles and BO(4) tetrahedra to create an AnO(8) hexagonal bipyramidal environment. The actinyl bond lengths are consistent with actinide contraction across this series. The borate anions bridge between actinyl units to create sheets. Additional BO(3) triangles and BO(4) tetrahedra extend from the polyborate layers and connect these sheets together to form a three-dimensional chiral framework structure. UV-vis-NIR absorption and fluorescence spectroscopy confirms the hexavalent oxidation state in all three compounds. Bond-valence parameters are developed for Np(VI).

  14. Role of Anions and Reaction Conditions in the Preparation of Uranium(VI), Neptunium(VI), and Plutonium(VI) Borates

    SciTech Connect

    none,

    2011-02-03

    U(VI), Np(VI), and Pu(VI) borates with the formula AnO2[B8O11(OH)4] (An = U, Np, Pu) have been prepared via the reactions of U(VI) nitrate, Np(VI) perchlorate, or Pu(IV) or Pu(VI) nitrate with molten boric acid. These compounds are all isotypic and consist of a linear actinyl(VI) cation, AnO22+, surrounded by BO3 triangles and BO4 tetrahedra to create an AnO8 hexagonal bipyramidal environment. The actinyl bond lengths are consistent with actinide contraction across this series. The borate anions bridge between actinyl units to create sheets. Additional BO3 triangles and BO4 tetrahedra extend from the polyborate layers and connect these sheets together to form a three-dimensional chiral framework structure. UV-vis-NIR absorption and fluorescence spectroscopy confirms the hexavalent oxidation state in all three compounds. Bond-valence parameters are developed for Np(VI).

  15. Rate Constants for the Reactions of OH with CO, NO and NO2, and of HO2 with NO2 in the Presence of Water Vapour at Lower-Tropospheric Conditions

    NASA Astrophysics Data System (ADS)

    Rolletter, Michael; Fuchs, Hendrik; Novelli, Anna; Ehlers, Christian; Hofzumahaus, Andreas

    2016-04-01

    Recent studies have shown that the chemistry of gaseous nitrous acid (HONO) in the lower troposphere is not fully understood. Aside from heterogenous reactions, the daytime HONO formation in the gas-phase is not well understood (Li et al., Science, 2014). For a better understanding of HONO in the gas-phase, we have reinvestigated the reaction rate constants of important tropospheric reactions of the HOx radical family (OH and HO2) with nitrogen oxides at realistic conditions of the lower troposphere (at ambient temperature/pressure and in humid air). In this study we apply a direct pump and probe technique with high accuracy, using small radical concentrations to avoid secondary chemistry. Pulsed laser photolysis/laser-induced fluorescence (LP/LIF) was used to investigate the reaction rate constants of OH with CO, NO, NO2, and HO2 with NO2 in synthetic air at different water vapor concentrations (up to 5 x 1017 molecules cm-3). Photolysis of ozone in the presence of gaseous water was the source of OH. The reactions took place in a flow-tube at room temperature and atmospheric pressure. The chemical decay of the radicals was monitored by laser-induced fluorescence detection in a low-pressure cell, which sampled air continuously from the end of the flow-tube. Knowing the reactant concentrations subsequently allowed to calculate the bimolecular reaction rate constants at 1 atm from the pseudo-first-order decays. In order to observe HO2 reactions, OH was converted into HO2 with an excess of CO in the flow-tube. The newly measured rate constants for OH with CO, NO and NO2 agree very well with current recommendations by NASA/JPL and IUPAC and have an improved accuracy (uncertainty < 5%). These rate coefficients are independent of the presence of water vapour. The measured rate constant of HO2 with NO2 was found to depend significantly on the water-vapour concentration (probably due to formation of HO2*H2O complexes) and to exceed current recommendations by NASA/JPL and

  16. [Reaction of organism to the reduced partial oxygen pressure in inhaled air of highly-qualified female sportsmen in mountain condition].

    PubMed

    Radziievs'kyĭ, P O; Radziievs'ka, M P

    2006-01-01

    Functional respiration system (FRS) state and its changes in highly-qualified sportsmen after decrease of the O2 partial tension (pO2) in inhaled air was investigated. Significant decrease of oxygen regimen efficacy accompanied by alteration of FRS was registered in the first day of altitude hypoxia. In sportsmen well adapted to hypoxia and whose professional activity is associated with low and extremely low pO2 in inhaled air there are no changes in FRS after moving to mountain conditions.

  17. CO2 Reaction Induced Wettability Alteration and its Impacts on CO2 Storage: Pore to Core Scale Reservoir Condition Experimental Studies

    NASA Astrophysics Data System (ADS)

    Wan, J.; Tokunaga, T. K.; Kim, Y.; Jung, J.; Kim, T.; Dong, W.

    2013-12-01

    Wettability of the mineral surfaces plays an important role in subsurface multiphase flow and transport. Wettability affects the capillary pressure-saturation (Pc- S) relations, relative permeability (kr) of each fluid phase, and relative phase occupancy in reservoir pores. Although wettability issues have been studied extensively in other fields, significant knowledge gaps remain when applying the existing understanding to geological carbon sequestration; due largely to the unique physical-chemical properties of supercritical (sc) CO2 relative to other common non-wetting fluids such as air and oil. Here, we report our recent progress on wettability alteration upon reaction with CO2 and the resulting differences in capillary trapping of CO2 versus air. (1) Pore Scale Studies. There are conflict predictions in the literature concerning the effect of wettability on capillary trapping; some find that larger contact angles lead to lower capillary trapping while others have found opposite behavior. We hypothesized that spontaneous imbibition becomes energetically unfavorable with decreased wettability, so that increased residual trapping of scCO2 should occur during the post-injection inbibition stage. We developed a laboratory high-pressure and elevated temperature microscopic-micromodel system that is capable of controlling fine scale capillary pressure of scCO2-brine, and enabled us to conduct imbibition under controlled capillary pressures at the pore scale. We found that the de-wetting enhanced scCO2 capillary trapping is significant. These results suggest that scCO2 reaction induced dewetting can result in higher degrees of CO2 residual trapping in the post-injection stage than previously predicted. (2) Core Scale Studies. Capillary scaling is used routinely to predict Pc(S) relations for scCO2-brine systems at field scale, based on relations measured with air-water or mercury porosimetry. However, scaling-based predictions for CO2-brine systems have not been

  18. Role of chemical composition in the enhanced catalytic activity of Pt-based alloyed ultrathin nanowires for the hydrogen oxidation reaction under alkaline conditions

    SciTech Connect

    Megan E. Scofield; Wong, Stanislaus S.; Zhou, Yuchen; Yue, Shiyu; Wang, Lei; Su, Dong; Tong, Xiao; Vukmirovic, Miomir B.; Adzic, Radoslav R.

    2016-05-11

    With the increased interest in the development of hydrogen fuel cells as a plausible alternative to internal combustion engines, recent work has focused on creating alkaline fuel cells (AFC), which employ an alkaline environment. Working in alkaline as opposed to acidic media yields a number of tangible benefits, including (i) the ability to use cheaper and plentiful precious-metal-free catalysts, due to their increased stability, (ii) a reduction in the amount of degradation and corrosion of Pt-based catalysts, and (iii) a longer operational lifetime for the overall fuel cell configuration. However, in the absence of Pt, no catalyst has achieved activities similar to those of Pt. Herein, we have synthesized a number of crystalline ultrathin PtM alloy nanowires (NWs) (M = Fe, Co, Ru, Cu, Au) in order to replace a portion of the costly Pt metal without compromising on activity while simultaneously adding in metals known to exhibit favorable synergistic ligand and strain effects with respect to the host lattice. In fact, our experiments confirm theoretical insights about a clear and correlative dependence between measured activity and chemical composition. We have conclusively demonstrated that our as-synthesized alloy NW catalysts yield improved hydrogen oxidation reaction (HOR) activities as compared with a commercial Pt standard as well as with our as-synthesized Pt NWs. The Pt7Ru3 NW system, in particular, quantitatively achieved an exchange current density of 0.493 mA/cm2, which is higher than the corresponding data for Pt NWs alone. In addition, the HOR activities follow the same expected trend as their calculated hydrogen binding energy (HBE) values, thereby confirming the critical importance and correlation of HBE with the observed activities.

  19. Role of chemical composition in the enhanced catalytic activity of Pt-based alloyed ultrathin nanowires for the hydrogen oxidation reaction under alkaline conditions

    DOE PAGES

    Megan E. Scofield; Wong, Stanislaus S.; Zhou, Yuchen; ...

    2016-05-11

    With the increased interest in the development of hydrogen fuel cells as a plausible alternative to internal combustion engines, recent work has focused on creating alkaline fuel cells (AFC), which employ an alkaline environment. Working in alkaline as opposed to acidic media yields a number of tangible benefits, including (i) the ability to use cheaper and plentiful precious-metal-free catalysts, due to their increased stability, (ii) a reduction in the amount of degradation and corrosion of Pt-based catalysts, and (iii) a longer operational lifetime for the overall fuel cell configuration. However, in the absence of Pt, no catalyst has achieved activitiesmore » similar to those of Pt. Herein, we have synthesized a number of crystalline ultrathin PtM alloy nanowires (NWs) (M = Fe, Co, Ru, Cu, Au) in order to replace a portion of the costly Pt metal without compromising on activity while simultaneously adding in metals known to exhibit favorable synergistic ligand and strain effects with respect to the host lattice. In fact, our experiments confirm theoretical insights about a clear and correlative dependence between measured activity and chemical composition. We have conclusively demonstrated that our as-synthesized alloy NW catalysts yield improved hydrogen oxidation reaction (HOR) activities as compared with a commercial Pt standard as well as with our as-synthesized Pt NWs. The Pt7Ru3 NW system, in particular, quantitatively achieved an exchange current density of 0.493 mA/cm2, which is higher than the corresponding data for Pt NWs alone. In addition, the HOR activities follow the same expected trend as their calculated hydrogen binding energy (HBE) values, thereby confirming the critical importance and correlation of HBE with the observed activities.« less

  20. [The reaction of hormones of hypophysis-thyroid gland's endocrinal axis on vibration pathology and on condition of it's correction with liquid oxygen and anabolic steroids].

    PubMed

    Abzianidze, E N

    2007-06-01

    The experiment was held on white male rats. After the tests had been finished, by means of immunofermental method the concentration of thyroid (T3 and T4) and thyrotrophic (TSH) hormones were defined in the blood of animals in condition of vibropathology and it's correction with liquid oxygen and retabolil. The research showed, that the level of TSH, T3 and T4 decreased in condition of vibropathology and it's correction with anabolic steroid compare with control groups. But against of background liquid oxygen's injection the level of TSH increased, but the concentration of T3 and T4 were reduced compare with control group, though they were increased compare with the rest groups of experimental animals. As a result of the search, it was established, that the impact of vibration on the organism of male rats causes important changes in the hypophysis-thyroid gland's endocrinal axis, particularly it takes place the hypofunction of thyroid gland. And it's worth to mention that the correction of vibropathology with liquid oxygen cause positive influence and changes in the organism. There is a positively expressed normalization of thyroid and thyrotrophic hormones' concentration, but the correction of vibropathology with anabolic steroid has not been a successful one.

  1. Studying Biological Rhythms of Person's Skin-galvanic Reaction and Dynamics of Light Transmission by Isomeric Substance in Space Flight Conditions

    NASA Technical Reports Server (NTRS)

    Glushko, Vladimir

    2004-01-01

    Intensity and amplitude of human functional systems and human most important organs are wavelike, rhythmic by nature. These waves have constant periodicity, phase and amplitude. The mentioned characteristics can vary, however their variations have a pronounced reiteration in the course of time. This indicates a hashing of several wave processes and their interference. Stochastic changes in wave processes characteristics of a human organism are explained either by 'pulsations' associated with hashing (superposition) of several wave processes and their interference, or by single influence of environmental physical factors on a human organism. Human beings have respectively periods of higher and lower efficiency, state of health and so on, depending not only of environmental factors, but also of 'internal' rhythmic factor. Sometimes peaks and falls periodicity of some or other characteristics is broken. Disturbance of steady-state biological rhythms is usually accompanied by reduction of activity steadiness of the most important systems of a human organism. In its turn this has an effect on organism's adaptation to changing living conditions as well as on general condition and efficiency of a human being. The latter factor is very important for space medicine. Biological rhythmology is a special branch of biology and medicine, it studies rhythmic activity mechanisms of organs, their systems, individuals and species. Appropriate researches were also carried out in space medicine.

  2. Kinetic Evidence for Near Irreversible Nonionic Micellar Entrapment of N-(2′-Methoxyphenyl)phthalimide (1) under the Typical Alkaline Reaction Conditions

    PubMed Central

    Khan, M. Niyaz; Sim, Yoke-Leng; Ariffin, Azhar

    2014-01-01

    The values of pseudo-first-order rate constants (kobs) for alkaline hydrolysis of 1, obtained at 1.0 mM NaOH and within [ CmEnT] (total concentration of CmEn) range of 3.0–5.0 mM for C12E23 and 10–20 mM for C18E20, fail to obey pseudophase micellar (PM) model. The values of the fraction of near irreversible CmEn micellar trapped 1 molecules (FIT1) vary in the range ~0–0.75 for C12E23 and ~0–0.83 for C18E20 under such conditions. The values of FIT1 become 1.0 at ≥10 mM C12E23 and 50 mM C18E20. Kinetic analysis of the observed data at ≥10 mM C12E23 shows near irreversible micellar entrapment of 1 molecules under such conditions. PMID:24574900

  3. Reactions of (+)-catechin with salivary nitrite and thiocyanate under conditions simulating the gastric lumen: production of dinitrosocatechin and its thiocyanate conjugate.

    PubMed

    Takahama, U; Yamauchi, R; Hirota, S

    2014-08-01

    Catechins are ingested as food components and supplements. It is known that catechins are transformed to dinitrosocatechins by nitrite under acidic conditions, suggesting the possibility of their formation in the stomach because saliva contains nitrite. This paper deals with nitrite-induced transformation of (+)-catechin in methanol extracts of adzuki bean into 6,8-dinitrosocatechin in acidified saliva (pH ≈ 1.9). As the mechanism of its formation, addition of nitric oxide (NO) to (+)-catechin semiquinone radical, both of which were produced in nitrous acid/(+)-catechin systems, was proposed. The dinitrosocatechin was oxidized to the quinone by nitrous acid, and the quinone reacted with a salivary component thiocyanate producing 6'-thiocyanato-6,8-dinitrosocatechin. Since quinones are toxic, we propose a function of thiocyanate as a scavenger of the o-quinone formed from dinitrosocatechins in the stomach.

  4. Unsteady MHD Mixed Convection Slip Flow of Casson Fluid over Nonlinearly Stretching Sheet Embedded in a Porous Medium with Chemical Reaction, Thermal Radiation, Heat Generation/Absorption and Convective Boundary Conditions.

    PubMed

    Ullah, Imran; Bhattacharyya, Krishnendu; Shafie, Sharidan; Khan, Ilyas

    2016-01-01

    Numerical results are presented for the effect of first order chemical reaction and thermal radiation on mixed convection flow of Casson fluid in the presence of magnetic field. The flow is generated due to unsteady nonlinearly stretching sheet placed inside a porous medium. Convective conditions on wall temperature and wall concentration are also employed in the investigation. The governing partial differential equations are converted to ordinary differential equations using suitable transformations and then solved numerically via Keller-box method. It is noticed that fluid velocity rises with increase in radiation parameter in the case of assisting flow and is opposite in the case of opposing fluid while radiation parameter has no effect on fluid velocity in the forced convection. It is also seen that fluid velocity and concentration enhances in the case of generative chemical reaction whereas both profiles reduces in the case of destructive chemical reaction. Further, increase in local unsteadiness parameter reduces fluid velocity, temperature and concentration. Over all the effects of physical parameters on fluid velocity, temperature and concentration distribution as well as on the wall shear stress, heat and mass transfer rates are discussed in detail.

  5. Unsteady MHD Mixed Convection Slip Flow of Casson Fluid over Nonlinearly Stretching Sheet Embedded in a Porous Medium with Chemical Reaction, Thermal Radiation, Heat Generation/Absorption and Convective Boundary Conditions

    PubMed Central

    Ullah, Imran; Bhattacharyya, Krishnendu; Shafie, Sharidan; Khan, Ilyas

    2016-01-01

    Numerical results are presented for the effect of first order chemical reaction and thermal radiation on mixed convection flow of Casson fluid in the presence of magnetic field. The flow is generated due to unsteady nonlinearly stretching sheet placed inside a porous medium. Convective conditions on wall temperature and wall concentration are also employed in the investigation. The governing partial differential equations are converted to ordinary differential equations using suitable transformations and then solved numerically via Keller-box method. It is noticed that fluid velocity rises with increase in radiation parameter in the case of assisting flow and is opposite in the case of opposing fluid while radiation parameter has no effect on fluid velocity in the forced convection. It is also seen that fluid velocity and concentration enhances in the case of generative chemical reaction whereas both profiles reduces in the case of destructive chemical reaction. Further, increase in local unsteadiness parameter reduces fluid velocity, temperature and concentration. Over all the effects of physical parameters on fluid velocity, temperature and concentration distribution as well as on the wall shear stress, heat and mass transfer rates are discussed in detail. PMID:27776174

  6. Gene Expression Reaction Norms Unravel the Molecular and Cellular Processes Underpinning the Plastic Phenotypes of Alternanthera Philoxeroides in Contrasting Hydrological Conditions

    PubMed Central

    Gao, Lexuan; Geng, Yupeng; Yang, Hongxing; Hu, Yonghong; Yang, Ji

    2015-01-01

    Alternanthera philoxeroides is an amphibious invasive weed that can colonize both aquatic and terrestrial habitats. Individuals growing in different habitats exhibit extensive phenotypic variation but little genetic differentiation. Little is known about the molecular basis underlying environment-induced phenotypic changes. Variation in transcript abundance in A. philoxeroides was characterized throughout the time-courses of pond and upland treatments using RNA-Sequencing. Seven thousand eight hundred and five genes demonstrated variable expression in response to different treatments, forming 11 transcriptionally coordinated gene groups. Functional enrichment analysis of plastically expressed genes revealed pathway changes in hormone-mediated signaling, osmotic adjustment, cell wall remodeling, and programmed cell death, providing a mechanistic understanding of the biological processes underlying the phenotypic changes in A. philoxeroides. Both transcriptional modulation of environmentally sensitive loci and environmentally dependent control of regulatory loci influenced the plastic responses to the environment. Phenotypic responses and gene expression patterns to contrasting hydrological conditions were compared between A. philoxeroides and its alien congener Alternanthera pungens. The terricolous A. pungens displayed limited phenotypic plasticity to different treatments. It was postulated based on gene expression comparison that the interspecific variation in plasticity between A. philoxeroides and A. pungens was not due to environmentally-mediated changes in hormone levels but to variations in the type and relative abundance of different signal transducers and receptors expressed in the target tissue. PMID:26617628

  7. Retrospective clinical and molecular analysis of conditioned laboratory dogs (Canis familiaris) with serologic reactions to Ehrlichia canis, Borrelia burgdorferi, and Rickettsia rickettsii.

    PubMed

    Scorpio, Diana G; Wachtman, Lynn M; Tunin, Richard S; Barat, Nicole C; Garyu, Justin W; Dumler, J Stephen

    2008-09-01

    Dogs are susceptible to different tickborne infections, including members of the Anaplasmataceae (Ehrlichia canis, E. ewingii, E. chaffeensis, Anaplasma phagocytophilum, A. platys), Borrelia burgdorferi, and Rickettsia rickettsii. These diseases can manifest with clinical signs including fever, anorexia, malaise, lameness, rash, and bleeding episodes; however, these signs are nonpathognomonic, and infections can occur in the absence of clinical signs. Hematologic abnormalities can include leukopenia, thrombocytopenia, hyperproteinemia and hypergammaglobulinemia. In biomedical research, diseases such as canine monocytic ehrlichiosis, Lyme disease, and Rocky Mountain spotted fever may cause morbidity among exposed dogs and confound research results. Random-source dogs are susceptible to these diseases because of their increased risk of arthropod exposure. Nonpurpose bred, randomly selected conditioned dogs (n = 21) were examined; blood samples were taken for hematology, biochemistry analysis, tickborne pathogen serology, and PCR. Of these, 2 dogs (10% of the population) presented with illness characterized by fever, malaise, lameness, or hemostatic abnormalities, and 15 (71%) had antibodies to one or more tickborne pathogens. No specific hematologic or biochemical differences were apparent between seronegative dogs and seropositive dogs reactive to all 3 pathogens. E. canis and B. burgdorferi PCR of tissues and blood were negative for all dogs. PCR amplification of several Ehrlichia and Anaplasma genes yielded no positive samples. From this cohort of dogs, serologic and molecular results indicate prior exposure without active infection or clinical disease. Exposure to and potential for infection with these bacteria and other pathogens may contribute to blood and tissue alterations that could confound experiments and lead to misinterpretation of data in canine models.

  8. Reaction-space analysis of homogeneous charge compression ignition combustion with varying levels of fuel stratification under positive and negative valve overlap conditions

    SciTech Connect

    Kodavasal, Janardhan; Lavoie, George A.; Assanis, Dennis N.; Martz, Jason B.

    2015-10-26

    injection. The final study evaluated positive valve overlap and negative valve overlap valve events with direct injection. Furthermore, relative to positive valve overlap, the negative valve overlap condition had a wider reactivity stratification, a longer burn duration and higher NO and CO emissions associated with reduced fuel–air mixing.

  9. Reaction-space analysis of homogeneous charge compression ignition combustion with varying levels of fuel stratification under positive and negative valve overlap conditions

    DOE PAGES

    Kodavasal, Janardhan; Lavoie, George A.; Assanis, Dennis N.; ...

    2015-10-26

    evaluated positive valve overlap and negative valve overlap valve events with direct injection. Furthermore, relative to positive valve overlap, the negative valve overlap condition had a wider reactivity stratification, a longer burn duration and higher NO and CO emissions associated with reduced fuel–air mixing.« less

  10. Anthemis xylopoda flowers aqueous extract assisted in situ green synthesis of Cu nanoparticles supported on natural Natrolite zeolite for N-formylation of amines at room temperature under environmentally benign reaction conditions.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Hatamifard, Arezo

    2015-12-15

    Zeolites, which are nontoxic, abundant, and cheap, are very promising supports for the design and preparation of new and environmentally benign catalysts. In this study, Cu nanoparticles (NPs) were immobilized on the surface of natural Natrolite zeolite by Anthemis xylopoda flowers aqueous extract as a reducing and stabilizing agent. Afterward, the catalytic performance of the prepared catalyst was investigated for N-formylation of amines at room temperature under environmentally benign reaction conditions. The catalyst could be reused at least 5 times without any decrease in activity. The advantages of the present protocol include the use of green catalyst, easy isolation of the products, reusability of catalyst, absence of nontoxic reagents, and excellent yield of the products.

  11. Role of the Support and Reaction Conditions on the Vapor-Phase Deoxygenation of m-Cresol over Pt/C and Pt/TiO2 Catalysts

    SciTech Connect

    Griffin, Michael B.; Ferguson, Glen A.; Ruddy, Daniel A.; Biddy, Mary J.; Beckham, Gregg T.; Schaidle, Joshua A.

    2016-03-23

    The catalytic deoxygenation of biomass fast pyrolysis vapors offers a promising route for the sustainable production of liquid transportation fuels. However, a clear understanding of the mechanistic details involved in this process has yet to be achieved, and questions remain regarding the role of the catalyst support and the influence of reaction conditions. In order to gain insight into these questions, the deoxygenation of m-cresol was investigated over Pt/C and Pt/TiO2 catalysts using experimental and computational techniques. The performance of each catalyst was evaluated in a packed-bed reactor under two conditions (523 K, 2.0 MPa and 623 K, 0.5 MPa), and the energetics of the ring hydrogenation, direct deoxygenation, and tautomerization mechanisms were calculated over hydrogen-covered Pt(111) and oxygen vacancies on the surface of TiO2(101). Over Pt(111), ring hydrogenation to 3-methylcyclohexanone and 3-methylcyclohexanol was found to be the most energetically favorable pathway. Over TiO2(101), tautomerization and direct deoxygenation to toluene were identified as additional energetically favorable routes. These calculations are consistent with the experimental data, in which Pt/TiO2 was more active on a metal site basis and exhibited higher selectivity to toluene at 623 K relative to Pt/C. On the basis of these results, it is likely that the reactivity of Pt/TiO2 and Pt/C is driven by the metallic phase at 523 K, while contributions from the TiO2 support enhance deoxygenation at 623 K. These results highlight the synergistic effects between hydrogenation catalysts and reducible metal oxide supports and provide insight into the reaction pathways responsible for their enhanced deoxygenation performance.

  12. FACILITATED CHEMICAL SYNTHESIS UNDER ALTERNATE REACTION CONDITIONS

    EPA Science Inventory

    The chemical research in the late 1990's witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into the atmo...

  13. Drug Reactions

    MedlinePlus

    Most of the time, medicines make our lives better. They reduce aches and pains, fight infections, and control problems such as high blood pressure or diabetes. But medicines can also cause unwanted reactions. One problem is ...

  14. Title: Elucidation of Environmental Fate of Artificial Sweeteners (Aspartame, Acesulfame K and Saccharin) by Determining Bimolecular Rate Constants with Hydroxyl Radical at Various pH and Temperature Conditions and Possible Reaction By-Products

    NASA Astrophysics Data System (ADS)

    Teraji, T.; Arakaki, T.; Suzuka, T.

    2012-12-01

    Use of artificial sweeteners in beverages and food has been rapidly increasing because of their non-calorie nature. In Japan, aspartame, acesulfame K and sucralose are among the most widely used artificial sweeteners. Because the artificial sweeteners are not metabolized in human bodies, they are directly excreted into the environment without chemical transformations. We initiated a study to better understand the fate of artificial sweeteners in the marine environment. The hydroxyl radical (OH), the most potent reactive oxygen species, reacts with various compounds and determines the environmental oxidation capacity and the life-time of many compounds. The steady-state OH concentration and the reaction rate constants between the compound and OH are used to estimate the life-time of the compound. In this study, we determine the bimolecular rate constants between aspartame, acefulfame K and saccharin and OH at various pH and temperature conditions using a competition kinetics technique. We use hydrogen peroxide as a photochemical source of OH. Bimolecular rate constant we obtained so far for aspartame was (2.6±1.2)×109 M-1 s-1 at pH = 3.0 and (4.9±2.3)×109 M-1 s-1 at pH = 5.5. Little effect was seen by changing the temperatures between 15 and 40 oC. Activation energy (Ea) was calculated to be -1.0 kJ mol-1 at pH = 3.0, +8.5 kJ mol-1 at pH = 5.5, which could be regarded as zero. We will report bimolecular rate constants at different pHs and temperatures for acesulfame K and saccharin, as well. Possible reaction by-products for aspartame will be also reported. We will further discuss the fate of aspartame in the coastal environment.

  15. Allergic Reactions

    MedlinePlus

    ... that is right for you. In many instances, allergy immunotherapy in the form of shots or tablets is an effective, cost-efficient long term treatment approach. While there is not yet ... Healthy Tips • Allergy symptoms are the result of a chain reaction ...

  16. Fundamental reaction pathways during coprocessing

    SciTech Connect

    Stock, L.M.; Gatsis, J.G. . Dept. of Chemistry)

    1992-12-01

    The objective of this research was to investigate the fundamental reaction pathways in coal petroleum residuum coprocessing. Once the reaction pathways are defined, further efforts can be directed at improving those aspects of the chemistry of coprocessing that are responsible for the desired results such as high oil yields, low dihydrogen consumption, and mild reaction conditions. We decided to carry out this investigation by looking at four basic aspects of coprocessing: (1) the effect of fossil fuel materials on promoting reactions essential to coprocessing such as hydrogen atom transfer, carbon-carbon bond scission, and hydrodemethylation; (2) the effect of varied mild conditions on the coprocessing reactions; (3) determination of dihydrogen uptake and utilization under severe conditions as a function of the coal or petroleum residuum employed; and (4) the effect of varied dihydrogen pressure, temperature, and residence time on the uptake and utilization of dihydrogen and on the distribution of the coprocessed products. Accomplishments are described.

  17. Facile electrochemical co-deposition of a graphene-cobalt nanocomposite for highly efficient water oxidation in alkaline media: direct detection of underlying electron transfer reactions under catalytic turnover conditions.

    PubMed

    Guo, Si-Xuan; Liu, Yuping; Bond, Alan M; Zhang, Jie; Esakki Karthik, P; Maheshwaran, I; Senthil Kumar, S; Phani, K L N

    2014-09-21

    A facile electrochemical co-deposition method has been developed for the fabrication of graphene-cobalt nanocomposite modified electrodes that achieve exceptionally efficient water oxidation in highly alkaline media. In the method reported, a graphene-cobalt nanocomposite film was deposited electrochemically from a medium containing 1 mg ml(-1) graphene oxide, 0.8 mM cobalt nitrate and 0.05 M phytic acid (pH 7). The formation of the nanocomposite film was confirmed using electrochemical, Raman spectroscopic and scanning electron microscopic techniques. The nanocomposite film exhibits excellent activity and stability towards water oxidation to generate oxygen in 1 M NaOH aqueous electrolyte media. A turn over frequency of 34 s(-1) at an overpotential of 0.59 V and a faradaic efficiency of 97.7% were deduced from analysis of data obtained by rotating ring disk electrode voltammetry. Controlled potential electrolysis data suggests that the graphene supported catalyst exhibits excellent stability under these harsh conditions. Phytate anion acts as stabilizer for the electrochemical formation of cobalt nanoparticles. Fourier transformed ac voltammetry allowed the redox chemistry associated with catalysis to be detected directly under catalytic turnover conditions. Estimates of formal reversible potentials obtained from this method and derived from the overall reactions 3Co(OH)2 + 2OH(-) ⇌ Co3O4 + 4H2O + 2e(-), Co3O4 + OH(-) ⇌ 3CoOOH + e(-) and CoOOH + OH(-) ⇌ CoO2 + H2O + e(-) are 0.10, 0.44 and 0.59 V vs. Ag/AgCl, respectively.

  18. Liraglutide protects Rin-m5f β cells by reducing procoagulant tissue factor activity and apoptosis prompted by microparticles under conditions mimicking Instant Blood-Mediated Inflammatory Reaction.

    PubMed

    Gleizes, Céline; Constantinescu, Andrei; Abbas, Malak; Bouhadja, Houda; Zobairi, Fatiha; Kessler, Laurence; Toti, Florence

    2014-07-01

    Instant Blood-Mediated Inflammatory Reaction (IBMIR) occurs at the vicinity of transplanted islets immediately after intraportal infusion and is characterized by cytokine secretion, tissue factor (TF) expression, and ß cell loss. Microparticles (MPs) are cellular effectors shed from the plasma membrane of apoptotic cells. Modulation of the properties of ß cell-derived MPs by liraglutide was assessed in a cellular model designed to mimic IBMIR oxidative and inflammatory conditions. Rin-m5f rat β cells were stimulated by H2 O2 or a combination of IL-1β and TNF-α. Cell-derived MPs were applied to naive Rin-m5f for 24 h. Apoptosis, MP release, TF activity, P-IκB expression, and MP-mediated apoptosis were measured in target cells. Direct protection by liraglutide was shown by a significant decrease in the oxidative stress-induced apoptosis (18.7% vs. 7.6%, P < 0.0001 at 1 μm liraglutide) and cellular TF activity (-40% at 100 nm liraglutide). Indirect cytoprotection led to 20% reduction in MP generation, thereby lowering MP-mediated apoptosis (6.3% vs. 3.7%, P = 0.022) and NF-κB activation (-50%) in target cells. New cytoprotective effects of liraglutide were evidenced, limiting the expression of TF activity by ß cells and the generation of noxious MPs. Altogether, these data suggest that liraglutide could target pro-apoptotic and pro-inflammatory MPs in transplanted islets.

  19. "Greening up" the Suzuki Reaction

    ERIC Educational Resources Information Center

    Aktoudianakis, Evangelos; Chan, Elton; Edward, Amanda R.; Jarosz, Isabel; Lee, Vicki; Mui, Leo; Thatipamala, Sonya S.; Dicks, Andrew P.

    2008-01-01

    This article describes the rapid, green synthesis of a biaryl compound (4-phenylphenol) via a Pd(0)-catalyzed Suzuki cross-coupling reaction in water. Mild reaction conditions and operational simplicity makes this experiment especially amenable to both mid- and upper-level undergraduates. The methodology exposes students to purely aqueous…

  20. Section i: Thermodynamic Properties of Hydrocarbon Radicals, Peroxy Hydrocarbon and Peroxy Chlorohydrocarbon Molecules and Radicals. Section II. Kinetics and Reaction Mechanisms For: (1) Chloroform Pyrolysis and Oxidation; (2) Benzene and Toluene Oxidation Under Atmospheric Conditions.

    NASA Astrophysics Data System (ADS)

    Lay, Tsan-Horng

    1995-01-01

    Alkyl radicals are important active intermediates in gas phase photochemistry and combustion reaction systems. With the exception of a limited number of the most elementary radicals, accurate thermodynamic properties of alkyl radicals are either not available or only rough estimations exist. An H atom Bond Increment approach is developed and a data base is derived, for accurately estimating thermodynamic properties (Delta H_{f }^circ298, S ^circ298 and Cp(T)) for generic classes of hydrocarbon radical species. Reactions of alkyl radicals with molecular oxygen are one of the major reaction paths for these radicals in atmospheric photochemistry, oxidation of hydrocarbon liquids and combustion process. Alkyl hydroperoxides are subsequently formed through the alkyl peroxy radicals reactions with varied chemical species present in the reaction system. Thermodynamic properties of the alkyl hydroperoxides and related radicals are therefore frequently required in gas phase modeling and kinetic studies on these systems. The thermodynamic properties of alkyl hydroperoxides, alkyl peroxy radicals and hydroperoxyl-1-ethyl radicals including the species with fluorine and chlorine substituents on the alpha-carbon are evaluated using molecular orbital calculations. Chloroform is used as a model chlorocarbon system with high Cl/H ratio to investigate thermal decomposition processes of chlorocarbons in oxidative and pyrolytic reaction environments. A detailed reaction mechanism is developed to describe the important features of products and reagent loss and is shown to predict the experimental data well. Reaction pathways and rate constants are developed for CCl _3, CCl_2 and rm C_2Cl_3 radical addition to O_2 and combination with O, OH HO_2 and ClO. The reversible addition reaction of OH radical with benzene to form the hydroxyl-2,4-cyclohexadienyl (benzene -OH) adduct and the subsequent reactions of this benzene -OH adduct with O_2 are important initial steps for the

  1. Racemization in Prins Cyclization Reactions

    PubMed Central

    Jasti, Ramesh

    2008-01-01

    Isotopic labeling experiments were performed in order to elucidate a new mechanism for racemization in Prins cyclization reactions. The loss in optical activity for these reactions was shown to occur by 2-oxonia-Cope rearrangements by way of a (Z)-oxocarbenium ion intermediate. Reaction conditions such as solvent, temperature, and the nucleophile employed played a critical role in whether an erosion in enantiomeric excess was observed. Additionally, certain structural features of Prins cyclization precursors were also shown to be important for preserving optical purity in these reactions. PMID:17031979

  2. Freeze Enhanced Halate Halide Reactions

    NASA Astrophysics Data System (ADS)

    Newberg, J. T.; Weaver, K.; Broderick, A.

    2014-12-01

    Relatively little is known about halate ion species (XO3-; X = I, Br, Cl) in atmospheric condensed phases. It was initial thought that iodate was a terminal stable species upon iodide oxidation. However, it is becoming increasingly recognized that reactions involving iodate can lead to reactive iodine, and this chemistry is accelerated under acidic conditions. The environmental concentrations and chemistry of bromate and chlorate are largely unexplored in environmental ices. We present results from a series of aqueous phase halate ion reactions with halides under acidic conditions, showing that the kinetics are strongly enhanced upon freezing. The products of these reactions are reactive halogens, which have important implications to marine boundary layer chemistry.

  3. A 3D-RISM-SCF method with dual solvent boxes for a highly polarized system: application to 1,6-anhydrosugar formation reaction of phenyl α- and β-D-glucosides under basic conditions.

    PubMed

    Aono, Shinji; Hosoya, Takashi; Sakaki, Shigeyoshi

    2013-05-07

    One of the difficulties in application of the usual reference interaction site model self-consistent field (RISM-SCF) method to a highly polarized and bulky system arises from the approximate evaluation of electrostatic potential (ESP) with pure point charges. To improve this ESP evaluation, the ESP near a solute is directly calculated with a solute electronic wavefunction, that distant from a solute is approximately calculated with solute point charges, and they are connected with a switching function. To evaluate the fine solvation structure near the solute by incorporating the long-range solute-solvent Coulombic interaction with low computational cost, we introduced the dual solvent box protocol; one small box with the fine spacing is employed for the first and the second solvation shells and the other large box with the normal spacing is employed for long-range solute-solvent interaction. The levoglucosan formation from phenyl α- and β-d-glucosides under basic conditions is successfully inspected by this 3D-RISM-SCF method at the MP2 and SCS-MP2 levels, though the 1D-RISM-SCF could not be applied to this reaction due to the presence of highly polarized and bulky species. This 3D-RISM-SCF calculation reproduces the experimentally reported higher reactivity of the β-anomer. The 3D-RISM-SCF-calculated activation free energy for the β-anomer is closer to the experimental value than the PCM-calculated one. Interestingly, the solvation effect increases the difference in reactivity between these two anomers. The reason is successfully elucidated with 3D-RISM-SCF-calculated microscopic solvation structure and decomposition analysis of solute-solvent interaction.

  4. Formation of three N-acetyl-L-cysteine monoadducts and one diadduct by the reaction of S-(1,2-dichlorovinyl)-L-cysteine sulfoxide with N-acetyl-L-cysteine at physiological conditions: chemical mechanisms and toxicological implications.

    PubMed

    Barshteyn, Nella; Elfarra, Adnan A

    2007-10-01

    Previously, our laboratory has shown that S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS), a Michael acceptor produced by a flavin-containing monooxygenase 3 (FMO3)-mediated oxidation of S-(1,2-dichlorovinyl)-L-cysteine (DCVC), is a more potent nephrotoxicant than DCVC. In the present study, we characterized reactions of DCVCS with nucleophilic amino acids. DCVCS incubations with N-acetyl-L-cysteine (NAC) at pH 7.4 and 37 degrees C for 1 h resulted in the formation of three monoadducts and one diadduct characterized by LC/MS, 1H NMR, and 1H-detected heteronuclear single quantum correlation. The formation of all adducts (with relative ratios of 29, 31, 24, and 12%, respectively) was rapid and time-dependent; the half-lives of the two DCVCS diastereomers in the presence of NAC were 13.8 (diastereomer I) and 9.4 min (diastereomer II). Adducts 1 and 2 were determined to be diastereomers of S-[1-chloro-2-(N-acetyl-L-cystein- S-yl)vinyl]-L-cysteine sulfoxide formed by Michael addition of NAC to the terminal vinylic carbon of DCVCS followed by loss of HCl. Adduct 4 was determined to be S-[2-chloro-2-(N-acetyl-L-cystein- S-yl)vinyl]-L-cysteine sulfoxide formed from the initial Michael addition product followed by a less favorable loss of HCl and/or by a rearrangement of adduct 2 through the formation of a cyclic chloronium ion. The addition of another molecule of NAC to monoadducts 1, 2, or 4 resulted in the formation of the novel diadduct, S-[2,2-( N-acetyl-L-cystein-S-yl)vinyl]-L-cysteine sulfoxide (adduct 3), whose detection in relatively large amount suggests that DCVCS could act as a cross-linking agent. DCVCS was not reactive with N-acetyl-L-lysine or L-valinamide at similar incubation conditions. Collectively, the results suggest selective reactivity of DCVCS toward protein sulfhydryl groups. Furthermore, the cross-linking properties of DCVCS may in part explain its high nephrotoxic potency.

  5. Adverse cutaneous drug reaction.

    PubMed

    Nayak, Surajit; Acharjya, Basanti

    2008-01-01

    In everyday clinical practice, almost all physicians come across many instances of suspected adverse cutaneous drug reactions (ACDR) in different forms. Although such cutaneous reactions are common, comprehensive information regarding their incidence, severity and ultimate health effects are often not available as many cases go unreported. It is also a fact that in the present world, almost everyday a new drug enters market; therefore, a chance of a new drug reaction manifesting somewhere in some form in any corner of world is unknown or unreported. Although many a times, presentation is too trivial and benign, the early identification of the condition and identifying the culprit drug and omit it at earliest holds the keystone in management and prevention of a more severe drug rash. Therefore, not only the dermatologists, but all practicing physicians should be familiar with these conditions to diagnose them early and to be prepared to handle them adequately. However, we all know it is most challenging and practically difficult when patient is on multiple medicines because of myriad clinical symptoms, poorly understood multiple mechanisms of drug-host interaction, relative paucity of laboratory testing that is available for any definitive and confirmatory drug-specific testing. Therefore, in practice, the diagnosis of ACDR is purely based on clinical judgment. In this discussion, we will be primarily focusing on pathomechanism and approach to reach a diagnosis, which is the vital pillar to manage any case of ACDR.

  6. Infant Defensive Reactions to Visual Occlusion.

    ERIC Educational Resources Information Center

    Adamson, Lauren; Tronick, Edward

    This paper describes the initial organization of the infant's reaction to having his vision occluded by an opaque cloth; traces the development of this reaction over the first six months; and probes the role the occlusion of vision plays in provoking the reaction. Fifty videotaped sessions of infants during two conditions - eyes covered with an…

  7. Incidents of chemical reactions in cell equipment

    SciTech Connect

    Baldwin, N.M.; Barlow, C.R.

    1991-12-31

    Strongly exothermic reactions can occur between equipment structural components and process gases under certain accident conditions in the diffusion enrichment cascades. This paper describes the conditions required for initiation of these reactions, and describes the range of such reactions experienced over nearly 50 years of equipment operation in the US uranium enrichment program. Factors are cited which can promote or limit the destructive extent of these reactions, and process operations are described which are designed to control the reactions to minimize equipment damage, downtime, and the possibility of material releases.

  8. Effect of droplet size distribution on reaction heat in a liquid-liquid heterogeneous reaction process.

    PubMed

    Yasuhiro, Fujimoto

    2004-11-11

    In heterogeneous liquid-liquid reaction processes, explosions have been reported. An aim of this study is to simulate the accident stories, which might be caused by inappropriate mixing conditions in the heterogeneous reaction process. The reaction of water-insoluble anhydride and water was selected as a model process. The experimental trend data of droplet size with agitation in a batch reactor were fitted to an empirical equation. The good fittings show the applicability of the equation in our reaction conditions.

  9. Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

    NASA Technical Reports Server (NTRS)

    Liechty, Derek S.; Lewis, Mark J.

    2010-01-01

    Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

  10. Diamine Ligands in Copper-Catalyzed Reactions

    PubMed Central

    Surry, David S.

    2012-01-01

    The utility of copper-mediated cross-coupling reactions has been significantly increased by the development of mild reaction conditions and the ability to employ catalytic amounts of copper. The use of diamine-based ligands has been important in these advances and in this review we discuss these systems, including the choice of reaction conditions and applications in the synthesis of pharmaceuticals, natural products and designed materials. PMID:22384310

  11. Synthesis of 5-alkylated barbituric acids and 3-alkylated indoles via microwave-assisted three-component reactions in solvent-free conditions using Hantzsch 1,4-dihydropyridines as reducing agents.

    PubMed

    Baruah, Biswajita; Seetham Naidu, P; Borah, Pallabi; Bhuyan, Pulak J

    2012-05-01

    Reaction of barbituric acids with aldehydes and dihydropyridines in one pot under microwave (MW) irradiation in the absence of solvent, affords 55–82% of the 5-benzylated barbituric acids. Use of alkyl nitriles or barbituric acids with indole-3-aldehyde and dihydropyridine (DHP) afforded 3-alkylated indoles in 57–76 % yield. In each case DHPs are converted to pyridines.

  12. Reactions of stabilized Criegee Intermediates

    NASA Astrophysics Data System (ADS)

    Vereecken, Luc; Harder, Hartwig; Novelli, Anna

    2014-05-01

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

  13. Experimental Study of Serpentinization Reactions

    NASA Technical Reports Server (NTRS)

    Cohen, B. A.; Brearley, A. J.; Ganguly, J.; Liermann, H.-P.; Keil, K.

    2004-01-01

    Current carbonaceous chondrite parent-body thermal models [1-3] produce scenarios that are inconsistent with constraints on aqueous alteration conditions based on meteorite mineralogical evidence, such as phase stability relationships within the meteorite matrix minerals [4] and isotope equilibration arguments [5, 6]. This discrepancy arises principally because of the thermal runaway effect produced by silicate hydration reactions (here loosely called serpentinization, as the principal products are serpentine minerals), which are so exothermic as to produce more than enough heat to melt more ice and provide a self-sustaining chain reaction. One possible way to dissipate the heat of reaction is to use a very small parent body [e.g., 2] or possibly a rubble pile model. Another possibility is to release this heat more slowly, which depends on the alteration reaction path and kinetics.

  14. Thermally multiplexed polymerase chain reaction

    PubMed Central

    Phaneuf, Christopher R.; Pak, Nikita; Saunders, D. Curtis; Holst, Gregory L.; Birjiniuk, Joav; Nagpal, Nikita; Culpepper, Stephen; Popler, Emily; Shane, Andi L.; Jerris, Robert; Forest, Craig R.

    2015-01-01

    Amplification of multiple unique genetic targets using the polymerase chain reaction (PCR) is commonly required in molecular biology laboratories. Such reactions are typically performed either serially or by multiplex PCR. Serial reactions are time consuming, and multiplex PCR, while powerful and widely used, can be prone to amplification bias, PCR drift, and primer-primer interactions. We present a new thermocycling method, termed thermal multiplexing, in which a single heat source is uniformly distributed and selectively modulated for independent temperature control of an array of PCR reactions. Thermal multiplexing allows amplification of multiple targets simultaneously—each reaction segregated and performed at optimal conditions. We demonstrate the method using a microfluidic system consisting of an infrared laser thermocycler, a polymer microchip featuring 1 μl, oil-encapsulated reactions, and closed-loop pulse-width modulation control. Heat transfer modeling is used to characterize thermal performance limitations of the system. We validate the model and perform two reactions simultaneously with widely varying annealing temperatures (48 °C and 68 °C), demonstrating excellent amplification. In addition, to demonstrate microfluidic infrared PCR using clinical specimens, we successfully amplified and detected both influenza A and B from human nasopharyngeal swabs. Thermal multiplexing is scalable and applicable to challenges such as pathogen detection where patients presenting non-specific symptoms need to be efficiently screened across a viral or bacterial panel. PMID:26339317

  15. Catalysis of Photochemical Reactions.

    ERIC Educational Resources Information Center

    Albini, A.

    1986-01-01

    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  16. Concordant chemical reaction networks and the Species-Reaction Graph.

    PubMed

    Shinar, Guy; Feinberg, Martin

    2013-01-01

    In a recent paper it was shown that, for chemical reaction networks possessing a subtle structural property called concordance, dynamical behavior of a very circumscribed (and largely stable) kind is enforced, so long as the kinetics lies within the very broad and natural weakly monotonic class. In particular, multiple equilibria are precluded, as are degenerate positive equilibria. Moreover, under certain circumstances, also related to concordance, all real eigenvalues associated with a positive equilibrium are negative. Although concordance of a reaction network can be decided by readily available computational means, we show here that, when a nondegenerate network's Species-Reaction Graph satisfies certain mild conditions, concordance and its dynamical consequences are ensured. These conditions are weaker than earlier ones invoked to establish kinetic system injectivity, which, in turn, is just one ramification of network concordance. Because the Species-Reaction Graph resembles pathway depictions often drawn by biochemists, results here expand the possibility of inferring significant dynamical information directly from standard biochemical reaction diagrams.

  17. Concordant Chemical Reaction Networks and the Species-Reaction Graph

    PubMed Central

    Shinar, Guy; Feinberg, Martin

    2015-01-01

    In a recent paper it was shown that, for chemical reaction networks possessing a subtle structural property called concordance, dynamical behavior of a very circumscribed (and largely stable) kind is enforced, so long as the kinetics lies within the very broad and natural weakly monotonic class. In particular, multiple equilibria are precluded, as are degenerate positive equilibria. Moreover, under certain circumstances, also related to concordance, all real eigenvalues associated with a positive equilibrium are negative. Although concordance of a reaction network can be decided by readily available computational means, we show here that, when a nondegenerate network’s Species-Reaction Graph satisfies certain mild conditions, concordance and its dynamical consequences are ensured. These conditions are weaker than earlier ones invoked to establish kinetic system injectivity, which, in turn, is just one ramification of network concordance. Because the Species-Reaction Graph resembles pathway depictions often drawn by biochemists, results here expand the possibility of inferring significant dynamical information directly from standard biochemical reaction diagrams. PMID:22940368

  18. Reaction Coordinates and Mechanistic Hypothesis Tests

    NASA Astrophysics Data System (ADS)

    Peters, Baron

    2016-05-01

    Reaction coordinates are integral to several classic rate theories that can (a) predict kinetic trends across conditions and homologous reactions, (b) extract activation parameters with a clear physical interpretation from experimental rates, and (c) enable efficient calculations of free energy barriers and rates. New trajectory-based rare events methods can provide rates directly from dynamical trajectories without a reaction coordinate. Trajectory-based frameworks can also generate ideal (but abstract) reaction coordinates such as committors and eigenfunctions of the master equation. However, rates and mechanistic insights obtained from trajectory-based methods and abstract coordinates are not readily generalized across simulation conditions or reaction families. We discuss methods for identifying physically meaningful reaction coordinates, including committor analysis, variational transition state theory, Kramers-Langer-Berezhkovskii-Szabo theory, and statistical inference methods that can use path sampling data to screen, mix, and optimize thousands of trial coordinates. Special focus is given to likelihood maximization and inertial likelihood maximization approaches.

  19. Effect the conditions of the acid-thermal modification of clinoptilolite have on the catalytic properties of palladium-copper complexes anchored on it in the reaction of carbon monoxide oxidation

    NASA Astrophysics Data System (ADS)

    Rakitskaya, T. L.; Kiose, T. A.; Ennan, A. A.; Golubchik, K. O.; Oleksenko, L. P.; Gerasiova, V. G.

    2016-06-01

    The dependence of the physicochemical and structural-adsorption properties of natural and acid-thermal modified clinoptilolite, and of Pd(II)-Cu(II) catalysts based on them, on the duration of acid-thermal modification is investigated. The samples under study are described via XRD and thermal gravimetric (DTG and DTA) analysis, IR, DR UV-Vis, EPR spectroscopy, and water vapor adsorption. Values of both the specific surface area ( S sp) and pH of aqueous suspensions are determined. The resulting catalysts are tested in the reaction of low-temperature carbon monoxide oxidation with air oxygen. A conclusion is drawn about the nature of surface bimetallic Pd(II)-Cu(II) complexes. The greatest catalytic activity is shown by complexes based on clinoptilolite and modified with 3 M HNO3 for 0.5 and 1 h.

  20. Platinum-cobalt catalysts for the oxygen reduction reaction in high temperature proton exchange membrane fuel cells - Long term behavior under ex-situ and in-situ conditions

    NASA Astrophysics Data System (ADS)

    Schenk, Alexander; Grimmer, Christoph; Perchthaler, Markus; Weinberger, Stephan; Pichler, Birgit; Heinzl, Christoph; Scheu, Christina; Mautner, Franz-Andreas; Bitschnau, Brigitte; Hacker, Viktor

    2014-11-01

    Platinum cobalt catalysts (Pt-Co) have attracted much interest as cathode catalysts for proton exchange membrane fuel cells (PEMFCs) due to their high activity toward oxygen reduction reaction (ORR). Many of the reported catalysts show outstanding performance in ex-situ experiments. However, the laborious synthesis protocols of these Pt-Co catalysts disable an efficient and economic production of membrane electrode assemblies (MEAs). We present an economic, flexible and continuous Pt-M/C catalyst preparation method as part of a large scale membrane electrode assembly manufacturing. In comparison, the as-prepared Pt-Co/C based high temperature (HT)-PEM MEA showed an equal performance to a commercially available HT-PEM MEA during 600 h of operation under constant load, although the commercial one had a significantly higher Pt loading at the cathode.

  1. Green synthesis of palladium nanoparticles mediated by black tea leaves (Camellia sinensis) extract: Catalytic activity in the reduction of 4-nitrophenol and Suzuki-Miyaura coupling reaction under ligand-free conditions.

    PubMed

    Lebaschi, Sadaf; Hekmati, Malak; Veisi, Hojat

    2017-01-01

    The present study was conducted to synthesize palladium nanoparticles (Pd NPs) through a facile and green route using non-toxic and renewable natural black tea leaves (Camellia sinensis) extract, as the reducing and stabilizing agent. The as-prepared Pd@B.tea NPs catalyst was characterized by UV-vis spectroscopy, X-ray diffraction (XRD), fourier transformed infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). The Pd@B.tea NPs catalyst could be used as an efficient and heterogeneous catalyst for Suzuki coupling reactions between phenylboronic acid and a range of aryl halides (X=I, Br, Cl) and also the reduction of 4-nitrophenol (4-NP) using sodium borohydride in an environmental friendly medium. Excellent yields of products were obtained with a wide range of substrates and the catalyst was recycled 7 times without any significant loss of its catalytic activity.

  2. An Analysis of the Algebraic Method for Balancing Chemical Reactions.

    ERIC Educational Resources Information Center

    Olson, John A.

    1997-01-01

    Analyzes the algebraic method for balancing chemical reactions. Introduces a third general condition that involves a balance between the total amount of oxidation and reduction. Requires the specification of oxidation states for all elements throughout the reaction. Describes the general conditions, the mathematical treatment, redox reactions, and…

  3. Skin reactions to sunscreens.

    PubMed

    Nixon, R L; Frowen, K E; Lewis, A E

    1997-06-01

    Sunscreen reactions are said not to be uncommon. A population referred to a patch testing clinic was evaluated for reactions to sunscreen by questionnaire initially and then, if relevant, by patch testing to sunscreen products and their components. Irritant reactions were more common than allergic contact dermatitis. Allergic reactions to sunscreens were less common than to non-sunscreen chemicals present in sunscreen products.

  4. The Glyoxal Clock Reaction

    ERIC Educational Resources Information Center

    Ealy, Julie B.; Negron, Alexandra Rodriguez; Stephens, Jessica; Stauffer, Rebecca; Furrow, Stanley D.

    2007-01-01

    Research on the glyoxal clock reaction has led to adaptation of the clock reaction to a general chemistry experiment. This particular reaction is just one of many that used formaldehyde in the past. The kinetics of the glyoxal clock makes the reaction suitable as a general chemistry lab using a Calculator Based Laboratory (CBL) or a LabPro. The…

  5. Mixtures and Mineral Reactions

    NASA Astrophysics Data System (ADS)

    Rumble, D.

    The monograph Mixtures and Mineral Reactions contains a large amount of information of value to mineralogists, petrologists, and geochemists. The first four chapters are a succinct account of the thermodynamic description of crystalline solutions. In these early chapters a comparison is made between different mathematical treatments of activitycomposition models, there is a discussion of the unmixing by exsolution of a single solution into two phases, and methods of computing phase equilibria in assemblages of different minerals are given. If the reader is perplexed by the discussion of standard states (cf. Figure 1.3), not to worry. That is a normal condition for anyone forced to choose between equivalent reference frames yet knowing, somewhere down the line, that the choice will ultimately make one's computational life more or less difficult.

  6. Chromosomal Conditions

    MedlinePlus

    ... 150 babies is born with a chromosomal condition. Down syndrome is an example of a chromosomal condition. Because ... all pregnant women be offered prenatal tests for Down syndrome and other chromosomal conditions. A screening test is ...

  7. Hydrazones as substrates for cycloaddition reactions

    NASA Astrophysics Data System (ADS)

    Belskaya, N. P.; Eliseeva, A. I.; Bakulev, V. A.

    2015-12-01

    The [2+2]-, [4+2]- and [3+2]-cycloaddition reactions of hydrazones and 1,2-diazabuta-1,3-dienes, azomethine imines, nitrile imines and azomethine ylides formed upon hydrazone transformations with dienophiles, dipolarophiles and dienes are considered. The principal issues of structure and reactivity of active substrates and the influence of the reaction conditions and catalysts on the reaction regioselectivity and efficiency are discussed. The bibliography includes 288 references.

  8. Preventing Corrosion by Controlling Cathodic Reaction Kinetics

    DTIC Science & Technology

    2016-03-25

    electrochemical reaction rates of processes that drive corrosion, e.g. the oxygen reduction reaction (ORR). To this end, we have used reactive...for the alkaline conditions expected to obtain when acting as the noble material in a galvanic couple, the electrochemical properties of the oxide...closely follows the approach of N0rskov et. al. ( 10.1 021/jp04 7349j) by using electrochemical scaling relationships to determine the reaction

  9. Ionic Reactions of Atmospheric Importance.

    DTIC Science & Technology

    1984-08-31

    Kingdom E.E. Ferguson* Laboratoire de Resonance Electronique et Ionique Universitd de Paris-Sud, Orsay, France Abstract Reaction rate coefficients have...reactions from N2(v = 1) to 02+ (v -0) and NO+(v = 0) E. E. Ferguson*) Laboratoire de Resonance Electronique el lonique Universiti de Paris-Sud, Orsay...practice, however, this condition cannot be realised and so ne(z) is first determined in the absence of attaching gas to derive uD , neZ ) then

  10. Innovative effect of illite on improved microbiological conversion of L-tyrosine to 3,4 dihydroxy phenyl L-alanine (L-DOPA) by Aspergillus oryzae ME2 under acidic reaction conditions.

    PubMed

    Sikander, Ali; Ikram-ul-Haq

    2006-11-01

    In the present investigation, the previous ultraviolet irradiated mutant strain of Aspergillus oryzae UV-7 was further improved in terms of 3,4 dihydroxy phenyl L-alanine (L-DOPA) activity after chemical mutagenesis through 1-methyl 3-nitro 1-nitroso guanidine (MNNG = 250-1500 microg/ml) treatment (0-30 min). Among several mutant variants, the one that produced a larger amount of L-DOPA from L-tyrosine was designated to as ME2 and it was made 2-deoxy-D-glucose-resistant by growing it at various concentrations of 2 dg (0.01-0.025 %, w/v) in Vogel's agar medium. Relatively better production of L-DOPA (> 0.60 mg/ml) was obtained when 2.0% (w/v) glucose was used as a carbon source in the mycelium production medium and the tyrosinase activity increased constitutively (1.08 mg/ml), which resulted in a greater production of L-DOPA. At optimum pH0 (pH 6.0) and reaction time (60 min), more than 65% sugar was utilized for cell mass formation. The maximum conversion of L-tyrosine to L-DOPA (0.428 mg/ml) was achieved 60 min after the biochemical reaction. Mould mycelium was used for microbiological conversion of L-tyrosine to L-DOPA because tyrosinases, beta-carboxylases, and tyrosine hydroxylases are intracellular enzymes. The effect of illite (1.0 x 10(6)-6.0 x 10(6) M) on biochemical conversion of L-tyrosine to L-DOPA by Aspergillus oryzae ME(2 )was also carried out. Best results of L-DOPA biosynthesis were observed when the concentration of illite was 3.5 x 10(-6) M (1.686 mg/ml L-DOPA produced with 1.525 mg/ml consumption of L-tyrosine). It was noted that the addition of illite not only increased enzyme activity but also enhanced the permeability of cell membrane to facilitate the secretion of enzymes into the reaction broth. The comparison of kinetic parameters showed the ability of mutant to yield L-DOPA (i.e., Yp/x 7.360 +/- 0.04 mg/mg). When the culture grown on various illite concentrations was monitored for Qp, Qs, and qp, there was significant enhancement (p < 0

  11. Competitive Deprotonation and Superoxide [O2 -•] Radical-Anion Adduct Formation Reactions of Carboxamides under Negative-Ion Atmospheric-Pressure Helium-Plasma Ionization (HePI) Conditions

    NASA Astrophysics Data System (ADS)

    Hassan, Isra; Pinto, Spencer; Weisbecker, Carl; Attygalle, Athula B.

    2016-03-01

    Carboxamides bearing an N-H functionality are known to undergo deprotonation under negative-ion-generating mass spectrometric conditions. Herein, we report that N-H bearing carboxamides with acidities lower than that of the hydroperoxyl radical (HO-O•) preferentially form superoxide radical-anion (O2 -•) adducts, rather than deprotonate, when they are exposed to the glow discharge of a helium-plasma ionization source. For example, the spectra of N-alkylacetamides show peaks for superoxide radical-anion (O2 -•) adducts. Conversely, more acidic amides, such as N-alkyltrifluoroacetamides, preferentially undergo deprotonation under similar experimental conditions. Upon collisional activation, the O2 -• adducts of N-alkylacetamides either lose the neutral amide or the hydroperoxyl radical (HO-O•) to generate the superoxide radical-anion ( m/z 32) or the deprotonated amide [ m/z (M - H)-], respectively. For somewhat acidic carboxamides, the association between the two entities is weak. Thus, upon mildest collisional activation, the adduct dissociates to eject the superoxide anion. Superoxide-adduct formation results are useful for structure determination purposes because carboxamides devoid of a N-H functionality undergo neither deprotonation nor adduct formation under HePI conditions.

  12. Adsorption Isotherms and Surface Reaction Kinetics

    ERIC Educational Resources Information Center

    Lobo, L. S.; Bernardo, C. A.

    1974-01-01

    Explains an error that occurs in calculating the conditions for a maximum value of a rate expression for a bimolecular reaction. The rate expression is derived using the Langmuir adsorption isotherm to relate gas pressures and corresponding surface coverages. (GS)

  13. The Mechanism of the Formaldehyde Clock Reaction.

    ERIC Educational Resources Information Center

    Burnett, M. G.

    1982-01-01

    Provides background information and problems with the formaldehyde clock reaction, including comparisons of experimental clock times reported in the literature and conditions for the reliable use of the formaldehyde clock based on a method discussed. (JN)

  14. Reaction theory for exotic nuclei

    SciTech Connect

    Bonaccorso, Angela

    2014-05-09

    Exotic nuclei are usually defined as those with unusual N/Z ratios. They can be found in the crust of neutron stars enbedded in a sea of electrons or created in laboratory by fragmentation of a primary beam (in-flight method) or of the target (ISOL method). They are extremely important for nuclear astrophysics, see for example Ref.[1]. Furthermore by studying them we can check the limits of validity of nuclear reaction and structure models. This contribution will be devoted to the understanding of how by using reaction theory and comparing to the data we can extract structure information. We shall discuss the differences between the mechanisms of transfer and breakup reactions, an we will try to explain how nowadays it is possible to do accurate spectroscopy in extreme conditions.

  15. Reaction rates for mesoscopic reaction-diffusion kinetics

    DOE PAGES

    Hellander, Stefan; Hellander, Andreas; Petzold, Linda

    2015-02-23

    The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In thismore » paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. Finally, we show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results.« less

  16. Reaction rates for mesoscopic reaction-diffusion kinetics

    SciTech Connect

    Hellander, Stefan; Hellander, Andreas; Petzold, Linda

    2015-02-23

    The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In this paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. Finally, we show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results.

  17. Electrosynthesis of Metal-Organic Frameworks (MOFs)Based on Nickel(II) and Benzene 1,3,5-Tri Carboxylic Acid (H3BTC): An Optimization Reaction Condition

    NASA Astrophysics Data System (ADS)

    Lestari, W. W.; Winarni, I. D.; Rahmawati, F.

    2017-02-01

    Electrosynthesis of metal-organic frameworks based on nickel(II) and benzen 1,3,5-tricarboxylic acid (H3BTC) to form [Ni3(BTC)2] has been conducted. This study aims to determine the optimum electro-synthetic conditions of [Ni3(BTC)2] by varying the solvents, electrolytes, as well as the voltages. The optimum condition was determined based on the percent yield of the product which upon washing and drying at room temperature showed pale green precipitate. The materialhas high crystallinityaccording to XRD analysis with the main peak observed at 2θ 19° and 28° and appropriate with [Ni3(BTC)2] pattern (CCDC No. 1274034). The refinement results using Le Bail methods revealed the Rp and Rwp values are 3.29% and 3.47%, respectively. The coordination between nickel(II) and carboxylate moeties of the linker has been characterized using FTIR and showed significant shift from 1723 cm-1 to 1608 cm-1. The compound has thermal stability up to 400 °C according to TG/DTA analysis. The SEM analysis confirmed that compound has morphology nanoplates shape with a thickness of 75 ± 0.023 nm. Another interesting feature of the obtained material is the occupancy of the reversible frameworks, which proved after methanol absorption. The optimum condition of the electro-synthesis of [Ni3(BTC)2] achieved in the methanol with TBATFB (0.1 M) as electrolyte, and the voltage of 15 V at room temperature with a yield of 99.99%.

  18. Sequential evolution of different phases in metastable Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 (0.0 ≤ x ≤ 2.0) system: crucial role of reaction conditions.

    PubMed

    Shukla, Rakesh; Sayed, Farheen N; Phapale, Suhas; Mishra, Ratikant; Tyagi, Avesh K

    2013-07-15

    The Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 (0.0 ≤ x ≤ 2.0) series was synthesized by the gel combustion method. This system exhibited the presence of a fluorite-type phase, along with a narrow biphasic region, depending upon the Ce/Gd content in the sample. Thermal stability of these new compounds under oxidizing and reducing conditions has been investigated. The products obtained on decomposition of Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 in oxidizing and reducing conditions were found to be entirely different. It was observed that in air the fluorite-type solid solutions of Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 composition undergo phase separation into perovskite GdAlO3 and fluorite-type solid solutions of Gd-Ce-Zr-O or Ce-Zr-Al-O depending upon the extent of Ce and Al substitution. On the other hand, Gd(2-x)Ce(x)Zr(2-x)Al(x)O7 samples on heating under reducing conditions show a phase separation to CeAlO3 perovskite and a defect-fluorite of Gd2Zr2O7. The extent of metastability for a typical composition of Gd(1.2)Ce(0.8)Zr(1.2)Al(0.8)O7 (nano), Gd(1.2)Ce(0.8)Zr(1.2)Al(0.8)O(6.6) (heated under reduced conditions), Gd(1.2)Ce(0.8)Zr(1.2)Al(0.8)O7 (heated in air at 1200 °C) has been experimentally determined employing a high temperature Calvet calorimeter. On the basis of thermodynamic stability data, it could be inferred that the formation of a more stable compound in the presence of two competing cations (i.e., Gd(3+) and Ce(3+)) is guided by the crystallographic stability.

  19. Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions

    PubMed Central

    Balof, Shawna L; Nix, K Owen; Olliff, Matthew S; Roessler, Sarah E; Saha, Arpita; Müller, Kevin B; Behrens, Ulrich; Valente, Edward J

    2015-01-01

    Summary Three new ruthenium alkylidene complexes (PCy3)Cl2(H2ITap)Ru=CHSPh (9), (DMAP)2Cl2(H2ITap)Ru=CHPh (11) and (DMAP)2Cl2(H2ITap)Ru=CHSPh (12) have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2’,6’-dimethyl-4’-dimethylaminophenyl)-4,5-dihydroimidazol-2-ylidene). Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP) and ring closing metathesis (RCM) reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA), however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD) and mixtures of DCPD with cyclooctene (COE) in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes. PMID:26664616

  20. Epidemiology of cutaneous drug-induced reactions.

    PubMed

    Naldi, L; Crotti, S

    2014-04-01

    Cutaneous reactions represent in many surveillance systems, the most frequent adverse events attributable to drugs. The spectrum of clinical manifestations is wide and virtually encompasses any known dermatological disease. The introduction of biological agents and so-called targeted therapies has further enlarged the number of reaction patterns especially linked with cytokine release or in balance. The frequency and clinical patterns of cutaneous reactions are influenced by drug use, prevalence of specific conditions (e.g., HIV infection) and pharmacogenetic traits of a population, and they may vary greatly among the different populations around the world. Studies of reaction rates in cohorts of hospitalized patients revealed incidence rates ranging from, 1 out 1000 to 2 out 100 of all hospitalized patients. For drugs such as aminopenicillines and sulfamides the incidence of skin reactions is in the order of 3-5 cases out of 100 exposed people. Although the majority of cutaneous reactions are mild and self-limiting, there are reactions such as Stevens Johnson syndrome (SJS), toxic epidermal necrolysis (TEN), and drug reaction with eosinophilia and systemic symptoms (DRESS) which are associated with significant morbidity and mortality. Surveillance systems routed on sound epidemiologic methodology, are needed to raise signals and to assess risks associated with specific reactions and drug exposures. Identification of risk factors for adverse reactions and appropriate genetic screening of groups at higher risk may improve the outcomes of skin reactions.

  1. Carbon-Fixing Reactions of Photosynthesis.

    PubMed

    2016-07-01

    Summaryplantcell;28/7/tpc.116.tt0716/FIG1F1fig1Photosynthesis in plants converts the energy of sunlight into chemical energy. Although photosynthesis involves many proteins and catalytic processes, it often is described as two sets of reactions, the light-dependent reactions and the carbon-fixing reactions. This lesson introduces the core biochemistry of the carbon-fixing reactions of photosynthesis, as well as its variations, C4 and CAM. Finally, it addresses how and why plants are affected by rising atmospheric CO2 levels, and research efforts to increase photosynthetic efficiency in current and future conditions.

  2. Knoevenagel Reaction of Unprotected Sugars

    NASA Astrophysics Data System (ADS)

    Scherrmann, Marie-Christine

    The Knoevenagel reaction of unprotected sugars was investigated in the 1950s using zinc chloride as promoter. The so-called Garcia Gonzalez reaction had been almost forgotten for 50 years, until the emergence of new water tolerant catalysts having Lewis acid behavior. The reaction was thus reinvestigated and optimal conditions have been found to prepare trihydroxylated furan derivatives from pentose or β-tetrahydrofuranylfuran from hexoses with non-cyclic β-keto ester or β-diketones. Other valuable compounds such as β-linked tetrahydrobenzofuranyl glycosides or hydroxyalkyl-3,3,6,6,-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione can be obtained using cyclic β-dicarbonylic derivatives. Apart from one report in the 1950s, the Knoevenagel reaction of unprotected carbohydrate in basic condition has been studied only in the mid-1980s to prepare C-glycosyl barbiturates from barbituric acids and, later on, from non-cyclic β-diketones, β-C-glycosidic ketones. The efficient method exploited to prepare such compounds has found an industrial development in cosmetics.

  3. Dynamical model of surrogate reactions

    SciTech Connect

    Aritomo, Y.; Chiba, S.; Nishio, K.

    2011-08-15

    A new dynamical model is developed to describe the whole process of surrogate reactions: Transfer of several nucleons at an initial stage, thermal equilibration of residues leading to washing out of shell effects, and decay of populated compound nuclei are treated in a unified framework. Multidimensional Langevin equations are employed to describe time evolution of collective coordinates with a time-dependent potential energy surface corresponding to different stages of surrogate reactions. The new model is capable of calculating spin distributions of the compound nuclei, one of the most important quantities in the surrogate technique. Furthermore, various observables of surrogate reactions can be calculated, for example, energy and angular distribution of ejectile and mass distributions of fission fragments. These features are important to assess validity of the proposed model itself, to understand mechanisms of the surrogate reactions, and to determine unknown parameters of the model. It is found that spin distributions of compound nuclei produced in {sup 18}O+{sup 238}U{yields}{sup 16}O+{sup 240}*U and {sup 18}O+{sup 236}U{yields}{sup 16}O+{sup 238}*U reactions are equivalent and much less than 10({h_bar}/2{pi}) and therefore satisfy conditions proposed by Chiba and Iwamoto [Phys. Rev. C 81, 044604 (2010)] if they are used as a pair in the surrogate ratio method.

  4. Transition metal-free decarboxylative alkylation reactions.

    PubMed

    Liu, Ping; Zhang, Guanghui; Sun, Peipei

    2016-11-22

    This review summarizes advances in the decarboxylative alkylation of carboxylic acids and their derivatives under transition metal-free conditions in recent years. Unlike most transition metal-catalyzed decarboxylative coupling reactions which tend to undergo catalytic cycles, the mechanisms of reactions under metal-free conditions are usually diverse and even ambiguous in some cases. This article offers an overview of reaction types and their corresponding mechanisms, highlights some of the advantages and limitations, and focuses on introducing UV and visible light-induced, organocatalyst and peroxide promoted radical processes for decarboxylative alkylation and the formation of C-C bonds.

  5. Microscale Thermite Reactions.

    ERIC Educational Resources Information Center

    Arnaiz, Francisco J.; Aguado, Rafael; Arnaiz, Susana

    1998-01-01

    Describes the adaptation of thermite (aluminum with metal oxides) reactions from whole-class demonstrations to student-run micro-reactions. Lists detailed directions and possible variations of the experiment. (WRM)

  6. Microfluidic chemical reaction circuits

    SciTech Connect

    Lee, Chung-cheng; Sui, Guodong; Elizarov, Arkadij; Kolb, Hartmuth C; Huang, Jiang; Heath, James R; Phelps, Michael E; Quake, Stephen R; Tseng, Hsian-rong; Wyatt, Paul; Daridon, Antoine

    2012-06-26

    New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

  7. Allergic reactions (image)

    MedlinePlus

    Allergic reaction is a sensitivity to a specific substance, called an allergen, that is contacted through the skin, inhaled into the lungs, swallowed or injected. The body's reaction to an allergen can be mild, such as ...

  8. Allergic reactions (image)

    MedlinePlus

    Allergic reaction can be provoked by skin contact with poison plants, chemicals and animal scratches, as well as by ... dust, nuts and shellfish, may also cause allergic reaction. Medications such as penicillin and other antibiotics are ...

  9. What is a "DNA-Compatible" Reaction?

    PubMed

    Malone, Marie L; Paegel, Brian M

    2016-04-11

    DNA-encoded synthesis can generate vastly diverse screening libraries of arbitrarily complex molecules as long as chemical reaction conditions do not compromise DNA's informational integrity, a fundamental constraint that "DNA-compatible" reaction development does not presently address. We devised DNA-encoded reaction rehearsal, an integrated analysis of reaction yield and impact on DNA, to acquire these key missing data. Magnetic DNA-functionalized sensor beads quantitatively report the % DNA template molecules remaining viable for PCR amplification after exposure to test reaction conditions. Analysis of solid-phase bond forming (e.g., Suzuki-Miyaura cross-coupling, reductive amination) and deprotection reactions (e.g., allyl esters, silyl ethers) guided the definition and optimization of DNA-compatible reaction conditions (>90% yield, >30% viable DNA molecules), most notably in cases that involved known (H(+), Pd) and more obscure (Δ, DMF) hazards to DNA integrity. The data provide an empirical yet mechanistically consistent and predictive framework for designing successful DNA-encoded reaction sequences for combinatorial library synthesis.

  10. First trial postural reactions to unexpected balance disturbances: a comparison with the acoustic startle reaction.

    PubMed

    Oude Nijhuis, Lars B; Allum, John H J; Valls-Solé, Josep; Overeem, Sebastiaan; Bloem, Bastiaan R

    2010-11-01

    Unexpected support-surface movements delivered during stance elicit "first trial" postural reactions, which are larger and cause greater instability compared with habituated responses. The nature of this first trial reaction remains unknown. We hypothesized that first trial postural reactions consist of a generalized startle reaction, with a similar muscle synergy as the acoustic startle response, combined with an automatic postural reaction. Therefore we compared acoustic startle responses to first trial postural reactions. Eight healthy subjects stood on a support surface that unexpectedly rotated backwards 10 times, followed by 10 startling acoustic stimuli, or vice versa. Outcome measures included full body kinematics and surface EMG from muscles involved in startle reactions or postural control. Postural perturbations and startling acoustic stimuli both elicited a clear first trial reaction, as reflected by larger kinematic and EMG responses. The ensuing habituation rate to repeated identical stimuli was comparable for neck and trunk muscles in both conditions. Onset latencies in neck muscles occurred significantly later for first trial perturbations compared with startle responses, but earlier in trunk muscles. Our results show that platform tilting initially induces reactions larger than needed to maintain equilibrium. For neck and trunk muscles, these first trial postural reactions resembled acoustic startle reflexes. First trial postural reactions may be triggered by interaction of afferent volleys formed by somatosensory and vestibular inputs. Acoustic startle reactions may also be partially triggered by vestibular inputs. Similar muscle activation driven by vestibular inputs may be the common element of first trial postural responses and acoustic startle reactions.

  11. Learning to predict chemical reactions.

    PubMed

    Kayala, Matthew A; Azencott, Chloé-Agathe; Chen, Jonathan H; Baldi, Pierre

    2011-09-26

    Being able to predict the course of arbitrary chemical reactions is essential to the theory and applications of organic chemistry. Approaches to the reaction prediction problems can be organized around three poles corresponding to: (1) physical laws; (2) rule-based expert systems; and (3) inductive machine learning. Previous approaches at these poles, respectively, are not high throughput, are not generalizable or scalable, and lack sufficient data and structure to be implemented. We propose a new approach to reaction prediction utilizing elements from each pole. Using a physically inspired conceptualization, we describe single mechanistic reactions as interactions between coarse approximations of molecular orbitals (MOs) and use topological and physicochemical attributes as descriptors. Using an existing rule-based system (Reaction Explorer), we derive a restricted chemistry data set consisting of 1630 full multistep reactions with 2358 distinct starting materials and intermediates, associated with 2989 productive mechanistic steps and 6.14 million unproductive mechanistic steps. And from machine learning, we pose identifying productive mechanistic steps as a statistical ranking, information retrieval problem: given a set of reactants and a description of conditions, learn a ranking model over potential filled-to-unfilled MO interactions such that the top-ranked mechanistic steps yield the major products. The machine learning implementation follows a two-stage approach, in which we first train atom level reactivity filters to prune 94.00% of nonproductive reactions with a 0.01% error rate. Then, we train an ensemble of ranking models on pairs of interacting MOs to learn a relative productivity function over mechanistic steps in a given system. Without the use of explicit transformation patterns, the ensemble perfectly ranks the productive mechanism at the top 89.05% of the time, rising to 99.86% of the time when the top four are considered. Furthermore, the system

  12. Learning to Predict Chemical Reactions

    PubMed Central

    Kayala, Matthew A.; Azencott, Chloé-Agathe; Chen, Jonathan H.

    2011-01-01

    Being able to predict the course of arbitrary chemical reactions is essential to the theory and applications of organic chemistry. Approaches to the reaction prediction problems can be organized around three poles corresponding to: (1) physical laws; (2) rule-based expert systems; and (3) inductive machine learning. Previous approaches at these poles respectively are not high-throughput, are not generalizable or scalable, or lack sufficient data and structure to be implemented. We propose a new approach to reaction prediction utilizing elements from each pole. Using a physically inspired conceptualization, we describe single mechanistic reactions as interactions between coarse approximations of molecular orbitals (MOs) and use topological and physicochemical attributes as descriptors. Using an existing rule-based system (Reaction Explorer), we derive a restricted chemistry dataset consisting of 1630 full multi-step reactions with 2358 distinct starting materials and intermediates, associated with 2989 productive mechanistic steps and 6.14 million unproductive mechanistic steps. And from machine learning, we pose identifying productive mechanistic steps as a statistical ranking, information retrieval, problem: given a set of reactants and a description of conditions, learn a ranking model over potential filled-to-unfilled MO interactions such that the top ranked mechanistic steps yield the major products. The machine learning implementation follows a two-stage approach, in which we first train atom level reactivity filters to prune 94.00% of non-productive reactions with a 0.01% error rate. Then, we train an ensemble of ranking models on pairs of interacting MOs to learn a relative productivity function over mechanistic steps in a given system. Without the use of explicit transformation patterns, the ensemble perfectly ranks the productive mechanism at the top 89.05% of the time, rising to 99.86% of the time when the top four are considered. Furthermore, the system

  13. Time- and space-resolved high energy operando X-ray diffraction for monitoring the methanol to hydrocarbons reaction over H-ZSM-22 zeolite catalyst in different conditions

    NASA Astrophysics Data System (ADS)

    del Campo, Pablo; Slawinski, Wojciech Andrzej; Henry, Reynald; Erichsen, Marius Westgård; Svelle, Stian; Beato, Pablo; Wragg, David; Olsbye, Unni

    2016-06-01

    The conversion of methanol to hydrocarbons (MTH) over H-ZSM-22 was studied by operando time- and space-resolved X-ray diffraction (XRD) at 370-385 °C and WHSV = 2 g/g h at the Swiss-Norwegian Beamline at ESRF. The performance of a commercial H-ZSM-22 sample was compared before and after acid-base treatment, and with and without propanol co-feed, respectively. N2 adsorption, Scanning Electron Microscopy and propyl amine desorption experiments showed that acid-base treatment led to enhanced accessibility of acid sites, mainly due to the formation of mesopores between agglomerated H-ZSM-22 crystals. The catalytic set-up allowed us to simultaneously observe the catalyst activity and unit cell volume variations by time- and space-resolved HXRD in operando conditions. The expansion of the unit cell and final flattening at different positions in the catalytic bed matched very nicely with the catalytic activity gradients. Different scenarios provided different behaviors and gave insights in the effect of morphology and co-feed process on the activity in the MTH process. This technique is the only one which has so far been able to provide direct evidence of the behavior of the species inside the catalytic reactor.

  14. Subdiffusion-reaction processes with A →B reactions versus subdiffusion-reaction processes with A +B→B reactions

    NASA Astrophysics Data System (ADS)

    Kosztołowicz, Tadeusz; Lewandowska, Katarzyna D.

    2014-09-01

    We consider the subdiffusion-reaction process with reactions of a type A +B→B (in which particles A are assumed to be mobile, whereas B are assumed to be static) in comparison to the subdiffusion-reaction process with A →B reactions which was studied by Sokolov, Schmidt, and Sagués [Phys. Rev. E 73, 031102 (2006), 10.1103/PhysRevE.73.031102]. In both processes a rule that reactions can only occur between particles which continue to exist is taken into account. Although in both processes a probability of the vanishing of particle A due to a reaction is independent of both time and space variables (assuming that in the system with the A +B→B reactions, particles B are distributed homogeneously), we show that subdiffusion-reaction equations describing these processes as well as their Green's functions are qualitatively different. The reason for this difference is as follows. In the case of the former reaction, particles A and B have to meet with some probability before the reaction occurs in contradiction with the case of the latter reaction. For the subdiffusion process with the A +B→B reactions we consider three models which differ in some details concerning a description of the reactions. We base the method considered in this paper on a random walk model in a system with both discrete time and discrete space variables. Then the system with discrete variables is transformed into a system with both continuous time and continuous space variables. Such a method seems to be convenient in analyzing subdiffusion-reaction processes with partially absorbing or partially reflecting walls. The reason is that within this method we can determine Green's functions without a necessity of solving a fractional differential subdiffusion-reaction equation with boundary conditions at the walls. As an example, we use the model to find the Green's functions for a subdiffusive reaction system (with the reactions mentioned above), which is bounded by a partially absorbing wall

  15. Diastereoselective Ugi reaction of chiral 1,3-aminoalcohols derived from an organocatalytic Mannich reaction

    PubMed Central

    Caputo, Samantha; Basso, Andrea; Moni, Lisa; Riva, Renata; Rocca, Valeria

    2016-01-01

    Summary Enantiomerically pure β-aminoalcohols, produced through an organocatalytic Mannich reaction, were subjected to an Ugi multicomponent reaction under classical or Lewis acid-promoted conditions with diastereoselectivities ranging from moderate to good. This approach represents a step-economical path to enantiomerically pure, polyfunctionalized peptidomimetics endowed with three stereogenic centers, allowing the introduction of five diversity inputs. PMID:26877816

  16. Multifractality in intracellular enzymatic reactions.

    PubMed

    Aranda, Juan S; Salgado, Edgar; Muñoz-Diosdado, Alejandro

    2006-05-21

    Enzymatic kinetics adjust well to the Michaelis-Menten paradigm in homogeneous media with dilute, perfectly mixed reactants. These conditions are quite different from the highly structured cell plasm, so applications of the classic kinetics theory to this environment are rather limited. Cytoplasmic structure produces molecular crowding and anomalous diffusion of substances, modifying the mass action kinetic laws. The reaction coefficients are no longer constant but time-variant, as stated in the fractal kinetics theory. Fractal kinetics assumes that enzymatic reactions on such heterogeneous media occur within a non-Euclidian space characterized by a certain fractal dimension, this fractal dimension gives the dependence on time of the kinetic coefficients. In this work, stochastic simulations of enzymatic reactions under molecular crowding have been completed, and kinetic coefficients for the reactions, including the Michaelis-Menten parameter KM, were calculated. The simulations results led us to confirm the time dependence of michaelian kinetic parameter for the enzymatic catalysis. Besides, other chaos related phenomena were pointed out from the obtained KM time series, such as the emergence of strange attractors and multifractality.

  17. Noncanonical reactions of flavoenzymes.

    PubMed

    Sobrado, Pablo

    2012-11-05

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

  18. Reaction spreading on graphs.

    PubMed

    Burioni, Raffaella; Chibbaro, Sergio; Vergni, Davide; Vulpiani, Angelo

    2012-11-01

    We study reaction-diffusion processes on graphs through an extension of the standard reaction-diffusion equation starting from first principles. We focus on reaction spreading, i.e., on the time evolution of the reaction product M(t). At variance with pure diffusive processes, characterized by the spectral dimension d{s}, the important quantity for reaction spreading is found to be the connectivity dimension d{l}. Numerical data, in agreement with analytical estimates based on the features of n independent random walkers on the graph, show that M(t)∼t{d{l}}. In the case of Erdös-Renyi random graphs, the reaction product is characterized by an exponential growth M(t)e{αt} with α proportional to ln(k), where (k) is the average degree of the graph.

  19. Photoneutron Reactions in Nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Utsunomiya, Hiroaki

    Photoneutron reactions are discussed in the context of nucleosynthesis with emphasis on a unified understanding of (γ, n) and (n, γ) reactions for heavy nuclei through the γ-ray strength function and a revisit to explosive nucleosynthesis of 9Be through the reciprocity theorem. The role of photonuclear reactions in nucleosynthesis is supplemented by the photonuclear data project (IAEA-CRP F42032) and will be strengthened in the Extreme Light Infrastructure-Nuclear Physics (ELI-NP) in the future.

  20. Nuclear reaction studies

    SciTech Connect

    Alexander, J.M.; Lacey, R.A.

    1994-11-01

    Research focused on the statistical and dynamical properties of ``hot`` nuclei formed in symmetric heavy-ion reactions. Theses included ``flow`` measurements and the mechanism for multifragment disassembly. Model calculations are being performed for the reactions C+C, Ne+Al, Ar+Sc, Kr+Nb, and Xe+La. It is planned to study {sup 40}Ar reactions from 27 to 115 MeV/nucleon. 2 figs., 41 refs.

  1. Two-Body and Three-Body Atomic Recombination Reactions.

    ERIC Educational Resources Information Center

    Alvarino, Jose M.; Martinez, E.

    1983-01-01

    Discusses how, in some circumstances, a two-body reaction (association in absence of a third body) is the only possible association, and how reactions proceed in this case. Taking competition between two/three-body reactions into account, considers relative importance of such combinations and conditions under which the former can be competitive.…

  2. No Evidence of Reaction Time Slowing in Autism Spectrum Disorder

    ERIC Educational Resources Information Center

    Ferraro, F. Richard

    2016-01-01

    A total of 32 studies comprising 238 simple reaction time and choice reaction time conditions were examined in individuals with autism spectrum disorder (n?=?964) and controls (n?=?1032). A Brinley plot/multiple regression analysis was performed on mean reaction times, regressing autism spectrum disorder performance onto the control performance as…

  3. The smallest chemical reaction system with bistability

    PubMed Central

    Wilhelm, Thomas

    2009-01-01

    Background Bistability underlies basic biological phenomena, such as cell division, differentiation, cancer onset, and apoptosis. So far biologists identified two necessary conditions for bistability: positive feedback and ultrasensitivity. Results Biological systems are based upon elementary mono- and bimolecular chemical reactions. In order to definitely clarify all necessary conditions for bistability we here present the corresponding minimal system. According to our definition, it contains the minimal number of (i) reactants, (ii) reactions, and (iii) terms in the corresponding ordinary differential equations (decreasing importance from i-iii). The minimal bistable system contains two reactants and four irreversible reactions (three bimolecular, one monomolecular). We discuss the roles of the reactions with respect to the necessary conditions for bistability: two reactions comprise the positive feedback loop, a third reaction filters out small stimuli thus enabling a stable 'off' state, and the fourth reaction prevents explosions. We argue that prevention of explosion is a third general necessary condition for bistability, which is so far lacking discussion in the literature. Moreover, in addition to proving that in two-component systems three steady states are necessary for bistability (five for tristability, etc.), we also present a simple general method to design such systems: one just needs one production and three different degradation mechanisms (one production, five degradations for tristability, etc.). This helps modelling multistable systems and it is important for corresponding synthetic biology projects. Conclusion The presented minimal bistable system finally clarifies the often discussed question for the necessary conditions for bistability. The three necessary conditions are: positive feedback, a mechanism to filter out small stimuli and a mechanism to prevent explosions. This is important for modelling bistability with simple systems and for

  4. Sleeve reaction chamber system

    DOEpatents

    Northrup, M. Allen; Beeman, Barton V.; Benett, William J.; Hadley, Dean R.; Landre, Phoebe; Lehew, Stacy L.; Krulevitch, Peter A.

    2009-08-25

    A chemical reaction chamber system that combines devices such as doped polysilicon for heating, bulk silicon for convective cooling, and thermoelectric (TE) coolers to augment the heating and cooling rates of the reaction chamber or chambers. In addition the system includes non-silicon-based reaction chambers such as any high thermal conductivity material used in combination with a thermoelectric cooling mechanism (i.e., Peltier device). The heat contained in the thermally conductive part of the system can be used/reused to heat the device, thereby conserving energy and expediting the heating/cooling rates. The system combines a micromachined silicon reaction chamber, for example, with an additional module/device for augmented heating/cooling using the Peltier effect. This additional module is particularly useful in extreme environments (very hot or extremely cold) where augmented heating/cooling would be useful to speed up the thermal cycling rates. The chemical reaction chamber system has various applications for synthesis or processing of organic, inorganic, or biochemical reactions, including the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction.

  5. Catalytic Conia-ene and related reactions.

    PubMed

    Hack, Daniel; Blümel, Marcus; Chauhan, Pankaj; Philipps, Arne R; Enders, Dieter

    2015-10-07

    Since its initial inception, the Conia-ene reaction, known as the intramolecular addition of enols to alkynes or alkenes, has experienced a tremendous development and appealing catalytic protocols have emerged. This review fathoms the underlying mechanistic principles rationalizing how substrate design, substrate activation, and the nature of the catalyst work hand in hand for the efficient synthesis of carbocycles and heterocycles at mild reaction conditions. Nowadays, Conia-ene reactions can be found as part of tandem reactions, and the road for asymmetric versions has already been paved. Based on their broad applicability, Conia-ene reactions have turned into a highly appreciated synthetic tool with impressive examples in natural product synthesis reported in recent years.

  6. Mukaiyama Aldol Reactions in Aqueous Media

    PubMed Central

    Kitanosono, Taku; Kobayashi, Shū

    2013-01-01

    Mukaiyama aldol reactions in aqueous media have been surveyed. While the original Mukaiyama aldol reactions entailed stoichiometric use of Lewis acids in organic solvents under strictly anhydrous conditions, Mukaiyama aldol reactions in aqueous media are not only suitable for green sustainable chemistry but are found to produce singular phenomena. These findings led to the discovery of a series of water-compatible Lewis acids such as lanthanide triflates in 1991. Our understanding on these beneficial effects in the presence of water will be deepened through the brilliant examples collected in this review. 1 Introduction 2 Rate Enhancement by Water in the Mukaiyama Aldol Reaction 3 Lewis Acid Catalysis in Aqueous or Organic Solvents 3.1 Water-Compatible Lewis Acids 4 Lewis-Base Catalysis in Aqueous or Organic Solvents 5 The Mukaiyama Aldol Reactions in 100% Water 6 Asymmetric Catalysts in Aqueous Media and Water 7 Conclusions and Perspective PMID:24971045

  7. Cascade enzymatic reactions for efficient carbon sequestration.

    PubMed

    Xia, Shunxiang; Zhao, Xueyan; Frigo-Vaz, Benjamin; Zheng, Wenyun; Kim, Jungbae; Wang, Ping

    2015-04-01

    Thermochemical processes developed for carbon capture and storage (CCS) offer high carbon capture capacities, but are generally hampered by low energy efficiency. Reversible cascade enzyme reactions are examined in this work for energy-efficient carbon sequestration. By integrating the reactions of two key enzymes of RTCA cycle, isocitrate dehydrogenase and aconitase, we demonstrate that intensified carbon capture can be realized through such cascade enzymatic reactions. Experiments show that enhanced thermodynamic driving force for carbon conversion can be attained via pH control under ambient conditions, and that the cascade reactions have the potential to capture 0.5 mol carbon at pH 6 for each mole of substrate applied. Overall it manifests that the carbon capture capacity of biocatalytic reactions, in addition to be energy efficient, can also be ultimately intensified to approach those realized with chemical absorbents such as MEA.

  8. Oscillating Reactions: Two Analogies

    ERIC Educational Resources Information Center

    Petruševski, Vladimir M.; Stojanovska, Marina I.; Šoptrajanov, Bojan T.

    2007-01-01

    Oscillating chemical reactions are truly spectacular phenomena, and demonstrations are always appreciated by the class. However, explaining such reactions to high school or first-year university students is problematic, because it may seem that no acceptable explanation is possible unless the students have profound knowledge of both physical…

  9. Degradations and Rearrangement Reactions

    NASA Astrophysics Data System (ADS)

    Zhang, Jianbo

    This section deals with recent reports concerning degradation and rearrangement reactions of free sugars as well as some glycosides. The transformations are classified in chemical and enzymatic ways. In addition, the Maillard reaction will be discussed as an example of degradation and rearrangement transformation and its application in current research in the fields of chemistry and biology.

  10. Photoinduced Multicomponent Reactions.

    PubMed

    Garbarino, Silvia; Ravelli, Davide; Protti, Stefano; Basso, Andrea

    2016-12-12

    The combination of multicomponent approaches with light-driven processes opens up new scenarios in the area of synthetic organic chemistry, where the need for sustainable, atom- and energy-efficient reactions is increasingly urgent. Photoinduced multicomponent reactions are still in their infancy, but significant developments in this area are expected in the near future.

  11. Lithium Cell Reactions.

    DTIC Science & Technology

    1983-12-01

    SUPPLEMENTARY NOTES It. KEY WORDS (Continue on reverse .,ide if necessary and Identify by block number) Batteries Thionyl Chloride Batteries Lithium ...Batteries Lithium Cells Primary Batteries Thionyl Chloride Cells Non Rechargeable Batteries Electrochemical Reactions 20. ABSTRACT (Continue on reverse...INVESTIGATION OF CHEMICAL, ELECTROCHEMICAL AND PARASITIC REACTIONS IN LITHIUM - THIONYL CHLORIDE CELLS .......................................... 1 1.0 IN TRO D UC

  12. Clock Reaction: Outreach Attraction

    ERIC Educational Resources Information Center

    Carpenter, Yuen-ying; Phillips, Heather A.; Jakubinek, Michael B.

    2010-01-01

    Chemistry students are often introduced to the concept of reaction rates through demonstrations or laboratory activities involving the well-known iodine clock reaction. For example, a laboratory experiment involving thiosulfate as an iodine scavenger is part of the first-year general chemistry laboratory curriculum at Dalhousie University. With…

  13. Hydrogen evolution reaction catalyst

    DOEpatents

    Subbaraman, Ram; Stamenkovic, Vojislav; Markovic, Nenad; Tripkovic, Dusan

    2016-02-09

    Systems and methods for a hydrogen evolution reaction catalyst are provided. Electrode material includes a plurality of clusters. The electrode exhibits bifunctionality with respect to the hydrogen evolution reaction. The electrode with clusters exhibits improved performance with respect to the intrinsic material of the electrode absent the clusters.

  14. REUSABLE REACTION VESSEL

    DOEpatents

    Soine, T.S.

    1963-02-26

    This patent shows a reusable reaction vessel for such high temperature reactions as the reduction of actinide metal chlorides by calcium metal. The vessel consists of an outer metal shell, an inner container of refractory material such as sintered magnesia, and between these, a bed of loose refractory material impregnated with thermally conductive inorganic salts. (AEC)

  15. Reactions to Attitudinal Deviancy.

    ERIC Educational Resources Information Center

    Levine, John M.; Allen, Vernon L.

    This paper presents a critical review of empirical and theoretical treatments of group reaction to attitudinal deviancy. Inspired by Festinger's (1950) ideas on resolution of attitudinal discrepancies in groups, Schachter (1951) conducted an experiment that has greatly influenced subsequent research and theory concerning reaction to attitudinal…

  16. Applications of Reaction Rate

    ERIC Educational Resources Information Center

    Cunningham, Kevin

    2007-01-01

    This article presents an assignment in which students are to research and report on a chemical reaction whose increased or decreased rate is of practical importance. Specifically, students are asked to represent the reaction they have chosen with an acceptable chemical equation, identify a factor that influences its rate and explain how and why it…

  17. Chemical Reaction Problem Solving.

    ERIC Educational Resources Information Center

    Veal, William

    1999-01-01

    Discusses the role of chemical-equation problem solving in helping students predict reaction products. Methods for helping students learn this process must be taught to students and future teachers by using pedagogical skills within the content of chemistry. Emphasizes that solving chemical reactions should involve creative cognition where…

  18. The solid-phase Nicholas reaction: scope and limitations.

    PubMed

    Gachkova, Natalie; Cassel, Johan; Leue, Stefanie; Kann, Nina

    2005-01-01

    Two libraries of alpha-substituted alkynes has been prepared on solid phase using a sequential Sonogashira/Nicholas reaction approach. The scope of nucleophiles in the Nicholas reaction on solid phase has been investigated, including carbon, oxygen, nitrogen, sulfur, fluoride, and hydride nucleophiles. The conditions for the reaction sequence have been optimized in terms of Lewis acid, catalyst for the Sonogashira step, temperature, reaction time, and decomplexation method, enabling the five-step sequence to be performed in 1 day.

  19. Reactions and their management.

    PubMed

    Ganapati, R; Pai, V V

    2004-12-01

    The uneventful response to chemotherapy in leprosy is marked by clinically disturbing episodes encountered in 20-30% of patients and these phenomena are called "reactions". Generally they are classified as reversal reaction (type-1) and erythema nodosum leprosum (type-2). The cutaneous menifestations are: (1) Type-2 reactions in LL, BL types constituting erythema nodosum leprosum, erythema multiforme, erythema necroticans, subcutaneous nodules, lepromatous exacerbation. (2) Type-1 reactions in borderline and tuberculoid leprosy. The other manifestations include: Acute neuritis, lymphadenitis, arthritis, oedema of the hands and feet, ocular lesions, etc. Sequelae of reactions are: Paralytic deformities, non-paralytic deformities, extensive scarring and renal damage. A simple guideline to identify the risk-prone cases has been narrated. Prednisolone in standard dosage schedule as recommended by WHO is now being widely used in control programmes.

  20. REACTIONS AT SUPERCRITICAL CONDITIONS: FUNDAMENTALS AND APPLICATIONS. (R824729)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  1. Presidential Green Chemistry Challenge: 2009 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2009 award winner, CEM Corporation, developed a fast, automated analytical process using less toxic reagents and less energy to distinguish protein from the food adulterant, melamine.

  2. Presidential Green Chemistry Challenge: 2012 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2012 award winner, Cytec Industries, developed the MAX HT sodalite scale inhibitor for heat exchangers and pipes in the Bayer process, which converts bauxite into alumina.

  3. Presidential Green Chemistry Challenge: 2002 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2002 award winner, Cargill Dow, developed the NatureWorks process to make biobased, compostable, and recyclable polylactic acid polymers for fibers and plastic packaging.

  4. Presidential Green Chemistry Challenge: 1998 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 1998 award winner, Argonne National Laboratory, developed an efficient, membrane-based process to synthesize lactate esters from sugars. These esters can replace toxic solvents.

  5. Presidential Green Chemistry Challenge: 1999 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 1999 award winner, Nalco Chemical Co., developed homogeneous dispersion polymerization with water as the solvent to make polymers to treat water in industrial and municipal operations.

  6. Presidential Green Chemistry Challenge: 2001 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2001 award winner, Novozymes North America, developed BioPreparation, an enzyme technology to separate natural waxes, oils, and contaminants from cotton before it is made into fabric.

  7. Presidential Green Chemistry Challenge: 2003 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2003 award winner, DuPont, developed a genetically engineered microorganism jointly with Genencor International to manufacture 1,3-propanediol, a building block for Sorona polyester.

  8. Presidential Green Chemistry Challenge: 2004 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2004 award winner, Buckman Laboratories International, developed Optimyze technology, which uses an esterase enzyme to remove sticky contaminants from paper products prior to recycling.

  9. Presidential Green Chemistry Challenge: 2010 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2010 award winners, Merck & Co. and Codexis, developed an enzymatic synthesis for sitagliptin (Januvia) that reduces waste, improves yield and safety, and eliminates a metal catalyst.

  10. EFFICIENT CHEMICAL TRANSFORMATIONS USING ALTERNATIVE REACTION CONDITIONS AND MEDIA

    EPA Science Inventory

    The diverse nature of chemical entities requires various green' strategic pathways in our quest towards attaining sustainability. A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of less-expensive and recyclable...

  11. Presidential Green Chemistry Challenge: 2006 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2006 award winner, Codexis, directed the evolution of three designer enzymes to produce the key chiral building block for atorvastatin, the active ingredient in the drug Lipitor.

  12. Presidential Green Chemistry Challenge: 1997 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 1997 award winner, Imation, developed DryView Imaging Systems, which use a special photographic film for medical imaging that replaces hazardous developer chemicals and water with heat.

  13. CHEMICAL SYNTHESIS USING 'GREENER' ALTERNATIVE REACTION CONDITIONS AND MEDIA

    EPA Science Inventory

    The chemical research during the last decade has witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into ...

  14. GREENER CHEMICAL SYNTHESES USING ALTERNATIVE REACTION CONDITIONS AND MEDIA

    EPA Science Inventory

    A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of recyclable mineral supports such as alumina, silica, clay, or 'doped' surfaces is presented which is applicable to a wide range of cleavage, condensation, cycl...

  15. GREENER ORGANIC SYNTHESES USING ALTERNATIVE REACTION CONDITIONS AND MEDIA

    EPA Science Inventory

    The diverse nature of chemical entities requires various green' strategic pathways in our quest towards attaining sustainability. A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of less-expensive and recyclable...

  16. ENVIRONMENTALLY FRIENDLIER SYNTHESES USING MICROWAVES AND ALTERNATIVE REACTION CONDITIONS

    EPA Science Inventory

    A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of less-expensive and recyclable mineral supports such as alumina, silica, clay, or doped surfaces is presented which is applicable to a wide range of cleavage, c...

  17. Presidential Green Chemistry Challenge: 2011 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2011 award winner, Kraton Performance Polymers, developed halogen-free, high-flow NEXAR polymer membranes using less solvent that save energy during reverse osmosis to desalinate water.

  18. Presidential Green Chemistry Challenge: 2007 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2007 award winner, Headwaters Technology Innovation, developed a metal nanocatalyst to synthesize hydrogen peroxide directly from hydrogen and oxygen, eliminating hazardous chemicals.

  19. Presidential Green Chemistry Challenge: 2016 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2016 award winner, Dow Agrosciences LLC, developed Instinct®, a technology that reduces fertilizer nitrate leaching to ground and surface waters and atmospheric nitrous oxide emissions. More corn and reduces CO2.

  20. ENVIRONMENTALLY FRIENDLIER SYNTHESIS USING ALTERNATIVE REACTION CONDITIONS AND MEDIA

    EPA Science Inventory

    The diverse nature of chemical universe requires various 'greener' strategic pathways in our quest towards attaining sustainability. A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of less-expensive and recycla...

  1. Presidential Green Chemistry Challenge: 2000 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2000 award winners, Bayer and Bayer AG, Covestro, developed high-performance, water-based, two-component polyurethane (PU) coatings that eliminate most or all VOCs and HAPs in other PU coatings.

  2. Presidential Green Chemistry Challenge: 2005 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 2005 award winner, BASF, invented a one-component, urethane acrylate oligomer primer system for automobile refinishing that is UV-curable, has VOCs, and is free of diisocyanates.

  3. Presidential Green Chemistry Challenge: 1996 Greener Reaction Conditions Award

    EPA Pesticide Factsheets

    Presidential Green Chemistry Challenge 1996 award winner, Dow Chemical Company, developed a process to manufacture polystyrene foam sheet packaging that uses carbon dioxide (CO2) as a blowing agent, eliminating CFC-12 and HCFC-22.

  4. Enhancing chemical reactions

    DOEpatents

    Morrey, John R.

    1978-01-01

    Methods of enhancing selected chemical reactions. The population of a selected high vibrational energy state of a reactant molecule is increased substantially above its population at thermal equilibrium by directing onto the molecule a beam of radiant energy from a laser having a combination of frequency and intensity selected to pump the selected energy state, and the reaction is carried out with the temperature, pressure, and concentrations of reactants maintained at a combination of values selected to optimize the reaction in preference to thermal degradation by transforming the absorbed energy into translational motion. The reaction temperature is selected to optimize the reaction. Typically a laser and a frequency doubler emit radiant energy at frequencies of .nu. and 2.nu. into an optical dye within an optical cavity capable of being tuned to a wanted frequency .delta. or a parametric oscillator comprising a non-centrosymmetric crystal having two indices of refraction, to emit radiant energy at the frequencies of .nu., 2.nu., and .delta. (and, with a parametric oscillator, also at 2.nu.-.delta.). Each unwanted frequency is filtered out, and each desired frequency is focused to the desired radiation flux within a reaction chamber and is reflected repeatedly through the chamber while reactants are fed into the chamber and reaction products are removed therefrom.

  5. Algorithm for reaction classification.

    PubMed

    Kraut, Hans; Eiblmaier, Josef; Grethe, Guenter; Löw, Peter; Matuszczyk, Heinz; Saller, Heinz

    2013-11-25

    Reaction classification has important applications, and many approaches to classification have been applied. Our own algorithm tests all maximum common substructures (MCS) between all reactant and product molecules in order to find an atom mapping containing the minimum chemical distance (MCD). Recent publications have concluded that new MCS algorithms need to be compared with existing methods in a reproducible environment, preferably on a generalized test set, yet the number of test sets available is small, and they are not truly representative of the range of reactions that occur in real reaction databases. We have designed a challenging test set of reactions and are making it publicly available and usable with InfoChem's software or other classification algorithms. We supply a representative set of example reactions, grouped into different levels of difficulty, from a large number of reaction databases that chemists actually encounter in practice, in order to demonstrate the basic requirements for a mapping algorithm to detect the reaction centers in a consistent way. We invite the scientific community to contribute to the future extension and improvement of this data set, to achieve the goal of a common standard.

  6. Modeling of surface reactions

    SciTech Connect

    Ray, T.R.

    1993-01-01

    Mathematical models are used to elucidate properties of the monomer-monomer and monomer-dimer type chemical reactions on a two-dimensional surface. The authors use mean-field and lattice gas models, detailing similarities and differences due to correlations in the lattice gas model. The monomer-monomer, or AB surface reaction model, with no diffusion, is investigated for various reaction rates k. Study of the exact rate equations reveals that poisoning always occurs if the adsorption rates of the reactants are unequal. If the adsorption rates of the reactants are equal, simulations show slow poisoning, associated with clustering of reactants. This behavior is also shown for the two-dimensional voter model. The authors analyze precisely the slow poisoning kinetics by an analytic treatment for the AB reaction with infinitesimal reaction rate, and by direct comparison with the voter model. They extend the results to incorporate the effects of place-exchange diffusion, and they compare the AB reaction with infinitesimal reaction rate and no diffusion to the voter model with diffusion at rate 1/2. They also consider the relationship of the voter model to the monomer-dimer model, and investigate the latter model for small reaction rates. The monomer-dimer, or AB[sub 2] surface reaction model is also investigated. Specifically, they consider the ZGB-model for CO-oxidation, and in generalizations of this model which include adspecies diffusion. A theory of nucleation to describe properties of non-equilibrium first-order transitions, specifically the evolution between [open quote]reactive[close quote] steady states and trivial adsorbing states, is derived. The behavior of the [open quote]epidemic[close quote] survival probability, P[sub s], for a non-poisoned patch surrounded by a poisoned background is determined below the poisoning transition.

  7. Cycloaddition reactions of ICNO

    NASA Astrophysics Data System (ADS)

    Pasinszki, Tibor; Krebsz, Melinda; Hajgató, Balázs

    2009-05-01

    The mechanism and selectivity of cycloaddition reactions of iodonitrile oxide, ICNO, have been studied with theoretical methods for the first time using MR-AQCC coupled-cluster and B3LYP DFT methods. Calculations have predicted that the favoured ICNO dimerisation process is a multi-step reaction to diiodofuroxan involving dinitrosoethylene-like intermediates. The ICNO cycloaddition with nitriles and ethynyl derivatives is a synchronous process favouring the formation of 1,2,4-oxadiazole and 1,2-oxazole derivatives, respectively. The cycloaddition reactions of ICNO have been studied experimentally by generating ICNO from AgCNO and iodine. Diiodofuroxan is obtained, however, even at the presence of nitriles.

  8. NEUTRONIC REACTION SYSTEM

    DOEpatents

    Wigner, E.P.

    1963-09-01

    A nuclear reactor system is described for breeding fissionable material, including a heat-exchange tank, a high- and a low-pressure chamber therein, heat- exchange tubes connecting these chambers, a solution of U/sup 233/ in heavy water in a reaction container within the tank, a slurry of thorium dioxide in heavy water in a second container surrounding the first container, an inlet conduit including a pump connecting the low pressure chamber to the reaction container, an outlet conduit connecting the high pressure chamber to the reaction container, and means of removing gaseous fission products released in both chambers. (AEC)

  9. Force approach to radiation reaction

    SciTech Connect

    López, Gustavo V.

    2016-02-15

    The difficulty of the usual approach to deal with the radiation reaction is pointed out, and under the condition that the radiation force must be a function of the external force and is zero whenever the external force be zero, a new and straightforward approach to radiation reaction force and damping is proposed. Starting from the Larmor formula for the power radiated by an accelerated charged particle, written in terms of the applied force instead of the acceleration, an expression for the radiation force is established in general, and applied to the examples for the linear and circular motion of a charged particle. This expression is quadratic in the magnitude of the applied force, inversely proportional to the speed of the charged particle, and directed opposite to the velocity vector. This force approach may contribute to the solution of the very old problem of incorporating the radiation reaction to the motion of the charged particles, and future experiments may tell us whether or not this approach point is in the right direction.

  10. Force approach to radiation reaction

    NASA Astrophysics Data System (ADS)

    López, Gustavo V.

    2016-02-01

    The difficulty of the usual approach to deal with the radiation reaction is pointed out, and under the condition that the radiation force must be a function of the external force and is zero whenever the external force be zero, a new and straightforward approach to radiation reaction force and damping is proposed. Starting from the Larmor formula for the power radiated by an accelerated charged particle, written in terms of the applied force instead of the acceleration, an expression for the radiation force is established in general, and applied to the examples for the linear and circular motion of a charged particle. This expression is quadratic in the magnitude of the applied force, inversely proportional to the speed of the charged particle, and directed opposite to the velocity vector. This force approach may contribute to the solution of the very old problem of incorporating the radiation reaction to the motion of the charged particles, and future experiments may tell us whether or not this approach point is in the right direction.

  11. Surface catalyzed mercury transformation reactions

    NASA Astrophysics Data System (ADS)

    Varanasi, Patanjali

    Mercury is a known pollutant that has detrimental effect on human health and environment. The anthropogenic emissions of mercury account for 10 to 30% of worldwide mercury emissions. There is a need to control/reduce anthropogenic mercury emissions. Many mercury control technologies are available but their effectiveness is dependent on the chemical form of mercury, because different chemical forms of mercury have different physical and chemical properties. Mercury leaves the boiler in its elemental form but goes through various transformations in the post-combustion zone. There is a need to understand how fly ash and flue gas composition affect speciation, partitioning, and reactions of mercury under the full range of post-combustion zone conditions. This knowledge can then be used to predict the chemical transformation of mercury (elemental, oxidized or particulate) in the post combustion zone and thus help with the control of mercury emissions from coal-burning power plants. To accomplish this goal present study was conducted using five coal fly ashes. These ashes were characterized and their catalytic activity was compared under selected reaction conditions in a fixed bed reactor. Based on the results from these fly ash experiments, three key components (carbon, iron oxide and calcium oxide) were chosen. These three components were then used to prepare model fly ashes. Silica/alumina was used as a base for these model fly ashes. One, two or three component model fly ashes were then prepared to investigate mercury transformation reactions. The third set of experiments was performed with five different oxidation catalysts to further understand the mercury oxidation process. Based on the results of these three studies the key components were predicted for different fly ash compositions under variety of flue gas conditions. A fixed bed reactor system was used to conduct this study. In all the experiments, the inlet concentration of Hg0(g) was maintained at 35 mug

  12. Bad Reaction to Cosmetics?

    MedlinePlus

    ... Devices Radiation-Emitting Products Vaccines, Blood & Biologics Animal & Veterinary Cosmetics Tobacco Products For Consumers Home For Consumers ... Reactions From Cosmetics More in Consumer Updates Animal & Veterinary Children's Health Cosmetics Dietary Supplements Drugs Food Medical ...

  13. Reactor for exothermic reactions

    DOEpatents

    Smith, Jr., Lawrence A.; Hearn, Dennis; Jones, Jr., Edward M.

    1993-01-01

    A liquid phase process for oligomerization of C.sub.4 and C.sub.5 isoolefins or the etherification thereof with C.sub.1 to C.sub.6 alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120.degree. to 300.degree. F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

  14. Untoward penicillin reactions

    PubMed Central

    Guthe, T.; Idsöe, O.; Willcox, R. R.

    1958-01-01

    The literature on untoward reactions following the administration of penicillin is reviewed. These reactions, including a certain number of deaths which have been reported, are of particular interest to health administrations and to WHO in view of the large-scale programmes for controlling the treponematoses which are now under way—programmes affecting millions of people in many parts of the world. The most serious problems are anaphylactic sensitivity phenomena and superinfection or cross-infection with penicillin-resistant organisms, and the reactions involved range in intensity from the mildest to the fatal; the incidence of the latter is estimated at 0.1-0.3 per million injections. The authors point out that with increasing use of penicillin, more persons are likely to become sensitized and the number of reactions can therefore be expected to rise. The best prevention against such an increase is the restriction of the unnecessary use of penicillin. PMID:13596877

  15. Translated chemical reaction networks.

    PubMed

    Johnston, Matthew D

    2014-05-01

    Many biochemical and industrial applications involve complicated networks of simultaneously occurring chemical reactions. Under the assumption of mass action kinetics, the dynamics of these chemical reaction networks are governed by systems of polynomial ordinary differential equations. The steady states of these mass action systems have been analyzed via a variety of techniques, including stoichiometric network analysis, deficiency theory, and algebraic techniques (e.g., Gröbner bases). In this paper, we present a novel method for characterizing the steady states of mass action systems. Our method explicitly links a network's capacity to permit a particular class of steady states, called toric steady states, to topological properties of a generalized network called a translated chemical reaction network. These networks share their reaction vectors with their source network but are permitted to have different complex stoichiometries and different network topologies. We apply the results to examples drawn from the biochemical literature.

  16. Common Reactions After Trauma

    MedlinePlus

    ... Loss of intimacy or feeling detached Recovery from stress reactions Turn to your family and friends when ... someone is thinking about killing themselves, call the Suicide Prevention Lifeline 1-800-273-TALK (8255) http:// ...

  17. Reaction wheel assembly

    NASA Technical Reports Server (NTRS)

    1976-01-01

    The fabrication and testing of three reaction wheels with associated drive and system monitoring electronics and brushless dc spin motors are discussed; the wheels are intended for use in a teleoperator simulator. Test results are included as graphs.

  18. Reactor for exothermic reactions

    DOEpatents

    Smith, L.A. Jr.; Hearn, D.; Jones, E.M. Jr.

    1993-03-02

    A liquid phase process is described for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

  19. Oral Hypersensitivity Reactions

    MedlinePlus

    ... often flavored with agents like cinnamon, peppermint or menthol, which can trigger hypersensitivity reactions in susceptible individuals. ... potential allergens such as cinnamon, peppermint, eugenol and menthol. Even dental floss and denture cleansers may contain ...

  20. Iodine Clock Reaction.

    ERIC Educational Resources Information Center

    Mitchell, Richard S.

    1996-01-01

    Describes a combination of solutions that can be used in the study of kinetics using the iodine clock reaction. The combination slows down degradation of the prepared solutions and can be used successfully for several weeks. (JRH)

  1. Response reactions: equilibrium coupling.

    PubMed

    Hoffmann, Eufrozina A; Nagypal, Istvan

    2006-06-01

    It is pointed out and illustrated in the present paper that if a homogeneous multiple equilibrium system containing k components and q species is composed of the reactants actually taken and their reactions contain only k + 1 species, then we have a unique representation with (q - k) stoichiometrically independent reactions (SIRs). We define these as coupling reactions. All the other possible combinations with k + 1 species are the coupled reactions that are in equilibrium when the (q - k) SIRs are in equilibrium. The response of the equilibrium state for perturbation is determined by the coupling and coupled equilibria. Depending on the circumstances and the actual thermodynamic data, the effect of coupled equilibria may overtake the effect of the coupling ones, leading to phenomena that are in apparent contradiction with Le Chatelier's principle.

  2. Skin Reactions to Cold

    PubMed Central

    Talpash, Orest

    1976-01-01

    Although skin reactions to cold are seen surprisingly infrequently in Canada, it is important to manage them correctly when they do occur. Frostbite, cold urticarias, Raynaud's disease and phenomenon, and several miscellaneous changes are discussed. PMID:21308019

  3. Chemisorption And Precipitation Reactions

    EPA Science Inventory

    The transport and bioavailability of chemical components within soils is, in part, controlled by partitioning between solids and solution. General terms used to describe these partitioning reactions include chemisorption and precipitation. Chemisorption is inclusive of the suit...

  4. An Illuminating Reaction.

    ERIC Educational Resources Information Center

    Matthews, Catherine E.

    1996-01-01

    Describes the use of carbide lights as an excellent mechanism for introducing or reviewing many basic chemistry concepts including elements and compounds, endothermic and exothermic reactions, physical and chemical changes, and balancing chemical equations. (JRH)

  5. [Occurrence of drug reactions].

    PubMed

    Pastorello, E; Qualizza, R M; Luraghi, M T; Ispano, M; Villa, A M; Ortolani, C; Zanussi, C

    1986-01-01

    The aim of this prospective study was to evaluate the incidence of allergic reactions to drugs compared to other kinds of medical emergencies admitted to the main Hospital in Milan during a 6 months period. At the same time we drew a list of drugs most frequently involved in allergic reactions, and a list of the most frequent symptoms. Using special forms, the medical staff collected patients' data: age, history of atopy, identification of the drug causing the reaction, and any previous reactions. Among 11,407 cases of medical emergencies, we found 163 (1.43%) patients showing drug reactions: the mean age was 27.3; 58.90% were female; atopy was present in 16.56%. The drugs most frequently involved were: pyrazon group (22%); ASA (20.86%); penicillin and derivatives (9.20%); sulfa drugs (6.14%); group B vitamins (4.30%); tetanus toxoid (4.30%); hyposensitizing extracts (3.68%); propionic acid derivatives (2.46%); paracetamol (1.84%); indomethacin (1.23%); rifampicin (1.23%); erythromycin (1.23%); glafenine (1.23%); others (17.80%). Urticaria and/or angioedema were the most frequent symptoms (86.51%), then anaphylactic shock (9.81%) and asthma (3.68%) with regard to anaphylactic shock only 6.20% of the patients had had a previous reaction to the same drug. From these data we can see that the incidence of drug reactions is very low compared to other medical emergencies; penicillin evidenced fewer reactions than expected, while the pyrazon group and ASA confirmed the data from literature.

  6. Anaphylactoid reaction to ethanol.

    PubMed

    Kelso, J M; Keating, M U; Squillace, D L; O'Connell, E J; Yunginger, J W; Sachs, M I

    1990-05-01

    We studied a 14-year-old boy who developed a pruritic rash and facial swelling after ingestion of beer or wine. A blinded challenge with purified ethanol was positive demonstrating ethanol itself to be the offending agent. An IgE-mediated reaction to ethanol or one of its metabolites as a hapten is possible, or the reaction may involve unusual metabolism of ethanol with accumulation of acetaldehyde and/or direct mast cell degranulation.

  7. Oxygen evolution reaction catalysis

    DOEpatents

    Haber, Joel A.; Jin, Jian; Xiang, Chengxiang; Gregoire, John M.; Jones, Ryan J.; Guevarra, Dan W.; Shinde, Aniketa A.

    2016-09-06

    An Oxygen Evolution Reaction (OER) catalyst includes a metal oxide that includes oxygen, cerium, and one or more second metals. In some instances, the cerium is 10 to 80 molar % of the metals in the metal oxide and/or the catalyst includes two or more second metals. The OER catalyst can be included in or on an electrode. The electrode can be arranged in an oxygen evolution system such that the Oxygen Evolution Reaction occurs at the electrode.

  8. Critical evaluation and rate constants of chemoselective ligation reactions for stoichiometric conjugations in water.

    PubMed

    Saito, Fumito; Noda, Hidetoshi; Bode, Jeffrey W

    2015-04-17

    Chemoselective ligation reactions have contributed immensely to the development of organic synthesis and chemical biology. However, the ligation of stoichiometric amounts of large molecules for applications such as protein-protein conjugates is still challenging. Conjugation reactions need to be fast enough to proceed under dilute conditions and chemoselective in the presence of unprotected functional groups; the starting materials and products must be stable under the reaction conditions. To compare known ligation reactions for their suitability under these conditions, we determined the second-order rate constants of ligation reactions using peptide substrates with unprotected functional groups. The reaction conditions, the chemoselectivity of the reactions, and the stability of the starting materials and products were carefully evaluated. In some cases, the stability could be improved by modifying the substrate structure. These data obtained under the ligation conditions provide a useful guide to choose an appropriate ligation reaction for synthesis of large molecules by covalent ligation reactions of unprotected substrates in water.

  9. Dynamical Properties of Discrete Reaction Networks

    PubMed Central

    Paulevé, Loïc; Craciun, Gheorghe; Koeppl, Heinz

    2013-01-01

    Reaction networks are commonly used to model the dynamics of populations subject to transformations that follow an imposed stoichiometry. This paper focuses on the efficient characterisation of dynamical properties of Discrete Reaction Networks (DRNs). DRNs can be seen as modeling the underlying discrete nondeterministic transitions of stochastic models of reaction networks. In that sense, a proof of non-reachability in a given DRN has immediate implications for any concrete stochastic model based on that DRN, independent of the choice of kinetic laws and constants. Moreover, if we assume that stochastic kinetic rates are given by the mass-action law (or any other kinetic law that gives non-vanishing probability to each reaction if the required number of interacting substrates is present), then reachability properties are equivalent in the two settings. The analysis of two types of global dynamical properties of DRNs is addressed: irreducibility, i.e., the ability to reach any discrete state from any other state; and recurrence, i.e., the ability to return to any initial state. Our results consider both the verification of such properties when species are present in a large copy number, and in the general case. The necessary and sufficient conditions obtained involve algebraic conditions on the network reactions which in most cases can be verified using linear programming. Finally, the relationship of DRN irreducibility and recurrence with dynamical properties of stochastic and continuous models of reaction networks is discussed. PMID:23722628

  10. Children's understanding of psychogenic bodily reactions.

    PubMed

    Notaro, P C; Gelman, S A; Zimmerman, M A

    2001-01-01

    One hundred twenty-eight children in preschool through fifth grade (range = 4,3-11,4) and 76 adults serving as a comparison group participated in two studies that examined how children reason about psychogenic bodily reactions, that is, ailments or nonconscious physiological responses with origins in the mind (e.g., stress-induced headache). Psychogenic bodily reactions provide an opportunity to study how children integrate knowledge between the domains of bodily response and psychology. In Study 1, participants were asked whether various familiar psychogenic bodily reactions were possible (e.g., can someone get a tummyache from worrying?). In Study 2, participants were presented with a novel domain (hypothetical "aliens" from outer space) and were asked whether various unfamiliar bodily conditions (e.g., toes swelling) could arise from various physical or psychological causes. As predicted, adults typically reported that psychogenic bodily reactions were possible, and that unfamiliar bodily conditions could result from either psychological or physical causes. In contrast, young children typically denied that psychogenic bodily reactions could occur and predicted that unfamiliar bodily conditions resulted from physical causes only. The results support a developmental path: younger children view psychogenic bodily responses as wholly physical, but with age, view them as both physical and psychological phenomena.

  11. [Cutaneous adverse drug reactions].

    PubMed

    Lebrun-Vignes, B; Valeyrie-Allanore, L

    2015-04-01

    Cutaneous adverse drug reactions (CADR) represent a heterogeneous field including various clinical patterns without specific features suggesting drug causality. Exanthematous eruptions, urticaria and vasculitis are the most common forms of CADR. Fixed eruption is uncommon in western countries. Serious reactions (fatal outcome, sequelae) represent 2% of CADR: bullous reactions (Stevens-Johnson syndrome, toxic epidermal necrolysis), DRESS (drug reaction with eosinophilia and systemic symptoms or drug-induced hypersensitivity syndrome) and acute generalized exanthematous pustulosis (AGEP). These forms must be quickly diagnosed to guide their management. The main risk factors are immunosuppression, autoimmunity and some HLA alleles in bullous reactions and DRESS. Most systemic drugs may induce cutaneous adverse reactions, especially antibiotics, anticonvulsivants, antineoplastic drugs, non-steroidal anti-inflammatory drugs, allopurinol and contrast media. Pathogenesis includes immediate or delayed immunologic mechanism, usually not related to dose, and pharmacologic/toxic mechanism, commonly dose-dependent or time-dependent. In case of immunologic mechanism, allergologic exploration is possible to clarify drug causality, with a variable sensitivity according to the drug and to the CADR type. It includes epicutaneous patch testing, prick test and intradermal test. However, no in vivo or in vitro test can confirm the drug causality. To determine the cause of the eruption, a logical approach based on clinical characteristics, chronologic factors and elimination of differential diagnosis is required, completed with a literature search. A reporting to pharmacovigilance network is essential in case of a serious CADR whatever the suspected drug and in any case if the involved drug is a newly marketed one or unusually related to cutaneous reactions.

  12. TRIMOLECULAR REACTIONS OF URANIUM HEXAFLUORIDE WITH WATER

    SciTech Connect

    Westbrook, M.; Becnel, J.; Garrison, S.

    2010-02-25

    The hydrolysis reaction of uranium hexafluoride (UF{sub 6}) is a key step in the synthesis of uranium dioxide (UO{sub 2}) powder for nuclear fuels. Mechanisms for the hydrolysis reactions are studied here with density functional theory and the Stuttgart small-core scalar relativistic pseudopotential and associated basis set for uranium. The reaction of a single UF{sub 6} molecule with a water molecule in the gas phase has been previously predicted to proceed over a relatively sizeable barrier of 78.2 kJ {center_dot} mol{sup -1}, indicating this reaction is only feasible at elevated temperatures. Given the observed formation of a second morphology for the UO{sub 2} product coupled with the observations of rapid, spontaneous hydrolysis at ambient conditions, an alternate reaction pathway must exist. In the present work, two trimolecular hydrolysis mechanisms are studied with density functional theory: (1) the reaction between two UF{sub 6} molecules and one water molecule, and (2) the reaction of two water molecules with a single UF{sub 6} molecule. The predicted reaction of two UF{sub 6} molecules with one water molecule displays an interesting 'fluorine-shuttle' mechanism, a significant energy barrier of 69.0 kJ {center_dot} mol{sup -1} to the formation of UF{sub 5}OH, and an enthalpy of reaction ({Delta}H{sub 298}) of +17.9 kJ {center_dot} mol{sup -1}. The reaction of a single UF{sub 6} molecule with two water molecules displays a 'proton-shuttle' mechanism, and is more favorable, having a slightly lower computed energy barrier of 58.9 kJ {center_dot} mol{sup -1} and an exothermic enthalpy of reaction ({Delta}H{sub 298}) of -13.9 kJ {center_dot} mol{sup -1}. The exothermic nature of the overall UF{sub 6} + 2 {center_dot} H{sub 2}O trimolecular reaction and the lowering of the barrier height with respect to the bimolecular reaction are encouraging; however, the sizable energy barrier indicates further study of the UF{sub 6} hydrolysis reaction mechanism is

  13. Enantioselective aldol reactions with masked fluoroacetates

    NASA Astrophysics Data System (ADS)

    Saadi, Jakub; Wennemers, Helma

    2016-03-01

    Despite the growing importance of organofluorines as pharmaceuticals and agrochemicals, the stereoselective introduction of fluorine into many prominent classes of natural products and chemotherapeutic agents is difficult. One long-standing unsolved challenge is the enantioselective aldol reaction of fluoroacetate to enable access to fluorinated analogues of medicinally relevant acetate-derived compounds, such as polyketides and statins. Herein we present fluoromalonic acid halfthioesters as biomimetic surrogates of fluoroacetate and demonstrate their use in highly stereoselective aldol reactions that proceed under mild organocatalytic conditions. We also show that the methodology can be extended to formal aldol reactions with fluoroacetaldehyde and consecutive aldol reactions. The synthetic utility of the fluorinated aldol products is illustrated by the synthesis of a fluorinated derivative of the top-selling drug atorvastatin. The results show the prospects of the method for the enantioselective introduction of fluoroacetate to access a wide variety of highly functionalized fluorinated compounds.

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

    PubMed

    Kraka, Elfi; Cremer, Dieter

    2010-05-18

    (A(n,s) < 0) the curving of the path, and thus the structural changes of the reaction complex. URVA can show the mechanism of a reaction expressed in terms of reaction phases, revealing the sequence of chemical processes in the reaction complex and making it possible to determine those electronic factors that control the mechanism and energetics of the reaction. The magnitude of adiabatic curvature coupling coefficients is related to strength and polarizability of the bonds being broken. Transient points along the reaction path are associated with hidden intermediates and hidden transition states, which can be converted into real intermediates and transition states when the reaction conditions or the substitution pattern of the reaction complex are appropriately changed. Accordingly, URVA represents a theoretical tool with tremendous experimental potential, offering the chemist the ability to assert greater control over reactions.

  15. Accelerated Chemical Reactions and Organic Synthesis in Leidenfrost Droplets.

    PubMed

    Bain, Ryan M; Pulliam, Christopher J; Thery, Fabien; Cooks, R Graham

    2016-08-22

    Leidenfrost levitated droplets can be used to accelerate chemical reactions in processes that appear similar to reaction acceleration in charged microdroplets produced by electrospray ionization. Reaction acceleration in Leidenfrost droplets is demonstrated for a base-catalyzed Claisen-Schmidt condensation, hydrazone formation from precharged and neutral ketones, and for the Katritzky pyrylium into pyridinium conversion under various reaction conditions. Comparisons with bulk reactions gave intermediate acceleration factors (2-50). By keeping the volume of the Leidenfrost droplets constant, it was shown that interfacial effects contribute to acceleration; this was confirmed by decreased reaction rates in the presence of a surfactant. The ability to multiplex Leidenfrost microreactors, to extract product into an immiscible solvent during reaction, and to use Leidenfrost droplets as reaction vessels to synthesize milligram quantities of product is also demonstrated.

  16. Capture reactions on C-14 in nonstandard big bang nucleosynthesis

    NASA Technical Reports Server (NTRS)

    Wiescher, Michael; Gorres, Joachim; Thielemann, Friedrich-Karl

    1990-01-01

    Nonstandard big bang nucleosynthesis leads to the production of C-14. The further reaction path depends on the depletion of C-14 by either photon, alpha, or neutron capture reactions. The nucleus C-14 is of particular importance in these scenarios because it forms a bottleneck for the production of heavier nuclei A greater than 14. The reaction rates of all three capture reactions at big bang conditions are discussed, and it is shown that the resulting reaction path, leading to the production of heavier elements, is dominated by the (p, gamma) and (n, gamma) rates, contrary to earlier suggestions.

  17. Role of Microbes in the Smectite-to-Illite Reaction

    USGS Publications Warehouse

    Kim, J.; Dong, H.; Seabaugh, J.; Newell, S.W.; Eberl, D.D.

    2004-01-01

    Temperature, pressure, and time have been thought to control the smectiteto-illite (S-I) reaction, an important diagenetic process used for petroleum exploration. We demonstrated that microorganisms can promote the S-I reaction by dissolving smectite through reduction of structural FE(III) at room temperature and 1 atmosphere within 14 days. This reaction typically requires conditions of 300?? to 350??C, 100 megapascals, and 4 to 5 months in the absence of microbial activity. These results challenge the conventional concept of the S-I reaction and of reaction kinetic models.

  18. Effective Analysis of Reaction Time Data

    ERIC Educational Resources Information Center

    Whelan, Robert

    2008-01-01

    Most analyses of reaction time (RT) data are conducted by using the statistical techniques with which psychologists are most familiar, such as analysis of variance on the sample mean. Unfortunately, these methods are usually inappropriate for RT data, because they have little power to detect genuine differences in RT between conditions. In…

  19. Organocatalytic aza-Michael/retro-aza-Michael reaction: pronounced chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction.

    PubMed

    Cai, Yong-Feng; Li, Li; Luo, Meng-Xian; Yang, Ke-Fang; Lai, Guo-Qiao; Jiang, Jian-Xiong; Xu, Li-Wen

    2011-05-01

    A detailed experimental investigation of an aza-Michael reaction of aniline and chalcone is presented. A series of Cinchona alkaloid-derived organocatalysts with different functional groups were prepared and used in the aza-Michael and retro-aza-Michael reaction. There was an interesting finding that a complete reversal of stereoselectivity when a benzoyl group was introduced to the cinchonine and cinchonidine. The chirality amplification vs. time proceeds in the quinine-derived organocatalyst containing silicon-based bulky group, QN-TBS, -catalyzed aza-Michael reaction under solvent-free conditions. In addition, we have demonstrated for the first time that racemization was occurred in suitable solvents under mild conditions due to retro-aza-Michael reaction of the Michael adduct of aniline with chalcone. These indicate the equilibrium of retro-aza-Michael reaction and aza-Michael reaction produce the happening of chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction under different conditions, which would be beneficial to the development of novel chiral catalysts for the aza-Michael reactions.

  20. Chemical reactions at aqueous interfaces

    NASA Astrophysics Data System (ADS)

    Vecitis, Chad David

    2009-12-01

    Interfaces or phase boundaries are a unique chemical environment relative to individual gas, liquid, or solid phases. Interfacial reaction mechanisms and kinetics are often at variance with homogeneous chemistry due to mass transfer, molecular orientation, and catalytic effects. Aqueous interfaces are a common subject of environmental science and engineering research, and three environmentally relevant aqueous interfaces are investigated in this thesis: 1) fluorochemical sonochemistry (bubble-water), 2) aqueous aerosol ozonation (gas-water droplet), and 3) electrolytic hydrogen production and simultaneous organic oxidation (water-metal/semiconductor). Direct interfacial analysis under environmentally relevant conditions is difficult, since most surface-specific techniques require relatively `extreme' conditions. Thus, the experimental investigations here focus on the development of chemical reactors and analytical techniques for the completion of time/concentration-dependent measurements of reactants and their products. Kinetic modeling, estimations, and/or correlations were used to extract information on interfacially relevant processes. We found that interfacial chemistry was determined to be the rate-limiting step to a subsequent series of relatively fast homogeneous reactions, for example: 1) Pyrolytic cleavage of the ionic headgroup of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorbed to cavitating bubble-water interfaces during sonolysis was the rate-determining step in transformation to their inorganic constituents carbon monoxide, carbon dioxide, and fluoride; 2) ozone oxidation of aqueous iodide to hypoiodous acid at the aerosol-gas interface is the rate-determining step in the oxidation of bromide and chloride to dihalogens; 3) Electrolytic oxidation of anodic titanol surface groups is rate-limiting for the overall oxidation of organics by the dichloride radical. We also found chemistry unique to the interface, for example: 1

  1. Reaction/Momentum Wheel

    NASA Technical Reports Server (NTRS)

    1997-01-01

    CTA Space Systems, Inc. has been licensed to sell commercially a reaction/momentum wheel originally developed for NASA's scientific satellites. NASA originally identified a need for the wheel in its Small Explorer program. The Submillimeter Wave Astronomy Satellite required extremely low jitter and a reaction/momentum wheel with a torque greater than any comparably sized commercially available wheel to keep the instrument pointed at celestial objects to a high degree of precision. After development, a market assessment by Research Triangle Institute was completed, showing commercial potential for the flywheel technology. A license was granted to CTA in the fall of 1996. The company currently uses the technology in its complete spacecraft fabrication services and has built over 10 reaction/momentum wheels for commercial, scientific, and military customers.

  2. Inflammatory Skin Conditions Associated With Radiotherapy.

    PubMed

    Hernández Aragüés, I; Pulido Pérez, A; Suárez Fernández, R

    2017-04-01

    Radiotherapy for cancer is used increasingly. Because skin cells undergo rapid turnover, the ionizing radiation of radiotherapy has collateral effects that are often expressed in inflammatory reactions. Some of these reactions-radiodermatitis and recall phenomenon, for example-are very familiar to dermatologists. Other, less common radiotherapy-associated skin conditions are often underdiagnosed but must also be recognized.

  3. Velocity pump reaction turbine

    DOEpatents

    House, Palmer A.

    1984-01-01

    An expanding hydraulic/two-phase velocity pump reaction turbine including a dual concentric rotor configuration with an inter-rotor annular flow channel in which the inner rotor is mechanically driven by the outer rotor. In another embodiment, the inner rotor is immobilized and provided with gas recovery ports on its outer surface by means of which gas in solution may be recovered. This velocity pump reaction turbine configuration is capable of potential energy conversion efficiencies of up to 70%, and is particularly suited for geothermal applications.

  4. Velocity pump reaction turbine

    DOEpatents

    House, Palmer A.

    1982-01-01

    An expanding hydraulic/two-phase velocity pump reaction turbine including a dual concentric rotor configuration with an inter-rotor annular flow channel in which the inner rotor is mechanically driven by the outer rotor. In another embodiment, the inner rotor is immobilized and provided with gas recovery ports on its outer surface by means of which gas in solution may be recovered. This velocity pump reaction turbine configuration is capable of potential energy conversion efficiencies of up to 70%, and is particularly suited for geothermal applications.

  5. Velocity pump reaction turbine

    SciTech Connect

    House, P.A.

    1984-02-07

    An expanding hydraulic/two-phase velocity pump reaction turbine including a dual concentric rotor configuration with an inter-rotor annular flow channel in which the inner rotor is mechanically driven by the outer rotor. In another embodiment, the inner rotor is immobilized and provided with gas recovery ports on its outer surface by means of which gas in solution may be recovered. This velocity pump reaction turbine configuration is capable of potential energy conversion efficiencies of up to 70%, and is particularly suited for geothermal applications.

  6. Velocity pump reaction turbine

    SciTech Connect

    House, P.A.

    1982-06-01

    An expanding hydraulic/two-phase velocity pump reaction turbine including a dual concentric rotor configuration with an interrotor annular flow channel in which the inner rotor is mechanically driven by the outer rotor. In another embodiment, the inner rotor is immobilized and provided with gas recovery ports on its outer surface by means of which gas in solution may be recovered. This velocity pump reaction turbine configuration is capable of potential energy conversion efficiencies of up to 70%, and is particularly suited for geothermal application

  7. Velocity pump reaction turbine

    DOEpatents

    House, P.A.

    An expanding hydraulic/two-phase velocity pump reaction turbine including a dual concentric rotor configuration with an inter-rotor annular flow channel in which the inner rotor is mechanically driven by the outer rotor. In another embodiment, the inner rotor is immobilized and provided with gas recovery ports on its outer surface by means of which gas in solution may be recovered. This velocity pump reaction turbine configuration is capable of potential energy conversion efficiencies of up to 70%, and is particularly suited for geothermal applications.

  8. Reactions of butadiyne. 1: The reaction with hydrogen atoms

    NASA Technical Reports Server (NTRS)

    Schwanebeck, W.; Warnatz, J.

    1984-01-01

    The reaction of hydrogen (H) atoms with butadiene (C4H2) was studied at room temperature in a pressure range between w mbar and 10 mbar. The primary step was an addition of H to C4H2 which is in its high pressure range at p 1 mbar. Under these conditions the following addition of a second H atom lies in the transition region between low and high pressure range. Vibrationally excited C4H4 can be deactivated to form buten-(1)-yne-(3)(C4H4) or decomposes into two C2H2 molecules. The rate constant at room temperature for primary step is given. The second order rate constant for the consumption of buten-(1)-yne-(3) is an H atom excess at room temperature is given.

  9. α-Regioselective Barbier Reaction of Carbonyl Compounds and Allyl Halides Mediated by Praseodymium.

    PubMed

    Wu, San; Li, Ying; Zhang, Songlin

    2016-09-02

    The first utility of praseodymium as a mediating metal in the Barbier reaction of carbonyl compounds with allyl halides was reported in this paper. In contrast to the traditional metal-mediated or catalyzed Barbier reactions, exclusive α-adducts were obtained in this one-pot reaction with a broad scope of substrates and feasible reaction conditions.

  10. Reaction product imaging

    SciTech Connect

    Chandler, D.W.

    1993-12-01

    Over the past few years the author has investigated the photochemistry of small molecules using the photofragment imaging technique. Bond energies, spectroscopy of radicals, dissociation dynamics and branching ratios are examples of information obtained by this technique. Along with extending the technique to the study of bimolecular reactions, efforts to make the technique as quantitative as possible have been the focus of the research effort. To this end, the author has measured the bond energy of the C-H bond in acetylene, branching ratios in the dissociation of HI, the energetics of CH{sub 3}Br, CD{sub 3}Br, C{sub 2}H{sub 5}Br and C{sub 2}H{sub 5}OBr dissociation, and the alignment of the CD{sub 3} fragment from CD{sub 3}I photolysis. In an effort to extend the technique to bimolecular reactions the author has studied the reaction of H with HI and the isotopic exchange reaction between H and D{sub 2}.

  11. Introducing the Wittig Reaction.

    ERIC Educational Resources Information Center

    Armstead, D. E. F.

    1979-01-01

    An experiment is described which provides a simple example of the application of the Wittig reaction to the synthesis of unsaturated compounds. The experiment was designed with British HNC chemistry students in mind, but it is also suitable as a project-type exercise for final year GCE A-level students. (Author/BB)

  12. Enantioselective Vinylogous Organocascade Reactions.

    PubMed

    Hepburn, Hamish B; Dell'Amico, Luca; Melchiorre, Paolo

    2016-08-01

    Cascade reactions are powerful tools for rapidly assembling complex molecular architectures from readily available starting materials in a single synthetic operation. Their marriage with asymmetric organocatalysis has led to the development of novel techniques, which are now recognized as reliable strategies for the one-pot enantioselective synthesis of stereochemically dense molecules. In recent years, even more complex synthetic challenges have been addressed by applying the principle of vinylogy to the realm of organocascade catalysis. The key to the success of vinylogous organocascade reactions is the unique ability of the chiral organocatalyst to transfer reactivity to a distal position without losing control on the stereo-determining events. This approach has greatly expanded the synthetic horizons of the field by providing the possibility of forging multiple stereocenters in remote positions from the catalyst's point of action with high selectivity, while simultaneously constructing multiple new bonds. This article critically describes the developments achieved in the field of enantioselective vinylogous organocascade reactions, charting the ideas, the conceptual advances, and the milestone reactions that have been essential for reaching highly practical levels of synthetic efficiency.

  13. Chain Reaction Polymerization.

    ERIC Educational Resources Information Center

    McGrath, James E.

    1981-01-01

    The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

  14. Chemical Reactions at Surfaces

    SciTech Connect

    Michael Henderson and Nancy Ryan Gray

    2010-04-14

    Chemical reactions at surfaces underlie some of the most important processes of today, including catalysis, energy conversion, microelectronics, human health and the environment. Understanding surface chemical reactions at a fundamental level is at the core of the field of surface science. The Gordon Research Conference on Chemical Reactions at Surfaces is one of the premiere meetings in the field. The program this year will cover a broad range of topics, including heterogeneous catalysis and surface chemistry, surfaces in environmental chemistry and energy conversion, reactions at the liquid-solid and liquid-gas interface, electronic materials growth and surface modification, biological interfaces, and electrons and photons at surfaces. An exciting program is planned, with contributions from outstanding speakers and discussion leaders from the international scientific community. The conference provides a dynamic environment with ample time for discussion and interaction. Attendees are encouraged to present posters; the poster sessions are historically well attended and stimulate additional discussions. The conference provides an excellent opportunity for junior researchers (e.g. graduate students or postdocs) to present their work and interact with established leaders in the field.

  15. Reaction Formulation: A Bibliography.

    ERIC Educational Resources Information Center

    Pedrini, D. T.; Pedrini, Bonnie C.

    Reaction formation was studied by Sigmund Freud. This defense mechanism may be related to repression, substitution, reversal, and compensation (or over-compensation). Alfred Adler considered compensation a basic process in his individual psychology. Anna Freud discussed some defense mechanisms, and Bibring, Dwyer, Huntington, and Valenstein…

  16. Lithium Cell Reactions.

    DTIC Science & Technology

    1985-02-01

    Page 1. INVESTIGATION OF CHEMICAL, ELECTROCHEMICAL AND PARASITIC REACTIONS IN LITHIUM - THIONYL CHLORIDE CELLS ....... ................. 1 1.1 INTRODUCTION...OF LITHIUM - THIONYL CHLORIDE CELLS. ................ 56 1.4.1 Carbon Limited Overdischarge...............56 1.4.1.1 Background... LITHIUM THIONYL - CHLORIDE CELLS. .. ............ ...... 101 1.5.1 Background. ....... ............ .... 101 1.5.2 Microphotography

  17. Confronting Combat Stress Reactions

    DTIC Science & Technology

    2010-03-22

    of the scalp, skull , or brain. 4 Combat stress reaction is categorized as a range of behaviors resulting from the stress of battle which decreases...3) experiencing rage aimed at discriminate and indiscriminate targets, (4) psychic numbing or emotional shutdown, (5) alienation from themselves and

  18. A Superintendent's Reaction

    ERIC Educational Resources Information Center

    Lytle, James H.

    2004-01-01

    This article presents a superintendent's reaction to Catherine Marshall and Michael Ward's article on research on social justice and training for leadership. The author states that there is a problem with Marshall and Ward's article which begins with the title, particularly with the word "training." The author contends that there is a significant…

  19. Polymerase chain reaction system

    DOEpatents

    Benett, William J.; Richards, James B.; Stratton, Paul L.; Hadley, Dean R.; Milanovich, Fred P.; Belgrader, Phil; Meyer, Peter L.

    2004-03-02

    A portable polymerase chain reaction DNA amplification and detection system includes one or more chamber modules. Each module supports a duplex assay of a biological sample. Each module has two parallel interrogation ports with a linear optical system. The system is capable of being handheld.

  20. Exocharmic Reactions up Close

    ERIC Educational Resources Information Center

    Ramette, R. W.

    2007-01-01

    The exocharmic reactions that can be observed microscopically are discussed. The students can discover the optimal concentration of an acidic lead nitrate solution, so that a crystal of potassium iodide, nudged to the edge of a drop, results in glinting golden hexagons of lead iodide.